Field Methods Compendium (FMC) Draft


OERR# 9285.2-11

FIELD METHODS COMPENDIUM (FMC)

DRAFT

Produced by

United States Environmental Protection Agency
Offices of Emergency and Remedial Response
Hazardous Site Evaluation Division
Analytical Operation Branch
Washington, D. C.

August, 1996

-------
DISCLAIMER

The methodology in this compendium are presented to enable Superfund personnel and other parties providing
field sampling and analytical services across widely dsipersed geographic areas to share information on sampling
and analytical procedures currently being used. They do not constitute rulemaking by the Agency, and may not
be relied upon to create a substatiative or procedural right enforceable by any other person. Mention of trade
names or commercial products does not constitute endorsement or recommendation for use.

-------
It Introduction tto the Compendium

The Field Methods Compendium is a technical document produced by the United States Environmental
Protection Agency's Office of Emergency and Remedial Response's Analytical Operations Branch. The
document is a compilation of methods that are being used in the regions. The methods have been supplied by the
parties identified in the begining of the methods. While some methods contain no performance information, most
methods are site-specific adaptations of validated methods, for instance FMC-VW-004 is based on the Office of
Drinking Water's (ODW) Method 501.2 a multi-laboratory validated method, with a lot of performance data from
ODW's water supply studies. This method has become obsolete for drinking water purposes, but remains
adequate for filed screening purposes and is supported by the historical data, for the analytes listed in the method.
Other methodology is based on evlauations of technology or processes done for the Office of Emergency and
Remedial Response (OERR) by ORD (EMSL-LV) under the Superfund Innovative Technology Program (SITE).
Many of the methods in the Compendium were peer reviewed in the original document, as those in the present
document will be.

The Compendium was developed to pull together field methods used across the country at various sites which
may not be available to RPMs and SMs in another region, and to provide options based on the specific needs of
the sampling/analytical activity.

This is a draft document to make available valid field methods for use, while work continues to combine
redundant methods, and move toward methods which meet performance based criteria.

In order to improve the assessment of data quality and data usability achieved by the methods in the compendium,
it's critical that the Analytical Operations Branch (AOB) get feedback on data, particularly the QC indicators used
in the methods. While this is not feasible for every project, it's requested that as this type of information is
developed for larger, long term projects, that it be forwarded to AOB.

Successful use of the methods depends on staying within the scope and applicability of the methods.

-------
TABLE OF CONTENTS

PART B:	ANALYTICAL METHODS

Chapter

1.0 Volatiles in Water

1.1	Volatile Organics in Water by Purge and Trap: FMC-VW-001 (F080.004)

1.2	Volatile Organics in Water by Automated Headspace - External Standard Method:
FMC-VW-002 (F080.005)

1.3	Volatile Organics in Water by Automated Headspace -Internal Standard Method:
FMC-VW-003 (F080.006)

1.4	Volatile Organics in Water by Manual Headspace: FMC-VW-004 (F080.007)

1.5	VOA/Water/Pentane Ext/GC-ECD: FMC-VW-005 (CSL)

1.6	VOA/Water/Carbon Disulfide Ext/GC-FID: FMC-VW-006 (CSL)

1.7	VOA/Water/Headspace/GC-PID: FMC-VW-007 (CSL)

1.8	Field Screening of Target Purgeable Volatile Organic Compounds (Aqueous Matrix):
FMC-VW-008 (NUS Region 3)

1.9	Method for Field Screening of Volatile Organic Compounds in Water and Soil by
Headspace Analysis Using the HNu 301P Gas Chromatograph: FMC-VW-009
(Region 5 ESD)

1.10	Method for Field Screening of Volatile Organic Compounds in Water and Soil by
Headspace Analysis Using the Photovac 1 OS 10 Gas Chromatograph: FMC-VW-010
(Region 5 ESD)

1.11	VOA/Water, Soil, Sediment/Methanol, Water Extraction/GC-PID, EL CD: FMC-VW-
011(CSL)

1.12	Volatile Organic Compound Verification By Purge And Trap With PID/ELCD
Detection: FMC-VW-012 (CSL)

1.13	Volatile Organic Screening By Heated Headspace With FID Detection: FMC-VW-013
(CSL)

1.14	Analysis of Volatile Organic Compounds in Water by Purge and Trap: FMC-VW-014
(ESAT Region 10)

2.0 Volatiles in Soil and Sediment

2.1	Volatile Organics in Soil/Sediment by Purge and Trap: FMC-VS-001 (F080.001)

2.2	Volatiles Organics in Soil/Sediment by Automated Headspace - External Standard
Method: FMC-VS-002 (F080.002)

2.3	VOA/Soil/Pentane Ext/GC-ECD: FMC-VS-003 (CSL)

2.4	VOA/Soil/Carbon Disulfide Ext/GC-FID: FMC-VS-004 (CSL)

2.5	V OA/Soil/Headspace/GC -PID: FMC-VS-005 (CSL)

2.6	Field Screening of Target Purgeable Volatile Organic Compounds (Solid Matrix):
FMC-VS-006 (NUS Region 3)

2.7	Analysis of Halogenated and Aromatic Volatile Organics Compounds in Soil and
Water by Purge and Trap Gas Chromatograph: FMC-VS-007 (FASP F93001)

1

-------
ANALYTICAL METHODS (Continued)

Chapter

3.0 Volatiles in Soil-Gas

3.1	Volatile Organics in Soil Gas - Adsorbent Tube Method: FMC-VG-001 (F080.008)

3.2	Volatile Organics in Soil Gas Using Electrolytic Conductivity Detector - Direct
Analysis: FMC-VG-002 (F080.009)

3.3	Halogenated Volatile Organics in Soil Gas Using Electron Capture Detector - Direct
Analysis: FMC-VG-003 (F080.010)

3.4	VOA/Soil Gas/Charcoal/GC-ECD: FMC-VG-004 (CSL)

3.5	VOA/Soil Gas/Canisters/GC-PID: FMC-VG-005 (CSL)

3.6	Field Screening Analysis of Volatile Contaminants in Soil Gas Matrix: FMC-VG-006
(NUS Region 3)

3.7	Analysis of Halogenated and Aromatic Volatile Compounds in Air and Soil Gas by
Thermal Desorption Gas Chromatograph: FMC-VG-007 (FASP F93011)

3.8	Volatile Organics in Soil Gas: FMC-VG-008 (ESAT Region 10)

3.9	Field Method for Volatile Indicator Parameters in Soil Gas Samples Using Photovac
GC/PID: FMC-VG-009 (Region 5 ESD)

3.10	Sampling and Field Gas Chromatographic Analysis for Volatile Organics in Soil
Gases: FMC-VG-010 (EMSL 8022)

3.11	Analysis of Halogenated and Aromatic Volatile Organics Compounds in Whole Gas
Samples by Purge and Trap Gas Chromatograph: FMC-VG-011 (FASP F93013)

4.0 Volatiles in Air

4.1	Volatile Organics in Air - Adsorbent Tube Method: FMC-VA-001 (F080.011)

4.2	Halogenated Volatile Organics in Air Using Electrolytic Conductivity	Detector
- Direct Analysis: FMC-VA-002 (F080.012)

4.3	Volatile Organics in Air - Portable Direct Analysis: FMC-VA-003 (F080.013)

4.4	Volatile Organics in Air Using Electron Capture Detector - Direct Analysis: FMC-
VA-004 (F080.014)

4.5	Field Screening Analysis of Ambient Air: FMC-VA-005 (NUS Region 3)

4.6	Manual Analysis of Ambient Air for Selected Volatile Organic Compounds by a
Portable Gas Chromatograph: FMC-VA-006 (Region 5 CRL)

4.7	Standard Operating Procedure for the Analysis of Ambient Air for Selected Volatile
Organic Compounds by a Portable Gas Chromatograph: FMC-VA-007 (Region 5
CRL)

4.8	Automated Analysis of Ambient Air for Selected Volatile Organic Compounds by a
Portable Gas Chromatograph: FMC-VA-008 (Region 5 CRL)

5.0 Semivolatiles

5.1	SV/Water/Carbon Disulfide Ext/GC-FID: FMC-S-001 (CSL)

5.2	Field Screening of Target Semivolatile Organic Compounds (Aqueous
Matrix): FMC-S-002 (NUS Region 3)

5.3	SV/Soil/MeCl Ext/GC-FID: FMC-S-003 (CSL)

2

-------
ANALYTICAL METHODS (Continued)

Chapter

5.4 Field Screening of Target Semivolatile Organic Compounds (Solid Matrix): FMC-S-
004 (NUS Region 3)

6.0 Pesticides

6.1	Chlorinated Pesticides in Soil: FMC-P-001 (F050.001)

6.2	Field Screening of Organochlorine Pesticides (Solid Matrix): FMC-P-002 (NUS
Region 3)

6.3	Chlorinated Pesticides in Water: FMC-P-003 (F050.002)

6.4	Field Screening of Organochlorine Pesticides (Aqueous Matrix): FMC-P-004 (NUS
Region 3)

6.5	Organophosphorus Pesticides in Water FMC-P-005 (F050.004)

6.6	Organophosphorus Pesticides in Soil/Sediment: FMC-P-006 (F050.003)

6.7	Phenoxyherbicides in Soil/Sediment: FMC-P-007 (F050.005)

6.8	Phenoxyherbicides in Water: FMC-P-008 (F050.006)

6.9	CLP Pesticide/PCB Analysis by Gas Chromatograph: FMC-P-009 (FASP F93006)

6.10	Preparation of Sediment, Soil, and Water Samples for Pesticide Analysis: FMC-P-010
(FASP F93005)

6.11	Field Extraction and Analysis of Chlorinated Pesticides in Soil by ECD: FMC-P-011
(ESAT Region 10)

7.0 Poly chlorinated Biphenyls

7.1	Polychlorinated Biphenyls (PCBs) in Oil: FMC-PCB-001 (F040.003)

7.2	Field Screening of Polychlorinated Biphenyl (PCB) Compounds (Solid Matrix): FMC-
PCB-002 (NUS Region 3)

7.3	Polychlorinated Biphenyls (PCBs) in Water: FMC-PCB-003 (F040.002)

7.4	Field Screening of Polychlorinated Biphenyl (PCB) Compounds (Aqueous Matrix):
FMC-PCB-004 (NUS Region 3)

7.5	PCB, Pest/Soil/Hexane Extraction/GC-ECD: FMC-PCB-005 (CSL)

7.6	PCB/Soil/Solvent Extraction/Perchlorinated/GC-ECD: FMC-PCB-006 (CSL)

7.7	Preparation and Analysis of Samples for Polychlorinated Biphenyls: FMC-PCB-007
(FASP F93007)

7.8	Field Analysis of PCBs: FMC-PCB-008 (ESAT Region 10)

7.9	Polychlorinated Biphenyls (PCBs) in Soil: FMC-PCB-009 (F040.001)

8.0 Polynuclear Aromatic Hydrocarbons (PAHs)

8.1	Field Gas Chromatographic Analysis for Polynuclear Aromatic Hydrocarbons (in
Water and Soil): FMC-PAH-001 (ORD/EMSL-LV)

8.2	Polynuclear Aromatic Hydrocarbons (PAH)/Water/Hexane Ext/GC-FID: FMC-PAH-
002(CSL)

8.3	Polynuclear Aromatic Hydrocarbons (PAH)/Soil/Hexane Ext/GC-FID: FMC-PAH-003
(CSL)

8.4	Total Polynuclear Aromatic Hydrocarbon Screening Procedure for Sediments: FMC-
PAH-004 (Region 10 Laboratory)

8.5	Polycyclic Aromatic Hydrocarbons in Soil/Sediment: FMC-PAH-005 (F060.001)

8.6	Polycyclic Aromatic Hydrocarbons in Water: FMC-PAH-006 (F060.002)

3

-------
ANALYTICAL METHODS (Continued)

Chapter

8.7	Polycyclic Aromatic Hydrocarbons in Oil: FMC-PAH-007 (F060.003)

8.8	PAH/Soil/Methanol Extraction, Somcation/UV: FMC-PAH-008 (CSL)

8.9	Analysis of PAH by Gas Chromatograph: FMC-PAH-009 (FASP F93009)

8.10	Preparation of Sediment Soil and Water Samples for Semivolatile Compounds: PAH,
Phenols: FMC-PAH-010 (FASP F93008)

8.11	Extraction and Analysis of PAH in Soil by GC/FID: FMC-PAH-011 (ESAT Region
10)

8.12	FASP Extraction and Analysis of PAH by HPLC: FMC-PAH-012 (ESAT Region 10)
9.0 Other Organics

9.1	Pentachlorophenol in Soil/Sediment: FMC-O-OOl (F070.001)

9.2	TPH/Soil/Freon Extraction/IR: FMC-O-002 (CSL)

9.3	TPH-G/Soil/Methanol Extraction/GC-PID, EL CD: FMC-O-003 (CSL)

9.4	TPH-HCID/Soil/Methylene Chloride Extraction/GC-FID: FMC-O-004 (CSL)

9.5	Analysis of Phenols by Gas Chromatograph: FMC-O-005 (FASP F93010)

9.6	Analysis of Total Petroleum Hydrocarbons by Headspace Gas Chromatography: FMC-
0-006 (FASP F93002)

9.7	Low Level Methane Analysis of Summa Canister Gas Sample: FMC-O-007 (ERT)

9.8	Extraction and Analysis of Pentachlorophenol in Soil by Electron Capture: FMC-O-
008 (ESAT Region 10)

9.9	Field Extraction and Analysis of TPH in Soil by FID: FMC-O-009 (ESAT Region 10)

10.	Inorganic Metals

10.1	Selected Metals in Soil/Sediment by X-Ray Fluorescence: FMC-I-001 (F100.001)

10.2	Inorganics/Soil/Acid Digestion/AA-Flame: FMC-I-002 (CSL)

10.3	Hexavalent Chromium/Soil/Alkaline Digestion/Spectrophotometer: FMC-I-003(CSL)

10.4	Inorganics/Water/Acid Digestion/AA-Flame: FMC-I-004 (CSL)

10.5	Mercury Analysis by Cold Vapor Atomic Absorption Spectrometry: FMC-I-005
(FASP F93004)

10.6	FASP Mercury Cold Vapor Atomic Absorption: FMC-I-006 (ESAT Region 10)

11.	Water, Soil and Waste Characterization

11.1	Alkalinity/Water/Titration: FMC-C-001 (CSL)

11.2	Chemical Oxygen Demand/Water/Open Reflux: FMC-C-002 (CSL)

11.3	Chloride, Nitrate, and Sulfate Amons/Water/IC: FMC-C-003 (CSL)

11.4	Hardness/Water/EDTA Colorimetric: FMC-C-004 (CSL)

11.5	Oil and Grease/Water/Gravimetric: FMC-C-005 (CSL)

11.6	Total Dissolved Solids/Water/Dried: FMC-C-006 (CSL)

11.7	Total Organic Carbon/Water/Analyzer: FMC-C-007 (CSL)

11.8	Total Suspended Solids/Water/Dried: FMC-C-008 (CSL)

4

-------
ANALYTICAL METHODS (Continued)

Chapter

11.9	10-Day Chronic Toxicity Test Using Daphnia Magna or Daphnia Pulex'. FMC-C-009
(ERT)

11.10	Extractable Organics/Soil/Gravimetric: FMC-C-010 (CSL)

11.11	Moisture/Soil/Drying oven: FMC-C-011 (CSL)

11.12	Paint Filter Test/Soil/Paint Filters: FMC-C-012 (CSL)

11.13	Ph/Soil/Ph Meter: FMC-C-013 (CSL)

11.14	Specific Gravity/Soil: FMC-C-014 (CSL)

11.15	Total Carbon/Soil/Combustion Tram: FMC-C-015 (CSL)

11.16	Total, Fixed, and Volatile Solids/Soil: FMC-C-016 (CSL)

11.17	Water Level Measurement: FMC-C-017 (ERT)

11.18	Controlled Pumping Test: FMC-C-018 (ERT)

11.19	Slug Test: FMC-C-019 (ERT)

11.20	General Surface Geophysics: FMC-C-020 (ERT)

11.21	7-Day Standard Reference Toxicity Test Using Larval Pimephales Promelas: FMC-
C-021 (ERT)

11.22	24-Hour Rangefinding Test Using Daphnia Magna or Daphnia Pulex'. FMC-C-022
(ERT)

11.23	96-Hour Acute Toxicity Test Using Larval Pimephales Promelas'. FMC-C-023 (ERT)

11.24	24-hour Rangefinding Test Using Larval Pimephales Promelas'. FMC-C-024 (ERT)

11.25	48-Hour Acute Toxicity Test Using Dap hnia Magna or Daphnia Pulex'. FMC-C-025
(ERT)

11.26	7-Day Renewal Toxicity Test Using Ceriodaphnia Dubia: FMC-C-026 (ERT)

11.27	7-Day Static Toxicity Test Using Larval Pimephales Promelas'. FMC-C-027 (ERT)

11.28	96-Hour Static Toxicity Test Using Selenastrum Capricornutum '. FMC-C-028 (ERT)

12.	Field Kits

12.1	Hazard Categorization: FMC-K-001 (Region 4 TAT, Weston)

12.2	Compatibility Testing: FMC-K-002 (Region 5 TAT, Weston)

13.	Radiological Analyses

13.1	Radiological/Quality Control For Sample Preparation, Counting, and Data Handling:
FMC-R-001 (CSL)

13.2	Radiological/Determination Of Gross Alpha/Beta In Soil Samples [simplified
methods]: FMC-R-002 (CSL)

13.3	Radiological/Soil Sample Preparation: FMC-R-003 (CSL)

13.4	Radiological/Determination Of Gross Alpha/Beta In Water Samples: FMC-R-004
(CSL)

13.5	Radiological/Determination Of Gross Alpha/Beta Activity In Water Samples [dot
level]: FMC-R-005 (CSL)

13.6	Radiological/Determination Of Gross Alpha/Gross Beta In Core Samples, Soil, Bottom
Sediments, Sludges, And Silts Samples [high organic samples]: FMC-R-006 (CSL)

5

-------
ANALYTICAL METHODS (Continued)

Chapter

13.7	Radiological/Determination Of Gross Alpha/Beta In Biota, vegetation/food stuff,
[simplified methods]: FMC-R-007 (CSL)

13.8	Determination Of Gross Alpha/Beta In Biota [vegetation/food stuff][extended
methods]: FMC-R-008 (CSL)

II. INSTRUMENTATION METHODS

14.	Inorganic Analysis

14.1	X-MET 880 Field Portable X-Ray Fluorescence Operating Procedure: FMC-IA-001
(ERT)

14.2	Operation of the X-MET 880 X-Ray Fluorescence Spectrometer: FMC-IM-002 (ESAT
Region 10)

14.3	Field Flame Atomic Absorption Analysis SOP: FMC-IM-003 (ESAT Region 10)

15.	Organic Analysis

15.1	Sentax Scentograph Gas Chromatograph Field Use: FMC-OA-OOl (ERT)

15.2	GC/MS Analysis of Tenax/CMS Cartridges and Summa Canisters: FMC-OA-002
(ERT)

15.3	Photonionization Detector (PID) HNU: FMC-OA-003 (ERT)

15.4	Photovac 10A10 Portable Gas Chromatograph Operation: FMC-OA-004 (ERT)

15.5	Photovac 10S50, 10S55, and 10S70 Gas Chromatograph Operation: FMC-OA-005
(ERT)

15.6	Photovac GC Analysis for Soil, Water, and Air/Soil Gas: FMC-OA-005 (ERT)

16.	Radiological Analysis

16.1	Radiological/Determination Of Detection Levels For Gross Alpha And Gross Beta
Analysis: FMC-RA-001 (CSL)

16.2	Radiological/Radiochemical Analysis Efficiency, Background, And Recovery
Standards (Counter) Preparation: FMC-RA-002 (CSL)

16.3	Radiological Operation Of The LB5100 Gas Proportional Counter: FMC-RA-003
(CSL)

16.4	Radiological/Setup And Operation Of The Counter Top Centrifuge: FMC-RA-004
(CSL)

III. SAMPLING METHODS

17.	Sample Equipment Decontamination

17.1 Sample Equipment Decontamination: FMC-SM-001 (ERT)

18.	Surface Water and Sediment

18.1 Surface Water Sampling: FMC-SWSS-001 (ERT)

6

-------
SAMPLING METHODS (Continued)

Chapter

18.2 Sediment Sampling: FMC-SWSS-002 (ERT)
19. Waste

19.1	Drum Sampling: FMC-WS-001 (ERT)

19.2	Tank Sampling: FMC-WS-002 (ERT)

19.3	Chip, Wipe, and Sweep Sampling: FMC-WS-003 (ERT)

19.4	Waste Pile Sampling: FMC-WS-004 (ERT)

20. Soil

20.1	Soil Sampling: FMC-SS-001 (ERT)

20.2	Soil Gas Sampling: FMC-SS-002 (ERT)

21. Groundwater

21.1 Groundwater Well Sampling: FMC-GWS-001 (ERT)

22. Gaseous

22.1 Collection of Gaseous Samples by Using Tedlar Bags: FMC-GS-001 (F93012)

QUALITY ASSURANCE/QUALITY CONTROL

23. Quality Assurance/Quality Control

23.1 Quality Assurance/Quality Control Samples: FMC-QA-001 (ERT)

7

-------
FASP Method Number F080.004
VOLATILE ORGANICS IN WATER BY PURGE AND TRAP

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various volatile organic compounds (VOCs) in water samples, using purge and trap technology
and gas chromatography (GC) analysis.

1.2 This method yields tentative identification and estimated quantitation of the analytes listed in Table 1.
Approximate method quantitation limits (QL) are also listed in Table 1. Reported values are on an "as-received"
basis; no dry weights are used.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of
ongoing work in the field. Identification of specific target compounds and prior knowledge regarding potential
matrix interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for
Contract Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of
sample concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 Five milliliters of a water sample is injected into a sparging vessel. The sample is purged with helium
to extract all VOCs onto a Tenax trap, or equivalent. The trapped sample is then desorbed directly onto a packed
glass column or a megabore capillary column installed in a temperature-programmed GC. VOCs are detected
with a photoionization detector (PID) and a Hall electrolytic conductivity detector connected in series.
Quantitation and identification are based on relative peak areas and relative retention times using the internal
standard method.

3.0 INTERFERENCES

3.1 Impurities in the purge gas, organic compounds outgassing from the plumbing ahead of the trap, and
solvent vapors in the laboratory account for the majority of contamination problems. The analytical system must
be demonstrated to be free from contamination under the conditions of the analysis by running laboratory reagent
blanks. The use of non-Teflon tubing, non-Teflon thread sealants, or flow controllers with rubber components in
the purging device should be avoided.

3.2 Contamination by carry-over can occur whenever high-level and low-level samples are sequentially
analyzed. To reduce carryover, the sampling syringe must be rinsed with reagent water between sample analyses.
Whenever an unusually concentrated sample is encountered, it should be followed by an analysis of reagent water
to check for cross contamination. For samples containing large amounts of suspended solids, high boiling
compounds, or high purgeable levels, it may be necessary to wash out the purging device with a detergent
solution, rinse it with distilled water, and then dry it in an oven at 105°C between analyses. The trap and other
parts of the system are also subject to contamination; therefore, frequent bakeout and purging of the entire system
may be required.

FMC-VW-001-1

-------
Table 1

FASP METHOD F080.004 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit in Water

(W?/L)

T richlorofluoromethane

75-69-4

10.0

1,1 -Dichloroethene

75-35-4

10.0

Methylene Chloride

75-09-2

10.0

trans-1,2-Dichloroethene

540-59-0

10.0

1,1 -Dichloroethane

75-34-3

10.0

Chloroform

67-66-3

10.0

1,1,1 -Trichloroethane

71-55-6

10.0

Carbon Tetrachloride

56-23-5

10.0

Benzene

71-43-2

10.0

1,2-Dichloroethane

107-06-2

10.0

Trichloroethene

79-01-6

10.0

1,2-Dichloropropane

78-87-5

10.0

Bromodichloromethane

75-25-4

10.0

cis-1,3 -Dichloropropene

10061-01-5

10.0

T oluene

108-88-3

10.0

trans-1,3 -Dichloropropene

10061-02-6

10.0

1,1,2-Trichloroethene

127-18-4

10.0

T etrachloroethene

127-18-4

10.0

Dibromochloromethane

124-48-1

10.0

(continued on next page)

Specific quantitation limit values are highly matrix dependent. The quantitation limits herein are provided
for guidance and may not always be achievable.

FMC-VW-001-2

-------
Table 1 (continued)

FASP METHOD F080.004 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit in
Water (|ig/L)

Chlorobenzene

108-90-7

10.0

Ethylbenzene

100-41-4

10.0

m,p-Xylenes

1330-20-7

10.0

o-Xylene

1330-20-7

10.0

Bromoform

75-25-2

10.0

1,1,2,2-T etrachloroethane

79-34-5

10.0

* Specific quantitaion limit values are highly matrix dependent. The quantitation limits herein are provided
for guidance and may not always be achievable.

3.3 The volatile analysis laboratory should be as completely free of interfering solvents as possible.

3.4 Interferences coextracted from samples are matrix and site specific. It is possible that techniques used
in either FASP or CLP Routine Analytical Services (RAS) methods may fail to eliminate interferences. Highly
specialized CLP Special Analytical Services (SAS) techniques may be required to produce acceptable analytical
results.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems

4.1.1 Gas chromatograph: An analytical system complete with a temperature-programmable GC
suitable for on-column injection is required and all necessary accessories including injector and detector
systems designed or modified to accept the appropriate analytical columns (packed or megabore). The
system shall have a data-handling system attached to the detectors that is capable of retention time labeling,
relative retention time comparisons, and providing relative and absolute peak height and peak area
measurements.

4.1.1.1 Packed column: 1.8 m x 3 mm I.D. glass column packed with 1 percent SP-1000 on
Carbopack B (60/80 mesh) or equivalent.

4.1.1.2 Capillary column: 30 m x 0.53 mm I.D. DB-624 fused silica megabore column (J&W
Scientific) or equivalent.

4.1.1.3 Detectors: A PID with a 10.2 eV lamp and a makeup gas supply at the detector inlet
should be connected in series to a Hall detector with a short length of deactivated fused silica capillary
column.

FMC-VW-001-3

-------
4.1.1.4 Gas supply: The purge gas, carrier gas and makeup gas should be ultrapure helium.
The reaction gas required for the Hall detector is ultrapure hydrogen. All gases should pass through
oxygen traps prior to the analytical system to prevent degradation of the column's analytical coating.

4.1.2 Purge and trap device: The purge and trap device consists of 3 separate pieces of equipment:
the sample purger, the trap, and the desorber. Several complete devices are commercially available. The
purge and trap device may be assembled as a separate unit or be coupled to a GC.

4.1.2.1 Sample sparger: The sample sparger must be designed to accept 5-mL samples or 25-
mL samples if lower detection limits are desired. The purge gas must pass through the water column
as finely divided bubbles.

4.1.2.2 Trap: The trap must be packed with the appropriate absorbent material(s) to collect
volatile organics from water.

4.1.2.3 Desorber: The desorber should be capable of rapidly heating the trap to 180°C. The
trap should not be heated higher than 220°C during the bakeout mode.

4.2 Other Laboratory Equipment

4.2.1 Microsvringes: 10- to 1000-^L.

4.2.2 Syringe: 5-mL Luer lock or 25-mL Luer lock, gas tight with Teflon valve.

4.2.3 Volumetric flasks: With ground glass or Teflon stoppers.

4.2.4 Vials: 1.8-mL for purgeable standards with Teflon-lined septa.

4.2.5 Drying oven: Capable of maintaining temperatures of greater than or equal to 200°C.

4.2.6 Desiccator: Glass and stainless steel (no plastic materials).

4.2.7 Oxygen traps: Supelpure-O-Trap and OM-1 indicating tube, or equivalent.

4.2.8 Leak detector: Snoop liquid or equivalent for packed column operations or GOW-MAC gas
leak detector, or equivalent, for megabore capillary operations.

4.2.9 Chromatographic data stamp: Used to record instrument operating conditions.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1 Solvents

5.1.1 1-Propanol: Pesticide quality, or equivalent.

5.1.2 Methanol: Pesticide quality, or equivalent.

5.2 Reagent Water: Reagent water is defined as water in which an interferant is not observed at the QL of
the analyte of interest. Reagent water may be generated using a carbon filter bed containing activated carbon

FMC-VW-001-4

-------
(Calgon Corporation, Filtrasorb-300 or equivalent), a water purification system (Milli-Q Plus with Organex Q
cartridge, Barnstead Water-1 Systems, or equivalent), or purchased from commercial laboratory supply houses.

5.3 Gases

5.3.1 Helium: Ultrapure or chromatographic grade, used in conjunction with an oxygen trap.

5.3.2 Hydrogen: Ultrapure or chromatographic grade, used in conjunction with an oxygen trap.

5.4 Stock Standard Solutions: Stock standard solutions should be purchased in methanol as manufacturer
certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This procedure is done through volumetric dilution of the stock standards with water. The
lowest concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining
standard concentrations should define the approximate working range of the GC: one at the upper linear range
and the other midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed
glass bottles. Calibration solutions must be replaced weekly, or whenever comparison with check standards
indicates a problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist
other than the calibration standard preparer.

5.7 Internal Standards: The 3 internal standards used are fluorobenzene, bromochloromethane, and
p-bromofluorobenzene, at 80 ng/L at time of purge.

5.7.1 Prepare an internal standard mix through volumetric dilution of individual stock standards with
methanol. It is recommended that the secondary dilution standard be prepared at a concentration of 200
Hg/mL of each internal standard compound. The addition of 2 (iL of this standard to 5 mL of sample or 5
mL of calibration standard would be equivalent to 80 ng/L.

5.7.2 All standards must be stored in a freezer in glass vials with Teflon-lined septa caps and be
protected from light. Internal standard solutions must be replaced weekly after the Teflon-lined septum has
been punctured, or whenever comparison with previous analyses indicates a problem.

5.8 Matrix Spike Solutions: Matrix spike solutions should be prepared by dilution of stock standard
solutions so that no more than 250 (iL of spike solution is required to provide a final sample spike level within the
advised quality control (QC) limits.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody
following current EPA regulations and recommendations in force at the time of sample collection.

6.2 Aqueous samples should be preserved with 2 drops hydrochloric acid (added to the sample vial before
filling with sample), and shipped on ice in the 40-mL sample vial with the Teflon-lined septa.

6.3 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for VOCs in water 14 days from
sampling to analysis (if preserved) and 7 days from sampling to analysis (if unpreserved).

7.0 PROCEDURE

FMC-VW-001-5

-------
7.1 Sample Extraction: This procedure is recommended for the Tekmar LSC-1 (upgraded), LSC-3, and
LSC-2000 purge and trap systems. Specific purge and trap system procedures and parameters may be found in
Appendices A and B.

7.1.1 Attach a water sparging vessel to the purge and trap 3-way valve system.

7.1.2 Carefully fill a 5-mL Luer lock tip gas-tight sample syringe to the 5-mL mark. If a 25-mL
sample is desired, use a 25-mL Luer lock tip, gas-tight sample syringe, and fill to the 25-mL mark. Make
sure there are no entrapped air bubbles.

7.1.3 Inject the internal standard mix into the water sample through the tip of the syringe.

7.1.4 Immediately attach the syringe to the 3-way valve and turn valve lever to allow injection of the
sample.

7.1.5 Inject the sample into the sparging vessel. Close the valve lever, then pull some air into the
syringe and inject into the sparge vessel to clear sample from the valve and injector line. Close the 3-way
valve.

7.1.6 Make sure the trap temperature is 30°C or less. Purge the water sample for 12 minutes. Check
for foaming.

7.1.7 The sample is ready to be desorbed.

7.2 Sample Desorption:

7.2.1 The purged sample may be preheated to 60°C on the trap, and is desorbed at 160°C-180°C for
4 minutes. The GC system begins data collection and temperature program concurrently with sample
desorption.

7.2.2 While the sample is being desorbed into the GC, empty the sparging vessel and then wash the
vessel with a minimum of one 5-mL flush of reagent water to avoid carryover of target analytes.

7.2.3 After the sample is desorbed, the purge and trap system should be returned to the purge mode,
and the trap should be baked. Gas should flow through the trap during the bake, and the trap should be
heated to 200°C for at least 5 minutes.

7.2.4 After baking the trap, allow it to cool to 30°C before desorbing the next sample.

FMC-VW-001-6

-------
7.3 Calibration

7.3.1 Initial Calibration:

7.3.1.1 After an experienced chromatographer has ensured that the entire chromatographic
system is functioning properly; that is conditions exist such that resolution, retention times, area
reporting, and interpretation of chromatograms are within acceptable QC limits, the GC may be cali-
brated by internal standard technique (Section 7.5). Using at least 3 calibration standards prepared as
described in Section 5.5, generate initial calibration curves (relative response versus mass of standard
injected) for each target analyte (refer to Section 7.4 for chromatographic procedures).

7.3.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.5) based on
each VOCs 3 relative calibration factors (RCFs, see Section 7.5) to determine the acceptability
(linearity) of the curve. Unless otherwise specified the %RSD must be less than or equal to

25 percent, or the calibration is invalid and must be repeated. Any time the GC system is altered (e.g.,
new column, or change in gas supply, change in oven temperature) or shut down, a new initial
calibration curve must be established.

7.3.2 Continuing calibration:

7.3.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing calibration
validation. This single point analysis follows the same analytical procedures used in the initial
calibration. Instrument response is used to compute the RCF, which is then compared to the mean
initial calibration factor (RCF), and a relative percent difference (RPD, see Section 7.5) is calculated.
Unless otherwise specified, the RPD must be less than or equal to 25 percent for the continuing
calibration to be considered valid. Otherwise, the calibration must be repeated. A continuing
calibration remains valid for a maximum of 24 hours providing the GC system remains unaltered
during that time.

7.3.2.2 Use the continuing calibration in all target analyte sample concentration calculations
(Section 7.5) for the period over which the calibration has been validated.

7.3.3 Final calibration: Obtain the final calibration at the end of each batch of sample analyses. The
maximum allowable RPD between the mean initial calibration and the final calibration factors for each
analyte must be less than or equal to 50 percent. A final calibration that achieves an RPD less than or equal
to 25 percent may be used as an ongoing continuing calibration.

7.4 Instrumental Analysis

7.4.1 Instrument parameters: Table 2 summarizes an example of acceptable instrument operating
conditions for the GC. Other instruments, columns, and/or chromatographic conditions may be employed if
this method's QC criteria are met.

7.4.2 Chromatograms:

FMC-VW-001-7

-------
Table 2

EXAMPLE TEMPERATURE-PROGRAMMABLE GC OPERATING CONDITIONS

S)))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))) Q

Purge and Trap Device:

Instrument:

Integrator:

Column:

Carrier Gas:

Make-up Gas:

Reaction Gas:

Column Oven:

Injector Temperature:
Detector Temperature:

Tekmar LSC-1 Liquid Sample Concentrator with upgrade package and heated
transfer line. (Trap composition: 1-cm 3% SP-2100, 15-cm Tenax, 8-cm silica
gel 15).

Shimadzu GC Mini-3 equipped with an HNu Systems PID detector with a
10.2-eV lamp connected in series to an O.I. Corporation Hall detector.

Nelson Analytical PC Integrator with a dual channel interface and hard disk drive for
data storage.

J&W DB-624 fused silica megabore column, 30 m x 0.53 mm. I.D.

Ultrapure helium, 10 mL/min.

Ultrapure helium, 40 mL/min.

Ultrapure hydrogen, 100 mL/min.

Initial temperature: 35°C
Initial time: 4 min.

Ramp rate: 4°C/min.

Final temperature: 105°C.

150oC.

PID:200oC
Hall: 800°C

GC Analysis Time:

20 mins

FMC-VW-001-8

-------
peak response should be greater than 25 percent and less than 100 percent of full-scale deflection to
allow visual recognition of the various VOCs.

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gas and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.4.3 VOC identification:

7.4.3.1 Qualitative identification of VOCs is based on both detector selectivity and relative
retention time as compared to known standards using the internal standard method.

7.4.3.2 For a compound that is detected on both the PID and Hall detector, the compound must
be identified in both chromatograms for a positive identification to be made.

7.4.3.3 Generally, individual peak relative retention time windows should be less than or equal
to 5 percent for packed column analysis or less than or equal to 2 percent for megabore capillary
columns. Alternatively, the individual peak relative retention time windows may be calculated based
on 3 times the standard deviation of at least 3 non-consecutive standard analyses. These analyses
must be representative of normal system variations, subject to the professional judgement of an
experienced analyst.

7.4.3.4 It may not be possible or practical to separate all volatile organic target analytes on a
single column. In such cases, these target analytes should be denoted as the appropriate combination
of VOCs.

7.4.4 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided as "Specific Instrument Parameters" in Appendix B of this method.

7.4.5 Analytical sequence:

7.4.5.1 Instrument blank.

7.4.5.2 Initial calibration.

7.4.5.3 Check standard solution or performance evaluation sample (if available).

7.4.5.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.5.5 Associated QC lot method blank.

7.4.5.6 Twenty samples and associated QC lot spike and duplicate.

7.4.5.7 Repeat sequence beginning at 7.4.5.5 until all sample analyses are completed or
another continuing calibration is required.

FMC-VW-001-9

-------
7.4.5.8 Final calibration when all sample analyses are complete.

7.5 Calculations

7.5.1 Identification and quantitation of VOCs should be based on the internal standard method. The
corresponding internal standard for each analyte is listed in Tables 3 (PID) and 4 (Hall detector). A
compound which is detected by both the PID and Hall detector should be quantitated using the detector
which gives the higher response for that specific compound. The second detector should be used for con-
firmation of the presence of that compound.

7.5.2 The peak areas of the internal standards should be monitored and evaluated for each standard
sample, blank, duplicate, and matrix spike. If the peak area for any internal standard changes by more than a
factor of 2 (-50 to +100 percent), the sample must be reanalyzed.

7.5.3 If after reanalysis the peak areas for all internal standards are inside the QC limits (-50 to +100
percent), only report data from the analysis with peak areas within the QC limits.

7.5.4 If the reanalysis of the sample does not solve the problem for both analyses, then do not report
sample data.

7.5.5 Initial calibration: Analyze each calibration standard, adding the internal standard spiking
solution directly to the syringe.

7.5.5.1 Tabulate the area response of each target analyte against concentration for each

compound and internal standards and calculate RCF for each target compound using the following

equation.

A C.

RCF = —- x —

A. C

IS X

where: Ax = area of the peak for the compound of interest

Ais = area of the peak for the appropriate internal standard
Cis = concentration of the internal standard
Cx = concentration of the compound to be measured

7.5.5.2 Using the RCF values, calculate the %RSD for each target analyte at all concentration

levels using the following equation.

ST)

%RSD = 4=- x 100

where SD, the Standard Deviation, is given by

FMC-VW-001-10

-------
Table 3

VOLATILE ORGANIC COMPOUNDS DETECTED BY THE PID
AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS2 fFluorobenzene')

1,1 -Dichloroethene

trans-1,2-Dichloroethene

Benzene

Trichloroethene

2-Chloroethylvinylether

cis-1,3 -Dichloropropene

m-Xylene

IS3 (p-Bromofluorobenzene')
T oluene

trans-1,3 -Dichloropropene
T etrachloroethene
Chlorobenzene
Ethylbenzene
o,p-Xylene

Table 4

VOLATILE ORGANIC COMPOUND DETECTED BY THE HALL
DETECTOR AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS1 fBromochloromethane')

T richlorofluoromethane
1,1 -Dichloroethene
Methylene chloride
trans-1,2-Dichloroethene
1,1 -Dichloroethane
Chloroform
1,1,1 -Trichloroethane
Carbon tetrachloride
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromodichloromethane

IS3 (p-Bromofluorobenzene')

cis-1,3 -Dichloropropene
trans-1,3 -Dichloropropene
1,1,2-Trichloroethane
T etrachloroethene
Dibromochloromethane
Chlorobenzene
Bromoform

1,1,2,2-T etrachloroethane

FMC-VW-001-11

-------
SD

(X.-X):
(N-l)

where: X; = Individual RCF (per analyte)

X = Mean of all initial RCF s (per analyte)

N = Number of calibration standards

7.5.6 Continuing calibration:

7.5.6.1 Sample quantitation is based on analyte RCF values calculated from continuing
calibrations. Midrange standards for all initial calibration target analytes must be analyzed at
specified intervals (less than or equal to 24 hours).

7.5.6.2 The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

\RCF~-RCFr\

RPD = 1 — x 100

RCFI+RCFc

where: RCF, = Mean CF from the initial calibration for each analyte

RCFc = Measured CF from the continuing calibration for the same analyte

7.5.7 Final calibration:

7.5.7.1 Obtain the final calibration at the end of any batch of samples analyzed.

7.5.7.2 The maximum allowable RPD between the mean initial calibration and final calibration
factors for each PCB target analyte must be less than or equal to 50 percent. A final calibration that
achieves an RPD less than or equal to 25 percent may be used as an ongoing continuing calibration.

RCF -RCF
RPD = 1 — x 100

rcfi+rcff

where: RCF, = Mean CF from the initial calibration for each analyte
RCFf = Final CF for the same analyte

7.5.8 Sample quantitation:

7.5.8.1 Calculate the concentration in the sample using the following equation for internal
standards. The relative response can be measured by automated relative peak height or relative peak
area measurements from an integrator.

7.5.8.2 The RCF from the continuing calibration analysis is used to calculate the concentration
in the sample. Use the relative calibration factor as determined in Section 7.5.5 and the following
equation.

FMC-VW-001-12

-------
Concentrationfuq/L) = 			-	

Uis) (RCF) (Vo)

where: Ax	=	Area of the peak for the compound to be measured

Ais	=	Area of peak for the specific internal standard from Table 3 or 4

Is	=	Amount of internal standard added (ng)

RCF	=	The relative calibration factor for the compound to be measured

V0	=	Volume of water purged (mL) (take into account any dilutions)

7.5.8.3	Report results in micrograms per liter (ng/L) without correction for blank or spike
recovery.

7.5.8.4	Coeluted analytes should be quantitated and reported as the combination of the
unseparated VOC target analytes.

7.5.8.5	Sample chromatograms may not match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum
possible concentration (qualified as less than the numerical value) which allows the data user to
determine if additional (e.g. CLP analyses) work is required, or, if the reported concentration is below
action levels and project objectives and DQOs have been met, to forego further analysis.

7.5.8.6 Similarly, when sample concentration exceeds the linear range, the analyst may report
a probable minimum level (qualified as greater than the numerical value) which allows the data user to
determine if additional (e.g., CLP RAS or SAS) work is required, or, if the reported concentration is
above action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R)
and duplicate RPD are presented in Table 5. This method must be used in conjucnction with the quality
assurance and control (QA/QC) section of this catalog.

FMC-VW-001-13

-------
Table 5

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.004 (VOCs in Water)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD
(%)

T richlorofluoromethane

30 to 200

±75

1,1 -Dichloroethene

30 to 200

±75

Methylene Chloride

30 to 200

±75

trans-1,2-Dichloroethane

30 to 200

±75

1,1 -Dichloroethane

30 to 200

±75

Chloroform

30 to 200

±75

1,1,1 -Trichloroethane

30 to 200

±75

Carbon Tetrachloride

30 to 200

±75

Benzene

30 to 200

±75

1,2-Dichloroethane

30 to 200

±75

Trichloroethene

30 to 200

±75

1,2-Dichloropropane

30 to 200

±75

Bromodichloromethane

30 to 200

±75

cis-1,3 -Dichloropropane

30 to 200

±75

T oluene

30 to 200

±75

trans-1,3 -Dichloropropene

30 to 200

±75

1,1,2-Trichloroethane

30 to 200

±75

T etrachloroethene

30 to 200

±75

Dibromochloromethane

30 to 200

±75

(continued on next page)

* If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for
duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-VW-001-14

-------
Table 5, (continued)

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.004 (VOCs in Water)

Advisory Quality Control Limits*

Analyte

Spike %R (%)

Duplicate RPD (%)

Chlorobenzene

30 to 200

±75

Ethylbenzene

30 to 200

±75

m,p-Xylenes

30 to 200

±75

o-Xylene

30 to 200

±75

Bromoform

30 to 200

±75

1,1,2,2-T etrachloroethane

30 to 200

±75

* If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for
duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-VW-001-15

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatograms are examples of GC chromatograms for volatile organic analytes as
detected by the FID and Hall detectors.

Figure 1
Gas chromatogram A-PID

Column:

Column Temperature:

Detector/Injector Temperature:
Gas:

Detector:

J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Initial temperature - 35°C for 4 mins

Ramp - 4°C/min

Final temperature - 105°C

150°C

Carrier; ultrapure helium, 10 mL/min.

Make-up; ultrapure helium, 40 mL/min.

HNu PID with a 10.2 eV lamp.

FMC-VW-001-16

-------
Figure 2

Gas chromatogram B - Hall detector

Column:

Column Temperature:

Detector/Injector Temperature:
Gas:

J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Initial temperature - 35°C for 4 mins

Ramp - 4°C/min

Final temperature - 105°C

150°C

Carrier; ultrapure helium, 10 mL/min.

Make-up; ultrapure helium, 40 mL/min.

Reaction gas; ultrapure hydrogen, 100 mL/min.

Detector:

O.I. Corporation Hall electrolyte conductivity detector.

FMC-VW-001-17

-------
9.2 Method F080.004 examples of sample QA/QC results: Spike and duplicate sample results are
presented as examples of FASP Method F080.004 empirical data (see Tables 6 and 7)

Table 6

FASP METHOD F080.004
WATER MATRIX SPIKE PERCENT RECOVERY (%R)

Analytes

Sample

Spike
Amount
Added

Spiked
Sample

Percent
Recovery

T richlorofluoromethane

10 UF

80

87 F

109

1,1 -Dichloroethene

10 UF

80

81 F

101

Methylene chloride

10 UF

80

71 F

89

trans-1,2-Dichloroethene

10 UF

80

96 F

120

1,1 -Dichloroethane

10 UF

80

90 F

113

Chloroform

20 UF

80

85 F

106

1,1,1 -Trichloroethane

10 UF

80

85 F

106

Carbon tetrachloride

10 UF

80

85 F

106

1,2-Dichloroethane

10 UF

80

79 F

99

Trichloroethene

10 UF

80

78 F

98

1,2-Dichloropropane

10 UF

80

83 F

104

Bromodichloromethane

10 UF

80

47 F

59

2-Chloroethylvinylether

20 UF

80

.. *

.. *

cis-1,3 -Dichloropropene

10 UF

80

45 F

56

trans-1,3 -Dichloropropene

10 UF

80

42 F

53

(continued on next page)

U - The material was analyzed for but was not detected. The associated numerical value is a method
quantitation limit, adjusted for sample volume.

F - Data have been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

* 2-Chloroethylvinylether is unstable. Concentrations found in standard solutions are not guaranteed by the
manufacturer. This compound was not found in the standard mix used for the matrix spike solution.

FMC-VW-001-18

-------
Table 6 (continued)

FASP METHOD F080.004
WATER MATRIX SPIKE PERCENT RECOVERY (%R)

Analytes

Sample

Spike
Amount
Added

Spiked
Sample

Percent
Recovery

1,1,2-Trichloroethene

10 UF

80

32 F

40

T etrachloroethene

10 UF

80

30 F

38

Dibromochloromethane

10 UF

80

42 F

53

Chlorobenzene

10 UF

80

24 F

30

Bromoform

10 UF

80

73 F

91

1,1,2,2-T etrachloroethane

10 UF

80

67 F

84

U - The material was analyzed for but was not detected. The associated numerical value is a method
quantitation limit, adjusted for sample volume.

F - Data have been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

FMC-VW-001-19

-------
Table 7

FASP METHOD F080.004
WATER DUPLICATE SAMPLE ANALYSIS
RELATIVE PERCENT DIFFERENCE (RPD)

Analytes

Sample
Results

Duplicate
Sample
Results

RPD (%)

T richlorofluoromethane

10 UF

10 UF

0

1,1 -Dichloroethene

10 UF

10 UF

0

Methylene chloride

10 UF

10 UF

0

trans-1,2-Dichloroethene

10 UF

10 UF

0

1,1 -Dichloroethane

10 UF

10 UF

0

Chloroform

20 UF

20 UF

0

1,1,1 -Trichloroethane

10 UF

10 UF

0

Carbon tetrachloride

10 UF

10 UF

0

1,2-Dichloroethane

10 UF

10 UF

0

Trichloroethene

18.8F

15.4 F

20

1,2-Dichloropropane

10 UF

10 UF

0

Bromodichloromethane

10 UF

10 UF

0

2-Chloroethylvinylether

20 UF

20 UF

0

cis-1,3 -Dichloropropene

10 UF

10 UF

0

trans-1,3 -Dichloropropene

10 UF

10 UF

0

(continued on next page)

U - The material was analyzed for but was not detected. The associated numerical value is a method
quantitation limit, adjusted for sample volume.

F - Data have been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

FMC-VW-001-20

-------
Table 7 (continued)

FASP METHOD F080.004
WATER DUPLICATE SAMPLE ANALYSIS
RELATIVE PERCENT DIFFERENCE (RPD)

Analytes

Sample

Duplicate
Sample
Results

RPD (%)

1,1,2-Trichloroethene

10 UF

10 UF

0

T etrachloroethene

10 UF

10 UF

0

Dibromochloromethane

10 UF

10 UF

0

Chlorobenzene

10 UF

10 UF

0

Bromoform

10 UF

10 UF

0

1,1,2,2-T etrachloroethane

10 UF

10 UF

0

U - The material was analyzed for but was not detected. The associated numerical value is a method
quantitation limit, adjusted for sample volume.

F - Data have been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

10.0 REFERENCES

Infromation not available.

FMC-VW-001-21

-------
APPENDIX A

FASP Method F080.004

Instrument Options:
Purge and Trap Device:

GC System:

Data Handling System 1:
Data Handling System 2:
Data Handling System 3:

Data Handling System 4:

Tekmar LSC-1 Liquid Sample Concentrator with upgrade package and heated
transfer line (Trap composition: 1-cm 3% SP-2100, 15-cm Tenax, 8-cm silica
gel 15).

Shimadzu GC-mini 3 (temperature-programmable) with an HNu PID
connected in series to an O.I. Corporation Hall detector modified with a direct
conversion and make-up gas adapter for megabore capillary column
operations.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display
unit and Shimadzu FDD-1A Floppy Disk Drive.

P.E. Nelson 2100 dual-channel integrator with 960 Series Intelligent Interface,
Hyundai 80286 computer, and Epson LX800 printer.

FMC-VW-001-22

-------
APPENDIX B

FASP Method F080.004

Specific Instrument Parameters:
Purge and Trap Device:

G.C.:

Integrator:

Columns:

Carrier Gas:

Make-up Gas:

Reaction Gas:

Column (Oven) Temperature:

Detector Temperature:

Injector Temperature:

Tekmar LSC-1 Liquid Sample Concentrator with upgrade package
and heated transfer line. (Trap composition: 1-cm 3% SP-2100,
15-cm Tenax, 8-cm silica gel 15).

Shimadzu GC-mini 3 (temperature-programmable) with an HNu PID
connected in series to an O.I. Corporation Hall detector.

Shimadzu Chromatopac C-R3A Data Processor.

J&W 30 m x 0.53 mm DB-624 fused silica megabore capillary
column.

Ultrapure helium, 10 mL/min.

Ultrapure helium, 40 mL/min.

Ultrapure hydrogen, 100 mL/min.

Initial temperature 35°C for 4 mins. Ramp 4°C/min. Final
temperature 105°C.

150oC.

150oC.

FMC-VW-001-23

-------
FASP Method Number F080.005
VOLATILE ORGANICS IN WATER BY AUTOMATED HEADSPACE

EXTERNAL STANDARD METHOD

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the relative
concentrations of various volatile organic compounds (VOCs) in aqueous samples.

1.2 This method yields tentative identification and estimated relative quantitation of the analytes listed in
Table 1. Approximate quantitation limits (QL) are also listed in Table 1. Reported values are on an "as-received"
basis.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.5 This FASP method is intended only to generate screening data that can be used to direct ongoing field
work, identify samples that need additional analysis, or determine relative concentrations of target analytes. The
headspace technique assumes that for volatile compounds, the concentration of an analyte found in the headspace
over the water sample directly relates to the actual concentration of the analyte in the sample. This assumption is
usually valid, however, complex matrices such as oily wastes, multiphase samples, and samples containing
high-level organic or inorganic interferences may prevent the assumed partitioning between the liquid and
gas/vapor phases in the headspace vial.

2.0 SUMMARY OF METHOD

2.1 A measured amount of water sample is placed into a headspace vial. The headspace volume is made
constant for all samples and standards. The containers are sealed and allowed to equilibrate at a temperature near
the boiling point of the most volatile target analyte in the headspace sampler. A sample is withdrawn from the
headspace and injected onto a temperature-programmed gas chromatograph equipped with a packed or megabore
capillary column. Volatile organic compounds are detected with a photoionization detector (PID) and a Hall
electrolytic conductivity detector connected in series. Quantitation and identification are based on relative peak
areas and relative retention times using the external standard method.

3.0 INTERFERENCES

3.1 Impurities in the purge gas, organic compounds out-gassing from the plumbing ahead of the trap, and
solvent vapors in the laboratory account for the majority of contamination problems. The analytical system must
be demonstrated to be free from contamination under the conditions of the analysis by running laboratory reagent
blanks. The use of non-Teflon tubing, non-Teflon thread sealants, or flow controllers with rubber components in
the purging device should be avoided.

FMC-VW-002-1

-------
Table 1

FASP METHOD F080.005 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit in Water

(W?/L)

T richlorofluoromethane

75-69-4

10

1,1 -Dichloroethene

75-35-4

10

Methylene Chloride

75-09-2

10

trans-1,2-Dichloroethene

540-59-0

10

1,1 -Dichloroethene

75-34-3

10

Chloroform

67-66-3

10

1,1,1 -Trichloroethane

71-55-6

10

Carbon Tetrachloride

56-23-5

10

Benzene

71-43-2

10

1,2-Dichloroethene

107-06-2

10

Trichloroethene

79-01-6

10

1,2-Dichloropropane

78-87-5

10

Bromodichloromethane

75-25-4

10

cis-1,3 -Dichloropropene

10061-01-5

10

T oluene

108-88-3

10

trans-1,3 -Dichloropropene

10061-02-6

10

1,1,2-Trichloroethane

79-00-5

10

T etrachloroethene

127-18-4

10

Dibromochloromethane

124-48-1

10

(continued on next page)

* Specific quantitation limit values are highly matrix dependent. The quantitation limits herein are provided
for guidance and may not always be achievable.

FMC-VW-002-2

-------
Table 1 (continued)

FASP METHOD F080.005 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit in
Water (ng/L)

Chlorobenzene

108-90-7

Ethylbenzene

100-41-4

m,p-Xylenes

1330-20-7

o-Xylene

1330-20-7

Bromoform

75-25-2

1,1,2,2-T etrachloroethane

79-34-5

* Specific quantitaion limit values are highly matrix dependent. The quantitation limits herein are provided
for guidance and may not always be achievable.

3.2 Contamination by carry-over can occur whenever high-level and low-level samples are sequentially
analyzed. To reduce carryover, the sampling syringe must be rinsed with reagent water between sample analyses.
Whenever an unusually concentrated sample is encountered, it should be followed by an analysis of reagent water
to check for cross contamination. For samples containing large amounts of suspended solids, high boiling
compounds, or high purgeable levels, it may be necessary to wash out the purging device with a detergent
solution, rinse it with distilled water and then dry it in an oven at 105°C between analyses. The trap and other
parts of the system are also subject to contamination; therefore, frequent bakeout and purging of the entire system
may be required.

3.3 The volatile analysis laboratory should be as completely free of interfering solvents as possible.

3.4 Henry's Law states that the concentration of the volatile analyte in the headspace above the solution is
proportional to the concentration of the analyte in solution. This proportionality, known as Henry's Constant, is
temperature and pressure dependent. Henry's Law holds for dilute solutions. Dilute solutions can be
conveniently defined as solutions with less than 1 percent total dissolved species. In practice, the upper
concentration limit is defined by the water solubility of the analyte being measured, which is typically on the
order of 100 to 1,000 ng/L. The upper concentration limit can be reduced by diluting the samples that contain
concentrations higher than the solubility limit. Caution in the interpretation of results for samples needing
dilution should be exercised especially if free product is present in the original sample.

3.5 Interferences coextracted from samples are matrix and site specific. It is possible that techniques used
in either FASP or CLP Routine Analytical Services (RAS) methods may fail to eliminate interferences. Highly
specialized CLP Special Analytical Services (SAS) techniques may be required to produce acceptable analytical
results.

4.0 APPARATUS AND MATERIALS

FMC-VW-002-3

-------
4.1 Analytical System

4.1.1.1 Column 1: 1.8 m x 3 mm I.D. glass column packed with 1% SP-1000 on Carbopack
B (60/80 mesh), or equivalent.

4.1.1.2 Column 2: 30 m x 0.53 mm ID DB-624 fused silica megabore column (J&W
Scientific), or equivalent.

4.1.1.4 Gas supply: The carrier gas and makeup gas should be ultrapure helium. The
reaction gas required for the Hall detector is ultrapure hydrogen. All gases should pass through
oxygen traps prior to the analytical system to prevent degradation of the column's analytical coating.

4.1.1.5 Headspace sampler: Sample introduction is accomplished using a Hewlett-Packard
19395A headspace sampler, or equivalent. This sampler should be capable of automatically heating a
group of samples to a constant temperature (set at the boiling point of the most volatile target analyte)
for a specified period of time. The Hewlett-Packard 19395A headspace sampler automatically
withdraws a 1-mL sample from the headspace of the sample to be analyzed. A 3-mL loop is available
if extra sensitivity is required. The sample carousel, sample loop, and transfer line inserted into the
GC injector are heated, which minimizes sample carryover.

4.2 Other Laboratory Equipment

4.2.1 Microsvringes: 10-^L, 25-^L, and larger.

4.2.2 Syringes: 0.5-mL, 1.0-mL, gas tight with Teflon valve.

4.2.3 Volumetric flasks: With ground glass or Teflon stoppers.

4.2.4 Vials: 1.8-mL for purgeable standards with Teflon-lined septa.

4.2.5 Headspace vials: With Teflon-lined septa and aluminum crimp caps or screw caps, appropriate
size to fit headspace sampler.

4.2.6 Vortex mixer.

4.2.7 Desiccator: Glass and stainless steel (no plastic materials).

4.2.8 Teflon wash bottles: 500-mL.

4.2.9 Crimper pliers: To seal headspace vials with crimp caps.

FMC-VW-002-4

-------
4.2.10 Drying oven: Capable of maintaining temperatures of greater than or equal to 200°C.

4.2.11 Oxygen traps: Supelpure-O-Trap and OM-1 indicating tube, or equivalent.

4.2.12 Leak detector: Snoop liquid, or equivalent for packed column operations or GOW-MAC gas
leak detector, or equivalent, for megabore capillary operations.

4.2.13 Chromatographic data stamps: Used to record instrument operating conditions.
5.0 REAGENTS

5.1 Solvents

5.1.1 1-Propanol: Pesticide quality, or equivalent.

5.1.2 Methanol: Pesticide quality, or equivalent.

5.2 Miscellaneous Reagents

5.2.1 Reagent water: Reagent water is defined as water in which an interferent is not observed at the
QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing activated
carbon (Calgon Corporation, Filtrasorb-300 or equivalent), a water purification system (Milli-Q Plus with
Organex Q cartridge, Barnstead Water-1 Systems, or equivalent), or purchased from commercial laboratory
supply houses.

5.3 Gases

5.3.1 Helium: Ultrapure or chromatographic grade, used in conjunction with an oxygen trap.

5.3.2 Hydrogen: Ultrapure or chromatographic grade, used in conjunction with an oxygen trap.

5.4 Stock Standard Solutions: Stock standard solutions should be purchased in methanol as manufacturer
certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This procedure is done through volumetric dilution of the stock standards with water. The
lowest concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining
standard concentrations should define the approximate working range of the GC: one at the upper linear range and
the other midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass
bottles. Calibration solutions must be replaced weekly, or sooner if comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist
other than the calibration standard preparer.

5.7 Matrix Spike Solutions: Matrix spike solutions should be prepared by dilution of stock standard
solutions so that no more than 250 (iL of spike solution is required to provide a final sample spike level within the
advised quality control (QC) limits.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

FMC-VW-002-5

-------
6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody
following current EPA regulations and recommendations in force at the time of sample collection. The sole
exceptions to this rule are the sample volumes required by the laboratory. Aqueous samples should be preserved
with 2 drops hydrochloric acid (added to the sample vial before filling with sample), and shipped on ice in a 40-
mL sample vial with Teflon-lined septa.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for VOCs in water is 14 days from
sampling to analysis if preserved, or 7 days from sampling to analysis if unpreserved.

7.0 PROCEDURE

7.1 Preparation: The sample preparation technique for VOCs in water is as follows:

7.1.1 Add the appropriate amount of sample to a headspace sample vial. All samples, standards, and
QC samples must have consistent final volumes in order to allow for consistent headspace volume.

7.1.2 Immediately add 20 (iL (or the appropriate volume) of surrogate standard to the sample vial
with a syringe.

7.1.3 Immediately seal the headspace vial with a Teflon-coated septum and aluminum crimp cap or
screw cap.

7.1.4 Place the vial in the headspace sampler, and equilibrate at the appropriate temperature (usually
at least 30 minutes).

NOTE: Samples, standards, and/or QC samples should be prepared as a group.

7.1.5 Samples are ready for GC injection.

7.2 Calibration

7.2.1 Initial calibration:

7.2.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution, retention
times, area reporting, and interpretation of chromatograms are within acceptable QC limits. Using at
least 3 calibration standards prepared as described in Section 5.5, generate initial calibration curves
(relative response versus mass of standard injected) for each target analyte (refer to Section 7.3 for
chromatographic procedures).

7.2.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.4) based on
each VOCs 3 calibration factors (CFs, see Section 7.4) to determine the acceptability (linearity) of the
curve. Unless otherwise specified the %RSD must be less than or equal to 25 percent, or the
calibration is invalid and must be repeated. Establish a new calibration curve any time the GC system
is altered (e.g., new column, or change in gas supply, change in oven temperature) or shut down.

7.2.2 Continuing calibration:

FMC-VW-002-6

-------
calibration. Instrument response is used to compute the CF, which is then compared to the mean
initial calibration factor (CF), and a relative percent difference (RPD, see Section 7.4) is calculated.
Unless otherwise specified, the RPD for all target analytes must be less than or equal to 25 percent for
the continuing calibration to be considered valid. A continuing calibration remains valid for a
maximum of 24 hours providing the GC system remains unaltered during that time.

7.2.2.2 Use the continuing calibration in all sample concentration calculations (Section 7.4)
for the period over which the calibration has been validated.

7.2.3 Final calibration: Obtain the final calibration at the end of each batch of samples analyzed.
The allowable RPD between the mean initial calibration and final calibration factors for each analyte must
be less than or equal to 50 percent. A final calibration that achieves an RPD less than or equal to 25 percent
may be used as an ongoing continuing calibration.

7.3 Instrumental Analysis

7.3.1 Instrument parameters: Tables 2 and 3 summarize acceptable instrument operating conditions
for the analytical system. Other instruments, columns, and/or chromatographic conditions may be used if
this method's QC criteria are met.

7.3.2 Chromato grams:

7.3.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks are
on scale up to a 100-fold range are acceptable. To prevent retention time shifts by column or detector
overload, however, they can be no greater than a 100-fold range. Generally, peak response should be
greater than 25 percent and less than 100 percent of full-scale deflection to allow visual recognition of
VOCs.

7.3.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.3.3 VOC identification:

7.3.3.1 Qualitative identification of VOCs is based on both detector selectivity and relative
retention time as compared to known standards using the external standard method.

7.3.3.2 For a compound that is detected on both the PID and Hall detector, the compound
must be identified in both chromatograms for a positive identification to be made.

7.3.3.3 Generally, individual peak relative retention time windows should be less then or
equal to 5 percent for packed column analysis or less than or equal to 2 percent for megabore capillary
columns. Alternately, the individual peak relative retention time windows may be calculated based on

FMC-VW-002-7

-------
3 times the standard deviation of at least 3 non-consecutive standard analyses. These analyses must
be representative of normal system variations, subject to the professional judgement of an experienced
analyst.

7.3.3.4 It may not be possible or practical to separate all volatile organic target analytes on a
single column. In such cases, these target analytes should be denoted as the appropriate combination
of VOCs.

7.3.4 Analytical sequence:

7.3.4.1 Instrument blank.

7.3.4.2 Initial calibration.

7.3.4.3 Check standard solution or performance evaluation sample (if available).

7.3.4.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.3.4.5 Associated QC lot method blank.

7.3.4.6 Twenty samples and associated QC lot spike and duplicate.

7.3.4.7 Repeat sequence beginning at 7.3.4.5 until all sample analyses are completed or
another continuing calibration is required.

7.3.4.8 Final calibration when all sample analyses are complete.

7.4 Calculations

7.4.1 Identification and quantitation of target compound VOCs should be based on the external
standard method. A compound which is detected by both the PID and Hall detector should be quantitated
using the detector which gives the higher response for that specific compound. The second detector should
be used for confirmation of the presence of that compound.

7.4.2 Initial calibration:

7.4.2.1 Analyze each calibration standard. Tabulate the area response of each target analyte
against concentration for each compound and calculate CFs for each target compound using the
following equation.

FMC-VW-002-8

-------
Table 2

EXAMPLE OPERATING CONDITIONS FOR THE HEADSPACE SAMPLER

S)))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))) Q

TEMPERATURE SETTINGS

Sampler bath temperature:
Valve loop temperature:

60°C

100°C

GAS PRESSURES AND SETTINGS
(For Hewlett Packard Model 19395A)

Gas Mode
Carrier
Auxiliary
Servo Air

Type of Gas
Helium
Helium
Air

Tank Pressure (Lbs')
40
40
60

Barr Setting
0.7
1.1
3.1

PROGRAMMING TIMING FOR VALVE OPERATION EVENTS

Set Point Displays
01"

03"

13"

14"

25"

26"

227"

228"

Key to Press
PROBE
PRESSURE
PRESSURE
VENT/FILL LOOP
VENT/FILL LOOP
INJECT

INJECT

PROBE

F unction/Activitv
Probe enters vial
Starts pressurization
Stops pressurization
Starts venting
Stops venting
Starts injection

Stops injection
Raises probe from vial

FMC-VW-002-9

-------
Table 3

EXAMPLE CAPILLARY COLUMN
TEMPERATURE-PROGRAMMED GC OPERATING CONDITIONS

S)))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))) Q

Headspace Sampler:
Instrument:

Hewlett-Packard 19395A Automatic Headspace Sampler with heated transfer line.

Shimadzu GC Mini-3 equipped with an HNu Systems PID detector with a 10.2-eV
lamp connected in series to an O.I. Corporation Hall detector.

Integrator:	Nelson Analytical PC Integrator with a dual channel interface and 30 MB hard disk drive for

data storage.

Column:	J&W DB-624 fused silica megabore column, 30 m x 0.53 mm. I.D.

Carrier Gas:	Ultrapure helium, lOmL/min.

Make-up Gas:	Ultrapure helium, 40 mL/min.

Reaction Gas:	Ultrapure hydrogen, 100 mL/min.

Column Oven:	Initial temperature: 35°C

Initial time: 4 min.

Ramp rate: 4°C/min.

Final temperature: 105°C

Injector Temperature:
Detector Temperature:

GC Analysis Time:

150°C

PID:200°C

Hall: 800°C (Reactor)

20 mins

Sample Injection: A 1-mL aliquot of the headspace gas is automatically injected into the GC via the heated
transfer line. If increased sensitivity is desired, a 3-mL sample loop may be employed.

FMC-VW-002-10

-------
CF

Area of Peak

Mass Injected (nanograms)

7.4.2.2 Using the calibration factors, calculate the %RSD for each target analyte at all
concentration levels using the following equation.

ST)

RSD = 4=r x 100
X

where SD, the Standard Deviation, is given by

SD

^ (X.-X)'
h. (N-l)

where: X; = Individual CF (per analyte)

X = Mean of initial CF s (per analyte)

N = Number of calibration standards

7.4.2.3 The %RSD must be less than or equal to 25.0 percent.

7.4.3 Continuing calibration:

7.4.3.1	Sample quantitation is based on analyte CFs calculated from continuing calibrations.
Midrange standards for all initial calibration target analytes must be analyzed at specified intervals
(less than or equal to 24 hours).

7.4.3.2	The RPD calculated using the equation below for each analyte must be less than or
equal to 25 percent.

I ~CF~-CFn',

RPD = 		

CFI+CFc

where: CF, = Mean CF from the initial calibration for each analyte

CFc = Measured CF from the continuing calibration for the same analyte

7.4.4 Final calibration:

7.4.4.1	The final calibration is obtained at the end of each 24-hour period in which samples
are analyzed.

7.4.4.2	The maximum allowable RPD between the mean initial calibration and final
calibration factors for each target analyte must be less than or equal to 50 percent. A final calibration
which achieves less than or equal to 25 percent RPD may be used as an ongoing continuing
calibration.

FMC-VW-002-11

-------
\CF -CF \
RPD = - 1 — x 100

cfi+cff

where: CF, = Mean CF from the initial calibration for each analyte

CFc = Measured CF from the continuing calibration for the same analyte

7.4.5 Sample quantitation:

7.4.5.1 External standard calibration is used for the calculation of the compounds of interest.
The concentration of each calibrated analyte may be determined by the following formula:

Concentration (]ig/L)

(V) (CFc)

where: Ax = Area of the peak for the analyte to be measured

V = Volume (mL) of sample in vial

CFc = Calibration factor for the analyte to be measured

7.4.5.2 Report results in micrograms per liter (ng/L) without correction for blank or spike
recovery.

7.4.5.3 Coeluted analytes should be quantitated and reported as the combination of the
unseparated volatile organic target analytes.

7.4.5.4 Sample chromatograms may not match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum possible
concentration (qualified as less than the numerical value) which allows the data user to determine if
additional (e.g. CLP analyses) work is required, or, if the reported concentration is below action levels
and project objectives and DQOs have been met, to forego further analysis.

7.4.5.5 Similarly, when sample concentration exceeds the linear range, the analyst may report
a probable minimum level (qualified as greater than the numerical value) which allows the data user to
determine if additional (e.g., CLP RAS or SAS) work is required, or, if the reported concentration is above
action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. Advisory limits for spike %R and duplicate RPD
are presented in Table 4. This method should be used in conjunction with the quality assurance and control (QA/QC)
section of this catalog.

FMC-VW-002-12

-------
Table 4

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.005 (VOCs in Water)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD (%)

T richlorofluoromethane

30 to 150

±75

1,1 -Dichloroethene

30 to 150

±75

Methylene Chloride

30 to 150

±75

trans-1,2-Dichloroethane

30 to 150

±75

1,1 -Dichloroethane

30 to 150

±75

Chloroform

30 to 150

±75

1,1,1 -Trichloroethane

30 to 150

±75

Carbon Tetrachloride

30 to 150

±75

Benzene

30 to 150

±75

1,2-Dichloroethane

30 to 150

±75

Trichloroethene

30 to 150

±75

1,2-Dichloropropane

30 to 150

±75

Bromodichloromethane

30 to 150

±75

cis-1,3 -Dichloropropene

30 to 150

±75

T oluene

30 to 150

±75

trans-1,3 -Dichloropropene

30 to 150

±75

1,1,2-Trichloroethane

30 to 150

±75

T etrachloroethene

30 to 150

±75

Dibromochloromethane

30 to 150

±75

(continued on next page)

* If the concentration of an analyte is less than 5 times the quantitation limit, the advisory control limits for
duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-VW-002-13

-------
Table 4 (continued)

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.005 (VOCs in Soil)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD (%)

Chlorobenzene

30 to 150

±75

Ethylbenzene

30 to 150

±75

m,p-Xylenes

30 to 150

±75

o-Xylene

30 to 150

±75

Bromoform

30 to 150

±75

1,1,2,2-T etrachloroethane

30 to 150

±75

* If the concentration of an analyte is less than 5 times the quantitation limit, the advisory control limits for
duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-VW-002-14

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatograms are examples of gas chromatograms for volatile organic analytes as detected
by the PID and Hall detectors.

Figure 1
Gas chromatogram A-PID

Column:

Column Temperature:

Detector/Injector Temperature:
Gas:

Detector:

J&W 30 m x 0.53 mm ID DB-624 fused silica megabore capillary
column.

Initial temperature: 35°C for 4 mins.

Ramp: 4°C/min

Final temperature: 105°C

150°C

Carrier; ultrapure helium, 10 mL/min.

Make-up; ultrapure helium, 40 mL/min.

HNu PID with a 10.2 eV lamp.

FMC-VW-002-15

-------
Figure 2

Gas chromatogram B - Hall detector

Column:

Column Temperature:

Detector/Injector Temperature:
Gas:

J&W 30 m x 0.53 mm ID DB-624 fused silica megabore capillary
column.

Initial temperature: 35°C for 4 mins.

Ramp: 4°C/min

Final temperature: 105°C

150°C

Carrier; ultrapure helium, 10 mL/min.

Make-up; ultrapure helium, 40 mL/min.

Reaction gas; ultrapure hydrogen, 100 mL/min.

Detector:

Hall electrolyte conductivity detector.

FMC-VW-002-16

-------
10.0 REFERENCES

Information not available.

FMC-VW-002-17

-------
FASP Method Number F080.006
VOLATILE ORGANICS IN WATER BY AUTOMATED HEADSPACE

INTERNAL STANDARD METHOD

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the relative
concentrations of various volatile organic compounds (VOCs) in aqueous samples.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

1.5 This FASP method is intended only to generate screening data that can be used to direct ongoing field
work, identify samples that need additional analysis, or determine relative concentrations of target analytes. The
headspace technique assumes that for volatile compounds, the concentration of an analyte found in the headspace over
the water sample directly relates to the actual concentration of the analyte in the sample. This assumption is usually
valid, however, complex matrices such as oily wastes, multiphase samples, and samples containing high-level organic
or inorganic interferences may prevent the assumed partitioning between the liquid and gas/vapor phases in the
headspace vial.

2.0 SUMMARY OF METHOD

2.1 A measured amount of water sample is placed into a headspace vial. The headspace volume is made
constant for all samples and standards. The containers are sealed and allowed to equilibrate at a temperature near
the boiling point of the most volatile target analyte in the headspace sampler. A sample is withdrawn from the
headspace and injected onto a temperature-programmed gas chromatograph (GC) equipped with a packed or megabore
capillary column. Volatile organic compounds are detected with a photoionization detector (PID) and a Hall
electrolytic conductivity detector connected in series. Quantitation and identification are based on relative peak areas
and relative retention times using the internal standard method.

3.0 INTERFERENCES

3.1 Impurities in the purge gas, organic compounds outgassing from the plumbing in the headspace sampler,
and solvent vapors in the laboratory account for the majority of contamination problems. The analytical system must
be demonstrated to be free from contamination under the conditions of the analysis by running laboratory reagent
blanks. The use of non-Teflon tubing, non-Teflon thread sealants, or flow controllers with rubber components in the
purging device should be avoided.

FMC-VW-003-1

-------
Table 1

FASP METHOD F080.006 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit in Water

(W?/L)

T richlorofluoromethane

75-69-4

10

1,1 -Dichloroethene

75-35-4

10

Methylene Chloride

75-09-2

10

trans-1,2-Dichloroethene

540-59-0

10

1,1 -Dichloroethene

75-34-3

10

Chloroform

67-66-3

10

1,1,1 -Trichloroethane

71-55-6

10

Carbon Tetrachloride

56-23-5

10

Benzene

71-43-2

10

1,2-Dichloroethene

107-06-2

10

Trichloroethene

79-01-6

10

1,2-Dichloropropane

78-87-5

10

Bromodichloromethane

75-25-4

10

cis-1,3 -Dichloropropene

10061-01-5

10

T oluene

108-88-3

10

trans-1,3 -Dichloropropene

10061-02-6

10

1,1,2-Trichloroethane

79-00-5

10

T etrachloroethene

127-18-4

10

Dibromochloromethane

124-48-1

10

(continued on next page)

* Specific quantitation limit values are highly matrix dependent. The quantitation limits herein are provided for
guidance and may not always be achievable.

FMC-VW-003-2

-------
Table 1 (continued)

FASP METHOD F080.006 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit in
Water (ng/L)

Chlorobenzene

108-90-7

Ethylbenzene

100-41-4

m,p-Xylenes

1330-20-7

o-Xylene

1330-20-7

Bromoform

75-25-2

1,1,2,2-T etrachloroethane

79-34-5

* Specific quantitation limit values are highly matrix dependent. The quantitation limits herein are provided for
guidance and may not always be achievable.

3.2 Contamination by carry-over can occur whenever high-level and low-level samples are sequentially
analyzed. To reduce carryover, the sampling syringe (if used) must be rinsed with methanol, dried in an oven, then
stored in a dessiccator between sample analyses. Whenever an unusually concentrated sample is encountered, it
should be followed by an analysis of the headspace over reagent water and the sampling syringe filled with reagent
air to check for cross contamination. For samples containing large amounts of water solubles, suspended solids, high
boiling compounds, or high purgeable levels, it may be necessary to boil the sampling syringe with water for several
minutes, rinse with methanol, and then dry it in an oven at 105°C between analyses. The headspace sampler (if used)
and other parts of the system are also subject to contamination; therefore, frequent purging of the entire system may
be required.

3.3 The volatile analysis laboratory should be as completely free of interfering solvents as possible.

3.4 Henry's Law states that the concentration of the volatile analyte in the headspace above the solution is
proportional to the concentration of the analyte in solution. This proportionality, known as Henry's Constant, is
temperature and pressure dependent. Henry's Law holds for dilute solutions. Dilute solutions can be conveniently
defined as solutions with less than 1 percent total dissolved species. In practice, the upper concentration limit is
defined by the water solubility of the analyte being measured, which is typically on the order of 100 to 1,000 ng/L.
The upper concentration limit can be reduced by diluting the samples that contain concentrations higher than the
solubility limit. Caution in the interpretation of results for samples needing dilution should be exercised especially
if free product is present in the original sample.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System

FMC-VW-003-3

-------
4.1.1 Gas chromatograph: An analytical system complete with a temperature-programmable GC suitable
for on-column injection is required and all necessary accessories including injector and detector systems
designed or modified to accept the appropriate analytical columns (packed or megabore). The system shall have
a data-handling system attached to the detectors that is capable of retention time labeling, relative retention time
comparisons, and providing relative and absolute peak height and peak area measurements.

4.1.1.1 Column 1: 1.8 m x 3 mm I.D. glass column packed with 1% SP-1000 on Carbopack B
(60/80 mesh), or equivalent.

4.1.1.2 Column 2: 30 m x 0.53 mm ID DB-624 fused silica megabore column (J&W Scientific),
or equivalent.

4.1.1.4 Gas supply: The carrier gas and makeup gas should be ultrapure helium. The reaction
gas required for the Hall detector is ultrapure hydrogen. All gases should pass through oxygen traps prior
to the analytical system to prevent degradation of the column's analytical coating.

4.1.1.5 Headspace sampler: Sample introduction is accomplished using a Hewlett-Packard
19395A headspace sampler, or equivalent. This sampler should be capable of automatically heating a
group of samples to a constant temperature (set at the boiling point of the most volatile target analyte) for
a specified period of time. The Hewlett-Packard 19395A headspace sampler automatically withdraws a
1-mL sample from the headspace of the sample to be analyzed. A 3-mL loop is available if extra
sensitivity is required. The sample carousel, sample loop, and transfer line inserted into the GC injector
are heated, which minimizes sample carryover.

4.2 Other Laboratory Equipment

4.2.1 Microsvringes: 10-^L, 25-^L, and larger.

4.2.2 Syringes: 0.5-mL, 1.0-mL, gas tight with Teflon valve.

4.2.3 Volumetric flasks: With ground glass stoppers.

4.2.4 Vials: 1.8-mL for purgeable standards with Teflon-lined septa.

4.2.5 Headspace vials: With Teflon-lined septa and aluminum crimp caps or screw-caps, appropriate
size to fit headspace sampler.

4.2.6 Vortex mixer.

4.2.7 Glass desiccator: Glass and stainless steel (no plastic materials).

4.2.8 Teflon wash bottles: 500-mL.

4.2.9 Crimper pliers: To seal headspace vials with crimp caps.

4.2.10 Drying oven: Capable of maintaining temperatures of greater than or equal to 200°C.

4.2.11 Oxygen traps: Supelpure-O-Trap and OM-1 indicating tube, or equivalent.

FMC-VW-003-4

-------
4.2.12 Leak detector: Snoop liquid, or equivalent for packed column operations or GOW-MAC gas leak
detector, or equivalent, for megabore capillary operations.

4.2.13 Chromatographic data stamps: Used to record instrument operating conditions.
5.0 REAGENTS

5.1 Solvents

5.1.1 1-Propanol: Pesticide quality, or equivalent.

5.1.2 Methanol: Pesticide quality, or equivalent.

5.2 Miscellaneous Reagents

5.2.1 Reagent Water: Reagent water is defined as water in which an interferent is not observed at the
QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing activated
carbon (Calgon Corporation, Filtrasorb-300 or equivalent), a water purification system (Milli-Q Plus with
Organex Q cartridge, Barnstead Water-1 Systems, or equivalent), or purchased from commercial laboratory
supply houses.

5.3 Gases

5.3.1 Helium: Ultrapure or chromatographic grade, used in conjunction with an oxygen trap.

5.3.2 Hydrogen: Ultrapure or chromatographic grade, used in conjunction with an oxygen trap.

5.4 Stock Standard Solutions: Stock standard solutions should be purchased in methanol as manufacturer
certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This procedure is done through volumetric dilution of the stock standards with water. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced weekly, or sooner if comparison with check standards indicates a problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

5.7 Internal Standards:

5.7.1 The 3 internal standards used are fluorobenzene, bromochloromethane, and p-bromofluorobenzene,
at 80 (iL at time of purge.

5.7.2 An internal standard mix should be prepared through volumetric dilution of individual stock
standards with methanol. It is recommended that the secondary dilution standard be prepared at a concentration
of 200 ng/mL of each internal standard compound. The addition of 2 (iL of this standard to 5.0 mL of sample
or 5 mL of calibration standard would be equivalent to 80 (ig/L.

FMC-VW-003-5

-------
5.7.3 All standards must be stored in a freezer in glass vials with Teflon-lined septa caps and be
protected from light. Internal standard solutions must be replaced weekly after the Teflon-lined septum have
been punctured, or whenever comparison with previous analyses indicates a problem.

5.8 Matrix Spike Solutions: Matrix spike solutions should be prepared by dilution of stock standard solutions
so that no more than 250 (iL of spike solution is required to provide a final sample spike level within the advised
quality control (QC) limits.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Aqueous samples should be preserved with 2 drops
hydrochloric acid (added to the sample vial before filling with sample), and shipped on ice in a 40-mL sample vial
with Teflon-lined septa.

7.0 PROCEDURE

7.1 Preparation: The sample preparation technique for VOCs in water is as follows:

7.1.1 Add the appropriate amount of sample to a headspace sample vial. All samples, standards, and
QC samples must have consistent final volumes in order to allow for consistent headspace volume.

7.1.2 Immediately add the appropriate volume of internal standard to the sample vial with a syringe.

7.1.3 Immediately seal the headspace vial with a Teflon-coated septum and aluminum crimp cap.

7.1.4 Place the vial in the headspace sampler, and equilibrate at the appropriate temperature (usually at
least 30 minutes).

NOTE: Samples, standards, and/or QC samples should be prepared as a group.

7.1.5 Samples are ready for GC injection.

7.2 Calibration

7.2.1 Initial calibration:

7.2.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution, retention
times, area reporting, and interpretation of chromatograms are within acceptable QC limits. Using at least
3 calibration standards prepared as described in Section 5.5, generate initial calibration curves (relative
response versus mass of standard injected) for each target analyte (refer to Section 7.3 for chromato-
graphic procedures).

7.2.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.4) based on each
VOCs 3 relative calibration factors (RCFs, see Section 7.4) to determine the acceptability (linearity) of
the curve. Unless otherwise specified the %RSD must be less than or equal to 25 percent, or the

FMC-VW-003-6

-------
calibration is invalid and must be repeated. Establish a new calibration curve any time the GC system is
altered (e.g., new column, or change in gas supply, change in oven temperature) or shut down.

7.2.2 Continuing calibration:

7.2.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing calibration
validation. This single point analysis follows the same analytical procedures used in the initial calibration.
Instrument response is used to compute the RCF, which is then compared to the mean initial calibration
factor (RCF), and a relative percent difference (RPD, see Section 7.4) is calculated. Unless otherwise
specified, the RPD for all target analytes must be less than or equal to 25 percent for the continuing
calibration to be considered valid. A continuing calibration remains valid for a maximum of 24 hours
providing the GC system remains unaltered during that time.

7.2.2.2 Use the continuing calibration in all sample concentration calculations (Section 7.4) for
the period over which the calibration has been validated.

7.2.3 Final calibration: Obtain the final calibration at the end of each batch of samples analyzed. The
allowable RPD between the mean initial calibration and final calibration factors for each analyte must be less
than or equal to 50 percent. A final calibration that achieves less than or equal to 25 percent RPD may be used
as an ongoing continuing calibration.

7.3 Instrumental Analysis

7.3.1 Instrument parameters: Tables 2 and 3 summarize acceptable instrument operating conditions for
the analytical system. Other instruments, columns, and/or chromatographic conditions may be used if this
method's QC criteria are met.

7.3.2 Chromato grams:

7.3.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks are on
scale up to a 100-fold range are acceptable. To prevent retention time shifts by a column or detector
overload, however, they can be no greater than a 100-fold range. Generally, peak response should be
greater than 25 percent and less than 100 percent of full-scale deflection to allow visual recognition of
VOCs.

7.3.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.3.3 VOC identification:

7.3.3.1 Qualitative identification of VOCs is based on both detector selectivity and relative
retention time as compared to known standards using the internal standard method.

FMC-VW-003-7

-------
7.3.3.2	For a compound that is detected on both the PID and Hall detector, the compound must
be identified in both chromatograms for a positive identification to be made.

7.3.3.3	Generally, individual peak relative retention time windows should be less then or equal
to 5 percent for packed column analysis or less than or equal to 2 percent for megabore capillary columns.

7.3.3.4	It may not be possible or practical to separate all volatile organic target analytes on a
single column. In such cases, these target analytes should be denoted as the appropriate combination of
VOCs.

7.3.4 Analytical sequence:

7.3.4.1	Instrument blank.

7.3.4.2	Initial calibration.

7.3.4.3	Check standard solution or performance evaluation sample (if available).

7.3.4.4	Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.3.4.5	Associated QC lot method blank.

7.3.4.6	Twenty samples and associated QC lot spike and duplicate.

7.3.4.7	Repeat sequence beginning at 7.3.5.5 until all sample analyses are completed or another
continuing calibration is required.

7.3.4.8	Final calibration when all sample analyses are complete.

FMC-VW-003-8

-------
Table 2

EXAMPLE OPERATING CONDITIONS FOR THE HEADSPACE SAMPLER

S)))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))) Q

TEMPERATURE SETTINGS

Sampler bath temperature
Valve loop temperature

60°C

100°C

GAS PRESSURES AND SETTINGS
(For Hewlett Packard Model 19395A)

Gas Mode

Carrier
Auxiliary
Servo Air

Type of Gas

Helium
Helium
Air

Tank Pressure (Lbs')

40
40
60

Barr Setting

0.7
1.1
3.1

PROGRAMMING TIMING FOR VALVE OPERATION EVENTS

Set Point Displays

Kev to Press

"01"

PROBE

"03"

PRESSURE

"13"

PRESSURE

"14"

VENT/FILL LOOP

"25"

VENT/FILL LOOP

"26"

INJECT

"227"

INJECT

"228"

PROBE

F unction/Activitv

Probe enters vial

Starts pressurization
Stops pressurization
Starts venting
Stops venting
Starts injection
Stops injection

Raises probe from vial

FMC-VW-003-9

-------
Table 3

EXAMPLE CAPILLARY COLUMN
TEMPERATURE-PROGRAMMED GC OPERATING CONDITIONS

S)))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))) Q

Headspace Sampler:

Instrument:

Integrator:

Column:

Carrier Gas:
Make-up Gas:
Reaction Gas:
Column Oven:

Injector Temperature:
Detector Temperature:

GC Analysis Time:
Sample Injection:

Hewlett-Packard 19395A Automatic Headspace Sampler with heated transfer
line.

Shimadzu GC Mini-3 equipped with an HNu Systems PID detector with a 10.2-
eV lamp connected in series to an O.I. Corporation Hall detector.

Nelson Analytical PC Integrator with a dual channel interface and 30 MB hard disk drive
for data storage.

J&W DB-624 fused silica megabore column, 30 m x 0.53 mm. I.D.

Ultrapure helium, 10 mL/min.

Ultrapure helium, 40 mL/min.

Ultrapure hydrogen, 100 mL/min.

Initial temperature: 35°C
Initial time: 4 min.

Ramp rate: 4°C/min.

Final temperature: 105°C

150°C

PID:200oC

Hall: 800°C (Reactor)

20 mins

A 1-mL aliquot of the headspace gas is automatically injected into the GC via the heated
transfer line. If increased sensitivity is desired, a 3 mL sample loop may be employed.

FMC-VW-003-10

-------
7.4 Calculations

7.4.1 Identification and quantitation of target compound VOCs should be based on the internal standard
method. The corresponding internal standard for each compound is listed in Tables 4 (PID) and 5 (Hall
Detector). A compound which is detected by both the PID and Hall detector should be quantitated using the
detector which gives the higher response for that specific compound. The second detector should be used for
confirmation of the presence of that compound.

7.4.2 The peak areas of the internal standards should be monitored and evaluated for each standard
sample, blank, duplicate, and matrix spike. If the peak area for any internal standard changes by more than a
factor of 2 (-50 to +100 percent), the sample must be reanalyzed.

7.4.3 If after reanalysis the peak areas for all internal standards are inside the QC limits (-50 to +100
percent), only report data from the analysis with peak areas within the QC limits.

7.4.4 If the reanalysis of the sample does not solve the problem for both analyses, then do not report
sample data.

7.4.5 Initial calibration:

7.4.5.1 Analyze each calibration standard, adding the internal standard directly to the sample vial
containing the standard before sealing.

7.4.5.2 Tabulate the area response of each target analyte against concentration for each compound
and internal standard and calculate RCF s for each target compound using the following equation.

A C.

RCF = —- x —

A. C

IS X

where: Ax = Area of the peak for the compound of interest

Ais = Area of the peak for the appropriate internal standard
Cis = Concentration of the internal standard
Cx = Concentration of the compound to be measured

7.4.5.3 Using the RCF values, calculate the %RSD for each target analyte at all concentration
levels using the following equation.

ST)

%RSD = 4=r x 100

where SD, the Standard Deviation, is given by

SD = .

^ (X.-X)'
h. (N-l)

where: X; = Individual RCF (per analyte)

X = Mean of initial RCF s (per analyte)
N = Number of calibration standards

FMC-VW-003-11

-------
Table 4

VOLATILE ORGANIC COMPOUNDS DETECTED BY THE PID
AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS2 fFluorobenzene')

1,1 -Dichloroethene

trans-1,2-Dichloroethene

Benzene

Trichloroethene

2-Chloroethylvinylether

cis-1,3 -Dichloropropene

m-Xylene

IS3 (p-Bromofluorobenzene')
T oluene

trans-1,3 -Dichloropropene
T etrachloroethene
Chlorobenzene
Ethylbenzene
o,p-Xylene

Table 5

TCL VOLATILE ORGANIC COMPOUND DETECTED BY THE HALL
DETECTOR AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS1 fBromochloromethane')

T richlorofluoromethane
1,1 -Dichloroethene
Methylene chloride
trans-1,2-Dichloroethene
1,1 -Dichloroethane
Chloroform
1,1,1 -Trichloroethane
Carbon tetrachloride
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromodichloromethane

IS3 (p-Bromofluorobenzene')

cis-1,3 -Dichloropropene

trans-1,3 -Dichloropropene
1,1,2-Trichloroethane
T etrachloroethene
Dibromochloromethane
Chlorobenzene
Bromoform

1,1,2,2-T etrachloroethane

FMC-VW-003-12

-------
7.4.6 Continuing calibration:

7.4.6.1	Sample quantitation is based on analyte RCFs calculated from continuing calibrations.
Midrange standards for all initial calibration target analytes must be analyzed at specified intervals (less
than or equal to 24 hours).

7.4.6.2	The RPD calculated using the equation below for each analyte must be less than or equal
to 25 percent.

\RCF~-RCFr\

RPD =	1	— x 100

RCFI+RCFc

2

where: RCF, = Mean CF from the initial calibration for each analyte

RCFc = Measured CF from the continuing calibration for the same analyte

7.4.7 Final calibration:

7.4.7.1	Obtain the final calibration at the end of each 24-hour period in which samples are
analyzed.

7.4.7.2	The maximum allowable RPD between the mean initial calibration and final calibration
factors for each target analyte must be less than or equal to 50 percent. A final calibration which achieves
an RPD less than or equal to 25 percent may be used as an ongoing continuing calibration.

\RCF~-RCFr\

RPD =	1	— x 100

RCFI+RCFc

2

where: RCR, = Mean CF from the initial calibration for each analyte

RCFc = Measured CF from the continuing calibration for the same analyte

7.4.8 Sample quantitation:

7.4.8.1 Calculate the concentration in the sample using the following equation for internal
standards:

(A ) (I )

Concentrationluq/L) = 			-	

Uis) (RCF) (Vo)

where: Ax	=	Area of the peak for the analyte to be measured

Ais	=	Area of the specific internal standard from Table 4 or 5

Is	=	Amount of internal standard added (ng)

RCF	=	The relative calibration factor for the compound to be measured

V0	=	Volume of water purged (mL) (take into account any dilutions)

7.4.8.2	Report results in micrograms per liter (ng/L) without correction for blank or spike
recovery.

FMC-VW-003 -13

-------
7.4.8.3 Coeluted analytes should be quantitated and reported as the combination of the
unseparated volatile organic target analytes.

7.4.8.4	Sample chromatograms may not match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum possible
concentration (qualified as less than the numerical value) which allows the data user to determine if
additional (e.g. CLP analyses) work is required, or, if the reported concentration is below action levels
and project objectives and DQOs have been met, to forego further analysis.

7.4.8.5	Similarly, when sample concentration exceeds the linear range, the analyst may report
a probable minimum level (qualified as greater than the numerical value) which allows the data user to
determine if additional (e.g., CLP RAS or SAS) work is required, or, if the reported concentration is above
action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 6. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-VW-003 -14

-------
TABLE 6

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.006 (VOCs in Water)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD

T richlorofluoromethane

30 to 200

± 100

1,1 -Dichloroethene

30 to 200

± 100

Methylene Chloride

30 to 200

± 100

trans-1,2-Dichloroethane

30 to 200

± 100

1,1 -Dichloroethane

30 to 200

± 100

Chloroform

30 to 200

± 100

1,1,1 -Trichloroethane

30 to 200

± 100

Carbon Tetrachloride

30 to 200

± 100

Benzene

30 to 200

± 100

1,2-Dichloroethane

30 to 200

± 100

Trichloroethene

30 to 200

± 100

1,2-Dichloropropane

30 to 200

± 100

Bromodichloromethane

30 to 200

± 100

cis-1,3 -Dichloropropene

30 to 200

± 100

T oluene

30 to 200

± 100

trans-1,3 -Dichloropropene

30 to 200

± 100

1,1,2-Trichloroethane

30 to 200

± 100

T etrachloroethene

30 to 200

± 100

Dibromochloromethane

30 to 200

± 100

(continued on next page)

* If the concentration of an analyte is less than 5 times the quantitation limit, the advisory control limits for
duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-VW-003 -15

-------
Table 6 (continued)

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.006 (VOCs in Soil)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD

Chlorobenzene

30 to 200

± 100

Ethylbenzene

30 to 200

± 100

m,p-Xylenes

30 to 200

± 100

o-Xylene

30 to 200

± 100

Bromoform

30 to 200

± 100

1,1,2,2-T etrachloroethane

30 to 200

± 100

* If the concentration of an analyte is less than 5 times the quantitation limit, the advisory control limits for
duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-VW-003 -16

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatograms are examples of gas chromatograms for volatile organic analytes as detected
by the PID and Hall detectors.

Figure 1

Gas chromatogram A-PID

Column:

Column Temperature:

Detector/Injector Temperature:
Gas:

Detector:

J&W 30 m x 0.53 mm ID DB-624 fused silica megabore capillary column.

Initial temperature: 35°C for 4 mins.

Ramp: 4°C/min

Final temperature: 105°C

150°C

Carrier; ultrapure helium, 10 mL/min.

Make-up; ultrapure helium, 40 mL/min.

HNu PID with a 10.2 eV lamp.

FMC-VW-003 -17

-------
Figure 2

Gas chromatogram B - Hall detector

Column:

Column Temperature:

Detector/Injector Temperature:
Gas:

J&W 30 m x 0.53 mm ID DB-624 fused silica megabore capillary column.

Initial temperature: 35°C for 4 mins.

Ramp: 4°C/min

Final temperature: 105°C

150°C

Carrier; ultrapure helium, 10 mL/min.

Make-up; ultrapure helium, 40 mL/min.

Reaction gas; ultrapure hydrogen, 100 mL/min.

Detector:

O.I. Corporation Hall detector.

FMC-VW-003 -18

-------
10.0 REFERENCES

Information not available.

FMC-VW-003 -19

-------
FASP Method Number F080.007
VOLATILE ORGANICS IN WATER BY MANUAL HEADSPACE

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various volatile organic compounds (VOCs) in water samples using manual headspace techniques
and gas chromatography (GC) with a photoionization detector (PID).

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

1.5 This FASP headspace technique is intended only for sample screening, due to several assumptions used
in the method for volatile compounds. For example, it is assumed that the quantity and number of compounds found
in the headspace over the liquid sample directly relate to the actual concentrations of compounds in the water sample.
This is often a valid assumption, especially in relatively clean or noncomplex matrices. This assumption begins to
break down, however, for the complex matrices often found during environmental investigations. Examples of
complex matrices are oily wastes, multiphase samples, and many samples containing high levels of 1 or several
compounds that might prevent the usual partitioning between the liquid and gas/vapor phases in the sample bottle.
Synergistic (enhancing) or antagonistic (masking) effects may either artificially increase or decrease the resulting
concentrations of specific compounds in the sample.

1.6 This method should be used only to generate screening data that can be used to direct ongoing fieldwork,
identify samples that need additional analysis, or determine relative concentrations of target compounds.

2.0 SUMMARY OF METHOD

2.1 The headspace volume must be constant for all samples and standards since the headspace method
assumes that the concentration of the compound in the headspace over the standard solution directly relates to the
actual concentration of the compound in the aqueous phase. The standard and sample containers are sealed and
allowed to equilibrate to ambient temperature. A sample is withdrawn from the headspace and injected onto a GC
equipped with a packed or megabore capillary column. VOCs are detected with a PID. Tentative identification and
quantitation are based on comparison of the retention times and relative peak area or heights between the standard
and sample.

FMC-VW-004-1

-------
Table 1

FASP METHOD F080.007 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit
in W ater
(M-R/L)

1,1 -Dichloroethene

75-35-4

5.0

Methylene chloride

75-09-2

5.0

trans-1,2-Dichloroethene

540-59-0

20.0

1,1,1 -Trichloroethene

71-55-6

5.0

Benzene

71-43-2

5.0

Trichloroethene

79-01-6

5.0

T oluene

108-88-3

5.0

T etrachloroethene

127-18-4

5.0

Chlorobenzene

108-90-7

5.0

Ethylbenzene

100-41-4

5.0

m,p-Xylenes

1330-20-7

5.0

o-Xylene

1330-20-7

5.0

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for
guidance and may not always be achievable.

3.0 INTERFERENCES

3.1 The laboratory where volatile analysis is performed should be completely free of solvents. If the method
is used in an open area (i.e., behind the hot line at a site), vehicle exhaust fumes and other possible sources of volatile
contamination should be removed or kept away.

3.2 Henry's Law states that the concentration of the volatile analyte in the headspace above the solution is
proportional to the concentration of the analyte in solution. This proportionality, known as Henry's constant, is
temperature and pressure dependent. Henry's Law holds for dilute solutions. Dilute solutions can be defined as
solutions with less than 1 percent total dissolved species.

3.3 In practice, the upper concentration limit is defined by the water solubility of the analyte being measured,
which is typically on the order of 100 to 1,000 ng/L. The upper concentration limit can be reduced by diluting the
samples that contain concentrations higher than the solubility limit. Caution should be exercised especially if free
product is present in the original sample.

4.0 APPARATUS AND MATERIALS

FMC-VW-004-2

-------
4.1 Analytical Systems

4.1.1 Listed below is a GC option that meets the requirements of this method. Other GC configurations
may be substituted if they also meet this method's requirements.

4.1.2 Gas chromatograph: A portable GC equipped with a PID and all necessary accessories including
the appropriate analytical column (packed or megabore) is required. The GC should have an internal data
handling system capable of retention time labeling and providing relative and absolute peak height and/or peak
area measurements. If the GC is not equipped with an internal integrator, an external strip-chart recorder, or
integrator can be utilized.

4.1.2.1 Column 1: 4 ft x 1/8 in I.D. Teflon column packed with SE-30 (80/100 mesh), or
equivalent.

4.1.2.2 Column 2: 10 m x 0.53 mm ID CP Sil 5CB megabore column, or equivalent.

4.1.2.3 Oven (optional): The portable GC may be equipped with an isothermal oven. The
isothermal oven will ensure retention time stability and slightly faster analysis times.

4.1.2.4 Detector: PID with a 10.6 eV lamp.

4.1.2.5 Gas supply: The carrier gas should be ultra-zero grade air.

4.2 Other Laboratory Equipment

4.2.1 Microsvringes: 10-(iL, 25-(iL, and larger.

4.2.2 Sample syringes: 100-(iL, 250-(iL, 500-(iL, and larger gastight syringes.

4.2.3 Volumetric flasks: With ground glass stoppers.

4.2.4 Leak detector: Snoop liquid, or equivalent, for packed column operations or GOW-MAC gas leak
detector, or equivalent, for megabore capillary operations.

4.2.5 Chromatographic data stamp: Used to record instrument operating conditions.
5.0 REAGENTS

5.1 Solvents: Methanol, analytical grade.

5.2 Reagent Water: Reagent water is defined as water in which an interferent is not observed at the QL of
the analyte of interest. Reagent water may be generated using a carbon filter bed containing activated carbon (Calgon
Corporation, Filtrasorb-300, or equivalent) or a water purification system (Milli-Q Plus with Organex Q cartridge,
or equivalent), or purchased from commercial supply houses.

5.3 Carrier Gas: Ultra-zero grade air.

5.4 Stock Standard Solutions: Stock standard solutions or neat standards should be purchased as
manufacturer-certified solutions.

FMC-VW-004-3

-------
standard should be equal to 2 times the QL as listed in Table 1. The remaining concentration levels should define
the approximate working range of the GC: one standard at the upper linear range and the other midway between it
and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles. Calibration solutions
must be replaced after 6 months, or sooner, if comparison with check standards indicates a problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

5.7 Internal Standard fOptional)

5.7.1 The internal standard should be a compound that is (a) not expected to be found in the samples,
(b) has a retention time toward the end of the run (where the greatest retention time shifts occur), and (c) is in
the middle of the expected concentration range.

5.7.2 In this method, an internal standard can be used with the Photovac 105 Series of GCs to recalibrate
retention time windows that change due to ambient temperature variations. If the Photovac is not equipped with
an isothermal oven, it is very susceptible to these temperature variations. If a retention time shift occurs, the
operator can change the internal standard retention time value in the Photovac's library. The GC will then adjust
the retention time windows for all other compounds in the library and match any peaks in the chromatogram with
the new retention time values. This will alleviate the need to inject a new calibration standard every time there
is a change in the ambient temperature.

5.8 Matrix Spike Solutions: Matrix spike solutions should be prepared by dilution of stock standard solutions
so that no more than 250 (iL of spike solution is required to provide a final sample spike level within the advised
quality control (QC) limits.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exception to this
rule is the sample volumes required by the laboratory. Water samples may be preserved with 2 drops of hydrochloric
acid (added to the volatile organic analysis (VOA) vial before filling with the sample), and shipped on ice in 40-mL
VOA vials with Teflon-lined septa.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for VOCs in water is 14 days from
sampling to analysis if preserved, or 7 days from sampling to analysis if unpreserved.

7.0 PROCEDURE

7.1 Sample Preparation

7.1.1 Collect water samples the usual manner in 40-mL vials with Teflon-coated septa. After collection,
store the samples in a refrigerator at 4°C or packed in ice if not analyzed immediately. Upon analysis, allow
the samples and standards to equilibrate to ambient temperature.

7.1.2 Prepare samples by withdrawing exactly 10 mL of water from the vial using a 10-mL syringe. Also
place a vent needle through the septum so that air can enter the vial to replace the water that is removed.
Remove the needles and shake the vial for at least 1 minute. Place the vial on the counter septum-side down
(to prevent potential loss of volatiles) for at least 1 minute to allow for equilibration of the headspace sample.
The sample is then ready for analysis.

FMC-VW-004-4

-------
Calibration

7.2.1 Initial calibration:

7.2.1.1 Inject a standard containing each compound of interest into the GC during calibration to
establish a retention time and response factor for quantitation. Some portable GCs will only do a
single-point calibration; however, the PID detector is linear over a wide concentration range. Document
instrument linearity by bracketing the expected sample concentration range with standards of known
concentrations. The analyst should prepare a mid concentration standard as the continuing calibration
standard. After calibration, run the low concentration and high concentration standards in the same way
as samples. If the instrument is linear, the low and high standards will be quantitated correctly. A correct
quantitation is within 10 percent of the true value. Inaccurate quantitation can be the result of a nonlinear
working range or inaccurate standards.

7.2.1.2 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution, retention
times, response reporting, and interpretation of chromatograms are within acceptable QC limits (Section
7.4). Using at least 3 calibration standards for each compound prepared as described in Section 5.5,
generate initial calibration curves (response versus standard concentration) for each compound (refer to
Section 7.3 for chromatographic procedures).

7.2.1.3 Compute the percent relative standard deviation (%RSD) based on each compound's 3
calibration factors (CFs, see Section 7.4) to determine the acceptability (linearity) of the curve. Unless
otherwise specified, the %RSD must be less than or equal to 25 percent, or the calibration is invalid and
must be repeated. Establish a new initial calibration curve anytime the GC system is altered (e.g., new
column, change in gas supply, change in oven temperature, etc.) or shut down.

7.2.2 Continuing calibration:

7.2.2.2 Use instrument response to compute the CF which is then compared to the mean initial
calibration factor (CF), and calculate a relative percent difference (RPD, see Section 7.4). Unless other-
wise specified, the RPD must be less than or equal to 25 percent for the continuing calibration to be
considered valid, or the calibration must be repeated.

7.2.2.3 If an internal standard is not used, analyze the continuing calibration standard after each
sample that shows a retention time shift, and reanalyze the sample. For the Photovac 10A10 GC without
an isothermal oven, it is recommended to analyze the continuing calibration standard every 8 to 10
injections or every 2 hours, whichever is more frequent. For the Photovac 10S50 GC with an isothermal
oven, the continuing calibration standard does not need to be reanalyzed as frequently. It is recommended
to reanalyze the continuing calibration standard every 4 hours if an isothermal oven is being used. After
each continuing calibration standard, inject a blank to verify a clean baseline.

7.2.2.4 Employ the continuing calibration in all target analyte sample concentration calculations
(Section 7.4) for the period over which the calibration has been validated.

7.2.3 Final calibration: Obtain a final calibration at the end of each batch of sample analysis. The
lum allowable RPD between the mean initial calibration and final calibration CF s for each analyte is less

FMC-VW-004-5

-------
than or equal to 50 percent. A final calibration which achieves an RPD less than or equal to 25 percent may be
used as an ongoing continuing calibration.

7.3 Instrumental Analysis

7.3.1 Instrument parameters: Table 2 summarizes 2 examples of acceptable instrument operating
conditions for the GC. Other instruments, columns, and/or chromatographic conditions may be employed if this
method's QC criteria are met.

7.3.2 Chromato grams:

7.3.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks are on
scale over a 100-fold range are acceptable. To prevent retention time shifts by column or detector
overload, however, this can be no greater than a 100-fold range. Generally, peak response should be
greater than 25 percent and less than 100 percent of full-scale deflection.

7.3.2.2 The following information must be recorded on each chromatogram:

• Instrument/detector identification;

• Column packing/coating, length, and ID;

• Oven temperature (if applicable);

• Gases and flow rates;

• Site name;

• Sample volume;

• Gain/attenuation;

• Sample number;

• Date and time; and

• GC operator initials.

7.3.3 VOC identification:

7.3.3.1 Qualitative identification of VOCs is based on both the PID selectivity and relative
retention time as compared to known standards.

7.3.3.2 Generally, individual peak relative retention time windows should be less than or equal
to 5 percent for packed columns and less than or equal to 2 percent for megabore capillary columns. It
may not be possible or practical to separate all VOCs on a single column (e.g., methylene chloride and
1,1-dichloroethene coelute on some columns). In such cases, these VOCs should be denoted as the
appropriate combination of VOCs, or the sample can be reanalyzed on a confirmation column.

FMC-VW-004-6

-------
Table 2

EXAMPLE ISOTHERMAL GC OPERATING CONDITIONS

Instrument 1: Photovac 10S50 GC equipped with a PID with a 10.6 eV lamp.

Column:

10 m x 0.53 mm ID CP Sil 5CB megabore column

Carrier Gas:

Ultra-zero grade air.

Column Oven: 30°C, 40°C, or 50°C.

GC Analysis Time: 18 min (compound specific).

Instrument 2: Photovac 10530 GC equipped with a PID with a 10.6 eV lamp.

Column:

4' x 1/8" SP-2100 packed column.

Carrier Gas:

Ultra-zero grade air.

GC Analysis Time: 18 min (compound specific).

7.3.4 Analytical sequence:

7.3.4.1	Instrument blank.

7.3.4.2	Initial calibration.

7.3.4.3	Syringe blank.

7.3.4.4	Check standard solution and/or performance evaluation sample (if available).

7.3.4.5	Syringe blank.

7.3.4.6	Sample 1.

7.3.4.7	Syringe blank (if the sample is contaminated).

7.3.4.8	Sample 2.

7.3.4.9	Syringe blank (if the sample is contaminated).

7.3.4.10	Continue for samples 3 to 10.

7.3.4.11	Continuing calibration standard (Photovac 10A10: after the 10th injection or 2 hours,
whichever is more frequent; Photovac 10S50 with isothermal oven: approximately every 4 hours).

7.3.4.12	Syringe blank.

FMC-VW-004-7

-------
7.3.4.13	Repeat, beginning at 7.3.4.8.

7.3.4.14	Final calibration at end of day.

7.4 Calculation

7.4.1 Initial calibration:

7.4.1.1 Analyze each calibration standard, adding the internal standard spiking solution (optional)
directly to the sample vial containing the standard before sealing. Tabulate the area response against
concentration for each target analyte and calculate CFs using the following equation.

__	Area of Peak

Cr

Mass Injected (ng)

7.4.1.2 Using the CF value calculated above, calculate the %RSD for each compound at the 3
concentration levels using the equation below. The %RSD must be less than or equal to 25 percent.

ST)

iRSD = 4=- x 100
X

where SD, the standard deviation, is given by

\

SD

^ (x. - X):
hi N ~ 1

where: X; = Individual calibration factor (per analyte)

X = Mean of all initial CF s (per analyte)

N = Number of calibration standards

7.4.2 Continuing calibration:

7.4.2.1	Sample quantitation is based on analyte CFs calculated from continuing calibrations.
Midrange standards for all initial calibration analytes must be analyzed as continuing calibration standards
at specified intervals (less than or equal to 24 hours).

7.4.2.2	The maximum allowable RPD calculated using the equation below for each analyte must
be less than or equal to 25 percent.

l ~T ~ CFC\

RPD = -	1	— x 100

CFx + CFc

2

where: CF, = Mean CF from the initial calibration for each compound

CFc = Measured CF from the continuing calibration for the same compound

7.4.3 Final calibration: Obtain the final calibration at the end of each batch of samples analyzed. The
maximum allowable RPD between the mean initial calibration and final calibration CF s for each analyte must
be less than or equal to 50 percent. A final calibration that achieves an RPD less than or equal to 25 percent may
be used as an ongoing continuing calibration.

FMC-VW-004-8

-------
CF - CF
RPD = - 1 — x 100

cft + cff

where: CF, = Mean initial CF for each compound
CFf = Final CF for the same compound

7.4.4 Sample quantitation:

7.4.4.1 Calculate the concentrations of target analytes in the sample using the following
equations. Measure the response by automated relative peak height or relative peak area measurements
from an integrator. The Photovac 10S50 GC will automatically calculate the sample concentration based
on the standard listed in the library.

7.4.4.2 The CF value from the continuing calibration analysis is used to calculate the
concentration in the sample. Use the CF as determined in Section 7.4.1 and the equation below.
Corrections must be made for changes in volumes and gain/attenuation between the samples and
standards.

(A ) (1000)

Concentration (uq/L) =

(V) (CF)

where: Ax = Area of the peak for the compound to be measured
V = Volume of sample in vial (mL)

CF = The CF for the analyte to be measured

7.4.4.3 Report results in micrograms per liter (|ig/L) without correction for blank or spike
recovery.

7.4.4.4 When identification is questionable, the chemist may calculate and report a maximum
possible concentration (qualified as less than the numerical value). This allows the data user to determine
if additional (e.g., CLP RAS or SAS analysis) work is required, or if the reported concentration is below
action levels and project objectives and DQOs have been met, to forego further analysis.

7.4.4.5 Coeluted analytes should be quantitated and reported as the combination of the
unseparated volatile organic target analytes or reanalyzed on a confirmation column.

7.4.4.6 Similarly, when sample concentration exceeds the linear range, the analyst may report
a probable minimum level (qualified as greater than the numerical value). This allows the data user to
determine if additional (e.g., CLP analyses) work is required, or if the reported concentration is above
action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 3. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-VW-004-9

-------
Table 3

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.007 (VOCs in Water by Manual Headspace)

Advisory Quality Control Limits

Analyte

Spike %R

Duplicate RPD
(%)

1,1 -Dichloroethene

30 - 200

± 100

trans-1,2-Dichloroethene

30 - 200

± 100

Chloroform

30 - 200

± 100

Benzene

30 - 200

± 100

Trichloroethene

30 - 200

± 100

T oluene

30 - 200

± 100

T etrachloroethene

30 - 200

± 100

Dibromochloromethane

30 - 200

± 100

Chlorobenzene

30 - 200

± 100

Ethylbenzene

30 - 200

± 100

m,p-Xylenes

30 - 200

± 100

o-Xylene

30 - 200

± 100

FMC-VW-004-10

-------
9.0 METHOD PERFORMANCE

9.1 The following is an example of a GC chromatogram for several target analytes.

Figure 1
Gas chromatogram

Instrument:	Photovac 10S30.

Column:	4 ft x 1/8 in SP-2100.

Gas:	Ultra-zero grade air at a flow rate of 15 mL/min.

Detector:	PID with a 10.6 eV lamp.

FMC-VW-004-11

-------
9.2 Method F080.007 examples of sample OA/OC results: Spike and duplicate sample results are presented
as examples of FASP Method F080.007 empirical data (see Tables 4 and 5).

Table 4

FASP METHOD F080.007
WATER MATRIX SPIKE PERCENT RECOVERY (%R)

(To be completed as data becomes available.)

FMC-VW-004-12

-------
Table 5

FASP METHOD F080.007
WATER DUPLICATE SAMPLE RELATIVE PERCENT DIFFERENCE (RPD)

(To be completed as data becomes available.)

FMC-VW-004-13

-------
10.0 REFERENCES

Information not available.

FMC-VW-004-14

-------
CSL Method

VOA/WATER/PENTANE EXT/GC-ECD

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of water for volatile hydrocarbon parameters that are indicative
of contamination at the site. It is presented as a means to rapidly characterize contamination in water samples. The
method is semiqualitative and semiquantitative for the list of target constituents listed in Table 1. Other compounds
may be added as data become available.

1.2 Application of this method is limited to the screening analysis of water for the target constituents. The
chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of water contamination associated with other non-targeted compounds in the sample extracts. Positive identification
and quantification of specific constituents, such as these constituents and other organic priority pollutants, should be
supported by analyses of duplicate and other composited samples at a remote CLP laboratory employing EPA
approved testing protocols.

1.3 Preliminary method validation data indicate analysis recoveries of upwards of 90 percent.

1.4 The method detection limits (MDL) for the target constituents are estimated to be 10 (ig/L. These
estimates are the result of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The method presented here is based on EPA Method 501.2" Analysis of Trihalomethanes in Drinking
Water bv Liquid/Liquid Extraction." EPA-EMSL, Cincinnati, Ohio, November 6, 1979, and on liquid-liquid
extraction techniques as investigated by Glase and Lin for EPA-EMSL. In brief, pentane is used to effect extraction
of the target constituents from the sample matrix. The extract is subsequently analyzed on a capillary gas
chromatograph (GC) using an electron capture detector (ECD).

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target constituents may cause a positive bias in the
results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples having
high levels of background organics or other interferences.

3.4 The response factors for uncalibrated peaks that are significantly different than those of the target
constituents may produce errors in the estimation of the total target constituent contamination.

4.0 APPARATUS AND MATERIALS

4.1 Water Sampling Equipment: described in the "Quality Assurance Project Plan."

4.2 Reacti-flasks: 50-mL capacity with screw cap and septum liner.

FMC-VW-005-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Water (p.g/L)

Carbon Tetrachloride

10

1,1 -Dichloroethylene

10

trans-1,2-Dichloroethy lene

10

Ethylene Dibromide

10

Perchloroethylene

10

1,2,4-Trichlorobenzene

10

1,1,1 -Trichloroethane

10

1,1,2-Trichloroethane

10

T richloroethy lene

10

4.3	Sample Syringe: glass, 10-mL with Teflon plunger.

4.4	Glassware: class A volumetric pipets and flasks; beakers, vials, Pasteur pipets, and miscellaneous
glassware as necessary for preparation and handling of samples and standards.

4.5	Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation of
dilutions, and spiking of samples.

4.6	Gas Chromatograph: Hewlett-Packard Model 5890A; temperature-programming, electronic integration,
report annotation, automatic sampler, and ECD.

4.7	Analytical column: suitable for separation of target constituents and that provides good overall separation
for noncalibration peaks.

5.0 REAGENTS

5.1	Solvents

5.1.1 Pentane: Spectro grade, 99.9 percent.

5.2	Gases

5.2.1	Nitrogen: Carrier gas, prepurified grade.

5.2.2	Argon-methane: Makeup gas, prepurified grade.

5.3	Stock Standards: Prepare or purchase standard materials at approximately 1000 mg/L in methanol.

FMC-VW-005-2

-------
5.4 Working Standards: Prepared from stock standards by precise dilution in pentane.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.1 The target constituents are either identified as or suspected of being carcinogens. All samples are
assumed to be hazardous. Handle all stock and working calibration standards, as well as all samples, with the
utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all times
when preparing and handling standards and field and laboratory samples.

7.1.3 Prepare standards and samples in a fume hood.

7.1.4 Pentane (C5H12) is regulated by NIOSH. The suggested permissible exposure level (PEL) is 120
ppm with a ceiling level of 610 ppm. Exposure pathways are oral, dermal, and airway. Effects of short-term
exposure are drowsiness and irritation of eyes and nose; large doses may cause unconsciousness. Prolonged
overexposure may cause

irritation of the skin. The odor threshold of n-pentane is reported as 2.2 ppm. Pentane is highly flammable and
is incompatible with strong oxidizing agents.

7.1.5 Store sample extracts and standards prepared in flammable solvents in an explosion-proof
refrigerator or cooler (outside the laboratory).

7.1.6 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Any situation which leads to or causes noticeable odors or produces any physical symptoms in the
workers shall be investigated immediately followed by appropriate corrective action.

7.1.7 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit available for use at all times.

7.1.8 Separate and dispose of laboratory wastes properly. The wastes include: used sample aliquots,
initial wash water, chemical wastes generated in the analysis, and disposables used in the preparation of the
samples. Collect and deposit these wastes in a drum clearly marked as "CSL Lab Wastes Only—Hazardous".
Consider water used for final rinsing of glassware hazardous, and release it into a 50 gallon drum outside the
laboratory trailer. Dispose of these wastes in accordance with the appropriate and relevant disposal methods.

7.2 Sample Preparation and Extraction

7.2.1 To a pre-cleaned 12-mL reacti-flask, volumetrically pipet 2 mL of pentane.

7.2.2 Transfer 10 mL of the water sample from the VOA vial into the barrel of the 10-mL syringe. Insert
the plunger into the syringe, and invert and waste away the trapped air and excess sample until the desired
sample aliquot is contained in the syringe.

7.2.3 Transfer the sample aliquot to the reacti-flask, cap the flask, and vigorously shake for 2 minutes
to achieve extraction of the sample.

FMC-VW-005-3

-------
7.2.4 Following the extraction, leave the flask undisturbed for one minute to permit separation of the
pentane and sample. Using a Pasteur pipet, transfer a suitable aliquot of the pentane solvent extract (extract)
from the flask into a labeled GC autosampler vial, and cap immediately with septum crimp seals. Refrigerate
the sample extracts until use.

7.3 Calibration

7.3.1 External calibration: Use four-level calibration with standards at approximately 10.0, 1.0, 0.1, and
0.01 (ig/mL for the target constituents.

7.3.2 Working calibration: Perform working calibration with the analysis of each working day's lot of
samples or with each lot of 20 samples, whichever is more frequent. Verify working calibration by use of a
mid-range standard mix. If the response factors and retention times vary by more than ±15 percent or 0.10 min.
from the initial calibration, then recalibrate on freshly prepared working standards.

7.4 Instrumental Analysis

7.4.1 Perform GC analysis on the extract using the instrument conditions similar to those listed in
Appendix 1.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range, dilute
the sample extract such that concentrations fall within the calibration range.

7.4.3 Check the retention values for each of the target constituents against the expected (calibration)
value. Qualify those results where the retention time does not fall within ± 0.05 minutes of the expected value.
Reject those results where the retention time does not fall with ± 0.10 minutes of the expected value.

7.4.4 Use a retention time marker (a solvent impurity) as an indicator of the reliability of each sample
injection and GC run. The retention time marker should fall within the same windows as the target constituents
and should be within ±15 percent area counts of its initial calibration value. If these criteria are not met,
re-evaluate the data using relative retention times. Reruns should occur to resolve data suspicions.

7.5 Calculations: Base quantification of the target compounds on the integrated areas of the samples in
comparison to the integrated areas of the calibration standards for each analyte. The integrator reports the
concentrations in (ig/mL in the extracts. Calculate the concentration for each target constituent in the original sample
as follows:

A x Vt x DF
Concentration (]ig/L) = x 1000

where: A = Amount of target constituent found in the extract in (ig/L,

Vt = Volume of solvent added to the reactor flask, 2.0 mL,

DF = Dilution factor, if required,

1000 = Dimensional correction factor, and

Vs = Volume of the sample added to the reactor flask in mL.

8.0 QUALITY CONTROL

8.1 Quality control measures shall include as a minimum:

FMC-VW-005-4

-------
8.1.1	Daily mid-range calibration checks performed prior to the analysis of each day's lot of samples or
with each lot of 20 samples, whichever is more frequent.

8.1.2	Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day whichever is
more frequent.

8.1.3	Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory
blanks show contamination, the cause of the contamination should be investigated and corrective action taken.

8.1.4	Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1/day, whichever is more
frequent.

8.1.5	Analysis of mid-range matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1/day, whichever is more frequent.

8.1.6	Use of the retention time marker during the analysis of all samples and standards.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VW-005-5

-------
CSL Method

VP A/WATER/CARBON DISULFIDE EXT/GC-FID

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of water for volatile hydrocarbon parameters that are indicative
of contamination at the site. It is presented as a means to rapidly characterize contamination in water samples. The
method is semiqualitative and semiquantitative for target constituents listed in Table 1. Other compounds may be
added as data become available.

1.2 Application of this method is limited to the screening analysis of water for the target constituents. The
chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of water contamination associated with other nontargeted compounds in the sample extracts. Positive identification
and quantification of specific constituents, such as these constituents and other organic priority pollutants, should be
supported by analyses of duplicate and other composited samples at a remote CLP laboratory employing EPA
approved testing protocols.

1.3 Preliminary method validation data indicate analysis recoveries of upwards of 90 percent.

1.4 The method detection limits (MDL) for the target constituents are estimated to be 1.0 ppm (^g/g). These
estimates are the result of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The methods presented here are based on liquid-liquid extraction techniques as investigated by Glase and
Lin (1983) for EPA-EMSL. In brief, carbon disulfide is used to effect extraction of the target constituents from the
sample matrix. The extract is subsequently analyzed on a two-channel capillary gas chromatograph (GC) using a
flame ionization detector (FID).

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target constituents may cause a positive bias in the
results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples having
high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 Water Sampling Equipment: described in the " Site Sampling Plan."

4.2 Reacti-flasks: 50-mL capacity with screw cap and septum liner.

FMC-VW-006-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Water (ng/g)

4-Methyl-2-pentanone

1.0

T oluene

1.0

Xylenes

1.0

4.3	Sample Syringe: glass, 10-mL with Teflon plunger for sample delivery.

4.4	Glassware: class A volumetric pipets and flasks; beakers, vials, Pasteur pipets, and miscellaneous
glassware, as necessary for preparation and handling of samples and standards.

4.5	Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation of
dilutions, and spiking of samples.

4.6	Gas Chromatograph: Hewlett-Packard Model 5890A; temperature- programming, electronic integration,
report annotation, automatic sampler, 30-meter megabore capillary column (DB-1, 1.50 micron film thickness), and
FID.

5.0 REAGENTS

5.1	Carbon Disulfide: Reagent grade, 99.9 percent.

5.2	Sodium Sulfate: Reagent grade, anhydrous powder form.

5.3	Stock Standards: Prepared from standard materials at approximately 1000 mg/L in CS2.

5.4	Working Standards: Prepared from stock standards by precise dilution in CS2.

5.5	Gases

5.5.1	Nitrogen: Carrier gas, prepurified grade.

5.5.2	Hydrogen: FID gas, prepurified grade.

5.5.3	Air: FID gas, zero grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not available.

FMC-VW-006-2

-------
PROCEDURE

7.1 Safety

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all times
when preparing and handling standards and field and laboratory samples.

7.1.3 Prepare standards and samples in a fume hood.

7.1.4 Carbon disulfide (CS2) is regulated by NIOSH. The suggested permissible exposure level (PEL)
is 1 ppm with a ceiling level of 10 ppm. Exposure pathways are oral, dermal, and airway. Effects of short-term
exposure are headaches, nausea, drop in blood pressure, dizziness, and unconsciousness. High concentrations
may cause irritation to the skin, eyes, and nose.

7.1.5 Store sample extracts and standards prepared in flammable solvents in an explosion-proof
refrigerator or cooler (outside the laboratory).

7.1.6 Sample preparation should be performed in a fume hood with adequate skin, eye, and hearing pro-
tection provided for and used by the analysts. Both carbon disulfide and pentane have good warning properties
since their discernable odor thresholds are well below their PELS. Correct any situation creating odor levels.
Handle carbon disulfide in minimum quantities to minimize fire and health hazards.

7.1.7 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Any situation which leads to or causes noticeable odors or produces any physical symptoms in the
workers shall be investigated immediately followed by appropriate corrective action.

7.1.8 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit available for use at all times.

7.1.9 Separate and dispose of laboratory wastes properly. The wastes include: used sample aliquots,
initial wash water, chemical wastes generated in the analysis, and disposables used in the preparation of the
samples. Collect and deposit these wastes in a drum clearly marked as "CSL Lab Wastes Only—Hazardous".
Consider water used for final rinsing of glassware hazardous, and release it into a 50 gallon drum outside the
laboratory trailer. Dispose of these wastes in accordance with the appropriate and relevant disposal methods.
All of the target compounds are reported in the NIOSH manual as having "good warning properties." Any
situation which leads to or causes noticeable odors or produces any physical symptoms in the workers shall be
investigated immediately followed by appropriate corrective action.

7.2 Sample Preparation and Extraction

7.2.1 To a precleaned 12-mL reacti-flask, volumetrically pipet 2 mL of CS2.

7.2.2 Transfer 10 mL of the water sample from the VOA vial into the barrel of the 10-mL syringe. Insert
the plunger into the syringe and invert. Waste away the trapped air and excess sample until the desired sample
aliquot is contained in the syringe.

FMC-VW-006-3

-------
7.2.3 Transfer the sample aliquot to the reacti-flask, cap the flask, and vigorously shake for 2 minutes
to achieve extraction of the sample. Following the extraction, leave the flask undisturbed for one minute to per-
mit separation of the CS2 and sample.

7.2.4 Using a Pasteur pipet, transfer a suitable aliquot of the CS2 solvent extract from the flask into a
labeled GC autosampler vial and cap immediately with septum crimp seals. Refrigerate the sample extracts until
use.

7.3 Calibration

7.3.1 External calibration: Use a three-level calibration with standards at approximately 40.0, 10.0, and
1.0 (ig/mL for the target constituents.

7.3.2 Working calibration: Perform a working calibration with the analysis of each working day's lot
of samples or with each lot of 20 samples, whichever is more frequent. Verify working calibration by use of
a mid-range standard mix. If the response factors and retention times vary by more than ±15 percent or 0.10
min. from the initial calibration, then recalibrate on freshly prepared working standards.

7.4 Instrumental Analysis

7.4.1 Perform GC analysis on the extract using the instrument conditions similar to those listed in
Appendix 1.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range, dilute
the sample extract such that concentrations fall within the calibration range.

7.4.4 Use a retention time marker as an indicator of the reliability of each sample injection and GC run.
The retention time marker should fall within the same windows as the target constituents and should be within
±15 percent area counts of its initial calibration value. If these criteria are not met, re-evaluate the data using
relative retention times. Reruns should occur to resolve data suspicions.

A x Vt x DF
Concentration (]ig/L) = x 1000

where: A = Amount of target constituent found in the extract in (ig/L,
Vt = Volume of solvent added to the reactor flask, 2.0 mL,
DF = Dilution factor, if required, and

Vs = Volume of the sample added to the reactor flask in mL.
,0 QUALITY CONTROL

8.1 Quality control measures shall include as a minimum:

FMC-VW-006-4

-------
8.1.1	Daily mid-range calibration checks performed prior to the analysis of each day's lot of samples or
with each lot of 20 samples, whichever is more frequent.

8.1.2	Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day, whichever
is more frequent.

8.1.3	Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory
blanks show contamination, the cause of the contamination should be investigated and corrective action taken.

8.1.4	Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1/day, whichever is more
frequent.

8.1.5	Analysis of mid-range matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1/day, whichever is more frequent.

8.1.6	Use of the retention time marker during the analysis of all samples and standards.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VW-006-5

-------
CSL Method

VP A/WATER/HEAD SP ACE/GC -PIP

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of water for volatile hydrocarbon parameters that are indicative
of contamination at the site. It is presented as a means to rapidly characterize contamination in water samples. The
method is customized to measure the target constituents listed in Table 1. Other compounds may be added as data
become available.

1.2 Application of this method is limited to the screening analysis of water for the target constituents. The
chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of water contamination associated with other nontargeted compounds in the sample extracts. Positive identification
and quantification of specific constituents, such as these constituents and other organic priority pollutants, should be
supported by analyses of duplicate and other composited samples at a remote CLP laboratory employing EPA
approved testing protocols.

1.3 The method detection limits (MDL) for the target constituents are estimated to be 10 (ig/L. This estimate
is the result of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The method presented here is based on EPA Method 3810, "Headspace Analysis," found in EPA SW-846,
Test Methods for Evaluating Solid Waste. 3rd ed., November 1986. In brief, a water sample is collected in a sealed
glass container and allowed to equilibrate at room temperature. The subsequent headspace is analyzed by gas
chromatography (GC).

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target constituents may cause a positive bias in the
results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples having
high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 Sample Bottles: 250-mL capacity with Teflon caps; pre-cleaned as purchased from I-Chem.

4.2 Balance: Sartorius; top-loading electronic with 300 gram capacity and ± 0.01 gram sensitivity.

4.3 Glassware: class A volumetric pipets and flasks; beakers, vials, and miscellaneous glassware as necessary
for the preparation and handling of samples and standards.

FMC-VW-007-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Water (p.g/L)

Benzene

10

1,2-Dichloroethylene

10

Perchloroethylene

10

T oluene

10

1,1,1 -Trichloroethane

10

T richloroethy lene

10

Xylenes

10

4.4	Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation of
dilutions, and spiking of samples.

4.5	Gas Chromatograph: Photovac Model 1OS70; isothermal oven, electronic integration, report annotation,
10m capillary column, and photoionization detector (PID).

5.0 REAGENTS

5.1	Deionized Water.

5.2	Standards: Purchase neat solvents and prepare 10 ppm standard mixture.

5.3	Working Standards: Prepared by precise dilution.

5.4	Ultrapure Air: Carrier gas purchased from Scott-Marrin.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1 The target constituents are either identified as or suspected of being carcinogens. All samples are
assumed to be hazardous. Prepare all stock and working calibration standards, as well as all samples, with the
utmost care using good laboratory techniques in order to avoid harmful exposure.

FMC-VW-007-2

-------
7.1.2 Analysts shall wear laboratory coats, safety glasses, and surgical gloves at all times while preparing
and handling standards and field and laboratory samples.

7.1.3 Prepare standards and samples in a fume hood.

7.1.4 Store sample extracts and standards prepared in flammable solvents in an explosion-proof
refrigerator or cooler (outside the laboratory).

7.1.5 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Investigate any situation which leads to or causes noticeable odors or produces any physical
symptoms in the workers immediately and follow with appropriate corrective action.

7.1.6 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit available for use at all times.

7.1.7 Separate and dispose of laboratory wastes properly. The wastes include: used sample aliquots,
initial wash water, chemical wastes generated in the analysis, and disposables used in the preparation of the
samples. Collect and deposit these wastes in a drum clearly marked as "CSL Lab Wastes Only—Hazardous".
Consider water used for final rinsing of glassware nonhazardous, and release it into a 50 gallon drum outside
the laboratory trailer. Dispose of these wastes in accordance with the appropriate and relevant disposal methods.

7.2 Sample Preparation and Extraction

7.2.1 After receiving samples from the field, screen the sample using an HNu organic analyzer, and
record the HNu reading on the samples' bottle.

7.2.2 Place the sample bottle in an ambient temperature water bath. Allow the sample bottle contents
to reach constant room temperature.

7.2.3 Agitate the water sample for one minute, allowing for the gas-liquid equilibrium to be established.

7.3 Calibration

7.3.1 External calibration: Use headspace analysis of water standards for a four-level calibration at
approximately 10, 1, 0.1, and 0.01 (ig/mL for the target constituents.

7.3.2 Working calibration: Perform working calibration with the analysis of each working day's lot of
samples or with each lot of 20 samples, whichever is more frequent. Verify working calibration by use of a
mid-range standard mix (i.e., 0.1 (ig/mL standard mix). If the response factors and retention times vary by more
than ±15 percent or 0.10 minutes from the initial calibration, then perform recalibration on freshly prepared
working standards.

7.4 Instrumental Analysis

7.4.1 Perform GC analysis on the sample headspace using the instrument conditions which were
determined during method development.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range, dilute
the sample extract such that concentrations fall within the calibration range.

FMC-VW-007-3

-------
Reject those results where the retention time does not fall within ± 0.10 minutes of the expected value. Take
corrective action if the results continue to fall outside of the proper range.

7.5 Calculations: Base quantification of the target compounds on comparison of the integrated areas of the
samples with the integrated areas of the calibration standards for each analyte. The integrator reports the
concentrations in ppm or ppb in the headspace. Calculate the concentration for each target constituent in the original
sample on an as received basis as follows:

Concentration (g/L) = A x DF x 1000

where: A = Amount of target constituent found in the extract in (ig/mL
DF = Dilution factor, if required

8.0 QUALITY CONTROL

8.1 Quality control measures shall include as a minimum:

8.1.1 Daily mid-range calibration checks performed prior to the analysis of each day's lot of samples or
with each lot of 20 samples, whichever is more frequent.

8.1.2 Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day, whichever
is more frequent.

8.1.3 Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory
blanks show contamination, the cause of the contamination should be investigated and corrective action taken.

8.1.4 Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1/day, whichever is more
frequent.

8.1.5 Analysis of mid-range matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1/day, whichever is more frequent.

8.1.6 Use of the retention time marker during the analysis of all samples and standards.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VW-007-4

-------
NUS SOP Number 5.1

FIELD SCREENING OF TARGET PURGEABLE VOLATILE ORGANIC COMPOUNDS

(AQUEOUS MATRIX)

1.0 SCOPE AND APPLICATION

1.1 The following methodology describes a modification of EPA 600 series purge and trap gas
chromatographic procedures suitable for the determination of volatile organic contaminants in aqueous matrix
samples.

1.2 The appropriate method detection limit (MDL) for this methodology may be statistically calculated using
results generated for the initial linearity study and continuing calibrations, or, MDLs may be substantiated by the
analysis of a low standard at the level of the anticipated MDL.

1.3 Table 1 provides a list of potential volatile target compounds.

2.0 SUMMARY OF METHODS

2.1 In this methodology, a portion of neat sample or dilution is placed into a glass sparging vessel which is
sealed onto a purging device. The contained sample aliquot is subjected to a stream of inert gas which is allowed to
bubble through the matrix. This mechanical bubbling action effectively strips the contaminants (now volatilized) from
the aqueous matrix and sweeps them onto a packed sorbent tube (i.e., trap), where they are subsequently desorbed
(by the action of heat and reverse gas flow) onto a suitable column housed in a pre-programmed gas chromatograph
(GC). The contaminants become separated and resolved as they travel through the GC column. Eventually, the
contaminants elute through an appropriate detector. The detector signals are processed and interpreted via a
previously programmed integrator.

2.1.1 Low level analysis: Use of a 20-mL neat sample aliquot is suggested in order to achieve reportable
detection limits of approximately 5 (ig/L. Sample aliquots should be introduced into the sparger using a 10-mL GC
syringe. Sample aliquots should not be pipetted, as the action of pipetting may compromise sample integrity due to
mechanical stripping.

2.1.2 Medium level analysis: Proportioned dilutions may be achieved by using a reduced sample aliquot
plus a complementary portion of organic-free water for sparging. For example, a 4-fold dilution can be simulated by
injecting 5 mL of neat sample plus 15 mL of organic-free water. Similarly, extremely high concentration samples
may be analyzed by spiking (iL aliquots of neat sample in 19+ mL of organic-free water.

3.0 INTERFERENCES

3.1 Interferences can result from many sources, considering the environmental settings of most hazardous
waste sites. However, most interfering impurities are artifacts originating from organic compounds within the
specialty gases and the plumbing within the purging mechanism. Interferences in the analytical system are monitored
by the analysis of method blanks. Method blanks

are analyzed under the same conditions and at the same time as standards and samples to establish an average
background response.

FMC-VW-008-1

-------
Table 1

SUMMARY OF POTENTIAL TARGET COMPOUNDS

Volatile Organics Analysis

Acetone

Benzene

Bromoform

Carbon tetrachloride

Chlorobenzene

Chloroform

Ethylbenzene

Methylene Chloride

1,1 -Dichloroethene

Total 1,2-Dichloroethenes

1,1 -Dichloroethane

1,2-Dichloroethane

1,1,1 -Trichloroethane

T etrachloroethene

T oluene

Trichloroethene

Total Dichlorobenzenes

Total Xylenes

2-Butanone (MEK)

4-Methyl-2-pentanone (MIBK)

3.2 Samples can become contaminated by the diffusion of high concentration contaminants to lower
concentrated samples through container seals during shipping and storage. If opted as part of the analysis plan,
organic-free trip blanks may be developed and carried by the sampling team together with field samples to assess the
existence and the magnitude of this phenomenon.

3.3 Artifacts, which manifest themselves as carryover in the next analytical run, can also occur within the
analytical apparatus whenever a highly contaminated sample is introduced. To preclude this from occurring, the
sample line and sparge vessel are thoroughly rinsed with organic-free water prior to the bake cycle of each highly
contaminated sample run.

4.0 APPARATUS AND MATERIALS

4.1 Purge and Trap Device: Tekmar Company Model LSC-2, or equivalent, complete with a 25-mL glass
sparge vessel and a 1/8 inch O.D. x 25 cm long stainless steel trap. The trap may be packed solely with Tenax.
Alternatively, trap packing may consist of 1.0 cm of 3 percent OV-1, 15 cm of Tenax, and 8 cm of silica gel.
Appropriate trap selection is contingent upon the target compounds being analyzed.

4.2 Gas Chromatograph: Hewlett-Packard 5890, or equivalent. The analytical system should be equipped
for temperature programming, packed and/or capillary column analysis, and direct-column injection.

FMC-VW-008-2

-------
4.3 Detector: Photoionization detector/flame ionization detector (PID/FID) or photoionization detector/Hall
electrolytic conductivity detector (PID/HECD) in series; FID only. Optimum detector selection should be based upon
the sensitivities of the target compounds being analyzed.

4.4 Analytical Column: Glass or stainless steel column packed with 1% SP-1000 on 60/80 mesh Carbopack
B. Alternatively, a suitable capillary column may be used.

4.5 Syringes: 5-|iL, 25-^L, 100-|iL, 1-mL, and 10-mL.

4.6 Analytical Balance: Capable of accurately weighing 0.0001 g.

4.7 Oven: Constant temperature for the regeneration of contaminated apparatus.

4.8 Refrigerators: One dedicated refrigerator each for separate sample and standard storage. Each should be
capable of maintaining a stable temperature of 4°C.

5.0 REAGENTS

5.1 Methanol: Pesticide grade, or equivalent.

5.2 Organic-free water: Supplied by laboratory or purchased.

5.3 Neat solvents: 96 percent purity, or better, for each compound of interest.

5.4 Standards: Prepare calibration standards containing the compounds of interest in methanol by either
diluting commercially purchased stock standard mixes or by creating in-house standards from pure solvents. Prepare
in-house calibration standards gravimetrically, in that an appropriate aliquot of each target compound is introduced
into a known volume of methanol. The appropriate aliquot of compound is based upon the compound's density and
response to the selected detector. Calibration standards are created at a level such that a 2- to 5-(iL spike of standard
into 20 mL of organic-free water is suitable for continuing calibration purposes.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 The primary purpose of field screening is to provide cost-effective, specific data on a near-to-real time
turnaround basis. For this reason, samples submitted to the mobile laboratory should be analyzed as soon as possible.

6.2 Samples awaiting analysis are stored at 4°C in a dedicated refrigerator. If, because of loading, it is not
possible to analyze all samples taken daily, the suggested holding time for the analysis of volatile organics in aqueous
matrix is 7 days prior to analysis. If holding times are exceeded, the affected data should be qualified as suspect.

7.0 PROCEDURE

7.1 Calibration: Calibrate the analytical system by the external standard method in which response factors
(RF) for each compound are obtained by the analysis of a standard mix of known concentration. Following the
analysis of this known standard mix, create an electronic file establishing each peak's identity, retention time (RT),
RF, and known concentration. Determine the RF for each target compound by dividing the known concentration by
the associated peak response (area or height units). For initial calibration, determine each compound's average RF
by averaging the peak response results generated for the initial linearity study. Program these average RFs into the
integrator to allow for direct concentration reading of contaminants found in subsequent sample analyses.

7.1.1 Initial linearity:

FMC-VW-008-3

-------
7.1.1.1 Generate an initial 3-point calibration curve by the analysis of multiple aliquot injections
of calibration standard. For example, if the calibration standard is created such that a 2-\xL spike into
organic-free water yields results at the level of the reported detection limits, a 3-point calibration curve
may be achieved by the analysis of 2-^L, 5-^L, and 10-(iL aliquot spikes.

7.1.1.2 Compute the percent relative standard deviation (%RSD see 7.3.1) based on each
compound's RFs (see 7.4) to determine the acceptability (linearity) of the curve. The %RSD should be
less than 20 percent. Reanalyze standard runs yielding data that does not meet the %RSD criterion.

7.1.1.3 Conduct the linearity study for field screening in such a way as to substantiate the
performance of the detector at the level of the reportable limits. It is not performed to demonstrate the
entire range of detector capability. The primary objective of field screening is the determination of "clean"
versus "dirty" and all results are, therefore, considered to be semi-quantitative.

7.1.2 Continuing calibration:

7.1.2.1 Update the calibration of the analytical system 3 times daily, using the mid concentration
standard: (1) preceding the daily analysis, (2) midday, and (3) after the daily analyses.

7.1.2.2 Analyze standards run for continuing calibration purposes at a level equal to the reported
detection limits. Continuing calibration RF s for each parameter should fall within 25 percent difference
(%D, see 7.3.3) of the average RF calculated for that particular compound during the initial linearity study.
Qualify data associated with individual parameter not meeting the %D criterion as suspect.

7.1.3 Peak identification: Compound identities may be substantiated by the analysis of each individual
component, thereby, documenting compound retention time.

7.2 Gas Chromatography

7.2.1 Analytical sequence: Conduct analyses in sets of 10, whenever possible, with 1 laboratory
duplicate spike analysis run per set. Bracket each set of sample analyses by the analysis of a standard, with a
method blank analysis following each standard run. The number of analyses per sample set and the associated
quality assurance/quality control (QA/QC) varies per contract. Consult the project work plan to verify that all
contractual obligations were met.

7.2.2 Preconcentrate sample contaminants through the purge and trap process in which stripped volatile
contaminants are adsorbed onto a sorbent trap. The affinity the volatilized organic contaminants have for the
special packing inside the sorbent tube causes them to be retained within the tube (i.e., adsorbed onto the
packing), while other inert components pass through the tube. The purge and trap process consists of a pre-purge
cycle (optional), a purge cycle (during which contaminants are stripped away from the sample matrix and are
trapped within the sorbent tube), a dry purge cycle (optional), a desorb cycle (in which the contaminants are
backflushed off the sorbent tube and onto the GC column), and a bake cycle (in which the sorbent tube or trap
is heated, with flow to a high temperature regeneration of the trap). The selection of the appropriate temperature
options and duration of the purge and trap processes are contingent upon the target compounds being analyzed.
Generally, the following range of conditions apply:

Cycle

T emperature

Duration

Purge

Ambient

8-10 minutes

FMC-VW-008-4

-------
Desorb

180°C

2-4 minutes

Bake

215°C

7-10 minutes

7.2.3 Desorption of the adsorbed contents of the sorbent trap onto the head of a previously conditioned
GC analytical column allows for subsequent analysis by temperature-programmed GC. First hold the desorbed
contaminants at constant temperature (usually in the range of 45 to 55 °C) at the head of the analytical column
for a period of 3 to 5 minutes. After this initial time period, raise the GC oven temperature at a constant rate
(usually 8 to 15°C/min) until a final temperature of 200 to 225°C is reached. The final temperature is
customarily held for a period of 3 to 10 minutes.

7.2.4 The affinity of the volatile contaminants to either the analytical column's mobile or stationary
phase, the effect of elevated temperature, and the action of the carrier gas flow through the column cause the
volatile contaminants to become separated and resolved, allowing them to elute in bands through the selected
detector. As long as the analytical conditions remain constant, each type of volatile component will elute at a
characteristic retention time. In this manner, sample contaminants are identified and quantified by comparison
to a run of a standard mix containing known compound concentrations.

7.3 Calculations

7.3.1 Calculate %RSD using the following equation:

ST)

%RSD = — x 100

where:

A (x - x)2
SD = >

M N - 1

and X is the mean of initial RFs (per compound).

7.3.2 Calculate relative percent difference (RPD) values using the following equation:

D1 ~ D2
RPD = i — x 100

+ g2>

where: D[ = First sample value, and
D2 = Second sample value.

7.3.3 Calculate the %D using the following equation:

%D = — — x 100

FMC-VW-008-5

-------
where: X[ = RF of first result, and
X2 = RF of second result.

7.3.4 Calculate percent recovery (%R) using the following equation:

S

where: SSR = Spike sample results,

SR = Sample result, and
S = Amount of spike added.

7.4 Sample Quantitation: The quantitation of volatile contaminants in aqueous matrix samples is calculated
based upon the following formula:

Concentrationsample (]ig/L) = target analyte peak response x RF x DF

where: RF = [Target analyte concentration in std (|ig/L)]/[Target analyte peak
response in std]

DF = Dilution factor, when applicable.

8.0 QUALITY CONTROL

8.1 Overview:

8.1.1	Field screening generates Level II data. As Level II data, the concurrent analysis of laboratory
duplicates and matrix spike analyses and the use of surrogate spike compounds is not required. However,
beyond the maintenance of practical Standard Operating Procedures (SOPs), certain elements of QC (if opted)
can greatly enhance the interpretation of and the confidence in the data generated. These traditional elements
of QC are discussed here as to how they are adapted to meet the demands of a successfully applied field
screening QA/QC program.

8.1.2	The primary purposes of an appropriate QA/QC program are to: (1) substantiate system
performance and give credence to the accuracy of the results generated, (2) to define aberrations and give
guidance to the interpretation of data, and (3) to achieve these goals through realistic efforts that do not impede
the forward progress of the analytical set.

8.1.3	The discussion presented here deals with only direct analytical QC. Additional elements of
QA/QC, such as field duplicate sample submissions, blind spike analysis, and external audits are not discussed.
Also not discussed are elements of QA/QC that are inherent to good chromatographic technique. Examples of
these accepted laboratory practices include (but are not limited to) the following: (1) the proper conditioning of
analytical columns and traps, (2) use of the solvent flush technique for the creation of standards and for direct
injections, and (3) the appropriate maintenance of selected detectors. Details regarding these accepted practices
are given in the referenced methodologies.

8.2	Laboratory Duplicates: One laboratory duplicate should be analyzed per sample set. Laboratory duplicate
analyses should generate results of RPD within 30 percent (see 7.3.2).

8.3	Matrix Spikes: Matrix spikes should be conducted at a level of 1 to 4 times the concentration of the
reported detection limits. One matrix spike analysis should be run per every 20 samples. Advised recovery ranges
vary with respect to the compound being analyzed. Recoveries of 35 to 150 percent are generally acceptable (see
7.3.4).

FMC-VW-008-6

-------
8.4	Surrogate Spikes: The use of at least 1 surrogate spike compound is highly recommended. The identity,
concentration and addition of the appropriate surrogate spike varies with the procedure being used. Each associated
referenced methodology should be consulted for guidance. Surrogate spike recoveries should fall within ±30 percent
(see 7.3.4). Sample analyses yielding %R values outside this 30 percent window should be reanalyzed or the
associated data should be qualified as suspect.

8.5	Method Blanks: Method blanks are prepared and analyzed in exactly the same manner as sample matrices.
A method blank analysis should follow every standard run and sample of high concentration. Ideally, method blank
results should yield no interferences to the chromatographic analysis and interpretation of target compounds. If
interferences are present, associated data should be qualified as suspect and/or target detection limits should be
adjusted accordingly.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VW-008-7

-------
Region V ESD Method

METHOD FOR FIELD SCREENING OF VOLATILE ORGANIC COMPOUNDS
IN WATER AND SOIL BY HEADSPACE ANALYSIS
USING THE HNU-301P GAS CHROMATOGRAPH

1.0 SCOPE AND APPLICATION

1.1 This method is applicable to water and soil samples.

1.2 This method is intended to analyze for the volatile organic compounds listed in Table 1. Other compounds
may be added to Table 1 as data become available.

1.3 Detection limits for some compounds for both water and soil are given in Table 1.

2.0 SUMMARY OF METHOD

2.1 This method is used to rapidly screen water and soil samples by analyzing the headspace vapor over a
known amount of the sample. It employs an HNU-301P gas chromatograph (GC) operating at ambient temperature
with sequential Photoionization (PID) and Flame Ionization (FID) detection. Separation of compounds is acheived
with a 6 ft. SE-30 chromatographic column. The PID is sensitive to aromatic compounds while some other
compounds may be detected by the FID.

3.0 INTERFERENCES

Information not available

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph

4.1.1 HNU-301P GC with serial PIP-FID.

4.1.2 Column: 6 ft. X 1/8 inches stainless steel column packed with 3% SE-30.

4.2 Vials: 40-mL, with Teflon backed seals.

4.3 Syringe: 25-mL, with hypodermic needles.

4.4 Syringes: 1.0-^L and 1 0-jj.L.

4.5 Syringes: 0.1-mL and 2.0-mL, gas tight.

4.6 Recorder: Linseis, portable dual pen.

4.7 Pan Balance: Single, capable of weighing to the nearest 0.1 g.

4.8 HNU-301P field pack: with battery charger and disposable nitrogen and hydrogen tanks.

FMC-VW-009-1

-------
Table 1

METHOD DETECTION LIMITS (MDL) IN WATER AND SOIL FOR SELECTED COMPOUNDS

Compound

Water MDL* (ppb)

Soil MDL" (ppb)

Benzene

T oluene

Chlorobenzene

145

400

o-Xylene

330

1,1 -Dichloroethane

1700

Chloroform

410

4300

* MDLs were determined using laboratory organic free water. These figures will vary depending on the type of
water sample analyzed.

** MDLs were determined using an artificial soil that is contamination free. These figures will vary depending
on the type of soil sample analyzed.

5.0 REAGENTS

See Table 2 for calibration mixtures and necessary quantities.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Water: Collect sample in 40-mL septum vials with no headspace, and keep sample at 4°C until
time of analysis. At least one sample in 10 should be collected in duplicate to provide precision data.

6.2 Soil: Collect enough soil to fill a 40-mL vial about one quarter full, and keep sample at 4°C until
analysis. At least one sample in 10 should be collected in duplicate to provide precision data. Weigh and record
the weight of the vial. Subtract the average weight of the empty vials to get the net amount of soil collected.
Record this net weight for the sample.

7.0 PROCEDURE

7.1 GC Operation Conditions

7.1.1 Temperature: Ambient.

7.1.2 Carrier gas flow: 15 psi head pressure (approximately 20 mL/min).

7.1.3 Chart speed: about 0.5 cm/min.

7.1.4 PIP output: about 8X1.

7.1.5 FID output: about 16X1.

FMC-VW-009-2

-------
Table 2

CALIBRATION MIXTURE AND NECESSARY QUANTITIES*

Compound

3 \iL

5 \iL

8 \iL

Benzene

T oluene

133

Chlorobenzene

240

400

640

0-Xylene

165

275

440

1,1 -Dichloroethane

200

333

533

Chloroform

700

1165

1864

Amounts of standard mixtures in microliters and concentrations in ppb.

7.1.6 Auto Zero: Activate as needed.

7.2 Calibration: The instrument should be calibrated at least daily by generating a three point calibration
curve. Add each amount of the calibration mixtures as shown in Table II to 30 mL of water in 40-mL vials to give
the concentration shown. Prepare and analyze each vial according to the analytical procedures in Section 7.3.

7.2.1 Initial calibration:

7.2.1.1 Measure the height of each peak at its apex from the baseline at each concentration level
in millimeters, and calculate a calibration factor (CF) for each compound at each concentration level using
the formula:

^ _ peak height
F ppb of Std.

7.2.1.2 Calculate the average CF for each compound, and also calculate its standard deviation
for each set of CFs. Finally, calculate the percent relative standard deviation (% RSD) for each compound
using the formula:

Std.

% RSD = ^viatio^ x 100%
average CF

7.2.1.3 This figure should be under 20% for each compound. If it is not, reinject a freshly
prepared standard vial at the level which showed the largest difference from the average CF for the
compound in question. Recalculate the CF and standard deviation using the new value. Calculate the %
RSD. If it is still greater than 20%, consider any quantitation of the compound as estimated only.

FMC-VW-009-3

-------
7.2.2 Continuing calibration:

7.2.2.1 A continuing standard at the mid point level should be injected after every 5 sample
injections to insure GC stability. The percent difference (% D) of each CF should be calculated according
to the formula:

%D = averaSre CF - CF x 10Q
average CF

7.2.2.2 If the %D is less than 30% of the average CF from the initial standardcurve, the following
5 samples may be quantitated using the continuing CF. If the %D for a compound is greater than 30%,
reinject a freshly prepared standard. If it is still beyond 30% difference, generate a new three point curve
or continue with the realization that any quantitation for the compound in question for the following
sample is estimated only.

7.2.2.3 The retention time (RT) of each peak is measured from either the point of injection or the
pen deflection after injection to the apex of the peak. This procedure must be done in a consistant manner
for the standard and all samples.

7.2.2.4 The RTs should not vary by more than 5% from one standard nor to another. If they do,
the GC conditions have probably changed, i.e., temperature and/or flow rate.

7.2.2.5 If the peak heights decrease using a fresh continuing standard during the course of
analysis, the battery may need replacement. Other symptoms are a barely visible light from the PID lamp
and a noticeably quieter air pump. If they are not apparent, the gas tight syringe may be a problem.
Change syringe and reinject a standard.

7.3 Sample Preparation

7.3.1 Water: Allow the sample vials to reach ambient temperature. Before analysis withdraw 10 mL
from the vial by inserting the needle of the 25-mL syringe into the septum along with another needle to allow
air to enter as water is withdrawn. Shake the vial for at least one minute, and allow the vial to rest upside down
for 1 minute to reach equalibrium. The sample is now ready for analysis.

7.3.2 Soil: Add enough blank water via the 25-mL syringe and extra needle method to leave
approximately 10 mL of headspace in the vial. Shake the vial for at least one minute, and allow it to sit upside
down for five minutes before analysis. Allow the vial to reach ambient temperature, and shake it briefly to
remove any soil from the septum.

7.4 Sample Analysis
7.4.1 Water:

7.4.1.1 Before analysis inject 500 (iL of ambient air to check for any background problems.
Allow time for all possible compounds of interest to elute before proceeding.

7.4.1.2 Although sample size may vary from 10 (iL to 1 mL, try a 500-(iL volume of headspace
vapor on waters that are "clean". This volume should be sufficient for low level work.

7.4.1.3 If the sample is suspected of containing solvents or the sample has a strong smell, start
with a 10-(iL injection, and increase the injection amount until peaks at half scale deflection are
encountered. This volume can then be used for quantitation.

FMC-VW-009-4

-------
7.4.1.4 An ambient air blank of 500 |±L should be injected after each positive that may reach full
scale deflection or greater to assure that the column and syringe will not produce any carry over.

7.4.2 Soil:

7.4.2.1 Analyze the headspace by injecting 500 (iL into the GC.

7.4.2.2 Follow the procedure for analysis of water as given in Section 7.3.1.
7.5 Identification and Quantitation

7.5.1 Water: The retention times of positive responses on the PID and FID should be compared with
the standard responses for these detectors. If they agree within a ± 5% window, a tentative identification exists.
This positive can then be quantitated by the formula:

Compound _ Peak Height v Std Inj. (]il)

Cone. (ppb) cF (Std) Sample Inj. (]il)

The second term in the right hand side of the equation is unity if the amounts injected for the standards and
sample are the same.

7.5.2 Soil: Although the qualitation of positive responses is handled in the same manner as with water
samples, quantitation is slightly different. The extraction volume is used which adjusts the final results into
weight units. The formula becomes:

Peaks Extract 1nnn

Compound _ Heights * Volume (]il) * x Std Inj. (]il)

Cone, (ppb) cp x wt. (g) Sample Inj. (ul)

8.0 QUALITY CONTROL

8.1 Duplicates: At least one sample in 10 should be collected in duplicate to provide precision data.

8.2 Instrument Calibration

8.2.1 Initial calibration: The instrument should be calibrated at least daily by generating a three point
calibration curve.

8.2.2 Continuing calibration: A continuing standard at the mid point level should be injected after every
5 sample injections to insure GC stability.

8.3 Blanks: Before analysis, an air blank (500 (iL of ambient air) should be injected to check for any
background problems. An ambient air blank of 500 |±L should be injected after each positive that may reach full scale
deflection or greater to assure that the column and syringe will not produce any carry over.

9.0 METHOD PERFORMANCE

Information not available.

FMC-VW-009-5

-------
10.0 REFERENCES

Information not available.

FMC-VW-009-6

-------
Region V ESD Method

METHOD FOR FIELD SCREENING OF VOLATILE ORGANIC COMPOUNDS
IN WATER AND SOIL BY HEADSPACE ANALYSIS USING THE PHOTOVAC
10S10 GAS CHROMATOGRAPH

1.0 SCOPE AND APPLICATION

1.1 This method is applicable to water and soil samples.

1.2 This method is intended to analyze for the organic compounds listed in Table 1. Other compounds may
be added to Table 1 as data become available.

1.3 Method detection limits (MDLs) for some compounds for both water and soil are also given in Table 1.

2.0 SUMMARY OF METHOD

2.1 This method is intended for the rapid screening of water and soil samples by analyzing the headspace
vapor over a known amount of the sample. It employs a Photovac 1 OS 10 gas chromatograph (GC) operating at
ambient temperatures with a photoionization (PID) detector. Rapid separation of compounds for qualitative analysis
may be achieved by a CSP-20M column, or for further qualitative and quantitative analysis by an SE-30 column.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph

4.1.1 Photovac IPS 10 GC: Refer to the Photovac 1 OS 10 Operating Manual or instrument instructions
before using this GC.

4.1.2 Detector: PID.

4.1.3 Columns

4.1.3.1 Column 1: 4 ft. x 1/8 in. I.D. Teflon column packed with 5% SE-30 on 100/120 mesh
Chromosorb G-AW.

4.1.3.2 Column 2: 4 ft. x 1/8 in. I.D. Teflon column packed with Carbopack B-HT 60/80 mesh,
also known as CSP-20M.

4.2 Vials: 40-mL with Teflon-backed seals.

4.3 Syringe: 25-mL with hypodermic needles.

4.4 Other Syringes: 1.0-^L and 1 0-jj.L.

FMC-VW-010-1

-------
Table 1

Method Detection Limits (MDL) in Water and Soil
for Selected Compounds

Compound

Water MDL* (ppb)

Soil MDL** (ppb)

trans-1,2-Dichloroethy lene

1.2

4.0

Benzene

1.1

4.2

T richloroethy lene

1.2

3.3

T oluene

2.1

11.0

Chlorobenzene

5.3

46.0

Ethylbenzene

5.8

22.0

o-Xylene

0.5

20.0

Methylene chloride

13

	

1,1,1 -Trichloroethane

80

	

1,1,2-Trichloroethane

100

___

* MDLs were determined using laboratory organic-free water. These will vary depending on the type of water
sample analyzed.

** MDLs were determined using an artificial soil that is contamination free. These will vary depending on the type
of soil analyzed.

4.5	Gastight Syringes: 0.1-mL and 2.0-mL.

4.6	Single-pen Portable Recorder.

4.7	Compressed Air: Lecture size bottles of dry-grade or zero-grade.

4.8	Single-pan Balance: Capable of weighing to the nearest 0.1 g.

5.0 REAGENTS

See Table 2 for calibration mixtures and necessary quantities.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1	Water: Collect samples in 40-mL Teflon-backed septum vials with no headspace, and keep at 4°C until
time of analysis. At least 1 sample in 10 should be collected in duplicate to provide precision data.

6.2	Soil: Collect enough soil to fill a 40-mL vial about one quarter full, and keep sample at 4°C until analysis.
At least 1 sample in 10 should be collected in duplicate to provide precision data.

FMC-VW-010-2

-------
Table 2

CALIBRATION MIXTURES AND NECESSARY QUANTITIES*

Compound

1 iiL

3 iiL

5 iiL

10 iiL

15 iiL

trans-1,2-Dichloroethy lene

11.5

34.5

57.5





Benzene

10

30

50

	

	

T richloroethy lene

10

30

50

	

	

T oluene

20

60

100

	

	

Chorobenzene

67

201

335

	

	

Ethylbenzene

33

99

165

	

	

o-Xylene

42

126

210

	

	

Methylene chloride

	

	

83

166

249

1,1,1 -Trichloroethane

	

	

500

1000

1500

1,1,2-Trichloroethane

___

___

500

1000

1500

Amounts of standard mixes are in microliters, and concentrations are in ppb.

7.0 PROCEDURE

7.1	GC Operating Conditions

7.1.1	Temperature: Ambient; operating range 10°C (50°F) to 38°C (100°F).

7.1.2	Carrier gas flow: 40 mL/min for SE-30 column; and 10 mL/min for CSP-20M column.

7.1.3	Chart speed: About 0.5 cm/min.

7.1.4	Gam: 20.

7.1.5	Offset: As needed.

7.1.6	Chart range: 1 volt full-scale deflection (FSD).

7.2	Calibration: For quantitative work, calibrate the instrument at least daily by generating a 3-point
calibration curve. Add each amount	of calibration mixtures as shown in Table 2 to 30 mL of water in a 40-mL
vial to give the concentration shown. Prepare and analyze each vial according to section 7.3.

FMC-VW-010-3

-------
7.2.1 Initial calibration:

7.2.1.1 Measure the height of each peak at its apex from the baseline at each concentration level
in millimeters. Calculate a calibration factor (CF) for each compound at each concentration level using
the formula:

_ Peak height

Cr —

ppb of Std.

7.2.1.2 Calculate the average CF for each compound, and also calculate its standard deviation
(SD) for each set of CFs.

7.2.1.3 Finally, calculate the percent relative standard deviation (%RSD) for each compound
using the formula:

bRSD =

1=1

(X.-X):
n-1

x 100

7.2.1.4 This value should be under 15 percent for each compound of interest in the standard. If
it is not, reinject a freshly prepared standard vial at the level which showed the largest difference from the
average CF for the compound in question. Recalculate the average CF and the SD using the new value.
Calculate the %RSD. If it is still greater than 15 percent, consider any quantitation of the compound as
estimated only.

7.2.2 Continuing calibration:

7.2.2.1 Inject a continuing standard at the mid-point level after every 5 sample injections to insure
GC stability. Calculate the percent difference (%D) of each CF factor by using the formula:

CF - CF
%D = X 100

7.2.2.2 If the %D is less than 30 percent of the average CF, the next 5 samples may be quantitated
using the continuing CF. If the %D for a compound of interest is greater than 30 percent, reinject a freshly
prepared standard. If it is still beyond 30 percent, either generate a new 3-point calibration curve or
continue with the understanding that any quantitation for that compound in the following samples is
estimated only.

7.2.2.3 Measure the retention time (RT) of each peak from either the point of injection or the pen
deflection after injection to the apex of the peak. This procedure must be done in a consistent manner for
the standards and all samples.

7.2.2.4 The RTs should not vary by more than 5 percent from one standard run to another. If they
do, the GC conditions have probably changed (i.e., temperature and/or flow rate).

7.2.2.5 If peak heights decrease using fresh standards during the course of the analysis, the
battery may need charging, or a leak may have developed in the GC column fitting, septum, or in the
injection syringe. Check the battery charge, replace the septum, and check the column fittings for
tightness. Reinject and examine peak heights. If still not up to original standard injection, change the
syringe and try again.

FMC-VW-010-4

-------
7.3 Sample Preparation

7.3.1 Water: Allow the sample vials to reach ambient temperature. Before analysis, withdraw 10 mL
from the vial by inserting the needle of a 25-mL syringe into the septum along with another needle to allow air
to enter as water is withdrawn. Shake the vial for at least 1 minute, and allow the vial to rest upside down for
1 minute to reach equilibrium. The sample is now ready for analysis.

7.3.2 Soil: Weigh and record the weight of the vial to the nearest 0.1 gram. Subtract the average weight
of empty vials to get the net amount of soil collected. Record this net weight for the sample. Add enough blank
water via the 25-mL syringe and extra needle method to leave approximately 10 mL of headspace in the vial.
Shake the vial for at least 1 minute, and allow it to sit upside down for 5 minutes before analysis. Allow the vial
to reach ambient temperature, and shake it briefly to remove any soil from the septum.

7.4 Sample Analysis

7.4.1 Water:

7.4.1.1 Before a series of analytical runs, inject 500 (iL of ambient air to check background
problems. Allow time for all possible compounds of interest to elute before proceeding.

7.4.1.2 Although sample size may vary from 10 (iL to 1 mL, try a 500-(iL volume of
headspace vapor on water that is "clean". This should be sufficient for low level work.

7.4.1.3 If the sample is suspected of containing solvents or the sample has a strong smell, start
with a 10-(iL injection and increase the amount injected until peaks at half-scale deflection are
encountered. This volume can then be used for quantitation.

7.4.1.4 Inject an ambient (clean) air blank of 500 (iL after each positive that may reach full scale
deflection, or greater, to assure that the column and syringe will not produce any carryover.

7.4.2 Soil:

7.4.2.1 Analyze the headspace by injecting 500 (iL into the GC.

7.4.2.2 Follow the procedure for analysis of water as given in Section 7.4.1.

7.5 Identification and Quantitation

7.5.1 Water: Compare the RTs of positive responses with the standard responses for the column being
used. If they are within a ±5 percent window, a tentative identification exists. Corroborative identification may
be obtained on the second column in the same way as above. Quantitate the positives from water samples using
the formula:

Compound _ Peak Height Std. Inj. (]iL)

Cone, {ppb) cF (std.) Sample Inj. (]iL)

7.5.2 Soil: Compare the RTs of positive responses with the standard responses for the column being
used. If they are within a ±5 percent window, a tentative identification exists. Corroborative identification may
be obtained on the second column in same way as above. Quantitate positives from soil samples using the
formula:

FMC-VW-010-5

-------
Peak	Extract

Compound _ Heights Volume {]iL)	Std. Inj. (pi)

Cone, {ppb)	cF x wt. (q)	Sample Inj. (]iL)

8.0 QUALITY CONTROL

8.1	Duplicates: At least 1 sample in 10 should be collected in duplicate to provide precision data.

8.2	Instrument Calibration

8.2.1	Initial calibration: The instrument should be calibrated at least daily by generating a 3-point
calibration curve.

8.2.2	Continuing calibration: A continuing standard at the mid-point level should be injected after every
5 sample injections to insure GC stability.

8.3	Blanks: Before analysis, an air blank (500 (iL of ambient air) should be injected to check for any
background problems. An ambient air blank of 500 |±L should be injected after each positive that may reach full-scale
deflection, or greater, to assure that the column and syringe will not produce any carryover.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VW-010-6

-------
CSL Method

VOA/WATER. SOIL. SEDIMENT /METHANOL. WATER/GC-PID. EL CD

1.0 SCOPE AND APPLICATION

1.1 This method is being proposed for field screening of water samples from the site for volatile hydrocarbon
parameters that are indicative of site contamination. It is presented as a means to rapidly characterize contamination
in water and soil samples. This method is customized to measure the SW-846 methods 8010, 8020, 601, and 602 list
of target consitituents.

1.2 Application of this method is limited to the screening analysis of water for target constituents. The
chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of soil and groundwate contamination associated with other nontargeted compounds in the samples. Positive
identification and quantification of specific constituents, such as these constituents and other organic priority
pollutants, will be supported by analyses of duplicate and other composited samples at a remote CLP laboratory
employing EPA approved testing protocols.

1.3 The method detection limits (MDL) for the target constituents are estimated to be 10 fxgfL. This
estimate is the result of previous method development work.

2.0 SUMMARY OF THE METHODS

2.1 The method presented here is based on EPA Methods 601/602 and 8010/8020, "Purgeable Organics,"
found in EPA SW846, Test Methods for Evaluating Solid Waste, 3rd ed., November 1986.

2.2 In brief, water samples are analyzed directly by bubbling an inert gas through a 5 mL or 25 mL sample
contained in a specifically designed purging chamber at ambient temperature.

2.3 Soil and sediment samples are extracted and analyzed by one of two methods depending on the
concentration of volatile components in the matrix. For low level solid samples, the matrix is suspended in water,
and the suspension is purged in a heated sparging chamber. High level solid samples are extracted with methanol.
An aliquot of the methanol extracted is spiked into reagent water and analyzed according to procedures described for
water samples.

2.4 The volatile components from the different matrices are efficiently transferred from the aqueous phase
to the vapor phase. The vapor is swept through a sorbent column where the volatiles are trapped. After purging is
completed, the sorbent column is heated and back-flushed with an inert gas. The volatile components are transferred
onto a gas chromatographic column which is temperature programmed to separate the compounds. The gas
chromatograph is equipped with a photoionization detector connected in series with a Hall detector. The
photoionization detector detects the aromatic compounds, and the Hall detector detects the halogenated compounds.

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute or overlap with the target constituents may cause a positive
bias in the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

FMC-VW-011-1

-------
elevated when dilution of the simple is necessary because a single target or nontarget analyte is present in high
concentrations.

4.0 APPARATUS AND MATERIALS

4.1 Sample Containers: 40-mL VOA vials with septem screw caps; precleaned as purchased from Eagle

Pitcher.

4.2 Purge and Trap System:

4.2.1 autosampling device O.I Corporation Model ASM or equivalent for water sample analyses.

4.2.2 purge and trap device O.I. Corporation 4460A or equivalent.

4.3 Gas Chromatograph: Hewlett Packard Model 5890 Series II or equivalent.

4.4 Data System: Hewlett Packard Vectra QS20 Chemstation or equivalent.

4.5 Detectors: 01 electrolytic conductirity detector and photoionizing detector (10.2 eV).

4.6 Gas Chromatographic Column: column 1-60 M x 0.53 mm ID 502.2, 3 /im film thickness, Restek or
equivalent.

4.7 Trap: commercially prepared per specification in Method 5030. The trap must be at least 25 cm long
and have an inside diameter of at least 0.105 inch. The trap must be packed with 1/3 each of Tenax, silica gel, and
1/3 charcoal.

4.8 Syringes: Hamilton gas tight syringes

4.8.1 /jL syringes: 10, 25, 50, 100, 500, and 1,000-juL

4.8.2 ml syringes: 5, 10, and 25-mL

4.9 Volumetric Flasks: 10, 25, 50, 100, and 1,000-mL
5.0 REAGENTS

5.1 Methanol: Purge and trap methanol obtained from Burdick and Jackson or equivalent. The methanol
must be demonstrated to be free of volatile target analytes.

5.2 Stock Standard Solutions

5.2.1 Supelco Purgeable A and B stock standards commercially prepared and obtained from
Supelco, Inc. Catalog numbers 4-8851 and 4-8852 or equivalent.

5.2.2 a,a,a-Trifluorotoluene Surrogate-Neat material-Chem Service. Catalog number F4503 or
equivalent.

5.2.3 Bromochloromethane Surrogate-Neat material obtained from Chem Service. Catalog number
F-206 or equivalent.

FMC-VW-011-2

-------
5.3 Working Standard Solutions: Using the stock standard solutions, prepare secondary or working standard
solutions by making appropriate dilutions in methanol. The working standard solutions should be prepared in such
a manner that the calibration standards shall bracket the working range of the analytical system.

5.3.1 Initial Calibration Working Standards: prepare a minimum of five concentrations of
standands that define the linear range of the instrument. The concentration levels should be prepared at 1.0,
4.0, 10, 20, and 40-/ig/L for aqueous samples and 1.0, 4.0, 10, 20, and 40-/ig/Kg for soil samples.

5.3.2 Continuing Calibration Working Standards: the continuing calibration standard should be
selected from the initial calibration standards, and it should be the standard that is closest to the mid point
of the calibration range.

5.3.3 Surrogate Spike Working Standards: prepare a surrogate spiking standard at a concentration
that provides a response similar to the response of the target analytes in the continuing calibration.

5.3.4 Quality Control (OC) Check Sample Solutions: the QC check standards are obtained from
EPA or and independent vendor. The QC check standard must be prepared independently from the standards
used for initial and continuing calibration standards. If commercially prepared, the QC check standards must
be from another vendor or have a different lot number.

5.4 Gases:

5.4.1 Hydrogen: Grade 5.

5.4.2 Helium: Grade 5.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1 The target constituents are identified as or suspected of being carcinogens. All samples are
assumed to be hazardous. All stock and working calibration standards, as well as all samples, shall be
handled with the utmost care using good laboratory practices in order to avoid harmful exposure.

7.1.2 The lab Chemical Hygiene Plan must be followed at all times.

7.1.3 Lab analysts shall wear lab coats, safety glasses, and surgical gloves at all times when
preparing and handling analytical standards and solvents. Standards and samples shall be prepared in a hood.

7.1.4 Sample preparation should be performed in a fume hood with adequate skin and eye
protection. Any situation creating odors should be immediately corrected. Solvents should be handled in
minimum quantities to minimize fire and health hazards.

7.1.5 Safety equipment, including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit, shall be available for use at all times.

FMC-VW-011-3

-------
are placed in waste drums clearly labeled for water vials. Unused water samples are poured out of the VOA
vials into specifically labeled drums labeled CSL waste water and the empty vials are deposited into the
water vials drums. Unused soil samples are placed in CSL waste drums labeled specifically for soil jars.
Unused samples are held by the CSL for seven days before disposal. Water used for final rinsing of
glassware will be considered nonhazardous and will be released down the sanitary sewer.

7.2 Sample extraction: The sample extraction technique for soil, and sediment samples is as follows:

7.2.1 Mix the contents of the sample container well, and weigh 5 grams of the matrix into a tarred
40-mL vial. Using a toploading balance, weigh the sample to the nearest 0.1 gram. Quickly add 5.0 ml of
methanol to the vial. Cap the vial and shake for 2 minutes. This extraction procedure must be performed
in a laboratory free of solvent fumes.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 The linear calibration range of the instrument must be determined before the
analysis of any samples. The instrument must be calibrated using the same instrument conditions
that are used to analyze the samples.

NOTE: If 25 mLs of water is purged to achieve lower detection limits, then both the
initial and continuing calibrations must be performed by purging 25 mL of the aqueous
standards.

7.3.1.2 Prepare aqueous calibration standards at a minimum of five concentration levels
for each parameter analyzed. The concentrations of the aqueous standards should bracket the linear
range of the instrument.

7.3.1.3 Using the stock standards prepare secondary dilutions of the intenal standard and
surrogate compounds into a common spiking solution. The spiking solution must be added to all
standards, blanks, and samples. The surrogates and internal standards must be at a concentration
which provides a response similar to the response of the target analytes in the mid point standard
used for continuing calibration.

7.3.1.4 Analyze each calibration standard and calculate the relative response factor (RRF)
for each of the compounds according to the following equation:

RRF = —

Where: As = Area of analyte

cs = Concentration of analyte

NOTE: Certain data processors may calculate the RRF differently.

7.3.1.5 Calculate the standard deviation (S) and the relative standard deviation (%RSD)
of RRFs for the compounds using the following equations:

E( RRF. ~ RRF ) 2

X 1 m '

* ~M

FMC-VW-011-4

-------
Where: RRF; = Individual RRF

RRFm = Mean RRF

N = Number RRFs

and

RSD - SX 100
RRF

7.3.1.6 The relative standard deviation of each compound must be less than 30 percent.
This criteria must be achieved for the calibration to be valid.

7.3.1.7 If the relative standard deviation is less than 20 percent, the RRF of the compound
can be assumed to be invariant, and the average RRF can be used for calculations.

7.3.1.8 If the relative standard deviation is between 20 and 30 percent, calculations must
be made from the calibration curve. Both the slope and the intercept of the curve must be used to
perform calculations.

7.3.1.9 The validity of the calibration curve may be validated further by the analysis of
a QC check sample. The QC check sample must be obtained from EPA, another vendor, or it must
be from another lot number. The QC check sample, verifies the validity of the concentration of the
standards used to obtain the initial calibration.

7.3.1.10 Prepare and analyze a mid point aqueous QC check standard. For each
parameter, calculate the percent recovery. All parameters in the QC check standard must be
recovered within 70 to 130 percent. If any parameter exceeds this criterion, then a new calibration
curve must be established. All sample results for a target analyte can only be reported from valid
initial calibrations.

7.3.2 Continuing Calibration

The working calibration curve or relative response factor for each analyte must be verified daily by
the analysis of a continuing calibration standard. The ongoing daily continuing calibration must be compared
to the initial calibration curve to verify that the operation of the measurement system is in control.

7.3.2.1 The frequency of the continuing calibration check must be performed for each day
of analysis to verily the continuing calibration of the instrument. A day is defined as 24 hours from
the start run time of the last valid continuing calibration.

7.3.2.2 Verification of continuing calibration is performed by the analysis of a mid point
standard containing all of the parameters of interest.

7.4 Instrument Operating Conditions

7.4.1 Gas chromatograph: the following instrument operating conditions are provided as a guide.
Different instruments may require different operating conditions.

7.4.1.1 Oven temperature program: 35°C (10 min) to 150°C (5min) at 8°C/min.

NOTE: A fast ramp of the capillary column to 220 °C at data acquisition can be useful for
boiling off late eluting non-target analytes.

FMC-VW-011-5

-------
7.4.1.2 Injector temperature: 220°C

7.4.1.3 Detector temperature: 250°C

7.4.1.4 Carrier gas flow: 5 mL/min (capillary)
7.4.2 Purge and trap:

7.4.2.1 Purge flow: 40 mL/min

7.4.2.2 Purge time: 11 minutes

7.4.2.3 Desorb time: 4 minutes

7.4.2.4 Desorb temperature: 180°C

7.4.2.5 Bake time: 10 minutes minumum

7.4.2.6 Bake temperature: 220°C
7.4.3 Photoionization detector:

7.4.3.1 Heater temperature: approximately 200°C, do not exceed 250°C
7.4.4 Hall detector:

7.4.4.1 Reaction temperature: 850°C

7.4.4.2 H2 gas flow: approximately 40 mL/min

7.4.4.3 Auxiliary gas: helium at approximately 100 mL/min
7.5 Sample Analysis

7.5.1 Continuing Calibration Check: Each day before the analysis of samples, prepare and analyze
a mid point water standard according to directions given in Section 7.1.4. The calibration analysis should
be performed according to the method used to analyze samples. Verification of continuing calibration must
be checked against a calibration curve that was determined using the same sample volumes and instrument
conditions.

7.5.2 Method Blank: Analyze a method blank to verify that the analytical system is free of
contamination under the conditions of analysis. Use the same sample volumes, reagents, and instrument
conditions used for the samples.

7.5.3 Analysis of Water Samples:

7.5.3.1 Allow all samples and standard solutions to come to ambient temperature before
analysis. The sample is placed onto the autosampler and the sample location, as well as the sample
run information, is programmed onto the Chem Station computer. See the O.I. Corporation and the
Hewlett Packard operating manuals for instruction.

FMC-VW-011-6

-------
7.5.3.2 If dilution of the sample is needed, the dilutions should be made with volumetric
flasks and the sample syringe. NOTE: Pipettes should not be used to measure aliquots of water
samples for volatiles.

7.5.3.3 Add the surrogate and internal standard spiking solution by injecting through the
VOA bottle septa into the sample.

7.5.3.4 All target analytes detected must be within the linear calibration range established
for the instrument. If a target analyte exceeds the calibration range, the sample must be diluted in
such a manner that response of the major constituents are in the upper half of the calibration range.

7.5.4 Analysis of Sediment/Soil Samples: Sediment or soil samples are analyzed by the medium
level method.

7.5.4.1 The medium level method is based on the analysis of a methanol extract of the soil
matrix. An aliquot of the methanol extract is spiked into blank water, and purged at ambient
temperature as prescribed for water samples.

7.5.4.2 The quantity of the extract that is spiked into the blank water is determined by
prior screening or analysis results. The maximum amount of methanol should not exceed 100 fxL
per 6 ml of spike water. It is important that the volume of the methanol remain the same for all
samples, blanks, and standards. If less than 100 fxL is needed for proper dilution, then add
additional reagent methanol as necessary to maintain a total volume of 100 fxL added to the syringe.

7.6 Calculation

7.6.1 Calculate the concentration of traget analytes in the sample using the following equation:

NOTE: The following equations can only be used if the instrument calculate the RRFs according
to the equations in Section 7.3.1.4.

7.6.1.1 Water:

Concentration ( ]ig/L ) =

RRF x V

Where: Ax = Area for the compound to be measured.

V0 = Volume of water purged mLs, take into account any dilutions.

7.6.1.2 Medium level soil/sediment:

A x v

Concentration ( \ig/Kg ) =

RRF x V. x D x W

Where: Ax = Area for the compound to be measured.

Vt = Volume of total extract (mLs).

V; = Volume of extract added for purging (mL).

Ws = Grams of soil/sediment extracted

D = (100 - % moisture)/100

8.0 QUALITY CONTROL

FMC-VW-011-7

-------
8.1 The analytical system must be demonstrated to be free from contamination under the conditions of the
analysis by the analysis of method blanks. Each day before the analysis of samples, an organic free water blank must
be analyzed to demonstrate that the system is clean.

8.2 Contamination by carryover can also occur when high level and low level samples are analyzed in
squence. To reduce the possibility of carryover, the purging device and sample syringe must be rinsed with organic
free water between samples. Also, frequent bakeout and purging of the entire system may be required. For samples
containing high concentrations of any volatile analyte, an organic free water blank should be analyzed immediately
afterwards to verify that the analytical system is clean before the analsis of other samples. If samples are analyzed
by an autosampler, all sample analytical results following a high level sample must be examined for the possibility
of crossover. If target analytes are found in the, samples that are common to a previously analyzed high samples must
be re-analyzed after demonstration of a clean analytical system by analysis of blanks.

8.3 The blank analyzed for the high level soil methanol extraction method must include the same amount
of the reagent methanol that is added during the analysis of the samples.

8.4 The results of blank analyses must be reported along with the results for samples. The blank results
should not be subtracted from the sample analytical results.

8.5 A method blank must contain no greater than five times (5x) the stated method detection limit of
common laboratory solvents such as methylene chloride. For all other volatile compounds, the method blank
must contain less than the stated detection limit. If the method blank exceed these criteria, the laboratory must
consider the analytical system out of control. Appropriate corrective actions must be taken and documented
before further sample analysis.

8.6 The validity of the calibration curve must be verified by the analysis of a QC check sample that has
been obtained from another source before the analysis of any samples. The QC check sample verifies the validity
of the concentrations of the standards used to prepare the calibration curve. The QC check sample must be ob-
tained from EPA, or another vendor or from another lot number. The initial calibration curve is valid if all target
analytes are within 70 to 130 percent recovery. After the curve is verified from independent standards, continuing
calibration of the system can be verified daily from the mid point standard that was used to prepare the initial
calibration curve.

8.7 At least one set of MS/MSD samples must be analyzed for each 20 samples to acquire data for
measurement of accuracy and precision. If one of the target analytes exceed the acceptance criteria, a continuing
calibration check sample must be analyzed to check instrument calibration. If continuing calibration criteria are
not achived for the parameters that failed the limits for spike recovery, the affected samples must be re-analyzed
using a new calibration curve. If continuing calibration criteria are achieved ( ± 25 percent D), the poor
recoveries can be attributed to a matrix effect. The results from both sample analyses must be reported.

8.8 All sample and blanks must be spiked with surrogate compounds prior to purging. Data for the
surrogates for all analyses must be tabulated and routinely processed statistically.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-VW-011-8

-------
CSL Method

VOLATILE ORGANIC COMPOUND VERIFICATION BY
PURGE AND TRAP WITH PID/EICD DETECTION

1.0 SCOPE AND APPLICATION

1.1 This standard operating procedure describes the procedures used to confirm results of the headspace
analyses using purge and trap gas chromatographic techniques for analysis of selected volatile organic
compounds.

1.2 Table 1 lists the target analytes and method detection limits for the analysis of soil and water
samples. The detection limits were verified by the performance of a validation experiment. The validation
process requires the analysis of a minimum of seven replicates of a known concentration of the compounds in
water. The concentration of the replicate analyses must be one to five times the estimated nominal detection
limit. The estimated detection limit is calculated by multililying the standard deviation of the replicate results (in
/ig/L) by 3. This estimated detection limit is valid if the mean result of the seven replicate standards is less than 3
times the resulting standard deviation. The soil sample detection limits are adjusted to account for the differences
in the mass of the sample analyzed.

1.3 Application of this method is limited to the analysis of solid and water samples for the target
parameters.

2.0 SUMMARY OF THE METHODS

2.1 Water samples are analyzed directly by bubbling an inert gas through a 10 mL sample contained in a
specifically designed purging chamber at ambient temperature.

2.2 Solid samples are weighed (5 g) directly into purge chambers with 10 mL of HPLC grade water and
analyzed according to procedures described for groundwater.

2.3 The volatile components from the different matrices are efficiently transferred from the aqueous
phase to the vapor phase. The vapor is swept through a sorbent column where the volatiles are trapped. After
purging is completed, the sorbent column is heated and back-flushed with an inert gas. The volatile components
are transferred onto a gas chromatographic column which is temperature programmed to separate the compounds.
The gas chromatograph is equipped with a phooionization detector (PID) connected in series with a Hall
Electrolytic Conductivity Detector (EICD). The (PID) detects unsaturated compounds, and the EICD detects
halogenated compounds.

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute or overlap with the target constituents may cause a
positive bias in the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may
result in false identifications.

3.3 The MDL's for the target constituents may be suppressed by baseline noise associated with samples
having high levels of background organics or other interferences. The MDL's for the target constituents may be
elevated when dilution of the simple is necessary because a single target or nontarget analyte is present in high
concentrations.

FMC-VW-012-1

-------
Table 1

CSL METHOD TARGET CONSTITUENTS LIST AND METHOD DETECTION LIMIT

Analyte

Method Detection Limit in Water and Soil Cug/L)

1,1,1 -Trichloroethane

1.0

1,2-Dichloroethane

1.0

cis-1,2-Dichloroethene

1.0

1,1 -Dichloroethene

1.0

1,1 -Dichloroethane

1.0

Trichloroethene

1.0

trans-1,2-Dichloroethene

1.0

Vinyl chloride

1.0

T etrachloroethene

1.0

4.0 APPARATUS AND MATERIALS

4.1 Purge and Trap System: Tekmar autosampling device model AIS 2016 and Tekmar purge and trap
device model LSC 2000. Equivalent equipment may be used but the autosampler and purge and trap devices
must be a matched set for proper communications between instruments.

4.2 Gas Chromatograph: Hewlett Packard Model 5890A Series II or equivalent.

4.3 Data System: Hewlett Packard Vectra QS20 Chemstation 3365 Series II or equivalent.

4.4 Detectors: O.I. Analytical electrolytic conductivity (HALL or EICD) detector and photoionizing
detector (10.2 eV).

4.5 Gas Chromatographic Column: column 1-30 meters x 0.53 mm ID, 3 /im film thickness, VOCOL or
equivalent.

4.6 Trap: commercially prepared per specification in EPA Method 5030. The trap must be at least 25
cm long and have an inside diameter of at least 0.105 inch. The trap must be packed with equal parts of Tenax,
silica gel, and charcoal.

4.7 Syringes: Hamilton gas tight syringes

4.7.1 /jL syringes: 10, 25, 50, 100, 500, and 1,000-juL

4.7.2 ml syringes: 5, 10, and 25-mL

4.8 Volumetric Flasks: 10, 25, 50, 100, and 1,000-mL

5.0 REAGENTS

FMC-VW-012-2

-------
5.1 Methanol: Purge and trap methanol obtained from Burdick and Jackson or equivalent. The methanol
must be demonstrated to be free of volatile target analytes.

5.2 Stock Standard Solutions

5.2.1 Supelco stock standards commercially prepared in MeOH and obtained from Supelco,

Inc.

Analvte

Concentration (ug/mL'l

1,1,1 -Trichloroethane
1,2-Dichloroethane
cis-1,2-Dichloroethene
1,1 -Dichloroethene
1,1 -Dichloroethane
Trichloroethene
trans-1,2-Dichloroethene
Vinyl chloride
T etrachloroethene

5,000
5,000

200
5,000

5,000
5,000
5,000
1,000
5,000

5.3 Surrogate Stock Solution:

4-Bromofluorobenzene

25,000

5.4 Working Standard Solutions: Using the stock standard solutions, prepare secondary or working
standard solutions by making appropriate dilutions in methanol. The working standard solutions should be
prepared in such a manner that the calibration standards shall bracket the working range of the analytical system.

5.4.1 Initial Calibration Working Standards: Prepare a minimum of five concentrations of
standands that define the linear range of the instrument. The standards should be prepared at 5, 10, 25,
50, and 100-jUg/L.

5.4.2 Continuing Calibration Working Standards: The continuing calibration standard should
be selected from the initial calibration standards, and it should be the standard that is closest to the mid
point of the calibration range.

5.4.3 Surrogate Spike Working Standards: Prepare a surrogate spiking standard at a
concentration that provides a response similar to the response of the target analytes in the continuing
calibration.

5.4.4 Laboratory Control Sample fLCS): The LCS check standards are obtained from EPA or
and independent vendor. The check standard must be prepared independently from the standards used
for initial and continuing calibration standards. The LCS is to be analyzed daily, prior to the testing of
field samples.

5.5 Propanol: Purge and trap grade.

5.6 Gases

5.6.1 Hydrogen: Ultra pure carrier grade.

FMC-VW-012-3

-------
5.6.2 Helium: Ultra pure carrier grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Groundwater: 40-mL vials with screw caps with a hole in the center of the cap. A Teflon-faced
silicone septum is placed inside the screw cap so only the Teflon comes into contact with the water samples.

6.2 Soil: 4-oz. precleaned glass jars with Teflon lid liners. Jars and vials must be filled completely,
sealed tightly and maintained at approximately 4°C to avoid losses of volatile compounds before analysis.

7.0 PROCEDURE

7.1 Safety

7.1.1 The target constituents are identified as or suspected of being carcinogens. All samples
are assumed to be hazardous. All stock and working calibration standards, as well as all samples,
shall be handled with the utmost care using good laboratory practices in order to avoid harmful exposure.

7.1.2 Lab analysts shall wear lab coats, safety glasses, and surgical gloves at all times when
preparing and handling analytical standards and solvents. Standards and samples shall be prepared in a
hood.

7.1.3 Sample preparation should be performed in a fume hood with adequate skin and eye
protection. Any situation creating odors should be immediately corrected. Solvents should be handled in
minimum quantities to minimize fire and health hazards.

7.1.4 Safety equipment, including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit, shall be available for use at all times.

7.1.5 Lab wastes shall be separated and properly disposed. The wastes include: used sample
aliquots in headspace vials or disposable purge chambers, unused soil and water samples, and small
quantities of alcohol waste generated by standard preparations and syringe rinsing. Used headspace vials
are placed in waste drums clearly labeled for water vials. Unused water samples are poured out of the
VOA vials into specifically labeled drums labeled CSL waste water and the empty vials are deposited
into the water vials drums. Unused soil samples are placed in CSL waste drums labeled specifically for
soil jars. Unused samples are held by the CSL for seven days before disposal. Water used for final
rinsing of glassware will be considered nonhazardous and will be released down the sanitary sewer.

7.2 Calibration

7.2.1 Initial calibration:

7.2.1.1 The linear calibration range of the instrument must be determined before the
analysis of any samples. The instrument must be calibrated using the same instrument
conditions that are used to analyze the samples.

7.2.1.2 Prepare aqueous calibration standards at a minimum of five concentration
levels for each parameter analyzed. The concentrations of the aqueous standards should bracket
the linear range of the instrument.

7.2.1.3 Using the stock standards prepare secondary dilutions of the intenal standard
and surrogate compounds into a common spiking solution. The spiking solution must be added
to all standards, blanks, and samples. The surrogates and internal standards must be at a

FMC-VW-012-4

-------
concentration which provides a response similar to the response of the target analytes in the mid
point standard used for continuing calibration.

7.2.1.4 Calculate the standard deviation (S) and the relative standard deviation
(%RSD) of the compounds using the following equations and the relative repsonse factors
(RRFs):

E( RRF. ~ RRF ) 2

X 1 m '

N - 1

Where: RRFt
RRFm

Individual RRF
Mean RRF
Number RRFs

and

% RSD =

S x 100
RRF

7.2.1.5 The relative standard deviation of each compound must be less than 30 percent.
This criteria must be achieved for the calibration to be valid.

7.2.1.6 If the relative standard deviation is less than 20 percent, the RRF of the
compound can be assumed to be invariant, and the average RRF can be used for calculations.

7.2.1.7 If the relative standard deviation is between 20 and 30 percent, calculations
must be made from the calibration curve. Both the slope and the intercept of the curve must be
used to perform calculations.

7.2.1.8 The validity of the calibration curve may be validated further by the analysis of
a LCS. The LCS must be obtained from EPA, another vendor, or it must be from another lot
number. The LCS verifies the validity of the concentration of the standards used to obtain the
initial calibration. All parameters in the LCS should be recovered within the advisory limits
provided with the LCS. If any parameters exceeds this criterion, then a new calibration curve
may be required. Sample results for a target analyte can only be reported from vaild initial
calibration.

7.2.2 Continuing Calibration

The working calibration curve or relative response factor for each analyte must be verified daily
by the analysis of a continuing calibration standard. The ongoing daily continuing calibration must be
compared to the initial calibration curve to verify that the operation of the measurement system is in
control.

7.2.2.1 The frequency of the continuing calibration check must be performed for each
day of analysis to verify the continuing calibration of the instrument. A day is defined as 24
hours from the start run time of the last valid continuing calibration.

7.2.2.2 Continuing calibration is verified by analyzing a standard containing all of the
parameters of interest. Continuing calibration of the measurement system is verified by
analyzing the continuing calibration standard and calculating the relative percent difference for
each of the target analytes using the following equation:

FMC-VW-012-5

-------
[ RRF ~ RRF ] x 100
% D = -

RRF

Where: RRFm = The mean response from the initial calibration curve.

RRF = The daily response from the continuing calibration point.

7.2.2.3 The criterion for acceptable continuing calibration is 25 percent D. No
analytes can exceed the acceptance limits (NOTE: If the target analytes exceed the 25 percent D
criterion, then a new calibration of the instrument must be performed for that target analyte, and
the sample must be reanalyzed after a valid initial calibration is achieved.) If the acceptance
criteria are achieved, the calibration curve can be used to calculate the results of sample
analyses. If the criteria are not achieved, another new calibration curve must be prepared.

7.2.2.4 Sample results for any target analyte can only be reported from a valid initial
and continuing calibration.

7.3 Instrument Operating Conditions

7.3.1 Gas chromatograph: the following instrument operating conditions are provided as a
guide. Different instruments may require different operating conditions.

7.3.1.1 Oven temperature program: 40°C (2 min) to 180°C (5min) at 8°C/min.

NOTE: A fast ramp of the capillary column to 200°C can be useful for boiling off late
eluting non-target analytes.

7.3.1.2 PID detector temperature: 220°C

7.3.1.3 EICD detector temperature: 950°C

7.3.1.4 Carrier gas flow: 8 mL/min (capillary)

7.3.2 Purge and trap:

7.3.2.1 Purge flow: 40 mL/min

7.3.2.2 Purge time: 11 minutes

7.3.2.3 Dry purge: 0.0 minutes

7.3.2.4 Desorb preheat: 200°C

7.3.2.5 Desorb time: 1.4 minutes

7.3.2.6 Desorb temperature: 225°C

7.3.2.7 Bake time: 10 minutes minumum

7.3.2.8 Bake temperature: 225°C

7.3.2.9 Valve temperature: 100°C

FMC-VW-012-6

-------
7.3.2.10 Transfer line temperature: 100°C

7.3.2.11 Mount temperature: 40°C

7.3.2.12 Valve temperature: 100°C (autosampler)

7.3.3 Photoionization detector:

7.3.3.1 Sweep gas (hydrogen-also serves as reaction gas for EICD): 100 mL/min

7.3.3.2 Helium makeup gas: 20 mL/min

7.3.3.3 Lamp: 10.2 eV

7.3.3.4 Lamp power supply setting: #5

7.3.4 Hall electrolytic conductivity detector:

7.3.4.1 Furnace temperature: 950°C

7.3.4.2 H2 gas flow: provided by PID sweep gas

7.3.4.3 Halogen mode
7.4 Sample Analysis

7.4.1 Instrument Blank flBLK): Each 24-hour day of analyses begins with an IBLK to
condition the instrument and verify freedom from contamination. See section eight for a detailed
description.

7.4.2 Reagent blank fRBLK): The laboratory reagents are demonstrated to be free from
contamination by the daily testing of an RBLK. See section eight for a detailed description.

7.4.3 Laboratory Control Sample fLCS): The instrument calibration is independently verified
for selected target compounds by the analysis of an LCS before testing any field samples. See section
eight for a detailed description.

7.4.4 Continuing Calibration Verification (CCV): Each day before the analysis of samples,
prepare and analyze a water standard at the mid-range calibration level. The calibration analysis should
be performed according to the method used to analyze samples. Verification of continuing calibration
must be checked against a calibration curve that was determined using the same sample volumes and
instrument conditions.

7.4.5 Method Blank fMBLK): Analyze a method blank to verify that the analytical system is
free of contamination under the conditions of analysis. Test the MBLK after the CCV but before field
samples to verify that instrumental carryover is not significant at the CCV level. Use the same sample
volumes, reagents, and instrument conditions used for the samples. A method blank is to be analyzed
with every sample preparation process.

7.4.6 Analysis of Water Samples: Water samples must be screened, by headspace analysis or
other means prior to analysis by PAT to prevent gross contamination of the PAT system. Once the
sample is determined to be a candidate for PAT/GC/PID/EICD and the best detection limits are desired,
then approximately 10 mL of the sample is accurately weighed into a tared purge chamber. If the sample

FMC-VW-012-7

-------
needs dilution then add 1 mL to a tared purge chamber containing 9 mL of purge and trap grade water.
Allow all samples and standard solutions to come to ambient temperature before purging begins. The
sample is poured into the tared, disposable purge chamber, spiked with surrogate (5 fxL of 4-BFB @
125/ig/mL) and immediately loaded onto the autosampler. The sample ID and multiplier is programmed
onto the ChemStadon computer. See the Tekmar and the Hewlett-Packard operating manuals for
instruction.

NOTE: Syringes should not be used to draw up aliquots of water samples for volatiles analysis.
The sample should be poured directly into the purge chamber or poured into a gastight 5 mL syringe after
removing the plunger, and then carefully replacing the plunger to dispense the sample.

7.4.6.1 Add the surrogate/internal standard spiking solution immediately to the sample
and quickly attach the chamber to the autosampler.

7.4.6.2 All target analytes detected must be within 1.5 times the linear range
established for the instrument. If a target analyte exceeds the linear range by a factor of 1.5, the
sample must be diluted in such a manner that response of the major constituents are in the upper
half of the calibration range. If sample must be diluted to reduce the major components into the
calibration range, the reported detection limits for that sample must be increased to reflect the
extra dilution of the sample.

7.4.7 Analysis of Soil Samples: The soil samples are to be analyzed by purge and trap only
after screening by headspace or other means to avoid gross contamination of the analytical system. Once
the sample is verified as a candidate for PAT/GC/PID/EICD and the best detection limits are desired,
then approximately 5 grams is accurately weighed into a tared, prebaked, cool purge chamber and 10 mL
of purge and trap grade water is immediately added to the soil. The sample is then analyzed by the
method prescribed for water samples. The sample aliquot used may be reduced to 0.2-1.0 grams if the
screening analysis shows moderate contamination allowing purge and trap testing with higher detection
limits. In such cases the reported detection limit must be modified to reflect the larger dilution.

7.5 Calculation

7.5.1 Water results calculation: The ChemStation will calculate the concentration of target
analytes (in /ig/L) in the sample from the initial calibration curve equation and the internal standard
recovery and the multiplier which is entered in the sample table.

7.5.2 Soil results calculation: The ChemSattion will calculate the cincnetration of target
analytes in /ig/L which can directly converted to jj,g/Kg.

8.0 QUALITY CONTROL

8.1 Instrument Blanks: Each 24-hour day of testing begins with an instrument blank. The instrument
blank is empty purge chamber which is placed on the autosampler to verify that the purge and trap/GC system is
not contaminated. The instrument blank (IBLK) also serves as a "dry run" to condition the system for testing of
the reagent blank.

8.2 Reagent Blank: The purge and trap grade water and the surrogate solution are verified to be free of
contamination by the daily testing of a reagent blank (RBLK) after the IBLK.

8.3 Method Blank: The analytical system must be demonstrated to be free from contamination under the
conditions of the analysis by testing a method blanks each day after verifying the calibration with an LCS and

FMC-VW-012-8

-------
CCV but before the analysis of samples. Method blanks consist of 10 mL of purge and trap water with 5 grams
of EPA approved blank soil matrix.

8.3.1 Contamination by carryover can also occur when high level and low level samples are
analyzed in squence. To reduce the possibility of carryover, the purging device and sample syringe must
be rinsed with organic free water between samples. Also, frequent bakeout and purging of the entire
system may be required. For samples containing high concentrations of any volatile analyte, an organic
free water blank should be analyzed immediately afterwards to verify that the analytical system is clean
before the analsis of other samples. If samples are analyzed by an autosampler, all sample analytical
results following a high level sample must be examined for the possibility of crossover. If target
analytes are found in the, samples that are common to a previously analyzed high samples must be
re-analyzed after demonstration of a clean analytical system by analysis of blanks.

8.3.2 The results of blank analyses must be reported along with the results for samples. The
blank results should not be subtracted from the sample analytical results.

8.3.3 A method blank must contain no greater than five times (5x) the stated method detection
limit of common laboratory solvents such as methylene chloride. For all other volatile compounds, the
method blank must contain less than the stated detection limit. If the method blank exceed these criteria,
the laboratory must consider the analytical system out of control. Appropriate corrective actions must be
taken and documented before further sample analysis.

8.4 Laboratory Control Samples: The validity of the method and instrument operation are to be verified
by the analysis of a LCS once at the beginning of each 24-hour day. The LCS must be obtained the EPA or
another certtified vendor. The method is operating in a valid manner if all target analytes are within 70-130
percent recovery or within the advisory limits specified by the EPA or certified vendor.

8.5 Matrix Spikes/Matrix Spike Duplicate fMS/MSDI: At least one set of MS/MSD samples must be
analyzed for each 20 samples to acquire data for measurement of accuracy and precision. If one of the target
analytes exceed the acceptance criteria, a continuing calibration check sample must be analyzed to check
instrument calibration. If continuing calibration criteria are not achived for the parameters that failed the limits
for spike recovery, the affected samples must be re-analyzed using a new calibration curve. If continuing
calibration criteria are achieved, the poor recoveries can be attributed to a matrix effect.

8.6 Surrogate Spike Results: All sample, standards, and blanks (except instrument blanks-IBLKs) must
be spiked with surrogate compound(s) prior to purging. Data for the surrogates for all analyses must be tabulated
and routinely processed statistically for determination of warning and control limits. The control limits for the
surrogates are considered to be ± 3 standard deviations form the mean. If a surrogate exceeds the control limits,
the sample must be re-analyzed, if the surrogate recoveries are still more than 3 standard deviation from the
mean after re-analysis, then the sample results must be reported with a qualifying statement that the data is
suspect due to matrix effects.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-VW-012-9

-------
CSL Method

VOLATILE ORGANIC SCREENING BY HEATED HEADSPACE WITH FID DETECTION

1.0 SCOPE AND APPLICATION

1.1 This method uses heated headspace sample introduction and capillary gas chromatography with
flame ionization detection (GC/FID) to analyze samples for the presence of the target constituents.

1.2 Application of this method is limited to the analysis of soil and water samples for the target
parameters.

1.3 The target constituents and their method detection limits (MDL) are listed in Table 1.

2.0 SUMMARY OF METHOD

2.1 The heated headspace procedure is based on SW-846 method 3810, Headspace. The analysis is
based on SW-846 method 8015, Nonhalogenated Volatile Organics.

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target constituents may cause a false positive
bias in the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may
cause false positive results.

3.3 The MDLs for the target constituents may be elevated due to baseline noise associated with samples
with large amounts of background organic compounds or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 Glassware: Class A volumetric pipets and flasks, beakers, vials, pasteur pipets, and miscellaneous
glassware as necessary for preparation and handling of samples and standards.

4.2 Lab ware: As necessary for preparing and handling samples and standards.

4.3 Syringes: Hamilton glass type as required for preparation of dilutions, and spilting of samples.

4.4 Gas Chromatograph: Hewlett Packard 5890A Series III gas chromatograph (GC) with temperature
programmable oven operated from 40°C to 150°C with a 530/iM ID X 30M SPB-1 3.0 /iM film capillary column,
and flame ionization detector (FID).

4.5 Heated Headspace Unit: Tekmar 7000/7050.

4.6 Computer System: DOS based 486 25 Mhz, with accompanying monitor and printer. The computer
must contain the following software, HP Chemstation, Windows, and Excel.

4.7 Laboratory Fume Hood: Self contained carbon scrubber type or equivalent.

Table 1

FMC-VW-013-1

-------
CSL METHOD TARGET CONSTITUENTS LIST AND METHOD DETECTION LIMIT

Analyte

Method Detection Limit in Water and Soil (pig/Kg)

1,1,1 -Trichloroethane

5.0

1,2-Dichloroethane

5.0

cis-1,2-Dichloroethene

5.0

1,1 -Dichloroethene

5.0

1,1 -Dichloroethane

5.0

Trichloroethene

5.0

trans-1,2-Dichloroethene

5.0

T etrachloroethene

5.0

4.8 Top-loading Analytical Balance: With 10-mg, resolution with 200 gr capacity.

5.0 REAGENTS

5.1 Stock Standards: Prepare or purchase standard materials at approximately 2 mg/mL in methanol.

5.2 Working Standards: Prepared from stock standards by precise dilution in methanol.

5.3 Ultra Pure Carrier Grade Air: Oxidant for the flame.

5.4 Ultra Pure Carrier Grade Helium: For use as carrier gas.

5.5 Ultra Pure Carrier Grade Hydrogen: Fuel for the flame.

5.6 Methanol: Purge & trap grade.

6.0 SAMPLE COLLECTION, PRESERVATIVE, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1 The target constituents are identified as or suspected of being carcinogens. All samples
are assumed to be hazardous. All stock and working calibration standards, as well as all samples,
shall be handled with the utmost care using good laboratory practices in order to avoid harmful exposure.

7.1.2 The lab Chemical Hygiene Plan must be followed at all times.

FMC-VW-013-2

-------
7.1.4 Sample preparation should be performed in a fume hood with adequate skin and eye
protection. Any situation creating odors should be immediately corrected. Solvents should be handled in
minimum quantities to minimize fire and health hazards.

7.1.5 Safety equipment, including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit, shall be available for use at all times.

7.1.6 Lab wastes shall be separated and properly disposed. The wastes include: used sample
aliquots in headspace vials or disposable purge chambers, unused soil and water samples, and small
quantities of alcohol waste generated by standard preparations and syringe rinsing. Used headspace vials
are placed in waste drums clearly labeled for water vials. Unused water samples are poured out of the
VOA vials into specifically labeled drums labeled CSL waste water and the empty vials are deposited
into the water vials drums. Unused soil samples are placed in CSL waste drums labeled specifically for
soil jars. Unused samples are held by the CSL for seven days before disposal. Water used for final
rinsing of glassware will be considered nonhazardous and will be released down the sanitary sewer.

7.2 Sample Preparation and Extraction

7.2.1 General

7.2.1.1 Log balance calibration with 1 gram and 10 gram standards.

7.2.1.2 Enter the samples to be prepared into the, sample prep logbook.

7.2.1.3 Prelabel all sample vials using a permanent marker.

7.2.1.4 Sample vials shall be heated in an oven for a minimum of 5 hours at 80°, allow
the vials to cool to room temperature prior to use.

7.2.1.5 Record preparation for all BLK'S, LCS'S, CCV'S, and samples in sample prep
log book. Each page of the log book should contain the following columns; Lab #, sample wt.
(gram), Headspace (mL), multiplier, Prep by, and Prep date.

7.2.1.6 A sample multiplier is part of the method calculation. A calculated multiplier
is included in the sample table for each sample. The multiplier acts as a dilution factor. The
multiplier takes into account the dilution ratio between the standard (10 gram) and the sample (5
- 10 gram) and the variance in the sample vial headspace (9 - 12 mLs). The variability of the
sample headspace comes from the difference in soil densities (i.e. clay versus sand).

7.2.2 Instrument blank preparation procedure

7.2.2.1 Prelabel a prebaked HS vial "IBLK-datseq" (i.e., IBLK-082801). Assure from
sample preparation log and standards log that the seq # is unique (i.e., If IBLK 0828-01 is
already used name it IBLK 0828-02). Cap vial without adding any water or surrogate. The
multiplier for this sample is 1.0.

7.2.3 Reagent blank preparation procedure

7.2.3.1 Prelabel HS vial "RBLK-dateseq". Test the water dispenser accuracy by weighing
on a calibrated balance. Add 10 mL HPLC-grade water to HS vial, add 10 /jL CBP surrogate
solution (200 /ig/mL CBP in MeOH) with a syringe under the water surface and quickly cap the
vial. The multiplier for this sample is 1.0.

FMC-VW-013-3

-------
7.2.4 Laboratory control sample fLCS) preparation procedure

7.2.4.1 Prelabel aHS vial "LCS-dateseq". Weigh approximately 5 gram of control sample
matrix into the vial, add 5 fxL of LCS solution by placing syringe needle under soil and dispensing
solution. Quickly add 10 mL water and 10 fxL of surrogate. Quickly cap vial.

7.2.4.2 Place sample in the sonication bath for 1 to 3 minutes. Measure HS and use the
following formula to calculate the multiplier.

Multiplier = ( 10 / sample weight ) x ( remaining HS / 12 )

7.2.5 Continuing calibration verification standard preparation procedure

7.2.5.1 Prelabel HS vial "CCV-dateseq". Add 10 mL water, 10 fxL surrogate, and quickly
add 20 /jL "8-mix" standard *solution (50 /ig/mL of each target compound in MEOH). Quickly cap
vial. The multiplier for this sample is 1.0.

7.2.6 Method blank preparation procedure

7.2.6.1 Prelabel HS vial "MBLK-dateseq". Weigh 5 gram of control soil sample into a HS
vial. Add 10 mL water to vial, add 10 fiL CBP surrogate solution (200 /ig/mL CBP in MEOH) with
syringe under water surface. Quickly cap.

7.2.6.2 Place the sample in sonication bath for 1 to 3 minutes. Measure HS and use the
following formula to calculate the multiplier.

Multiplier = ( 10 / sample weight ) x ( remaining HS / 12 )

7.2.7 Matrix spike / matrix spike duplicate procedure

7.2.7.1 Weigh approximately 5 gram of sample into a HS vial. Attempt to use the same
weight of sample as used for the non-spiked sample.

7.2.7.2 Add 20 /jL of "8-mix" calibration standard solution (8 target compounds each at
50 /ig/ml in MEOH) by placing syringe needle under soil/water surface and dispensing solution.
Quickly add 10 mL water and 10 /jL surrogate. Quickly cap vial.

7.2.7.3 To help disperse the soil into water, place the sample in the sonic bath for 1-3
minutes. The multiplier for this sample is 1.0.

7.2.8 Sample preparation procedure

7.2.8.1 Weigh approximately 5 gram of sample into vial. Add 10 mL water, and 10 /A
surrogate solution. Quickly cap the sample.

7.2.8.2 Place in sonicator bath for 1-3 minutes to help disperse the sample into the water

solution.

7.2.8.3 Measure the remaining HS in the vial aid use the following formula to calculate
the multiplier.

Multiplier = ( 10 / sample weight ) x ( remaining HS / 12 )

FMC-VW-013-4

-------
7.3 Calibration

7.3.1 Initial calibration

7.3.1.1 Five-level calibration at approximately 10, 25, 50, 100 and 200 Mg/L. These
concentrations define the liner calibration range of the instrument. The linear range of the
instrument has been been demonstrated up to 50 ppm.

7.3.1.2 The calibration curve should be validated further by the analysis of a laboratory
control sample (LCS). The LCS must be obtained from an independent, EPA authorized,
second source. The LCS will verify the concentration of the standards used to obtain the initial
calibration.

7.3.2 Continuing calibration

7.3.2.1 The continuing calibration standard (CCV) should be selected from the initial
calibration standards, and it should be the standard that is closest to the mid point of the
calibration range. The working calibration curve for each analyte must be verified daily by the
analysis of a continuing calibration standard. The ongoing daily continuing calibration must be
compared to the initial calibration curve to verify that the operation of the measurement system
is in control. A day is defined as 24 hours from the start run time of the last valid continuing
calibration.

7.3.2.2 For each analyte, calculate the percent difference of the continuing calibration
from the initial curve using the following equation:

[ RRF - RRF ] x 100
% D = -

RRF

Where: RRFm = The mean response from the initial calibration curve.

RRF = The daily response from the continuing calibration standard.

7.3.2.3 The acceptance criterion for this screening method's continuing calibration is
40 percent D. If one of the target analytes that exceeded the 40 percent D criteria is detected in
a sample, then a new calibration of the instrument must be performed for that target analyte, and
the sample must be reanalyzed after a valid initial calibration is achieved. If the acceptance
criteria are achieved, the calibration curve can be used to calculate the results of sample
analyses.

7.3.2.4 Sample results for any target analyte can only be reported if the initial and
continuing calibrations are valid.

7.3.3 Surrogate Recovery

7.3.3.1 1 -Chloro-2-bromopropane shall be used as a surrogate. Prepare secondary
dilutions of the surrogate compound. This spiking solution must be added to all standards,
blanks (except the instrument blanks), and samples. The surrogates must be at a concentration
which provides a response similar to the response of the target analytes in the mid point
standard used for continuing calibration.

7.4 Laboratory Check Standard fLCS)

FMC-VW-013-5

-------
7.4.1 The LCSs are to be obtained from the EPA or an EPA approved vendor. The LCSs must
be prepared independently from the standards used for initial and continuing calibration standards.

7.4.2 Prepare and analyze a LCS at the beginning of each work day. For each parameter,
calculate the percent recovery. All parameters in the LCS should be recovered within the precision
requirements of the project (60 to 140 percent). If any parameter exceeds this criterion, this a new
calibration curve should be established. Sample results for a target analyte can only be reported if the
initial calibration of the instrument is valid.

7.5 Instrumental Analysis

7.5.1 Perform GC analysis using the described instrument conditions found in the instrument
parameter printout (see Appendix 1).

7.5.2 If the analysis indicates that the results are greater than the linear range of the instrument,
prepare a dilution of the sample to yield concentrations that fall within the calibration range.

7.5.3 Check the retention times for each of the reference peaks against the expected
(calibration) value. Unless peak patterns allow for the identification of all reference peaks, reject those
results in which the retention time does not fall within 5 percent of the expected value.

7.6 Calculations

7.6.1 Quantification of the target compounds is based on comparing the integrated peak areas of
the samples to the integrated peak areas of the calibration standards for each analysis. The Chemstation
data system reports the concentrations in /ig/Kg or fxgfL as appropriate for each sample.

8.0 QUALITY CONTROL

8.1 Daily continuing calibration performed before the analysis of each day's samples. The linear
calibration range of the instrument must be determined before the analysis any samples. The instrument
must be calibrated using the same instrument conditions that are used to analyze the samples. Prepare
groundwater calibration standards at a minimum of five concentration levels for each parameter
analyzed. The concentrations of the groundwater standards should bracket the linear range of the
instrument.

8.2 Daily LCS performed before the analysis of each day's samples. The instrument calibration must be
confirmed with a LCS before the analysis of any samples. This sample must be analyzed using the same
instrument conditions that are used to analyze the samples.

8.3 Daily analysis of an instrument blank, performed before the analysis of each day's samples. If the
result of the instrument blank show contamination, the cause of the contamination should be investigated
and corrective action taken.

8.4 Daily analysis of a reagent blank, performed before the analysis of each day's samples. If the results
of the reagent blank show contamination, the cause of the contamination should be investigated and
corrective action taken.

8.5 Analysis of a method blank. A method blank is to be performed at a frequency of one in 20 samples
of the same matrix. A method blank must contain no greater than five times the stated MDL of blank
contaminants. For all other volatile compounds, the method blank must contain less than the stated
detection limit. If the method blank exceeds these criteria, the laboratory must consider the analytical

FMC-VW-013-6

-------
system out-of-control. Appropriate corrective actions must be taken and documented before further
sample analysis.

8.6 Contamination by carryover can also occur when high-level and low-level samples are analyzed in
sequence. To reduce the possibility of carryover, disposable headspace vials are used only once and only
after being baked at 70-85°C and samples are weighed directly into the headspace vials. Also, frequent
baking and purging of the entire system may be required. For samples thought to contain high
concentrations of any volatile analyte, an organic free water blank should be analyzed immediately
afterwards to verify that the analytical system is clean before the analysis of other samples. All sample
analytical results following a high level sample must be examined for the possibility of carryover. If
target analytes are found in the samples that are common to a previously analyzed high sample, the
samples may be re-analyzed after it is demonstrated that the analytical system is clear by analysis of
blanks. Method blanks are tested immediately after matrix spikes to demonstrate that the system is not
prone to carryover.

8.7 The results of blank analyses must be reviewed before results for samples are reported. The blank
results should not be subtracted from the sample analytical results.

8.8 Surrogate recoveries from every sample will be calculation and control charted. Any sample with a
surrogate recovery greater than or less than three standard deviations from the daily mean surrogate
recovery will be reanalyzed.

8.9 Analyses of mid-range matrix spike and matrix spike duplicate samples at a frequency of one in 20
samples of the same matrix.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-VW-013-7

-------
APPENDIX 1

CSL METHOD SPECIFIC INSTRUMENT PARAMETERS

Tekmar 7000/7050 Headspace Autosampler System

The Tekmar 7000 Headspace Autosampler is fitted with the 50-place Tekmar 7050 sample carrousel and
set up for 22 mL headspace vials. The stainless steel sample loop is 1 mL in volume and the system is operated
in the Constant Heating Time Operating Mode

Instrument Parameters are as follows:

Platen: 80°C

Platen Equilibration: 10.00 min

Sample Equilibration: 20.0 min

Vial Size: 20 mL

Mixer: Off

Mix: No

Mix Power: No

Stabilization: No

Press: 0.25 min

Press Equilibration: 0.25 min

Loop: 0.25 min

Loop Equilibration: 0.20 min

Injection: 1.00 min

Valve: 105°C

Line: 110°C

GC Cycle Time: 21

Parameter Optimization: Off

Hewlett-Packard 5890A Series II GC/FID/Chemstation System

The BP 5890 equipped with HP IB board and interface cables is used in conjunction with the Tekmar
Headspace system.

The heated nickel transfer line from the Tekmar system is directly connected to the GC column within the GC
oven using a low dead volume fitting.

FMC-VW-013-8

-------
ESAT Region 10 Method
ANALYSIS OF VOLATILE ORGANIC COMPOUNDS IN WATER BY PURGE AND TRAP

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining estimated
quantities of volatile organic compounds (VOCs) in water. Target compounds and the method quantitation limits
are listed in Table 1. This method may be modified at the discretion of the analyst in order to meet project
specific goals (ie. detection limit modifications, larger or smaller analyte lists, or to optimization of
chromatographic conditions for specific target compounds).

1.2 This method is intended for use by or under the supervision of analysts experienced in gas
chromatography (GC), in the use of purge and trap sample concentrator, and in the interpretation of GC
chromatograms.

1.3 It is strongly recommended that 10% of the samples be submitted for analysis by this method be
split and submitted for confirmational analysis using an EPA regulated method. Confirmational analyses are
recommended for Level II field analysis per Data Quality Objectives for Remedial Response Activities
(EPA/540/G-87/003) and are required for QA2 analyses (not required for QA1 analyses) per Quality
Assurance/Quality Control Guidance for Removal Activities (EPA/540/G-90/004). Any site specific
information pertaining to the requested analysis would greatly enhance the support capabilities of the FASP team
(i.e., action levels, known interferences, etc.)

2.0 SUMMARY OF METHOD

2.1 A measured amount of water is added to a purge and trap apparatus, concentrated to a Tenax trap,
then is thermally desorbed with a helium purge directly on to megabore column installed in a temperature
programmed gas chromatograph. Identification is based on comparison of retention times and relative peak
intensities between samples and standards.

3.0 INTERFERENCES

3.1 Impurities in the purge gas, outgassing of organic compounds from the plumbing ahead of the trap
and solvent vapors in the laboratory account for a majority of contamination problems. The analytical system
must be demonstrated to be free from contamination under the conditions of the analysis by running laboratory
reagent blanks.

3.2 Samples can be contaminated by diffusion of volatile organics through the septum seal of the sample
vial during shipment and storage. A field reagent blank prepared from reagent water and carried through
sampling and handling protocols serves as a check on such contamination.

3.3 Contamination by carryover can occur whenever high-level and low-level samples are analyzed
sequentially. Whenever an unusually concentrated sample is analyzed, it should be followed by an analysis of
reagent water to check for cross-contamination. The trap and other parts of the system are subject to
contamination; therefore, frequent bake-out and purging of the entire system may be required.

FMC-VW-014-1

-------
Table 2

TARGET COMPOUND LIST AND QUANTITATION LIMITS

Volatile Organic Compound	* Quantitation Limit

	(Hg/L)	

Benzene



2.0

Carbon Tetrachloride



0.2

Chlorobenzene



0.2

1,2-Dichlorobenzene



0.2

1,1,1 -Trichloroethane



0.2

1,1 -Dichlorobenzene



0.2

1,1,2-Trichloroethane



0.2

1,1,2,2-T etrachloroethane



0.2

Chloroethane



0.2

2-Chloroethyl Vinyl Ether



0.2

Chloroform



0.2

1,2-Dichlorobenzene



0.2

1,3-Dichlorobenzene



0.2

1,4-Dichlorobenzene



0.2

1,1 -Dichloroethylene



0.2

1,2-trans-Dichloroethylene



0.2

1,2-Dichloropropane



0.2

1,3-cis-Dichloropropene



0.2

1,3-trans-Dichloropropene



0.2

Ethylbenzene



2.0

Methylene Chloride



0.2

Bromoform



0.2

Bromodichloromethane



0.2

T richlorofluoromentane



0.2

Chlorodibromomethane



0.2

T etrachloroethy lene



0.2

T oluene

2.0



T richloroethy lene



0.2

Vinyl Chloride



0.2

o-Xylene



2.0

m-Xylene



2.0

p-Xylene



2.0

* The above quantitation limits are estimates

4.0 APPARATUS AND MATERIALS

4.1 Analytical System: The following option meets the requirements of this method. Other GC-
concentrator configurations may be used if they meet method requirements.

4.1.1 Gas Chromatograph: An analytical system complete with a temperature-programmable
GC suitable for on-column injection is required. All necessary accessories including injector and
detector systems must be designed to accept the appropriate analytical column. The system must have a
data handling system attached to the detectors that is capable of retention time labeling, relative retention
time comparisons, and providing relative and absolute peak height and/or peak area measurements.

FMC-VW-014-2

-------
4.1.1.1 Column: 30m x 0.53mm I.D. DB-624 fused silica megabore capillary column
(J&W Scientific) or equivalent.

4.1.1.2 Detectors:

4.1.1.2.1 Electrolytic conductivity detector (Hall).

4.1.1.2.2 Photoionization detector (PID)

4.1.2 Purge and Trap Device: The purge and trap device consists of three pieces of equipment:
The sample purger, the trap, and the desorber. This method utilizes a Tekmar purge and trap system to
desorb samples directly onto the GC column. Several other devices are commercially available.

4.1.2.1 Sample Purger: The purging chamber must be designed to accept 5mL
samples. The purge gas must pass through the water column as finely divided bubbles.

4.1.2.2 Trap: The trap must be 25 cm long and have an inside diameter of 0.318 cm.
Before initial use, the trap should be conditioned overnight at 180°C while backflushing with an
inert gas flow of at least 20mL/min. Prior to daily use, the trap should be conditioned for 10
min. at 180°C with backflushing.

4.1.2.3 Desorber: The sample desorber should be capable of rapidly heating the trap to
180°C for sample desorption.

4.2 Other Laboratory Equipment

4.2.1 Syringes: 10(iL, 100(iL and 5mL

4.2.2 Vials: 1.8mL with Teflon lined septa for purgeable standards.

5.0 REAGENTS

5.1 Reagent Water: Reagent water may be generated using a carbon filter bed containing activated
carbon (Calgon Corporation, Filtrasorb-300 or equivalent), a water purification system (Milli-Q, Barnsteak
Water-1 systems or equivalent), or purchased from commercial laboratory supply houses.

5.2 Solvents

5.2.1 1-Propanol: Pesticide quality or equivalent.

5.2.2 Methanol: Pesticide quality or equivalent.
5.3 Gases

5.3.1 Helium: Ultra-pure or chromatographic grade.

5.3.2 Hydrogen: Ultra-pure or chromatographic grade.

5.4 Stock Standard Solutions: Stock standard solutions in methanol should be purchased as
manufacturer certified solutions. Stock standard solutions must be replaced within two years after opening.

FMC-VW-014-3

-------
above, the method detection limit. The remaining concentration levels should define the working range of the
instrument. Calibration standards must be protected from light and stored in Teflon sealed screw-cap bottles at
4°C.

5.6 Surrogate Standards: The analyst will monitor the performance of the desorbtion and analytical
system by spiking each sample, blank and matrix spike with one or two surrogates not expected to be present in
the sample. The surrogates used in this method include fluorobenzene, bromochloromethane, l-chloro-2-
bromopropane, and 1,4-dichlorobutane.

5.7 Matrix Spikes: Matrix spike solutions may be prepared by dilution of stock standard solutions. The
spiking level should be approximately five times the analyte concentration in the native sample.

6.0 INTERFERENCES

6.1 All samples must be iced or refrigerated from the time of collection until analysis. If the sample
contains free or combined chlorine, add sodium thiosulfate preservative (10mg/40mL) to the empty sample bottle.

6.2 Grab samples must be collected in glass containers having a total volume of at least 25mL. Fill the
sample bottle just to overflowing in such a manner that no air bubbles pass through the sample as the bottle is
being filled. Seal the bottle so that no air has been added, shake vigorously for 1 minute to dissolve the
preservative. Maintain the hermetic seal on the sample bottle until time of analysis.

7.0 PROCEDURE

7.1 Safety

7.1.1 The toxicity or carcinogenicity of each reagent used in this method has not been precisely
defined; however, each chemical compound must be treated as a potential health hazard. Accordingly,
exposure to these chemicals must be reduced to the lowest possible level.

7.1.2 The analysts should be familiar with the location and proper use of the fume hoods, eye
washes, safety showers, and fire extinguishers. In addition, the analysts must wear protective clothing at
all times. Contact lenses may not be worn while working in the laboratory.

7.1.3 Fume hoods must be utilized whenever possible to avoid potential exposure to organic

solvents.

7.1.4 Work with solvents or chemicals may be performed only when at least one other chemist
is in the area.

7.1.5 Waste must be disposed of by placing it in an appropriately marked container beneath the
fume hoods in the extraction rooms or other designated area. All waste containers must be labeled with
the start date, end date, and type of waste (ie. halogenated or non-halogenated solvents).

7.2 Calibration

7.2.1 Initial Calibration:

7.2.1.1 Generate initial calibration curves using an external standard technique with at
least three calibration levels for each target compound as described in Section 6.5. The
calibration curves are generated by injecting 10(iL of standard into 5mL of water. The water

FMC-VW-014-4

-------
and standard are then purged with helium for 10 minutes onto a Tenax trap and then thermally
desorbed as described in Table 2.

7.2.1.2 Correlation coefficients (r2) for each calibration curve must be greater than 0.95
or the RSD of calibration factors must be less than ±25% to be valid. A new initial calibration
curve must be run generated whenever the GC is altered or shut down for long periods of time.

7.2.2 Continuing Calibration:

7.2.2.1 A continuing calibration must be performed on a regular basis. The midrange
initial calibration standard is used for continuing calibration validation. For a continuing
calibration to be valid, the percent difference (%diff) must be less than or equal to ±25%. If this
criteria is not met, reshoot the standard and if still out, a new initial calibration curve must be
run.

7.3 Sample Desorbtion: This sample desorbtion technique for VOCs in water is recommended for the
Tekmar LSC-2000 purge and trap system. Specific parameters may be found in Table 2.

7.3.1 Fill a 5mL syringe with sample.

7.3.2 Inject 10(iL of surrogate into the syringe.

7.3.3 Immediately add the sample to the LSC-2000 purge chamber.

7.3.4 Make sure the trap temperature is 30°C or less.

7.3.5 Purge sample with helium for 10 min. directly onto the trap.

7.3.6 Thermally desorb the trap at 180°C for 4 minutes. The GC system begins data collection
and temperature program with sample desorbtion.

7.3.7 Once the sample is desorbed, bake the trap for 10 minutes at 200°C.

7.3.8 After baking the trap, allow it to cool to 30°C; wait for the GC temperature program to
end and the data to be processed; then desorb the trap again to demonstrate that the trap is free from
contaminants.

7.4 Instrumental Analysis

7.4.1 Instrument Parameters: Table 2 summarizes acceptable operating conditions for the GC
and purge and trap system.

7.4.2 Chromatograms:

7.4.2.1 The following information must be recorded in the instrument logbook:

Instrument and detector identification
Column coating, length and ID
Oven temperature
Injector/detector temperature
Gases and flow rates
Site name
Sample numbers

FMC-VW-014-5

-------
Date and time
GC operator initials

7.4.3	VOC Identification:

7.4.3.1	Qualitative identification of target VOCs is based on retention time matching
of the sample with standard chromatograms.

7.4.3.2	For compounds which can be detected on both the PID and Hall detector, the
compound must be identified in both chromatograms for positive identification to be made.

7.4.3.3	Individual retention time windows should be less than ±2 percent difference

(%D).

7.4.4	Analytical Sequence:

Trap Blank;

Initial calibration;

Associated QC method blank and matrix spikes;

Ten samples each followed by blank runs; and

Continuing calibration.

8.0 QUALITY CONTROL

8.1 Quality assurance guidelines must be met for all analyses. Matrix spike and matrix spike duplicate
recoveries must fall between 50-150 %REC. Percent recoveries for the surrogates must meet the same criteria as
the matrix spikes. Refer to DOC# ESAT 10A-5188 "Quality Assurance Guidelines for Field Analysis" for
specific criteria.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

Information not available.

FMC-VW-014-6

-------
Table 2

Recommended Operating Conditions
Purge and Trap Device	Tekmar LSC-2000

Desorbtion Temperature 180°C for 4 minutes

Bakeout Temperature
Gas Chromatograph
Detectors

Data Processor

Column
Carrier Gas
Makeup Gas
Reaction Gas
Column Oven

Detector Temperature
GC Analysis Time

200°C for 10 minutes
Tracor series 585

PID with a 10.2 eV lamp connected in
series with a Hall Electrolytic Conductivity
Detector.

Nelson Analytical PC with a dual channel
interface and 30-MB hard disk drive for
data storage.

J&W DB-624 fused silica 30m x 0.53 mm I.D.

Ultrapure helium, 5mL/min

Ultrapure helium, 30 mL/min

Ultrapure hydrogen, 20 mL/min

Initial temperature: 40°C
Initial time: 3 minutes
Ramp rate: 6 deg/min
Final temperature: 220°C
Final time: 5 minutes

PID:240°C
HALL: 800°C

26 minutes

FMC-VW-014-7

-------
FASP Method Number F080.001
VOLATILE ORGANIC COMPOUNDS IN SOIL AND SEDIMENT

BY PURGE AND TRAP

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various volatile organic compounds (VOCs) in soil and sediment samples, using purge and trap
technology and gas chromatographic (GC) analysis.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

2.0 SUMMARY OF METHOD

2.1 Five grams (5 g) of soil or sediment, weighed to the nearest 0.01 g, are placed into a soil sparging
apparatus. The sample is purged with helium to extract all VOCs onto a Tenax trap, or equivalent. The trapped
sample is then desorbed directly onto a packed glass column or a megabore capillary column installed in a
temperature-programmed GC. VOCs are detected with a Photoionization Detector (PID) and a Hall Electrolytic
Conductivity Detector (ELCD) connected in series. Quantitation and identification are based on relative peak
areas and relative retention times using the internal standard method.

3.0 INTERFERENCES

3.2 Contamination by carryover can occur whenever high level samples are analyzed. To reduce carry-
over, the purging device must be rinsed with reagent water between sample analyses. Whenever an unusually
concentrated sample is encountered, it should be followed by an analysis of reagent water to check for
cross-contamination. For samples containing high purgeable levels, it may be necessary to wash out the purging
device with a detergent solution, rinse it with distilled water, and then dry it in a 105°C oven between analyses.
The trap and other parts of the system are also subject to contamination; therefore, frequent bakeout and purging
of the entire system may be required.

3.3 The volatile analysis laboratory should be as completely free of interfering solvents as possible.

FMC-VS-001-1

-------
Table 1

FASP METHOD F080.001 TARGET COMPOUND LIST AND QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limits
in Soil/Sediment**
(US/kg)

Trichlorofluoromethane

75-69-4

10.0

1,1 -Dichloroethene

75-35-4

10.0

Methylene Chloride

75-09-2

10.0

trans-1,2-Dichloroethene

540-59-0

10.0

1,1 -Dichloroethane

75-34-3

10.0

Chloroform

67-66-3

20.0

1,1,1 -Trichloroethane

71-55-6

10.0

Carbon Tetrachloride

56-23-5

10.0

Benzene

71-43-2

10.0

1,2-Dichloroethane

107-06-2

10.0

Trichloroethene

79-01-6

10.0

1,2-Dichloropropane

78-87-5

10.0

Bromodichloromethane

75-25-4

10.0

cis-1,3 -Dichloropropene

10061-01-5

10.0

Toluene

108-88-3

10.0

tras-l,3-Dichloropropene

10061-02-6

10.0

1,1,2-trichloroethane

79-00-5

10.0

T etrachloroethene

127-18-4

10.0

Dibromochloromethane

124-48-1

10.0

Chlorobenzene

108-90-7

10.0

Ethylbenzene

100-41-4

10.0

m,p-Xylenes

1330-20-7

10.0

o-Xylene

1330-20-7

10.0

Bromoform

75-25-2

10.0

1,1,2,2-Tetrachloroethane

79-34-5

10.0

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for guidance and may not
always be achievable.

** Quantitation limits listed for soil or sediment are on an "as-received" basis; no dry weights are used.laboratory reagent blanks. The use of
non-Teflon tubing, non-Teflon thread sealants, or flow controllers with rubber components in the purging device should be avoided.

FMC-VS-001-2

-------
3.4 Interferences coextracted from samples are matrix and site specific. It is possible that techniques used
in either FASP or CLP Routine Analytical Services (RAS) methods may fail to eliminate interferences. Highly
specialized CLP Special Analytical Services (SAS) techniques may be required to produce acceptable analytical
results.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems

4.1.1 Gas chromatograph: An analytical system complete with a temperature programmable GC
suitable for on-column injection is required. All necessary accessories including injector and detector
systems must be designed or modified to accept the appropriate analytical columns (packed or megabore).
The system shall have a data handling system attached to the detectors that is capable of retention time
labeling, relative retention time comparisons, and providing relative and absolute peak height and peak area
measurements.

4.1.1.1 Column 1: 1.8 m x 3 mm I.D. glass column packed with 1% SP-1000 on Carbopack
B (60/80 mesh), or equivalent.

4.1.1.2 Column 2: 30 m x 0.53 mm I.D. DB-624 fused silica megabore column (J&W
Scientific), or equivalent.

4.1.1.3 Detectors: A PID with a 10.2 eV lamp and a makeup gas supply at the detector inlet
should be connected in series to a Hall detector.

4.1.1.4 Gas supply: The purge gas, carrier gas, and makeup gas should be ultrapure helium.
The reaction gas required for the Hall detector is ultrapure hydrogen. All gases should pass through
oxygen traps prior to the analytical system to prevent degradation of the column's analutical coating.

4.1.2.1 Sample sparger: The sample sparger must be able to hold a 5-mL sample and the
purge gas must pass through the sample as finely divided bubbles.

4.1.2.2 Trap: The trap must be packed with the appropriate adsorbent materials to collect
VOCs from soil or sediment.

4.1.2.3 Desorber: The desorber should be capable of rapidly heating the trap to 180°C. The
trap should not be heated higher than 220°C during the bakeout mode.

4.2 Other Laboratory Equipment

4.2.1 Microsvringes: 10- to 1000-^L.

4.2.2 Syringe: 5-mL luer-lock.

4.2.3 Volumetric flasks: With ground glass or Teflon stoppers.

4.2.4 Vials: 1.8 mL, for purgeable standards with Teflon-lined septa; 22-mL screw-cap vials with
Teflon-lined caps (Supelco catalog number 2-3250) or an appropriate size to fit the sample impinger.

FMC-VS-001-3

-------
4.2.5 Drying oven: Capable of maintaining temperatures of greater than or equal to 280°C.

4.2.6 Desiccator: Glass and stainless steel (no plastic materials).

4.2.7 Oxygen traps: Supelpure-O-Trap and OMJ-1 indicating tube, or equivalent.

4.2.8 Leak detector: Snoop liquid, or equivalent, for packed column operations, or GOW-MAC gas
leak detector, or equivalent, for megabore capillary operations.

4.2.9 Chromatographic data stamps: Used to record instrument operating conditions, if not provided
by the data handling system.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1 Solvents

5.1.1 1-Propanol: Pesticide quality, or equivalent.

5.1.2 Methanol: Pesticide quality, or equivalent.

5.2 Miscellaneous Reagents

5.2.1 Reagent water: Reagent water is defined as water in which an interferent is not observed at the
QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing activated
carbon (Calgon Corporation, Filtrasorb-300, or equivalent), a water purification system (Milli-Q Plus with
Organex Q cartridge, Barnstead Water-1 Systems [provided with the Base Support Facilities], or
equivalent), or purchased from commercial laboratory supply houses.

5.3 Gases:

5.3.1 Helium: Ultrapure or chromatographic grade (used in conjunction with an oxygen trap).

5.3.2 Hydrogen: Ultrapure or chromatographic grade (used in conjunction with an oxygen trap).

5.4 Stock Standard Solutions: Stock standard solutions of the analyte should be purchased in methanol as
manufacturer certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with water. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining
concentrations should define the approximate working range of the GC: one at the upper linear range and the
other midway between it and lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist
other than the calibration standard preparer.

5.7 Internal Standards

FMC-VS-001-4

-------
5.7.1 The 3 internal standards used are fluorobenzene, bromochloromethane, and
p-bromofluorobenzene, at 80 Hg/kg at time of purge.

5.7.2 An internal standard mix should be prepared through volumetric dilution of individual stock
standards with methanol. It is recommended that the secondary dilution standard be prepared at a
concentration of 200 ng/mL of each internal standard compound. The addition of 2 (iL of this standard to 5
g of sample or 5 mL of calibration standard would be equivalent to 80 Hg/kg.

5.7.3 All standards must be stored in a freezer in glass vials with Teflon-lined septa caps and be
protected from light. Internal standard solutions must be replaced weekly after the Teflon-lined septum has
been punctured, or whenever comparison with previous analyses indicates a problem.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be handled, preserved, and shipped maintaining a chain-of-custody following current
EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this rule
are the sample volumes required by the laboratory. Soil or sediments are collected in special 22-mL vials with
Teflon-lined septa caps (see equipment list, Section 4.2). Vials are pre-identified, pre-weighed, and pre-marked
for samplers to add (approximately 5 g) soil or sediment sample. Samples are stored and shipped at or below
4°C.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for VOCs in soil or sediment is 7
days from sampling to analysis.

7.0 PROCEDURE

7.1 Extraction: This procedure is recommended for the Tekmar LSC-1 (upgraded), LSC-3, and LSC-2000
purge and trap systems. Alternative region specific purge and trap system procedures and parameters may be
found in Appendices A and B.

7.1.1 Sample extraction: The sample extraction technique for VOCs in soil or sediment is as
follows:

7.1.1.1 Attach the soil sparging apparatus (impinger with microconnectors) to the purge and
trap 3-way valve.

7.1.1.2 Check the stainless steel tube position in the glass sparge tube. It should be retracted
1/8 inch from full insertion to allow gas flow through the taper.

7.1.1.3 Check the sealing gasket for the sample containers. Dirt or scratches on the seal
material will cause gas leaks during purge. Clean or replace a damaged gasket.

7.1.1.4 Reweigh (to the nearest 0.01 g) the previously tared vial to determine the sample

weight.

7.1.1.5 Open the vial containing 5 g of sediment sample. Clean the mouth of the vial with a
Chem Wipe and immediately attach it to a sparge apparatus.

FMC-VS-001-5

-------
7.1.1.6 Fill a 5-mL luer-lock tip, gastight syringe to the 5 mL mark with carbon-free water.

7.1.1.7 Inject 2 (iL of the 200 (ig/mL internal standard mix (bromochloromethane,
fluorobenzene, and p-bromofluorobenzene in methanol) in the water sample through the tip.

7.1.1.8 Immediately attach the syringe to the 3-way valve. Turn valve lever until the arrow
points to the sample inlet port.

7.1.1.9 Inject the water and internal standards into the sparge vessel. Close the valve lever.
Remove the syringe. Draw air into the syringe and inject it into the sparge vessel to clear sample from
the valve and injector line. Close the 3-way valve.

7.1.1.10 Make sure the trap temperature is at 30°C or less. Turn purge timer to 12minutes.

7.1.1.11 If the sample is of an unknown matrix, make sure the sample does not foam.

7.1.1.12 The sample is ready to be desorbed.

7.1.2 Sample desorption:

7.1.2.1 The purged sample may be preheated to 60°C on the trap to remove excess water, and
desorbed at 160°C to 180°C for 4 minutes. The GC system begins data collection and temperature
program concurrently with sample desorption.

7.1.2.2 While the sample is being desorbed into the GC, the sample vial may be removed and
another vial attached to the sparging vessel.

7.1.2.3 After the sample is desorbed, the purge and trap system should be returned to the
purge mode, and the trap should be baked. Gas should flow through the trap during the bake, and the
trap should be heated to 200°C for at least 5 minutes.

7.1.2.4 After baking the trap, allow it to cool to 30°C before purging the next sample.
Calibration

7.2.1 Initial calibration:

7.2.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution, retention
times, response reporting, and interpretation of chromatograms are within acceptable QC limits
(Section 7.4). Using at least 3 calibration standards for pentachlorophenol as described in Section 5,
generate the initial calibration curve (response versus mass of standard injected) for each target
analyte (refer to Section 7.1 and 7.3 for chromatographic procedures).

7.2.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.4) based on
pentachlorophenol's 3 calibration factors (CFs, see Section 7.4) to determine the acceptability
(linearity) of the curve. Unless otherwise specified, the %RSD must be less than or equal to 25
percent or the calibration is invalid and must be repeated. Establish a new initial calibration curve any
time the GC system is altered (e.g., new column, change in gas supply, change in oven temperature) or
shut down.

7.2.2 Continuing calibration:

FMC-VS-001-6

-------
7.2.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing calibration
validation. This single-point analysis follows the same analytical procedures used in the initial
calibration. Use instrument response to compute the CF which is then compared to the mean initial
calibration factor (CF), and calculate a relative percent difference (RPD, see Section 7.4). Unless
otherwise specified, the RPD must be less than or equal to 25 percent for the continuing calibration to
be considered valid. Otherwise, the calibration must be repeated. A continuing calibration remains
valid for a maximum of 24 hours provided the GC system remains unaltered during that time.

7.2.2.2 Use the continuing calibration in all target analyte sample concentration calculations
(Section 7.4) for the period over which the calibration has been validated.

7.2.3 Final calibration: The final calibration is obtained at the end of each batch of sample analyses.
The maximum allowable RPD between the mean initial and final calibration CF for each target analyte must
be less than or equal to 50 percent. A final calibration that achieves an RPD less than or equal to 25 percent
may be used as an ongoing continuing calibration.

7.3 Instrumental Analysis

7.3.1 Instrument parameters: Table 2 summarizes acceptable instrument operating conditions for the
GC. Other instruments, columns, and chromatographic conditions may be used only if this method's QC
criteria are met.

7.3.2 Chromato grams:

7.3.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks are
on scale over a 100-fold range are acceptable. However, this can be no greater than a 100-fold range.
This is to prevent retention time shifts by column or detector overload. Generally, peak response
should be greater than 25 percent and less than 100 percent of the full-scale deflection to allow visual
pattern recognition of the VOCs.

7.3.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperatures;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.3.3 VOC identification:

7.3.3.1 Qualitative identification of VOCs is based on both detector selectivity and relative
retention time as compared to known standards using the internal standard method.

7.3.3.2 For a compound that is detected on both the PID and Hall detector, the compound
must be identified in both chromatograms for a positive identification to be made.

FMC-VS-001-7

-------
7.3.3.3 Generally, individual peak relative retention time windows should be less than 5
percent for packed column analysis or less than 2 percent for megabore capillary columns.
Alternatively, the individual peak relative retention time windows may be calculated based on 3 times
the standard deviation of at least 3 non-consecutive standard analyses. These analyses must be
representative of normal system variations, subject to the professional judgement of an experienced
analyst.

7.3.3.4 It may not be possible or practical to separate all VOC target analytes on a single
column. In such cases, these target analytes should be denoted as the appropriate combination of
VOCs.

7.3.4 System performance: Degradation of volatiles may occur in the GC system especially if the
injector and/or column inlet is contaminated.

7.3.5 Specific instrument options: Specific instrument operating parameters that have been used are
provided in Appendix B of this method.

7.3.6 Analytical sequence:

7.3.6.1 Instrument blank.

7.3.6.2 Initial calibration.

7.3.6.3 Check standard solution and/or performance evaluation sample (if available).

7.3.6.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.3.6.5 Associated QC lot method blank.

7.3.6.6 Twenty samples and associated QC lot spike and duplicate.

7.3.6.7 Repeat sequence beginning at step 7.3.6.5 until all sample (batch) analyses are
completed or another continuing calibration is required.

7.3.6.8 Final calibration when all sample analyses are complete.

7.4 Calculations

7.4.1 Identification and quantitation of VOCs should be based on the internal standard method. The
corresponding internal standards for each target compound are listed in Tables 3 (PID) and 4 (ELCD). A
compound detected by both the PID and ELCD should be quantitated using the detector

FMC-VS-001-8

-------
Table 2

EXAMPLE TEMPERATURE PROGRAM GC OPERATING CONDITIONS

Purge and Trap Device:

Instrument:

Integrator:

Column:

Carrier Gas:

Make-Up Gas:

Reaction Gas:

Column Oven:

Injector Temperature:
Detector Temperature:

Tekmar LSC-1 liquid sample concentrator with upgrade package and heated
transfer line. (Trap composition: 1 cm 3% SP-2100, 15 cm Tenax, 8 cm silica
gel 15).

Shimadzu GC Mini-3 equipped with an HNu systems PID detector with a 10.2
eV lamp connected in series to an O.I. Corporation Hall ELCD.

Nelson Analytical PC Integrator with a dual channel interface and 30-MB hard disk
drive for data storage.

J&W DB-624 fused silica megabore column, 30 m x 0.53 mm I.D.

Ultrapure helium, 10 mL/min.

Ultrapure helium, 40 mL/min.

Ultrapure hydrogen, 100 mL/min.

Initial temperature: 35°C.

Initial time: 4 min.

Ramp rate: 4°C/min.

Final temperature: 105°C.

150oC.

PID: 200oC.

Hall: 800°C.

GC Analysis Time:

20 min.

FMC-VS-001-9

-------
Table 3

VOLATILE ORGANICS COMPOUNDS DETECTED BY THE PID
AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS, (Fluorobenzene)

IS, (p-Bromofluorobenzene)

1,1- Dichloroethene

T oluene

trans-1,2-Dichloroethene

trans-1,3 -Dichloropropene

Benzene

T etrachloroethene

Trichloroethene

Chlorobenzene

2-Chloroethylvinylether

Ethylbenzene

cis-1,3 -Dichloropropene

o,p-Xylene



m-Xylene

Table 4

VOLATILE ORGANIC COMPOUNDS DETECTED BY THE HALL DETECTOR
AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS, (Bromochloromethane)

IS, (p-Bromoflurobenzene)

T richlorofluoromethane

cis-1,3 -Dichloropropene

1,1 -Dichloromethane

trans-1,3 -Dichloropropene

Methylene Chloride

1,1,2-Trichloroethane

trans-1,2-Dichloroethene

T etrachloroethene

1,1 -Dichloroethane

Dibromochloromethane

Chloroform

Chlorobenzene

1,1,1 -Trichloroethane

Bromoform

Carbon Tetrachloride

1,1,2,-T etrachloroethane

1,2-Dichloroethane



Trichloroethene



1,2-Dichloropropane



Bromodichloromethane



that gives the higher response for that specific compound. The second detector should be used for con-
firmation of the presence of that compound.

FMC-VS-001-10

-------
7.4.2 The peak areas of the internal standards should be monitored and evaluated for each standard,
sample, blank, duplicate, and matrix spike. If the peak area for any internal standard changes by more than a
factor of 2 (-50 to +100 percent), the sample must be reanalyzed.

7.4.3 If after reanalysis, the peak areas for all internal standards are inside the QC limits (-50 to +100
percent), only report data from the analysis with peak areas within the QC limits.

7.4.4 If the reanalysis of the sample does not solve the problem for both analyses, then do not report
the sample data.

7.4.5 Initial calibration:

7.4.5.1 Analyze each calibration standard, adding the internal standard spiking solution
directly to the syringe. Tabulate the area response of each target analyte against the concentration for
each compound and internal standard and calculate the CF for each target compound using the
following equation:

A C.

RCF = —- x —^

A. C

where: Ax = Area of the peak for the compound of interest

Ais = Area of the peak for the appropriate internal standard

Cis = Concentration of the internal standard

Cx = Concentration of the compound to be measured.

7.4.5.2 Using the CF values, calculate the %RSD for each target analyte at all concentration
levels using the following equation. The %RSD must be less than or equal to 25 percent.

ST)

%RSD = 4=r x 100
X

where SD, the standard deviation, is given by

i=i

(X. - X):
N - 1

where: X; = Individual CF (per analyte)

X = Mean of all initial CF s (per analyte)

N = Number of calibration standards

7.4.6 Continuing calibration:

7.4.6.1 Sample quantitation is based on analyte CF values calculated from continuing
calibrations. Midrange standards for all initial calibration target analytes must be analyzed as
continuing calibration standards at specified intervals (less than or equal to 24 hours).

7.4.6.2 The maximum allowable RPD calculated for each analyte must be less than or equal
to 25 percent.

FMC-VS-001-11

-------
| CF - CF \
RPD = -	1	— x 100

CFx + CFc

2

where: CF, = Mean CF from the initial calibration for each analyte

CFc = Measured CF from the continuing calibration for the same analyte.

7.4.7 Final calibration:

7.4.7.1	Obtain the final calibration at the end of any batch of samples analyzed.

7.4.7.2	The maximum allowable RPD between the mean initial calibration and final
calibration CF values for each target analyte must be less than or equal to 50 percent. A final
calibration which achieves an RPD less than or equal to 25 percent may be used as an ongoing
continuing calibration.

l ~T ~ CFF\

RPD = -	1	— x 100

cft + cff
2

where: CF, = Mean CF from the initial calibration for each analyte
CFf = Final CF for the same analyte.

7.4.8 Sample quantitation:

7.4.8.1	Calculate the concentration in the sample using the following equation for internal
standards. The relative response can be measured by automated relative peak height or relative peak
area measurements from an integrator.

7.4.8.2	The CF from the continuing calibration analysis is used to calculate the concentration
in the sample. Use the CF as determined in Section 7.4.1 and the following equation.

UJ UJ

Concentration (]ig/kg)

(A.) (CF) (W)

where: Ax	=	Area of the peak for the compound to be measured

Ais	=	Area of the peak for the specific internal standard from Table 3 or 4

Is	=	Amount of internal standard added (ng)

W0 =	Weight of sample purged (g)

CF	=	The calibration factor for the compound to be measured.

7.4.8.3	Report results in micrograms per kilogram (ng/kg) without correction for blank or
spike recovery, or percent moisture.

7.4.8.4	Coeluted analytes should be quantitated and reported as the combination of the
unseparated VOC target analytes.

FMC-VS-001-12

-------
7.4.8.5 Sample chromatograms may not match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum
possible concentration (qualified as less than the numerical value) which allows the data user to
determine if additional work (e.g., CLP analyses) is required (or, if the reported concentration is below
action levels and project objectives and DQOs have been met, to forego further analysis).

7.4.8.6 Similarly, when the sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) that allows the data
user to determine if additional (e.g., CLP analyses,) work is required, or if the reported concentration
is above action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R)
and laboratory duplicate RPD are presented in Table 4. This method should be used in conjunction with the
quality assurance and control (QA/QC) section of this catalog.

FMC-VS-001-13

-------
Table 5

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.001 (VOCs in Soil and Sediment)

Advisory Quality Control Limits*

Analyte

Spike Percent Recovery
(%R)

Duplicate RPD

(%)

Trichlorofluoromethane

30 - 200

±75

1,1 -Dichloroethene

30 - 200

±75

Methylene Chloride

30 - 200

±75

trans- 1,2-Dichloroethane

30 - 200

±75

1,1 -Dichloroethane

30 - 200

±75

Chloroform

30 - 200

±75

1,1,1 -Trichloroethane

30 - 200

±75

Carbon Tetrachloride

30 - 200

±75

Benzene

30 - 200

±75

1,2-Dichloroethane

30 - 200

±75

Trichloroethene

30 - 200

±75

1,2-Dichloropropane

30 - 200

±75

Bromodichloromethane

30 - 200

±75

cis-1,3 -Dichloropropene

30 - 200

±75

Toluene

30 - 200

±75

trans- 1,3-Dichloropropene

30 - 200

±75

1,1,2-Trichloroethane

30 - 200

±75

T etrachloroethene

30 - 200

±75

Dibromochloromethane

30 - 200

±75

Chlorobenzene

30 - 200

±75

Ethylbenzene

30 - 200

±75

m,p-Xylenes

30 - 200

±75

o-Xylene

30 - 200

±75

Bromoform

30 - 200

±75

1,1,2,2-Tetrachlorethane

30 - 200

±75

* If the concentration of an analyte is less than 5 times the quantitation limi, advisory quality control limits for duplicate RPD values
become ±3 times the quantitation limit for that individual analyte.

FMC-VS-001-14

-------
9.0 METHOD PERFORMANCE

9.1 The following are examples of gas chromatograms for volatile organic analytes as detected by the PID
and Hall detectors.

Figure 1
Gas Chromatogram A - PID

Column:	J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Column Temperature:	Initial temperature: 35°C

Initial time: 4 min
Ramp: 4°C/min.

Final temperature: 105°C.

Detector/Injector Temperature: 150°C.

Gas:	Carrier: Ultrapure helium, 10 mL/min.

Makeup: Ultrapure helium, 40 mL/min.

Detector:	HNu PID with a 10.2 eV lamp.

FMC-VS-001-15

-------
Figure 2

Gas Chromatogram B - Hall Detector

Column:	J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Column Temperature:	Initial temperature: 35°C

Initial time: 4 min.

Ramp: 4°C/min.

Final temperature: 105°C.

Detector/Injector Temperature:
Gas:

150°C.

Carrier: Ultrapure helium, 10 mL/min.

Makeup: Ultrapure helium, 40 mL/min.
Reaction gas: Ultrapure hydrogen, 100 mL/min.

Detector:

O.I. Corporation Hall electrolyte conductivity detector.

FMC-VS-001-16

-------
9.2 Method F080.001 examples of sample OA/OC results: Spike and duplicate sample results are presented
as examples of FASP Method F080.001 empirical data (see Tables 6 and 7).

Table 6

FASP METHOD F080.001
MATRIX SPIKE PERCENT RECOVERY
VOLATILE ORGANIC COMPOUNDS IN SOIL AND SEDIMENT (jig/kg)

Analyte

Spiked Sample

Sample

Spike Amount
Added

Percent Recovery
(%)

T richlorofluoromethane

87 F

10 UF

80

109

1,1 -Dichloroethene

81 F

10 UF

80

101

Methylene chloride

71 F

10 UF

80

89

trans-1,2-Dichloroethene

96 F

10 UF

80

120

1,1 -Dichloroethane

90 F

10 UF

80

113

Chloroform

85 F

10 UF

80

106

1,1,1 -Trichloroethane

85 F

10 UF

80

106

Carbon tetrachloride

85 F

10 UF

80

106

1,2-Dichloroethane

79 F

10 UF

80

99

Trichloroethene

78 F

10 UF

80

98

1,2-Dichloropropane

83 F

10 UF

80

104

Bromodichloromethane

47 F

10 UF

80

59

2-Chloroethylvinylether

.. *

10 UF

80

.. *

cis-1,3 -Dichloropropene

45 F

10 UF

80

56

trans-1,3 -Dichloropropene

42 F

10 UF

80

53

1,1,2-Trichloroethane

32 F

10 UF

80

40

T etrachloroethene

30 F

10 UF

80

38

Dibromochlomethane

42 F

10 UF

80

53

Chlorobenzene

24 F

10 UF

80

30

Bromoform

73 F

10 UF

80

91

1,1,2,2-T etrachloroethane

67 F

10 UF

80

84

U - The material was analyzed for but was not detected. The associated numerical value is a method quantification
limit, adjusted for sample volume.

FMC-VS-001-17

-------
Data have been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

2-Chloroethylvinylether is unstable. Concentrations found in standard solutions are not guaranteed by the
manufacturer. This compound was not found in the standard mix used for the matrix spike solution.

FMC-VS-001-18

-------
Table 7

FASP METHOD F080.001
DUPLICATE SAMPLE ANALYSIS RELATIVE PERCENT DIFFERENCE
VOLATILE ORGANIC COMPOUNDS IN SOIL AND SEDIMENT (jig/kg)

Analyte

Sample Results

Duplicate Sample
Results

Relative Percent
Difference

T richlorofluoromethane





0

1,1 -Dichloroethene





0

Methylene chloride





0

trans-1,2-Dichloroethene





0

1,1 -Dichloroethane





0

Chloroform





0

1,1,1 -Trichloroethane





0

Carbon tetrachloride





0

1,2-Dichloroethane





0

Trichloroethene





20

1,2-Dichloropropane





0

Bromodichloromethane





0

2-Chloroethylvinylether





0

cis-1,3 -Dichloropropene





0

trans-1,3 -Dichloropropene





0

1,1,2-Trichloroethane





0

T etrachloroethene





0

Dibromochlomethane





0

Chlorobenzene





0

Bromoform





0

1,1,2,-T etrachloroethane





0

U - The material was analyzed for but was not detected. The associated numerical value is a method quantification
limit, adjusted for sample volume.

F - Data have been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

FMC-VS-001-19

-------
10.0 REFERENCES

Information not available.

FMC-VS-001-20

-------
APPENDIX A

FASP METHOD F080.001

Instrument Options:
Purge and Trap Device:

GC System:

Data Handling System 1:
Data Handling System 2:
Data Handling System 3:

Data Handling System 4:

Tekmar LSC-1 liquid sample concentrator with upgrade package and heated
transfer line (Trap composition: 1 cm 3% SP-2100, 15 cm Tenax, 8 cm silica gel
15).

Shimadzu GC Mini-3 (temperature programmable) with an HNu PID connected
in series to an O.I. Corporation Hall detector modified with a direct conversion
and makeup gas adapter for megabore capillary column operations.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit
and Shimadzu FDD-1A floppy disk drive.

P.E. Nelson 2100 dual-channel integrator with 960 Series Intelligent Interface,
Hyundai 80286 computer, and Epson LX800 printer.

FMC-VS-001-21

-------
APPENDIX B
FASP METHOD F080.001

Specific Instrument Parameters:
Purge and Trap Device:

Gas Chromatograph:

Tekmar LSC-1 liquid sample concentrator with upgrade package and heated
transfer line. (Trap composition: 1 cm 3% SP-2100, 15 cm Tenax, 8 cm silica gel
15).

Shimadzu GC-mini 3 (temperature-programmable) with an HNu PID connected
in series to an O.I. Corporation Hall detector.

Integrator:

Columns:

Carrier Gas:

Makeup Gas:

Reaction Gas:

Column (Oven) Temperature

Detector Temperature:
Injector Temperature:

Shimadzu Chromatopac C-R3A Data Processor.

J&W 30 m x 0.53 mm DB-624 fused silica megabore capillary column.

Ultrapure helium, 10 mL/min.

Ultrapure helium, 40 mL/min.

Ultrapure hydrogen, 100 mL/min.

Initial temperature: 35°C
Initial time: 4 min
Ramp: 4°C/min
Final temperature: 105°C.

150oC

150oC

FMC-VS-001-22

-------
FASP Method Number F080.002
VOLATILE ORGANICS IN SOIL/SEDIMENT BY AUTOMATED HEADSPACE

EXTERNAL STANDARD METHOD

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the relative
concentrations of various volatile organic compounds (VOCs), in soil and sediment samples using automated
headspace technology and analysis by gas chromatography (GC) analysis.

1.2 This method yields tentative identification and estimated relative quantitation of the analytes listed in
Table 1. Approximate method quantitation limits (QL) are also listed in Table 1. Report values are on an
"as-received" basis; no dry weights are used.

1.3 This method should be used only by trained analysts under the super-vision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of this method. This method is not equivalent to or a replacement
for Contract Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of
sample concentrations, is recommended.

1.5 This method is intended only to generate screening data that can be used to direct ongoing field work,
identify samples that need additional analysis, or determine relative concentrations of target analytes. The headspace
technique assumes that for volatile compounds, the concentration of an analy te found in the headspace over the water
sample directly relates to the actual concentration of the analyte in the sample. This assumption is usually valid.
However, complex matrices such as oily wastes, multiphase samples, and high-level samples may cause interferences
which could prevent the assumed partitioning between the liquid and gas/vapor phases in the headspace vial.

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil or sediment sample is placed into a headspace vial. The headspace volume
is made constant for all samples and standards. The containers are sealed and allowed to equilibrate at a constant
temperature in the headspace analyzer. A sample is withdrawn from the headspace and injected onto a GC equipped
with a packed or megabore capillary column. Volatile organic compounds are detected with a photoionization
detector (PID) and a Hall electrolytic conductivity detector connected in series. Quantitation and identification are
based on relative peak areas and relative retention times using the external standard method.

3.0 INTERFERENCES

3.1 Impurities in the purge gas, organic compounds out-gassing from the plumbing in the headspace sampler,
and solvent vapors in the laboratory account for the majority of contamination problems. The analytical system must
be demonstrated to be free from contamination under the conditions of the analysis by running reagent blanks. The
use of non-Teflon tubing, non-Teflon thread sealants, or flow controllers with rubber components in the purging
device should be avoided.

FMC-VS-002-1

-------
Table 1

FASP METHOD F080.002 TARGET COMPOUND LIST
AND QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit in
Soil/Sediment** (ng/kg)

T richlorofluoromethane

75-69-4

100

1,1 -Dichloroethene

75-35-4

100

Methylene Chloride

75-09-2

100

trans-1,2-Dichloroethene

540-59-0

100

1,1 -Dichloroethane

75-34-3

100

Chloroform

67-66-3

100

1,1,1 -Trichloroethane

71-55-6

100

Carbon Tetrachloride

56-23-5

100

Benzene

71-43-2

100

1,2-Dichloroethane

107-06-2

100

Trichloroethene

79-01-6

100

1,2-Dichloropropane

78-87-5

100

Bromodichloromethane

75-25-4

100

cis-1,3 -Dichloropropene

10061-01-5

100

T oluene

108-88-3

100

trans-1,3 -Dichloropropene

10061-02-6

100

1,1,2-Trichloroethene

127-18-4

100

T etrachloroethene

127-18-4

100

Dibromochloromethane

124-48-1

100

(continued on next page)

* Specific quantitation limit values are highly matrix dependent. The quantitation limits herein are provided for
guidance and may not always be achievable.

** Quantitation limits listed for soil/sediment are on an "as-received" basis.

FMC-VS-002-2

-------
Table 1 (continued)

FASP METHOD F080.002 TARGET COMPOUND LIST
AND QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit
Soil/Sediment** (ng/kg)

Chlorobenzene

108-90-7

100

Ethylbenzene

100-41-4

100

m,p-Xylenes

1330-20-7

100

o-Xylene

1330-20-7

100

Bromoform

75-25-2

100

1,1,2,2-T etrachloroethane

79-34-5

100

* Specific quantitaion limit values are highly matrix dependent. The quantitation limits herein are provided for
guidance and may not always be achievable.

** Quantitation limits listed for soil/sediment are on an "as-received basis".

3.2 Contamination by carry-over can occur whenever high-level and low-level samples are sequentially
analyzed. To reduce carryover, the sampling syringe (if used) should be rinsed with methanol, dried in an oven, then
stored in a desiccator between sample analyses. Whenever an unusually concentrated sample is encountered, it should
be followed by an analysis of the headspace over reagent water and/or the sampling syringe filled with reagent air
to check for cross contamination. For samples containing large amounts of water soluble materials, suspended solids,
high boiling compounds, or high purgeable levels, it may be necessary to boil the sampling syringe with water for
several minutes, rinse with methanol, dry it in an oven at 105°C, and store in a desiccator between analyses. The
headspace sampler (if used) and other parts of the system are also subject to contamination; therefore, frequent
purging of the entire system may be required.

3.3 The surrounding area where volatile analysis is performed should be completely free of solvents.

3.4 Henry's Law states that the concentration of the volatile analyte in the headspace above the solution is
proportional to the concentration of the analyte in solution. This proportionality, known as Henry's Constant, is
temperature and pressure dependent. Henry's Law holds for dilute solutions. Dilute solutions can be conveniently
defined as solutions with less than 1 percent total dissolved species. In practice, the upper concentration limit is
defined by the water solubility of the analyte being measured, which is typically on the order of 100 to 1,000 ng/L.
The upper concentration limit can be reduced by diluting the samples that contain concentrations higher than the
solubility limit. Caution in the interpretation of results for samples needing dilution should be exercised especially
if free product is present in the original sample.

4.0 APPARATUS AND MATERIALS

FMC-VS-002-3

-------
4.1 Analytical Systems

4.1.1 Gas chromatograph: An analytical system complete with a temperature-programmable GC suitable
for on-column injection and all necessary accessories including injector and detector systems designed or
modified to accept the appropriate analytical columns (packed or megabore) is required. The system should have
a data-handling system attached to the detectors that is capable of retention time labeling, relative retention time
comparisons, and providing relative and absolute peak height and/or peak area measurements.

4.1.2 Analytical column

4.1.2.1 Packed column: 1.8 m x 3 mm I.D. glass column packed with 1% SP-1000 on Carbopack

B (60/80 mesh), or equivalent.

4.1.2.2 Capillary column: 30 m x 0.53 mm I.D. DB-624 fused silica megabore column (J&W

Scientific), or equivalent.

4.1.3 Detectors: A PID with a 10.2 eV lamp and a makeup gas supply at the detector inlet should be
connected in series to a Hall detector.

4.1.4 Gas supply: The carrier gas and makeup gas should be ultrapure helium. The reaction gas required
for the Hall detector is ultrapure hydrogen. All gases should pass through oxygen traps prior to the analytical
system to prevent degradation of the column's analytical coating.

4.1.5 Headspace sampler: Sample introduction is accomplished using a Hewlett-Packard 19395A
headspace sampler or equivalent. This sampler should be capable of automatically heating a group of samples
to a constant temperature for a specified period of time. The Hewlett-Packard 19395A headspace sampler
automatically withdraws a 1-mL sample from the headspace of the sample to be analyzed. A 3-mL loop is
available if extra sensitivity is required. The sample carousel, sample loop, and transfer line inserted into the
GC injector are heated to minimize sample carryover. Alternatively, the headspace sample may be collected
from the equilibrated vial with a syringe and injected manually onto the GC.

4.2 Other Laboratory Equipment

4.2.1 Microsvringes: 10-^L, 25-^L, and larger.

4.2.2 Sample syringes: 0.5-mL, 1.0-mL, gas tight with Teflon valve.

4.2.3 Volumetric flasks: With ground glass stoppers.

4.2.4 Vials: 1.8-mL for purgeable standards with Teflon-lined septa.

4.2.5 Headspace vials: With Teflon-lined septa and aluminum crimp caps, appropriate size to fit
headspace sampler.

4.2.6 Vortex mixer.

4.2.7 Glass desiccator.

4.2.8 Teflon squeeze bottles: 500-mL.

4.2.9 Crimper pliers: To seal headspace vials.

FMC-VS-002-4

-------
4.2.10 Drying oven.

4.2.11 Oxygen traps: Supelpure-O-Trap and OM-1 indicating tube, or equivalent.

4.2.12 Leak detector: Snoop liquid or equivalent for packed column operations or GOW-MAC gas leak
detector, or equivalent for megabore capillary operations.

4.2.13 Chromatographic data stamps: Used to record instrument operating conditions.

4.2.14 Spatulas: Stainless steel.

4.2.15 Balance: ±0.1 g.

5.0 REAGENTS

5.1 Solvents

5.1.1 1-Propanol: Pesticide quality, or equivalent.

5.1.2 Methanol: Pesticide quality, or equivalent.

5.2 Miscellaneous Reagents

5.3 Gases

5.3.1 Helium: Ultrapure, used in conjunction with an oxygen trap.

5.3.2 Hydrogen: Ultrapure, used in conjunction with an oxygen trap.

5.4 Stock Standard Solutions: Stock standard solutions should be purchased in methanol as manufacturer
certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with water. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced weekly, or sooner if comparison with check standards indicates a problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

5.7 Matrix spike solutions: Matrix spike solutions should be prepared by dilution of stock standard solutions
so that no more than 250 (iL of spike solution is required to provide a final sample spike level within the advised
quality control (QC) limits.

FMC-VS-002-5

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Soil and sediment samples are collected in 40-mL vials with
Teflon-lined septa caps. Approximately 5 g of sample is collected and stored/shipped at or below 4°C.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for VOCs in soil and sediment is
7 days from sampling to analysis.

7.0 PROCEDURE

7.1 Sample Preparation

7.1.1 Add the appropriate amount of sample to a headspace sample vial. All samples, standards, and
QC samples must have consistent final volumes in order to allow for consistent headspace volume.

7.1.2 Immediately add 20 (iL (or appropriate volume) of surrogate standard to the sample vial with a
syringe.

7.1.3 Immediately seal the headspace vial with a Teflon-coated septum and aluminum crimp cap.

7.1.4 Place the vial in the headspace sampler, and equilibrate at the appropriate temperature (usually at
least 30 minutes).

NOTE: Samples, standards, and/or QC samples should be prepared as a group.

7.1.5 Samples are ready for GC injection.

7.2 Calibration

7.2.1 Initial calibration:

7.2.1.1 After an experienced chromatographer has ensured that the entire chromatographic system
is functioning properly; that is, conditions exist such that resolution, retention times, response reporting,
and interpretation of chromatographic spectra are within acceptable QC limits, the GC may be calibrated
(Section 7.4). Using at least 3 calibration standards prepared as described in Section 5.5, initial calibration
curves (relative response versus mass of standard injected) are generated for each target analyte (refer to
Section 7.3 for chromatographic procedures).

7.2.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.4) based on each
VOC's 3 calibration factors (CFs, see Section 7.4) to determine the acceptability (linearity) of the curve.
Unless otherwise specified the %RSD must be less than or equal to 25 percent or the calibration is invalid
and must be repeated. Any time the GC system is altered (e.g., new column, or change in gas supply,
change in oven temperature) or shut down, a new initial calibration curve must be established.

7.2.2 Continuing calibration:

FMC-VS-002-6

-------
calibration. Instrument response is used to compute the CF, which is then compared to the mean initial
calibration factor (CF), and a relative percent difference (RPD, see Section 7.4) is calculated. Unless
otherwise specified, the RPD must be less than or equal to 25 percent for the continuing calibration to be
considered valid. Otherwise, the calibration must be repeated. A continuing calibration remains valid
for a maximum of 24 hours providing the GC system remains unaltered during that time.

7.2.2.2 The continuing calibration is used in all target analyte sample concentration calculations
(Section 7.4) for the period over which the calibration has been validated.

7.2.3 Final calibration: The final calibration must be obtained at the end of each batch of sample
analyses. The maximum allowable RPD between the mean initial calibration and the final calibration factors
for each analyte must be less than or equal to 50 percent. A final calibration that achieves an RPD less than or
equal to 25 percent may be used as an ongoing continuing calibration.

7.3 Instrumental Analysis

7.3.1 Instrument parameters: Tables 2 and 3 summarize an example of acceptable instrument operating
conditions for the GC. Other instruments, columns, and/or chromatographic conditions may be employed if QC
criteria are met.

7.3.2 Chromato grams:

7.3.2.1 Computer reproduction of chromatograms that are attenuated to ensure all peaks are on
scale over a 100-fold range are acceptable. To prevent retention time shifts by column or detector
overload, however, they can be no greater than a 100-fold range. Generally, peak response should be
greater than 25 percent and less than 100 percent of full-scale deflection to allow visual recognition of the
various VOCs.

7.3.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

FMC-VS-002-7

-------
Table 2

EXAMPLE PARAMETERS FOR THE HEADSPACE SAMPLER

TEMPERATURE SETTINGS

Sampler bath temperature	60°C

Valve loop temperature	100°C

GAS PRESSURES AND SETTINGS
(TOR HEWLETT PACKARD MODEL 19395A1

Gas Mode

Type of Gas

Tank Pressure Lbs

Barr Setting

Carrier

Helium

40

0.7

Auxiliary

Helium

40

1.1

Servo Air

Air

60

3.1

PROGRAMMING TIMING FOR VALVE OPERATION EVENTS

Set Point Displays

Key to Press

F unction/Activity

"01"

PROBE

Probe enters vial

"03"

PRESSURE

Starts pressurization

"13"

PRESSURE

Stops pressurization

"14"

VENT/FILL LOOP

Starts venting

"25"

VENT/FILL LOOP

Stops venting

"26"

INJECT

Starts injection

"227"

INJECT

Stops injection

"228"

PROBE

Raises probe from vial

FMC-VS-002-8

-------
Table 3

EXAMPLE TEMPERATURE-PROGRAMMED GC OPERATING CONDITIONS

Headspace Sampler:
Instrument:

Integrator:

Column:

Carrier Gas:
Make-up Gas:
Reaction Gas:
Column Oven:

Injector Temperature:
Detector Temperature:

Hall Vent Time:
GC Analysis Time:
Sample Injection:

Hewlett-Packard 19395A Automatic Headspace Smpler with heated transfer line.

An analytical system complete with a temperature programmable GC and all
required accessories including analytical columns, gases, and equipped with a
PID detector with a 10.2 eV lamp connected in series to a Hall detector.

Nelson Analytical PC Integrator with a dual channel interface and hard disk drive for data
storage.

J&W DB-624 fused silica megabore column, 30 m x 0.53 mm. I.D.

Ultrapure helium, 10 mL/min.

Ultrapure helium, 40 mL/min.

Ultrapure hydrogen, 100 mL/min.

Initial temperature: 50°C
Initial time: 4 mins
Ramp rate: 8°C/min
Final temperature: 4 mins

150°C.

PID:200oC
Hall: 800°C

0.25 mins

30 mins

A 1-mL aliquot of the headspace gas is automatically injected into the GC via the heated
transfer line. If increased sensitivity is desired, a 3 mL sample loop may be employed.

FMC-VS-002-9

-------
• Gas and flow;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.3.3 VOC Identification:

7.3.3.1 Qualitative identification of VOCs is based on both detector selectivity and relative
retention time as compared to known standards using the external standard method.

7.3.3.2 For a compound which is detected on both the PID and Hall detector, the compound must
be identified in both chromatograms for a positive identification to be made.

7.3.3.3 Generally, individual peak relative retention time windows should be less than or equal
to 5 percent for packed column analysis or less than or equal to 2 percent for megabore capillary columns.

7.3.4 Analytical sequence:

7.3.4.1 Instrument blank.

7.3.4.2 Initial calibration.

7.3.4.3 Check standard solution and/or performance evaluation sample (if available).

7.3.4.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.3.4.5 System performance check sample.

7.3.4.6 Associated QC lot method blank.

7.3.4.7 Twenty samples and associated QC lot spike and duplicate.

7.3.4.8 Repeat sequence beginning at 7.3.4.5 until all sample analyses are completed or another
continuing calibration is required.

7.3.4.9 Final calibration when all sample analyses are complete.

7.4 Calculations: Identification and quantitation of target VOCs should be based on the external standard
method. A compound which is detected by both the PID and Hall Detector should be quantitated using the detector
which gives the higher response for that specific compound. The second detector should be used for confirmation
of the presence of that compound.

7.4.1 Initial calibration: Analyze each calibration standard, and tabulate the area response of each target
analyte against concentration for each compound.

7.4.1.1 Calculate CFs for each target compound using the following equation:

FMC-VS-002-10

-------
CF =

Area of Peak

Mass Injected (innanograms)

7.4.1.2 Using the CF values, calculate the %RSD for each target analyte at all concentration
levels using the following equation.

ST)

hRSD = 4=r x 100
X

where SD, the standard deviation, is given by

SD

^ (x. - X):
hi N - 1

where: X; = Individual CF (per analyte)

X = Mean of all initial CF s (per analyte)

N = Number of calibration standards

7.4.1.3 The %RSD must be less than or equal to 25.0 percent.

7.4.2 Continuing calibration:

7.4.2.1	Sample quantitation is based on analyte calibration factors calculated from continuing
calibrations. Midrange standards for all initial calibration target analytes must be analyzed at specified
intervals (less than or equal to 24 hours).

7.4.2.2	The maximum allowable RPD calculated using the equation below for each analyte must
be less than or equal to 25 percent.

I ~CF~-CF^

RPD = 		

CFI+CFc

where: CF, = Mean CF from the initial calibration for each analyte

CFc = Measured CF from the continuing calibration for the same analyte

7.4.3 Final calibration:

7.4.3.1	Obtain the final calibration at the end of any batch of samples analyzed.

7.4.3.2	The maximum allowable RPD between the mean initial calibration and final calibration
factors for each VOC target analyte must be less than or equal to 50 percent. A final calibration that
achieves an RPD of less than or equal to 25 percent may be used as an ongoing continuing calibration.

\~-CF |

RPD = -	1	— x 100

cfi+cff
2

FMC-VS-002-11

-------
where: CF, = Mean CF from the initial calibration for each analyte
CFf = Final CF for the same analyte

7.4.4 Sample quantitation:

7.4.4.1 External standard calibration is used for the calculation of the compounds of interest. The
concentration of each calibrated analyte may be determined by the following formula:

Concentration (]xg/kg) _ (Ax)

(wet weight)	(CF ) (W)

where: Ax	= Area of the peak for the analyte in the sample.

W	= Weight (g) of sample in vial.

CFc	= CF from the continuing calibration for the analyte to be measured.

7.4.4.2 Report results in micrograms per kilogram (ng/kg) without correction for blank or spike
recovery.

7.4.4.3	Coeluted analytes should be quantitated and reported as the combination of the
unseparated volatile organic target analytes.

7.4.4.4	Sample chromatograms may not match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum possible
concentration (qualified as less than the numerical value) which allows the data user to determine if
additional (e.g. CLP analyses) work is required, or, if the reported concentration is below action levels
and project objectives and DQOs have been met, to forego further analysis.

7.4.4.5 Similarly, when sample concentration exceeds the linear range, the analyst may report
a probable minimum level (qualified as greater than the numerical value) which allows the data user to
determine if additional (e.g., CLP RAS or SAS) work is required, or, if the reported concentration is above
action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 4. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-VS-002-12

-------
Table 4

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.002 (VOCs in Soil)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD
(%)

T richlorofluoromethane

30 to 200

± 100

1,1 -Dichloroethene

30 to 200

± 100

Methylene Chloride

30 to 200

± 100

trans-1,2-Dichloroethane

30 to 200

± 100

1,1 -Dichloroethane

30 to 200

± 100

Chloroform

30 to 200

± 100

1,1,1 -Trichloroethane

30 to 200

± 100

Carbon Tetrachloride

30 to 200

± 100

Benzene

30 to 200

± 100

1,2-Dichloroethane

30 to 200

± 100

Trichloroethene

30 to 200

± 100

1,2-Dichloropropane

30 to 200

± 100

Bromodichloromethane

30 to 200

± 100

cis-1,3 -Dichloropropane

30 to 200

± 100

T oluene

30 to 200

± 100

trans-1,3 -Dichloropropene

30 to 200

± 100

1,1,2-Trichloroethane

30 to 200

± 100

T etrachloroethene

30 to 200

± 100

Dibromochloromethane

30 to 200

± 100

(continued on next page)

* If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for duplicate
RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-VS-002-13

-------
Table 4 (continued)

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.002 (VOCs in Soil)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD (%)

Chlorobenzene

30 to 200

± 100

Ethylbenzene

30 to 200

± 100

m,p-Xylenes

30 to 200

± 100

o-Xylene

30 to 200

± 100

Bromoform

30 to 200

± 100

1,1,2,2-T etrachloroethane

30 to 200

± 100

* If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for duplicate
RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-VS-002-14

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatograms are examples of GC chromatograms for this method's volatile organic
analytes, as detected by the FID and Hall detectors.

Figure 1
Gas chromatogram A-PID

Column:

Column Temperature:

Detector/Injector Temperature:
Gas:

Detector:

J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Initial temperature: 35°C for 4 mins

Ramp: 4°C/min

Final temperature: 105°C

150°C

Carrier; ultrapure helium, 10 mL/min.

Make-up; ultrapure helium, 40 mL/min.

HNu PID with a 10.2 eV lamp.

FMC-VS-002-15

-------
Figure 2

Gas chromatogram B - Hall detector

Column:

Column Temperature:

Detector/Injector Temperature:
Gas:

J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Initial temperature: 35°C for 4 mins

Ramp: 4°C/min

Final temperature: 105°C

150°C

Carrier; ultrapure helium, 10 mL/min.

Make-up; ultrapure helium, 40 mL/min.

Reaction gas; ultrapure hydrogen, 100 mL/min.

Detector:

Electrolyte conductivity (Hall) detector.

FMC-VS-002-16

-------
10.0 REFERENCES

Information not available.

FMC-VS-002-17

-------
CSL Method

VOA/SOIL/PENTANE EXT/GC-ECD

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of soil and solid samples for volatile hydrocarbon parameters that
are indicative of contamination at the site. It is presented as a means to rapidly characterize contamination in water
samples. The method is semiqualitative and semiquantitative for the list of target constituents listed in Table 1. Other
compounds may be added as data become available.

1.2 Application of this method is limited to the screening analysis of soil for the target constituents. The
chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of soil contamination associated with other nontargeted compounds in the sample extracts. Positive identification
and quantification of specific constituents, such as these constituents and other organic priority pollutants, should be
supported by analyses of duplicate and other composited samples at a remote CLP laboratory employing EPA
approved testing protocols.

1.3 Preliminary method validation data indicate analysis recoveries of upwards of 90 percent.

1.4 The method detection limits (MDL) for the target constituents are estimated to be 10 Hg/kg. These
estimates are the result of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The methods presented here are loosely based on EPA Method 3550, sonification extraction, found in the
EPA SW-846, Test Methods for Evaluating Solid Waste. 3rd ed., November 1986. In brief, pentane is used in
conjunction with sonification to effect extraction of the target constituents from the sample matrix. The extract is
subsequently analyzed on a capillary gas chromatograph (GC) using an electron capture detector (ECD).

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target constituents may cause a positive bias in the
results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples having
high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 VOA sample vials: 40-mL capacity with septum screw caps.

4.2 Balance: Sartorius; top loading electronic with 1,500 g capacity with a 0.01 g sensitivity.

FMC-VS-003-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Soil (ng/kg)

Carbon Tetrachloride

10

1,1 -Dichloroethylene

10

trans-1,2-Dichloroethy lene

10

Ethylene Dibromide

10

Perchloroethylene

10

1,2,4-Trichlorobenzene

10

1,1,1 -Trichloroethane

10

T richloroethy lene

10

4.3	Glassware: class A volumetric pipets and flasks; beakers, vials, Pasteur pipets, and miscellaneous
glassware as necessary for the preparation and handling of samples and standards.

4.4	Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation of
dilutions, and spiking of samples.

4.5	Gas Chromatograph: Hewlett-Packard Model 5890A; temperature programming, electronic integration,
report annotation, automatic sampler, 30-meter megabore capillary column (DB-1, 1.50 micron film thickness) and
ECD.

4.6	Sonifier: Heat Systems ultrasonic sonicator with variable control up to 375 watt output and watercooled
cup horn.

5.0 REAGENTS

5.1	Pentane: Spectro grade, 99.9 percent.

5.2	Stock Standards: Prepare or purchase standard materials at approximately 1000 mg/L in methanol.

5.3	Working Standards: Prepared from stock standards by precise dilution in pentane.

5.4	Nitrogen: Carrier gas, prepurified grade.

5.5	Sodium Sulfate: Reagent grade, anhydrous powder form.

FMC-VS-003-2

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all times
when preparing and handling standards and field and laboratory samples.

7.1.3 Prepare standards and samples in a fume hood.

irritation of the skin. The odor threshold of n-pentane is reported as 2.2 ppm. Pentane is highly flammable and
is incompatible with strong oxidizing agents.

7.1.5 Store sample extracts and standards prepared in flammable solvents in an explosion-proof
refrigerator or cooler (outside the laboratory).

7.1.7 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit available for use at all times.

7.2 Sample Preparation and Extraction

7.2.1 In a labeled VOA vial, volumetrically pipet 5.0 mL of pentane and record the volume added. Place
the vial on the top loading balance and record its tare weight. Add an aliquot of soil, approximately 5 to 10
grams to the vial, and accurately record the soil sample weight to the nearest 0.01 grams.

7.2.2 If the sample is wet or a highly consolidated material (i.e., clay), then add about 2 g of sodium
sulfate and mix.

FMC-VS-003-3

-------
a grain-like appearance. If not, then add an additional 1 g of sodium sulfate and resonify. Repetitions of this
process may be needed to properly extract some samples.

7.2.4 After sonification, let the VOA vial stand until the solids have settled. Using a Pasteur pipet,
transfer a suitable aliquot of the pentane solvent (extract) from the vial into a labeled GC autosampler vial and
cap immediately with septum crimp seals. Refrigerate the sample extracts until analyzed.

7.3 Calibration

7.3.1 External calibration: Use a four-level calibration with standards at approximately 10.0, 1.0, 0.1,
and 0.01 (ig/mL for the target constituents in pentane.

7.4 Instrumental Analysis

7.4.1 Perform GC analysis on the extract.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range, dilute
the sample extract such that concentrations fall within the calibration range.

A x Vt x DF

Concentration (g/Kg) = x 100

where: A = Amount of target constituent found in the extract in (ig/L.

Vt = Volume of solvent added to the reactor flask, 2.0 mL.

DF = Dilution factor, if required.

1,000 = Dimensional correction factor.

Ws = Weight of the sample added to the VOA vial in grams.

8.0 QUALITY CONTROL

8.1 Quality control measures shall include as a minimum:

8.1.1 Daily mid-range calibration checks performed prior to the analysis of each day's lot of samples or
with each lot of 20 samples, whichever is more frequent.

FMC-VS-003-4

-------
8.1.2	Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day, whichever
is more frequent.

8.1.3	Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory
blanks show contamination, the cause of the contamination should be investigated and corrective action taken.

8.1.4	Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1/day, whichever is more
frequent.

8.1.5	Analysis of mid-range matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1/day, whichever is more frequent.

8.1.6	Use of the retention time marker during the analysis of all samples and standards.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VS-003-5

-------
CSL Method

VOA/SOIL/CARBON DISULFIDE EXT/GC-FID

l.OSCOPE AND APPLICATION

1.1 This method is used for field screening of soil and solid samples for volatile hydrocarbon parameters that
are indicative of contamination at the site. It is presented as a means to rapidly characterize contamination in soil
samples. The method is semiqualitative and semiquantitative for the target constituents listed in Table 1. Other
compounds may be added as data become available.

1.2 Application of this method is limited to the screening analysis of soil for the target constituents. The
chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of soil contamination associated with other non-targeted compounds in the sample extracts. Positive identification
and quantification of specific constituents, such as these constituents and other organic priority pollutants, should be
supported by analyses of duplicate and other composited samples at a remote CLP laboratory employing EPA
approved testing protocols.

1.3 Preliminary method validation data indicate analysis recoveries of upwards of 90 percent.

1.4 The method detection limits (MDL) for the target constituents are estimated to be 0.1 ppm (^g/g). These
estimates are the result of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The methods presented here are loosely based on EPA Method 3550, sonification extraction, found in the
EPA SW-846, Test Methods for Evaluating Solid Waste. 3rd ed., November 1986. In brief, carbon disulfide is used
in conjunction with sonification to effect extraction of the target constituents from the sample matrix. The extract
is subsequently analyzed on a two-channel capillary gas chromatograph (GC) using a flame ionization detector (FID).

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target constituents may cause a positive bias in the
results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples having
high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 VOA Sample Vials: 40-mL capacity with septum screw cap; precleaned as purchased from I-Chem.

FMC-VS-004-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Soil (ng/g)

4-methyl-2-pentanone

0.1

Perchloroethylene

0.1

T oluene

0.1

1,1,1 -Trichloroethane

0.1

T richloroethy lene

0.1

1,1,2-Trichloroethylene

0.1

Xylenes

0.1

4.2	Balance: Sartorius; top loading electronic with 1,500 g capacity with 0.01 g sensitivity.

4.3	Glassware: class A volumetric pipets and flasks; beakers, vials, Pasteur pipets, and miscellaneous
glassware as necessary for the preparation and handling of samples and standards.

4.4	Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation of
dilutions, and spiking of samples.

4.5	Sonifier: Heat Systems Ultrasonic Sonicator with variable control up to 375 watt output and watercooled
cup horn.

4.6	Gas Chromatograph: Hewlett-Packard Model 5890A; temperature programming, electronic integration,
report annotation, automatic sampler, 30 meter megabore capillary column (DB-1, 1.50 micron film thickness), and
FID.

5.0 REAGENTS

5.1	Carbon Disulfide: Reagent grade, 99.9 percent.

5.2	Sodium Sulfate: Reagent grade, anhydrous powder form.

5.3	Stock Standards: Prepared from standard materials at approximately 1000 mg/L in CS2.

5.4	Working Standards: Prepared from stock standards by precise dilution in CS2.

5.5	Gases

5.5.1	Nitrogen: Carrier gas, prepurified grade.

5.5.2	Hydrogen: FID gas, prepurified grade.

5.5.3	Air: FID gas, zero grade.

FMC-VS-004-2

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all times
when preparing and handling standards and field and laboratory samples.

7.1.3 Prepare standards and samples in a fume hood.

7.1.5 Store sample extracts and standards prepared in flammable solvents in an explosion-proof
refrigerator or cooler (outside the laboratory).

7.1.8 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit available for use at all times.

7.2 Sample Preparation and Extraction

7.2.1 In a labeled VOA vial, accurately weigh out approximately 5 to 10 grams of soil, recording the
weight to the nearest 0.01 g. To the sample vial, volumetrically pipet 5.0 mL of CS2 containing the retention
time marker (a solvent impurity). This should be done immediately after weighing to avoid potential losses of
analytes.

FMC-VS-004-3

-------
7.2.2 Sample treatment: If the sample is wet or a highly consolidated material, then add about 2 g of so-
dium sulfate and mix.

7.2.3 With the VOA vial cap tightly in place, sonicate at an output setting of 30 percent for approxi-
mately 5 minutes. The resulting sonified sample should be dispersed throughout the CS2 solvent and have a
grain-like appearance. If not, then add an additional 1 g of sodium sulfate and resonify. Repetitions of this
process may be needed to properly extract some samples.

7.2.4 After sonification, let the VOA vial stand until the solids have settled. Using a Pasteur pipet,
transfer a suitable aliquot of the CS2 solvent (extract) from the vial into a labeled GC autosampler vial and cap
immediately with septum crimp seals. Refrigerate the sample extracts until use.

7.3 Calibration

7.3.1 External calibration: Use three-level calibration with standards at approximately 40.0, 10.0, and
1.0 (ig/mL for the target constituents.

7.2.2 Working calibration: Perform working calibration with the analysis of each working day's lot of
samples or with each lot of 20 samples, whichever is more frequent. Verify working calibration by use of a
mid-range standard mix. If the response factors and retention times vary by more than ±15 percent or 0.10
minuntes from the initial calibration, then recalibrate on freshly prepared working standards.

7.4 Analysis

7.4.1 Perform GC analysis on the extract.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range, dilute
the sample extract such that concentrations fall within the calibration range.

7.5 Calculations

7.5.1 Base quantification of the target compounds on the integrated areas of the samples in comparison
to the integrated areas of the calibration standards for each analyte. The integrator reports the concentrations
in ng/mL in the extracts. Calculate the concentration for each target constituent in the original sample as
follows:

A x Vt x DF

Concentration (g/Kg) = x 100

where: A = Amount of target constituent found in the extract in (ig/L.

Vt = Volume of solvent added to the reactor flask, 2.0 mL.

DF = Dilution factor, if required.

1,000 = Dimensional correction factor.

FMC-VS-004-4

-------
Ws = Weight of the sample added to the VOA vial in grams.

8.0 QUALITY CONTROL

8.1 Quality control measures shall include as a minimum:

8.1.1	Daily mid-range calibration checks performed prior to the analysis of each day's lot of samples or
with each lot of 20 samples, whichever is more frequent.

8.1.2	Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day, whichever
is more frequent.

8.1.3	Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory
blanks show contamination, the cause of the contamination should be investigated and corrective action taken.

8.1.4	Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1/day, whichever is more
frequent.

8.1.5	Analysis of mid-range matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1/day, whichever is more frequent.

8.1.6	Use of the retention time marker during the analysis of all samples and standards.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VS-004-5

-------
CSL Method

VOA/SOIL/HEADSPACE/GC-PID

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of soil for volatile hydrocarbon parameters that are indicative of
contamination at the site. It is presented as a means to rapidly characterize contamination in soil samples. The
method is customized to measure the target constituents listed in Table 1. Other compounds may be added as data
become available.

1.3 The method detection limits (MDL) for the target constituents are estimated to be 10 Hg/kg. This estimate
is the result of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The method presented here is based on EPA Method 3810, "Headspace Analysis," found in EPA SW-846,
Test Methods for Evaluating Solid Waste. 3rd ed., November 1986. In brief, a soil sample is extracted with water,
allowed to equilibrate, and the resultant headspace is analyzed by gas chromatography.

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target constituents may cause a positive bias in the
results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples having
high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 Sample Bottles: 250-mL capacity with Teflon caps.

4.2 Balance: Sartorius; top-loading electronic with 300 gram capacity and ± 0.01 gram sensitivity.

4.3 Glassware: class A volumetric pipets and flasks; beakers, vials, Pasteur pipets, and miscellaneous
glassware, as necessary for preparation and handling of samples and standards.

FMC-VS-005-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Soil (g/kg)

Benzene

10

1,2-Dichloroethylene

10

T oluene

10

1,1,1 -Trichloroethylene

10

Xylenes

10

Perchloroethylene

10

4.4	Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation of
dilutions, and spiking of samples.

4.5	Gas Chromatograph fGCl: Photovac Model 1OS70; isothermal oven, electronic integration, report
annotation, 10m capillary column, and photoionization detector (PID).

5.0 REAGENTS

5.1	Deionized Water.

5.2	Standards: Purchase neat solvents and prepare 10 ppm standard mixture.

5.3	Working Standards: prepared by precise dilution.

5.4	Ultrapure Air: carrier gas purchased from Scott-Marrin.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1	The target constituents are either identified as or suspected of being carcinogens. All samples are
assumed to be hazardous. All stock and working calibration standards, as well as all samples, shall be handled
with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2	Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all times
when preparing and handling standards and field and laboratory samples.

7.1.3	Prepare standards and samples in a fume hood.

FMC-VS-005-2

-------
7.1.4 Store sample extracts and standards prepared in flammable solvents in an explosion-proof
refrigerator or cooler (outside the laboratory).

7.1.5 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Investigate any situation which leads to or causes noticeable odors or produces any physical
symptoms in the workers, and immediately follow with appropriate corrective action.

7.1.6 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit available for use at all times.

7.2 Calibration

7.2.1 External calibration: Use headspace analysis of water standards at approximately 10, 1, 0.1, and
0.01 ng/mL for the target constituents to calibrate at 4 levels.

7.2.2 Working calibration: Perform working calibration with the analysis of each working day's lot of
samples or with each lot of 20 samples, whichever is more frequent. Verify working calibration by use of a
mid-range standard mix (i.e., 0.1 (ig/mL standard mix). If the response factors and retention times vary by more
than ±15 percent or 0.10 minutes from the initial calibration, then recalibrate on freshly prepared working
standards.

7.3 Analysis

7.3.1 Perform GC analysis on the sample headspace using the instrument conditions which were
determined during method development.

7.3.2 If the analysis indicates that the results are more than 50 percent above the calibration range, dilute
the sample extract such that concentrations fall within the calibration range.

7.3.3 Check the retention values for each of the target constituents against the expected (calibration)
value. Qualify those results where the retention time does not fall within ± 0.05 minutes of the expected value.
Reject those results where the retention time does not fall with ± 0.10 minutes of the expected value. Take
corrective action if the results continue to fall outside of the proper range.

7.4 Calculations: Base quantification of the target compounds on the integrated areas of the samples in
comparison to the integrated areas of the calibration standards for each analyte. The integrator reports the
concentrations in ppm or ppb in the headspace. Calculate the concentration for each target constituent in the original
sample on an "as received" basis as follows:

Information not available.

8.0 QUALITY CONTROL

8.1 Quality control measures shall include as a minimum:

8.1.1 Daily mid-range calibration checks performed prior to the analysis of each day's lot of samples or
with each lot of 20 samples, whichever is more frequent.

FMC-VS-005-3

-------
8.1.2	Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day, whichever
is more frequent.

8.1.3	Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory
blanks show contamination, the cause of the contamination should be investigated and corrective action taken.

8.1.4	Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1/day, whichever is more
frequent.

8.1.5	Analysis of mid-range matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1/day, whichever is more frequent.

8.1.6	Use of the retention time marker during the analysis of all samples and standards.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VS-005-4

-------
NUS SOP Number 5.2

FIELD SCREENING OF TARGET PURGEABLE VOLATILE ORGANIC COMPOUNDS

fSOLID MATRIX)

1.0 SCOPE AND APPLICATION

1.1 The following methodology describes a modification of SW-846 analytical procedures suitable for the
determination of volatile organic contaminants in solid matrix samples.

1.3 Table 1 provides a list of potential volatile target compounds.

2.0 SUMMARY OF METHODS

2.1 In this methodology, a portion of sample matrix or extract, is placed into a glass sparging vessel along with
5 to 10 mL of organic-free water. The sparge vessel is then sealed onto a purging device. The contained sample (or
extract) aliquot is heated while a stream of inert gas is bubbled through the slurry. The mechanical bubbling action
effectively strips the contaminants (now volatilized) from the matrix slurry and sweeps them onto a packed sorbent
tube (i.e., trap) where they are subsequently desorbed (by action of heat and reverse gas flow) onto a suitable column
housed by a pre-programmed gas chromatograph (GC). The volatile contaminants become separated and resolved
as they travel through the GC column. Eventually the contaminants elute through an appropriate detector. The
detector signals are processed and interpreted by a previously programmed integrator.

2.2 Low Level Analysis: Use of a 5 g sample is suggested to achieve reportable detection limits of
approximately 5 Hg/kg. The solid matrix (free of obvious pebbles and unrepresentative organic matter) should be
quickly measured directly into a tared sparge vessel. After the exact weight of sample is recorded, 5 mL of
organic-free water is introduced into the sparger. A heated purge is required.

2.3 Medium Level Analysis: Simple dilutions may be achieved by using a reduced portion of the solid matrix
(i.e., 1 to less than 5 g) and a complementary portion of 9 to 5 mL organic-free water. For example, a 2.5-fold
dilution can be simulated by adding 8 mL of organic-free water to 2 g of weighed matrix. Moderate to high
concentration samples are prepared by extracting a 5 g portion of solid matrix with 10 mL of methanol. A suitable
aliquot of the methanol extract (usually 1 (iL to 200 (iL) is then spiked into a sparge vessel containing 10 mL of
organic-free water. Note that the 1:2 ratio of sample to solvent has introduced a 2-fold dilution. The additional
dilution factor based upon the (iL injection used must also be taken into consideration.

3.0 INTERFERENCES

FMC-VS-006-1

-------
Table 1

SUMMARY OF POTENTIAL TARGET COMPOUNDS

Volatile Organics Analysis

Acetone

	Benzene	

	Bromoform	

	Carbon tetrachloride	

	Chlorobenzene	

	Chloroform	

	Ethylbenzene	

	Methylene Chloride	

	1,1 -Dichloroethene	

Total 1,2-Dichloroethenes

	1,1 -Dichloroethane	

	1,2-Dichloroethane	

1,1,1 -Trichloroethane

	T etrachloroethene	

	T oluene	

	Trichloroethene	

Total Dichlorobenzenes

	Total Xylenes	

	2-Butanone (MEK)	

4-Methyl-2-pentanone (MIBK)

3.2	Samples can become contaminated by the diffusion of high concentration contaminants to lower
concentrated samples through container seals during shipping and storage. If opted as part of the analysis plan,
organic-free trip blanks may be developed and carried by the sampling team together with field samples to assess the
existence and the magnitude of this phenomenon.

3.3	Artifacts, which manifest themselves as carryover in the next analytical run, can also occur within the
analytical apparatus whenever a highly contaminated sample is introduced. To preclude this from occurring, the
sample line and sparge vessel are thoroughly rinsed with organic-free water prior to the bake cycle of each highly
contaminated sample run.

FMC-VS-006-2

-------
4.0 APPARATUS AND MATERIALS

4.1 Purge and Trap Device: Tekmar Company Model LSC-2, or equivalent, complete with a 25-mL glass
sparge vessel and a 1/8 inch O.D. x 25 cm long stainless steel trap. The trap may be packed solely with Tenax.
Alternately, trap packing may consist of 1.0 cm of 3 percent OV-1, 15 cm of Tenax, and 8 cm of silica gel.
Appropriate trap selection is contingent upon the target compounds being analyzed.

4.2 Sparge Heater: Tekmar Model 4100, or equivalent (must be capable of maintaining constant temperature
during the purge process).

4.3 Gas Chromatograph: Hewlett-Packard 5890, or equivalent. The analytical system should be equipped
for temperature programming, packed and/or capillary column analysis, and direct-column injection.

4.4 Detector: Photoionization detector/flame ionization detector (PID/FID) or photoionization detector/Hall
electrolytic conductivity detector (PID/HECD) in series; FID only. Optimum detector selection should be based upon
the sensitivities of the target compounds being analyzed.

4.5 Analytical Column: Glass or stainless steel column packed with 1% SP-1000 on 60/80 mesh Carbopack
B. Alternatively, a suitable capillary column may be used.

4.6 Pipets (assorted): 1-mL, 5-mL, and 10-mL disposable glass.

4.7 Vials: 15-mL septum-seal for storage of sample extracts.

4.8 Vials: 40-mL septum-seal for use in extracting contaminants from sample matrix.

4.9 Glass Marking Pen: For labeling vials.

4.10 Laboratory Timer: For use during the extraction process.

4.11 Aluminum Weighing Pans: For use in determining moisture content of the sample matrix.

4.12 Syringes: 5-(iL, 25-(iL, 100-(iL, 1-mL, and 10-mL.

4.13 Analytical Balance: Capable of accurately weighing 0.0001 g.

4.14 Oven: Constant temperature for the regeneration of contaminated apparatus.

4.15 Refrigerators: One dedicated refrigerator each for separate sample and standard storage. Each should be
capable of maintaining a stable temperature of 4°C.

5.0 REAGENTS

5.1 Methanol: Pesticide grade, or equivalent.

5.2 Organic-free water: Supplied by laboratory or purchased.

5.3 Neat Solvents: 96 percent purity, or better, for each compound of interest.

FMC-VS-006-3

-------
response to the selected detector. Calibration standards are created at a level such that a 2- to 5-(iL spike of standard
into 20 mL of organic-free water is suitable for continuing calibration purposes.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Samples awaiting analysis are stored at 4°C in a dedicated refrigerator. If, because of loading, it is not
possible to analyze all samples taken daily, the suggested holding time for the analysis of volatile organics in solid
matrix is 10 days prior to analysis. If holding times are exceeded, the affected data should be qualified as suspect.

7.0 PROCEDURE

7.1 Sample Preparation: Extract medium to high concentration samples in methanol prior to chromatographic
analysis. The following extraction protocol is suggested:

7.1.1 Weigh and tare a 40-mL septum-seal vial using an analytical balance.

7.1.2 Add 5.0 g of sample matrix to the vial; record weight.

7.1.3 Pipet a 10-mL volume of methanol into the vial. Assuming 100 percent transference of
contaminants from matrix to methanol, note that a 2-fold dilution factor has been introduced.

7.1.4 Remove the vial from the analytical balance, cap and shake vigorously for 2 full minutes
(alternatively, vial contents may be sonicated).

7.1.5 Set the vial aside and allow the contents to settle for 5 minutes.

7.1.6 Pipet off the supernatant extract into a labeled 15-mL vial.

7.1.7 Perform a gas chromatographic analysis by spiking 10 to 200 (iL of the methanol extract into
approximately 10 mL of organic-free water. Calculate total dilution (deviation) from the original 5 g sample
base.

7.2 Percent Moisture (% moisture') Determination: Use a moisture correction factor (MCF) to adjust the value
generated for the amount of contaminant present in a solid matrix sample so that the value reflects the true (dry
weight) concentration of contaminant. Determine moisture content gravimetrically. The following protocol is
suggested for determining % moisture:

7.2.1 Mark and weigh an aluminum weighing pan using an analytical balance. Record weight; tare
balance.

7.2.2 Place 5 to 10 g of matrix (free from unrepresentative pebbles and organic matter) into the pan;
record weight.

7.2.3 Place the pan and its contents into a drying oven heated to 103 °C.

7.2.4 Dry the matrix for a period of 4 to 6 hours (or until weight is constant).

7.2.5 Remove the pan from the oven and allow to cool to room temperature.

FMC-VS-006-4

-------
7.2.6 Weigh the pan and record the weight.

7.2.7 Calculate the % moisture and the MCF (see 7.6)

7.3 Calibration: Calibrate the analytical system by the external standard method in which response factors
(RF) for each compound are obtained by the analysis of a standard mix of known concentration. Following the
analysis of this known standard mix, create an electronic file establishing each peak's identity, retention time (RT),
RF, and known concentration. Determine the RF for each target compound by dividing the known concentration by
the associated peak response (area or height units). For initial calibration, determine each compound's average RF
by averaging the peak response results generated for the initial linearity study. Program these average RFs into the
integrator to allow for direct concentration reading of contaminants found in subsequent sample analyses.

7.3.1 Initial linearity:

7.3.1.1 Generate an initial 3-point calibration curve by the analysis of multiple aliquot injections
of calibration standard. For example, if the calibration standard is created such that a 2-^L spike into
organic-free water yields results at the level of the reported detection limits, a 3-point calibration curve
may be achieved by the analysis of 2-^L, 5-^L, and 10-(iL aliquot spikes.

7.3.1.2 Compute the percent relative standard deviation (%RSD see 7.5.1) based on each
compound's RFs (see 7.6) to determine the acceptability (linearity) of the curve. The %RSD should be
less than 20 percent. Reanalyze standard runs yielding data that does not meet the %RSD criterion.

7.3.1.3 Conduct the linearity study for field screening in such a way as to substantiate the
performance of the detector at the level of the reportable limits. It is not performed to demonstrate the
entire range of detector capability. The primary objective of field screening is the determination of "clean"
versus "dirty" and all results are, therefore, considered to be semi-quantitative.

7.3.2 Continuing calibration:

7.3.2.1 Update the calibration of the analytical system 3 times daily using the mid concentration
standard: (1) preceding the daily analysis, (2) midday, and (3) after the daily analyses.

7.3.2.2 Analyze standards run for continuing calibration purposes at a level equal to the reported
detection limits. Continuing calibration RF s for each parameter should fall within 25 percent difference
(%D, see 7.5.3) of the average RF calculated for that particular compound during the initial linearity study.
Qualify data associated with individual parameter not meeting the %D criterion as suspect.

7.3.3 Peak identification: Compound identities may be substantiated by the analysis of each individual
component, thereby, documenting compound retention time.

7.4 Gas Chromatography:

7.4.1 Analytical sequence: Conduct analyses in sets of 10, whenever possible, with 1 laboratory
duplicate spike analysis run per set. Bracket each set of sample analyses by the analysis of a standard, with a
method blank analysis following each standard run. The number of analyses per sample set and the associated
quality assurance/quality control (QA/QC) varies per contract. Consult the project work plan to verify that all
contractual obligations were met.

7.4.2 Preconcentrate sample contaminants through the purge and trap process in which stripped volatile
contaminants are adsorbed onto a sorbent trap. The affinity the volatilized organic contaminants have for the
special packing inside the sorbent tube causes them to be retained within the tube (i.e., adsorbed onto the
packing), while other inert components pass through the tube. The purge and trap process consists of a pre-purge

FMC-VS-006-5

-------
cycle (optional), a purge cycle (during which contaminants are stripped away from the sample matrix and are
trapped within the sorbent tube), a dry purge cycle (optional), a desorb cycle (in which the contaminants are
backflushed off the sorbent tube and onto the GC column), and a bake cycle (in which the sorbent tube or trap
is heated, with flow to a high temperature regeneration of the trap). Pre-purge and dry purge options of the purge
and trap process are recommended; a heated purge is required. Sample prepurge enhances subsequent
chromatography by allowing air molecules present in the sparge vessel to be replaced by inert purge gas
molecules prior to the actual purge cycle. The dry purge option follows the purge cycle. Dry purge removes
water vapor from the trap tube prior to the desorb cycle. The selection of the appropriate temperature options
and duration of the purge and trap processes are contingent upon the target compounds being analyzed.
Generally, the following range of conditions apply:

Cycle

T emperature

Duration

Pre-purge/Preheat

Ambient/to 40 °C

2 mins/1 min

Purge

40°C

8-10 mins

Dry purge

40°C

2 mins

Desorb

180°C

3-5 mins

Bake

215°C

7-10 mins

7.4.3 Desorption of the adsorbed contents of the sorbent trap onto the head of a previously conditioned
GC analytical column allows for subsequent analysis by temperature-programmed GC. First hold the desorbed
contaminants at constant temperature (usually in the range of 45 to 55 °C) at the head of the analytical column
for a period of 3 to 5 minutes. After this initial time period, raise the GC oven temperature at a constant rate
(usually 8 to 15°C/min) until a final temperature of 200 to 225°C is reached. The final temperature is
customarily held for a period of 3 to 10 minutes.

7.4.4 The affinity of the volatile contaminants to either the analytical column's mobile or stationary
phase, the effect of elevated temperature, and the action of the carrier gas flow through the column cause the
volatile contaminants to become separated and resolved, allowing them to elute in bands through the selected
detector. As long as the analytical conditions remain constant, each type of volatile component will elute at a
characteristic retention time. In this manner, sample contaminants are identified and quantified by comparison
to a run of a standard mix containing known compound concentrations.

7.5 Calculations:

7.5.1 Calculate %RSD using the following equation:

ST)

%RSD = — x 100
X

where:

A (x - x)2
SD = >

M N - 1

and X is the mean of initial Rfs (per compound).

7.5.2 Calculate relative percent difference (RPD) values using the following equation:

FMC-VS-006-6

-------
D1 - D2
RPD = 	i	— x 100

(D1 + D2)

where: D[ = First sample value

D2 = Second sample value

7.5.3	Calculate %D using the following equation:

%D = —	— x 100

where: X[ = RF of first result

X2 = RF of second result

7.5.4	Calculate percent recovery (%R) using the following equation:

= SSR ~ SR x 100

s

where: SSR = Spike sample results,

SR = Sample result, and
S = Amount of spike added.

7.5.5	Sample Quantitation: Due to the extraction process and the need to correct the final value for
moisture content, the quantitation of volatile contaminants in solid matrix samples is calculated based upon the
following formula:

sample peak response	, , , T.

,	, . , . . x RF x final volume mL

„	... , ,, .	area or height)

Concentration ]ig kg) = 	;			—

wt of sample extract (g) x % solids

where: RF	= [Target analyte concentration in std (|ig/L)]/[Target analyte peak response in std]

% solids = 100 - % moisture
% moisture = (Wet wt. - dry wt.)/wet wt.

8.0 QUALITY CONTROL

8.1 Overview

8.1.1	Field screening generates Level II data. As Level II data, the concurrent analysis of laboratory
duplicates and matrix spike analyses and the use of surrogate spike compounds is not required. However,
beyond the maintenance of practical Standard Operating Procedures (SOPs), certain elements of QC (if opted)
can greatly enhance the interpretation of and the confidence in the data generated. These traditional elements
of QC are discussed here as to how they are adapted to meet the demands of a successfully applied field
screening QA/QC program.

8.1.2	The primary purposes of an appropriate QA/QC program are to: (1) substantiate system
performance and give credence to the accuracy of the results generated, (2) to define aberrations and give

FMC-VS-006-7

-------
guidance to the interpretation of data, and (3) to achieve these goals through realistic efforts that do not impede
the forward progress of the analytical set.

8.1.3 The discussion presented here deals with only direct analytical QC. Additional elements of
QA/QC, such as field duplicate sample submissions, blind spike analysis, and external audits are not discussed.
Also not discussed are elements of QA/QC that are inherent to good chromatographic technique. Examples of
these accepted laboratory practices include (but are not limited to) the following: (1) the proper conditioning of
analytical columns and traps, (2) use of the solvent flush technique for the creation of standards and for direct
injections, and (3) the appropriate maintenance of selected detectors. Details regarding these accepted practices
are given in the referenced methodologies.

8.2 Laboratory Duplicates: One laboratory duplicate should be analyzed per sample set. Laboratory duplicate
analyses should generate results of RPD within 30 percent (see 7.5.2).

8.3 Matrix Spikes: Matrix spikes should be conducted at a level of 1 to 4 times the concentration of the
reported detection limits. One matrix spike analysis should be run per every 20 samples. Advised recovery ranges
vary with respect to the compound being analyzed. Recoveries of 35 to 150 percent are generally acceptable (see
7.5.4).

8.4 Surrogate Spikes: The use of at least 1 surrogate spike compound is highly recommended. The identity,
concentration and addition of the appropriate surrogate spike varies with the procedure being used. Each associated
referenced methodology should be consulted for guidance. Surrogate spike recoveries should fall within ±30 percent
(see 7.5.4). Sample analyses yielding %R values outside this 30 percent window should be reanalyzed or the
associated data should be qualified as suspect.

8.5 Method Blanks: Method blanks are prepared and analyzed in exactly the same manner as sample matrices.
A method blank analysis should follow every standard run and sample of high concentration. Ideally, method blank
results should yield no interferences to the chromatographic analysis and interpretation of target compounds. If
interferences are present, associated data should be qualified as suspect and/or target detection limits should be
adjusted accordingly.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VS-006-8

-------
FASP Method F93001

ANALYSIS OF HALOGENATED AND AROMATIC VOLATILE ORGANIC COMPOUNDS IN

SOIL AND WATER BY PURGE AND TRAP GAS CHROMATOGRAPHY

1.0 SCOPE AND APPLICATION

1.1 This method covers the analysis of samples in the field by the Field Analytical Services Program (FASP)
Mobile Laboratory. This FASP method is a modification of approved EPA methods and is intended to supply rapid
turnaround analyses in the field. FASP data are not intended to be a substitute for analyses performed within the
Contract Laboratory Program and are not intended to be legally defensible. The FASP method analyte list is divided
into two parts. The primary analyte list presents the compounds that are routinely analyzed by FASP. The
supplemental analyte list presents additional analytes for which this method maybe appropriate. Analytes on the
supplemental analyte list may be requested on a project specific basis. Table 1 presents the FASP primary analyte
list with FASP reporting limits. Table 2 presents the FASP supplemental analyte list. Both retention times and
reporting limits will be added as data become available.

2.0 SUMMARY OF METHOD

2.1 Soil and water samples are analyzed by purge and trap gas chromatography. Groundwater and low level
soils are analyzed directly. Medium level soils are extracted with methanol and an aliquot of the extract is injected
into water and analyzed by purge and trap techniques. Detection of halogenated and aromatic compounds is
accomplished by the use of selective detectors operated in series. The external standard method of quantitation is
used and analyte identification is made by the use of retention time windows established by the analysis of standards.
The recovery of surrogate compounds added to every sample and standard is used to determine system performance
on a sample by sample basis. A laboratory control sample (LCS) is used to verify calibration accuracy and matrix
spikes and spike duplicate (MS/MSD) samples may be used to assess accuracy and precision.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph fGCl: Varian 3400 GC with a Hall electrolytic conductivity cell detector (ELCD) and
a photoionization detector (PID) installed in series.

4.2 Purge and Trap Equipment: Tekmar Model 2000 Purge and Trap concentrator.

4.3 Data System: Nelson Analytical.

5.0 REAGENTS

5.1 Hydrogen: Ultra pure or equivalent.

5.2 Helium: Ultra pure or equivalent.

FMC-VS-007-1

-------
Table 1

FASP PRIMARY ANALYTE LIST

ANALYTE	RETENTION TIME	REPORTING LIMIT

Chloromethane	4.13	5.0

Bromomethane	5.0

Vinyl chloride	4.13	5.0

Chloroethane	4.80	5.0

Methylene chloride	7.44	1.0

1,1-Dichloroethene	6.37	1.0

1.1-Dichloroethane	9.03	1.0
cis-l,2-Dichloroethene	10.50	1.0
trans-1,2-Dichloroethene 8.02 1.0
Chloroform	11.38	1.0

1.2-Dichloroethane	12.97	1.0

1.1.1-Trichloroethane	11.84	1.0
C arbon tetrachloride	12.32	1.0
Bromodichloromethane	16.46	1.0
1,2-Dichloropropene	15.52	1.0
1,1,2,2-Tetrachloroethane 31.66 1.0

1,2-Dichloropropane	15.52	1.0

trans-l,3-Dichloropropene	10

Trichloroethene	14.86	1.0

Dibromochloromethane	22.81	1.0

1.1.2-Trichloroethane	21.05	1.0
Benzene 12.73 1.0

cis-l,3-Dichloropropene	17.99	1.0

Bromoform	29.87	5.0

T etrachloroethene	21.63	1.0
Toluene 19.06 1.0

Chlorobenzene	25.32	1.0

Ethylbenzene	25.99	1.0

Total Xylenes	26.65	1.0

Styrene	28.83	1.0

1.2-Dichlorobenzene	1.0

1.3-Dichlorobenzene	1.0

1.4-Dichlorobenzene	1.0

FMC-VS-007-2

-------
Table 2

FASP SUPPLEMENTAL ANALYTE LIST

ANALYTE

RETENTION TIME

REPORTING LIMIT

Dichlorofluoromethane
T richlorofluoromethane
Dibromomethane

1,2-Dibromoethane (EDB)

1.2-Dibromo-3-chloropropane(DBCP)

1.3-Dichloropropane

17.87

30.64
16.68

1.0

1.0
1.0

2,2-Dichloropropane

1,1 -Dichloropropene

Hexachlorobutadiene

1,1,1,2-T etrachloroethane

1,2,3 - Trichloroprop ane

Bromobenzene

n-Butylbenzene

para-Isopropyltoluene

Naphthalene

1,2,3 -Trichlorobenzene

1,2,4-Trichlorobenzene

1.2.4-Trimethylbenzene

1.3.5-Trimethylbenzene
sec-Butylbenzene
tert-Butylbenzene
2-Chlorobenzene
4-Chlorobenzene

I sopropy lb enzene
n-Propylbenzene

5.3 Stock Primary Analvte List Standards: All stock standards are purchased from Supelco as traceable
solutions. The following mixes are provided for reference and their use does not constitute an endorsement.
Equivalent substitutions from other vendors may be used.

5.4	Stock Supplemental Analvte List Standards: Supplemental analyte list standards will be purchased as neat
materials or as EPA traceable solutions on an as needed basis.

5.5	Surrogate Spiking Standard: A mixture of 1 -chloro-2-bromopropane and fluorobenzene available as Supelco
catalogue number 4-8950M or equivalent. In cases where fluorobenzene detection is subject to interference, a mixture
of a,a,a-trifluorotoluene and 4-bromofluorobenzene may be used in addition to the above mixture.

Mix

Supelco Catalogue No.

VOC Mix 2
VOC Mix 3
VOC Mix 4
VOC Mix 5
Purgeable C

4-8452M
4-8453M
4-8957M
4-8950M
4-8853M
4-8822M
4-8823M
4-8824M

1.2-Dichlorobenzene

1.3-Dichlorobenzene

1.4-Dichlorobenzene

FMC-VS-007-3

-------
5.6 Matrix Spiking Standard: Matrix spiking solutions will be prepared from benzene, chlorobenzene, 1,1-
dichloroethene, toluene and trichloroethene or from solutions of specific target analytes. The stock matrix spiking
solution will either be prepared from neat materials or purchased as a solution. (Supelco catalogue number 4-8102M
or equivalent). The spiking level will be at the midpoint of the calibration range.

5.7 Laboratory Control Standard: A laboratory control standard will be prepared to determine the veracity of
the initial calibration standard. A laboratory control standard may be prepared from the following compounds:

5.7.1 The Laboratory Control Standard will be prepared from a source other than the one used to prepare
the calibration standards, such as the Supelco mixtures catalogue numbers 4-8462M and 4-8465M or equivalent.

5.8 Solvents: All solvents used as diluents will be HPLC grade or equivalent. Reagent organic free water will
be prepared from distilled, deionized water by purging with an inert gas.

5.9 Sorbent Traps: A multiphase trap is used containing Carbopack C, Carbopack B, Carboxen 1000, and
Carboxen 1001. (Supelco catalogue number 2-0308M or equivalent.)

5.10 Nitrogen: Ultra Pure or equivalent.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Analytical Sequence

7.1.1 Blank.

7.1.2 Initial Calibration.

2 ug/L
4 ug/L
10 ug/L
20 ug/L
40 ug/L

7.1.3 Blank.

7.1.4 Laboratory Control Standard (LCS).

7.1.5 Continuing Calibration Standard (CC)-20 ug/L (Not analyzed on day initial calibration performed).

7.1.6 10 samples.

7.1.7 LCS.

7.1.8 Continue steps f. and g. until 24 hours has passed since last CC

7.1.9 Blank.

Chloroform
T oluene
Chlorobenzene

Ethylbenzene

1,1 -Dichloroethene

1,1,2,2-T etrachloroethane

1,2-Dichloropropane
1,1 -Dichloroethane

FMC-VS-007-4

-------
7.1.10 CC.

7.1.11 Continue at step f.

7.2 Operating Conditions

7.2.1 Purge and Trap Operating Conditions:

Purge time	12.0 minutes

Dry purge time	8.0 minutes

Desorb time	4.0 minutes

Bake time	8.0 minutes

Purge pressure	20 psi

Purge flow	40 mL/minute

Valve temperature	110 °C

Transfer line temperature	110 °C

Desorb temperature	210 °C

Bake temperature	250 °C

7.2.2 Gas Chromatographic Operating Conditions:

Initial temperature
Initial time
Ramp

Intermediate temp.
Hold time
Ramp

Intermediate temp.
Hold time
Ramp

Final temperature
Analytical column

35 °C
3 minutes
3 °C/minute
77 °C
3 minutes
3 °C/minute
94 °C
3 minutes
10 °C/minute
175 °C

DB-624, 30 meters, 0.53 mm ID, fused silica
megabore capillary

7.2.3 Photoionization Detector Operating Conditions:

Base
Lamp

200 °C
10 ev

7.2.4 Hall Electrolytic Conductivity Detector Operating Conditions:

Reactor

Solvent, n-propanol
Hydrogen
Reaction tube

850 °C

0.50 mL/minute
90 mL/minute
nickel

7.2.5 Data System Operating Conditions: Information not available.

7.3 Calibration

7.3.1 Primary Standards: Primary calibration standards are prepared from purchased solutions described
in Section 5.3. The concentration of each of the VOC mixes is 2000 ug/mL; the concentration of the
dichlorobenzene standards is 5000 ug/mL; and the concentration of Purgeable C is 200 ug/mL.

FMC-VS-007-5

-------
7.3.2 Secondary Standards: Secondary calibration standards are prepared by dilution of the primary
standards in methanol.

7.3.2.1 Secondary VOC Standard Mixes: A 10-mL volumetric flask is filled halfway with
methanol and 1-mL of each of the VOC mixes is added. The flask is brought to volume. The
concentration of the Secondary VOC Mix Standard is 200 ug/mL. It may be stored up to six months or
until analyte losses are noted.

7.3.2.2 Secondary Dichlorobenzene Standard: A 25-mL volumetric flask is filled more than
halfway with methanol and 1-mL of each of the dichlorobenzene primary standards is added. The flask
is brought to volume. The concentration of the Secondary Dichlorobenzene Standard is 200 ug/mL. It
may be stored up to six months or until analyte losses are evident by decreases in analyte response factors.

7.3.2.3 Secondary Purgeable C Standard: Purgeable C contains the gaseous compounds in solution
at 200 ug/mL and is used to prepare the working standards without additional dilution. This solution is
transferred to a 1-mL autosampler vial and stored in the freezer. A new Purgeable C standard is used each
week.

7.3.2.4 Secondary Standards for Other Analvtes: The final concentration of all secondary
standards should be 200 ug/ml.

7.3.3 Working Standards: Working standards are prepared by dilution of the secondary calibration
standards. To produce each of the aqueous calibration standards, three aliquots of the secondary calibration
standards are diluted according to Table 3. The working standards are stored in autosampler vials sealed with
Teflon lined caps and with minimal headspace. Working standards are prepared on a weekly basis or sooner
if there is a notable decrease in the response of any analyte.

7.3.4 Aqueous Calibration Standards: Based on a 200 ug/mL secondary calibration standard
concentration and a 10-uL addition of the working calibration standard to 5-mL purge water volumes, the
calibration levels are 2, 5, 10, 20, and 40 ug/L. Other calibration ranges may be used as long as linearity of
response is maintained and a constant volume of methanol carrier, not to exceed 100 ul, is used for each
calibration level.

7.3.5 Surrogate Standards: A aliquot of a surrogate standard is added to every standard, field sample, and
blank to monitor system performance.

7.3.5.1 Water and Low Level Soil Surrogate Standard:

7.3.5.1.1 The stock surrogate solution is at a concentration of 2000 ug/mL. In a manner
analogous to the preparation of the secondary calibration standards, dilute the primary surrogate
standard with reagent methanol to a 10-mL final volume at 200 ug/mL.

7.3.5.1.2 Prepare a 1-mL working solution in methanol by addition of 50 uL of the
secondary surrogate standard to 950 uL of methanol. A 10-uL aliquot of the surrogate working
solution to 5 mL of an aqueous calibration standard, reagent water and field sample (low level soil
or water) will produce a final concentration of 20 ug/L.

7.3.5.2 High Level Soil Surrogate Standard:

7.3.5.2.1 High level soil samples are spiked prior to extraction at a level of 10 ug/mL in
a 10-mL extract volume with surrogate. A 50 uL aliquot of the secondary surrogate standard is
used. A 100-uL aliquot of the extract is removed for purge and trap analysis. The final surrogate
concentration is 20 ug/L in a 5-mL purge volume.

FMC-VS-007-6

-------
7.3.6 Laboratory Control Sample:

7.3.6.1 The stock laboratory control solutions are at concentrations of 2000 ug/mL. In a manner
analogous to the preparation of the secondary calibration standards, dilute the primary surrogate standard
with reagent methanol to a 10-mL final volume at 200 ug/mL.

7.3.6.2 Prepare a 1-mL working solution in methanol by addition of 50 uL of the secondary
surrogate standard to 950 uL of methanol. A 10-uL aliquot of the laboratory control working solution to
5 mL of reagent water will produce a final concentration of 20 ug/L.

7.3.7 Matrix Spike Standard:

7.3.7.1 Aqueous Samples and Low Level Soils:

7.3.7.1.1 The stock matrix spike solution is at a concentration of 2000 ug/mL. In a
manner analogous to the preparation of the secondary calibration standards, dilute the primary
surrogate standard with reagent methanol to a 10-mL final volume at 200 ug/mL.

7.3.7.1.2 Prepare a 1-mL working solution in methanol by addition of 50 uL of the
secondary surrogate standard to 950 uL of methanol. A 10-uL aliquot of the matrix spike working
solution to 5-mL sample volume will produce a final concentration of 20 ug/L.

7.3.7.2 High Level Soil:

7.3.7.2.1 High level soil samples are spiked at a level of 10 ug/mL in a 10 mL extract
volume with surrogate prior to methanol extraction. A 50 uL aliquot of the secondary matrix spike
standard is added to the 10 mL extract. A 100-uL aliquot of the extract is removed for purge and
trap analysis. The final matrix spiking concentration is 20 ug/L in a 5-mL purge volume.

FMC-VS-007-7

-------
Table 3

PREPARATION OF CALIBRATION WORKING STANDARDS

Aliquot of each 200
ug/mL Secondary
Calibration Standard

Total Volume
of Standard (3
aliquots)

Volume of
Diluent to
Produce 1-mL
Final Volume

Final Concentration of
Working Calibration
Standard

Concentration in 5
mL of Reagent
Water (10 uL
standard spike)

5 uL

15 uL

985 uL

1 ug/mL

2 ug/L

10 uL

30 uL

970 uL

2 ug/mL

4 ug/L

25 uL

75 uL

925 uL

5 ug/mL

10 ug/L

50 uL

150 uL

850 uL

10 ug/mL

20 ug/L

100 uL

300 uL

700 uL

20 mg/mL

40 ug/L

7.4 Sample Analysis

7.4.1 Water Sample Analysis:

7.4.1.1 Water samples are poured into a capped 5-mL Luer lock syringe. Once the syringe barrel
is completely filled, the plunger is inserted and the volume adjusted to 5 mL. The barrel is withdrawn
slightly and 10 uL of surrogate spiking standard is added through the luer tip of the syringe. The sample
is injected onto the purge and trap by attaching the luer tip to the sample introduction valve.

7.4.2 Soil Sample Analysis:

7.4.2.1 Low Level Sample Analysis: Low level soils are purged directly. Place approximately
1 gram of soil into a soil sparging tube. The sparge tube is installed on the concentrator and 5 mL of
reagent water spiked with 10 uL of water surrogate spiking solution is added through the sample
introduction valve.

7.4.2.2 High Level Soil Analysis: For samples which contain high levels of volatile compounds,
a methanol extraction is used. Four grams of soil are placed into a pretared vial and 10 mL of reagent
methanol and 100 uL of soil surrogate spiking solution are added. The vial is briefly agitated and an
aliquot of the extract is placed into a 1-mL vial with no headspace. (The 1-mL vial may be refrigerated
until analysis). A 100-uL aliquot of the methanolic extract is placed into a 5-mL portion of reagent water
through the luer tip of a 5-mL syringe. The aqueous sample is then placed into the purge and trap sparge
vessel and analyzed.

7.4.3 Quality Control fOC) Sample Analysis: A 5-mL sample volume is used for each QC sample. To
each QC sample 10 uL of surrogate spiking solution is added prior to analysis. Analyze each QC sample in the
manner described in Section 7.4.1 for water sample analysis.

7.4.3.1 Blank analysis is performed once each 24-hour period and after each high concentration
sample to monitor and prevent carryover.

7.4.3.2 Initial Calibration Standard analysis is performed at the beginning of each assignment and
when analytical conditions have changed to the extent that the continuing calibration standard no longer
meets quality control criteria. Initial calibration levels are 2, 4, 10, 20 and 40 ug/L. Other initial
calibration levels may be used as needed to bracket field sample concentrations.

FMC-VS-007-8

-------
7.4.3.3 Continuing Calibration Standard analysis is performed once each 24- hour period at a level
equal to the midpoint calibration standard.

7.4.3.4 Laboratory Control Saample analysis is performed after each initial and continuing
calibration, and after each group of 10 samples.

7.4.3.5 Matrix Spike and Spike Duplicate analyses are performed at a frequency of one set per 20
samples or one set per week.

7.5 Compound Identification: A retention time window of ± 0.75% is used to estimate analyte retention time.
Presence of a peak at a retention time ± 0.75% the retention time of an analyte in the daily calibration constitutes a
positive identification.

7.6 Compound Quantitation: Response factors are calculated as the ratio of the concentration of the analyte to
the area of the analyte peak in the daily standard. Concentration of the analyte in the sample is calculated by
multiplication of the response factor by the area of the analyte in the sample chromatogram.

8.0 QUALITY CONTROL

8.1 Because the mission of the FASP mobile laboratory is to provide quick turnaround analyses, some QC
requirements are advisory and, if they are not met, no corrective action will be taken, unless it is evident that a
significant malfunction or error has occurred. The acceptance requirements for blank, initial and continuing
calibration and laboratory control sample results are not advisory, and if the criteria for these analyses are not met,
corrective action will be taken and the acceptance criteria met, prior to analysis of field samples. The remaining QC
analyses are provided for the purposes of data evaluation. The acceptance criteria for surrogate recovery and matrix
spike and spike duplicate analyses are advisory.

8.2 Blanks: Blanks may not contain more than reporting limit of any target analyte.

8.3 Initial Calibration: The average relative percent difference (RPD) for the initial calibration must not exceed
25% for the site specific target compounds.

8.4 Daily Calibration: The percent difference between the response factor obtained from the daily calibration
and the average response factor from the initial calibration must not be greater than 25% for the site specific target
compounds.

8.5 Laboratory Control Sample: The recovery of analytes in the Laboratory Control Sample must be between
80% and 120%.

8.6 Surrogates: The recovery of surrogates must be between 75% and 125% for aqueous samples and 65%-
130%i for soils. Samples in which surrogates are below the 75% or 65% criteria are rerun if there is additional sample
available.

8.7 Matrix Spike and Spike Duplicate Analysis: The recovery of matrix spike compounds should be 70% to
125%i for waters and 65% to 130% for soils. The relative percent difference criteria between the spike duplicates are
25% for waters and 50% for soils. The FASP matrix spike QC limits are advisory, and unless

FMC-VS-007-9

-------
Summary of FASP Quality Control Requirements

QC Sample

Acceptance Criteria for Whole Gas Samples

Frequency

Blank

Less than reporting limit of all target analytes

1 blank analysis each 24 hours

Initial Calibration

Relative Standard Deviation < 25% for
average analyte concentration factors

As necessary

Continuing Calibration

Percent Difference for concentration factors
compared to initial calibration < 25%

1 Continuing Calibration each
24 hours

Laboratory Control
Sample

70%-125%

After each successful calibration
and each 10 samples

Surrogates

65%-130%

Every analysis

Matrix Spike and Spike
Duplicate

Recovery: 65%-130%
Precision: RSD <50%

1 set per each 20 field samples
analyzed or weekly

a site specific requirement, no reanalysis of matrix spike samples will be made in cases where QC criteria are not met.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1.	EPA Method 8021: Volatile Organic Compounds in Water bv Purge and Trap Capillary Column Gas
Chromatography with Photoionization and Electrolytic Conductivity Detectors Operated in Series

2.	EPA Method 5030: Purge and Trap

3.	EPA Method 8000: Gas Chromatography

These references are from Test Methods for Evaluating Solid Wastes. Physical/Chemical Methods. SW-846.
3rd Edition. Final Update 1. 1991 and are provided in Appendix A.

FMC-VS-007-10

-------
FASP Method Number F080.008
VOLATILE ORGANICS IN SOIL GAS - ADSORBENT TUBE METHOD

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various volatile organic compounds (VOCs) in soil gas samples, employing desorption technology
and gas chromatography (GC).

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 A soil gas sample tube is desorbed at 200°C for 5 minutes with helium to desorb all VOCs directly onto
a packed glass column or a megabore column installed in a temperature-programmed GC. VOCs are detected with
a photoionization detector (PID) and a Hall electrolytic conductivity detector connected in series. Quantitation and
identification are based on relative peak areas and relative retention times using the internal standard method.

3.0 INTERFERENCES

3.1 Impurities in the purge gas, outgassing of organic compounds from the plumbing ahead of the trap, and
solvent vapors in the laboratory account for the majority of contamination problems. The analytical system must be
demonstrated to be free from contamination under the conditions of the analysis by running laboratory reagent blanks.
The use of non-Teflon tubing, non-Teflon thread sealants, or flow controllers with rubber components in the purging
device should be avoided.

3.2 Contamination by carryover can occur whenever high level samples are analyzed. Whenever an unusually
concentrated sample is encountered, it should be followed by an analysis of a blank sample tube to check for cross-
contamination. The trap and other parts of the system are also subject to contamination; therefore, frequent bakeout
and purging of the entire system may be required between each analysis.

3.3 The volatile analysis laboratory should be as completely free of interfering solvents as possible.

3.4 Interferences coextracted from samples are matrix and site specific. It is possible that techniques
employed in either FASP or Routine Analytical Services (RAS) CLP methods may fail to eliminate interferences.
Highly specialized CLP Special Analytical Services (SAS) techniques may be required to produce acceptable
analytical results.

FMC-VG-001-1

-------
Table 1

FASP METHOD F080.008 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit
in Soil Gas**
(ng)

T richlorofluoromethane

75-69-4

20

1,1 -Dichloroethene

75-35-4

20

Methylene chloride

75-09-2

20

trans-1,2-Dichloroethene

540-59-0

20

1,1 -Dichlorethane

75-34-3

20

Chloroform

67-66-3

40

1,1,1 -Trichloroethane

71-55-6

20

Carbon tetrachloride

56-23-5

20

Benzene

71-43-2

20

1,2-Dichloroethane

107-06-2

20

Trichloroethene

79-01-6

20

1,2-Dichloropropane

78-87-5

20

Bromodichloromethane

75-25-4

20

cis-1,3 -Dichloropropene

10061-01-5

20

T oluene

108-88-3

20

trans-1,3 -Dichloropropene

10061-02-5

20

1,1,2-Trichloroethane

79-00-5

20

T etrachloroethene

127-18-4

20

(continued on next page)

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for
guidance and may not always be achievable.

** Quantitation limits are listed as nanograms (ng) injected. Actual concentrations will vary depending on the
volume of soil gas sampled.

FMC-VG-001-2

-------
Table 1 (continued)

FASP METHOD F080.008 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit
in Soil Gas**
(ng)

Dibromochloromethane

124-48-1

Chlorobenzene

108-90-7

Ethylbenzene

100-41-4

m,p-Xylenes

1330-20-7

o-Xylene

1330-20-7

Bromoform

75-25-2

1,1,2,2-T etrachloroethane

79-34-5

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for
guidance and may not always be achievable.

** Quantitation limits are listed as nanograms (ng) injected. Actual concentrations will vary depending on the
volume of soil gas sampled.

4.0 APPARATUS AND MATERIALS
4.1 Analytical Systems

4.1.1 Gas chromatograph: An analytical system complete with a temperature-programmable GC suitable
for on-column injection is required. All necessary accessories including injector and detector systems must be
designed or modified to accept the appropriate analytical columns (packed or megabore capillary). The system
shall have a data handling system attached to the detectors that is capable of retention time labeling, relative
retention time comparisons, and providing relative and absolute peak height and/or peak area measurements.

4.1.1.1 Column 1: 1.8 m x 3 mm I.D. glass column packed with 1% SP-1000 on Carbopack B
(60/80 mesh), or equivalent.

4.1.1.2 Column 2: 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column (J&W
Scientific), or equivalent.

4.1.1.3 Detectors: PID with a 10.2 eV lamp and a makeup gas supply at the detector inlet should
be connected in series to a Hall detector with a short length of deactivated fused silica capillary column.

FMC-VG-001-3

-------
4.1.1.4 Gas supply: The purge gas, carrier gas, and makeup gas should be ultrapure helium. The
reaction gas required for the Hall detector is ultrapure hydrogen. All gases should pass through oxygen
traps prior to the analytical system to prevent degradation of the column's analytical coating.

4.1.2 Desorption device: Several desorbers can be utilized as long as the appropriately sized adsorbent
tube is used and meets the sampling requirements. This method utilizes a Tekmar purge and trap device to
desorb samples directly onto the GC column. Several other complete devices are commercially available.

4.1.2.1 Desorption unit: A thermal desorption attachment (Tekmar, or equivalent) capable of
heating to at least 200°C and able to accept a 6 mm O.D. x 11 cm long soil gas sample tube with 7 cm
of packing material is required.

4.1.2.2 Trap: The trap must be packed with the appropriate adsorbent material(s) to collect VOCs
from the soil gas sample tube.

4.1.2.3 Desorber: The desorber should be capable of rapidly heating the trap to 180°C. The trap
should not be heated higher than 220°C during the bakeout mode.

NOTE: The desorption device may be assembled as a separate unit or coupled to a GC.

4.2 Other Laboratory Equipment

4.2.1 Soil gas sample tubes: Supelco Carbotrap 300, or equivalent, with appropriate packing to adsorb
target analytes. Soil gas sample tubes should be pre-cleaned before use by purging with nitrogen in a drying
oven at 125°C for 15 minutes. The nitrogen flow direction should be opposite of the sampling flow. The soil
gas tube should then be capped and stored in a desiccator.

4.2.2 Microsvringes: lO-^L, 25-(iL, and larger.

4.2.3 Vials: 1.8-mL for purgeable standards with Teflon-lined septa.

4.2.4 Drying oven: Capable of maintaining a temperature of 180°C.

4.2.5 Desiccator: Glass and stainless steel (no plastic materials).

4.2.6 Oxygen traps: Supelpure-O-Trap and OM-1 indicating tube, or equivalent.

4.2.7 Leak detector: Snoop liquid, or equivalent, for packed column operations or GOW-MAC gas leak
detector, or equivalent, for megabore capillary operations.

4.2.8 Chromatographic data stamps: Used to record instrument operating conditions if not provided by
data handling system.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

FMC-VG-001-4

-------
5.0 REAGENTS

5.1 Solvents

5.1.1 1-Propanol: Pesticide quality, or equivalent.

5.1.2 Methanol: Pesticide quality, or equivalent.

5.2 Reagent Water: Reagent water is defined as water in which an interferent is not observed as the QL of
the analyte of interest. Reagent water may be generated using a carbon filter bed containing activated carbon (Calgon
Corporation, Filtrasorb-300, or equivalent) or a water purification system (Milli-Q Plus with Organex Q cartridge,
Barnstead Water-1 Systems [provided with the Base Support Facilities], or equivalent), or purchased from commercial
laboratory supply houses.

5.3 Gases

5.3.1 Helium: Ultrapure or chromatographic grade (always used in conjunction with an oxygen trap).

5.3.2 Hydrogen: Ultrapure or chromatographic grade (always used in conjunction with an oxygen trap).

5.3.3 Nitrogen: Ultrapure or chromatographic grade (always used in conjunction with an oxygen trap).

5.4 Stock Standard Solution: Stock standard solutions in methanol should be purchased as manufacturer-
certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with methanol. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard concen-
tration should define the approximate working range of the GC: one at the upper linear range and the other midway
between it and the lowest standard. Calibration standards are injected directly into the soil gas tube packing material
for analysis. All calibration standards must be stored at 4°C in Teflon-sealed glass bottles. Calibration standard
solutions must be replaced after 6 months, or whenever comparison with check standards indicates a problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

5.7 Internal Standards

5.7.1 The 3 internal standards used are fluorobenzene, bromochloromethane, and p-bromofluorobenzene.
An internal standard mix should be prepared through volumetric dilution of individual stock standards with
methanol. It is recommended that the secondary dilution standard be prepared at a concentration of 200 ng/mL
of each internal standard compound. The addition of 2 (iL of this standard directly into the soil gas tube packing
material would be equivalent to 400 ng.

5.7.2 All standards must be stored in a freezer in glass vials with Teflon-lined septa and be protected
from light. Internal standard solutions must be replaced weekly after the Teflon-lined septum has been
punctured, or sooner, if comparison with previous analyses indicates a problem.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

FMC-VG-001-5

-------
appropriate volumes and sampling rates to prevent breakthrough of target analytes, then capped and shipped on ice
in insulated containers to prevent breakage of the tubes during transport.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for VOCs in soil gas is 24 hours from
sampling to analysis; however, it is recommended to analyze the samples as soon as possible.

7.0 PROCEDURE

7.1 Calibration

7.1.1 Initial calibration:

7.1.1.1 Calibrate the GC by the internal standard technique (Section 7.4) after an experienced
chromatographer has ensured that the entire chromatographic system is functioning properly; that is,
conditions exist such that resolution, retention times, response reporting, and interpretation of
chromatograms are within acceptable quality control (QC) limits. Using at least 3 calibration standards
prepared as described in Section 5.5, generate initial calibration curves (relative response versus mass of
standard injected) for each target analyte (refer to Sections 7.2 and 7.3 for chromatographic procedures).

7.1.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.4) based on each
target compound's 3 relative calibration factors (RCFs, see Section 7.4) to determine the acceptability
(linearity) of the curve. Unless otherwise specified, the %RSD must be less than or equal to 25 percent,
or the calibration is invalid and must be repeated. Establish a new initial calibration curve anytime the
GC system is altered (e.g., new column, change in gas supply, change in oven temperature) or shut down.

7.1.2 Continuing calibration:

7.1.2.2 Use the continuing calibration in all sample concentration calculations (Section 7.4) for
the period over which the calibration has been validated.

7.1.3 Final calibration: Obtain the final calibration at the end of each batch of samples analysed. The
maximum allowable RPD between the mean initial calibration and final calibration RCF s for each target analyte
must be less than or equal to 50 percent. A final calibration that achieves an RPD less than or equal to 25
percent may be used as an ongoing continuing calibration.

7.2 Sample Desorption

7.2.1 The sample desorption technique for VOCs in soil gas is as follows. This procedure is
recommended for the Tekmar LSC-1 (upgraded), LSC-3, and LSC-2000 purge and trap systems. Specific purge
and trap system procedures and parameters may be found in Appendices A and B.

7.2.1.1 Remove the caps from both ends of the soil gas sample tube.

FMC-VG-001-6

-------
7.2.1.2 Inject the internal standard mix into the soil gas sample tube packing material.

7.2.1.3 Immediately place the soil gas sample tube through the thermal desorber and attach it
directly to the sample and purge lines so that the gas flow is opposite of the sampling flow.

7.2.1.4 Make sure the trap temperature is 30°C or less. Thermally desorb the soil gas tube at
200°C onto the trap for 5 minutes.

7.2.1.5 The trapped sample is ready to be desorbed.

7.2.1.6 The purged sample may be preheated to 60°C on the trap, and is desorbed at 160°C to
180°C for 4 minutes. The GC system begins data collection and temperature program concurrently with
sample desorption.

7.2.1.7 After the sample is desorbed, return the purge and trap system the purge mode, and bake
the trap with a clean soil gas sample tube in line. Gas should flow through the trap during the bake, and
the trap should be heated to 200°C for at least 5 minutes.

7.2.1.8 After baking the trap, allow it to cool to 30°C before removing it and desorbing the next
sample.

7.2.1.9 Following sample desorption, decontaminate the soil gas tube by purging with nitrogen
in a drying oven at 125°C for 15 minutes. The nitrogen flow direction should be opposite of the sampling
flow. Cap the soil gas tube and store in a desiccator until needed for sampling.

7.3 Instrumental Analysis

7.3.1 Instrument parameters: Table 2 summarizes acceptable operating conditions for the GC. Other
instruments, columns, and/or chromatographic conditions may be employed only if this method's QC criteria
are met.

7.3.2 Chromato grams:

FMC-VG-001-7

-------
Table 2

	EXAMPLE OF TEMPERATURE PROGRAM GC OPERATING CONDITIONS	

Purge and Trap Device: Tekmar LSC-1 liquid sample concentrator with upgrade package, thermal desorber

attachment, and heated transfer line. (Trap composition: 1 cm 3% SP-2100, 15 cm
Tenax, and 8 cm silica gel 15.)

Instrument:	Shimadzu GC Mini-3 equipped with an HNu systems PID with a 10.2 eV lamp

connected in series to an O.I. Corporation Hall detector.

Integrator:	Nelson Analytical PC integrator with a dual-channel interface and 30-MB hard disk drive for data

storage.

Column:	J&W DB-624 fused silica megabore column, 30 m x 0.53 mm I.D.

Carrier Gas:	Ultrapure helium, lOmL/min.

Makeup Gas:	Ultrapure helium, 40 mL/min.

Reaction Gas:	Ultrapure hydrogen, 100 mL/min.

Column Oven:	Initial temperature: 35°C.

Initial time: 4 minutes.

Ramp rate: 4°C/min.

Final temperature: 105°C.

Injector Temperature:
Detector Temperature:

150oC.

PID: 200oC.
Hall: 800°C.

GC Analysis Time:

20 minutes.

FMC-VG-001-8

-------
7.3.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.3.3 VOC identification:

• Column packing, coating, length, and ID;

7.3.3.1 Qualitative identification of target VOCs is based on both detector selectivity and relative
retention time as compared to known standards using the internal standard method.

7.3.3.2 For a compound which is detected on both the PID and Hall detector, the compound must
be identified in both chromatograms for a positive identification to be made.

7.3.3.3 Generally, individual peak relative retention time windows should be less than or equal
to 5 percent for packed columns or less than or equal to 2 percent for megabore capillary columns.
Alternatively, the individual peak relative retention time windows may be calculated based on 3 times the
standard deviation of at least 3 nonconsecutive standard analyses. These analyses must be representative
of normal system variations, subject to the professional judgement of an experienced analyst.

7.3.3.4 It may not be possible or practical to separate all VOC target analytes on a single column.
In such cases, these target analytes should be denoted as the appropriate combination of VOCs.

7.3.4 System performance: Degradation of VOCs may occur in the GC system, especially if the injector
or column inlet is contaminated.

7.3.5 Specific instrument parameters: Specific instrument operating parameters that have been used are
provided as "Specific Instrument Parameters" in Appendix B of this method.

7.3.6 Analytical sequence:

7.3.6.1 Instrument blank.

7.3.6.2 Initial calibration.

7.3.6.3 Check standard solution and/or performance evaluation sample (if available).

7.3.6.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.3.6.5 Associated QC lot method blank.

7.3.6.6 Twenty samples and duplicates.

7.3.6.7 Repeat sequence beginning at step 7.3.6.5 until all sample analyses are completed or
another continuing calibration is required.

7.3.6.8 Final calibration when all sample analyses are complete.

FMC-VG-001-9

-------
7.4 Calculation

7.4.1	Identification and quantitation of target VOCs should be based on the internal standard method.
The corresponding internal standards for each target compound are listed in Tables 3 (PID) and 4 (Hall detector).
A compound which is detected by both the PID and Hall detector should be quantitated using the detector which
gives the higher response for that specific compound. The second detector should be used for confirmation of
the presence of that compound.

7.4.2	The peak areas of the internal standards should be monitored and evaluated for each standard
sample, blank and duplicate. If the peak area for any internal standard changes by more than a factor of 2 (-50
to +100 percent), the sample must be reanalyzed. If after reanalysis the peak areas for all internal standards are
inside the QC limits (-50 to +100 percent), only report data from the analysis with peak areas within the QC
limits. If the reanalysis of the sample does not solve the problem for both analyses, then do not report sample
data.

7.4.3	Initial calibration:

7.4.3.1	Analyze each calibration standard, adding the calibration solutions and the internal
standard spiking solution directly onto the blank soil gas tube. Tabulate the area response of each target
analyte against the amount injected in nanograms (ng) for each compound and internal standard, and
calculate the RCF for each target compound using the following equation.

A C.

RCF = —- x —

A. C

IS	X

where: Ax = Area of the peak for the compound of interest.

Ais = Area of the peak for the appropriate internal standard.

Cis = Amount of the internal standard injected (ng).

Cx = Amount of the compound to be measured (ng).

7.4.3.2	Using the RCF values, calculate the %RSD for each target analyte at all concentration
levels using the equation below.

ST)

%RSD = 4=- x 100

X

where SD, the standard deviation, is given by

\

SD

i

1=1

(X. - X):
N - 1

where: X; = Individual RCF (per analyte)

X = Mean of all initial RCF s (per analyte)
N = Number of calibration standards

FMC-VG-001-10

-------
Table 3

VOLATILE ORGANIC COMPOUNDS DETECTED BY THE PID
AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS2 (Fluorobenzene)

IS3 (p-Bromofluorobenzene)

1,1 -Dichloroethene

T oluene

trans-1,2-Dichloroethene

trans-1,3 -Dichloropropene

Benzene

T etrachloropropene

Trichlorethene

Chlorobenzene

2-Chloroethylvinylether

Ethylbenzene

cis-1,3 -Dichloropropene

o,p-Xylene



m-Xylene

Table 4

VOLATILE ORGANIC COMPOUNDS DETECTED BY THE HALL DETECTOR
AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS1 Bromochloromethane

IS3 (p-Bromofluorobenzene)

T richlorofluoromethane

cis-1,3 -Dichloropropene

1,1 -Dichloroethene

trans-1,3 -Dichloropropene

Methylene chloride

1,1,2-Trichloroethane

trans-1,2-Dichloroethene

T etrachloroethene

1,1 -Dichloroethane

Dibromochloromethane

Chloroform

Chlorobenzene

1,1,1 -Trichloroethane

Bromoform

Carbon tetrachloride

1,1,2,2-T etrachloroethane

1,2-Dichloroethane



Trichloroethene



1,2-Dichloropropane



Bromochloromethane



FMC-VG-001-11

-------
7.4.3.3 The %RSD must be less than or equal to 25 percent.

7.4.4 Continuing calibration:

7.4.4.1 Sample quantitation is based on analyte RCF values calculated from continuing
calibrations. Midrange standards for all initial calibration target analytes must be analyzed as continuing
calibration standards at specified intervals (less than or equal to 24 hours).

7.4.4.2 The maximum allowable RPD calculated using the equation below for each analyte is less
than or equal to 25 percent.

\RCF~ ~ RCF \

RPD = 1 — x 100

RCFI + RCFc

where: RCF, = Mean RCF from the initial calibration for each analyte

RCFc = Measured RCF from the continuing calibration for the same analyte

7.4.5 Final calibration:

7.4.5.1 Obtain the final calibration at the end of each batch of samples analyzed.

7.4.5.2 The maximum allowable RPD between the mean initial calibration and final calibration
RCF values for each target analyte must be less than or equal to 50 percent. A final calibration which
achieves an RPD less than or equal to 25 percent may be used as an ongoing continuing calibration.

RCF - RCF

RPD = 1 — x 100

RCFI + RCFf

where: RCF, = Mean RCF from the initial calibration for each analyte

RCFf = Measured RCF from the final calibration for the same analyte

7.4.6 Sample quantitation:

7.4.6.1 Calculate the concentration in the sample using the following equation for internal
standards. The relative response can be measured by automated relative peak height or relative peak area
measurements from an integrator.

7.4.6.2 Use the RCF from the continuing calibration analysis to calculate the concentration in
the sample. Use the RCF as determined in Section 7.4.4 and the following equation.

(A ) (I )

Concentration (nq/L) = -

U.s) (RCF) (Vo)

where: Ax = Area of the peak for the compound to be measured

Ais = Area of the peak for the specific internal standard from Table 3 or 4

Is = Amount of internal standard added in nanograms (ng)

V0 = Volume of soil gas collected onto soil gas sample tube in liters (L)

RCF = The RCF from the continuing calibration for the compound of interest

FMC-VG-001-12

-------
7.4.6.3 Report results in nanograms per liter (ng/L) without correction for the blank
concentration.

7.4.6.4 Coeluted analytes should be quantitated and reported as the combination of the
unseparated target analytes.

7.4.6.5 Sample chromatograms may not match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum possible
concentration (qualified as less than the numerical value) which allows the data user to determine if
additional work (e.g., CLP analyses) is required, or, if the reported concentration is below action levels
and project objectives and DQOs have been met, to forego further analysis.

7.4.6.6 Similarly, when sample concentration exceeds the linear range, the analyst may report
a probable minimum level (qualified as greater than the numerical value) which allows the data user to
determine if additional (e.g., CLP analyses) work is required, or, if the reported concentration is above
action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. Spiked samples and laboratory duplicate samples
cannot be analyzed by this method because the entire sample is consumed during analysis. However, field duplicate
samples may be collected simultaneously or in succession to determine field precision and RPD. Advisory limits for
field duplicate RPD are presented in Table 5. This method should be used in conjunction with the quality assurance
and control (QA/QC) section of this catalog.

FMC-VG-001-13

-------
Table 5

DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.008 (VOCs in Soil Gas - Adsorbent Tube Method)

Advisory Quality Control Limits*

Analyte

Duplicate RPD
(%)

T richlorofluoromethane

± 100

1,1 -Dichloroethene

± 100

Methylene chloride

± 100

trans-1,2-Dichloroethene

± 100

1,1 -Dichlorethane

± 100

Chloroform

± 100

1,1,1 -Trichloroethane

± 100

Carbon tetrachloride

± 100

Benzene

± 100

1,2-Dichloroethane

± 100

Trichloroethene

± 100

1,2-Dichloropropane

± 100

Bromodichloromethane

± 100

cis-1,3 -Dichloropropene

± 100

T oluene

± 100

trans-1,3 -Dichloropropene

± 100

1,1,2-Trichloroethane

± 100

T etrachloroethene

± 100

(continued on next page)

* If the concentration of a target analyte is less than 5 times the quantitation limit, advisory control limits for
duplicate RPD values become ±3 times the quantitation limit for that individual analyte.

FMC-VG-001-14

-------
Table 5 (continued)

DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.008 (VOCs in Soil Gas - Adsorbent Tube Method)

Analyte

Duplicate RPD
(%)

Dibromochloromethane

± 100

Chlorobenzene

± 100

Ethylbenzene

± 100

m,p-Xylenes

± 100

o-Xylene

± 100

Bromoform

± 100

1,1,2,2-T etrachloroethane

± 100

* If the concentration of a target analyte is less than 5 times the quantitation limit, FASP advisory control limits
for duplicate RPD values become ±3 times the quantitation limit for that individual analyte.

FMC-VG-001-15

-------
9.0 METHOD PERFORMANCE

9.1 The following are examples of gas chromatograms for target analytes as detected by the PID and Hall
detectors.

Figure 1
Gas chromatogram A - PID

Column:

Column Temperature:

Detector Temperature:
Injector Temperature:
Gas:

J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Initial Temperature: 35°C.

Initial Time: 4 mins.

Ramp Rate: 4°C/min.

Final Temperature: 105°C.

150°C.

150°C.

Carrier: Ultrapure helium, 10 mL/min.

Makeup: Ultrapure helium, 40 mL/min.

Detector:

HNu PID with a 10.2 eV lamp.

FMC-VG-001-16

-------
Column:

Column Temperature:

Detector Temperature
Injector Temperature:
Gas:

Detector:

Figure 2

Gas chromatogram B - Hall detector

J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Initial Temperature: 35°C.

Initial Time: 4 mins.

Ramp Rate: 4°C/min.

Final Temperature: 105°C.

150°C.

150°C.

Carrier: Ultrapure helium, 10 mL/min.

Makeup: Ultrapure helium, 40 mL/min.
Reaction gas: Ultrapure hydrogen, 100 mL/min.

O.I. Corporation Hall detector.

FMC-VG-001-17

-------
Method F080.008 examples of sample OA/OC results:

(to be completed as data becomes available)

FMC-VG-001-18

-------
10.0 REFERENCES

Information not available.

FMC-VG-001-19

-------
Instrument Options:
Purge and Trap Device:

GC System:

Data Handling System 1
Data Handling System 2
Data Handling System 3

Data Handling System 4

APPENDIX A

FASP Method F080.008

Tekmar LSC-1 liquid sample concentrator with upgrade package, thermal
desorption attachment, and heated transfer line. (Trap composition: 1 cm 3%
SP-2100, 15 cm Tenax, and 8 cm Silica gel 15.)

Shimadzu GC Mini-3 (temperature-programmable) with an HNu PID connected
in series to an O.I. Corporation Hall detector modified with a direct conversion
and makeup gas adapter for megabore capillary column operations.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit
and Shimadzu FDD-1A floppy disk drive.

P.E. Nelson 2100 dual-channel integrator with 960 Series Intelligent Interface,
Hyundai 80286 computer, and Epson LX800 printer.

FMC-VG-001-20

-------
APPENDIX B

FASP Method F080.008

Specific Instrument Parameters:

Purge and Trap Device:

Gas Chromatograph:

Integrator:

Columns:

Carrier Gas:

Makeup Gas:

Reaction Gas:
Temperature Program:

Detector Temperature:
Injector Temperature:

Tekmar LSC-1 liquid sample concentrator with upgrade package, thermal
desorption attachment, and heated transfer line. (Trap composition: 1 cm 3%
SP-2100, 15 cm Tenax, and 8 cm Silica gel 15.)

Shimadzu GC Mini-3 (temperature-programmable) with an HNu PID connected
in series to an O.I. Corporation Hall detector.

Shimadzu Chromatopac C-R3A data processor

J&W 30 m x 0.53 mm DB-624 fused silica megabore capillary column.

Ultrapure helium, 10 mL/min.

Ultrapure helium, 40 mL/min.

Ultrapure hydrogen, 100 mL/min.

Initial Temperature: 35°C.

Initial Time: 4 mins.

Ramp Rate: 4°C/min.

Final Temperature: 105°C.

150oC.

150oC.

FMC-VG-001-21

-------
FASP Method Number F080.009
VOLATILE ORGANICS IN SOIL GAS USING

ELECTROLYTIC CONDUCTIVITY DETECTOR - DIRECT ANALYSIS

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining relative
concentrations of halogenated volatile organic compounds (VOCs) in soil gas. The method employs direct analysis
of soil gas samples by gas chromatographic (GC) analysis using a Hall electrolytic conductivity detector (ELCD).

1.2 This method yields tentative identification and estimated quantitation of the analytes listed in Table 1.
Approximate method quantitation limits (QLs) are also listed in Table 1. Reported values are on an "as-received"
basis.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 A measured amount (usually 1 to 5 mL) of soil gas collected in a 1-L Tedlar bag or gas sample container
is injected into a GC equipped with a megabore capillary column and an ELCD. Halogenated VOCs are detected with
the ELCD. Quantitation and identification are based on comparison of retention times and relative peak areas
between samples and standards. Quantitation is based upon the external standard method.

2.2 This method should be used as a screening method only. The reasons for this are as follows:

2.2.1 Mathematical assumptions yield results that are only roughly equivalent to ppb values (Section

7.3).

2.2.2 Soil gas results cannot be converted directly to contaminant concentrations in groundwater or

subsurface soils.

2.2.3 Soil gas results should only be used to guide further confirmatory analyses. The results are

designated to show relative high and low concentrations that are internally consistent to the data set; that is, all

data are generated together using the analysis procedures as described in this method.

3.0 INTERFERENCES

3.1 Tedlar bags and gas sample containers can become contaminated if stored near standards or cleaning
solvents, elevated concentrations of solvents in ambient air, or contaminated soil gas sampling equipment. These
interferences can be avoided by not reusing Tedlar bags, or reduced by analyzing sampling containers before use to
insure that they are free of contamination.

FMC-VG-002-1

-------
Table 1

FASP METHOD F080.009 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit
in Soil Gas
(ng/L)

T etrachloroethene

127-18-4

1,1,2-Trichloroethane

79-00-5

Trichloroethene

79-01-6

1,2-Dichloroethene

540-59-0

1,2-Dichloropropene

78-87-5

1,1,2,2-T etrachloroethane

79-34-5

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for
guidance and may not always be achievable.

3.2 Several solvents elute simultaneously under certain conditions on the DB-624 column. This problem can
be alleviated by altering the temperature program.

3.3 Moisture can cause peak retention time shifts. Frequent bakeout of the GC may be necessary.

3.4 The ELCD may become saturated when analyzing high concentration samples. Increasing the column
temperature to 250°C for at least 30 minutes will bake out the contamination. Care should be taken that the detector
temperature is elevated above the column temperature. A syringe blank should be analyzed before any further
analysis of samples to ensure the complete bakeout of the column and detector.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System

4.1.1 Gas chromatograph: An analytical system complete with a temperature-programmable GC suitable
for on-column injection is required. All necessary accessories including injector and detector systems must be
designed or modified to accept the appropriate capillary columns. The system shall have a data handling system
attached to the detector that is capable of retention time labeling, relative retention time comparisons, and
providing relative and absolute peak height and peak area measurements.

4.1.1.1 Column 1: Vocol, 30 m x 0.53 mm I.D. fused silica megabore capillary column
(Supelco).

4.1.1.2 Column 2: DB-624, 30 m x 0.53 mm I.D. fused silica megabore capillary column (J&W
Scientific).

4.1.1.3 Detector: Hall ELCD (Tracor).

FMC-VG-002-2

-------
4.1.1.4 Gas supply: The carrier gas should be ultrapure helium. The detector gas should be
ultrapure hydrogen. All gases should pass through oxygen traps prior to the analytical system to prevent
degradation of the column coating.

4.2 Other Laboratory Equipment

4.2.1 Tedlar bags: 1-L.

4.2.2 Volumetric gas sample containers.

4.2.3 Syringes: 1-mL and 5-mL glass, gastight with replaceable needles.

4.2.4 Microsvringes: 10-^iL, 25-|iL, and larger.

4.2.5 Pipet: 10-mL, class A.

4.2.6 Safety bulb.

4.2.7 Standard vials: 15-mL, glass with Teflon-lined silicone septa.

4.2.8 Vortex mixer: Vortex Genie, or equivalent.

4.2.9 Oxygen traps: Supelpure-O-Trap and OM-1 indicating tube, or equivalent.

4.2.10 Leak detectors: GOW-MAC gas leak detector, or equivalent, for megabore capillary operations.

4.2.11 Activated carbon: Activated carbon to aid in keeping the mobile laboratory, standards, and
reagents free of solvent contamination.

4.2.12 Chromatographic data stamp: Used to record instrument operating conditions, if not provided by
the data handling system.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1 Solvent: Hexane, nanograde, or equivalent.

5.2 Reagent Water: Reagent water is defined as water in which an interferent is not observed at the QL of
the analyte of interest. Reagent water may be generated using a carbon filter bed containing activated carbon (Calgon
Corporation, Filtrasorb-300, or equivalent) or a water purification system (Milli-Q Plus with Organex Q cartridge,
Barnstead Water-1 Systems, or equivalent), or purchased from commercial laboratory supply houses.

FMC-VG-002-3

-------
5.3	Gases:

5.3.1	Helium: Ultrapure, or chromatographic grade (always used in conjunction with an oxygen trap).

5.3.2	Hydrogen: Ultrapure, or chromatographic grade (always used in conjunction with an oxygen trap).

5.4	Stock Standard Solutions: Stock standard solutions of the analytes and certified gas standards should be
purchased as manufacturer-certified solutions and standards.

5.5	Calibration Standards: Calibration standards at 3 concentration levels for each analyte of interest should
be prepared in 15-mL screw-cap vials with Teflon-lined silicone septa with 10 mL of hexane from neat solvent
solutions. A separate 10-(iL syringe is used for each neat solvent. The lowest concentration standard should be
approximately 2 times the QL as listed in Table 1. The remaining standard concentration should define the
approximate working range of the GC: one at the upper linear range and the other midway between it and the lowest
standard. All standards must be stored at 4°C in Teflon-sealed glass bottles. Calibration solutions must be replaced
after 6 months, or whenever comparison with check standards indicates a problem.

5.5.1 Liquid standards:

5.5.1.1 Preparation of 1000 ng/fiL standard:

5.5.1.1.1 In order to determine the amount of solvent to inject into 10 mL of hexane,
divide 10 mg by the density of the solvent (Table 2) using the equation:

10 mg	_ X i_i_L of solvent for

density of solvent	10 mg mass

(mg/]iL)

where X is the volume of solvent in (iL.

5.5.1.1.2 Inject the amount determined in 5.5.1.1.1 into 10 mL of hexane to achieve
a standard of 1,000 ng/(iL. The equation for a 1,000 ng/(iL standard is:

10 mg (10,000,000 ng) solvent

10 mL (10, 000 i_i_L) hexane

1,000 ng/L

5.5.1.2	Preparation of 1000 pg/fiL standard: Place 10 (iL of 1,000 ng/^L standard into 10 mL
of hexane.

5.5.1.3	Preparation of 100 pg/fiL standard: Place 1.0 (iL of 1,000 ng/^L standard into 10 mL of
hexane.

5.5.1.4	Preparation of 10 pg/fiL standard: Place 100 (iL of 1,000 pg/^L standard into 9.9 mL of
hexane.

NOTE: At times, the 10 pg/^L standard approaches the instrument detection limit and the GC

response is nonlinear. In this case, a 50 pg/^L standard is substituted.

FMC-VG-002-4

-------
Table 2

DENSITIES AND VOLUMES OF SELECTED
SOLVENTS USED TO PREPARE 1,000 ng/mL STANDARD

Compound (Solvent)

Density
(mg/nL)

(iL of Compound

Injected in
10 mL of Hexane

T etrachloroethene

1.623

6.2

1,1,2-Trichloroethane

1.4397

6.9

Trichloroethene

1.464

6.8

1,2-Dichloroethene

1.2837

7.8

1,2-Dichloropropane

1.1560

8.7

1,1,2,2-T etrachloroethane

1.5953

6.3

5.5.2 Gas standards: Certified gas standards are available from commercial manufacturers. The lower
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining
concentration levels should define the approximate working range of the GC: one at the upper linear range and
the other midway between it and the lowest standard.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for soil gas samples is 24 hours, but
it is recommended that all samples be analyzed within 1 hour of collection.

7.0 PROCEDURE

7.1 Calibration

7.1.1 Initial calibration:

7.1.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution, retention
times, response reporting, and interpretation of chromatograms are within acceptable quality control (QC)
limits. Using at least 3 calibration standards for each compound prepared as described in Section 5.5,
generate initial calibration curves (response versus mass of standard injected) for each compound (refer
to Section 7.2 for chromatographic procedures).

FMC-VG-002-5

-------
7.1.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.3) based on each
compound's 3 calibration factors (CFs, see Section 7.3) to determine the acceptability (linearity) of the
curve. Unless otherwise specified, the %RSD must be less than or equal to 25 percent, or the calibration
is invalid and must be repeated. Establish a new initial calibration curve anytime the GC system is altered
(e.g., new column, change in gas supply, change in oven temperature, etc.) or shut down.

7.1.2 Continuing calibration:

7.1.2.2 Use the continuing calibration in all target analyte sample concentration calculations
(Section 7.3) for the period over which the calibration has been validated.

7.1.3 Final calibration: Obtain the final calibration at the end of each batch of samples analyses. The
maximum allowable RPD between the mean initial calibration and final calibration CF s for each analyte is less
than or equal to 50 percent. A final calibration that achieves an RPD less than or equal to 25 percent may be
used as an ongoing continuing calibration.

7.2 Instrumental Analysis

7.2.1 Instrument parameters: Table 3 summarizes an example of acceptable instrument operating
conditions for the GC. Other instruments, columns, and chromatographic conditions may be used if this
method's QC criteria are met.

7.2.2 Chromato grams:

7.2.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks are on
scale over a 100-fold range are acceptable. However, this can be no greater than a 100-fold range to
prevent retention time shifts by column or detector overload. Generally, peak response should be greater
than 25 percent and less than 100 percent of full-scale deflection to allow visual pattern recognition of
halogenated compounds.

7.2.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperatures;

• Gases and flow rates;

FMC-VG-002-6

-------
Table 3

EXAMPLE TEMPERATURE PROGRAM GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Reaction Gas:

Column Oven:

Injector Temperature:
Detector Temperature:
GC Analysis Time:

Varian 3400 temperature-programmable GC and all required accessories
including analytical columns and gases equipped with a Tracor 1000 Hall EL CD.

Nelson Analytical PC Integrator with a dual-channel interface and hard disk drive for
data storage.

Vocol fused silica megabore capillary column (Supelco, or equivalent) 30 m x
0.53 mm I.D.

Ultrapure helium, 10 mL/min.

Ultrapure hydrogen, 50 mL/min.

Isothermal, 40°C.
llOoC.

800°C (reactor).

5 min.

FMC-VG-002-7

-------
• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.2.3 VOC identification:

7.2.3.1 Qualitative identification of VOCs is based on both detector selectivity and retention time
as compared to known standards using the external standard method.

7.2.3.2 Generally, individual peak retention time windows should be less than or equal
to 2 percent for capillary columns.

7.2.3.3 For the purpose of FASP analyses, peak intensity (height or area) matching for positive
identification is based on the chemist's best professional judgement in consultation with more experienced
chromatographic data interpretation specialists, when required. It is possible that interferences may
preclude positive identification of an analyte. In such cases, the chemist should report the presence of the
interferents with the maximum concentration possible.

7.2.4 System performance:

7.2.4.1 Degradation of VOCs in the GC system may occur especially if the injector and/or
column inlet is contaminated.

7.2.4.2 Before initial use of Tedlar bags, at least 10 percent of the bags should be filled with clean
air and sampled to confirm that they are free of contamination.

7.2.5 Specific instrument parameters: Specific instrument operating parameters that have been used are
provided as "Specific Instrument Parameters" in Appendix B of this method.

7.2.6 Analytical sequence:

7.2.6.1 Instrument blank.

7.2.6.2 Initial calibration.

7.2.6.3 Check standard solution and/or performance evaluation sample, if available.

7.2.6.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.2.6.5 Associated QC lot method blank.

7.2.6.6 Twenty 1 to 5 mL samples are injected into the GC depending on the concentration of
VOCs in the soil gas. Replicate injections are made for all positive hits.

7.2.6.7 A syringe blank must be analyzed initially and after any high concentration samples to
confirm proper decontamination.

7.2.6.8 Repeat sequence beginning at 7.2.6.5 until all sample analyses are completed or another
continuing calibration is required.

7.2.6.9 Final calibration when all sample analyses are complete.

FMC-VG-002-8

-------
Calculations

7.3.1 Initial calibration:

7.3.1.1	Identification and quantitation of target VOCs should be based on the external standard
method. A compound which is detected by the EL CD should be quantitated using the detector response
for that specific compound.

7.3.1.2	Analyze each calibration standard. Tabulate the area response of each target analyte
against concentration for each compound, and calculate CFs for each target compound using the following
equation.

__	Area of Peak

Cr

Mass Injected (ng)

7.3.1.3 Using the CF values, calculate the percent relative standard deviation (%RSD) for each
compound at a minimum of 3 concentration levels using the following equation.

ST)

iRSD = 4=- x 100
X

where SD, the standard deviation, is given by

\

SD

(X - X.) :

i

N-l

where: X; = Individual CF (per analyte)

X = Mean of initial 3 CFs (per analyte)

N = Number of calibration standards

7.3.1.4 The %RSD must be less than or equal to 25 percent.

7.3.2 Continuing calibration:

7.3.2.1	Sample quantitation is based on analyte CFs calculated from continuing calibrations.
Midrange standards for all initial calibration analytes must be analyzed at specified intervals (less than
or equal to 24 hours).

7.3.2.2	The maximum allowable relative percent difference (RPD) calculated using the equation
below for each analyte must be less than or equal to 25 percent.

|CF~ - CF„'

RPD = 		—

CFt + CFc

where: CF, = Mean CF from the initial calibration for each analyte

CFc = Measured CF from the continuing calibration for the same analyte

7.3.3 Final calibration:

FMC-VG-002-9

-------
7.3.3.1 Obtain the final calibration prior to the end of each batch of samples analyzed.

7.3.3.2 The maximum allowable RPD between the mean initial calibration and final calibration
CFs for each analyte must be less than or equal to 50 percent. A final calibration which achieves an RPD
less than or equal to 25 percent may be used as an ongoing continuing calibration.

l ~T ~ CFF\

RPD = - 1 — x 100

cft + cff
2

where: CF, = Mean CF from the initial calibration for each analyte
CFf = Final CF for the same analyte

7.3.4 Sample quantitation:

7.3.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements from an
integrator. Sample quantitation is based on analyte CFs calculated from continuing calibrations.

UJ (1000)

Concentration (ng/L) =

(CF) (V.)

where: Ax = Response for the analyte to be measured
V; = Volume of sample injected (mL)

CFc = CF from the continuing calibration for the same analyte

7.3.4.2 Two aliquots from each sample bulb are analyzed and the resulting values are averaged
to attain the final value. The average values (RPDs) should be within 75 percent. If the replicates are not
within 75 percent, a third replicate should be analyzed.

7.3.4.3 According to the Handbook of Chemistry and Physics at 20°C and 760 mm Hg (1 atm.),
the density of dry air is equal to 1.204 g/L. Therefore:

1 L of air = 1.204 g « 1 g;
ppb « ng/g = ng/L;
ppm « ng/g= ng/L.

7.3.4.4 Because the exact temperature and pressure are not measured at the time each soil gas
sample is collected, all results are reported as ng/L or (ig/L which are assumed to be roughly equivalent
to ppb and ppm, respectively.

7.3.4.5 Because of these assumptions, soil gas results should be considered screening results.
In addition, soil gas results cannot be converted to contaminant concentrations in groundwater. They are
to be compared to each other to determine relative high and low concentrations in the data set which infer
correspondingly high and low concentrations in groundwater, or the proximity to a subsurface contaminant
source.

7.3.4.6 Report results in nanograms per liter (ng/L) without correction for the blank.

7.3.4.7 Sample chromatograms may not match identically with those of analytical standards.
When identification is questionable, the chemist may calculate and report a maximum possible

FMC-VG-002-10

-------
concentration (qualified as less than the numerical value), which allows the data user to determine if
additional (e.g., CLP analyses) work is required, or if the reported concentration is below action levels
and project objectives and DQOs have been met, to forego further analysis.

7.3.4.8 Similarly, when sample concentration exceeds the linear range, the analyst may report
a probable minimum level (qualified as greater than the numerical value) that allows the data user to
determine if additional (e.g., CLP analyses) work is required, or if the reported concentration is above
action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. Advisory limits for replicate RPD are presented in
Table 4. This method should be used in conjunction with the quality assurance and quality control (QA/QC) section
of this catalog.

Table 4

REPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.009

Advisory Quality Control Limits*



Replicate RPD

Analyte

(%)

T etrachloroethene

±75

1,1,2-Trichloroethane

±75

Trichloroethene

±75

1,2-Dichloroethene

±75

1,2-Dichloropropane

±75

1,1,2,2-T etrachloroethane

±75

* If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for replicate
RPD values become ±3 times the quantitation limit for that individual analyte.

FMC-VG-002-11

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatogram is an example of a gas chromatogram for halogenated VOCs detected by
a Hall EL CD.

Figure 1

Gas chromatogram - Hall detector

Column:

Column Temperature:
Detector Temperature:
Injector Temperature:
Carrier Gas:

Reaction Gas:
Detector:

Vocol, 30 m x 0.53 mm I.D. fused silica capillary column (Supelco).
Isothermal, 40°C.

800°C (reactor).
llOoC.

Ultrapure helium, 10 mL/min.

Ultrapure hydrogen, 50 mL/min.

ELCD.

FMC-VG-002-12

-------
9.2 Method F080.009 examples of sample QA/QC results: Replicate sample results are presented as examples
of FASP Method F080.009 empirical data (see Table 5).

Table 5

REPLICATE SAMPLE ANALYSIS RELATIVE PERCENT DIFFERENCE

FASP Method F080.009 (Halogenated VOCs in Soil gas)

(ng/L)

(To be completed.)

U - The material was analyzed for but was not detected. The associated numerical value is a FASP quantitation
limit, adjusted for sample volume.

F - Data has been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

FMC-VG-002-13

-------
10.0 REFERENCES

Information not available.

FMC-VG-002-14

-------
APPENDIX A
FASP Method F080.009

Instrument Options:

Instrument Data Handling System: Varian 3400 GC/ELCD (Tracor), P.E. Nelson Integrator 2100 dual-

channel Integrator with 960 Series Intelligent Interface, Hyundai 286
computer, and Epson LX800 printer.

FMC-VG-002-15

-------
APPENDIX B
FASP Method F080.009

Specific Instrument Parameters:
Instrument:

Integrator:

Column:

Carrier Gas:

Reaction Gas:

Column Oven:

Injector Temperature:
Detector Temperature:

Varian 3400 temperature-programmable GC equipped with a Tracor 1000
Hall EL CD.

Nelson Analytical PC Integrator with a dual-channel interface and hard disk
drive for data storage.

Vocol fused silica capillary column (Supelco, or equivalent) 30 m x 0.53
mm I.D.

Ultrapure helium, 10 mL/min.

Ultrapure hydrogen, 50 mL/min.

Isothermal, 40°C.

llOoC.

800°C (reactor).

FMC-VG-002-16

-------
FASP Method Number F080.010
HALOGENATED VOLATILE ORGANICS IN SOIL GAS USING

ELECTRON CAPTURE DETECTOR - DIRECT ANALYSIS

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining relative
concentrations of halogenated volatile organic compounds (VOCs) in soil gas. The method employs direct soil gas
injection and gas chromatographic (GC) analysis using an electron capture detector (ECD).

1.3 The method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 A sample of 1 to 5 mL of soil gas collected in a 250-mL gas sample bulb is injected into a GC equipped
with a capillary column and an ECD. Halogenated VOCs are detected with the ECD. Quantitation and identification
are based on relative peak areas and retention times using the external standard method.

2.2 This method should be used as a screening method only. The reasons for this are as follows:

2.2.1 Mathematical assumptions yield results that are only roughly equivalent to ppb values (Section

7.3).

2.2.2 Soil gas results can not be converted directly to contaminant concentrations in groundwater or
subsurface soils.

2.2.3 Soil gas results should only be used to guide further confirmatory analyses. These results are
designed to show relative high and low concentrations that are internally consistent to the data set; that is, all
data are generated together using the analysis procedures as described in this method.

3.0 INTERFERENCES

3.1 Sample bulbs can become contaminated if stored near standards or cleaning solvents, elevated
concentrations of solvents in ambient air, or contaminated soil gas sampling equipment. These interferences can be
mitigated by analyzing sample bulbs before use to insure that they are free of contamination and by routinely running
equipment blanks.

FMC-VG-003-1

-------
Table 1

FASP METHOD F080.010 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit in Soil Gas
(ng/L)

Carbon tetrachloride

56-23-5

Chloroform

67-66-3

T etrachloroethene

127-18-4

1,1,1 -Trichloroethane

71-55-6

Trichloroethene

79-01-6

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for
guidance and may not always be achievable.

3.2 This method employs direct injection of soil gas into the GC equipped with an ECD. These samples
typically contain high amounts of oxygen and moisture. The presence of these 2 sample constituents can significantly
shorten the useful life of the GC column and ECD. Several ECD designs are very sensitive to oxygen and moisture
and do not work with this method. This method was developed using a Tracor 540 GC whose ECD is not adversely
affected by oxygen and moisture, except for occasional slight retention time shifts. Sometimes it is necessary to
increase the column temperature from 100°C to 200°C for 15 minutes or more to allow the instrument to stabilize.

3.3 When using this method, the analyst must be cautious about injecting soil gas directly into a GC equipped
with an ECD and understand that he\she might be adversely affecting the ECD (and GC column). If GC sensitivity
significantly decreases after injecting soil gas samples, the GC-ECD should not be used further.

3.4 The ECD may become saturated when analyzing high concentration samples. To allow the GC to
stabilize, the column temperature is increased from 150°C to 200°C for 15 minutes or longer, to bake out the
contaminants. This should be followed with a blank sample to check for sample carryover before proceeding.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System

4.1.1 Gas chromatograph: An analytical system complete with a temperature-programmable GC is
required and all necessary accessories including injector and detector systems designed or modified to accept
megabore capillary columns. The system shall have a data handling system attached to the detector that is
capable of retention time labeling, relative retention time comparisons, and providing peak height and/or peak
area measurements.

4.1.1.1 Column: 30 m x 0.53 mm I.D. DB 624 fused silica megabore capillary column (J&W
Scientific, or equivalent).

4.1.1.2 Detector: Linearized ECD employing a system, with make-up gas supply at the detector's
capillary inlet.

FMC-VG-003-2

-------
4.1.1.3 Gas supply: The carrier and make-up gases should be argon with 5 percent methane. The
gas should pass through oxygen traps prior to the GC to prevent degradation of the column's analytical
coating and detector foil.

4.2 Other Laboratory Equipment

4.2.1 Sample bulbs: 250-mL gas sample bulbs with Teflon stopcocks and a side port with replaceable
septa for sample withdrawal.

4.2.2 Gas sample bulb septa: Supelco Thermogren, or equivalent, septa for sample port of gas sample

bulbs.

4.2.3 Syringes: Glass syringes (1-mL and 5-mL) with replaceable needles.

4.2.4 Microsvringes: 10-|iL, 25-|iL, and larger.

4.2.5 Pipette: 10-mL class A pipette and safety bulbs.

4.2.6 Standard vials: 15-mL glass vials with Teflon-lined silicone septa.

4.2.7 Heat source: Heat source (hairdryer) and vacuum pump for decontaminating bulbs and syringes.

4.2.8 Vortex mixer: Vortex Genie, or equivalent.

4.2.9 Oxygen trap: Supelpure-O-Trap and OMJ-1 indicating tube, or equivalent.

4.2.10 Leak detector: GOW-MAC gas leak detector, or equivalent, for megabore capillary operations.

4.2.11 Activated carbon: Activated carbon to aid in keeping the mobile laboratory, standards, and
reagents free of solvent contamination.

4.2.12 Chromatographic data stamp: Used to record instrument operating conditions, if not provided by
the data handling system.

4.3 Instrument Options: Specific instrument options that have been used are provided as "Instrument Options"
in Appendix A of this method.

5.0 REAGENTS

5.1 Solvent: Hexane, nanograde, or equivalent.

5.2 Reagent Water: Reagent water is defined as water in which an interferent is not observed at the QL of
the analyte of interest. Reagent water may be generated using a carbon filter bed containing activated carbon (Calgon
Corporation, Filtrasorb-300 or equivalent) or a water purification system (Milli-Q Plus with Organex Q cartridge,
Barnstead Water-1 Systems, or equivalent), or purchased from commercial laboratory supply houses.

5.3 Gas: 5 percent methane in argon, ultrapure or chromatographic grade (always use in conjunction with an
oxygen trap).

5.4 Stock Standard Solutions: Neat stock standard solutions of the analytes and certified gas standards should
be purchased as manufacturer-certified solutions and standards.

FMC-VG-003-3

-------
5.5 Calibration Standards: Calibration standards at 3 concentration levels for each parameter of interest should
be prepared in 15-mL screw-cap vials with Teflon-lined silicone septa with 10 mL of hexane from neat solvent
solutions. A separate 10-(iL syringe is used for each neat solvent. The lowest concentration standard should be
approximately 2 times the QL as listed in Table 1. The remaining standard concentration should define the
approximate working range of the GC: one at the upper linear range and the other midway between it and the lowest
standard. All standards must be stored at 4°C in Teflon-sealed glass bottles. Calibration solutions must be replaced
after 6 months, or whenever comparison with check standards indicates a problem.

5.5.1 Liquid standards:

5.5.1.1 Preparation of 1000 ng/^L standard:

5.5.1.1.1	In order to determine the amount of solvent to inject into 10 mL of

hexane, divide 10 mg by the density of the solvent (Table 2) using the equation:

10 mg	_ X pi of solvent

density of	for 10 mg mass

solvent (mg/]iL)

where X is the volume of solvent in (iL.

5.5.1.1.2	Inject the amount determined above into 10 mL of hexane to achieve a

standard of 1000 ng/^L. The equation for a 1000 ng/^L standard is:

10 mg

(10,000,000 ng) solvent ~, T

—	-	-	—	 = 1000 ng/uL

10 mL

(10,000 pi) hexane

5.5.1.2	Preparation of 1000 pg/(iL standard: Place 10 (iL of 1000 ng/^L standard into 10 mL of
hexane.

5.5.1.3	Preparation of 100 pg/^L standard: Place 1.0 (iL of 1000 ng/^L standard into 10 mL of
hexane.

5.5.1.4	Preparation of 10 pg/^L standard: Place 100 (iL of 1000 pg/^L standard into 9.9 mL of
hexane.

NOTE: At times, the 10 pg/^L standard approaches the instrument detection limit and the GC response
is non-linear. In this case, a 50 pg/^L standard is substituted.

FMC-VG-003-4

-------
Table 2

DENSITIES AND VOLUMES OF SELECTED
SOLVENTS USED TO PREPARE 1000 ng/mL STANDARD

Compound (Solvent)

Density (mg/jiL)

(iL of Compound Injected in 10
mL of Hexane

Carbon tetrachloride

1.594

6.3

Chloroform

1.48

6.8

T etrachloroethene

1.623

6.2

1,1,1 -Trichloroethane

1.339

7.5

Trichloroethene

1.464

6.8

5.5.2 Gas standards: Certified gas standards are available from commercial manufacturers. The lower
concentration standard should be approximately 2 times the QL as listed in Table 1. Theremaining concentration
levels should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

7.0 PROCEDURE

7.1 Calibration

7.1.1 Initial calibration:

7.1.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution, retention
times, response reporting, and interpretation of chromatograms are within acceptable quality control (QC)
limits. Using at least 3 calibration standards for each analyte prepared as described in Section 5.5,
generate initial calibration curves (response versus mass of standard injected) for each analyte (refer to
Section 7.2 for chromatographic procedures).

FMC-VG-003-5

-------
is invalid and must be repeated. Establish a new initial calibration curve any time the GC system is
altered (e.g., new column, change in gas supply, change in oven temperature, etc.) or shut down.

7.1.2 Continuing calibration:

7.1.2.2 Use the continuing calibration in all target analyte sample concentration calculations
(Section 7.3) for the period over which the calibration has been validated.

7.1.3 Final calibration: Obtain the final calibration at the end of each 24-hour period in which samples
are analyzed. The maximum allowable RPD between the mean initial calibration and final calibration factors
for each analyte is less than or equal to 50 percent. A final calibration which achieves an RPD less than or equal
to 25 percent may be used as an ongoing continuing calibration.

7.2 Instrumental Analysis

7.2.2 Chromato grams:

7.2.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperatures;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

FMC-VG-003-6

-------
Table 3

EXAMPLE TEMPERATURE-PROGRAMMED GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Reaction Gas:

Column Oven:

Injector Temperature:
Detector Temperature:
GC Analysis Time:

Tracor 540 temperature-programmable GC and all required accessories
including analytical columns and gases, equipped with an ECD.

Spectraphysics 4290 Integrator with a dual-channel interface and hard
disk drive for data storage.

J&W DB 624 fused-silica megabore capillary column, 30 m x 0.53 mm
I.D.

Ultrapure argon/5 percent methane, 10 mL/min.

Ultrapure argon/5 percent argon, 35 mL/min.

Isothermal, 35°C.

250oC.

350oC.

10.2 - 18.2 min

FMC-VG-003-7

-------
7.2.3 VOC identification:

7.2.3.1 Qualitative identification of VOCs is based on both detector selectivity and retention time
as compared to known standards using the external standard method.

7.2.3.2 Generally, individual peak retention time windows should be less than or equal
to 2 percent for capillary columns.

7.2.3.3 The presence of moisture in the soil gas sample can sometimes cause a retention-time
shift in the chromatogram. If this is suspected, 5 (iL of the 1000 pg/^L standard is injected into a 250-mL
gas sample bulb, or a gas standard can be used. Five mL of this "gas standard" is introduced onto the GC
column, and the resulting retention times are used for sample identification.

7.2.3.4 For the purpose of FASP analyses, peak intensity (height or area) matching for positive
identification is based on the chemist's best professional judgement in consultation with more experienced
chromatographic spectral data interpretation specialists, when required. It is possible that interferences
may preclude positive identification of an analyte. In such cases, the chemist should report the presence
of the interferents with the maximum concentration possible.

7.2.4 System performance:

7.2.4.1 Degradation of VOCs in the GC system may occur especially if the injector and/or
column inlet is contaminated.

7.2.4.2 Before initial use and after each subsequent use, each numbered gas sample bulb is
analyzed to confirm that it is free of residual contamination.

7.2.5 Specific instrument parameters: Specific instrument operating parameters that have been used are
provided as "Specific Instrument Parameters" in Appendix B of this method.

7.2.6 Analytical sequence:

7.2.6.1 Instrument blank.

7.2.6.2 Initial calibration.

7.2.6.3 Check standard solution and/or performance evaluation sample, if available.

7.2.6.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.2.6.5 Associated QC lot method blank.

7.2.6.6 Twenty 1- to 5-mL samples are injected into the GC depending upon the concentration
of volatiles in the soil gas. Replicate injections are made for all positive hits.

7.2.6.7 A syringe blank must be analyzed initially and after any high-concentration samples to
confirm proper decontamination.

7.2.6.8 Repeat sequence beginning at 7.2.6.5 until all sample analyses are completed or another
continuing calibration is required.

7.2.6.9 Final calibration when all sample analyses are complete.

FMC-VG-003-8

-------
7.3 Calculations

7.3.1 Identification and quantitation of target VOCs should be based on the external standard method.
A compound which is detected by the Hall Detector should be quantitated using the detector response for that
specific compound.

7.3.2 Initial calibration:

7.3.2.1 Analyze each calibration standard. Tabulate the area response of each target analyte
against concentration for each compound and calculate CFs for each target compound using the following
equation.

__ Area of Peak

Mass Injected (ng)

7.3.2.2 Using the CF values, calculate the percent %RSD for each compound at a minimum of
3 concentration levels using the following equation.

ST)

iRSD = 4=- x 100
X

where SD, the standard deviation, is given by

(X - X.) :

N-l

where: X; = Individual CF (per analyte)

X = Mean of initial 3 CFs (per analyte)

N = Number of calibration standards

7.3.2.3 The %RSD must be less than or equal to 25 percent.

7.3.3 Continuing calibration:

7.3.3.1 Sample quantitation is based on analyte CFs calculated from continuing calibrations.
Midrange standards for all initial calibration analytes must be analyzed at specified intervals (less than
or equal to 24 hours).

7.3.3.2 The maximum allowable RPD calculated using the equation below for each analyte must
be less than or equal to 25 percent.

|CF~ - CF„'

RPD = —

cft +cfc

where: CF, = Mean CF from the initial calibration for each analyte

CFc = Measured CF from the continuing calibration for the same analyte

7.3.4 Final calibration:

FMC-VG-003-9

-------
7.3.4.1 Obtain the final calibration prior to the end of each batch of samples analyzed.

7.3.4.2 The maximum allowable RPD between the mean initial calibration and final calibration
CFs for each analyte must be less than or equal to 50 percent. A final calibration which achieves an RPD
less than or equal to 25 percent may be used as an ongoing continuing calibration.

l ~T ~ CFF\

RPD = 1 — x 100

cft +cff
2

where: CF, = Mean CF from the initial calibration for each analyte
CFf = Final CF for the same analyte

7.3.5 Sample quantitation:

7.3.5.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements from an
integrator. Sample quantitation is based on analyte calibration factors calculated from continuing
calibrations.

UJ (1000)

Concentration (ng/L) =

(CF) (V,)

where: Ax = Response for the analyte to be measured
V; = Volume of sample injected (mL)

CFc = Calibration factor from the continuing calibration for the same analyte

7.3.5.2 Analyze 2 aliquots from each sample bulb and average the resulting values to attain the
final value. The average values (RPDs) should be within 75 percent. If the replicates are not within 75
percent, a third replicate should be analyzed.

7.3.5.3 According to the Handbook of Chemistry and Physics at 20°C and 760 mm Hg (1 atm.),
the density of dry air is equal to 1.204 g/L. Therefore, 1 L of air = 1.204 g« 1 g; ppb « ng/g = ng/L; and
ppm « ng/g= ng/L.

7.3.4.5 Because of these assumptions, soil gas results should be considered screening results.
In addition, soil gas results can not be converted to contaminant concentrations in groundwater. They are
to be compared to each other to determine relative high and low concentrations in the data set which infer
correspondingly high and low concentrations in groundwater, or the proximity to a subsurface contaminant
source.

7.3.4.6 Report results in nanograms per liter (ng/L) without correction for the blank.

7.3.4.7 Sample chromatograms may not match identically with those of analytical standards.
When identification is questionable, the chemist may calculate and report a maximum possible
concentration (qualified as less than the numerical value), which allows the data user to determine if
additional (e.g., CLP analyses) work is required, or, if the reported concentration is below action levels
and project objectives and DQOs have been met, to forego further analysis.

FMC-VG-003-10

-------
7.3.4.8 Similarly, when sample concentration exceeds the linear range, the analyst may report
a probable minimum level (qualified as greater than the numerical value) that allows the data user to
determine if additional (e.g., CLP analyses) work is required, or if the reported concentration is above
action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. Advisory limits for replicate RPD are presented in
Table 4. This method should be used in conjunction with the quality assurance and quality control (QA/QC) section
of this catalog.

FMC-VG-003-11

-------
Table 4

REPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.010

Advisory Quality Control Limits*

Analyte

Replicate RPD (%)

Carbon tetrachloride

±75

Chloroform

±75

T etrachloroethane

±75

Trichloroethene

±75

1,1,1 -Trichloroethane

±75

* If the concentration of an analyte is less than 5 times the quantitation limits, advisory control limits for replicate
RPD values become ± 3 times the quantitation limits for that individual analyte.

FMC-VG-003-12

-------
9.0 METHOD PERFORMANCE

9.1 The following is a gas chromatogram for halogenated VOCs as detected by an ECD.

Figure 1
Gas chromatogram - ECD

Column:

Column Temperature:
Detector Temperature:
Injector Temperature:
Carrier Gas:

Make-up Gas:
Detector:

J&W DB 624 fused silica megabore capillary column, 30 m x 0.53 mm I.D.

Isothermal 35°C.

350°C.

250°C.

Ultrapure argon/5 percent methane - 10 mL/min.

Ultrapure argon/5 percent methane - 35 mL/min.

ECD

FMC-VG-003-13

-------
9.2 Method F080.010 examples of sample QA/QC results: Replicate sample results are presented in Table
4 as examples of FASP Method F080.010 empirical data.

Table 5

REPLICATE SAMPLE ANALYSIS RELATIVE PERCENT DIFFERENCE

FASP Method F080.010 (Halogenated VOCs in Soil Gas)

(ng/L)

Analytes

Sample Results

Replicate Sample
Results

Relative Percent
Difference (%)

Carbon tetrachloride

10 UF

10 UF

0

Chloroform

15 F

19 F

24

T etrachloroethene

60 F

73 F

20

1,1,1 -Trichloroethane

15 F

11 F

31

Trichloroethene

65 F

59 F

10

U - The material was analyzed for but was not detected. The associated numerical value is a FASP QL, adjusted
for sample volume.

F - Data has been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

FMC-VG-003-14

-------
10.0 REFERENCES

Information not available.

FMC-VG-003-15

-------
Instrument Options:
GC System:

Data Handling System

APPENDIX A

FASP Method F080.010

Tracor 540 temperature-programmable gas chromatograph with an ECD.

Spectraphysics 4290 integrator with dual channel interface and hard disk
drive for data storage.

FMC-VG-003-16

-------
APPENDIX B

FASP Method F080.010

Specific Instrument Parameters:
Instrument:

Integrator:

Column:

Carrier Gas:

Make-up Gas:

Column Oven:

Injector Temperature:
Detector Temperature:
GC Analysis Time:

Tracor 540 GC with ECD.

Spectraphysics 4290 integrator.

J&W DB 624 fused silica megabore column, 30 m x 0.53 mm I.D., or
equivalent.

Ultrapure argon/5 percent methane.

Ultrapure argon/5 percent methane.

Isothermal, 35°C.

250oC.

350oC.

10.2 - 18.2 minutes.

FMC-VG-003-17

-------
CSL Method

VOA/SOIL GAS/CHARCOAL/GC-ECD

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of soil gas for volatile hydrocarbon parameters that are indicative
of contamination at the site. It is presented as a means to rapidly characterize contamination in soils when used in
conjunction with a soil gas sampling program. The target constituents are listed in Table 1. Other compounds may
be added as data become available.

1.2 The method is presented as means to screen soil gas samples which have been collected on activated
charcoal adsorption tubes.

1.3 Application of this method in conjunction with a soil gas sampling program can be utilized for site
activities such as contaminant plume tracing. The results of this method are largely related to the prescribed soil gas
sampling program. Use of this method and the sampling technique need to be evaluated against the objectives of the
sampling program on a case-by-case basis.

1.4 This test should be presented as part of the project plan for approval.

1.5 Any modifications of this test method should be supported by method validation and quality assurance
checks.

1.6 The method detection limits (MDL) vary considerably depending upon the constituent. Generally, the
MDL will be between 1 and 10 (ig/L in the soil gas sample when calibrated against liquid/headspace standards.

2.0 SUMMARY OF METHOD

2.1 A quantity of gas is extracted from beneath the soil surface by methods described in the sampling plan.
This method is based on NIOSH Method P&CAM 127, as published in NIOSH Manual of Analytical Methods. 2nd
edition. Samples of soil gas are collected on charcoal and are analyzed by gas chromatography using electron capture
detection (GC/ECD). Calibration of the GC system permits semiqualitative and semiquantitative determination of
select target constituents, as well as an overall estimation of the volatile organic contamination of the soil. The
method is designed to provide screening analysis for large numbers of soil gas samples. The analysis requires
approximately 30 minutes per sample.

3.0 INTERFERENCES

3.1 Cross contamination by inadequately cleaned sampling equipment and sample containers are sources of

error.

3.2 Soil gas samples containing large numbers of volatile constituents may cause interference peaks to co-elute
with target constituents.

3.3 For target compounds having isomers that co-elute, false quantifications may occur.

3.4 Impurities in calibration standards, dilution solvents, and carrier gases are potential sources of
interferences.

FMC-VG-004-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Soil Gas (p.g/L)

Carbon Tetrachloride

1 to 10

Ethylene Dibromide

1 to 10

T etrachloroethy lene

1 to 10

1,1,1 -Trichloroethane

1 to 10

T richloroethy lene

1 to 10

3.5 When the amount of water vapor in the air is so great that condensation occurs in the charcoal tube,
organic vapors may not be reliably trapped.

4.0 APPARATUS AND MATERIALS

4.1 Charcoal Adsorbent Tube: activated coconut charcoal 20/40 mesh, packed in sections of 100 and 50
milligrams, tube size 6 mm 0D x 4 mm ID x

7 cm L.

4.2 Lab ware: as needed for preparation and extraction of charcoal tubes.

4.3 Gas Chromatograph: Hewlett-Packard model 5890-with temperature programming capabilities, electronic
integration, multilevel calibration, heated injection and detector ports, analytical column, and electron capture
detector.

4.4 Analytical Column: suitable for separation of volatile organics and target constituents, megabore capillary
column, 30 meter DB-1 with 1.5 micron film thickness, or equivalent.

5.0 REAGENTS

5.1 Solvents

5.1.1 Pentane: Spectro grade, 99.9 percent.

5.1.2 Carbon disulfide: Spectro grade, 99.9 percent.

5.2 Stock Standards: Prepared from pure standard materials, pentane or carbon disulfide, at approximately
1,000 ng/mL in methanol or carbon disulfide.

5.3 Working Standard: prepared from stock standards by dilution with pentane or carbon disulfide. Prepare
working standards within the expected working range, approximately 1.0, 0.1, and 0.01 (ig/mL in pentane for
calibration when employing electron capture detection.

5.4 Gases:

FMC-VG-004-2

-------
5.4.1 Nitrogen: Carrier gas, prepurified grade.

5.4.2 Air: Carrier or detector gas, ultrapure grade.

5.4.3 Hydrogen: Detector gas, prepurified grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Immediately after collection, samples should be capped, placed away from light, and delivered to the
laboratory for analysis.

7.0 PROCEDURE

7.1 Safety

7.1.1 The target constituents have been tentatively identified as known or suspected carcinogens.

7.1.2 Handle gas standards, and dilute standards in solvents carefully. Determine information such as
NIOSH permissive exposure level (PEL), odor threshold, exposure pathways, fire hazard, and physiological
effects of exposure for solvents, target constituents, and other suspect sample constituents. Observe safety
precautions at all times.

7.2 Sample Preparation and Desorption

7.2.1 In preparation for analysis, score each charcoal tube with a file in front of the first section of
charcoal and break open. Remove and discard the glass wool. Transfer the charcoal in the first (larger) section
to a small stoppered test tube. Remove and discard the separating section of foam; transfer the second section
to another test tube. Analyze these two sections separately.

7.2.2 Desorption of samples: Pipette 0.5 mL of pentane or carbon disulfide into each test tube.
Desorption is complete in 30 minutes; stir the sample occasionally during this period.

7.3 Calibration

7.3.1 External calibration: Use three-level calibration with standards at approximately 10.0, 1.0, 0.1,
and 0.01 (ig/mL for the target constituents in pentane.

7.3.2 Working calibration: Verify working calibration each day by preparation of fresh vapor phase or
liquid samples (prepared weekly). If response factors for target constituents vary by more than ± 20 percent,
recalibrate on freshly prepared calibration standards.

7.4 Analysis

7.4.1 Perform GC analysis on the extract.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range, dilute
the sample extract such that concentrations fall within the calibration range.

FMC-VG-004-3

-------
7.4.4 Use a retention time marker as an indicator of the reliability of each sample injection and GC run.
The retention time marker should fall within the same windows as the target constituents and should be within
±15 percent area counts of its initial calibration value. If these criteria are not met, re-evaluate the data using
relative retention times. Reruns should occur to resolve data suspicions.

7.5 Calculations

, ^ A x Vt x DF

Concentration {]xg/m ) = x 100

where: A = Amount of target constituent found in the extract in ng/L

Vt = Volume of solvent added to the reactor flask, 2.0 mL

DF = Dilution factor, if required

1000 = Dimensional correction factor

Va = Volume of the air sampled, L

8.0 QUALITY CONTROL

8.1 Quality control measures shall include as a minimum:

8.1.1 Daily mid-range calibration checks performed prior to the analysis of each day's lot of
samples or with each lot of 20 samples, whichever is more frequent.

8.1.2 Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day,
whichever is more frequent.

8.1.3 Analysis of laboratory blank samples at the same frequency. Should the results of the
laboratory blanks show contamination, the cause of the contamination should be investigated and
corrective action taken.

8.1.4 Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1/day, whichever
is more frequent.

8.1.5 Analysis of mid-range matrix spike samples and a matrix spike duplicate at a frequency
of 1 in 20 samples analyzed or 1/day, whichever is more frequent.

8.1.6 Use of the retention time marker during the analysis of all samples and standards.

8.1.7 Method validation: Perform spike recovery procedure to demonstrate precision and
accuracy of method prior to application in screen analysis.

8.1.8 Perform daily checks on reagent blanks and each time a new batch of reagents is used.

8.1.9 Analyze soil gas samples in duplicate at 10 percent frequency to monitor the precision
of sampling technique and analytical procedure. Calculate standard deviation and range on normalized
duplicate analysis.

9.0 METHOD PERFORMANCE

FMC-VG-004-4

-------
Information not available.
10.0 REFERENCES

Information not available.

FMC-VG-004-5

-------
CSL Method

VOA/SOIL GAS/CANISTERS/GC-PID

1.0 SCOPE AND APPLICATION

1.1 This method is utilized for field determination of soil gas constituents. It is intended as a means to
characterize volatile organic contaminants in soils when used in conjunction with a soil gas sampling program. This
method will characterize the extent of volatile organic contamination of soils while being specific for target
constituents. The target compound list, Table 1, can be expanded with additional method development and validation.

1.2 The method is presented as means to screen soil gas samples which have been collected in suitable gas
sampling vessels (i.e., stainless canisters).

1.3 Application of this method in conjunction with a soil gas sampling program can be utilized for site
activities such as contaminant plume tracing and preliminary site investigations. The results of this method are
largely related to the soil gas sampling program. Use of this method and the sampling technique needs to be evaluated
against the objectives of the sampling program on a case-by-case basis.

1.4 This test should be presented as part of the project plan for approval.

1.5 Any modifications of this test method should be supported by method validation and quality assurance
checks.

1.6 The method detection limits (MDL) vary considerably depending upon the constituent. Generally, the
MDL will be between 1 and 10 ppb in the soil gas sample.

2.0 SUMMARY OF METHOD

2.1 A quantity of gas is extracted from beneath the soil surface by methods described in the sampling plan.
Samples of soil gas collected are analyzed by gas chromatography with photoionization detection (GC/PID).
Calibration of the GC/PID system permits semiqualitative and semiquantitative determination of select target
constituents, as well as an overall estimation of the volatile organic contamination of the soil. The method is designed
to provide screening analysis for large numbers of soil gas samples. The analysis requires approximately 15 minutes
per sample.

3.0 INTERFERENCES

3.1 Cross contamination by inadequately cleaned sampling equipment and sample containers are sources of

error.

3.2 Soil gas samples containing large numbers of volatile constituents may cause interference peaks to co-elute
with target constitutes.

3.3 For target compounds having isomers that co-elute, false quantifications may occur.

3.4 Impurities in calibration standards, dilution solvents, and carrier gases are potential sources of
interferences.

FMC-VG-005-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Soil Gas (ng/L)

Perchloroethylene

1 to 10

1,1,2,2-T etrachloroethy lene

1 to 10

1,1,2-Trichloroethane

1 to 10

1,1,1 -Trichloroethane

1 to 10

4.0 APPARATUS AND MATERIALS

4.1 Sample Containers: pacified stainless steel canisters or glass sampling bulbs. Sample containers shall
be flow-through design with greaseless gas tight end seals and a sample port with replaceable seal.

4.2 Syringes: 10-, 25-, 50-, 100-, 250-, and 500-^iL gas-tight and liquid delivery syringes with replaceable
needles, spare needles, and plungers as required for injection of samples and standards.

4.3 Gas Chromatograph: HNu systems model 421 with temperature programming capabilities, electronic
integration, multilevel calibration, heated injection and detector ports, analytical column, and photoionization detector.

4.4 Analytical Column: suitable for separation of volatile organics and target constituents, SE 30, SP 2100,
SP 1000 (methyl silicone).

5.0 REAGENTS

5.1 Gases

5.1.1 Nitrogen: Carrier gas, prepurified grade.

5.1.2 Air: Carrier gas, ultrapure grade.

5.2 Stock Standards. Liquid: Prepared from pure standard materials at approximately 1,000 ppm in solvent.

5.3 Working Standards. Liquid: Prepared from stock standards by dilution with solvent. Prepare weekly
mixed working standards within the expected working range, normally 200 ppb, 20 ppb, and 2.0 ppb.

5.4 Stock Standard. Vapor: Prepared from pure standard materials in organic-free water at approximately
1,000 ppm.

5.5 Working Standard. Vapor: Prepared from vapor stock standard by dilution with organic-free water in the
VOA vial with head space. Prepare daily working standards with expected head space vapor concentrations within
the expected working range, normally 200 ppb, 20 ppb, and 2.0 ppb.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

FMC-VG-005-2

-------
6.1 Immediately after collection, samples should be placed away from light and delivered to the laboratory
for analysis.

7.0 PROCEDURE

7.1 Safety

7.1.1 The target constituents have been tentatively identified as known or suspected carcinogens.

7.1.2 Handle gas standards and dilute standards in solvents carefully. Determine information such as
NIOSH permissive exposure level (PEL), odor threshold, exposure pathways, fire hazard and physiological
effects of exposure for solvents, target constituents, and other suspect sample constituents. Observe safety
precautions at all times.

7.1.3 Perform sample analysis in a well-ventilated area and provide adequate skin, eye, and breathing
protection for the analysis.

7.2 Calibration

7.2.1 External calibration: Inject multilevel calibration standards at approximately 200 ppb, 20 ppb, and

2.0 ppb equivalent vapor concentration for each target constituent.

7.2.2 Working calibration: Verify each day by preparation of fresh vapor phase or liquid samples
(prepared weekly). If response factors for target constituents vary by more than ± 15 percent, recalibrate using
freshly prepared calibration standards.

7.3 Analysis: Withdraw a suitable aliquot of sample gas from the sample container with an injection syringe
by gas-flushing technique. Immediately inject the GC column and record the inject volume and sample identification.
Operate the GC at conditions that provide separation and resolution of target constituent peaks and provide a good
overview of uncalibrated peaks.

7.4 Calculations: For target constituents, base quantification on integrated area as compared to working range
standards, calibration, injection volume, and dilutions, if used. Calculate sample concentrations using a generalized
formula as follows:

Concentration _ peak area x response factors
(ppb,V/N) injection volume

Calculations of concentration is dependent on method of calibration, response factor, etc.

8.0 QUALITY CONTROL

8.1 Method validation: Perform spike recovery procedure to demonstrate precision and accuracy of method
prior to application in screen analysis of soil samples. Spike four representative soil samples that are saturated with
water at or near the MDL and ten times the MDL. Analyze each sample in triplicate, and calculate precision and
accuracy for each target constituent.

8.2 Perform daily checks on reagent blanks and each time a new batch of reagents is used.

8.3 Analyze soil gas samples in duplicate at 10 percent frequency to monitor the precision of sampling
technique and analytical procedure. Calculate standard deviation and range on normalized duplicate analysis.

FMC-VG-005-3

-------
8.4	At the start of each day, the GC/PID shall be checked to see that acceptable performance criteria are
achieved.

8.5	Detector response shall be with ±15 percent of calibration values for target constituents.

8.6	Column performance shall yield retention times within a ± 10 percent reference window for target
constituents.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VG-005-4

-------
NUS SOP Number 5.10
FIELD SCREENING ANALYSIS OF VOLATILE CONTAMINANTS

IN SOIL GAS MATRIX

1.0 SCOPE AND APPLICATION

1.1 The following methodology describes a modification of SW-846 and EPA Compendium methods as
applied to the determination of volatile organic contaminants in soil gas.

1.3 Table 1 provides a list of potential target compounds.

2.0 SUMMARY OF METHODS

2.1 In this methodology, a sorbent tube containing previously trapped volatile organic contaminants obtained
via the sampling of soil gas matrix is subsequently desorbed (by action of heat and reverse gas flow) onto a suitable
analytical column housed by a preprogrammed gas chromatograph (GC). The volatile organic contaminants become
separated and resolved as they travel through the GC's column. Eventually, the contaminants elute through an
appropriate detector. Detector signals are processed and interpreted via a previously programmed integrator.

3.0 INTERFERENCES

3.1 Interferences can result from many sources, considering the environmental settings of most hazardous
waste sites. However, most interfering impurities are artifacts originating from organic compounds within the
specialty gases and the plumbing within the trapping/desorption device. The presence of air molecules and excessive
water vapor and/or the degradation of the trap packing can also account for many artifacts.

3.2 Interferences in the analytical system are monitored by the analysis of inert gas method blanks. Method
blanks are analyzed under the same conditions and at the same time as standards and samples, to establish an average
background response.

4.0 APPARATUS AND MATERIALS

4.1 Purge and Trap Device: Tekmar Company Model LSC-2 or Model 5000. Traps may be packed solely
with Tenax or, alternatively, trap packing may consist of 10 cm of 3 percent OV-1, 15 cm of Tenax, and 8 cm of silica
gel. Appropriate trap selection is contingent upon the target compounds being analyzed.

4.2 Gas Chromatograph: Hewlett-Packard 5890, or equivalent. The analytical system should be equipped
for temperature programming, packed and/or capillary column analysis and on-column injection.

4.3 Detector: Photoionization detector/flame ionization detector (PID/FID) or photoionization detector/Hall
electrolytic conductivity detector (PID/HECD) in series; FID only. Optimum detector selection should be based upon
the sensitivities of the target compounds being analyzed.

FMC-VG-006-1

-------
Table 1

SUMMARY OF POTENTIAL TARGET COMPOUNDS

Volatile Organics Analysis

Acetone

Benzene

Bromoform

Carbon tetrachloride

Chlorobenzene

Chloroform

Ethylbenzene
Methylene Chloride
1,1 -Dichloroethene

Total 1,2-Dichloroethenes

1,1 -Dichloroethane

1,2-Dichloroethane

1,1,1 -Trichloroethane

T etrachloroethene

T oluene

Trichloroethene

Total Dichlorobenzenes

Total Xylenes
2-Butanone (MEK)

4-Methyl-2-pentanone (MIBK)

FMC-VG-006-2

-------
4.4 Analytical Column: Glass or stainless steel packed with 1% SP-1000 on 60/80 mesh Carbopack B.
Alternatively, a suitable capillary column may be used.

4.5 Syringes (assorted, gastighf): 5-|iL, 25-^L, 100-|iL, 1-mL, and 10-mL.

4.6 Volumetric Flasks: 10-mL, 25-mL, and 100-mL.

4.7 Tedlar bag: For making gaseous standards.

4.8 Flowmeter: For use in measuring the exact volume of gas introduced to the Tedlar bag.

4.9 Analytical Balance: Capable of accurately weighing 0.0001 g.

4.10 Vacuum Pump: Low draw, positive seal.

4.11 Refrigerator: Separate for sample and standard storage. Capable of maintaining a stable temperature of

4°C.

5.0 REAGENTS

5.1 Methanol: Pesticide grade, or equivalent.

5.2 Organic-free Water: Supplied by laboratory or purchased.

5.3 Neat Solvents: 96 percent purity, or better, for each compound of interest.

5.4 Ultra-high Purity Nitrogen: For use in generating standards and method blanks.

5.5 Standards: Calibration standards containing the compounds of interest are prepared in methanol by either
diluting commercially purchased stock standard mixes or by creating in-house standards from pure solvents. In-house
calibration standards are prepared gravimetrically, in that an appropriate (iL aliquot of each target compound is
introduced into a known volume of methanol. The appropriate (iL aliquot of compound is based upon the compound's
density and response to the selected detector. The calibration standards should be created at such a level that a 5- to
10-(iL spike into a 1-L Tedlar bag filled with nitrogen yields a concentration of 10 ng/L based upon the analysis of
a 500-mL aliquot. Aliquots are evacuated onto a clean trap. Alternatively, commercially prepared stock calibration
gases may be used.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Samples awaiting analysis are stored at 4°C in a dedicated refrigerator. If holding times are exceeded,
the affected data should be qualified as suspect.

7.0 PROCEDURE

7.1 Sample Preparation: Prior to the desorption and analysis of previously trapped soil gas contaminant tubes,
the introduction of a surrogate spike compound via a short purge is recommended. In addition to enhancing quality
assurance, this short purge cycle allows inert gas molecules to replace potentially destructive air molecules still
entrained within the trap tube. The surrogate spike compound should be introduced to the trap via the following
procedure:

FMC-VG-006-3

-------
7.1.1 Program the Tekmar LSC-2 device for a 3-min purge, 3-min desorb, and 8-min bake cycle.

7.1.2 Insert a previously trapped soil gas contaminant tube.

7.1.3 Spike 2 |±L of an appropriate surrogate spike solution (such as 1 Hg/^L 2-bromo-l-chloropropane)
into a glass sparge vessel containing 20 mL organic-free water.

7.1.4 Purge the surrogate spike onto the trap. Desorb and analyze.

7.2 Calibration: Calibrate the analytical system via the external standard method in which response factors
(RF) for each compound are obtained by the analysis of a standard mix of known concentration. Following the
analysis of this known standard mix, create an electronic file establishing each peak's identity, retention time (RT),
RF, and known concentration. Determine the RF for each target compound by dividing the known concentration by
the associated peak response (area or height units). For initial calibration, determine each compound's average RF
by averaging the peak response results generated for the initial linearity study. Program these average RFs are
programmed into the integrator to allow for direct concentration reading of contaminants found in subsequent sample
analyses.

7.2.1 Initial linearity:

7.2.1.1 An initial 3-point calibration curve is generated by the trapping and analysis of multiple
aliquots of calibration standard. For example, if the calibration standard is created such that analysis of
a 500-mL aliquot of standard yields results at the level of the reported detection limits, a 3-point
calibration curve may be achieved by the analysis of 500-, 700-, and 1,000-mL aliquots.

7.2.1.2 Compute the percent relative standard deviation (%RSD see 7.4.1) based on each
compound's RFs (see 7.5) to determine the acceptability (linearity) of the curve. The %RSD should be
less than 20 percent. Reanalyze standard runs yielding data that does not meet the %RSD criterion.

7.2.2 Continuing calibration:

7.2.2.1 Update the calibration of the analytical system 3 times daily: (1) preceding the daily
analyses, (2) midday, and (3) after the daily analyses.

7.2.2.2 Analyze standards run for continuing calibration purposes at a level equal to the reported
detection limits. Continuing calibration RF s for each parameter should fall within 25 percent difference
(%D, see 7.4.3) of the average RF calculated for that particular compound during the initial linearity study.
Qualify data associated with individual parameter not meeting the %D criterion as suspect.

7.2.2.3 Conduct the continuing calibration at a concentration level equal to the reported detection

limits.

7.2.3 Peak identification: Compound identities may be substantiated by the analysis of each individual
component, thereby documenting compound retention time.

7.3 Gas Chromatography:

7.3.1 Analytical sequence: Conduct analyses in sets of 10, whenever possible, with 1 laboratory
duplicate spike analysis run per set. Bracket each set of sample analyses by the analysis of a standard, with a
method blank analysis following each standard run. The number of analyses per sample set and the associated
quality assurance/quality control (QA/QC) varies per contract. Consult the project work plan to verify that all
contractual obligations were met.

FMC-VG-006-4

-------
7.3.2	Preconcentrate soil gas matrix contaminants through the sampling process in which the volatile
contaminants are adsorbed onto the sorbent trap. The affinity that the volatile organic contaminants have for
the special packing inside the sorbent tube causes them to be retained within the tube (i.e., adsorbed onto the
packing) while other components of the gaseous matrix pass through the tube.

7.3.3	Following the addition of a surrogate spike compound, desorb the adsorbed contents of the sorbent
trap (by action of heat and reverse gas flow) onto the head of a previously conditioned GC analytical column.
First hold the desorbed contaminants at constant temperature (usually between 45 to 55°C) for an initial time
period of 3 to 5 minutes. Subsequently analyze the desorbed contaminants by temperature-programmed GC in
which, following the initial hold, the GC oven temperature is raised at a constant rate (usually 8 to 15°C/minute)
until a final temperature of 200 to 225 °C is reached. The final temperature is customarily held for a period of
3 to 10 minutes.

7.3.4	The preferential affinity of the volatile contaminants to either the analytical column's mobile or
stationary phase, the effect of elevated temperature, and the action of carrier gas flow through the column cause
the volatile contaminants to become separated and resolved allowing them to elute in bands through the selected
detector. As long as analytical conditions remain constant, each type of volatile component will elute at a
characteristic RT. In this manner, sample contaminants are identified and quantified by comparison to a run of
standard of known concentration.

7.4 Calculations:

7.4.1	Calculate %RSD using the following equation:

ST)

%RSD = — x 100
X

where:

A (x - x)2
SD = > 			

M N - 1

and X is the mean of initial RFs (per compound).

7.4.2	Calculate relative percent difference (RPD) values using the following equation:

D1 ~ D2
RPD = 	i	— x 100

+ g2>

2

where: D[ = First sample value

D2 = Second sample value

7.4.3 Calculate the %D using the following equation:

%D = —	— x 100

where: X[ = RF of first result

X2 = RF of second result

FMC-VG-006-5

-------
7.4.4 Calculate percent recovery (%R) using the following equation:

where: SSR = Spike sample results
SR = Sample result
S = Amount of spike added

7.5 Sample quantitation: The quantitation of volatile contaminants is calculated based upon the following
formula:

Conentrationsgmple (]ig/L) = target analyte peak response x RF x DF

where: RF = Target analvte concentration in std ffig/L) target analvte peak response in std
DF = Dilution factor, when applicable

8.0 QUALITY CONTROL

8.1 Overview

8.1.1 Field screening generates Level II data. As Level II data, the concurrent analysis of laboratory
duplicates and matrix spike analyses and the use of surrogate spike compounds is not required. However,
beyond the maintenance of practical Standard Operating Procedures (SOPs), certain elements of QC (if opted)
can greatly enhance the interpretation of and the confidence in the data generated. These traditional elements
of QC are discussed here as to how they are adapted to meet the demands of a successfully applied field
screening QA/QC program.

8.1.2 The primary purposes of an appropriate QA/QC program are to: (1) substantiate system
performance and give credence to the accuracy of the results generated, (2) to define aberrations and give
guidance to the interpretation of data, and (3) to achieve these goals through realistic efforts that do not impede
the forward progress of the analytical set.

8.2 Laboratory Duplicates: One laboratory duplicate should be analyzed per sample set. Laboratory duplicate
analyses should generate results of RPD within 30 percent (see 7.4.2).

FMC-VG-006-6

-------
(see 7.4.4). Sample analyses yielding %R values outside this 30 percent window should be reanalyzed or the
associated data should be qualified as suspect.

8.5 Method Blanks: Method blanks are prepared and analyzed in exactly the same manner as sample matrices.
A method blank analysis should follow every standard run and sample of high concentration. Ideally, method blank
results should yield no interferences to the chromatographic analysis and interpretation of target compounds. If
interferences are present, associated data should be qualified as suspect and/or target detection limits should be
adjusted accordingly.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VG-006-7

-------
FASP Method F93011

ANALYSIS OF HALOGENATED AND AROMATIC VOLATILE ORGANIC COMPOUNDS IN

AIR AND SOIL GAS BY THERMAL DESORPTION GAS CHROMATOGRAPHY

1.0 SCOPE AND APPLICATION

1.1 This method covers the analysis of samples in the field by the Field Analytical Services Program (FASP)
Mobile Laboratory. This FASP method is a modification of approved EPA methods and is intended to supply rapid
turnaround analyses in the field. FASP data are not intended to be a substitute for analyses performed within the
Contract Laboratory Program and are not intended to be legally defensible. The FASP method analyte list is divided
into two parts. The primary analyte list presents the compounds that are routinely analyzed by FASP. The
supplemental analyte list presents analytes for which this method is appropriate. Analytes on the supplemental
analyte list may be requested on a project specific basis. Table 1 presents the FASP primary analyte list with FASP
reporting limits. At the completion of the MDL study, nominal retention times will be included. Table 2 presents
the FASP supplemental analyte list. Both retention times and reporting limits will be added as data become
available.

2.0 SUMMARY OF METHOD

2.1 Air and soil gas samples are analyzed by thermal desorption gas chromatography. Samples are adsorbed
on Carbotrap adsorbent tubes and introduced into the gas chromatograph via thermal desorption. Detection of
halogenated and aromatic compounds is accomplished by the use of selective detectors operated in series. The
external standard method of quantitation is used and analyte identification is made by the use of retention time
windows established by the analysis of standards. The recovery of surrogate compounds added to every sample and
standard is used to determine system performance on a sample by sample basis. A laboratory control sample (LCS)
is used to verily calibration accuracy and matrix spikes and spike duplicate (MS/MSD) samples may be used to assess
accuracy and precision.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph fGCl: Varian 3400 GC with a Hall electrolytic conductivity cell detector (ELCD) and
a photoionization detector (PID) installed in series.

4.2 Purge and Trap Equipment: Tekmar Model 2000 Purge and Trap concentrator fitted for thermal desorption.

4.3 Data System: Nelson Analytical
5.0 REAGENTS

5.1 Solvents

5.1.1 All solvents used as diluents will be HPLC grade or equivalent.

5.1.2 Reagent organic free water will be prepared from distilled, deionized water by purging with an inert

gas.

FMC-VG-007-1

-------
Table 1

FASP PRIMARY ANALYTE LIST

ANALYTE	RETENTION TIME	REPORTING LIMIT (ns)

Chloromethane	4.13	50.0

Bromomethane	50.0

Vinyl chloride	4.13	50.0

Chloroethane	4.80	50.0

Methylene chloride	7.44	50.0

1,1-Dichloroethene	6.37	10.0

1.1-Dichloroethane	9.03	10.0
cis-l,2-Dichloroethene	10.50	10.0
trans-1,2-Dichloroethene	8.02	10.0
Chloroform	11.38	10.0

1.2-Dichloroethane	12.97	10.0

1.1.1-Trichloroethane	11.84	10.0
Carbon tetrachloride	12.32	10.0
Bromodichloromethane	16.46	10.0
1,2-Dichloropropene	15.52	10.0
1,1,2,2-Tetrachloroethane	31.66	10.0

1,2-Dichloropropane	15.52	10.0
trans-l,3-Dichloropropene 10.0

Trichloroethene	14.86	10.0

Dibromochloromethane	22.81	10.0

1.1.2-Trichloroethane	21.05	10.0
Benzene	12.73	10.0
cis-l,3-Dichloropropene	17.99	10.0
Bromoform	29.87	10.0
Tetrachloroethene	21.63	10.0
Toluene	19.06	10.0
Chlorobenzene	25.32	10.0
Ethylbenzene	25.99	10.0
Total Xylenes	26.65,28.83	10.0
Styrene	28.83	10.0

1.2-Dichlorobenzene	10.0

1.3-Dichlorobenzene	10.0

1.4-Dichlorobenzene	10.0

FMC-VG-007-2

-------
Table 2

FASP SUPPLEMENTAL ANALYTE LIST

ANALYTE

RETENTION TIME

REPORTING LIMIT

Dichlorofluoromethane

T richlorofluoromethane

Dibromomethane

1,2-Dibromo-3-chloropropane

2,2-Dichloropropane

1,1 -Dichloropropene

Hexachlorobutadiene

1,1,1,2-T etrachloroethane

1,2,3 - Trichloroprop ane

Bromobenzene

n-Butylbenzene

para-Isopropyltoluene

Naphthalene

1,2,3 -Trichlorobenzene

1,2,4-Trichlorobenzene

1.2.4-Trimethylbenzene

1.3.5-Trimethylbenzene
sec-Butylbenzene
tert-Butylbenzene
2-Chlorobenzene
4-Chlorobenzene

I sopropy lb enzene
n-Propylbenzene

5.2 Stock Primary Analvte List Standards: All stock standards are purchased from Supelco as traceable
solutions. The following mixes are provided for reference and their use does not constitute an endorsement.
Equivalent substitutions from other vendors may be used.

5.3	Stock Supplemental Analvte List Standards: Supplemental analyte list standards will be purchased as neat
materials or as EPA traceable solutions on an as needed basis.

5.4	Surrogate Spiking Standard: A mixture of 1 -chloro-2-bromopropane and fluorobenzene available as Supelco
catalogue number 4-8950M or equivalent.

5.5	Matrix Spiking Standard: Matrix spiking solutions will be prepared from benzene, chlorobenzene, 1,1-
dichloroethene, toluene and trichloroethene. The stock matrix spiking solution will either be prepared from neat

Mix

Supelco Catalogue No.

VOC Mix 2
VOC Mix 3
VOC Mix 4
VOC Mix 5
Purgeable C

4-8452M
4-8453M
4-8957M
4-8950M
4-8853M
4-8822M
4-8823M
4-8824M

1.2-Dichlorobenzene

1.3-Dichlorobenzene

1.4-Dichlorobenzene

FMC-VG-007-3

-------
materials or purchased as a solution. (Supelco catalogue number 4-8102M or equivalent). The spiking level will be
at the midpoint of the calibration range.

5.6 Laboratory Control Standard: A laboratory control standard will be prepared that contains the following
compounds:

5.6.1 The laboratory Check Standard will be prepared from a source other than the one used to prepare
the calibration standards, such as the Supelco mixtures catalogue numbers 4-8462M and 4-8465M or equivalent.

5.7	Sorbent Traps: Supelco Carbotrap 300 or equivalent.

5.8	Hydrogen: Ultra Pure or equivalent.

5.9	Helium: Ultra Pure or equivalent.

5.10	Nitrogen: Ultra Pure or equivalent.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Analytical Sequence

7.1.1	Blank.

7.1.2	Initial Calibration.

10 ng
20 ng
50 ng
100 ng
200 ng

7.1.3	Blank.

7.1.4	Laboratory Control Standard (LCS).

7.1.5	Continuing Calibration Standard (CC)-100 ng (Not analyzed on day initial calibration performed).

7.1.6	10 samples.

7.1.7	LCS.

7.1.8	Continue steps f. and g. until 24 hours has passed since last CC.

7.1.9	Blank.

7.1.10	CC.

Chloroform
T oluene
Chlorobenzene

Ethylbenzene

1,1 -Dichloroethene

1,1,2,2-T etrachloroethane

1,2-Dichloropropane
1,1 -Dichloroethane

FMC-VG-007-4

-------
7.1.11 Continue at step f.

7.2 Operating Conditions

7.2.1 Purge and Trap Operating Conditions:

Purge time	12.0 minutes

Dry purge time	8.0 minutes

Desorb time	4.0 minutes

Bake time	8.0 minutes

Purge pressure	20 psi

Purge flow	40 mL/minute

Valve temperature	110 °C

Transfer line temperature	110 °C

Desorb temperature	210 °C

Bake temperature	250 °C

7.2.2 Gas Chromatographic Operating Conditions:

Initial temperature
Initial time
Ramp

Intermediate temp.
Hold time
Ramp

Intermediate temp.
Hold time
Ramp

Final temperature
Analytical column

35 °C
3 minutes
3 °C/minute
77 °C
3 minutes
3 °C/minute
94 °C
3 minutes
10 °C/minute
175 °C

DB-624, 30 meters, 0.53 mm ID, fused silica
megabore capillary

7.2.3 Photoionization Detector Operating Conditions:

Base
Lamp

200 °C
10 ev

7.2.4 Hall Electrolytic Conductivity Detector Operating Conditions:

Reactor

Solvent, n-propanol
Hydrogen
Reaction tube

850 °C

0.50 mL/minute
90 mL/minute
nickel

7.2.5 Data System Operating Conditions:
Information not available.
7.3 Calibration

FMC-VG-007-5

-------
7.3.1 Primary Standards: Primary calibration standards are prepared from purchased solutions described
in Section 5. The concentration of each of the VOC mixes is 2000 ug/mL; the concentration of the
dichlorobenzene standards is 5000 ug/mL; and the concentration of Purgeable C is 200 ug/mL.

7.3.2 Secondary Standards: Secondary calibration standards are prepared by dilution of the primary
standards in methanol.

7.3.3 Working Standards: Working standards are prepared by dilution of the secondary calibration
standards. To produce each of the aqueous calibration standards, the secondary calibration standards are diluted
according to Table 3. The working standards are stored in autosampler vials sealed with Teflon lined caps and
with minimal headspace. Working standards are prepared on a weekly basis or sooner if there is a notable
decrease in the response of any analyte.

7.3.4 Calibration Standards: Based on a 200 ug/mL secondary standard calibration and a 10-uL addition
of the working calibration standard to 5-mL purge water volumes, the calibration levels are 10, 20, 50, 100, and
200 ng. Other calibration ranges may be used as long as linearity of response is maintained and a constant
volume of methanol carrier, not to exceed 100 uL, is used for each calibration level.

7.3.5 Surrogate Standards: A aliquot of a surrogate standard is added to every standard, field sample, and
blank to monitor system performance.

7.3.5.1 The stock surrogate solution is at a concentration of 2000 ug/mL. In a manner analogous
to the preparation of the secondary calibration standards, dilute the primary surrogate standard with
reagent methanol to a 10-mL final volume at 200 ug/mL.

FMC-VG-007-6

-------
TABLE 3

Preparation of Calibration Working Standards

Aliquot of each 200
ug/mL Secondary
Calibration Standard

Total Volume
of Standard

Volume of
Diluent to
Produce 1-mL
Final Volume

Final Concentration of
Working Calibration
Standard

Concentration in 5
mL of Reagent
Water (10 uL
standard spike)

5 uL

15 uL

985 uL

1 ug/mL

2 ug/L

10 uL

30 uL

970 uL

2 ug/mL

4 ug/L

25 uL

75 uL

925 uL

5 ug/mL

10 ug/L

50 uL

150 uL

850 uL

10 ug/mL

20 ug/L

100 uL

300 uL

700 uL

20 mg/mL

40 ug/L

7.3.5.2 Prepare a 1-mL working solution in methanol by addition of 50 uL of the secondary
surrogate standard to 950 uL of methanol. A 10-uL aliquot of the surrogate working solution added to 5
mL of an aqueous calibration standard, reagent water and field sample (low level soil or water) will
produce a final concentration of 20 ug/L.

7.3.6	Laboratory Control Sample:

7.3.6.1	The stock laboratory control solutions are at concentrations of 2000 ug/mL. In a manner
analogous to the preparation of the secondary calibration standards, dilute the primary surrogate standard
with reagent methanol to a 10-mL final volume at 200 ug/mL.

7.3.6.2	Prepare a 1-mL working solution in methanol by addition of 50 uL of the secondary
surrogate standard to 950 uL of methanol. A 10-uL aliquot of the laboratory control working solution to
5 mL of reagent water will produce a final concentration of 20 ug/L.

7.3.7	Matrix Spike Standard:

7.3.7.1	The stock matrix spike solution is at a concentration of 2000 ug/mL. In a manner
analogous to the preparation of the secondary calibration standards, dilute the primary surrogate standard
with reagent methanol to a 10-mL final volume at 200 ug/mL.

7.3.7.2	Prepare a 1-mL working solution in methanol by addition of 50 uL of the secondary
surrogate standard to 950 uL of methanol. A 10-uL aliquot of the matrix spike working solution purged
onto a sample tube will produce a final concentration of 100 ng/sample.

7.4 Sample Analysis

7.4.1 Field Sample Analysis:

7.4.1.1 Air Samples: The sample carbotrap is fitted into the Tekmar LSC 2000 and the restraining
nuts are tightened to finger tightness. A 5-mL Luer Loc syringe is filled with 5 mL of water which is then
spiked with 10 uL of the surrogate spiking solution. This mixture is injected into the purge and trap
apparatus by attaching the Luer Loc tip to the sample introduction valve.

FMC-VG-007-7

-------
7.4.1.2 Quality Control (QC) Sample Analysis: A 5-mL sample volume is used for each QC
sample. To each QC sample 10 uL of surrogate spiking solution is added prior to analysis. Analyze each
QC sample in the manner described in Section 7.4.1 for water sample analysis.

7.4.1.2.1 Blank analysis is performed once each 24-hour period and after each high
concentration sample to prevent carryover.

7.4.1.2.2 Initial Calibration Standard analysis is performed at the beginning of each
assignment and when analytical conditions have changed to the extent the continuing calibration
standard no longer meets quality control criteria. Initial calibration levels are 2, 10, 20, 40 and 100
ug/L. Other initial calibration levels may be used as needed to bracket field sample concentrations.

7.4.1.2.3 Continuing Calibration Standard analysis is performed once each 24- hour
period at a level equal to the midpoint calibration standard.

7.4.1.2.4 Laboratory Control Standard analysis is performed after each initial and
continuing calibration, and after each group of 10 samples.

7.4.1.2.5 Matrix Spike and Spike Duplicate analyses are performed at a frequency of one
set per 20 samples or one set per week.

8.0 QUALITY CONTROL

8.2 Blanks: Blanks may not contain more than reporting limit of any target analyte.

8.3 Initial Calibration: The average relative percent difference (RPD) for the initial calibration must not exceed
25% for the site specific target compounds.

FMC-VG-007-8

-------
Summary of FASP Quality Control Requirements

QC Sample

Acceptance Criteria for Water

Acceptance Criteria for
Soil

Frequency

Blank

Less than reporting limit of all
target analytes

Same as for waters

1 blank analysis
each 24 hours

Initial Calibration

Relative Standard Deviation <
25% for average analyte
concentration factors

Same as for waters

As necessary

Continuing Calibration

Percent Difference for
concentration factors compared
to initial calibration < 15%

Same as for waters

1 Continuing
Calibration each
24 hours

Laboratory Control
Sample

80%-120%

Same as for waters

After each
successful
calibration and
each 10 samples

Surrogates

75%-125%

65%-130%

Every analysis

Matrix Spike and Spike
Duplicate

70%-125%

65-130%

1 set per each 20
field samples
analyzed or
weekly

8.5 Laboratory Control Sample: The recovery of analytes in the Laboratory Control Sample must be between
80% and 120%.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. EPA Method 8000: Gas Chromatography. This reference is from Test Methods for Evaluating Solid Wastes.
Phvsical/Chemical Methods. SW-846. 3rd Edition. Final Update 1. 1991 and are provided in Appendix A.

FMC-VG-007-9

-------
ESAT Region 10 Method

VOLATILE ORGANICS IN SOIL GAS

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed to determine the concentrations of certain
volatile organic compounds (VOCs) in soil gas samples.

1.2 This method is intended to provide estimated quantities of the analytes listed in Table 1.

1.3 This method is intended for, or under the supervision of, analysts experienced in the use of gas
chromatography (GC) and the interpretation of GC chromatograms.

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil gas is drawn through a Tenax trap and then thermally desorbed with a helium
purge onto a megabore column installed in a temperature-programmed GC.

3.0 INTERFERENCES

3.1 Impurities in the purge gas, outgassing of organic compounds from the plumbing ahead of the trap and
solvent vapors in the laboratory account for a majority of contamination problems. Each Tenax trap must be analyzed
to ensure freedom from contamination prior to sample collection.

3.2 Interferences due to cross-contamination in the field will be determined by collecting a blank soil gas sample
between sampling sites. In addition, transport blanks will be submitted for analysis along with the soil gas samples.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System: The following option meets the requirements of this method. Other Purge and Trap/GC
configurations may be used if they meet method requirements.

4.1.1 Gas Chromatograph: An analytical system complete with a temperature-programmable GC suitable
for on-column injection is required. All necessary accessories including injector and detector systems must be
designed to accept the appropriate analytical column. The system must have a data handling system attached
to the detectors that is capable of retention time labeling, relative retention time comparisons, and providing
relative and absolute peak height and/or peak area measurements.

4.1.1.1 Column 1: 30m x 0.53mm I.D. DB-624 fused silica megabore capillary column (J&W
Scientific), or equivalent.

4.1.1.2 Detectors: Photoionization detector (PID) with a 10.2 eV lamp with makeup gas supplied
at the detector inlet and connected in series to a Hall detector with a short length of deactivated fused
silica capillary column.

4.1.1.3 Gas Supply: The purge gas, carrier gas and makeup gas is ultrapure helium. The reaction
gas required for the Hall detector is ultrapure hydrogen.

FMC-VG-008-1

-------
Table 1

TARGET COMPOUND LIST AND QUANTITATION LIMITS

Volatile Organic Compound

Quantitation



(ng on colurr

Benzene

20

Carbon Tetrachloride

20

Chlorobenzene

20

1,2-Dichlorobenzene

20

1,1,1 -Trichloroethane

20

1,1 -Dichlorobenzene

20

1,1,2-Trichloroethane

20

1,1,2,2-T etrachloroethane

20

Chloroethane

20

2-Chloroethyl Vinyl Ether

20

Chloroform

20

1,2-Dichlorobenzene

20

1,3-Dichlorobenzene

20

1,4-Dichlorobenzene

20

1,1 -Dichloroethylene

20

1,2-trans-Dichloroethylene

20

1,2-dichloropropane

20

1,3-cis-Dichloropropene

20

1,3-trans-Dichloropropene

20

Ethylbenzene

20

Methylene Chloride

20

Bromoform

20

Bromodichloromethane

20

T richlorofluoromentane

20

Chlorodibromomethane

20

T etrachloroethy lene

20

T oluene

20

T richloroethy lene

20

Vinyl Chloride

20

o-Xylene

20

m-Xylene

20

p-Xylene

20

Carbon Disulfide

20

Acetone

20

Methyl Chloride

20

Methyl Bromide

20

Styrene

20

2-Hexanone

20

4-Methyl-2-Pentanone

20

FMC-VG-008-2

-------
4.1.2 Desorption Device: This method utilizes a Tekmar purge and trap system to desorb samples directly
onto the GC column. Several other complete devices are commercially available.

4.1.2.1 Trap: 12in x ,125in O.D. stainless steel Tenax, Supelco or equivalent.

4.1.2.2 Desorber: The desorber must be capable of rapidly heating the trap to 180°C.

4.2 Other Laboratory Equipment

4.2.1 Microsvringes: lOuL, lOOuL and 5ml

4.2.2 Vials: 1.8 ml with Teflon lined septa for purgeable standards.

5.0 REAGENTS

5.1 Solvents

5.1.1 1-Propanol: Pesticide quality, or equivalent.

5.1.2 Methanol: Pesticide quality, or equivalent.

5.2 Reagent Water: Reagent water may be generated using a carbon filter bed containing activated carbon
(Calgon Corporation, Filtrasorb-300, or equivalent) or a water purification system (Milli-Q, Barnstead Water-1
systems, or equivalent), or purchased from commercial laboratory supply houses.

5.3 Gases

5.3.1 Helium: Ultrapure or chromatographic grade.

5.3.2 Hydrogen: Ultrapure or chromatographic grade.

5.4 Stock Standard Solutions: Stock standard solutions in methanol should be purchased as manufacturer
certified solutions.

5.5 Calibration Standards: Calibration standards at a minimum of three concentration levels should be prepared
through dilution of the stock standards with methanol. One concentration level should be near, but not above, the
method detection limit. The remaining concentration levels should define the working range of the instrument.
Calibration standards must be protected from light and stored in Teflon sealed screw cap bottles at 4°C.

5.6 Surrogate Standards: The analyst will monitor the performance of the desorbtion and analytical system by
spiking each sample, blanks, and matrix spikes with one or two surrogates not expected to be present in the sample.

5.7 Matrix Spikes: Matrix spike solutions can be made by dilution of stock standard solutions.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be handled, preserved and shipped maintaining a chain of custody following the current
EPA regulations and recommendations in force at the time of sample collection. Soil gas samples should be collected
in Supelco Tenax tubes at appropriate volumes and sampling rates to prevent breakthrough of target analytes, then
capped and shipped on ice in insulated containers to the lab.

7.0 PROCEDURE

FMC-VG-008-3

-------
7.1 Safety

7.1.1 The toxicity and carcinogenicity of each reagent has not been precisely defined; however, each
chemical compound must be treated as a potential health hazard.

7.1.2 The analysts should be familiar with the location and proper use of the fume hoods, eye washes and
fire extinguishers. In addition, the analysts must wear protective clothing and safety glasses when performing
an analysis or extraction. Contact lenses cannot be worn in the laboratory.

7.1.3 Fume hoods must be utilized whenever possible to avoid potential exposure to organic solvents.
7.2 Calibration

7.2.1 Initial Calibration:

7.2.1.1 Generate initial calibration curves using an external standard technique using at least three
calibration standards for each target compound as described in Section 6.5. The calibration curves are
generated by injecting 10 uL of standard into 5 ml of water. The water and standard are then purged with
helium for 10 minutes onto a Tenax trap then thermally desorbed as described in Table 2.

7.2.1.2 Correlation coefficients (R2) for each calibration curve must be greater than 0.95 to be
valid. A new initial calibration curve must be run any time the GC is altered or shut down for long periods
of time.

7.2.2 Continuing Calibration:

7.2.2.1 A continuing calibration must be performed on a regular basis. The midrange initial
calibration standard is used for continuing calibration validation. For a continuing calibration to be valid,
a percent difference (%D) must be less than or equal to 25%. If this criteria is not met, a new initial
calibration curve must be run.

7.3 Sample Desorbtion: This sample desorbtion technique for VOCs in soil gas is recommended for the Tekmar
LSC-2000 purge and trap system. Specific parameters may be found in Table 2.

7.3.1 Remove the caps from both ends of the Tenax trap.

7.3.2 Inject the proper amount of surrogate into the trap packing material.

7.3.3 Immediately place the trap in the LSC-2000 and tighten.

7.3.4 Make sure the trap temperature is 30°C or less.

7.3.5 The sample is now ready to be desorbed directly onto the column.

FMC-VG-008-4

-------
Table 2

Recommended Operating Conditions

Purge and Trap Device Tekmar LSC-2000
Desorbtion Temperature 180°C for 4 minutes
Bakeout Temperature 200°C for 10 minutes
Gas Chromatograph Tracor series 585

Detectors PID with a 10.2 eV lamp connected in series with a Hall Electrolytic
Conductivity Detector.

Data Processor Nelson Analytical PC with a dual channel interface and 30-MB hard disk
drive for data storage.

Column J&W DB-624 fused silica 30m x 0.53 mm I.D.Carrier Gas Ultrapure helium, 10
ml/min

Makeup Gas Ultrapure helium, 30 ml/min

Reaction Gas Ultrapure hydrogen, 20 ml/min

Column Oven Initial temperature: 40°C

Initial time:	3 minutes

Ramp rate:	8 deg/min

Final temperature:	190°C

Final time:	5 minutes

Detector Temperature PID: 200°C

HALL: 800°C

GC Analysis Time 26 minutes

7.3.6	Thermally desorb the sample at 180°C for 4 minutes. The GC system begins data collection and
temperature program with sample desorbtion.

7.3.7	Once the sample is desorbed, bake the trap for 10 minutes at 200°C.

7.3.8	After baking the trap, allow it to cool to 30°C. Wait for the GC temperature program to end and the
data to be processed, then desorb the trap again to demonstrate that the trap is free from contaminants.

7.3.9	Remove clean trap from the system, cap both ends, and place trap in holder.

7.4 Instrumental Analysis

7.4.1 Instrument Parameters: Table 2 summarizes acceptable operating conditions for the GC and purge
and trap system.

FMC-VG-008-5

-------
7.4.2	Chromatograms:

7.4.2.1 The following information must be recorded on each chromatogram:

7.4.2.1.1	Instrument and detector identification.

7.4.2.1.2	Column coating, length and ID.

7.4.2.1.3	Oven temperature.

7.4.2.1.4	Inj ector/detector temperature.

7.4.2.1.5	Gases and flow rates.

7.4.2.1.6	Site name.

7.4.2.1.7	Sample number.

7.4.2.1.8	Date and time.

7.4.2.1.9	GC operator initials.

7.4.3	VOC Identification:

7.4.3.1	Qualitative identification of target VOCs is based on retention time matching of the sample
with standard chromato grams.

7.4.3.2	For a compound which can be detected on both the PID and Hall detector, the compound
must be identified in both chromatograms for a positive identification to be made.

7.4.3.3	Individual retention time windows should be less than 2 percent difference (%D).

7.4.4	Analytical Sequence:

7.4.4.1	Trap Blank.

7.4.4.2	Initial calibration.

7.4.4.3	Associated QC method blank and matrix spikes.

7.4.4.4	Ten samples each followed by blank runs.

7.4.4.5	Continuing calibration.

7.5 Calculations

7.5.1 Sample Quantitation:

7.5.1.1 Use the following calculation to determine the concentration in the sample. The response
can be measured by automated peak area measurements or from an integrator. Sample quantitation is
based on a three point initial external calibration of all target analytes as described in Section 7.2.1.

FMC-VG-008-6

-------
Concentration ( ng/L ) = —

Where A is the instrument peak area response (ng) and B is the volume of soil gas drawn through the trap.

7.5.2 Matrix Spike Recovery:

7.5.2.1 To calculate the percent recovery for the matrix spike and matrix spike duplicate use:

% Matrix Spike Recovery = — * 100

Where C is the instrument peak area response (ng) from the sample and D is the known concentration
spiked into the sample (ng).

7.5.2.2 Relative percent difference (RPD) is calculated using:

E - F

Relative Percent Difference = x 100

E + F

Where E is the known concentration of each compound and F is the peak area response in ng.

7.5.3 Surrogate Recovery:

7.5.3.1 Surrogate recovery is calculated using:

% Surrogate Recovery = — x 100

Where G is the instrument peak area response (ng) from the sample and H is the peak area response
determined from a standard.

7.5.4 Continuing Calibration:

7.5.4.1 Percent difference is calculated using:

% Difference = — — x 100

Where I is the known concentration of each compound and J is the peak area response in ng.

7.5.5 Retention Time Percent Difference:

7.5.5.1 Retention time percent difference is calculated the same as in 7.5.4 by replacing retention
times with concentrations.

8.0 QUALITY CONTROL

8.1 Quality control must be met for all analyses. Limits for matrix spike and matrix spike duplicate must fall
between 50%-150% relative percent difference (RPD). Percent recoveries for the surrogates must also meet the same
criteria as the matrix spikes.

FMC-VG-008-7

-------
9.0 METHOD PERFORMANCE

Information not available.
10.0 REFERENCES

Information not available.

FMC-VG-008-8

-------
Region V ESD Method
FIELD METHOD FOR VOLATILE INDICATOR PARAMETERS

IN SOIL GAS SAMPLES USING PHOTOVAC GC/PID

1.0 SCOPE AND APPLICATION

1.1 This method is used for field analysis of gas withdrawn from the soil using a soil gas sampling probe. It is
intended to characterize volatile organic contaminants in soils when used in conjunction with a soil gas sampling
program. This method will characterize the general extent of volatile organic contamination in soils, while being
specific for

1.2 Method detection limits (MDL) are about 25 ppb of gas when calibrated against gravimetric standards.
MDLs will be determined as part of the method validation.

1.3 This method provides Level II quality data and is used as a means to screen soil gas samples that have been
previously collected in glass sampling bulbs, tedlar gas sampling bags, or directly collected into an air-tight syringe.
No positive compound identification is performed. Compound identification is based solely on retention times
compared to standards.

1.4 Modifications of this analysis method should be supported by method validations and quality assurance
checks.

2.0 SUMMARY OF METHOD

2.1 A quantity of gas is extracted from beneath the soil surface by methods described in the soil gas sampling
plan. Samples of gas are collected in glass bulbs, tedlar bags, or directly into the injection syringe and analyzed by
gas chromatography using photoionizing detection (GC/PID). Calibration of the GC system permits semiqualitative
and semiquantitative determination of select target constituents. The method is designed to provide real-time, onsite
analysis for a large number of soil gas samples. The method takes about 20 minutes per sample, excluding QA/QC
sample analysis and instrument calibration.

3.0 INTERFERENCES

3.1 Samples can become contaminated by diffusion of volatile organics through the collection container septum
during handling and storage; and inadequately cleaned sampling equipment and sample containers.

3.2 Inaccurate quantification can occur from compounds or isomers that co-elute; samples containing large
numbers of volatile constituents that cause interference peaks to co-elute with target analytes; estimating the
concentration of nontarget constituents using the response factors from target constituents; impurities in calibration
standards, dilution solvents/gases, and carrier gases; contamination by carryover when high-level and low-level
samples are sequentially analyzed; and poor instrument performance.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph.

4.1.1 Photovac IOS5Q: Photoionizing detector, column back-flushing, electronic integration, column
heater, and report annotation or equal.

4.1.2 Column: 0.53 mm x 10 m capillary column; CPSIL-5; and blue phase, low polarity, or equal.
Including 1 m precolumn.

FMC-VG-009-1

-------
4.1.3 Septum: Nonsorbing chromatographic septum.

4.2 Laboratory Oven: Capable of maintaining a temperature of 40°C ± 2°C. The oven should be used near a
hood.

4.3 Water Bath: Capable of maintaining a temperature of 40°C ± 2°C. The bath should be used in a hood.

4.4 Refrigerator/Cooler: Capable of achieving a temperature of 4°C.

4.5 Syringes: 10, 50, 250, 500, 2,000 |±L gas-tight and liquid delivery syringes, with replaceable needles, spare
needles, and plungers as required for injection of samples and standards.

4.6 Sample/Standards Containers: Glass sampling bulbs (60 mL). Sample containers shall be flow-through
design with greaseless gas tight end seals and a sample port with replaceable seal.

4.7 Batterv/AC Adaptor: 12-volt delivery.

4.8 Flowmeter: Calibrated in the range of 0 to 100 mL/minute.

4.9 Ventilation System: Sampling equipment as described in the Site Sampling Plan.

5.0 REAGENTS

5.1 Air: Carrier gas, ultra-zero grade (<0.1 ppm total hydrocarbons).

5.2 Blank Gas: Air or nitrogen, 99.99 percent purity grade.

5.3 Methanol: GC grade, 99.9 percent purity grade.

5.4 Reagent Water: Water in which the interferant is not observed at the MDL of the parameters of interest
(HPLC grade or equivalent).

5.5 Stock Standards

5.5.1 Option 1: Gravimetric preparation from neat standard materials or purchased as certified solutions.

Store refrigerated and protected from light. Tetrachloroethene (PCE), 1.0 mg/mL in methanol.

5.5.2 Option 2: Purchased as certified gaseous standard. Tetrachloroethene (PCE), 1 ppm.

5.6 Calibration Standards: For each analyte of interest, prepare a calibration standard at a minimum of three
concentration levels. One of the external standards should be at a concentration near the method detection limit, but
above the method detection limit. The other concentrations should define the working range of the detector. Prepare
the calibration standards by injecting an aliquot of the working standard into the glass sampling bulb previously
purged with ultra-pure air. Heat the bulb at 40°C for 30 minutes to vaporize the methanolic standard.

5.7 Working Standards: See Section 5.6 for the procedure to prepare working standards for instrument
calibration.

5.8 Matrix Spiking Standards: See Section 5.6 for the procedure to prepare working standards for instrument
calibration. A matrix spike procedure is analogous, except that instead of using ultra-pure air, an actual sample is
prepared.

5.9 Matrix Spikes: Prepared at the midrange standard concentration.

FMC-VG-009-2

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

See soil gas sampling plan.

7.0 PROCEDURE

7.1 Safety.

7.1.1 The target constituents have been tentatively identified as known or suspected carcinogens.

7.1.2 Gas standards and dilute standards in co-solvents should be handled carefully. Information such
as NIOSH permissive exposure level (PEL), odor threshold, exposure pathways, fire hazard, and physiological
effects of exposure for solvents, target constituents, and other suspect sample constituents are shown in the site
safety plan. Safety precautions will be observed at all times.

7.1.3 Sample analysis will be performed in a well-ventilated area with adequate skin, eye, and breathing
protection provided for the analyst.

7.2 Sample Preparation

7.2.1 Remove the glass sample bulbs from storage and heat at 40°C for 30 minutes. Analysis of the soil
gas is performed while maintaining the sample temperature at 40°C. No additional sample preparation or
preconcentration procedures are required and the sample is ready for analysis.

7.2.2 Prepare matrix spike samples by injecting an aliquot of the working standard into a replicate sample

bulb.

7.2.3 Prepare laboratory blanks by purging a glass sample bulb with ultra-pure air.

7.3 Sample Analysis: Refer to Photovac 10S50 operating manual for specific instrument operating conditions.

7.3.1 Turn the Photovac power on and wait 30 minutes for the GC oven and PID to stabilize. Following
warm-up, run several blanks until a stable baseline has been established. Specific instrument operating
parameters will be provided after method validation.

7.3.2 Perform required instrument calibration. Instrument gain settings affect the calibration of the
equipment and should not be varied.

7.3.2.1 Initial calibration: The GC is calibrated using an external standard calibration procedure.
(See Section 5.6 for preparation of calibration standards.) Analyze each calibration standard using the
same technique that will be used to introduce the actual samples into the gas chromatograph. Tabulate
area responses against the concentration injected, and calculate response factors. If the percent relative
standard deviation is less than 35 percent over the working range, linearity through the origin can be
assumed, and the average response factor can be used to calculate sample concentrations. Tabulate
retention times (RT) of each target constituent, and calculate the mean RT. A new initial calibration will
be performed whenever equipment maintenance has been performed, or the calibration check standard
does not meet QC criteria. QC criteria for the calibration check is discussed below.

7.3.2.2 Calibration check: The average response factor must be checked at the start of each
working day and once every 10 samples by the injection of a midrange calibration standard. If the
response factor or RT for any analyte deviates from the predicted value by more than 50 percent or 15
percent, respectively, a new external calibration will be performed for that analyte. No samples will be
analyzed after the calibration check does not meet QC criteria. If the calibration check fails, one
additional check analysis may be performed to establish a successful calibration before corrective action

FMC-VG-009-3

-------
must be taken. Corrective action may include, but is not limited to, changing the septum, carrier gas
flows, detector lamp, oven temperature, or the column.

7.3.3 Using a 2.0-mL air-tight syringe, remove 1.0 mL of sample gas from the glass bulb and inject into
the GC. If the analysis indicates that the results are more than 50 percent above the upper calibration range,
inject a smaller sample volume (5 to 1,000 |±L). Note that varying the injection volumes is not expected to affect
instrument calibration. If total VOA content can be estimated from field data (i.e., using an HNu or similar
instrument), then a smaller volume of soil gas should be injected to minimize potential instrument
contamination.

7.3.4	Record pertinent information in the injection log (Appendix B).

7.3.5	Following completion of sample runs each day, the instrument will be left in purge mode
overnight to preclude the buildup of contaminants on the analytical column and allow the instrument to
stabilize. The PID may be turned off.

7.4 Calculations

„	r, , . / T, ,	Peak Area

Response Factor RF [Area/ ug/L)1 = 	¦	

Cone, of Analyte (]ig/L)

Mean RF [Area/ (]ig/L) ] = Average of the Response Factors

Mean RT (minutes) = Average of the Retention Time

n	j- r> i j- ¦ cj- j n ¦ j- ¦ / o \ Standard Deviation (n - 1) .

Percent Relative Standard Deviation (%) = 	 times 100

Mean Response Factor

Pqelk

Soil Gas Concentration (ug/L) = 	 times Dilution Factors

Mean RF

n	j- n i * , o i Expected - Observed .	nn

Percent Deviation (%) = 	±	 times 100

Expected

, / T, Sum of All Peak Areas

Total Soil Gas Concentration (ug/L) = 	

Average of All Mean RF

8.0 QUALITY CONTROL

8.1 Daily midrange calibration checks performed before the analysis of each days lot of samples or with
each lot of 10 samples, whichever is more frequent.

8.2 Analysis of laboratory blank samples performed before the analysis of each day's lot of samples or 1 per
20 samples, whichever is more frequent. Should the results of the laboratory blanks indicate contamination, the
cause of the contamination will be investigated and corrective action taken.

FMC-VG-009-4

-------
8.3	Analysis of a matrix spike and a matrix spike duplicate sample at a frequency of 1 per 20 samples
analyzed.

8.4	Use of the retention time marker during the analysis of all samples and standards for semiqualitative
identification.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VG-009-5

-------
EMSL METHOD 8022
SAMPLING AND FIELD GAS CHROMATOGRAPHIC

ANALYSIS FOR VOLATILE ORGANICS IN SOIL GASES

1.0 SCOPE AND APPLICATION

1.1 This method describes the sampling and gas chromatographic analysis of various volatile organic
compounds in soil gases. Table 1 indicates the typical retention times and method detection limits for compounds
that have been analyzed by this method. The field gas chromatographic procedures described are designed for use
on portable instruments with an emphasis on quick turn-around time for sample analysis. Method performance
may be affected by the type or condition of the gas chromatograph. Specifically, Method 8022 has been used to
detect the following compounds:

Benzene 1,1,2,2-T etrachloroethane

Trans-1,2-Dichloroethene Toluene

Ethy lbenzene 1,1,1 -Trichloroethane

T etrachloroethene T richloroethene

1.2 This method is recommended for use by, or under the close supervision of, analysts experienced in the
operation of gas chromatographic instrumentation.

1.3 Because this method is an indirect measurement of subsurface contamination, results are affected by
features specific to each site. Some of the variables that will affect soil gas measurements are depth to primary
contamination, soil type, barriers to subsurface vapor transport (e.g., clay lenses and zones of perched water), and
conditions favorable to degradation of the target analytes; such conditions can deplete target analytes to below
detectable limits.

1.4 This procedure is to be used only as a screening procedure in order to locate positions where more
representative methods of sampling and analyzing the primary source material will be used.

2.0 SUMMARY OF METHOD

2.1 Sample Collection: Samples are collected through a sampling probe inserted into the ground to the
desired depth. Prior to sample collection the probe is purged with at least 5 times its volume using a vacuum
pump. Samples are collected using a variety of gas sampling devices, such as gas-tight syringes, evacuated
canisters, metalized bags, and sorbent tubes.

2.2 Sample Analysis: Samples are analyzed by gas chromatography using direct injection (syringe, bag
samples) pressurization (canisters), purge and trap (Method 5030) sorbent tubes (Method 5040), or other methods
of introducing the sample into the instrument. The components are separated by a gas chromatographic column
and detected using a detector appropriate to the target analytes. Although other detectors may be used, this
method describes the use of electron capture and photoionization detectors.

3.0 INTERFERENCES

3.1 Contamination of the sampling apparatus can cause interferences. Potential sources of contamination
include syringes, sampling pumps, probes, manifolds, septa, etc. Probes should be thoroughly cleaned between
sampling events. Replaceable parts such as Teflon syringe plunger tips, and septa on the sampling manifolds or
glass bulbs should be replaced as needed. Pumps and manifolds should be periodically

FMC-VG-010-1

-------
Table 1

METHOD DETECTION LIMITS FOR VOLATILE ORGANICS*

compound
ECD

CAS
Number

Retention
Time (min)

Method
detection
limit
(picograms)

1,1,1 -Trichloroethane
Trichloroethene
T etrachloroethene
1,1,2,2-T etrachloroethane

71-55-6
79-01-6
127-18-4
79-34-5

1.52
2.05
3.97
11.48

0.4
1.0
0.4
2.7

PID

T rans-1,2-Dichloroethene
Benzene
Trichloroethene
T oluene

T etrachloroethene
Ethylbenzene

540-59-0

71-43-2

79-01-6

108-88-3

127-18-4

100-41-4

1.41
3.26
3.86
5.74
7.00
10.29

4.0
6.0
14.0
14.0
30.0
25.0

* - Detection limits and retention times taken from Field Evaluation of Four Portable Gas Chromatographs
(Reference 2).

1 - Shimadzu Mini-2 Gas Chromatograph. Column: 15-m DB-624 0.53 mm I.D. wide-bore capillary column, 3.0
(im film thickness. Col. temp.: 65°C (isothermal). Carrier gas: 15 cm3/min., nitrogen. Make-up gas: 5 cm3/min.,
nitrogen. Detector: ECD.

cleaned.

3.2 Samples or instrumentation can be contaminated by diffusion of volatile organics into sampling
devices or analytical instruments. Sources for such contamination include vehicle or generator exhaust, air
pollution, presence of standards in the analysis area, or particles of contaminated soil.

3.2.1	Instruments should be located upwind of any contamination source.

3.2.2	Samples of ambient air near the instrumentation should be checked regularly.

3.2.3	In a field laboratory, standards preparation and sample analysis are frequently performed
in close proximity. Minimum method quality assurance demands that standards, solvents, and wastes are
handled and stored away from the instruments. Ovens should be vented.

3.2.4	To maintain a clean operating environment, the analyst may not be assigned to take field

samples.

3.2.5	The use of solvent-containing materials, e.g. duct tape, marking pens, or electrical tape,
may contaminate samples or analytical instruments.

FMC-VG-010-2

-------
3.2.6 When demonstrating that a sample container is clean, care must be taken to use
hydrocarbon-free gas for all blank analyses. Instrument carrier gas can provide a source of such gas. Use
of high-purity gases and appropriate traps are required to reduce potential contaminants.

3.3 Contamination by carryover can occur whenever high-level samples are analyzed before low-level
samples. Carryover can be reduced by heating the syringe with a nitrogen purge at 40°C between sample injections.
As a cross-contamination check, a blank sample should be analyzed after the analysis of any high level samples.

4.0 APPARATUS AND MATERIALS

4.1 Field Sampling Apparatus

4.1.1 Probe, manifold, and pump system: All components of the sampling train must be
constructed of materials inert to volatile organic compounds.

4.1.2 Sample collection devices: Gas-tight side-port syringes of a volume at least 20% greater
than the anticipated sample volume are suggested.

4.2 Gas Chromatographic System

4.2.1 Gas chromatograph: A complete analytical system consisting of a gas chromatograph
(laboratory or portable) suitable for direct injections, and all required accessories, including detectors,
columns, column supplies, gases, syringes, and recorder or integrator. A data system that measures peak
heights and/or peak areas is recommended.

4.2.2 Chromatographic column: A column with sufficient resolution to provide baseline
resolution of method analytes and interfering peaks is required. For most applications, a 15-m length by
0.53-mm I.D., wide-bore capillary column with a 3.0-(im film thickness, (DB-624, J&W Scientific or an
equivalent) is recommended. Other columns (capillary or packed) may be used as long as the criteria
given in Section 8.0 are met.

4.2.3 Detectors: Electron capture or photoionization detector (10.2 eV).

4.3 Sample introduction apparatus: Refer to the purge-and-trap (Method 5030) or sorbent cartridge
(Method 5040) methods for the appropriate equipment for these sample introduction procedures.

5.0 REAGENTS

5.1 Solvents: Methanol, hexane (purge and trap grade).

5.2 Stock Standards: Stock standards may be prepared from pure standard materials or purchased as
certified solutions of known concentrations (e.g., EPA-traceable methanolic stock solutions) Prepare stock
standards in a solvent appropriate for the detector being used.

5.2.1 For preparation of stock standards, refer to Section 5.2 of Methods 8010 and 8020.

5.3 Secondary Dilution Standards: May be prepared for single or multiple components. Prepare by
dilution of stock solutions of known concentrations in methanol in 10.0-M1 or 25.0-M1 volumetric flasks. Transfer
the secondary dilution standard to a small-volume septum-capped container, such as an autosampler vial. Store,
with minimal headspace, at 0-5°C and protect from light.

5.4 Gas-Phase Calibration Standards: Dispense an aliquot of 1.0 to 10.0 mL of secondary standard into a
glass bulb of 500-mL volume using the solvent-flush technique. Prepare gas-phase calibration standards at a

FMC-VG-010-3

-------
minimum of three concentration levels. One of the concentrations should be near but above the method detection
limit. The remaining concentrations should correspond to the expected range of concentrations found in real
samples or should define the working range of the GC.

5.4.1 Gas-phase standards are not stable and must be discarded after 4 hours.

5.5 Gas-Phase Calibration Check Standard: A standard at a concentration that is in the mid-range of
expected sample concentrations.

5.6 Compressed Gas Standards: As an alternative to EPA stock standards, commercial gas standards may
be used. The accuracy of commercial standards should be certified with reference to an independent standard prior
to use.

5.6.1 Compressed gas standards may require dilution if used as calibration standards.
6.0 SAMPLE COLLECTION AND HANDLING

The EPA Guidance Document for Soil-Gas Measurement describes sample collection and handling.
7.0 PROCEDURE

7.1 Initial Preparation: Instruments must be set up and stabilized in the field analytical facility prior to

use.

7.1.1 Set up the instruments following the recommended chromatographic conditions listed in

Table 1.

7.1.2 Attach the column to the injector only, and set the oven temperature to 150°Ctobake
out any contaminants that may have been acquired during shipping.

7.1.3 Lower the oven temperature to the recommended starting temperature and attach the free
column end to the detector. Turn on the detector and allow the instrument to stabilize.

7.2 Calibration

7.2.1 Baseline check: check for baseline noise. The response of any analyte which is used for
calibration or quantitation must exceed the baseline noise by a factor of six.

7.2.2 Calibration must take place using the same sample introduction method that will be used
to analyze actual samples (e.g., 0.25 cm3 gas sample injections, purge and trap, etc.).

7.2.3 External Calibration Procedure: The procedure for external calibration should be used.
For each analyte of interest, prepare calibration standards at a minimum of three concentration levels by
adding volumes of secondary dilution standards to 500-mL glass bulbs, as described in Section 5.4 of this
method. One of the external standards should be at a concentration near, but above, the method detection
limit. The other concentrations should correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.

7.2.3.1 Refer to Section 7.4.2 of Method 8000 for calculation of calibration curves and
calibration factors.

7.2.3.2 If the percent relative standard deviation (%RSD) of the calibration factors is
less than 25% over the working range, linearity through the origin can be assumed and the

FMC-VG-010-4

-------
average calibration factor may be used. If the %RSD is greater than 25%, calibration curves must
be constructed for each analyte.

7.2.4 Retention Time Windows: Before establishing retention time windows, ensure that the
GC system is within optimum operating conditions. Retention time windows are established from the three
standards injected during the initial calibration.

7.2.4.1 Calculate the standard deviation of the three absolute retention times for each
single component using the initial calibration curve. Plus or minus three times the standard
deviation of the absolute retention times for each component in the standard will be used to define
the retention time window. If the retention time window is less than +0.01 minutes, then a +3%
window may be used.

7.2.4.2 An experienced analyst should be used for the interpretation of chromatograms.
In those cases where the retention time deviation for a particular analyte is greater than the
retention time window, the daily calibration check standard should be evaluated to determine if
the chromatographic system is operating properly.

7.3 Daily Calibration Check: Performed using the gas-phase calibration check standard, described in
Section 5.5. The daily calibration check is performed prior to the analysis of the first sample of the day, at mid-day
and following the last sample of the day. Also, a daily calibration check must be performed whenever operating
conditions are changed (e.g., carrier gas is replaced or the septum is changed), or whenever a change in instrument
performance is suspected. The frequency of performance verification is dependent on the detector. Detectors such
as the electron capture and photoionization detectors, which operate in the subnanogram range, are more
susceptible to changes in detector response than less sensitive detectors, such as flame ionization detectors.

7.3.1 The retention times of the analytes in the first daily check standard must fall within the
retention time windows established during the initial calibration.

7.3.1.1 If any retention times are outside of the established windows, corrective action
must be taken (refer to Section 7.4 of this method).

7.3.1.2 Establish daily retention time windows using the retention times from the first
daily check standard and the standard deviations determined in the initial calibration.

7.3.2 If the response for any analyte in the first daily check standard varies from the initial
response by more than ±25%, a new calibration curve must be prepared for that analyte.

R ~ R

% difference = — x 100

where:R[ = Calibration Factor from initial calibration curve or first daily check standard

analysis.

R2 = Calibration Factor from continuing analyses.

7.3.3 If the mid-point or final calibration check standard of the day does not meet the +25%
difference criterion, the calibration check standard must be reanalyzed. If the calibration factor still does
not meet the criterion, the target analytes in the samples analyzed since the last acceptable check standard
must be flagged and a new initial calibration should be performed if more samples are to be analyzed that
day.

FMC-VG-010-5

-------
7.4 Suggested Chromatographic System Maintenance for Capillary Columns: Corrective measures may
include any of the following remedial actions. Clean and deactivate or replace the glass injection port insert. Cut
off the first few inches, up to one foot, of the injection port side of the column. (Note: Non-perpendicular cuts of
the column may degrade system performance.) Remove the column and solvent backflush according to the
manufacturer's instructions. If these procedures fail to eliminate degradation problems, it may be necessary to
deactivate the metal injector body and/or replace the column. (Section 7.7.3, Method 8000).

7.5 Gas Chromatographic Analysis: Refer to Section 7.6 of to Method 8000 for analytical procedures.
Samples must be analyzed using the same sample introduction procedures used for instrument calibration.

7.6 Calculations: The concentration of each analyte in the samples may be determined using a computing
integrator programmed with calibration standard data, or may be calculated by hand. Refer to Section 7.8.1 of
Method 8000 for calculation of sample concentrations.

8.0 QUALITY CONTROL

8.1 Sampling OC

8.1.1 Before collecting samples, any potential sources of interference from the sampling
apparatus should be eliminated. Any sampling train components that could come in contact with samples
should be thoroughly cleaned.

8.1.1.1 Probes and manifolds should be cleaned with hot soapy water or steam cleaned
and rinsed with clean water. Sampling at locations with heavy soil contamination may require that
the probes and manifolds be solvent-rinsed and purged with nitrogen. Blank samples of ambient
air should be collected through the system in the same manner that soil-gas samples are collected
prior to probe emplacement.

8.1.1.2 If any chance exists for back-diffusion of contaminants from the sampling
pumps, the pumps should be thoroughly cleaned, especially following sampling of heavily
contaminated locations. Any parts that may absorb or emit volatile organic compounds (e.g.,
filters, 0-rings) should be cleaned or replaced.

8.1.2 Samples should be collected in duplicate. However, because of budget or schedule
constraints, it may not always be possible to analyze more than one sample per location. If two or more
samples are analyzed, the difference between the sample results should be within plus or minus 20% of the
initial results, or the point should be resampled.

8.2 Field Laboratory OC

8.2.1 Each laboratory that uses these methods is required to operate a quality control program.
The minimum requirements of this program consist of an initial demonstration of laboratory capability.
The laboratory must maintain records to document the quality of the data generated. Ongoing data quality
checks are compared with established performance criteria to determine if the results of analyses meet the
performance characteristics of this method.

8.2.2 Before processing any samples, the analyst should demonstrate, through the analysis of an
instrument blank, that interferences from the analytical system are not present.

8.2.3 Before processing any samples, the analyst should demonstrate, through analysis of blanks,
that all sample and standard containers and reagents are interference-free.

FMC-VG-010-6

-------
8.2.4 Each day analyses are performed, daily calibration checks (Section 7.3) should be evaluated
to determine if the chromatographic system is operating properly. Refer to Section 8.0 of Method 8000 for
additional procedures which may be used as diagnostic checks on instrument performance.

8.3 Recruited Instrument OC

8.3.1 Section 7.2.3.2 requires that the %RSD be less than 25% when comparing calibration
factors to determine if a three-point calibration curve is linear.

8.3.2 Section 7.3.2 sets a limit of +25% difference when comparing daily response of a given
analyte versus the initial response. If the limit is exceeded, a new standard curve must be prepared.

8.3.3 Sections 7.2.4.1 and 7.3.1 require the establishment of initial calibration and daily retention
time windows.

8.4 To establish the ability to generate acceptable precision, replicates of the gas-phase calibration check
standard should be analyzed on the first analytical day.

8.4.1 Analyze four aliquots of the check standard by the same procedures used to analyze actual

samples.

8.4.2 Calculate the average concentration and the standard deviation for each analyte of interest
using the four results. Calculate the percent relative standard deviation.

8.4.3 Results from the replicate calibrations check standards should be included in all analytical

reports.

8.5 Recruited Column OC

8.5.1 Section 4.2.2 requires that the column be able to achieve baseline resolution of analyte and
interference peaks.

8.5.2 Section 7.2.1 requires that the response of any analyte to be used for calibration or
quantitation must exceed the baseline noise by a factor of six.

9.0 METHOD PERFORMANCE

9.1 Calibration Performance

9.1.1 Mean calibration values of low range and high range standards from four days of field
analysis are presented in Table 2.

9.2 Linearity

9.2.1 Correlation coefficient values of linearity from four days of field calibration are presented
in Table 3.

9.3 Method Detection Limits

9.3.1 Method detection limits determined from four days of field analysis are presented in Table 3.
10.0 REFERENCES

FMC-VG-010-7

-------
1.	Mayer, C.L. , Guidance Document for Soil-Gas Measurement. Report for EPA
Contract 68-03-3245. (In Preparation.)

2.	Kerfoot, H.B., Pierett, S.L., Amick, E.N., Bottrell, D.W., Petty, J.D. 1989.

Field Evaluation of Four Portable Gas Chromatographs. Report for EPA Contract 6803-3249.

FMC-VG-010-8

-------
Table 2

ACCURACY AND PRECISION OF GAS CHROMATOGRAPHS

LOW-RANGE CALIBRATION*

SHIM ADZU-E CD1

1,1,1 -Trichloroethane

Trichloroethene

T etrachloroethene

1,1,2,2-T etrachloroethane

SRI 8610-PID2

Trans-1, 2-dichloroethene

Benzene

Trichloroethene

T oluene

T etrachloroethene
Ethylbenzene

Calc.
Value
ng/cm3

4.0
4.0
4.0
4.0

4.6
2.0
4.0
4.0
4.0
4.0

Mean
ng/cm3

4.01
4.61
3.19
4.48

4.69
1.93
4.09
3.11

4.07

3.08

Std.
Dev.
ng/cm3

0.98
1.17
1.13
1.05

0.31
0.21
0.50
0.66
0.60
0.97

%RSD

24
26
36
23

7

11

12
21
15
32

HIGH-RANGE CALIBRATION

SHIM ADZU-E CD

1,1,1 -Trichloroethane

Trichloroethene

T etrachloroethene

1,1,2,2-T etrachloroethane

SRI 8610-PID

T rans-1,2-dichloroethene

Benzene

Trichloroethene

T oluene

T etrachloroethene
Ethylbenzene	

Calc.

Value

ng/cm3

10.0
10.0
10.0
10.0

11.5

5.0

10.0

10.0

10.0

10.0

Mean
ng/cm3

9.47
11.09
8.18
11.19

11.37
5.51
9.89
8.72
9.72
8.77

Std.
Dev.
ng/cm3

2.29
0.85
1.44
1.44

1.78
2.04
1.74
2.11
1.39
2.11

%RSD

23
8

18

13

16
37

17

24

14
24

* - Calibration values taken fromField Evaluation of Four Portable Gas Chromatographireference 2).

NOTE: All gas-phase VOC standards were prepared in 500-mL glass bulbs as described in Section 5.4 of this method.

1	Shimadzu Mini-2 Gas Chromatograph. Column: 15-m DB-624 0.53 mm I.D. wide-bore capillary column, 3.0 jam film thickness. Col.
temp.: 65°C (isothermal). Carrier gas: 15 cni/min., nitrogen. Make-up gas: 5 cni/min., nitrogen. Detector: ECD.

2	SRI 8610 Gas Chromatograph. Column: 15-m DB-624 0.53 mm I.D. wide-bore capillary column. 3.0 jam film thickness. Col. temp.:c33
(isothermal). Carrier gas: 6 cni/min., nitrogen. Detector: PID (10.2 eV), 18(?C.

FMC-VG-010-9

-------
Table 3

GAS CHROMATOGRAPH LINEARITY*

SHIM ADZU-E CD

CAa
0.9903

TCEa
0.9994

PCEa
0.9985

TTCA'
0.993

Ethyl-

SRI 8610-PID

DCEa Benzene
0.9981 0.9982

TCEa
0.9978

Toluene PCE'
0.9948

Benzene
0.9960 0.9940

* - Linearity values taken from Field Evaluation of Four Portable Gas Chromatographs (reference 2).

a - TCA = 1,1,1 -Trichloroethane
TCE = Trichloroethene
PCE = Tetracholoethene
TTCA = 1,1,2,2-Tetrachloroethene
DCE - Trans-1,2-dichloroethene

FMC-VG-010-10

-------
FASP Method F93013

ANALYSIS OF HALOGENATED AND AROMATIC VOLATILE ORGANIC COMPOUNDS IN

WHOLE GAS SAMPLES BY PURGE AND TRAP GAS CHROMATOGRAPHY

1.0 SCOPE AND APPLICATION

1.1 This method covers the analysis of samples in the field by the Field Analytical Services Program (FASP)
Mobile Laboratory. This FASP method is a modification of approved EPA methods and is intended to supply rapid
turnaround analyses in the field. FASP data are not intended to be a substitute for analyses performed within the
Contract Laboratory Program and are not intended to be legally defensible. The FASP method analyte list is divided
into two parts. The primary analyte list presents the compounds that are routinely analyzed by FASP. The
supplemental analyte list presents additional analytes for which this method maybe appropriate. Analytes on the
supplemental analyte list may be requested on a project specific basis. Table 1 presents the FASP primary analyte list
with FASP reporting limits. Table 2 presents the FASP supplemental analyte list. Both retention times and reporting
limits will be added as data become available.

2.0 SUMMARY OF METHOD

2.1 Whole gas samples are collected according to FASP SOP F93012, or equivelent, and are analyzed by
purge and trap gas chromatography or by direct injection. Detection of halogenated and aromatic compounds is
accomplished by the use of selective detectors operated in series. The external standard method of quantitation is used
and analyte identification is made by the use of retention time windows established by the analysis of standards. The
recovery of surrogate compounds added to every sample and standard is used to determine system performance on a
sample by sample basis. A laboratory control sample (LCS) is used to verify calibration accuracy, and matrix spikes
and spike duplicate (MS/MSD) samples may be used to assess accuracy and precision in field sample results.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph fGC1

4.1.1 Varian 3400 GC with a Hall electrolytic conductivity cell detector (ELCD) and a
photoionization detector (PID) installed in series.

4.1.2 Varian 3400 GC with Dual electron capture detectors.

4.2 Purge and Trap Equipment: Tekmar Model 2000 Purge and Trap concentrator.

4.3 Data System: Nelson Analytical.

5.0 REAGENTS

5.1 Hydrogen: Ultra pure or equivalent.

5.2 Helium: Ultra pure or equivalent.

FMC-VG-011-1

-------
Table 1

FASP PRIMARY ANALYTE LIST

ANALYTE

RETENTION TIME
*T.P 1, 2
(minutes)

REPORTING LIMIT

(ng)

Chloromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
1,1 -Dichloroethene
1,1 -Dichloroethane
cis-1,2-Dichloroethene
trans-1,2-Dichloroethene
Chloroform
1,2-Dichloroethane
1,1,1 -Trichloroethane
Carbon tetrachloride
Bromodichloromethane
1,2-Dichloropropene
1,1,2,2-T etrachloroethane
1,2-Dichloropropane
trans-1,3 -Dichloropropene
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Benzene

cis-1,3 -Dichloropropene
Bromoform
T etrachloroethene
T oluene
Chlorobenzene
Ethylbenzene
Total Xylenes
Styrene

1.2-Dichlorobenzene

1.3-Dichlorobenzene

1.4-Dichlorobenzene

8.02

14.86

19.06

4.13

4.13
4.80
7.44
6.37
9.03
10.50

11.38
12.97
11.84
12.32,
16.46
15.52
31.66
15.52,

1.0

8.97

11.24

1.0
1.0

22.81
21.05
12.73
17.99
29.87
21.63

25.32
25.99

26.65, 28.83
28.83

1.0

10.0

10.0

10.0

10.0

1.0

1.0

1.0

1.0

1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0

1.0
1.0
1.0
1.0
5.0
1.0

1.0
1.0
1.0
1.0
1.0
1.0
1.0

*Temperature Program (TP) 1: See 7.2.2 TP 2: See 7.2.3

FMC-VG-011-2

-------
Table 2

FASP SUPPLEMENTAL ANALYTE LIST

ANALYTE

RETENTION TIME

*TP 2

(minutes)

REPORTING LIMIT

(ng)

Dichlorofluoromethane
T richlorofluoromethane
Dibromomethane

1,2-Dibromoethane (EDB)

1.2-Dibromo-3-chloropropane(DBCP)

1.3-Dichloropropane

17.87
30.64
16.68

1.0
1.0
1.0

2,2-Dichloropropane

1,1 -Dichloropropene

Hexachlorobutadiene

1,1,1,2-T etrachloroethane

1,2,3 - Trichloroprop ane

Bromobenzene

n-Butylbenzene

para-Isopropyltoluene

Naphthalene

1,2,3 -Trichlorobenzene

1,2,4-Trichlorobenzene

1.2.4-Trimethylbenzene

1.3.5-Trimethylbenzene
sec-Butylbenzene
tert-Butylbenzene
2-Chlorobenzene
4-Chlorobenzene

I sopropy lb enzene
n-Propylbenzene

TP 2: See 7.2.3

5.3 Stock Primary Analvte List Standards: All stock standards are purchased from Supelco as traceable
solutions. The following mixes are provided for reference and their use does not constitute an endorsement.
Equivalent substitutions from other vendors may be used.

5.4 Stock Supplemental Analvte List Standards: Supplemental analyte list standards will be purchased as
neat materials or as EPA traceable solutions on an as needed basis.

Mix

Supelco Catalogue No.

VOC Mix 2
VOC Mix 3
VOC Mix 4
VOC Mix 5
Purgeable C

4-8452M
4-8453M
4-8957M
4-8950M
4-8853M
4-8822M
4-8823M
4-8824M

1.2-Dichlorobenzene

1.3-Dichlorobenzene

1.4-Dichlorobenzene

FMC-VG-011-3

-------
5.5 Surrogate Spiking Standard: A mixture of l-chloro-2-bromopropane and fluorobenzene available as
Supelco catalogue number 4-8950M or equivalent. In cases where fluorobenzene detection is subject to interference, a
mixture of a,a,a-trifluorotoluene and 4-bromofluorobenzene may be used in addition to the above mixture.

5.6 Matrix Spiking Standard: Matrix spiking solutions will be prepared from benzene, chlorobenzene, 1,1-
dichloroethene, toluene and trichloroethene or from solutions of specific target analytes. The stock matrix spiking
solution will either be prepared from neat materials or purchased as a solution. (Supelco catalogue number 4-8102M
or equivalent). The spiking level will be at the midpoint of the calibration range.

Chloroform Ethylbenzene 1,2-Dichloropropane

Toluene 1,1-Dichloroethene 1,1-Dichloroethane

Chlorobenzene 1,1,2,2-T etrachloroethane

5.7.1 Alternative laboratory control standards may be prepared from specific target analytes.

5.7.2 The Laboratory Control Standard will be prepared from a source other than the one used to

prepare the calibration standards, such as the Supelco mixtures catalogue numbers 4-8462M and 4-8465M or

equivalent.

5.8 Solvents: All solvents used as diluents will be HPLC grade or equivalent. Reagent organic free water
will be prepared from distilled, deionized water by purging with an inert gas.

5.9 Sorbent Traps: A two phase trap is used containing Carbopack and Carbosieve (Tekmar catalogue 14-
3928-003 or equivalent).

5.10 Nitrogen: Ultra Pure or equivalent.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Analytical Sequence

7.1.1 Blank.

7.1.2 Initial Calibration.

2 ug/L
4 ug/L
10 ug/L
20 ug/L
40 ug/L

7.1.3 Blank.

7.1.4 Laboratory Control Standard (LCS).

FMC-VG-011-4

-------
7.1.5	Continuing Calibration Standard (CC)-20 ug/L (Not analyzed on day initial calibration

performed).

7.1.6	10 samples.

7.1.7	LCS.

7.1.8	Continue steps f. and g. until 24 hours has passed since last CC.

7.1.9	Blank.

7.1.10	CC.

7.1.11	Continue at step f.

7.2 Operating Conditions

7.2.1 Purge and Trap Operating Conditions:

Purge time

Dry purge time

Desorb time

Bake time

Purge pressure

Purge flow

Valve temperature

Transfer line temperature 110 °C

Desorb temperature

Bake temperature

12.0 minutes
8.0 minutes
4.0 minutes
8.0 minutes
20 psi

40 mL/minute
110 °C

210 °C
250 °C

7.2.2 Temperature Program 1 for Varian 3400. Hall and PIP operated in series:

Initial temperature
Initial time
Ramp

Intermediate temp.
Hold time
Ramp

Intermediate temp.
Hold time
Ramp

Final temperature
Analytical column

35 °C
3 minutes
3 °C/minute
77 °C
3 minutes
3 °C/minute
94 °C
3 minutes
10 °C/minute
175 °C

DB-624, 30 meters, 0.53 mm ID, fused silica
megabore capillary

7.2.3 Temperature Program 2 for Varian 3400. Hall and PIP operated in series:

Initial temperature
Ramp

Intermediate temp.
Hold time
Ramp

Intermediate temp.
Hold time

50 °C

3 °C/minute
77 °C
3 minutes
3 °C/minute
94 °C
3 minutes

FMC-VG-011-5

-------
Ramp

Final temperature
Analytical column

10 °C/minute
250 °C

DB-624, 30 meters, 0.53 mm ID, fused silica
megabore capillary

7.2.4 Temperature Program for Varian 3400 with dual ECD detectors:

Initial temperature
Ramp

Intermediate temp.
Hold time
Ramp

Final temperature
Analytical column

50 °C

3 °C/minute
77 °C
3 minutes
3 °C/minute
94 °C
3 minutes
10 °C/minute
250 °C

DB-624, 30 meters, 0.53 mm ID, fused silica
megabore capillary

7.2.5 Photoionization Detector Operating Conditions:

Base
Lamp

200 °C
10 ev

7.2.6 Hall Electrolytic Conductivity Detector Operating Conditions:

• Reactor

• Solvent, n-propanol

• Hydrogen

• Reaction tube nickel
7.2.7 Electron Capture Operating Conditions:

• Base

• Makeup gas

850 °C

0.50 mL/minute
90 mL/minute

300 °C

30 ml/minute Argon/Methane

7.2.8 Data System Operating Conditions: Nelson Operating System
7.3 Calibration

7.3.1 Primary Standards: Primary calibration standards are prepared from purchased solutions
described in Section 5.3 or from project specific analytes. The concentration of each of the VOC mixes listed
in 5.3 is 2000 ug/mL; the concentration of the dichlorobenzene standards is 5000 ug/mL; and the
concentration of Purgeable C is 200 ug/mL.

7.3.2 Secondary Standards: Secondary calibration standards are prepared by dilution of the primary
standards in methanol.

7.3.2.2 Secondary Dichlorobenzene Standard: A 25-mL volumetric flask is filled more than
halfway with methanol and 1 -mL of each of the dichlorobenzene primary standards is added. The

FMC-VG-011-6

-------
flask is brought to volume. The concentration of the Secondary Dichlorobenzene Standard is 200
ug/mL. It may be stored up to six months or until analyte losses are evident by decreases in analyte
response factors.

7.3.2.3 Secondary Purgeable C Standard: Purgeable C contains the gaseous compounds in
solution at 200 ug/mL and is used to prepare the working standards without additional dilution. This
solution is transferred to a 1-mL autosampler vial and stored in the freezer. A new Purgeable C
standard is used each week.

7.3.2.4 Secondary Standards for Other Analvtes: The final concentration of all secondary
standards should be 200 ug/ml.

7.3.5 Surrogate Standards: A aliquot of a surrogate standard is added to every standard, field
sample, and blank to monitor system performance. The surrogate is added to 5-mL of reagent water prior to
introduction of the whole gas sample as follows:

7.3.5.1 The stock surrogate solution is at a concentration of 2000 ug/mL. In a manner
analogous to the preparation of the secondary calibration standards, dilute 1 mL of the primary
surrogate standard with reagent methanol to a 10-mL final volume at 200 ug/mL.

FMC-VG-011-7

-------
Table 3

PREPARATION OF CALIBRATION WORKING STANDARDS

Aliquot of each 200
ug/mL Secondary
Calibration Standard

Total Volume
of Standard (3
aliquots)

Volume of
Diluent to
Produce 1-mL
Final Volume

Final Concentration of
Working Calibration
Standard

Concentration in 5
mL of Reagent
Water (10 uL
standard spike)

5 uL

15 uL

985 uL

1 ug/mL

2 ug/L

10 uL

30 uL

970 uL

2 ug/mL

5 ug/L

25 uL

75 uL

925 uL

5 ug/mL

10 ug/L

50 uL

150 uL

850 uL

10 ug/mL

20 ug/L

100 uL

300 uL

700 uL

20 mg/mL

40 ug/L

7.3.5.2 Prepare a 1-mL working solution in methanol by addition of 50 uL of the secondary
surrogate standard to 950 uL of methanol. A 10-uL aliquot of the surrogate working solution is
added to 5 mL of an aqueous calibration standard or reagent water, prior to introducton of the whole
gas sample. The final concentration is 20 ug/L.

7.3.6 Laboratory Control Sample: For whole gas analysis, laboratory control samples are second
source standards used to determine the validity of the initial calibration curves. They are prepared as follows:

7.3.6.1 The concentrations of stock laboratory control solutions may vary depending on the
analytes of interest. In a manner analogous to the preparation of the secondary calibration standards,
dilute the stock laboratory control standard with reagent methanol to a 10-mL final volume at 200
ug/mL.

7.3.6.2 Place 100 uL of a 200 ug/ml standard into a 2-L gas sampling bulb and warm gently
to drive the standarrd into the gas phase. Allow time for equilibrium to be reached prior to analysis.

7.3.6.3 Place five milliliters of reagent water into a 5-mL syringe. Once the syringe barrel
is completely filled, insert the plunger and adjust the volume to 5 mL. The barrel is withdrawn
slightly and 10 uLs of surrogate spiking standard is added through the luer tip of the syringe. The
water is then place into the sample sparger through the sample introduction valve.

7.3.6.4 A 5-ml aliquoit gas standard is withdrawn from the sample introduction valve on the
gas sampling bulb. The sample is slowly injected onto the purge and trap by attaching the Luer tip to
the sample introduction valve at the start of the purge step. The rate of sample introduction should
be equal to the 40 mL/minute purge gas flow, i.e. approximately 6 seconds for a 5-mL sample

7.3.7 Matrix Spike Standard: For whole gas samples, matrix spike samples are prepared by addition
of a 1-ml aliquoit of a 5 ug/L gaseous standard contained in a 2-L gas sampling bulb as follows:

7.3.7.1 The concentration of the stock matrix spike solutions may vary depending on the
anallytes of interest. Dilute the stock matrix spike standard with reagent methanol to a 10-mL final
volume at 200 ug/mL.

7.3.7.2 Place 100 uL of the 200 ug/mL standard into a 2-L gas sampling bulb and warm
gently to drive the standard into the gas phase. Withdraw a 1-ml aliquoit using a gas tight syringe

FMC-VG-011-8

-------
and introduce to the field sample through the sample collection valve. Allow time for equilibrium to
be reached prior to analysis.

7.3.7.3 Five milliliters of reagent water are placed into a 5-mL syringe. Once the syringe
barrel is completely filled, the plunger is inserted and the volume adjusted to 5 mLs. The barrel is
withdrawn slightly and 10 uL of surrogate spiking standard is added through the Luer tip of the
syringe. The water is then place into the sample sparger through the sample introduction valve.

7.3.7.4 A 5-ml aliquoit of the spiked sample is withdrawn from the Tedlar bag through the
sample introduction valve. The sample is slowly injected onto the purge and trap by attaching the
luer tip to the sample introduction valve at the start of the purge step. The rate of sample introduction
should be equal to the 40 mL/minute purge gas flow, i.e. approximately 6 seconds for a 5-mL sample

7.4 Sample Analysis

7.4.1 Five milliliters of reagent water are placed into a 5-ml syringe. Once the syringe barrel is
completely filled, the plunger is inserted and the volume adjusted to 5 mLs. The barrel is withdrawn slightly
and 10 uLs of surrogate spiking standard is added through the Luer tip of the syringe. The water is then place
into the sample sparger through the sample introduction valve.

7.4.2 A 25-ml aliquoit (or an aliquoit approriate to the expected sample concentration) of the whole
gas sample is withdrawn through the sample introduction valve on the Tedlar bag. The sample is slowly
injected into the purge and trap by attaching the Luer tip to the sample introduction valve at the start of the
purge step. The rate of sample introduction should be equal to the 40 mL/minute purge gas flow, i.e.
approximately 30 seconds for a 25-mL sample

7.4.3 Quality Control (OC) Sample Analysis:

7.4.3.1 Blanks are prepared from a aliquot of ambient air equal to the largest anticipated
sample aliqouit. Blank analysis is performed once each 24-hour period and after each high
concentration sample to monitor and prevent carryover.

7.4.3.2 Initial Calibration Standard analysis is performed at the beginning of each
assignment and when analytical conditions have changed to the extent that the continuing calibration
standard no longer meets quality control criteria. Initial calibration levels are 2, 4, 10, 20 and 40
ug/L. Other initial calibration levels may be used as needed to bracket field sample concentrations.

7.4.3.3 Continuing Calibration Standard analysis is performed once each 24- hour period at
a level equal to the midpoint calibration standard.

7.4.3.4 Laboratory Control Saample analysis is performed after each initial and continuing
calibration, and after each group of 10 samples.

7.4.3.5 Matrix Spike and Spike Duplicate analyses are performed at a frequency of one set
per 20 samples or one set per week.

7.6 Compound Quantitation: Response factors are calculated as the ratio of the concentration of the analyte
to the area of the analyte peak in the daily standard. Concentration of the analyte in the sample is calculated by
multiplication of the response factor by the area of the analyte in the sample chromatogram.

FMC-VG-011-9

-------
8.0 QUALITY CONTROL

8.1 Because the mission of the FASP mobile laboratory is to provide quick turnaround analyses, some QC
requirements are advisory and, if they are not met, no corrective action will be taken, unless it is evident that a
significant malfunction or error has occurred. The acceptance requirements for blank, initial and continuing calibration
and laboratory control sample results are not advisory, and if the criteria for these analyses are not met, corrective
action will be taken and the acceptance criteria met, prior to analysis of field samples. The remaining QC analyses are
provided for the purposes of data evaluation. The acceptance criteria for surrogate recovery and matrix spike and spike
duplicate analyses are advisory.

8.2 Blanks: Blanks may not contain more than reporting limit of any target analyte.

8.3 Initial Calibration: The average relative percent difference (RPD) for the initial calibration must not
exceed 25% for the site specific target compounds.

8.5 Laboratory Control Sample: The recovery of analytes in the Laboratory Control Sample must be between
70% and 125%.

8.6 Surrogates: The recovery of surrogates must be between 65%-130% for whole gas samples. Samples in
which surrogates are below the 65% criteria are rerun if there is additional sample available.

8.7 Matrix Spike and Spike Duplicate Analysis: The recovery requirement for matrix spike compounds is
65% to 130%i The relative percent difference criteria between the spike duplicates is 50% for whole gas samples. The
FASP matrix spike QC limits are advisory, and unless a site specific requirement, no reanalysis of matrix spike
samples will be made in cases where QC criteria are not met.

9.0 METHOD PERFORMANCE

Information not available.

FMC-VG-011-10

-------
Summary of FASP Quality Control Requirements

QC Sample

Acceptance Criteria for Whole Gas Samples

Frequency

Blank

Less than reporting limit of all target analytes

1 blank analysis each 24 hours

Initial Calibration

Relative Standard Deviation < 25% for
average analyte concentration factors

As necessary

Continuing Calibration

Percent Difference for concentration factors
compared to initial calibration < 25%

1 Continuing Calibration each
24 hours

Laboratory Control
Sample

70%-125%

After each successful calibration
and each 10 samples

Surrogates

65%-130%

Every analysis

Matrix Spike and Spike
Duplicate

Recovery: 65%-130%
Precision: RSD <50%

1 set per each 20 field samples
analyzed or weekly

10.0 REFERENCES

1.	EPA Method 8021: Volatile Organic Compounds in Water bv Purge and Trap Capillary Column Gas
Chromatography with Photoionization and Electrolytic Conductivity Detectors Operated in Series

2.	EPA Method 5030: Purge and Trap

3.	EPA Method 8000: Gas Chromatography

These references are from Test Methods for Evaluating Solid Wastes. Phvsical/Chemical Methods. SW-846.
3rd Edition. Final Update 1. 1991 and are provided in Appendix A.

FMC-VG-011-11

-------
FASP Method Number F080.011
VOLATILE ORGANICS IN AIR - ADSORBENT TUBE METHOD

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various volatile organic compounds (VOCs) in air samples.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 An air sample tube is desorbed at 200°C for 5 minutes with helium to desorb all VOCs directly onto a
packed glass column or a megabore column installed in a temperature-programmed gas chromatograph (GC). VOCs
are detected with a photoionization detector (PID) and an Hall electrolytic conductivity detector (EL CD) connected in
series. Quantitation and identification are based on relative peak areas and relative retention times using the internal
standard method.

3.0 INTERFERENCES

3.2 Contamination by carryover can occur whenever high level samples are analyzed. Whenever an un-
usually concentrated sample is encountered, it should be followed by an analysis of a blank sample tube to check for
cross-contamination. The trap and other parts of the system are also subject tocontamination; therefore, bakeout and
purging of the entire system may be required between each analysis.

3.3 The volatile analysis laboratory should be as completely free of interfering solvents as possible.

FMC-VA-001-1

-------
Table 1

FASP METHOD F080.011 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit
in Air**(ng)

T richlorofluoromethane

75-69-4

20

1,1 -Dichloroethene

75-35-4

20

Methylene Chloride

75-09-2

20

trans-1,2-Dichloroethene

540-59-0

20

1,1 -Dichloroethane

75-34-3

20

Chloroform

67-66-3

20

1,1,1 -Trichloroethane

71-55-6

20

Carbon Tetrachloride

56-23-5

20

Benzene

71-43-2

20

1,2-Dichloroethane

107-06-2

20

Trichloroethene

79-01-6

20

1,2-Dichloropropane

78-87-5

20

Bromodichloromethane

75-25-4

20

cis-1,3 -Dichloropropene

10061-02-6

20

T oluene

108-88-3

20

trans-1,3 -Dichloropropene

10061-02-6

20

1,1,2-Trichloroethane

79-00-5

20

T etrachloroethene

127-18-4

20

Dibromochloromethane

124-48-1

20

(continued on next page)

*	Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for

guidance and may not always be achievable.

** Quantitation limits are listed as nanograms (ng) injected. Actual concentrations will vary depending on the
volume of air injected.

FMC-VA-001-2

-------
Table 1 (continued)

FASP METHOD F080.011 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit
in Air** (ng)

Chlorobenzene

108-90-7

Ethylbenzene

100-41-4

m,p-Xylenes

1330-20-7

o-Xylene

1330-20-7

Bromoform

75-25-2

1,1,2,2-T etrachloroethane

79-34-5

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for

guidance and may not always be achievable.

** Quantitation limits are listed as nanograms (ng) injected. Actual concentrations will vary depending on the
volume of air injected.

4.0 APPARATUS AND MATERIALS
4.1 Analytical Systems

4.1.1 Gas chromatograph: An analytical system complete with a temperature-programmable GC
suitable for on-column injection is required. All necessary accessories including injector and detector systems
must be designed or modified to accept the appropriate analytical columns (packed or megabore). The system
shall have a data handling system attached to the detectors that is capable of retention time labeling, relative
retention time comparisons, and providing relative and absolute peak height and peak area measurements.

4.1.1.1 Column 1: 1.8 m x 3 mm I.D. glass column packed with 1% SP-1000 on Carbopack
B (60/80 mesh), or equivalent.

4.1.1.2 Column 2: 30 m x 0.53 mm I.D. DB-624 fused silica megabore column (J&W
Scientific), or equivalent.

4.1.1.3 Detectors: A PID with a 10.2 eV lamp and a makeup gas supply at the detector inlet
should be connected in series to an EL CD with a short length of deactivated fused silica capillary
column.

FMC-VA-001-3

-------
4.1.1.4 Gas supply: The purge gas, carrier gas, and makeup gas should be ultrapure helium.
The reaction gas required for the Hall detector is ultrapure hydrogen. All gases should pass through
oxygen traps prior to the analytical system to prevent degradation of the column's analytical coating.

4.1.2 Desorption device: Several desorbers can be utilized as long as the appropriately sized
adsorbent tube is used and meets the sampling requirements. This method utilizes a Tekmar purge and trap
device to desorb sampling tubes directly onto the GC column. Several other complete devices are
commercially available.

4.1.2.1 Desorption unit: A thermal desorption attachment (Tekmar, or equivalent) capable
of heating to at least 200°C and able to accept a 6 mm O.D. x 11 cm long air sample tube with 7 cm
of packing material is required.

4.1.2.2 Trap: The trap must be packed with the appropriate adsorbent material(s) to collect
VOCs from the air sample tube.

4.1.2.3 Desorber: The desorber should be capable of rapidly heating the trap to 180°C. The
trap should not be heated higher than 220°C during the bakeout mode.

NOTE: The desorption device may be assembled as a separate unit or coupled to a GC.

4.2 Other Laboratory Equipment

4.2.1 Air sample tubes: Supelco Carbotrap 300, or equivalent, with appropriate packing to adsorb
target analytes. Air sample tubes should be pre-cleaned before use by purging with nitrogen in a drying oven
at 125°C for 15 minutes. The nitrogen flow direction should be opposite of the sampling flow. The air
sample tube should then be capped and stored in a desiccator.

4.2.2 Microsvringes: lO-^L, 25-(iL, and larger.

4.2.3 Vials: 1.8-mL for purgeable standards with Teflon-lined septa.

4.2.4 Drying oven: Capable of maintaining a temperature of 180°C.

4.2.5 Desiccator: Glass and stainless steel (no plastic materials).

4.2.6 Oxygen traps: Supelpure-O-Trap and OM-1 indicating tube, or equivalent.

4.2.7 Leak detector: Snoop liquid, or equivalent, for packed column operations or GOW-MAC gas
leak detector, or equivalent, for megabore capillary operations.

4.2.8 Chromatographic data stamps: Used to record instrument operating conditions if not provided
by data handling system.

4.3 Instrument Options: Specific instrument options that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1 Solvents

5.1.1 1-Propanol: Pesticide quality, or equivalent.

FMC-VA-001-4

-------
5.1.2 Methanol: Pesticide quality, or equivalent.

5.2 Gases

5.2.1 Helium: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

5.2.2 Hydrogen: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

5.2.3 Nitrogen: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

5.3 Stock Standard Solutions: Stock standard solutions should be purchased as manufacturer-certified
solutions. Gas standards may also be used.

5.4 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with methanol. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard concen-
tration should define the approximate working range of the GC: one at the upper linear range and the other midway
between it and the lowest standard. Calibration standards are injected directly into the air sample tube packing
material for analysis. All calibration standards must be stored at 4°C in Teflon-sealed glass bottles. Calibration
standard solutions must be replaced after 6 months, or whenever comparison with check standards indicates a problem.

5.5 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

5.6 Internal Standards: The 3 internal standards used are fluorobenzene, bromochloromethane, and p-bromo-
fluorobenzene. An internal standard mix should be prepared through volumetric dilution of individual stock standards
with methanol. It is recommended that the secondary dilution standard be prepared at a concentration of 200 ng/mL of
each internal standard compound. The addition of 2 (iL of this standard directly into the air sample tube packing
material would be equivalent to 400 ng. All standards must be stored in a freezer in glass vials with Teflon-lined septa
and be protected from light. Internal standard solutions must be replaced weekly, after the Teflon-lined septum has
been punctured, or sooner, if comparison with previous analyses indicates a problem.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be handled, preserved, and shipped maintaining a chain-of-custody following current
EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this rule are
the sample volumes required by the laboratory. Air samples should be collected in Supelco Carbotrap 300 tubes at
appropriate volumes and sampling rates to prevent breakthrough of target analytes, then capped and shipped on ice in
insulated containers to prevent breakage of the tubes during transport.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for VOCs in air is 24 hours from
sampling to analysis; however, it is recommended to analyze the samples as soon as possible.

7.0 PROCEDURE

7.1 Desorption: This procedure is recommended for the Tekmar LSC-1 (upgraded), LSC-3, and LSC-2000
purge and trap systems.

7.1.1 Remove the caps from both ends of the air sample tube.

FMC-VA-001-5

-------
7.1.2 Inject the internal standard mix into the air sample tube packing material.

7.1.3 Immediately place the air sample tube through the thermal desorber and attach it directly to the
sample and purge lines so that the gas flow is opposite of the sampling flow.

7.1.4 Make sure the trap temperature is 30°C or less. Thermally desorb the air sample tube at 200°C
onto the trap for 5 minutes.

7.1.5 The trapped sample is ready to be desorbed.

7.1.6 The purged sample may be preheated to 60°C on the trap (to remove moisture), and then
desorbed at 160°C-180°C for 4 minutes. The gas chromatographic system begins data collection and
temperature program concurrently with sample desorption.

7.1.7 After the sample is desorbed, the purge and trap system should be returned to the purge mode,
and the trap should be baked with a clean air sample tube in line. Gas should flow through the trap during the
bake, and the trap should be heated to 200°C for at least 5 minutes.

7.1.8 After baking the trap, allow it to cool to 30°C before desorbing the next sample.

7.1.9 Following sample desorption, the air sample tube is decontaminated by purging with nitrogen
in a drying oven at 125°C for 15 minutes. The nitrogen flow direction should be opposite of the sampling
flow. The air sample tube should then be capped and stored in a desiccator until needed for sampling.

7.2 Calibration

7.2.1 Initial calibration:

7.2.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution,
retention times, response reporting, and interpretation of chromatograms are within acceptable quality
control (QC) limits. Using at least 3 calibration standards prepared as described in Section 5.4,
generate initial calibration curves (relative response versus mass of standard injected) for each target
analyte (refer to Sections 7.3 for chromatographic procedures).

7.2.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.4.) based on
each target compound's 3 relative calibration factors (RCFs, see Section 7.4) to determine the
acceptability (linearity) of the curve. Unless otherwise specified, the %RSD must be less than or
equal to 25 percent, or the calibration is invalid and must be repeated. Establish a new initial
calibration curve anytime the GC system is altered (e.g., new column, change in gas supply, change
in oven temperature) or shut down.

7.2.2 Continuing calibration:

7.2.2.1 Check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing calibra-
tion validation. This single-point analysis follows the same analytical procedures used in the initial
calibration. Instrument response is used to compute the RCF which is then compared to the mean
initial relative calibration factor (RCF) and a relative percent difference (RPD, see Section 7.4) is
calculated. Unless otherwise specified, the RPD for all target analytes must be less than or equal to
25 percent for the continuing calibration to be considered valid or the calibration must be repeated. A
continuing calibration remains valid for a maximum of 24 hours providing the GC system remains
unaltered during that time.

FMC-VA-001-6

-------
7.2.2.2 Use the continuing calibration in all sample concentration calculations (Section 7.4)
for the period over which the calibration has been validated.

7.2.3 Final calibration: Obtain the final calibration at the end of each batch of sample analyses. The
maximum allowable RPD between the mean initial and final RCF s for each target analyte must be less than or
equal to 50 percent. A final calibration that achieves an RPD less than or equal to 25 percent may be used as
an ongoing continuing calibration.

7.3 Instrumental Analysis

7.3.1 Instrument parameters: Table 2 summarizes acceptable instrument operating conditions for the
analytical system. Other instruments, columns, and/or chromatographic conditions may be used if this
method's QC criteria are met.

7.3.2 Chromatograms:

7.3.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks are
on scale up to a 100-fold range are acceptable. However, this can be no greater than a 100-fold range
to prevent retention time shifts by column or detector overload. Generally, peak response should be
greater than 25 percent and less than 100 percent of full-scale deflection to allow visual pattern
recognition of VOCs.

7.3.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

FMC-VA-001-7

-------
Table 2

EXAMPLE CAPILLARY COLUMN
TEMPERATURE-PROGRAMMED GC OPERATING CONDITIONS

Purge and Trap Device:

Instrument:

Integrator:

Column:

Carrier Gas:

Makeup Gas:

Reaction Gas:

Column Oven:

Injector Temperature:
Detector Temperature:

Tekmar LSC-1 liquid sample concentrator with upgrade package, thermal
desorber attachment, and heated transfer line. (Trap composition: 1 cm 3%
SP-2100, 15 cm Tenax, 8 cm silica gel 15).

Shimadzu GC Mini-3 equipped with an HNu Systems PID with a 10.2 eV
lamp connected in series to an O.I. Corporation Hall ELCD.

Nelson Analytical PC Integrator with a dual-channel interface and 30-MB hard
disk drive for data storage.

J&W DB-624 fused silica megabore column, 30 m x 0.53 mm I.D.

Ultrapure helium, 10 mL/min.

Ultrapure helium, 40 mL/min.

Ultrapure hydrogen, 100 mL/min.

Initial temperature: 35°C
Initial time: 4 min
Ramp rate: 4°C/min
Final temperature: 105°C

150oC

PID: 200oC
Hall: 800°C

GC Analysis Time:

20 mins

FMC-VA-001-8

-------
7.3.3 VOC identification:

7.3.3.1 Qualitative identification of VOCs is based on both detector selectivity and
relative retention time as compared to known standards using the internal standard method.

7.3.3.2 For a compound that is detected on both the PID and Hall detector, the
compound must be identified in both chromatograms for a positive identification to be made.

7.3.3.3 Generally, individual peak relative retention time windows should be less then
or equal to 5 percent for packed columns analysis or less than or equal to 2 percent for megabore
capillary columns. Alternatively, the individual peak relative retention time windows may be
calculated based on 3 times the standard deviation of at least 3 nonconsecutive standard
analyses. These analyses must be representative of normal system variations, subject to the
professional judgement of an experienced analyst.

7.3.3.4 It may not be possible or practical to separate all volatile organic target
analytes on a single column. In such cases, these target analytes should be denoted as the
appropriate combination of VOCs.

7.3.4 System performance: Degradation of VOCs may occur in the GC system, especially if
the injector or column inlet is contaminated.

7.3.5 Specific instrument parameters: Specific instrument parameters that have been used are
provided as "Specific Instrument Parameters" in Appendix B of this method.

7.3.6 Analytical sequence:

7.3.6.1 Instrument blank.

7.3.6.2 Initial calibration.

7.3.6.3 Check standard solution or performance evaluation sample (if available).

7.3.6.4 Continuing calibration; repeat within 24 hours of previous continuing
calibration.

7.3.6.5 Associated QC lot method blank.

7.3.6.6 Twenty samples and associated QC lot spike and duplicate.

7.3.6.7 Repeat sequence beginning at 7.3.6.5 until all sample analyses are completed
or another continuing calibration is required.

7.3.6.8 Final calibration when all sample analyses are complete.

7.4 Calculations

7.4.1 Identification and quantitation of target VOCs should be based on the internal standard
method. The corresponding internal standard for each compound is listed in Tables 3 (PID) and 4 (Hall
detector). A compound which is detected by both the PID and Hall detector should be quantitated using
the detector which gives the higher response for that specific compound. The second detector should be
used for confirmation of the presence of that compound.

FMC-VA-001-9

-------
7.4.2	The peak areas of the internal standards should be monitored and evaluated for each
standard, sample, blank, duplicate, and matrix spike. If the peak area for any internal standard changes
by more than a factor of 2 (-50 to +100 percent), the sample must be reanalyzed. If after reanalysis the
peak areas for all internal standards are inside the QC limits (-50 to +100 percent), only report data from
the analysis with peak areas within the QC limits. If the reanalysis of the sample does not solve the
problem for both analyses, then do not report sample data.

7.4.3	Initial calibration:

7.4.3.1	Analyze each calibration standard, adding the internal standard directly onto
the blank air tube.

7.4.3.2	Tabulate the area response of each target analyte against the amount injected in
nanograms for each compound and internal standard and calculate RCF for each target
compound using the following equation.

A C.

RCF = —- x —

A. C

where: Ax	=	Area of the peak for the compound of interest

Ais	=	Area of the peak for the appropriate internal standard

Cis	=	Amount of the internal standard injected

Cx	=	Amount of the compound to be measured

7.4.3.3 Using the RCF values, calculate the %RSD for each target analyte at all
concentration levels using the following equation.

ST)

% RSD = 4=r x 100
X

where SD, the standard deviation, is given by

SD

(x.-x)2

(N-l)

where: X; =	Individual RCF (per analyte)

X = Mean of initial RCF s (per analyte)
N =	Number of calibration standards

FMC-VA-001-10

-------
Table 3

VOLATILE ORGANIC COMPOUNDS DETECTED BY THE PID
AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS2 fFluorobenzene')

IS3 (p-Bromofluorobenzene')

1,1-Dichloroethene	Toluene

trans-1,2-Dichloroethene	trans-1,3 -Dichloropropene

Benzene	Tetrachloroethene

Trichloroethene	Chlorobenzene

2-Chloroethylvinylether	Ethylbenzene

cis-1,3 -Dichloropropene	o,p-Xylene
m-Xylene

Table 4

VOLATILE ORGANIC COMPOUNDS DETECTED BY THE HALL
DETECTOR AND THE CORRESPONDING INTERNAL STANDARD (IS)

IS1 fBromochloromethane')

IS3 (p-Bromofluorobenzene')

T richlorofluoromethane
1,1 -Dichloroethene
Methylene chloride
trans-1,2-Dichloroethene
1,1 -Dichloroethane
Chloroform
1,1,1 -Trichloroethane
Carbon tetrachloride
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromodichloromethane

cis-1,3 -Dichloropropene
trans-1,3 -Dichloropropene
1,1,2-Trichloroethane
T etrachloroethene

Dibromochloromethane

Chlorobenzene

Bromoform

1,1,2,2-T etrachloroethane

FMC-VA-001-11

-------
7.4.3.4 The %RSD must be less than or equal to 25 percent.

7.4.4 Continuing calibration:

7.4.4.1 Sample quantitation is based on analyte RCFs calculated from continuing
calibrations. Midrange standards for all initial calibration target analytes must be analyzed at
specified intervals (less than or equal to 24 hours).

7.4.4.2 The RPD calculated using the equation below for each analyte must be less
than or equal to 25 percent.

\RCF~-RCFr\

RPD = 1 — x 100

RCFI+RCFc

where: RCF, = Mean RCF from the initial calibration for each analyte

RCFc = Measured RCF from the continuing calibration for the same analyte

7.4.5 Final calibration:

7.4.5.1 The final calibration is obtained at the end of each batch of samples.

7.4.5.2 The maximum allowable RPD between the mean initial calibration and final
calibration factors for each target analyte must be less than or equal to 50 percent. A final
calibration which achieves an RPD less than or equal to 25 percent may be used as an ongoing
continuing calibration.

\RCF~-RCFr\

RPD = 1 — x 100

RCFI+RCFc

where: RCR, = Mean RCF from the initial calibration for each analyte

RCFc = Final RCF for the same analyte

7.4.6 Sample quantitation:

7.4.8.1 Calculate the concentration in the sample using the following equation for
internal standards. The relative response can be measured by automated relative peak height or
relative peak area measurements from an integrator.

UJ (c.J

Concentration{\ig/ L)

U.J (RCF) (V)

where: Ax = Area of the peak for the analyte to be measured

Ais = Aarea of the specific internal standard from Table 4 or 5

Cis = Amount of internal standard added (ng)

RCF = The relative calibration factor for the compound to be measured

FMC-VA-001-12

-------
V0 = volume of air collected onto air sample tube in liter (L)

7.4.8.2 Report results in micrograms per liter (ng/L) without correction for the blank
concentration.

7.4.8.3 Coeluted analytes should be quantitated and reported as the combination of the
unseparated VOC target analytes.

7.4.8.4 Sample chromatograms may not match identically with those of analytical
standards. When positive identification is questionable, the chemist may calculate and report a
maximum possible concentration (qualified as less than the numerical value) which allows the
data user to determine if additional (e.g., CLP analyses) work is required, or if the reported
concentration is below action levels and project objectives and DQOs have been met, to forego
further analysis.

7.4.8.5 Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) which allows
the data user to determine if additional (e.g., CLP RAS or SAS) work is required, or if the
reported concentration is above action levels and project objectives and DQOs have been met,
to forego further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Spiked samples cannot be analyzed by this method
because the entire sample is consumed during analysis. However, field duplicate samples may be collected
simultaneously or in succession to determine field precision and RPD. Advisory limits for field duplicate RPD
are presented in Table 5. This method should be used in conjunction with the quality assurance and quality
control (QA/QC) section of this catalog.

FMC-VA-001-13

-------
Table 5

FIELD DUPLICATE RPD ADVISORY LIMITS

Method F080.011 (VOCs in Air - Adsorbent Tube Method)

Advisory Quality Control Limits*

Analyte

Duplicate RPD (%)

T richlorofluoromethane

± 100

1,1 -Dichloroethene

± 100

Methylene Chloride

± 100

trans-1,2-Dichloroethene

± 100

1,1 -Dichloroethane

± 100

Chloroform

± 100

1,1,1 -Trichloroethane

± 100

Carbon Tetrachloride

± 100

Benzene

± 100

1,2-Dichloroethane

± 100

Trichloroethene

± 100

1,2-Dichloropropane

± 100

Bromodichloromethane

± 100

cis-1,3 -Dichloropropene

± 100

T oluene

± 100

trans-1,3 -Dichloropropene

± 100

1,1,2-Trichloroethane

± 100

T etrachloroethene

± 100

Dibromochloromethane

± 100

(continued on next page)

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ± 3 times the quantitation limit for that analyte.

FMC-VA-001-14

-------
Table 5 (continued)

FIELD DUPLICATE RPD ADVISORY LIMITS

Method F080.011 (VOCs in Air - Adsorbent Tube Method)

Advisory Quality Control Limits*

Analyte

Duplicate RPD (%)

Chlorobenzene

± 100

Ethylbenzene

± 100

m,p-Xylene

± 100

o-Xylene

± 100

Bromoform

± 100

1,1,2,2-T etrachloroethane

± 100

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ± 3 times the quantitation limit for that analyte.

FMC-VA-001-15

-------
9.0 METHOD PERFORMANCE

9.1 The following are examples of gas chromatograms for VOC analytes as detected by the PID and
Hall detectors.

Figure 1
Gas chromatogram A - PID

Column: J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Column Temperature: Initial temperature: 35°C

Initial time:	4 mins

Ramp rate:	4°C/min

Final temperature: 105°C

Detector/Injector Temperature: 150°C

Gas: Carrier: Ultrapure helium, 10 mL/min.

Makeup: Ultrapure helium, 40 mL/min.

Detector: HNu PID with a 10.2 eV lamp.

FMC-VA-001-16

-------
Figure 2

Gas chromatogram B - Hall detector

Column: J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary column.

Column Temperature:	Initial temperature: 35°C

Initial time:	4 min

Ramp rate:	4°C/min

Final temperature: 105°C

Detector/Injector Temperature: 150°C

Gas: Carrier: Ultrapure helium, 10 mL/min.

Makeup: Ultrapure helium, 40 mL/min.
Reaction gas: Ultrapure hydrogen, 100 mL/min.

Detector: O.I. Corporation Hall ELCD.

FMC-VA-001-17

-------
10.0 REFERENCES

Information not available.

FMC-VA-001-18

-------
APPENDIX A

FASP Method F080.011

Instrument Options:

Purge and Trap Device: Tekmar LSC-1 liquid sample concentrator with upgrade package, thermal desorption

attachment, and heated transfer line (Trap composition: 1 cm 3% SP-2100, 15 cm
Tenax, 8 cm silica gel 15).

GC System:	Shimadzu GC Mini-3 (temperature-programmable) with an HNu PID

connected in series to an O.I. Corporation Hall detector modified with a direct
conversion and makeup gas adapter for megabore capillary column operations.

Data Handling System 1: Shimadzu Data Processor Chromatopac C-R1B.

Data Handling System 2: Shimadzu Data Processor Chromatopac C-R3A.

Data Handling System 3: Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit and

Shimadzu FDD-1A Floppy Disk Drive.

Data Handling System 4: P.E. Nelson 2100 dual-channel integrator with 960 Series Intelligent Interface, Hyundai

80286 computer, and Epson LX800 printer.

FMC-VA-001-19

-------
APPENDIX B

FASP Method F080.011

Specific Instrument Parameters:
Purge and Trap Device:

GC:

Integrator:

Column:

Carrier Gas:

Makeup Gas:

Reaction Gas:

Column (Oven) Temperature:

Detector Temperature:

Injector Temperature:

Tekmar LSC-1 liquid sample concentrator with upgrade package, thermal
desorption unit, and heated transfer line. (Trap composition: 1-cm 3%
SP-2100, 15-cm Tenax, 8-cm silica gel 15).

Shimadzu GC Mini-3 (temperature-programmable) with an HNu PID
connected in series to an O.I. Corporation Hall detector.

Shimadzu Chromatopac C-R3A Data Processor.

J&W 30 m x 0.53 mm I.D. DB-624 fused silica megabore capillary
column.

Ultrapure helium, 10 mL/min.

Ultrapure helium, 40 mL/min.

Ultrapure hydrogen, 100 mL/min.

Initial temperature: 35°C
Initial time:	4 min

Ramp rate:	4°C/min

Final temperature: 105°C.

150oC.

150oC.

FMC-VA-001-20

-------
FASP Method Number F080.012
HALOGENATED VOLATILE ORGANICS IN AIR USING ELECTROLYTIC

CONDUCTIVITY DETECTOR - DIRECT ANALYSIS

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining relative
concentrations of halogenated volatile organic compounds (VOCs) in air. The method employs direct analysis of
air samples by gas chromatographic (GC) analysis using a Hall electrolytic conductivity detector (ELCD).

1.2 This method yields tentative identification and estimated quantitation of the analytes listed in Table
1. Approximate quantitation limits (QL) are also listed in Table 1. Reported values are on an "as-received" basis.

1.3 This method should be used only by trained analysts under the supervision of an experienced

chemist.

2.0 SUMMARY OF METHOD

2.1 A measured amount of air is collected in a 1-L Tedlar bag or gas sample container. The standard
and sample containers are sealed and allowed to equilibrate to ambient temperature. A 1- to 5-mL sample is
withdrawn and injected into a GC equipped with a megabore capillary column and a ELCD. Halogenated VOCs
are detected with the ELCD detector. Quantitation and identification are based on comparison of retention times
and relative peak areas between samples and standards. Quantitation is based upon the external standard method.

3.0 INTERFERENCES

3.1 Tedlar bags and gas sample containers can become contaminated if stored near standards or cleaning
solvents, elevated concentrations of solvents in ambient air, or contaminated air sampling equipment. These
interferences can be avoided by not reusing Tedlar bags, or reduced by analyzing sampling containers before use
to ensure that they are free of contamination.

3.2 Several solvents elute simultaneously under certain conditions on the DB-624 column. This
problem can be alleviated by altering the temperature program.

3.3 The ELCD may become saturated when analyzing high concentration samples. Increasing the
column temperature to 250°C for at least 30 minutes will bake out the contamination. Care should be taken that
the detector temperature is elevated above the column temperature. A syringe blank should be analyzed before
any further analysis of samples to ensure the complete bakeout of the column and detector.

FMC-VA-002-1

-------
Table 1

FASP METHOD F080.012 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile Organic Compound

CAS Number

Quantitation Limit in Air (ng/L)

T etrachloroethene

127-18-4

1,1,2-Trichloroethane

79-00-5

Trichloroethene

79-01-6

1,2-Dichloroethene

540-59-0

1,2-Dichloropropane

78-87-5

1,1,2,2-T etrachloroethane

79-34-5

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are

provided for guidance and may not always be achievable.

3.4 Moisture can cause peak retention time shifts. Frequent bakeout of the GC may be necessary.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System

4.1.1 Gas chromatograph: An analytical system complete with a temperature-programmable
GC suitable for on-column injection is required. All necessary accessories including injector and
detector systems must be designed or modified to accept the appropriate capillary columns. The system
shall have a data handling system attached to the detector that is capable of retention time labeling,
relative retention time comparisons, and providing relative and absolute peak height and peak area
measurements.

4.1.1.1 Column 1: Vocol, 30 m x 0.53 mm I.D. fused silica megabore capillary
column (Supelco).

4.1.1.2 Column 2: DB-624, 30 m x 0.53 mm I.D. fused silica megabore capillary
column (J&W Scientific).

4.1.1.3 Detector: Hall ELCD (Tracor).

4.1.1.4 Gas supply: The carrier gas should be ultrapure helium. The detector gas
should be ultrapure hydrogen. All gases should pass through oxygen traps prior to the analytical
system to prevent degradation of the column coating.

4.2 Other Laboratory Equipment

4.2.1 Tedlar bags: 1-L.

4.2.2 Volumetric gas sample containers.

FMC-VA-002-2

-------
4.2.3 Syringes: 1-mL and 5-mL, glass, gastight with replaceable needles.

4.2.4 Microsvringes: 10-^iL, 25-^L, and larger (for optional head-space standards).

4.2.5 Oxygen traps: Supelpure-O-Trap and OM-1 indicating tube or equivalent.

4.2.6 Leak detectors: GOW-MAC gas leak detector, or equivalent, for megabore capillary
operations.

4.2.7 Chromatographic data stamp: Used to record instrument operating conditions, if not
provided by the data handling system.

4.3 Instrument Options: Specific instrument options that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1 Solvents

5.1.1 Solvents are only needed for headspace standards, if used (see Section 5.4).
5.2 Gases

5.2.1 Helium: Ultrapure or chromatographic grade (always used in conjunction with oxygen

trap).

5.2.2 Hydrogen: Ultrapure or chromatographic grade (always used in conjunction with oxygen

trap).

5.3 Stock Standard Solutions: Stock standard solutions and certified gas standards should be purchased
as manufacturer-certified standards, when possible.

5.4 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for
each analyte of interest. The lowest concentration standard should be approximately 2 times the QL as listed in
Table 1. The remaining standard concentration should define the approximate working range of the GC: one at
the upper linear range and the other midway between it and the lowest standard.

5.4.1 Gas Standards: Certified gas standards are available from commercial manufacturers.

Various calibration standard concentrations are prepared by dilution of the stock standards into glass gas

vessels with known volumes.

5.4.2 Standards Made From Headspace Vapors: Standards can also be made using the
headspace vapor above pure solvents. The amount of head space needed depends on the specific vapor
pressure of each compound. In addition, the vapor pressure changes as a function of temperature and
pressure. Therefore, these variables must be accounted for when preparing standards. An example of
this method for preparation of a 5 ppm trichloroethylene standard is as follows:

5.4.2.1 Obtain the barometric pressure before going to the site.

5.4.2.2 Check the temperature at the site at the time the standards are prepared.

5.4.2.3 Based on the temperature and pressure information, calculate the vapor
pressure for site conditions from vapor pressure tables at standard temperature and pressure

FMC-VA-002-3

-------
(STP). (Vapor pressure references are somewhat obscure. Information for some compounds are
in the CRC Handbook for Chemistry and Physics.') Table 2 lists vapor pressures for
trichloroethylene at specific temperatures (at 1 atmosphere). For example, from Table 2, the
vapor pressure of 74.268 millimeters (mm) of mercury is obtained for 25°C. Correct for the
barometric pressure at the site, 30 inches of mercury (obtained from the weather service for that
day), as follows:

1 atmosphere = 760 mm of mercury, or 29.92 inches of water
Corrected vapor pressure of trichloroethylene =

74.268 x ^ ^ =74.070 mm of mercury
30

5.4.2.4 To make a 5 ppm standard of trichloroethylene in a 1000-mL gas collection
vessel, calculate the amount of headspace vapor as follows:

( Standard conc. ) x ( Vol. of vessel ) x —2^2.— = Amount of vapor

74.070

( 5]iL x 1L )

760

74 . 070

= 51. 3]iL

5.4.2.5 Inject 51.3 (iL of headspace into a 1000-mL gas collection vessel to a make a 5
ppm trichloroethylene standard.

5.5 Check Standards: Check standards are calibration standards independently prepared by a chemist
other than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1	Samples should be handled, preserved, and shipped maintaining a chain-of-custody following cur-
rent EPA regulations and recommendations in force at the time of sample collection. The sole exception to this
rule is the sample volumes required by the laboratory. The air sample is collected in a 1-L Tedlar bag or gas
sample container.

6.2	The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for air samples is 24 hours, but it is
recommended that all samples be analyzed within one hour of collection.

FMC-VA-002-4

-------
Table 2

VAPOR PRESSURE OF TRICHLOROETHYLENE

Temperature (°C)

Vapor Pressure (mm of Hg)

5

27.03251

10

35.35683

15

45.74057

16

48.0974

17

50.55512

18

53.11805

19

55.78667

20

58.5675

21

61.4631

22

64.47716

23

67.61339

24

70.87573

25

74.268

30

93.32106

35

116.256

40

143.6534

45

176.1468

7.0 PROCEDURE

7.1 Calibration

7.1.1 Initial calibration:

7.1.1.1	Calibrate the GC after an experienced chromatographer has ensured that the
entire chromatographic system is functioning properly; that is, conditions exist such that
resolution, retention times, response reporting, and interpretation of chromatograms are within
acceptable quality control (QC) limits. Using at least 3 calibration standards prepared as
described in Section 5.4, generate initial calibration curves (relative response versus mass of
standard injected) for each target analyte (refer to Section 7.2 for chromatographic procedures).

7.1.1.2	Compute the percent relative standard deviation (%RSD, see Section 7.3)
based on each target compound's 3 calibration factors (CFs, see Section 7.3) to determine the
acceptability (linearity) of the curve. Unless otherwise specified, the %RSD must be less than
or equal to 25 percent or the calibration is invalid and must be repeated. Establish a new initial

FMC-VA-002-5

-------
calibration curve anytime the GC system is altered (e.g., new column, change in gas supply,
change in oven temperature) or shut down.

7.1.2 Continuing calibration:

7.1.2.2 Use the continuing calibration in all sample concentration calculations (Section
7.3) for the period over which the calibration has been validated.

7.1.3 Final calibration: Obtain the final calibration at the end of each batch of sample analyses.
The maximum allowable RPD between the mean initial and final CFs for each target analyte must be
less than or equal to 50 percent. A final calibration that achieves an RPD less than or equal to 25 percent
may be used as an ongoing continuing calibration.

7.2 Instrumental Analysis

7.2.1 Instrument parameters: Table 3 summarizes acceptable instrument operating conditions
for the GC. Other instruments, columns, and chromatographic conditions may be used if this method's
QC criteria have been met.

7.2.2 Chromatograms:

7.2.2.1 Computer reproductions of chromatograms that are attenuated to ensure all
peaks are on scale up to a 100-fold range are acceptable. However, this can be no greater than a
100-fold range to prevent retention time shifts by column or detector overload. Generally, peak
response should be greater than 25 percent and less than 100 percent of full-scale deflection to
allow visual pattern recognition of VOCs.

7.2.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.2.3 VOC identification:

7.2.3.1 Qualitative identification of VOCs is based on both detector selectivity and
retention time as compared to known standards using the external standard method.

FMC-VA-002-6

-------
7.2.3.2 Generally, individual peak retention time windows should be less than or equal
to 5 percent for packed columns and less than or equal to 2 percent for capillary columns.

7.2.3.3 For the purpose of this method, peak intensity (height or area) matching for
positive identification is based on the chemist's best judgement in consultation with more
experienced chromatographic spectral data interpretation specialists, when required. It is
possible that interferences may preclude positive identification of an analyte. In such cases, the
chemist should report the presence of interferents with the maximum concentration possible.

7.2.4 System performance:

7.2.4.1 Degradation of VOCs in the GC system may occur especially if the injector
and/or column inlet is contaminated.

7.2.4.2 Before initial use of Tedlar bags, at least 10 percent of the bags should be filled
with clean air and sampled to confirm that they are free of contamination.

7.2.5 Specific instrument parameters: Specific instrument parameters that have been used are
provided as "Specific Instrument Parameters" in Appendix B of this method.

7.2.6 Analytical sequence:

7.2.6.1 Instrument blank.

7.2.6.2 Initial calibration.

7.2.6.3 Check standard solution and/or performance evaluation sample (if available).

7.2.6.4 Continuing calibration; repeat within 24 hours of previous continuing
calibration.

7.2.6.5 Associated QC lot method blank.

7.2.6.6 Inject 20 1- to 5-mL samples into the GC depending on the concentration of
volatiles in the air sample. Replicate injections should be made for all positive hits.

7.2.6.7 A syringe blank must be analyzed initially and after any high-concentration
samples to confirm proper decontamination.

7.2.6.8 Repeat sequence beginning at 7.2.6.5 until all sample analyses are completed
or until another continuing calibration is required.

FMC-VA-002-7

-------
Table 3

EXAMPLE TEMPERATURE-PROGRAMMED GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Reaction Gas:

Column Oven:

Injector Temperature:
Detector Temperature:
GC Analysis Time:

7.3 Calculations

Varian 3400 temperature-programmable GC and all required accessories
including analytical columns and gases equipped with a Tracor 1000 Hall
ELCD.

Nelson Analytical PC Integrator with a dual channel interface and hard disk
drive for data storage.

VoCol, fused silica megabore capillary column (Supelco, or equivalent) 30 m
x 0.53 mm I.D.

Ultrapure helium, 10 mL/min.

Ultrapure hydrogen, 50 mL/min.

Isothermal 40°C

110oC

800°C (reactor)

5 min

7.2.6.9 Final calibration when all sample analyses are complete.

7.3.1	Identification and quantitation of target VOCs should be based on the external standard
method. A compound which is detected by the ELCD should be quantitated using the detector response
for that specific compound.

7.3.2	Initial calibration:

7.3.2.1	Analyze each calibration standard.

7.3.2.2	Tabulate the area response of each target analyte against the concentration for
each compound, and calculate calibration factors (CF) for each target compound using the
following equation:

Area ofPeak

CF =

Mass Injected (ng)

7.3.2.3 Using the CF values, calculate the %RSD for each target analyte at all
concentration levels using the following equation.

ST)

RSD = 4=- x 100
X

FMC-VA-002-8

-------
where SD, the standard deviation, is given by

A (X-X)2

sd =. y, —-—

\ ^ / AT_1 \

{N-l)

where: X;
X
N

Individual CF (per analyte)

Mean of initial 3 CFs (per analyte)
Number of calibration standards

7.3.2.4 The %RSD must be less than or equal to 25.0 percent.

7.3.3 Continuing calibration:

7.3.3.1	Sample quantitation is based on analyte CFs calculated from continuing
calibrations. Midrange standards for all initial calibration target analytes must be analyzed at
specified intervals (less than or equal to 24 hours).

7.3.3.2	The maximum allowable RPD calculated using the equation below for each
analyte must be less than or equal to 25 percent.

7.3.4 Final calibration:

7.3.4.1	Obtain the final calibration at the end of any batch of samples analyzed.

7.3.4.2	The maximum allowable RPD between the mean initial and final CFs for each
VOC must be less than or equal to 50 percent. A final calibration that achieves an RPD of less
than or equal to 25 percent may be used as an ongoing continuing calibration.

\CF -CFJ

RPD = -	1	— x 100

CFI+CFc

2

where: CF,

CFc

Mean CF from the initial calibration for each analyte
Measured CF from the continuing calibration for the same analyte

\CF -CF |
RPD = -	1	— x 100

cfi+cff

2

where: CF

Mean CF from the initial calibration for each analyte

FMC-VA-002-9

-------
CFf = Final CF for the same analyte
7.3.5 Sample quantitation:

7.3.5.1 Use external standard calibration for the calculation of the compounds of
interest. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations.

(A ) (1000)

Concentration (nq/L) = 			

(CF ) (V.)

\ c' ^ l'

where: Ax =	Area of the peak for the analyte in the sample.

V; =	Volume of sample injected (mL).

CFc =	CF from the continuing calibration for the analyte to be measured.

7.3.5.2	Two aliquots from each sample bulb are analyzed and the resulting values are
averaged to attain the final value. The average values (RPDs) should be within 75 percent. If
the replicates are not within 7 5 percent, a third replicate should be analyzed.

7.3.5.3	Report results in nanograms per liter (ng/L) without correction for the blank.
Using the following approximations, ng/L are considered roughly equivalent to ppb.

7.3.5.4	According to the Handbook of Chemistry and Physics at 20°C and 760 mm Hg
(1 atm), the density of dry air is equal to 1.204 g/L.

Therefore:	1 L of air = 1.204 g« 1 g, and

ppb « ng/g « ng/L;
ppm « ng/g « ng/L

7.3.5.5	Sample chromatograms may not match identically with those of analytical
standards. When identification is questionable, the chemist may calculate and report a
maximum possible concentration (qualified as less than the numerical value) which allows the
data user to determine if additional (e.g., CLP analyses) work is required, or, if the reported
concentration is below action levels and project objectives and DQOs have been met, to forego
further analysis.

7.3.5.6	Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) that allows the
data user to determine if reported concentration is above action levels and project objectives and
DQOs have been met, forego further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for replicate RPD are presented in
Table 4. This method should be used in conjunction with the quality assurance and control (QA/QC) section of
this catalog.

FMC-VA-002-10

-------
Table 4

REPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.012 (Air Analysis)

Advisory Quality Control Limits*

Analyte

Replicate RPD (%)

T etrachloroethene

±75

1,1,2-Trichloroethane

±75

Trichloroethene

±75

1,2-Dichloroethene

±75

1,2-Dichloropropane

±75

1,1,2,2-T etrachloroethane

±75

*	If the concentration of a target analyte is less than 5 times the QL, advisory control limits for replicate

RPD values become ± 3 times the QL for that analyte.

FMC-VA-002-11

-------
9.0 METHOD PERFORMANCE

9.1 The following is an example of a gas chromatogram for halogenated VOCs detected by a Hall

detector.

Figure 1

Gas chromatogram - Hall detector

Column:	VoCol,	30 m x 0.53 mm I.D. fused silica capillary column (Supelco).

Column Temperature:	Isothermal 40°C

Detector Temperature:	800°C (reactor)

Inj ector Temperature:	110°C

Carrier Gas:	Ultrapure helium, lOmL/min.

Reaction Gas:	Ultrapure hydrogen, 50 mL/min.

Detector:	Hall detector

FMC-VA-002-12

-------
10.0 REFERENCES

Information not available.

FMC-VA-002-13

-------
APPENDIX A

FASP Method F080.012

Instrument Options:

GC System:	Varian 3400 gas chromatograph/electrolytic conductivity detector (Tracor).

Data Handling System:	P.E. Nelson 2100 dual-channel integrator with 960 Series Intelligent Interface,

Hyundai 286 computer, and Epson LX800 printer.

FMC-VA-002-14

-------
APPENDIX B

FASP Method F080.012

Specific Instrument Parameters:
GC:

Integrator:

Column:

Carrier Gas:

Reaction Gas:

Column Oven:

Injector Temperature:

Detector Temperature:

Varian 3400 temperature-programmable GC equipped with a Tracor 1000 Hall
detector.

Nelson Analytical PC Integrator with a dual-channel interface and hard disk
drive for data storage.

Vocol fused silica capillary column (Supelco, or equivalent) 30 m x 0.53 mm
I.D.

Ultrapure helium, 10 mL/min.

Ultrapure hydrogen, 50 mL/min.

Isothermal 40°C

110oC

800°C

FMC-VA-002-15

-------
FASP Method Number F080.013
VOLATILE ORGANICS IN AIR - PORTABLE DIRECT ANALYSIS

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various volatile organic compounds (VOCs) in air samples by portable direct gas
chromatographic (GC) analysis using a photoionization detector (PID).

1.2 This method yields tentative identification and estimated quantitation of the analytes listed in Table
1. Approximate meyhod quantitation limits (QL) are also listed in Table 1. Reported values are on an "as-
received" basis.

1.3 This method should be used only by trained analysts under the supervision of an experienced

chemist.

2.0 SUMMARY OF METHOD

2.1 A measured amount of air is collected in a 1-L Tedlar bag or gas sample container. The standard
and sample containers are sealed and allowed to equilibrate to ambient temperature. One to 5 mL of sample is
withdrawn and injected into a GC equipped with a packed or megabore analytical column. VOCs are detected
with a PID. Tentative identification and quantitation are based on comparison of the retention times and relative
peak area or heights between the standards and samples.

3.0 INTERFERENCES

3.1 Tedlar bags and gas sample containers can become contaminated if stored near standards or cleaning
solvents, elevated concentrations of solvents in ambient air or contaminated sampling equipment. These
interferences can be avoided by not reusing Tedlar bags, or reduced by analyzing sampling containers before use
to insure that they are free of contamination.

3.2 When using a portable GC such as the Photovac, it should be placed in an area out of direct sunlight
and extreme temperature variations to minimize shifts in retention times.

3.3 Care should be taken when analyzing an unknown sample not to inject high concentrations into the
GC. This may result in instrument contamination or detector saturation.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System: Listed below is a GC option that meets the requirements of this method. Other
GC configurations may be substituted if they also meet the method requirements.

FMC-VA-003-1

-------
Table 1

FASP METHOD F080.013 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Volatile
Organic Compound

CAS Number

Quantitation Limits in
Air**

(ng/L)

1,1 -Dichloroethene

75-35-4

5.0

Methylene Chloride

75-09-2

100.0

T rans-1,2-Dichloroethene

540-59-0

5.0

1,1,1 -Trichloroethane

71-55-6

100.0

Benzene

71-43-2

5.0

Trichloroethene

79-01-6

50.0

T oluene

108-88-3

5.0

T etrachloroethene

127-18-4

5.0

Chlorobenzene

108-90-7

5.0

Ethylbenzene

100-41-4

5.0

m,p-Xylenes

1330-20-7

5.0

o-Xylene

1330-20-7

5.0

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are

provided for guidance and may not always be achievable.

** Quantitation limits for VOCs in air are on "as-received" basis.

4.1.1 Gas chromatograph: A portable GC equipped with a PID and all necessary accessories
including the appropriate pre-analytical column (packed or megabore) are required. The GC should have
an internal data-handling system capable of retention time labeling and providing relative and absolute
peak height and/or peak area measurements. If the GC is not equipped with an internal integrator, an
external strip-chart recorder, or integrator can be utilized.

4.1.1.1 Column 1: 4' x 1/8" Teflon column packed with SE-30 (80/100 mesh), or
equivalent.

4.1.1.2 Column 2: 10 mx 0.53 mm ID CP Sil 5CB megabore column, or equivalent.

4.1.1.3 Oven (optional'): The portable GC may be equipped with an isothermal oven.
The isothermal oven will ensure retention time stability and slightly faster analysis times.

4.1.1.4 Detector: PID with a 10.6 eV lamp.

FMC-VA-003-2

-------
4.1.1.5 Gas supply: The carrier gas should be ultra-zero grade air.

4.2 Other Laboratory Equipment

4.2.1 Tedlar bags: 1-L.

4.2.2 Volumetric gas sample containers

4.2.3 Microsvringes (Tor optional headspace standards'): 10-^iL, 25- |iL, and larger.

4.2.4 Syringes: 1-mL and 5-mL, glass gastight syringes.

4.2.5 Leak detector: Snoop liquid, or equivalent, for packed column operations or GOW-MAC
gas leak detector, or equivalent, for megabore capillary operations.

4.2.6 Chromatographic data stamp: Used to record instrument operating conditions if not
provided by the data handling system.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1 Solvents: Solvents are only needed for headspace standards, if used (see section 5.5).

5.2 Miscellaneous Reagents: None.

5.3 Carrier Gas: Ultra-zero grade air.

5.4 Stock Standards: Stock gas standards should be purchased as manufacturer certified standards.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for
each analyte of interest. The lowest concentration standard should be equal to 2 times the QL as listed in Table 1.
The remaining concentration levels should define the approximate working range of the GC: one standard at the
upper linear range and the other midway between it and the lowest standard.

5.5.1 Gas Standards: Certified gas standards are available from commercial manufacturers.
Various calibration standard concentrations are prepared by dilution of the stock standards into glass gas
vessels with known volumes.

5.5.2 Standards Made From Headspace Vapors: Standards can also be made using the
headspace vapor above pure solvents. The amount of headspace needed depends on the specific vapor
pressure of each compound. In addition, the vapor pressure changes as a function of temperature and
pressure. Therefore, these variables must be accounted for when preparing standards. An example of
this method for preparation of a 5 ppm trichloroethylene standard is as follows:

5.5.2.1 Before going to the site, obtain the barometric pressure reading form the local
airport or weather station (for example, "30 inches and steady").

5.5.2.2 Check the temperature on the site at the time the standards are prepared (for
example, 25°C).

FMC-VA-003-3

-------
5.5.2.3 Based on the temperature and pressure information, calculate the vapor
pressure for site conditions from vapor pressure tables at standard temperature and pressure
(STP). (Vapor pressure references are somewhat obscure. Information for some compounds are
in the CRC Handbook for Chemistry and Physics.') Table 2 lists vapor pressures for
trichloroethylene at specific temperatures (at 1 atmosphere). From Table 2, the vapor pressure
of 74.268 millimeters (mm) of mercury is obtained for 25°C. Correct for the barometric
pressure at the site, 30 inches of mercury (obtained from the weather service for that day), as
follows:

1 atmosphere = 760 mm of mercury, or 29.92 inches of water
Corrected vapor pressure of trichloroethylene =

74.268 x 29'92 = 74.070 mm of Hg
30 . 0

5.5.2.4 To make a 5 ppm standard of trichloroethylene in a 1000-mL gas collection
vessel, the amount of headspace vapor to add is calculated as follows:

Amount of Vapor = (Standard conc.)(Vol. of vessel) x

74.070

(5 ]iL/L x 1 L) x

760
74 . 070

51.3 pi

5.5.2.5 Inject 51.3 (iL of headspace into a 1000-mL gas collection vessel to make a 5
ppm trichloroethylene standard.

5.6 Check Standards: Check standards are calibration standards independently prepared by a
Chemist other than the calibration standard preparer.

5.7 Internal Standards (optional')

5.7.1 The internal standard should be a compound that a) is not expected to be found in the
samples, b) has a retention time toward the end of the run (where the greatest retention time shifts
occur), and c) is in the middle of the expected concentration range.

5.7.2 In this method, an internal standard can be used with the Photovac 10S series of GCs to
recalibrate retention time windows that change due to ambient temperature variations. If the Photovac is
not equipped with an isothermal oven, it is very susceptible to these temperature variations. If a
retention time shift occurs, the operator can change the internal standard retention time value in the
Photovac's library. The GC will then adjust the retention time windows for all other compounds in the
library and match any peaks in the chromatogram with the new retention time values. This will alleviate
the need to inject a new calibration standard every time there is a change in the ambient temperature.

FMC-VA-003-4

-------
Table 2

Vapor Pressure of Trichloroethylene

T emperature

Vapor Pressure

(°C)

(mm of Hg)

5

27.03251

10

35.35683

15

45.74057

16

48.0974

17

50.55512

18

53.11705

19

55.78667

20

58.5675

21

61.4631

22

64.47716

23

67.61339

24

70.87573

25

74.268

30

93.32106

35

116.256

40

143.6534

45

176.1468

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1	Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody
following current EPA regulations and recommendations in force at the time of sample collection. The sole
exception to this rule is the sample volumes required by the laboratory. The air sample (grab) is collected in a 1-
L Tedlar bag or gas sample container.

6.2	The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for VOCs in air is 24 hours, but it
is recommended that all samples be analyzed within 1 hour of collection.

7.0 PROCEDURE

FMC-VA-003-5

-------
Calibration

7.1.1 Initial calibration:

7.1.1.1 Inject a standard containing each compound of interest into the GC during
calibration to establish a retention time and response factor for quantitation. Some portable GCs
will only do a single-point calibration; however, the PID detector is linear over a wide
concentration range. Instrument linearity can be documented by bracketing the expected sample
concentration range with standards of known concentrations. Prepare a mid-concentration
standard as the calibration standard. After calibration, the low concentration and high
concentration standards can be run in the same way as samples. If the instrument is linear, the
low and high standards will be quantitated correctly. A correct quantitation is within 10 percent
of the true value. Inaccurate quantitation can be the result of a nonlinear working range or
inaccurate standards.

7.1.1.2 Calibrate the GC after an experienced chromatographer has insured that the
entire chromatographic system is functioning properly; that is, conditions exist such that
resolution, retention times, response reporting, and interpretation of chromatograms are within
acceptable quality control (QC) limits (section 7.3). Using at least 3 calibration standards for
each compound prepared as described in section 5, generate initial calibration curves (response
versus standard concentration) for each compound (refer to section 7.2 for chromatographic
procedures).

7.1.1.3 Compute the percent relative standard deviation (%RSD) based on each
compound's 3 calibration factors (CFs, see section 7.3) to determine the acceptability (linearity)
of the curve. Unless otherwise specified the %RSD must be less than 25 percent or the
calibration is invalid and must be repeated. Establish a new initial calibration curve anytime the
GC system is altered (e.g., new column, change in gas supply, change in oven temperature, etc.)
or shut down.

7.1.2 Continuing calibration:

7.1.2.1 Check the GC system on a regular basis through the continuing calibration.
The midrange initial calibration standard is generally the most appropriate choice for continuing
calibration validation. This single-point analysis follows the same analytical procedures used in
the initial calibration. Use instrument response to compute the CF which is then compared to
the mean initial calibration factor (CF), and calculate a relative percent difference (RPD, see
section 7.3). Unless otherwise specified, the RPD must be less than or equal to 25 percent for
the continuing calibration to be considered valid, or the calibration must be repeated. If an
internal standard is not used, analyze the continuing calibration standard after each sample that
shows a retention time shift, and reanalyze the sample. For the Photovac 10A10 GC without an
isothermal oven, it is recommended to analyze the continuing calibration standard every 8 to 10
injections or every 2 hours whichever is more frequent. For the Photovac 10S50 GC with an
isothermal oven, the continuing calibration standard does not need to be reanalyzed as
frequently. It is recommended to reanalyze the continuing calibration standard every 4 hours if
an isothermal oven is being used. After each continuing calibration standard, inject a blank to
verify the clean baseline.

7.1.2.2 Employ the continuing calibration in all target analyte sample concentration
calculations (section 7.3) for the period over which the calibration has been validated.

7.1.3 Final calibration: Obtain a final calibration at the end of each batch of sample analyses,
maximum allowable RPD between the mean initial calibration and final calibration CF s for each

FMC-VA-003-6

-------
analyte is less than or equal to 50 percent. A final calibration which achieves an RPD less than or equal
to 25 percent may be used as an ongoing continuing calibration.

7.2 Instrumental Analysis

7.2.1 Instrument parameters: Table 3 summarizes 2 examples of acceptable instrument
operating conditions for the gas chromatograph. Other instruments, columns, and/or chromatographic
conditions may be employed if this method's QC criteria are met.

7.2.2 Chromato grams:

7.2.2.1 Computer reproductions of chromatograms that are attenuated to insure all
peaks are on scale over a 100-fold range are acceptable. However, this can be no greater than a
100-fold range. This is to prevent retention time shifts by column or detector overload.
Generally, peak response should be greater than 25 percent and less than 100 percent of
full-scale deflection.

7.2.2.2 The following information must be recorded on each chromatogram:

• Instrument/detector identification;

• Column packing/coating, length, and I.D.;

• Oven temperature (if applicable);

• Gases and flow rates;

• Site name;

• Sample volume;

• Gain/attenuation;

• Sample number;

• Date and time; and

• GC Operator initials.

7.2.3 VOC identification:

7.2.3.1 Qualitative identification of VOCs is based on both the PID selectivity and
relative retention times as compared to known standards.

7.2.3.2 Generally, individual peak relative retention time windows should be less than
or equal to 5 percent for packed columns and less than or equal to 2 percent for megabore
capillary columns. It may not be possible or practical to separate all VOCs on a single column
(i.e., methylene chloride and 1,1-dichloroethene coelute on some columns). In such cases, these
VOCs should be denoted as the appropriate combination of VOCs or the sample can be
reanalyzed on a confirmation column.

7.2.4 System performance:

7.2.4.1 Degradation of VOCs in the GC system may occur, especially if the injector
and/or column inlet is contaminated.

FMC-VA-003-7

-------
Table 3

EXAMPLE FASP ISOTHERMAL GC OPERATING CONDITIONS

Instrument 1:

Photovac 10S50 GC equipped with a PID with a 10.6 eV lamp.

Column:

10 m x 0.53 mm I.D. CP Sil 5CB megabore column.

Carrier Gas:

Ultra-zero grade air.

Column Oven:

30°C, 40°C, or 50°C.

GC Analysis Time:	18 min (compound specific).

Instrument 2:

Photovac 10S30 GC equipped with a PID with a 10.6 eV lamp.

Column:

4' x 1/8" SP-2100 packed column.

Carrier Gas:

Ultra-zero grade air.

Column Oven:

Ambient.

GC Analysis Time:	18 min (compound specific).

7.2.4.2 Before initial use of the Tedlar bags, at least 10 percent of the bags should be
filled with clean air and sampled to confirm that they are free of contamination.

7.2.5	Specific instrument parameters: Specific instrument parameters that have been used are
provided in Appendix B of this method.

7.2.6	Analytical sequence:

7.2.6.1	Instrument blank;

7.2.6.2	Initial calibration;

7.2.6.3	Syringe blank;

7.2.6.4	Check standard solution and/or performance evaluation sample (if available);

7.2.6.5	Syringe blank;

7.2.6.6	Sample 1;

7.2.6.7	Syringe blank (if the sample is contaminated);

7.2.6.8	Sample 2;

7.2.6.9	Syringe blank (if the sample is contaminated);

7.2.6.10	Sample 3;

7.2.6.11	Continue for samples 4 to 10;

FMC-VA-003-8

-------
7.2.6.12 Continuing calibration standard (Photovac 10A10 - after the 10th injection or
2 hours, whichever is more frequent; Photovac 10S50 with isothermal oven - after 30 samples or
after approximately every 4 hours whichever is more frequent);

7.2.6.13 Syringe blank;

7.2.6.14 Repeat, beginning at step 7.2.6.6 with the next batch of samples; and

7.2.6.15 Final calibration at end of day.

7.3 Calculations

7.3.1 Initial calibration:

7.3.1.1	Analyze each calibration standard, adding the internal standard spiking solution
(optional) directly to the gas vessel containing the standard. Injection of an internal standard
into a Tedlar bag may cause inaccurate quantitation of the internal standard unless the exact
volume of air is known. Therefore, when using an internal standard injection, the sample should
be in a ridged container such as a glass gas vessel with a known volume.

7.3.1.2	Analyze each calibration standard. Tabulate the area response for each target
analyte against the concentration for each compound and calculate CF s for each target
compound using the following equation:

7.3.1.3 Using the CFs calculated above, calculate the %RSD for each compound at the
3 concentration levels using the equation below. The %RSD must be less than or equal to
25 percent.

CF =

Area of Peak

Mass Injected (nanograms)

%RSD = — x 100
X

where SD, the standard deviation, is given by

sd = \ it-

\ i" i

Xi - X) 2

N - 1

where: X;
X
N

Individual CF (per compound)

Mean of initial CF s (per compound)
Number of calibration standards.

7.3.2 Continuing calibration:

FMC-VA-003-9

-------
7.3.2.1 Sample quantitation is based on analyte CFs calculated from continuing
calibrations. Midrange standards for all initial calibration analytes must be analyzed as
continuing calibration standards at specified intervals (less than or equal to 24 hours).

7.3.2.2 The maximum allowable RPD calculated using the equation below for each
analyte must be less than or equal to 25 percent.

l ~T ~ CFC\

RPD = - 1 — x 100

CFx + CFc
2

where: CF, = Mean calibration factor from the initial calibration for each compound

CFc = Measured calibration factor from the continuing calibration for the

same compound.

7.3.3 Final calibration:

7.3.3.1 Obtain the final calibration at the end of each batch of samples analyzed.

7.3.3.2 The maximum allowable RPD between the mean initial calibration and final
calibration CFs for each analyte must be less than or equal to 50 percent. A final calibration
that achieves an RPD less than or equal to 25 percent may be used as an ongoing continuing
calibration.

l ~T ~ CFF\

RPD = - 1 — x 100

cft + cff
2

where: CF, = Mean initial calibration factor for each compound

CFf = Final calibration factor for the same compound.

7.3.4 Sample quantitation:

7.3.4.1 Calculate the concentration in the sample using the following equations. The
response can be measured by automated relative peak height or peak area measurements from an
integrator. The Photovac 10S50 GC will automatically calculate the sample concentration
based on the standard listed in the library.

7.3.4.2 The CF from the continuing calibration analysis is used to calculate the
concentration in the sample. Use the CF as determined in section 7.3.1 and the equations
below. Corrections must be made for changes in volumes and gain/attenuation between the
samples and standards.

(A ) (1000)

Concentration (nq/L) =

(CF ) (V.)

\ c' ^ l'

FMC-VA-003-10

-------
where: A,

Area of the peak for the compound to be measured
Volume of sample injected (mL)

Calibration factor from the continuing calibration for the compound.

CFc

7.3.4.3 Report results in nanograms per liter (ng/L) without correction for the blank.
Using the following approximations, ng/L are considered roughly equivalent to ppb: According
to the Handbook of Chemistry and Physics at 20°C and 760 mm Hg (1 atm.), the density of dry
air is equal to 1.204 g/L.

7.3.4.4 When identification is questionable, the chemist may calculate and report a
maximum possible concentration (qualified as less than the numerical value). This allows the
data user to determine if additional (e.g., CLP RAS or SAS analysis) work is required, or if the
reported concentration is below action levels and project objectives and DQOs have been met,
to forego further analysis.

7.3.4.5 Coeluted analytes should be quantitated and reported as the combination of the
unseparated volatile organic target analytes or reanalyzed on a confirmation column.

7.3.4.6 Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as less than the numerical value). This allows the
data user to determine if additional (e.g., CLP analyses) work is required, or if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for duplicate RPD are presented in
Table 4. This method should be used in conjunction with the quality assurance and control (QA/QC) section of
this catalog.

Therefore, 1 L of air = 1.204 gs 1 g, and

ppb s ng/g = ng/L;
ppm s ^g/g= ng/L.

FMC-VA-003-11

-------
Table 4

DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.013 (VOCs in Air by Direct Analysis)

Advisory Quality Control Limits



Duplicate RPD

Analyte

(%)

1,1 -Dichloroethane

±75

trans-1,2-Dichloroethene

±75

Chloroform

±75

Benzene

±75

Trichloroethene

±75

T oluene

±75

T etrachlorethene

±75

Chlorobenzene

±75

Ethylbenzene

±75

m,p-Xylenes

±75

o-Xylene

±75

Methylene Chloride

±75

1,1,1 -Trichloroethane

±75

FMC-VA-003-12

-------
9.0 METHOD PERFORMANCE

9.1 The following is an example of a GC chromatogram for several target compounds.

Figure 1
Gas Chromatogram

Instrument:	Photovac 10S30

Column:	4' x 1/8" SP-2100

Gas:	Ultra-zero grade air at a flow rate of 15 mL/min

Detector:	PID with a 10.6 eV lamp

FMC-VA-003-13

-------
9.2 Method F080.013 examples of sample OA/OC results: Duplicate sample results are presented as
examples of FASP Method F080.013 empirical data (see Table 5).

Table 5

FASP METHOD F080.013
DUPLICATE SAMPLE ANALYSIS
RELATIVE PERCENT DIFFERENCE
VOLATILE ORGANIC COMPOUNDS IN AIR

(To be completed as data becomes available.)

FMC-VA-003-14

-------
10.0 REFERENCES

Information not available.

FMC-VA-003-15

-------
APPENDIX A

FASP Method F080.013

(To be completed by each Region.)

FMC-VA-003-16

-------
APPENDIX B

FASP Method F080.013

(To be completed by each Region.)

FMC-VA-003-17

-------
FASP Method Number F080.014
HALOGENATED VOLATILE ORGANICS IN AIR - DIRECT ANALYSIS

ELECTRON CAPTURE DETECTOR

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining relative
concentrations of halogenated volatile organic compounds (VOCs) in air samples. The method employs direct air
injection and gas chromatographic (GC) analysis using an electron capture detector (ECD).

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 One to 5 mL of air collected in a 250-mL gas sample bulb are injected into a gas chromatograph
equipped with a capillary column and an ECD. Halogenated VOCs are detected with the ECD. Quantitation and
identification are based on relative peak areas and retention times using the external standard method.

3.0 INTERFERENCES

3.1 Sample bulbs can become contaminated if stored near standards or cleaning solvents, elevated
concentrations of solvents in ambient air or contaminated air sampling equipment. These interferences can be
mitigated by analyzing sample bulbs before use to insure that they are free of contamination and by routinely running
equipment blanks.

3.2 This method employs direct injection of air into the GC equipped with an ECD. These samples typically
contain high amounts of and moisture. The presence of these 2 sample constituents can significantly shorten the
useful life of the GC column and ECD. There are several ECD designs that are very sensitive to oxygen and moisture
and do not work with this method. This method was developed using a Tracor 540 GC whose ECD is not adversely
effected by oxygen and moisture, except for occasional slight retention time shifts. Sometimes it is necessary to
increase the column temperature to 100 to 200°C for 15 or more minutes to allow the instrument to stabilize.

3.3 When using this method, the analyst must be cautious about injecting air directly into a GC equipped
with an ECD and understand that he might be adversely effecting the ECD (and GC column). If GC sensitivity
significantly decreases after injecting air samples, the GC/ECD should not be used further.

FMC-VA-004-1

-------
Table 1

FASP METHOD F080.014 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Compounds

CAS Number

Quantitation Limits
in Air**
(ng/L)

Carbon Tetrachloride

56-23-5

Chloroform

67-66-3

T etrachlorethene

127-18-4

1,1,1 -Trichlorethane

71-55-6

Trichloroethene

79-01-6

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided

for guidance and may not always be achievable.

** Quantitation limits for air are on "as-received" basis.

3.4 The ECD may become saturated when analyzing high concentration samples. To allow the GC to
stabilize, the column temperature is increased to 150 to 200°C for 15 minutes or longer to bake out the contaminants.
This should be followed with a blank sample to check for sample carryover before proceeding.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems

4.1.1 Gas chromatograph: An analytical system complete with a temperature programmable GC
is required, and all necessary accessories including injector and detector systems must be designed or
modified to accept megabore capillary columns. The system shall have a data handling system attached to
the detector that is capable of retention time labeling, relative retention time comparisons, and providing
peak height and/or peak area measurements.

4.1.1.1 Analytical column: 30 m x 0.53 mm ID DB 624 fused silica megabore capillary
column (J&W Scientific), or equivalent.

4.1.1.2 Detector: Linearized ECD employing a system with makeup gas supply at the
detector's capillary inlet.

4.1.1.3 Gas supply: The carrier and makeup gases should be argon with 5 percent
methane. The gas should pass through oxygen traps prior to the GC to prevent degradation of the
column's analytical coating and detector foil.

4.2 Other Laboratory Equipment

4.2.1 Sample bulbs: 250 mL gas sample bulbs with Teflon stopcocks and a side port with
replaceable septa for sample withdrawal.

FMC-VA-004-2

-------
4.2.2 Gas sample bulb septa : Supelco Thermogreen, or equivalent, septa for sample port of gas
sample bulbs.

4.2.3 Syringes: Glass syringes (1-mL and 5-mL) with replaceable needles.

4.2.4 Microsvringes: lO-^L, 25-|iL, and larger.

4.2.5 Pipet: 10-mL class A pipet and safety bulbs.

4.2.6 Standard vials: 15-mL glass vials with Teflon-lined silicone septa.

4.2.7 Heat source: Heat source (hairdryer) and vacuum pump for decontaminating bulbs and

syringes.

4.2.8 Vortex mixer: Vortex genie, or equivalent.

4.2.9 Oxygen trap: Supelpure-O-Trap and OMJ-1 indicating tube, or equivalent.

4.2.10 Leak detector: GOW-MAC gas leak detector, or equivalent, for megabore capillary
operations.

4.2.11 Activated carbon: Used to aid in keeping the mobile lab, standards, and reagents free of
solvent contamination.

4.2.12 Chromatographic data stamp: Used to record instrument operating conditions, if not
provided by the data handling system.

4.3 Instrument Options: Specific systems that have been used are provided as "Instrument Options" in
Appendix A of this method.

5.0 REAGENTS

5.1 Solvents: Solvents are only needed for headspace standards, if used (see Section 5.5).

5.2 Miscellaneous Reagents: None.

5.3 Gases: Ultrapure or chromatographic grade 5 percent methane in argon (always used in conjunction with
oxygen trap).

5.4 Stock Standards: Neat stock standard solutions and certified gas standards should be purchased as
manufacturer-certified standards, when possible.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. The lowest concentration standard should be approximately 2 times the QL as listed in Table 1.
The remaining concentration levels should define the approximate working range of the GC: one standard at the
upper linear range and the other midway between it and the lowest standard.

5.5.1 Gas standards: Certified gas standards are available from commercial manufacturers. The
lower concentration should be approximately 2 times the QL as listed in Table 1. The remaining
concentration levels should define the approximate working range of the GC: one at the upper liner range
and the other midway between it and the lowest standard.

FMC-VA-004-3

-------
5.5.2 Standards made from headspace vapors: Standards can also be made using the headspace
vapor above pure standards. The amount of headspace needed depends on the specific vapor pressure of
each compound. In addition, the vapor pressure changes as a function of temperature and pressure.
Therefore, these variables must be accounted for when preparing standards. An example of this method for
preparation of a 5 ppm trichloroethylene standard is as follows:

5.5.2.1 Before going to the site, obtain the barometric pressure reading from the local
airport or weather station (for example, "30 inches and steady").

5.5.2.2 Check the temperature on the site at the time the standards are prepared (for
example, 25°C).

5.5.2.3 Based on the temperature and pressure information, calculate the vapor pressure
for site conditions from vapor pressure tables at standard temperature and pressure (STP). (Vapor
pressure references are somewhat obscure. Information for some compounds are in the CRC
Handbook for Chemistry and Physics, but this is almost useless for FASP purposes. Tables
containing vapor pressures for all target compounds are being compiled by FASP and Photovac
personnel and will be available soon. An example is shown in Table 2). Table 2 lists vapor
pressures for trichloroethylene at specific temperatures (at 1 atmosphere). From Table 2, the vapor
pressure of 74.268 millimeters (mm) of mercury is obtained for 25°C. Correct for the barometric
pressure at the site, 30 inches of mercury (obtained from the weather service for that day), as
follows:

1 atmosphere = 760 mm of mercury, or 29.92 inches of water

Corrected vapor pressure of trichloroethylene =

74.268 x 29'92 = 74.070 mm of Hg
30 . 0

5.5.2.4 To make a 5 ppm standard of trichloroethylene in a 1000-mL gas collection vessel,
the amount of headspace vapor to add is calculated as follows:

Amount of Vapor = (Standard conc.)(Vol. of vessel) x

74.070

(5 ]iL/L x 1 L) x

760
74 . 070

51.3 pi

5.5.2.5 Inject 51.3 |±L of headspace into a 1000-mL gas collection vessel to make a 5 ppm
trichloroethylene standard.

5.6. Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

FMC-VA-004-4

-------
Table 2

Vapor Pressure of Trichloroethylene

T emperature

Vapor Pressure

(°C)

(mm of Hg)

5

27.03251

10

35.35683

15

45.74057

16

48.0974

17

50.55512

18

53.11705

19

55.78667

20

58.5675

21

61.4631

22

64.47716

23

67.61339

24

70.87573

25

74.268

30

93.32106

35

116.256

40

143.6534

45

176.1468

FMC-VA-004-5

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for air samples is 24 hours, but it is
recommended that all samples be analyzed within 1 hour of collection.

7.0 PROCEDURE

7.1 Calibration

7.1.1 Initial calibration:

7.1.1.1 Calibrate the GC after an experienced chromatographer has insured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution,
retention times, response reporting, and interpretation of chromatograms are within acceptable
quality control (QC) limits. Using at least 3 calibration standards for each analyte prepared as
described in Section 5, generate initial calibration curves (response versus mass of standard
injected) for each analyte (refer to Section 7.2 for chromatographic procedures).

7.1.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.3) based
on each compound's 3 calibration factors (CFs, see Section 7.3) to determine the acceptability
(linearity) of the curve. Unless otherwise specified, the %RSD must be less than 25 percent, or the
calibration is invalid and must be repeated. Establish a new initial calibration curve anytime the
GC system is altered (e.g., new column, change in gas supply, change in oven temperature, etc.)
or shut down.

7.1.2 Continuing calibration:

7.1.2.2 Employ the continuing calibration in all target analyte sample concentration
calculations (Section 7.3) for the period over which the calibration has been validated.

7.1.3 Final calibration: Obtain a final calibration at the end of each 24-hour period in which
samples are analyzed. The maximum allowable RPD between the mean initial calibration and final
calibration CF s for each analyte is less than or equal to 50 percent. A final calibration which achieves an
RPD less than or equal to 25 percent may be used as an ongoing continuing calibration.

7.2 Instrumental Analysis

FMC-VA-004-6

-------
7.2.1 Instrument parameters: Table 3 summarizes an example of acceptable instrument operating
conditions for the GC. Other instruments, columns, and chromatographic conditions may be used if this
method's QC criteria are met. (CAUTION: Read Section 3 concerning damage to ECDs.)

7.2.2 Chromatograms:

7.2.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks
are on scale over a 100-fold range are acceptable. However, this can not be greater than a 100-fold
range to prevent retention time shifts by column or detector overload. Generally, peak response
should be greater than 25 percent and less than 100 percent of full-scale deflection to allow visual
pattern recognition of halogenated compounds.

7.2.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperatures;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.2.3 VOC identification:

7.2.3.1 Qualitative identification of VOCs is based on both detector selectivity and
retention time as compared to known standards using the external standard method.

7.2.3.2 Generally, individual peak retention time windows should be less than or equal
to 2 percent for capillary columns.

7.2.3.3 For the purpose of FASP analyses, peak intensity (height or area) matching for
positive identification is based on the chemist's best professional judgement in consultation with
more experienced chromatographic spectral data interpretation specialists, when required. It is
possible that interferences may preclude positive identification of an analyte. In such cases, the
chemist should report the presence of the interferents with the maximum concentration possible.

7.2.4 System performance:

7.2.4.1 Degradation of VOCs in the GC system may occur especially if the injector and/or
column inlet is contaminated.

7.2.4.2 Before initial use and after each subsequent use, each numbered gas sample bulb
is analyzed to confirm that it is free of residual contamination.

FMC-VA-004-7

-------
Table 3

EXAMPLE TEMPERATURE PROGRAM GC OPERATING CONDITIONS

Instrument:

Tracor 540 temperature programmable GC and all required accessories including
analytical columns, gases, and an ECD.

Integrator:

Spectraphysics 4290 Integrator with a dual channel interface and hard disk drive
for data storage.

Column:

J&W DB 624 fused-silica megabore capillary column, 30 m x 0.53 mm ID.

Carrier Gas:

Ultrapure 5 percent methane in argon, 10 mL/min.

Reaction Gas:

Ultrapure 5 percent methane in argon, 35 mL/min.

Column Oven:

Isothermal, 35°C

Injector Temperature:

250oC

Detector Temperature:

350oC

GC Analysis Time:

10.2 to 18.2 min.

7.2.5 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided in Appendix B of this method.

7.2.6 Analytical sequence:

7.2.6.1 Instrument blank.

7.2.6.2 Initial calibration.

7.2.6.3 Check standard solution and/or performance evaluation sample, if available.

7.2.6.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.2.6.5 Associated QC lot method blank.

7.2.6.6 Twenty samples are injected into the GC depending upon the concentration of
volatiles in the air. Replicate injections are made for all positive hits. (A syringe blank must be
analyzed initially and after any high concentration samples to confirm proper decontamination.)

7.2.6.7 Repeat sequence beginning at Step 7.2.6.5 until all sample analyses are completed
or another continuing calibration is required.

7.2.6.8 Final calibration when all sample analyses are complete.

7.3 Calculations

7.3.1 Initial calibration:

FMC-VA-004-8

-------
7.3.1.1 Identification and quantitation of target VOCs should be based on the external
standard method. A compound which is detected by the ECD should be quantitated using the
detector response for that specific compound.

7.3.1.2 Analyze each calibration standard. Tabulate the area response of each target
analyte against concentration for each compound and calculate CFs for each target compound using
the following equation:

_ Area of Peak

Mass Injected (nanograms)

7.3.1.3 Using the CFs calculated above, %RSD for each compound at a minimum of 3
concentration levels using the following equation:

ST)

hRSD = 4=r x 100
X

where SD, the standard deviation, is given by

(X. - X)'
N ~ 1

where: X; = Individual CF (per compound)

X = Mean of initial CF s (per compound)

N = Number of calibration standards.

7.3.1.4 The %RSD must be less than or equal to 25 percent.

7.3.2 Continuing calibration:

7.3.2.1 Sample quantitation is based on analyte CFs calculated from continuing
calibrations. Midrange standards for all initial calibration analytes must be analyzed as continuing
calibration standards at specified intervals (less than or equal to 24 hours).

7.3.2.2 The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

l ~T ~ CFC\

RPD = - 1 — x 100

CFx + CFc
2

where: CF, = Mean CF from the initial calibration for each compound

CFc = Measured CF from the continuing calibration for the same compound.

7.3.3 Final calibration:

FMC-VA-004-9

-------
7.3.3.1	The final calibration is obtained at the end of each batch of samples analyzed.

7.3.3.2	The maximum allowable RPD between the mean initial calibration and final
calibration CFs for each analyte must be less than or equal to 50 percent. A final calibration that
achieves an RPD less than or equal to 25 percent may be used as an ongoing continuing calibration.

l ~T ~ CFF\

RPD = -	1	— x 100

cft + cff
2

where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.3.4 Sample quantitation:

7.3.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated relative peak height or peak area
measurements from an integrator. Sample quantitation is based on analyte CFs calculated from
continuing calibrations.

(A ) (1000)

Concentration (nq/L) = 			

(CF ) (V.)

\ c' ^ l'

where: Ax =	Response for the analyte to be measured

V; =	Volume of sample injected (mL)

CFc =	CF from the continuing calibration for the same compound.

7.3.4.2	Two aliquots from each sample bulb are analyzed and the resulting values are
averaged to attain the final value. The average values (RPDs) should be within 75 percent. If the
replicates are not within the RPD of 75 percent, then a third replicate should be analyzed and the
result averaged in.

7.3.4.3	According to the Handbook of Chemistry and Physics at 20°C and 760 mm Hg (1
atm), the density of dry air is equal to 1.204 g/L.

Therefore,	1 L of air = 1.204 g s 1 g, and

ppb E ng/g = ng/L;
ppm s ^g/g= ng/L.

7.3.4.4	Because the exact temperature and pressure are not measured at the time each air
sample collected, all results are reported as ng/L or ng/L which are assumed to be roughly
approximate to ppb and ppm, respectively. Because of these assumptions, air results should be
considered screening results.

7.3.4.5	Report results in nanograms per liter (ng/L) without correction for the blank.

7.3.4.6	Sample chromatograms may not match identically with those of analytical
standards. When identification is questionable, the chemist may calculate and report a maximum

FMC-VA-004-10

-------
possible concentration (qualified as less than the numerical value), which allows the data user to
determine if additional (e.g., CLP analyses) work is required, or if the reported concentration is
below action levels and project objectives and DQOs have been met, to forego further analysis.

7.3.4.7 Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) that allows the data
user to determine if additional (e.g., CLP analyses) work is required, or if the reported concentration
is above action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for replicate RPD are presented in
Table 4. This method should be used in conjunction with the quality assurance and control (QA/QC) section of this
catalog.

FMC-VA-004-11

-------
Table 4

DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F080.014 (Air Analysis)

Advisory Quality Control Limits



Duplicate RPD

Analyte

(%)

Carbon Tetrachloride

±75

Chloroform

±75

T etrachloroethane

±75

Trichloroethene

±75

1,1,1 -Trichloroethane

±75

FMC-VA-004-12

-------
9.0 METHOD PERFORMANCE

9.1 The following is an example of a gas chromatogram for halogenated VOCs as detected by an ECD

detector.

Figure 1
Gas Chromatogram - ECD

Column:

Column Temperature:
Detector Temperature:
Injector Temperature:
Carrier Gas:

Makeup Gas:

Detector:

J&W DB 624 fused silica megabore capillary column, 30 m x 0.53 mm

Isothermal, 35°C

350°C

350°C

Ultrapure 5 percent methane in argon, 10 mL/min.

Ultrapure 5 percent methane in argon, 35 mL/min.

ECD

FMC-VA-004-13

-------
9.2 Method F080.014 examples of sample OA/OC results: Replicate sample results are presented as
examples of FASP Method F080.014 empirical data (see Table 5).

Table 5
FASP METHOD F080.014
REPLICATE SAMPLE ANALYSIS
RELATIVE PERCENT DIFFERENCE
HALOGENATED VOCs in AIR

To be completed.

U - The material was analyzed for but was not detected. The associated numerical value is a FASP quantitation

limit, adjusted for sample volume.

F - Data has been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

FMC-VA-004-14

-------
10.0 REFERENCES

Information not available.

FMC-VA-004-15

-------
APPENDIX A

FASP Method F080.014

Instrument Options:

Tracor 540 temperature programmable GC with an ECD; Spectraphysics 4290 Integrator with dual-channel interface
and hard disk drive for data storage.

FMC-VA-004-16

-------
APPENDIX B

FASP Method F080.014

Specific Instrument Parameters:

Instrument:

Integrator:

Column:

Carrier Gas:

Makeup Gas:

Column Oven:

Injector Temperature:

Detector Temperature:

GC Analysis Time:

Tracor 540 GC with ECD.

Spectraphysics 4290 Integrator.

J&W DB 624 fused silica megabore column, 30 m x 0.53 mm, or equivalent.

Ultrapure 5 percent methane in argon.

Ultrapure 5 percent methane in argon.

Isothermal, 35°C.

250oC

350oC

10.2 to 18.2 mins.

FMC-VA-004-17

-------
NUS SOP Number 5.9

FIELD SCREENING ANALYSIS OF AMBIENT AIR

1.0 SCOPE AND APPLICATION

1.1 The following methodology describes a modification of EPA Compendium methods suitable for the
determination of volatile organic contaminants in ambient air.

1.3 Table 1 provides a list of potential target compounds.

1.4 The procedure described here is based upon the analysis of whole air samples collected in canisters or
Tedlar bags. However, this procedure can easily be adapted for the analysis of samples collected directly on sorbent
tubes or for source sample analysis using aliquot introduction into the gas chromatograph (GC) via direct gaseous
injection or an appropriate size commercial sample loop.

2.0 SUMMARY OF METHODS

2.1 In this methodology, an aliquot of gaseous sample is routed through a packed sorbent tube. Volatile
contaminants present in the gaseous sample are adsorbed onto the packing within the sorbent tube. The contents of
the sorbent tube are subsequently desorbed (by action of heat and reverse gas flow) onto a suitable column housed
by a preprogrammed GC. The contaminants become separated and resolved as they travel through the GC's column.
Eventually, the contaminants elute through an appropriate detector. Detector signals are processed and interpreted
via a previously programmed integrator.

3.0 INTERFERENCES

3.1 Interferences can result from many sources, considering the environmental settings of most hazardous
waste sites. However, most interfering impurities are artifacts originating from organic compounds within the
specialty gases and the plumbing within the trapping/desorption device. Interferences in the analytical system are
monitored by the analysis of inert gas method blanks. Method blanks are analyzed under the same conditions and
at the same time as standards and samples to establish an average background response.

4.0 APPARATUS AND MATERIALS

4.1 Purge and Trap Device: Tekmar Company Model LSC-2 or Model 5000. Traps may be packed solely
with Tenax or, alternatively, trap packing may consistof 1.0 cm of 3 percent OV-1, 15 cm of Tenax, and 8 cm of silica
gel. Appropriate trap selection is contingent upon the target compounds being analyzed.

4.2 Gas Chromatograph: Hewlett-Packard 5890, or equivalent. The analytical system should be equipped
for temperature programming, packed and/or capillary column analysis and on-column injection.

FMC-VA-005-1

-------
Table 1

SUMMARY OF POTENTIAL TARGET COMPOUNDS

Volatile Organics Analysis

Acetone

Benzene

Bromoform

Carbon tetrachloride

Chlorobenzene

Chloroform

Ethylbenzene
Methylene Chloride
1,1 -Dichloroethene

Total 1,2-Dichloroethenes

1,1 -Dichloroethane

1,2-Dichloroethane

1,1,1 -Trichloroethane

T etrachloroethene

T oluene

Trichloroethene

Total Dichlorobenzenes

Total Xylenes
2-Butanone (MEK)

4-Methyl-2-pentanone (MIBK)

FMC-VA-005-2

-------
4.3 Detector: Photoionization detector/flame ionization detector (P ID/FID) or photo ionization detector/Hall
electrolytic conductivity detector (PID/HECD) in series; FID only. Optimum detector selection should be based upon
the sensitivities of the target compounds being analyzed.

4.4 Analytical Column: Glass or stainless steel packed with 1% SP-1000 on 60/80 mesh Carbopack B.
Alternatively, a suitable capillary column may be used.

4.5 Syringes (assorted): 5-|iL, 25-^L, 100-|iL, 1-mL, and 10-mL.

4.6 Volumetric Flasks: 10-mL, 25-mL, and 100-mL.

4.7 Tedlar Bag: For making gaseous standards.

4.8 Flowmeter: For use in measuring the exact volume of gas introduced to the Tedlar.

4.9 Analytical Balance: Capable of accurately weighing 0.0001 g.

4.10 Vacuum Pump: Low draw, positive seal.

4.11 Refrigerator: Separate for sample and standard storage. Capable of maintaining a stable temperature

of 4°C.

5.0 REAGENTS

5.1 Methanol: Pesticide grade, or equivalent.

5.2 Organic-free Water: Supplied by laboratory or purchased.

5.3 Neat Solvents: 96 percent purity, or better, for each compound of interest.

5.4 Ultra-high Purity Nitrogen: For use in generating standards and method blanks.

5.5 Standards: Calibration standards containing the compounds of interest are prepared in methanol by
either diluting commercially purchased stock standard mixes or by creating in-house standards from pure solvents.
In-house calibration standards are prepared gravimetrically, in that an appropriate (iL aliquot of each target compound
is introduced into a known volume of methanol. The appropriate (iL aliquot of compound is based upon the
compound's density and response to the selected detector. The calibration standards should be created at such a level
that a 5- to 10-(iL spike into a 1-L Tedlar bag filled with nitrogen yields a concentration of 10 ng/L based upon the
analysis of a 500-mL aliquot. Aliquots are evacuated onto a clean trap. Alternatively, commercially prepared stock
calibration gases may be used.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Samples awaiting analysis are stored at 4°C in a dedicated refrigerator. If holding times are exceeded,
the affected data should be qualified as suspect.

7.0 PROCEDURE

FMC-VA-005-3

-------
7.1 Calibration: Calibrate the analytical system via the external standard method in which response factors
(RF) for each compound are obtained by the analysis of a standard mix of known concentration. Following the
analysis of this known standard mix, create an electronic file establishing each peak's identity, retention time (RT),
RF, and known concentration. Determine the RF for each target compound by dividing the known concentration by
the associated peak response (area or height units). For initial calibration, determine each compound's average RF
by averaging the peak response results generated for the initial linearity study. Program these average RFs into the
integrator to allow for direct concentration reading of contaminants found in subsequent sample analyses.

7.1.1 Initial linearity:

7.1.1.1 Generate an initial 3-point calibration curve is generated by the trapping and
analysis of multiple aliquots of calibration standard. For example, if the calibration standard is
created such that analysis of a 500-mL aliquot of standard yields results at the level of the reported
detection limits, a 3-point calibration curve may be achieved by the analysis of 500-, 700-, and
1,000-mL aliquots.

7.1.1.2 Compute the percent relative standard deviation (%RSD see 7.3.1) based on each
compound's RFs (see 7.4) to determine the acceptability (linearity) of the curve. The %RSD should
be less than 20 percent. Reanalyze standard runs yielding data that does not meet the %RSD
criterion,

7.1.2 Continuing calibration:

7.1.2.1 Update the calibration of the analytical system 3 times daily: (1) preceding the
daily analyses, (2) midday, and (3) after the daily analyses.

7.1.2.2 Analyze standards run for continuing calibration purposes at a level equal to the
reported detection limits. Continuing calibration RFs for each parameter should fall within 25
percent difference (%D, see 7.3.3) of the average RF calculated for that particular compound during
the initial linearity study. Qualify data associated with individual parameter not meeting the %D
criterion as suspect.

7.1.2.3 Conduct the continuing calibration at a concentration level equal to the reported
detection limits.

7.1.3 Peak identification: Compound identities may be substantiated by the analysis of each
individual component, thereby documenting compound RT.

7.2 Gas Chromatography

7.2.1 Analytical sequence: Conduct analyses in sets of 10, whenever possible, with 1 laboratory
duplicate spike analysis run per set. Bracket each set of sample analyses by the analysis of a standard, with
a method blank analysis following each standard run. The number of analyses per sample set and the
associated quality assurance/quality control (QA/QC) varies per contract. Consult the project work plan to
verify that all contractual obligations were met.

7.2.2 Preconcentrate sample contaminants through the trapping process in which the volatile
contaminants are adsorbed on to a sorbent trap. The affinity that the volatilized organic contaminants have
for the special packing inside the sorbent tube cause them to be retained within the tube (i.e., adsorbed onto
the packing) while other components of the gaseous aliquot pass through the tube.

7.2.3 Desorption of the adsorbed contents of the sorbent trap onto the head of a previously
conditioned GC analytical column allows for subsequent analysis by temperature-programmed GC. First

FMC-VA-005-4

-------
hold the desorbed contaminants at constant temperature (usually in the range of 45 to 55 °C) at the head of
the analytical column for a period of 3 to 5 minutes. After this initial time period, raise the GC oven
temperature at a constant rate (usually 8 to 15°C/min) until a final temperature of 200 to 225°C is reached.
The final temperature is customarily held for a period of 3 to 10 mins.

7.2.4 The preferential affinity of the volatile contaminants to either the analytical column's mobile
or stationary phase, the effect of elevated temperature, and the action of carrier gas flow through the column
cause the volatile contaminants to become separated and resolved allowing them to elute in bands through
the selected detector. As long as analytical conditions remain constant, each type of volatile component will
elute at a characteristic RT. In this manner, sample contaminants are identified and quantified by
comparison to a run of standard of known concentration.

7.3 Calculations

7.3.1	Calculate %RSD using the following equation:

ST)

%RSD = — x 100
X

where:

A (x - x)2
SD = > 			

M N - 1

and X is the mean of initial RFs (per compound).

7.3.2	Calculate relative percent difference (RPD) values using the following equation:

D1 ~ D2
RPD = 	i	— x 100

+ g2>

2

where:	D[ =	First sample value

D2 =	Second sample value

7.3.3	Calculate the %D using the following equation:

%D = —	— x 100

where:	X[ =	RF of first result

X2 =	RF of second result

7.3.4	Calculate percent recovery (%R) using the following equation:

= SSR ~ SR x 100

s

where:	SSR =	Spike sample results

SR =	Sample result

S	=	Amount of spike added

FMC-VA-005-5

-------
7.4 Sample Quantitation: The quantitation of volatile contaminants is based upon the following formula:

Conentration , (uq/L) = tarqet analyte peak response . x RF x DF

sample x r j: l l sample

where: RF = Target analvte concentration in std (\ieAS)

Target analyte peak response in std

DF = Dilution factor, when applicable

8.0 QUALITY CONTROL

8.1 Overview

8.1.1 Field screening generates Level II data. As Level II data, the concurrent analysis of
laboratory duplicates and matrix spike analyses and the use of surrogate spike compounds is not required.
However, beyond the maintenance of practical Standard Operating Procedures (SOPs), certain elements of
QC (if opted) can greatly enhance the interpretation of and the confidence in the data generated. These
traditional elements of QC are discussed here as to how they are adapted to meet the demands of a
successfully applied field screening QA/QC program.

8.1.2 The primary purposes of an appropriate QA/QC program are to: (1) substantiate system
performance and give credence to the accuracy of the results generated, (2) to define aberrations and give
guidance to the interpretation of data, and (3) to achieve these goals through realistic efforts that do not
impede the forward progress of the analytical set.

8.1.3 The discussion presented here deals with only direct analytical QC. Additional elements of
QA/QC, such as field duplicate sample submissions, blind spike analysis, and external audits are not
discussed. Also not discussed are elements of QA/QC that are inherent to good chromatographic technique.
Examples of these accepted laboratory practices include (but are not limited to) the following: (1) the proper
conditioning of analytical columns and traps, (2) use of the solvent flush technique for the creation of
standards and for direct injections, and (3) the appropriate maintenance of selected detectors. Details
regarding these accepted practices are given in the referenced methodologies.

8.2 Laboratory Duplicates: One laboratory duplicate should be analyzed per sample set. Laboratory
duplicate analyses should generate results of RPD within 30 percent (see 7.3.2).

8.4 Surrogate Spikes: The use of at least 1 surrogate spike compound is highly recommended. The identity,
concentration and addition of the appropriate surrogate spike varies with the procedure being used. Each associated
referenced methodology should be consulted for guidance. Surrogate spike recoveries should fall within ±30 percent
(see 7.3.4). Sample analyses yielding %R values outside this 30 percent window should be reanalyzed or the
associated data should be qualified as suspect.

8.5 Method Blanks: Method blanks are prepared and analyzed in exactly the same manner as sample
matrices. A method blank analysis should follow every standard run and sample of high concentration. Ideally,
method blank results should yield no interferences to the chromatographic analysis and interpretation of target
compounds. If interferences are present, associated data should be qualified as suspect and/or target detection limits
should be adjusted accordingly.

9.0 METHOD PERFORMANCE

FMC-VA-005-6

-------
Information not

available.

10.0 REFERENCES

Information not available.

FMC-VA-005-7

-------
Region V CRL SOP
MANUAL ANALYSIS OF AMBIENT AIR FOR SELECTED VOLATILE

ORGANIC COMPOUNDS BY A PORTABLE GAS CHROMATOGRAPH

1.0 SCOPE AND APPLICATION

1.1 This method is used for determining the amount of selected volatile organic compounds (VOCs) in grab
samples of air. It is dependent on the target compound being detected by a photoionization detector (PID)
incorporated in the Photovac gas chromatograph (GC) 10S series instrument.

1.2 This method presupposes the user has prior or independent knowledge (or that a high probability exists)
of the identity of specific VOCs to be determined at a site, so that the instrument can be calibrated for these VOCs
prior to use. Unambiguous identification of presumptively identified VOCs at a site requires reference to an
additional analytical system, because this Photovac instrument uses only 1 chromatography column and nonspecific
detector at a time. Possible tentative identification of other unknown VOCs with this Photovac system requires the
user to have independent knowledge of the retention time (RT) order of VOCs not used for instrument calibration for
the specific chromatography column being used.

1.3 The ionization potential of a molecule must generally be less than the

ionizing energy produced by the PID in order for it to be detected. Aromatic and unsaturated molecules are usually
detectable by the PID. However, other types of molecules may also demonstrate detectability.

1.4 Although other compounds may be measurable by this method, the following ones are known to be
detectable in air and are used as illustrative examples for calibration of the instrument. They are: vinyl chloride,
methylene chloride, trans-1,2-dichloroethylene, benzene, trichloroethylene, and toluene.

1.4.1 The sensitivity of these compounds varies, but the method covers a range of 0.05 ppm (v/v)

to 10 ppm (v/v) easily. The detection limits (MDLs) in air for this method are listed in Table 1.

1.4.2 A list of additional compounds that are detectable by this instrument is provided in Table 2.

1.5 Any program that requires rapid identification and quantitation of a known group of analytes that are
detectable by this instrument could use this procedure in general. However, modifications in instrument parameters
and analytical column would need to be made to address the need at hand.

1.6 Only personnel trained in the operation and calibration of the Photovac GC as well as the interpretation
of the raw data should use this method.

2.0 SUMMARY OF METHOD

2.1 Aliquots of air (up to 2 mL) are analyzed using a Photovac 1 OS 10 GC with a PID and a portable strip-
chart recorder.

2.2 The GC system can only be operated at ambient temperatures which are recommended to be in a range
from 55°F to 90°F. It is important that a proper field environment be provided in order to minimize temperature
fluctuation as much as possible.

FMC-VA-006-1

-------
Table 1

METHOD DETECTION LIMITS (MDLs) IN AIR
FOR SELECTED COMPOUNDS



MDL* in Air

Compound

ppb (v/v)

Vinyl chloride

7

Methylene chloride

240

trans-1,2-Dichloroethy lene

21

Benzene

25

T richloroethy lene

23

T oluene

55

*	MDLs were determined using (iL quantities of methanolic solutions of the compounds injected into a 0.5-L

gas sampling bulb. A 1-mL injection was made at a gain of 50 and a flowrate of 25 mL/min. They are the statistical
estimates from 7 replicate injections.

FMC-VA-006-2

-------
Table 2

ADDITIONAL DETECTABLE COMPOUNDS ON SE-30 COLUMN

Compound

Relative
Retention Time
(Relative to Benzene)

Shape of
Peak

Benzene

1.0000

A

Diethyl ether

0.5082

B

Chloroform

0.6557

A

T oluene

2.4426

B

DMDS

1.9911

B

Ethylmercaptan

0.3182

A

TBM

0.5455

A

n-Hexane

0.6084

A

2,4-Dimethylpentane

0.8182

A

2,4-Dimethylpentane

1.1818

B

2,2,4-Trimethylpentane

1.3182

B

n-Heptane

1.4545

B

2, ¦4/2,5 -D imethy lhexane

2.0909

C

2,3,4-Trimethylpentane

3.5000

C

n-Octane

3.3521

C

p-Cymene

6.1220

C

cis-1,2-Dichloroethylene

_

_

T etrachloroethy lene

_

_

Ethyl benzene

_

_

Dichlorobromomethane

_

_

Chlorobromomethane

_

_

o-Xylene

-

-

A - Sharp symmetric peak B - Broad peak shape C - Broad and skew peak shape

FMC-VA-006-3

-------
2.3 The only gas necessary for operation is compressed air as the carrier gas. It should be zero grade or

better.

2.4 The GC is calibrated using methanolic solutions of the target compounds at 3 concentrations. Retention
time (RT) windows as well as calibration factors (CF) are calculated for each VOC compound. RTs are used for
compound identification, and CF s are used in quantitating compounds.

2.5 During the analysis, frequent single concentration level calibrations are performed to update RTs and
check the fluctuation of CFs. This information is used to determine if the systems can be used for continuing analyses
or requires recalibration or maintenance.

2.6 Analytical samples are directly injected into the GC system, and results are compared to the standard
injection. The amount injected can be varied from 10 (iL to 2 mL depending on the contaminant levels.

3.0 INTERFERENCES

3.1 Many compounds that volatilize in ambient air may be detectable by a PID at widely different
concentration levels. Although a chromatographic column may separate compounds according to chemical and
physical traits, there is the likelihood that several compounds, if present, could coelute. If this happens to a target
compound, an interference occurs.

3.2 There may be only partial interferences with a target compound as evidenced by an elevated baseline
or peak shape. In such a case its identity and quantity may still be determined depending on the severity of the
problem. The data may need to be qualified as "estimated". In such a situation, an experienced chromatographer
should be consulted.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph: Photovac 10S10 with a 4 ft. length x 1/8 in. diameter Teflon column packed with
5% SE-30 on 100/120 mesh Chromosorb G-AW.

4.2 Portable Single-pen Strip-chart Recorder: Linear Instruments Model 142.

4.3 Gas Sampling Bulbs: Various sizes, 125-mL to 1-L.

4.4 Vacuum Pump: Small portable.

4.5 Tedlar Bags: 1-L with closures.

4.6 Large Vacuum Desiccator for rigid vessel'): For collecting samples in Tedlar bags.

4.7 Gastight Syringes: Various sizes, 0.1-mL to 2.0-mL, as those supplied by Precision Scientific Co.

4.8 Liquid Syringes: 10.0-^iL to 1.0-mL capacity.

4.9 Compressed Air: Lecture size bottles of zero-grade, or better.

4.10 Ruler: Capable of measuring in mm.

4.11 Pocket Calculator: With standard deviation functions.

5.0 REAGENTS

FMC-VA-006-4

-------
5.1 Stock standards of target VOCs in methanol in 5.000 to 10.000 fig/mL range.

5.2 Methanol: Reagent grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples may be collected in Tedlar bags that have not been previously used by placing the bag in a rigid
vessel, such as a vacuum desiccator, and removing the air. Ambient air can then be allowed to fill the vessel at the
sampling point.

6.2 A glass vessel for gas sampling may also be used. It is mandatory that a pump be used to draw air into
the vessel (downstream) instead of pushing air into it (upstream). This avoids contamination from the pump or tubing
used with it.

6.3 Finally, a gastight syringe may be used to collect a small sample of air, if it is to be analyzed
immediately.

6.4 No preservation is necessary since the samples should be analyzed as soon as possible. If the samples
are to be held for several hours, they should be kept out of the light to insure that photodecomposition does not occur,
depending on the target compounds.

7.0 PROCEDURE

7.1 Set-up of the Photovac IPS 10 Portable GC

7.1.1 The Photovac 1 OS 10 is a self-contained portable GC approximately 18x13x6 inches. It
can be operated at ambient temperatures either by external 115 volt AC power or internal battery power for
up to 8 hours before recharging.

7.1.1.1 The operating temperature range is between 50°F (10°C) and 100°F (38°C).

7.1.1.2 The GC conditions are given at a column flowrate of 25 mL/min through injector
#1 and a gain of 50.

7.1.2 Two analytical columns are attached to 1 PID via a 2-way valve. All of this is located
beneath the electronic panel in the center of the instrument.

7.1.3 Two flow controllers regulate the carrier gas which is compressed air. The carrier gas can
come from an external tank or from a refillable internal tank. Two pressure gauges are mounted on the
instrument to monitor the gas used.

7.1.4 Gas connections

7.1.4.1 External: There is 1 quick disconnect port for a 1/8 in. stainless gas line which
can be attached to the regulator of a lecture-sized bottle of compressed air. Set the secondary gauge
on the regulator to 40 psi, and open the inlet valve to allow the gas to flow into the GC. Reset the
gauge to 40 psi, if necessary, and note that the delivery gauge on the GC will finally indicate 40 psi
also.

7.1.4.2 Internal: Put compressed air into the reservoir via a high pressure filling station
hose from a large cylinder. The contents' pressure gauge should be at about 1600 psi when the
reservoir is filled. This should be enough for 8 hours of operation.

FMC-VA-006-5

-------
7.1.4.3 Regulate both internal and external gas supplies with the 2 flow controllers
attached to each column of the instrument. Counterclockwise turning decreases the flows in each
column. Keep the flowrate at 10 mL/min even when the column is not in use as a method of
keeping the columns free of contamination.

7.1.4.4 The port labelled "detector out" may be connected to a flowmeter to determine the
flowrate through the column as the flow controllers are adjusted. The flow in each column, in turn,
may be measured by turning the flow diverter valve located under the mid compartment 90° to
allow gas flow to each column.

7.1.4.5 Electrical connections: For external power operation, connect power cord from
instrument receptacle to an AC outlet. Internal battery powered operation requires only the "power
on" button be depressed. The recorder plug goes from the recorder outlet on the instrument to the
recorder with the 2-pronged plug placed so that the pen on the recorder remains at the left side of
the strip chart when it is in operation.

7.1.4.6 Start up:

7.1.4.6.1 With the carrier gas flowing through a column at the desired flowrate
(40 cc/min for SE-30 column and 10 cc/min for CSP-20 m column) for 20 to 30 minutes,
press the "power on" button. If the power is AC, black bars above the AC mark on the
LCD screen will appear. Press the "Diagnostics Batt" button. Black bars should appear
at the top of the screen and extend into the "check" range. If it does not, the battery will
need charging for off-line work.

7.1.4.6.2 If changing the battery is desired, press the "charge on" key and the
LCD will indicate "charge". Keep this on for about 12 hours then press "charge off". The
gain may now be put on the desired setting dictated by the method and the amount of
sensitivity needed. Black bars appearing at the top of the screen indicate the level of
background seen by the detector.

7.1.4.6.3 The offset knob can be used to reduce the background to an acceptable
level. The bars should not extend more than 10 to 20 percent of the distance across the
screen. The bars also will appear as a component elutes into the detector. The initial gain
setting is 50.

7.1.4.6.4 The recorder should be operated on the 1 volt fullscale setting with the
attenuator off. Keeping the zero switch on the recorder depressed, adjust the zero knob
until the pen is at about the 5 unit line on the paper. Release the switch and readjust the
pen position with the offset knob.

7.1.4.6.5 The background may fluctuate causing the pen to drift up or down. This
may be adjusted with the offset knob to keep the pen on scale.

7.1.4.6.6 The chart speed should be set to 0.5 cm/min. The system is now
operational for analysis of air or vapor samples ONLY.

7.2 Calibration

7.2.1 Initial calibration: Perform an initial 3-point calibration curve to determine RT windows and
CF values for target compounds under field conditions.

FMC-VA-006-6

-------
7.2.1.1 Four of the 6 target compounds are in a methanol solution, so they may be injected
simultaneously. They are trans-1,2-dichloroethylene, benzene, trichloroethylene, and toluene.
Table 3 gives the amounts of the solutions to inject into a 0.5-L gas sampling bulb to generate the
curve. Their concentrations are also given. Allow at least 5 minutes for the solution to vaporize
and for diffusion in the bulb to occur.

7.2.1.2 Inject 0.5 mL of the increasingly concentrated air standard to generate each data

point.

7.2.1.3 Perform a similar calibration for vinyl chloride and methylene chloride
simultaneously. However, add each to the bulb separately. Their amounts and concentrations are
also in Table 2.

7.2.1.4 Prepare mixtures of target compounds in the laboratory before going into the field.
However, if individual components need to be calibrated at a different level in the field, section 7.4
describes a calculation for determining concentrations of components in air.

7.2.1.5 Before each use, purge the sampling bulb for at least 5 minutes by drawing clean
air through it or by using air from a compressed air cylinder. Also, pump the 2.0-mL gastight
syringe used for injection several times in clean air before each use.

7.2.1.6 To make the 0.5-mL injection, draw about 1 mL of air standard from the bulb and,
with the needle still in the bulb, depress the plunger to the 0.5-mL mark. Withdraw the syringe and
place the needle immediately in the #1 injection port of the GC. Push the needle all the way in until
the shoulder of the syringe stops it. Inject in 1 snappy continuous motion and make a mark on the
strip chart to show the injection start time.

7.2.1.7 Since methanol and 2-propanol have been used as the solvent for the target
compounds, a broad hump or even an off-scale peak may appear near the RT of toluene. Allow
these disturbances to subside to near the original baseline before making another injection. This
should be in about 20 minutes, or less, at about 650 °F to 700 °F ambient temperature.

7.2.1.8 After all calibration data are gathered, calculate the individual RTs by measuring
from the injection mark to the apex of the individual peaks in mm. Assign a ±5 percent window
to the average RT.

7.2.1.9 The percent relative standard deviation (%RSD) should be less than 20 percent for
each compound. If it is not, prepare another standard at the level which showed the largest
difference from the CF for that compound and reinject. Recalculate using the new CF value.

7.2.1.10 If the %RSD is still greater than 20 percent, consider the quantitation of this
compound as estimated.

FMC-VA-006-7

-------
Table 3

EXAMPLE CALCULATIONS OF VOC STANDARD CONCENTRATIONS
FOR CALIBRATION CURVE

A. Amounts of standard mixture solut
contains 115 ng/mL trans-1,2-dich
500 ng/mL toluene. Amounts of s
into the Photovac GC.

ion to be used for calibration curve. Standard mixture solution
loroethene, 250 ng/mL benzene, 250 ng/mL trichloroethene, and
tandard mixture are added to a 0.5-L bulb; 0.5 mL is then injected

Compound

Amount of Standard Mixture (|iL)

trans-1,2-dichloroethene

116

232

Benzene

156

312

624

Trichloroethene

188

376

T oluene

266

532

1064

B. Amounts of individual standard so
contains 450 ng/mL vinyl chloride
solution is added to a 0.5-L bulb; C

lutions to be used for calibration curve. One standard solution
, and one has 10000 ng/mL methylene chloride. Each standard
.5 mL is then injected into the Photovac GC.

Amount of Standard Solution (nL)

0.2

0.5

0.8

1.0

1.5

1.6

Vinyl chloride

280

560

Methylene chloride

2900

5800

8700

7.2.2 Continuing calibration:

7.2.2.1 Perform the mid-level calibration after every 4 samples or after any long delays
in analysis in order to update RT windows and check the useability of the calibration curve.

7.2.2.2 Use the CFs calculated from this continuing calibration to calculate the percent
difference (%D) from the 3-point curve.

7.2.2.3 If %D is greater than 30 percent, perform a new 3-point curve to establish good
quantitation.

7.2.2.4 If %D is less than 30 percent, the CF established from the initial calibration curve
may still be used.

7.2.2.5 If peak heights decrease during the course of analysis using a fresh standard, the
battery may need charging or a leak may have developed in the GC column fittings, septum, or in
the syringe.

FMC-VA-006-8

-------
7.2.2.6 Check the battery charge, replace the septum, and check the column fittings so that
they are finger tight. Reinject and examine the responses. If it is still not responding properly,
change the syringe and try again. Also, change the septum in the sampling bulb.

7.2.2.7 A change in flowrate and ambient temperature may also cause fluctuations in peak

height.

7.2.2.8 Before analysis, inject a sample of clean air from a bulb that has been purged.
This will check the syringe and total system for contaminants.

7.2.3 Instrumental analysis:

7.2.3.1 Analysis of an aliquot of an air sample may now begin. If the sample is known
to contain large VOC concentrations, use an injection volume much less than the 0.5-mL standard
injection. Start with a 50-(iL injection.

7.2.3.2 Any peaks found should have their RTs compared to the RT listed for that
compound. If the RT falls within the ±5 percent window, a tentative identification exists.

7.3 Calculations

7.3.1 Initial calibration:

7.3.1.1 Calculate the CF values using the following equation:

_ Peak height
ppb (v/v) of std

7.3.2 Calculate the mean CF (CF) for each compound along with the standard deviation (SD).
Calculate the %RSD for each compound with:

ST)

%RSD = — x 100
CF

7.3.3 Continuing calibration:

7.3.3.1 Use the CFs calculated from this continuing calibration to calculate the percent
difference (%D) from the 3-point curve using:

CF - CF
%D = x 100

7.4 Quantitation Calculations

7.4.1 The measured peak height in millimeters must be within the range of the calibration curve
peak heights for proper quantitation. If it is, use the following formula to quantitate the concentration:

_ Peak height of sample pi std injected

ppb ~ for the identified std sample injected

7.4.2 For example, by injecting 50 (iL of air sample and identifying benzene with a CF of 0.058
and assuming a peak height of 30 mm, the peak height would be:

FMC-VA-006-9

-------
30 mm 500 uL

- = .X

ppb 0.058 mm/ppb 50 iaL

C = 512 0 ppb or 5.1 ppm (v/v)

7.4.3 MDLs are based on a 1-mL injection. If no peaks are seen with a 50-(iL injection, perform
up to a 1-mL injection. If no compounds are seen with a 1-mL injection and no interferences are present that
would compromise their identification, use the MDL value as listed to quantitate the compounds.

7.4.4 Purge the sampling bulb with clean air for 5 minutes before reuse. If a very high positive
response has been seen using the bulb, inject a blank from it after cleaning to insure it is suitable for reuse.

7.5 Sample Quantitation: The following formula is used to calculate the concentration of each component
in the air mixture:

4 . 1 x 10"8 x M x V

where: C

Concentration of compound in air in ppm (v/v)

Mass of compound added to the bulb in grams (g)

Molecular weight of the compound in a.m.u.

Volume of sampling bulb in liters

4.1 x 10 "8

Number of moles derived from the ideal gas equation, for l-(iL of gas

For example, if 1 (iL of 10000 (ig/mL solution of benzene (MW = 78) is added to 500 mL of air, what will be its
concentration? Since 10000 |ig/mL = 10 therefore,

= 10 x 10'6g

4.1 x 10"8 x 78 x 0.5 L

C = 0.062 ppm (62 ppb) of benzene.

7.6 Instrument Maintenance and Troubleshooting

7.6.1 If the GC and recorder are to be used with battery power, check the charge before going into
the field, and follow all recharging instructions in the manufacturer's manuals.

7.6.2 Take a proper supply of expendable items such as chart paper and pens, septa for GC and
bulbs, syringes, sampling bulbs, and even an extra GC column into the field. Also, take extra cylinders of
compressed air and regulators.

7.6.3 As stated in 7.1, air should continuously flow through the column at a low rate, especially
in the field. Since the column is Teflon and, therefore, somewhat permeable, exposure to a contaminated
atmosphere will allow some contaminants to collect on the packing material. A carrier gas flow will
continually sweep them from the column and prevent a build up.

7.6.4 The GC septum should be changed after every 10 to 15 injections to minimize the chance of
leakage at the injection port. This is one of the first things to check if calibration standards suddenly loose
sensitivity or there are large variations noticed from one injection to another.

FMC-VA-006-10

-------
7.6.5 All sampling bulb septa should be changed after every 5 to 10 injections.

7.6.6 The column connections should be finger tight. This should also be checked if a leak is
suspected.

7.6.7 The syringe should be checked for leaks at the removable needle connection by injecting air
while holding part of the syringe submerged in clean water. This will also check to see if an injection is
actually being made by observing any bubbles coming out of the needle tip.

7.6.8 If the needle is clogged, simply change it.

7.6.9 The instrument will operate out its optimum, if it is located in a stable temperature
environment. Retention times will remain stable and fewer continuing calibrations will be needed.

7.6.10 Table 4 has a list of common troubleshooting items and their probable cause.

7.7 Safety and Waste Handling:

7.7.1 Good laboratory practices should be the guide in field use of the Photovac GC, standard
materials, injection syringes, compressed air, and samples.

7.7.2 The exit port of the detector will need to be vented via a tubing away from the analytical area
so as not to allow standard compounds or contaminants to come into the breathing zone of the analyst and
coworkers.

7.7.3 Dispose of the remains of air samples from Tedlar bags and sampling bulbs by drawing them
through a large charcoal trap or other sorbent material known to retain the compounds of interest. Dispose
of the traps in a proper fashion.

7.7.4 Another safety consideration is handling the compressed air carrier gas. The Photovac 1 OS 10
has an internal reservoir which can be filled via a special high pressure gas filling tube supplied by the
manufacturer. It is made specifically for the instrument and must not be altered in any way.

7.7.5 The contents gauge should read 1600 psi when the reservoir is filled but must not exceed 1800
psi. The pressure relief valve on the filling tube should prevent this from happening.

7.7.6 A further safety measure is a rupture disc inside the instrument which is rated at 3200 psi.

FMC-VA-006-11

-------
Table 4

TROUBLESHOOTING

Symptom

Probable Cause

Remedial Action

Air cylinder runs out too fast.

Flow rate is high.
Leak.

Check flow. As a guide, cylinder
charged to 1600 psi should easily
last 2 days at a flowrate of 10
mL/min.

Check o-ring between
cylinder/regulator. Check all
external fittings with sparring
application of soap solution.
Check septum by changing and
reseating. Check column to
injection port fitting. Tighten/re-
flange.

Batteries run out too fast.

Inadequate charge.
Electronic problem.

Charge overnight on high and try
again.

Requires skilled service.

Peaks eluting too fast.

Flowrate too high.
Improper column choice.

Reduce.

Consult Photovac and/or try a
different column.

Peaks eluting too slowly.

Flow is too slow.

Possible leak at septum or column
to injector port fitting.

Improper column choice.

Increase.

Same remedy as for "No flow".

Consult Photovac and/or try a
different column.

FMC-VA-006-12

-------
Table 4 continued

TROUBLESHOOTING

Symptom

Probable Cause

Remedial Action

Baseline drifts constantly and
unacceptably up or down.

Unit is undergoing acclimatization
to a large temperature change.

Column is recovering from earlier
contamination.

At each injection, a portion of
some heavy contaminant is being
inadvertently added.

Allow to stabilize, move more to
equitable temperature zone, e.g.,
into shade.

Allow to stabilize with
accelerated flow, remove and
replace column with newly-
conditioned one.

This shows up as a stepwise
baseline increment with each
successive injection. Use faster
chromatography or consider
adding backflush option.
Sometimes caused by dirty
syringe.



If carrier gas has just been
changed, possibly new batch is
recommended.

Switch to alternate carrier.

Baseline constantly drifts up,
down during chromatography.
The effect is slow, takes place
over a space of 3 to 10 mins.

Peaks are appearing from earlier
injection(s) and interfering with
current analysis.

Allow to stabilize, so as to
confirm diagnosis. Consider
either speeding up the
chromatography or addition of
backflush option. Sometimes
caused by contaminated syringe.

Baseline moves up and down with
a regular pulsation every 1 min or
so.

Flowmeter left hooked up to vent.

Did you forget?

FMC-VA-006-13

-------
Table 4 continued

TROUBLESHOOTING

Symptom

Probable Cause

Remedial Action

No flow of carrier measured at
vent even though 40 psi is
indicated on delivery gauge.

Septum leak.

Leak at column to injection port
fitting.

Tighten retainer and check flow.

Tighten polypropylene fitting,
check with soap solution
sparingly used. If persisting,
check quality of column-end
flange. Re-flange.

With detector on, gain 2, and
offset fully counterclockwise,
display indicator is off.

UV source not on.
Electronic problem.

Confirm: proceed to detailed
remedy (end of this section).

Requires skilled service but is not
a common problem.

With detector on, gain 2, and
offset fully counterclockwise,
display reads full-scale and no
chromatographic response can be
obtained.

Detector is saturated.
Column dirty.

Carrier gas or regulator
contaminated.

Electronic problem.

Leave to flush with high carrier
flow or condition column.

Switch over to alternate supply,
nitrogen or helium can be used in
emergency to determine if this is
the cause.

Requires skilled service but is not
a common problem.

FMC-VA-006-14

-------
Table 4 continued

TROUBLESHOOTING

Symptom

Probable Cause

Remedial Action

Peak is misshapen and
nonsymmetric.

Improper column choice;
compound too polar for existing
column.

Use less polar column. Consult
Photovac.



Column is defective.

Change column.



Flow is too low.

Increase.

Deterioration of sensitivity.

Syringe has leak/blockage.

Check or change.



Leak at septum or column to
injector prot fitting.

Tighten retainer and check flow.
Tighten polypropylene fitting,
check with soap solution
sparingly used. If persisting,
check quality of column-end
flange. Re-flange.



UV lamp requires tuning.
UV lamp defective.

Tune as detailed summary.

Check and change as in detailed
summary.



High voltage low.
Column choice incorrect.

Check field indicator.

Consult Photovac or try a
different column.



Recorder not set to 1V FS.

Check.



Electronic problem.

Extremely unlikely but if so,
requires skilled service.



Possible miscalculation or
defective syringe in standard
preparation.

Recheck, assuming everything
could have gone wrong!

8.0 QUALITY CONTROL

8.1 Consideration of sample integrity, method monitoring, and record keeping needs to be made as part of
a quality assurance program.

FMC-VA-006-15

-------
8.2 Record keeping is important in accounting for analytical data collected in the field and to allow for
further consideration of data validity. Chromatograms should be labeled with a date, sample description and number,
amount injected, instrument gain, and analyst's initials.

8.3 All problems relating to the operation and analysis must be kept in a notebook. All analytical events
must be traceable and linked to the chromatographic data.

8.4 All of the above tasks must be considered and done even if the data quality objective is only to identify
the presence or absence of a target compound.

8.5 Quality Control

8.5.1 Precautions should be taken to assure that a sample is not contaminated by the vessel in which
it is collected or by the injection syringe. Clean air, either ambient air filtered through a sorbent material
or from a compressed air cylinder, should be used to decontaminate any vessel or syringe that has been used
for sampling. This step is alleviated by using Tedlar bags only once for the sample collection vessel.

8.5.2 After purging with clean air for 5 minutes, inject 1 mL of the air contained in the bulb as a
blank to determine if the vessel is suitable for continued use. If peaks are seen that will interfere with
analysis, continue the purging process and try again. This should always be done before analysis begins and
after any positive hits prior to the next analysis of a sample.

8.5.3 Monitoring the method and the system may be done by injection of the mid level calibration
standard that is freshly prepared after every 4 injections or an extended period of delay between analyses.
The %D is checked to assure good quantitation and the RTs are checked and updated to account for the
possible changes in the instrumental environment that may lead to incorrect identification of compounds.
This is done as stated in the calibration procedures.

8.5.4 An unknown spike solution will be used to check system daily.

8.5.5 Along with the analysis of field controls samples, a laboratory calibration of system for target
compounds is performed.

8.5.6 Field continuing calibration for all target compounds by vapor injection either bracketing
analytical runs or on a cyclic basis depending on analytes. This is used to update RTs for identification
purposes and to update response factors.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Photovac 1 OS 10 Operator's Manual.

2. Field Investigation Team (FIT) Screening Methods and Mobile Laboratories Complementary to Contract
Laboratory Program (CLP), October 17, 1986. (DRAFT)

3. Field Screening Methods Catalog, Users' Guide, October 30, 1987.

4. Various Remedial Investigation QAPPs.

5. Linear Instruments Model 142 Operator's Manual.

FMC-VA-006-16

-------
6. "Ambient Monitoring for Specific Volatile Organics Using a Sensitive Portable PID GC", Spittler, T.M.

FMC-VA-006-17

-------
Region V CRL SOP
STANDARD OPERATING PROCEDURE FOR SELECTED

ORGANIC VOLATILE COMPOUNDS IN AMBIENT AIR

1.0 SCOPE AND APPLICATION

1.1 This is a gas chromatographic (GC) method applicable to the determination of volatile organic
compounds (VOCs) in ambient air.

1.2 This method presupposes prior or independent knowledge exists on the identity of specific VOCs to be
determined in a sample set. It is incumbent for the data user to identify the VOCs to be used for instrument
calibration prior to sample analysis. Unambiguous identification of presumptive VOCs in a sample requires reference
to an additional analytical system.

1.3 The GC column specified in this procedure is the packed column commonly used for VOC
determinations of water by gas chromatography/mass spectrometry (GC/MS). It is applicable to aromatic VOCs with
boiling points comparable to n-propyl benzene, or less, and to halogenated, aromatic VOCs with boiling points
comparable to dichlorobenzenes, or less. It is applicable to halogenated propenes and ethenes when using the
photoionization detector (PID).

1.4 This method covers, as illustrative examples, the determination of certain VOCs listed in Table 1.

1.5 The PID or flame ionization detector (FID), or both detectors, will be used depending upon the VOCs
of interest.

1.6 Detection limits of some compounds for air are also given in Table 1 for the PID. Other compounds
may be added to Table 1 as data becomes available. The FID is probably 10-fold less sensitive.

1.7 This method is restricted to use by or under the supervision of analysts experienced in the use of GC and
interpretation of gas chromatograms.

2.0 SUMMARY OF METHOD

2.1 A measured volume of trapped ambient air is required for analysis. Compounds which are
predominantly in the gas phase at ambient temperature and pressure are sampled.

2.2 The samples are then separated by GC and the parameters are then measured with a PID and/or an FID.
3.0 INTERFERENCES

3.1 Method interferences may be caused by contaminants in sample containers, evacuation pumps, syringes,
and other sampling and processhardware that lead to discreet artifacts and/or elevated baselines in gas
chromatograms. All of these materials are routinely demonstrated to be free from interferences under the conditions
of the analysis by running blank air samples.

3.2 As the number of carbon atoms increases in the hydrocarbons and aromatics, the number of potential
isomers becomes increasingly large and difficult to completely resolve by GC.

FMC-VA-007-1

-------
Table 1

MOLECULAR WEIGHTS AND ESTIMATED DETECTION LIMITS OF
EXAMPLE VOLATILE ORGANIC COMPOUNDS (VOCs)

Compound

CAS #

Estimated Detection
Limit (PID)
ppb (v/v)

Molecular
Weight

Benzene

71-43-2

2000

T oluene

108-88-3

2500

Vinyl chloride

9003-22-9

2000

62.4

T richloroethy lene

79-01-6

2500

133.2

3.3 Matrix interferences may be caused by contaminants that exist with the sample compounds, and the
extent of the interferences may vary depending upon the nature of the sampling sites.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph: Tracor 540 GC equipped with glass-lined injection port.

4.2 Detectors: PID and/or FID.

4.3 Column Materials: Column - pyrex (8 ft x 2 mm I.D.); Glasswool silanized; packing - 1% SP-1000
60/80 Carbopack B.

4.4 Syringes: 1.0-^L to 1 0-jj.L.

4.5 Gastight Syringes: l-to2-mL.

4.6 Glass Bulbs: 125-mL, 250-mL, 500-mL, and 1000-mL.

4.7 Data System: A Nelson analytical software computer system is interfaced to the PID and FID detectors
that allows the continuous acquisition and storage of data.

NOTE: All GC materials are obtained pretested from Supelco, Inc.

5.0 REAGENTS

5.1 Standards obtained from EPA repository and Supelco, Inc. stock standards of target compounds in
methanol are in the 5,000 to 10,000 |ig/mL range.

5.2 The toxicity or carcinogenicity of each reagent using this method has not been precisely defined;
however, each chemical compound is treated as a potential health hazard. Exposure to these chemicals is reduced
to the lowest possible level by whatever means available.

5.3 The following parameters covered by this method have been tentatively classified as known or suspected
human or mammalian carcinogens: benzene, carbon tetrachloride, and vinyl chloride.

FMC-VA-007-2

-------
5.4 Primary standards of these toxic substances should be prepared in a hood. A NIOSH/MESA-approved
toxic gas respirator should be worn where the analyst handles high concentration of these toxic compounds. Due
caution for all standards used in this method should be a high priority.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Whole air samples are collected by means of rigid or nonrigid devices. Nonrigid devices include Tedlar
or Teflon plastic bags. Rigid containers are stainless steel canisters.

6.2 There are 2 ways of sampling: either by evacuation of the container in advance and then allowing the
sample to enter the vacuum, or by having both inlet and outlet valves open on the container and pulling the sample
through the container until equilibrium is obtained (e.g., after 5 to 10 volumes of sample have been flushed through
the system).

6.3 The first approach has the advantage that no sampling pump is required in the field. The latter approach
has the advantage that equilibrium with the container walls is more readily achieved, and high vacuum seals are not
required. Both ways of sampling are accepted with certain limitations.

6.4 Limitations of Rigid and Nonrigid Containers

6.4.1 Rigid containers:

6.4.1.1 Sample components of interest may be absorbed or decomposed through interaction
with container walls. At very high analyte levels (e.g., several ppm) condensation may be a
problem. This way of sampling is most useful for relatively stable, volatile compounds such as
hydrocarbons and chlorinated hydrocarbons with boiling points less than 150°C.

6.4.1.2 The container must be flushed (with moderate heating, if possible) with zero grade
nitrogen or air prior to sampling to remove trace contaminants.

6.4.2 Nonrigid containers: Tedlar or Teflon plastic bags are used to collect samples for analysis
within a few hours of sampling, since the rate of leakage and/or permeation of materials into and out of the
bag is relatively high.

6.5 Samples collected are stored at room temperature and analyzed within 48 hours if collected in rigid
containers, and within 24 hours in nonrigid containers.

6.6 Samples should be stored in warm dry areas away from moisture and cold temperatures.

6.7 Canisters and or plastic bags containing unused sample are placed in a closed hood, and the contents
are vented to the outside atmosphere.

7.0 PROCEDURE

7.1 Instrument Calibration

7.1.1 Calibrate the GC using methanol solutions of the target compounds at 3 concentrations.

7.1.2 Calculate retention time (RT) windows as well as response factors (RF) for each compound.
Use RTs for compound identification and RFs for quantitating compound concentrations. During the
analysis, perform frequent single concentration level calibrations to update RTs, and check the fluctuation
of RFs. Use this information to determine if the system can be used for continuing analysis or requires
recalibration or maintenance.

FMC-VA-007-3

-------
7.1.3	Generate an initial 3-point calibration curve to determine an RT window and an RF value for
the target compounds under given conditions.

7.1.4	Inject benzene and toluene mixtures in methanol into a 1 -L gas sampling bulb. Table 2 gives
the concentration and amount of the mixes to be injected.

7.2 Gas Chromatography

7.2.1 Column conditions:

7.2.1.1 Flowrate: 20 mL/min.

7.2.1.2	Initial column temperature: 45°C.

7.2.1.3	Initial hold time: 3 mins.

7.2.1.4	Ramp rate: 8°C/min.

7.2.1.5	Final column temperature: 220°C.

7.2.1.6	Final hold time: 15 mins.

7.2.2 Analytical procedure:

7.2.2.1	After the instrument has been calibrated and checked, analyze an aliquot of an air
sample. If the sample is known to contain large VOC concentrations, use an injection volume much
less than the 1 mL standard injection.

7.2.2.2	Any peaks found should have their RTs match the standards. If the RT falls within
the ±5 percent window, make a tentative identification. When a compound is found as a positive,
determine its concentration using the procedure in section 7.4, and confirm by GC/MS.

7.3 Calculations

7.3.1 The measured peak area must be within the range of the calibration curve for proper
quantitation. If it is, use the following formula to quantitate the concentration of the standard (refer to Table

2).

C

ppm n x M x V

FMC-VA-007-4

-------
Table 2

CONCENTRATION OF STANDARD COMPOUNDS/VOLUME INJECTED

Compound

PID detector: Volume of 5000 (ig/mL Standard
Injected in a 1-L bulb

1 iiL

2 iiL

3 iiL

Benzene ppb (v/v)

1560

3126

4690

Toluene ppb (v/v)

1320

2650

3976

where: C = Concentration of the compound in air in ppm,

M = Molecular weight of the compound in a.m.u.,

V = Volume of the sampling bulb in liters,

n = 4.1 x 10"8 = number of moles in l-(iL of an ideal gas at STP, and

m = Mass of the compound added to the bulb in grams.

7.3.2 Use the following formula to uantitate the sample:

^ _ peak area of sample x amt of std injected
ppb gp s-j-^ x amj- Qf sample injected

7.3.3 The detection limits for the 4 compounds listed in Table 3 were calculated by making 10
injections of the mixture of known concentration and using 7 results for tabulation of estimated detection
limits. Detection limits will be estimated in the future for additional VOCs that may be sensitive to PID or
FID.

8.0 QUALITY CONTROL

8.1 Precautions should be taken to assure that a sample is not contaminated by the collection vessel and/or
injection syringe. Clean air should be used to decontaminate any vessel or syringe that has been used for sampling.

8.2 After purging with clear air for 5 minutes, inject 1 mL of the air contained in the bulb as a blank to
determine the vessel is suitable for continuous use. If peaks are seen that will interfere with the analysis, continue
the purging process. This should always be done before the analysis and after any positive hits prior to the next
analysis of a sample.

8.3 Monitoring the method and the system may be done by injecting the mid-level calibration
standard that is freshly prepared after every 10 injections or extended period of delay between analysis. The percent
difference (%D) is checked to assure good quantitation, and the RTs are checked and updated to account for any
possible change.

FMC-VA-007-5

-------
Table 3

PID DETECTION LIMITS

Compound

Retention Time (mins)

Detection Limit (est.)
ppb (v/v)

Vinyl chloride

11.10

2000

T richloroethy lene

20.50

2500

Benzene

21.50

2000

T oluene

28.92

2500

8.4 Quality Control Samples

8.4.1	Field controls.

8.4.2	Laboratory controls: a blank air sample is injected to the analytical system to demonstrate
if the apparatus is free of contamination.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-VA-007-6

-------
Region V CRL SOP
AUTOMATED ANALYSIS OF AMBIENT AIR FOR SELECTED

VOLATILE ORGANIC COMPOUNDS BY A PORTABLE GAS CHROMATOGRAPH

1.0 SCOPE AND APPLICATION

1.1 This method is used for automated analysis of ambient air for selected organic compounds. It is
dependent on the target compounds being detectable by a photoionization detector (PID) incorporated in the Photovac
gas chromatograph (GC) 10S50 instrument.

1.2 This method presupposes the user has prior or independent knowledge (or that a high probability exists)
of the identity of specific volatile organic compounds (VOCs) to be determined at a site, so that the instrument can
be calibrated for these VOCs prior to use. Unambiguous identification of presumptive identified VOCs at a site
requires reference to an additional analytical system, because this Photovac instrument uses only one chromatography
column and nonspecific detector at a time. Possible tentative identification of other unknown VOCs with this
Photovac system requires the user to have independent knowledge of the retention time order of the other VOCs,
relative to the VOCs used for instrument calibration, for the specific chromatographic column being used.

1.3 The ionization potential of a molecule must generally be less than the ionizing energy produced by the
PID in order for it to be detected. Aromatic and unsaturated molecules are usually detectable by the PID. However,
other types of molecules may also demonstrate detectability.

1.4 Although other compounds may be measurable to this method, the following compounds are known to
be detectable in air and are provided as illustrative examples. They are: vinyl chloride, methylene chloride, trans-1,2-
dichloroethylene, benzene, trichloroethylene, and toluene.

1.4.1 The sensitivity of these compounds varies, but the method covers a range of 0.05 ppm (v/v)

to 10 ppm (v/v) easily. The method detection limits (MDL) using this instrument in the automated mode

have not been determined by the Central Regional Laboratory (CRL). However, MDLs determined manually

may be used as a working model until others are determined (Table 1).

1.4.2 A list of additional compounds that are detectable by this instrument is attached in Table 2.

1.5 Any program that requires rapid identification and quantitation of a known group of detectable analytes
could use this procedure. This extends to automated determination of time weighted average values. However,
modifications in instrument parameters and analytical columns would need to be made to address the need at hand.

1.6 Only personnel trained in the operation and calibration of the Photovac 10S50 GC as well as the
interpretation of the raw data should use this method.

2.0 SUMMARY OF METHOD

2.1 Aliquots of ambient air are automatically taken via an internal pump and sampling loop controlled by
timed valve events in a Photovac 10S50 portable GC.

FMC-VA-008-1

-------
Table 1

METHOD DETECTION LIMITS (MDLS) IN AIR
FOR SELECTED COMPOUNDS



MDL* in Air

Compound

ppb (v/v)

Vinyl chloride

7

Methylene chloride

240

trans-1,2-Dichloroethy lene

21

Benzene

25

T richloroethy lene

23

T oluene

55

*	MDLs were determined using (iL quantities of methanolic solutions of the compounds injected into a 0.5-L

gas sampling bulb. A 1-mL injection was made at a gain of 50 and a flowrate of 25 mL/min. They are the statistical
estimates from 7 replicate injections.

FMC-VA-008-2

-------
Table 2

ADDITIONAL DETECTABLE COMPOUNDS ON SE-30 COLUMN

Compound

Relative
Retention Time
(Relative to Benzene)

Shape of
Peak

Benzene

1.0000

A

Diethyl ether

0.5082

B

Chloroform

0.6557

A

T oluene

2.4426

B

DMDS

1.9911

B

Ethylmercaptan

0.3182

A

TBM

0.5455

A

n-Hexane

0.6084

A

2,4-Dimethylpentane

0.8182

A

2,4-Dimethylpentane

1.1818

B

2,2,4-Trimethylpentane

1.3182

B

n-Heptane

1.4545

B

2, ¦4/2,5 -D imethy lhexane

2.0909

C

2,3,4-Trimethylpentane

3.5000

C

n-Octane

3.3521

C

p-Cymene

6.1220

C

cis-1,2-Dichloroethylene

_

_

T etrachloroethy lene

_

_

Ethyl benzene

_

_

Dichlorobromomethane

_

_

Chlorobromomethane

_

_

o-Xylene

-

-

A - Sharp symmetric peak B - Broad peak shape C - Broad and skew peak shape

FMC-VA-008-3

-------
2.2 Only the eluate in the sample that contains the target compounds is allowed to pass through a precolumn
which is in series with the analytical column. The components with longer retention time (RT) are backflushed from
the precolumn before they can enter the analytical column and contaminate it, thereby, increasing analytical time per
sample. This is controlled by a timed event through the system computer.

2.3 The on-board computer system is calibrated for each target compound in the laboratory and updated in
the field. A calibrant containing one of the target compounds in air (usually the one with the longest RT) is injected
by a timed cycle event to update all the RT values for compound identification and to recalibrate the response factor
(RF) of all the target compounds for quantitation.

2.4 The chromatogram can be plotted and the final report printed with any values found for identified target
compounds. After a specified number of cycles, a timed weighted average (TWA) will be printed out if desired.

2.5 All of the timed events and cycled events depend on the target compounds being analyzed, the flowrates
during the backflush made and serial mode, the type and length of the precolumn and analytical column, and the
temperature of the environment under which the GC is operated. These are determined in the laboratory before
fieldwork can begin.

3.0 INTERFERENCES

3.2 There may be only partial interference with a target compound as evidenced by an elevated baseline or
peak shape. In such a case its identity and quantity may still be determined depending on the severity of the problem.
The data may need to be qualified as estimated. In such a situation an experienced chromatographer should be
consulted.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph: Photovac 10S50 with a 4 ft. length x 1/8 in. diameter Teflon analytical column
with 5% SE-30 on 100/120 mesh Chromosorb G-AW packing and a 6 in. Teflon precolumn with the same packing
specification. There is a 1:8 length ratio between the columns.

4.2 Tedlar Bags: 1-L with closures.

4.3 Teflon Tubing: 1/8 in. O.D.

4.4 Gastight Syringes: Various sizes, 0.1 -mL to 2.0-mL, such as those supplied by Precision Scientific Co.

4.5 Liquid Syringes: 1.0-(iL to 10.0-(iL capacity.

4.6 Compressed Air: Lecture size bottles of zero-grade, or better.

4.7 Flowrate Measuring Device or Bubble Meter.

4.8 Stop Watch.

5.0 REAGENTS

5.1 Stock standard of target compounds in methanol in 5.000 to 10.000 fig/mL range.

FMC-VA-008-4

-------
5.2 Neat standards of target compounds.

5.3 Cylinders of standard concentrations of target compounds in air (optional).

5.4 Cylinder of trichloroethvlene or toluene in air for use as calibrant.

5.5 Methanol: Reagent grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Since the sample is taken through a Teflon line up to 20 ft. long by an internal pump, no sample handling
and preservation is necessary. This is a cyclic real-time sampling.

6.2 The standard involved is in a pressurized can that is directly connected to the calibration port of the
instrument. Therefore, no standard handling is required other than checking the fittings on the cylinder and
instrument, and keeping the cylinder strapped in the cradle provided.

7.0 PROCEDURE

7.1 Set-up of the Photovac 10S50 GC: General operational procedures are described in the Photovac 10S50
Operating Manual. The settings and sequences of operations given in this method represent only one of many
variations that could be used depending on field conditions, target compounds, and data quality objectives.

7.1.1 Fill the internal reservoir via the special flexible filter hose to 1600 psi. The specific
instructions are in the 10S50 Operating Manual.

7.1.2 There are 3 flowrates to be adjusted for proper chromatography. Two of them are interactive
and are adjusted in the backflush mode, which is the standby mode of the instrument. Adjust them relative
to each other with the needle valve at the auxiliary out port and flow controller for injector #1.

7.1.3 Set the flowrate measured at the detector out port and controlled by injector #1 knob to about
25 mL/min. The measured flowrate at the auxiliary out port should be 5 to 10 mL/min greater than the
detector out flowrate. If it is not, adjust it with the needle valve.

7.1.4 Now, remeasure the flowrate at the detector and bring it back to about 25 mL/min if it has
changed significantly. Remeasure at the needle valve and see if the 5 to 10 mL/min difference is maintained.

7.1.5 This is obviously an iterative process that may take some time to adjust. Adjust it first in the
laboratory before doing the field work. Record all rates.

7.1.6 Depress the power on button and wait for the lamp to light. Now adjust the third flowrate.
Measure the third rate after the first 2 rates are established. Measure it during the foreflush mode or serial
mode in which the precolumn and analytical columns have the carrier gas directed through them in series.

This rate should be the same as the rate through the analytical column during the backflush mode.
Therefore, it should be about 25 mL/min and is measured at the detector out port.

7.1.7 In order to measure this flowrate and adjust it, enter the serial mode of operation. To do this
for adjustment purposes, put Event 3 "ON" at 10 seconds, and "OFF" at 0 seconds. This allows serial flow
continuously. When the proper flowrate has been reached using the injector #2 knob, change Event 3 to
some number greater than 10 seconds for its "OFF" status. This will put the instrument in the backflush
mode again.

7.1.8 Use Library #1 and update the internal calendar and clock.

FMC-VA-008-5

-------
7.1.9 Now enter the event settings as follows:

Event #

OFF

150

7.1.10 C alibrate the instrument.

7.2 Instrument Calibration

7.2.1 Add an appropriate amount (1 to 5 (iL) of methanolic solution of a mixture of the six target
compounds to a 1-L Tedlar bag of clear air. Allowing about 5 minutes for proper diffusion, attach it via a
Swagelock fitting to the probe in port on the instrument.

7.2.2 Calculate the concentration of each component in the air mixture using the equation in section

7.5.

7.2.3 Use a gain of 50 at concentrations of approximately 0.05 ppm (v/v) for vinyl chloride and 3
ppm (v/v) for methylene chloride.

7.2.4 Set the analysis time via the cycle key. The first question is the plotter delay which starts the
plotter. It should be set to 10 seconds. Then set the analysis time in seconds. Since the events and flowrates
are set for a 65° to 700° temperature range, set the run time at about 1000 seconds to be sure to get the
toluene peak. It can later be changed to fit conditions.

7.2.5 Now start the analysis and let it run to completion.

7.2.6 All of the 6 target compound peaks should be shown on the chromatogram. If the last peak,
which is somewhat broad, is not present, the analysis run time may have been too short or the Event 3
valving was turned off at too short a time.

7.2.7 Setting the off time for Event 3 is described in detail in the Operator's Manual. An example
is given below:

Assuming a 6 in. precolumn and a 4 ft. analytical column, the time the carrier flow should be in

series is determined by a simple proportion involving the elution time of the last eluant of interest.

In this case, it is toluene.

For example, if the RT of toluene is 900 seconds:

FMC-VA-008-6

-------
1/8 x 1000 = 125 seconds

This is the time it takes for most of the toluene to leave the precolumn and elute onto the analytical
columns. A factor of 20 percent is added to this time to allow for the tail of toluene to elute and
some room for drift due to environmental conditions.

Therefore, 150 seconds should be used as the Event 3 off time.

7.2.8 At the end of the analysis the report will give the peak number and RT in seconds as well as
its (millivolt-second) reading. The latter is a measure of the integrated peak area.

7.2.9 All of the compounds in the standard are first stored in the library using the store key and
answering the prompts displayed on the LED. The analyst must supply the name of the compounds and their
concentrations in ppm. If more peaks appear than are in the calibration mixture, only name those which are
known to be target compounds. Their peak numbers may be out of sequence.

7.2.10 After all are stored, list the library with the appropriate key. The ID numbers shown are
important in the calibration sequence.

7.2.11 Calibrate the system using the Cal key and answering the prompts for each compound. All
of the compounds will then be calibrated in the computer. The computer associates the area of each peak
with its concentration and with the RT for peak identification.

7.2.12 The library storage, listing, and subsequent calibration is fully described in the Operator's

Manual.

7.2.13 If all peaks were seen and integrated before the end of the run, the system is ready for
calibrations.

7.3 Sample Analysis

7.3.1 After calibration, set up the instrument to automatically sample the ambient air.

7.3.2 Set up the instrument to continually calibrate itself through a timed cycle sequence. This is
accessed through the Cycle key. Answer all the prompts including the TWA prompt if desired. All prompts
and use of the key is described in the Operator's Manual.

7.3.2.1 It should be noted that whichever calibrant is used for the automatic calibration
update, both the RT and the responses for all of the compounds in the original calibration will be
updated based on this one compound.

7.3.2.2 If the RT is 5 percent longer then the original, all target compound RTs will be
increased by 5 percent. If the response is 5 percent less, then all responses will be reduced by 5
percent. The concentration of the calibrant should be the same as that used in the original
calibration.

7.3.3 Other parameters necessary for the identification and quantitation of the peaks are set with
the Set-up keys on the instrument. These values may be used:

Gain - 50

Chart - on with setup speed 0.5 cm/min

Sensitivity - upslope: 15

downslope: 15

FMC-VA-008-7

-------
Window
Area

±10 seconds
5 mV

All of these parameters are explained in the Operator's Manual.

7.3.4 The amount of chart paper, battery power, carrier gas supply, chart pens, and calibrant should
be checked. There should be enough for the period of time the sampling is to continue.

7.3.5 Start the analysis and the system will continue to cycle for the required time. It may be left
unattended.

7.4 Quantitation Calculations

7.4.1 Although the on-board computer may be updated for RT and response, it should be
remembered that only 1 calibration concentration is entered for each compound. So long as levels of
contaminants are close to that level, the quantitative results should be good.

7.4.2 No study has yet been done by the CRL to determine how close the sample component
concentration needs to be for accurate quantitation. Therefore, an arbitrary limit of ± 50 percent of each
standard could presently be used. For example, if 1 of the target compound standards was 1 ppm (v/v) at
calibration, the level for good quantitation can be expected in the range of 0.5 ppm to 1.5 ppm. If values
outside of this range are computed and reported by the instrument, they should be considered "estimated
values".

7.4.3 The computer forms a ratio of the peak area of a component to its listed concentration in ppm.
If the sample is in the proper RT window, calculates its concentration by solving a simple proportional
equation such as:

concentration of standard concentration of sample component

7.4.4 The amount of the injection is invariant throughout the analytical cycle sequence, so this is
not a factor. If this value were to be changed by altering Event 5 " ON" time, a proportional change in the
quantitation would need to be made manually.

7.4.5 A 2-second injection time is equivalent to a 330-(iL injection of air. Therefore, 4-second
injections as presented in this method is equivalent to a 660-(iL injection. The MDLs in Table 1 were
determined for a 1-mL manual injection. So to use them as a working guide, they should all be increased
by a factor of 1.5.

7.5 Sample Quantitation: The following formula is used to calculate the concentration of each component

peak area standard

peak area of sample component

in the air mixture:

C =

4.1 x 10'B x M x V

where: C
m

Concentration of compound in air in ppm (v/v),

Mass of compound added to the bag in grams (g),

Molecular weight of the compound in a.m.u.,

Volume of sampling bag in liters, and

Number of moles derived from the ideal gas equation, contained in a l-(iL volume.

M
V

4.1 x 10 "8

FMC-VA-008-8

-------
For example, if 1 (iL of a solution containing benzene (MW = 78) at 500 ng/mL is added to 1 L of air, what will be
its concentration? Since 500 ng/mL = 0.5 then 1 (iL = 0.5 (ig = 5 x 10"6 g.

= 5 x 10'6g

4 . 1 x 10"8 x 78 x 1 L

C = 0.156 ppm or 156 ppb (v/v).

7.6 Instrument Maintenance and Troubleshooting

7.6.1 Obviously, all expendable items should be checked before any automated sequence to ensure
that the cycling will go to completion. This includes the battery charge if the system cannot be connected
to an AC source (see Operator's Manual).

7.6.2 Carrier gas flow should constantly go through the Teflon column since contaminants can
permeate it. In this way, they will be continuously swept from the column and not be allowed to become
concentrated on the packing.

7.6.3 The GC injection port septum should remain unpierced, so there should be no need to change
it during the course of the analysis.

7.6.4 If a leak is suspected, check the column fittings inside the instrument. They should be finger

tight.

7.6.5 The instrument will operate at its optimum if it is located in a stable temperature environment.

7.6.6 Table 3 has a list of common troubleshooting items and their probable cause and solution.

7.7 Safety and Waste Handling

7.7.1 Good laboratory practices should be the guide in field use of the Photovac GC, standard
materials, syringes, compressed gases, and samples.

7.7.3 Dispose of the remains of air samples from the Tedlar bags by drawing them through a large
charcoal trap, or other sorbent material known to retain the compounds of interest. Dispose of the traps in
a proper fashion.

7.7.4 Another safety consideration is handling the compressed gases. The calibration gas is a small
aerosol type can which is placed in the cradle provided in the instrument and fastened with Velcro strips.
A special adapter is needed to connect it to the "cal in" port. The can must have a maximum internal
pressure of 40 psi. If it is greater, the internal pressure sensor will interpret the calibrant as a sample.

7.7.5 The carrier gas (air) can be put into the internal reservoir of the Photovac GC via a special
high pressure gas filling tube supplied by the manufacturer. It is made specifically for the instrument and
must not be altered in any way.

7.7.6 The contents gauge should read 1600 psi when the reservoir is filled but must never exceed
1750 psi. The pressure relief valve of the filling tube should prevent this from happening. A further safety
measure is a rupture disc inside the instrument which is rated at 3000 psi.

FMC-VA-008-9

-------
8.0 QUALITY CONTROL

8.1 Outside of initial calibration and continued calibration updates, nothing can be done during an automated
run to monitor the system short of stopping the sequence. However, a mixture of target compound should be injected
through the probe in port or with the standards at the end of the sequence to determine if the system has operated
properly. The concentration of these target compounds should be different from the standards, and made from
different solutions.

8.2 Also, all chromatograms are automatically numbered in sequence by the plotter. If any problems were
noticed from the plots, for instance, a calibration update problem, a written record of the problem should be made and
all analyses associated with it should be labeled as suspect.

8.3 It is very important to document all procedures done with the system and date and initial them in a field
notebook. Any maintenance procedures must be listed along with the reasons they were needed.

8.4 Quality Control

8.4.1 Field controls samples.

8.4.2 A laboratory calibration of the instrument (Photovac 10S50) will be performed within each
analytical run.

8.4.3 For target compounds, a calibrant gas will go into the field with the instrument and will be
used to adjust retention times for identification purposes on every alternate cycle, thus, bracketing the
analytical runs. This will also serve as a rough check on calibration of all the target compounds.

9.0 METHOD PERFORMANCE

Information not available

FMC-VA-008-10

-------
Table 3

TROUBLESHOOTING

Symptom

Probable Cause

Remedial Action

LCD indicates LAMP NOT
READ PLEASE WAIT, more
than 3 mins after switch-on.

Source needs tuning.

Tune source (see CP1, end of this
section).

Instrument shuts itself down a
few seconds after switch-on.
Indicates low battery.

Battery needs charging.

Connect to mains, switch on,
disable CYCLE, if necessary, and
leave for 10 hrs to charge.

Upon starting analysis, printer
does not function at all.

Printer disabled.

Momentarily depress FEED key,
releases printer.

Upon starting, plotter starts then
stops immediately.

Analysis time is "0".

Set proper analysis time using
CYCLE key.

Upon starting, no peaks appear at
all.

Improper valve setting.

Obtain setting list by pressing
TEST + ENTER. Check settings
listed.



Leaky gas fittings.

Tighten all fittings but use fingers
only. BE VERY CAREFUL
NOT TO OVER-TIGHTEN
FITTINGS ON SOLENOID
VALVES.



Septum in injection port needs
changing or tightening.

Change/Tighten!

Early peaks do appear but later
peak(s) missing.

Too early backflush.

Increase Event 3 OFF time.

Unwanted late peaks appear,
maybe even during next analysis.

Too late backflush.

Decrease Event 3 OFF time.

Valve remains ON (as indicated
by LCD)

Improper timing, ON time greater
than OFF time.

Obtain LIST or check EVENT
status through LCD.

FMC-VA-008-11

-------
Table 3 continued

TROUBLESHOOTING

Symptom

Probable Cause

Remedial Action

Sensitivity seems too low.

Calibrant is wrong.

Check.



Leak in system.

Tighten (finger tight) all fittings.
Suspect column attachment
fittings and injection port. DO
NOT OVER-TIGHTEN
FITTINGS IN SOLENOID
VALVES.



Valve timing wrong.

Check EVENTS, it is possible the
backflush is too fast (see above).
Also possible INJECT time too
short.

Replace with spare and try again.



Lamp is failing.



Peak appears but is not
recognized.

Peak not calibrated.

Perform qualitative cal. as in
p.37.

Increase subsequent ca.
frequency.

Check that peak is listed in
library and that it was assigned
proper ID and plotter numbers.

Peaks appear too slowly.

Flowrate(s) too low.

Check all flowrates.

Peaks appear too quickly.

Flowrate(s) too high.

Check all flowrates.

FMC-VA-008-12

-------
Table 3 continued

TROUBLESHOOTING

Symptom

Probable Cause

Remedial Action

Battery life is too short.

Lamp power too high.

Printer/valve cycle is very
frequent.

Press TEST + ENTER to obtain
status report, if SOURCE
POWER is greater than 40, see
CP1.

If your cycle time is 2 mins and if
you are using full printout, the
battery life will be reduced. Use
external battery pack Cat#210 or
202. Also, minimize printer
format.

Instrument uses air carrier too
fast.

You have a high flowrate(s).
There is a leak.

Check flows.

Tighten all fittings, especially on
columns. DO NOT OVER-
TIGHTEN SOLENOID VALVE
FITTINGS.

FMC-VA-008-13

-------
10.0	REFERENCES

1.	Photovac 10S50 Operator's Manual, Rev. A.

2.	"Ambient Monitoring for Specific Volatile Organics Using a Sensitive Portable PID GC", Spittler, T.M.

3.	Various Remedial Investigations QAPPs.

FMC-VA-008-14

-------
CSL Method

SV/WATER/CARBON DISULFIDE EXT/GC-FID

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of water for semivolatile hydrocarbon parameters that are
indicative of contamination at the site. It is presented as a means to rapidly characterize contamination in water
samples. The method is semiqualitative and semiquantitative for the list of target constituents listed in Table 1. Other
compounds may be added as data become available.

1.2 Application of this method is limited to the screening analysis of water for the target constituents. The
chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of water contamination associated with other nontargeted compounds in the sample extracts. Positive identification
and quantification of specific constituents, such as these constituents and other organic priority pollutants, should be
supported by analyses of duplicate and other composited samples at a remote CLP laboratory employing EPA
approved testing protocols.

1.3 Preliminary method validation data indicate analysis recoveries of upwards of 90 percent.

1.4 The method detection limits (MDL) for the target constituents are estimated to be 1.0 ppm (^g/g). These
estimates are the result of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The methods presented here are based on liquid-liquid extraction techniques as investigated by Glase
and Lin (1983) for EPA-EMSL. In brief, carbon disulfide is used to effect extraction of the target constituents from
the sample matrix. The extract is subsequently analyzed on a two-channel capillary gas chromatograph (GC) using
a flame ionization detector (FID).

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target constituents may cause a positive bias in
the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples
having high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation
of dilutions, and spiking of samples.

FMC-S-001-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Water (ng/g)

2,4-Dimethylphenol

1

2-Methylphenol

1

4-Methylphenol

1

Phenol

1

4.2 Gas Chromatograph: Hewlett-Packard Model 5890A; temperature programming, electronic integration,
report annotation, automatic sampler, 30-meter megabore capillary column (DB-1, 1.50 micron film thickness), and
FID.

5.0 REAGENTS

5.1	Carbon Disulfide: Reagent grade, 99.9 percent.

5.2	Sodium Sulfate: Reagent grade, anhydrous powder form.

5.3	Stock Standards: Prepared from standard materials at approximately 1000 mg/L in CS2.

5.4	Working Standards: Prepared from stock standards by precise dilution in CS2.

5.5	Gases

5.5.1	Nitrogen: Carrier gas, prepurified grade.

5.5.2	Hydrogen: FID gas, prepurified grade.

5.5.3	Air: FID gas, zero grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1	The target constituents are either identified as or suspected of being carcinogens. All samples
are assumed to be hazardous. Handle all stock and working calibration standards, as well as all samples,
with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2	Laboratory coats, safety glasses, and surgical gloves shall be worn by laboratory analysts at
all times when preparing and handling standards and field and laboratory samples.

7.1.3	Prepare standards and samples in a fume hood.

FMC-S-001-2

-------
7.1.4 Carbon disulfide (CS2) is regulated by NIOSH. The suggested permissible exposure level
(PEL) is 1 ppm with a ceiling level of 10 ppm. Exposure pathways are oral, dermal, and airway. Effects of
short-term exposure are headaches, nausea, drop in blood pressure, dizziness, and unconsciousness. High
concentrations may cause irritation to the skin, eyes, and nose.

7.1.5 Store sample extracts and standards prepared in flammable solvents in an explosion-proof
refrigerator or cooler (outside the laboratory).

7.1.6 Sample preparation should be performed in a fume hood with adequate skin, eye, and hearing
protection provided for and used by the analysts. Carbon disulfide has good warning properties since its
discernable odor thresholds are well below their PEL. Correct any situation creating odor levels
immediately. Handle carbon disulfide in minimum quantities to minimize fire and health hazards.

7.1.7 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Any situation which leads to or causes noticeable odors or produces any physical symptoms in
the workers shall be investigated immediately followed by appropriate corrective action.

7.1.8 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical
spill clean-up kit available for use at all times.

7.2 Sample Preparation and Extraction

7.2.1 To a precleaned 12-mL reacti-flask, volumetrically pipet 2 mL of CS2.

7.2.2 Transfer 10 mL of the water sample from the VOA vial into the barrel of the 10-mL syringe.
Insert the plunger into the syringe and invert. Waste away the trapped air and excess sample until the desired
sample aliquot is contained in the syringe.

7.2.3 Transfer the sample aliquot to the reacti-flask, cap the flask, and vigorously shake for 2
minutes to achieve extraction of the sample.

7.2.4 Following the extraction, leave the flask undisturbed for one minute to permit separation of
the CS2 and sample.

7.2.5 Using a Pasteur pipet, transfer a suitable aliquot of the CS2 solvent extract from the flask into
a labeled GC autosampler vial and cap immediately with septum crimp seals. Refrigerate the sample
extracts until use.

7.3 Calibration

7.3.1 External calibration: Use three-level calibration with standards at approximately 40.0, 10.0,
and 1.0 ng/mL for the target constituents in pentane.

7.3.2 Working calibration: Perform working calibration with the analysis of each working day's
lot of samples or with each lot of 20 samples, whichever is more frequent. Verify working calibration by

FMC-S-001-3

-------
use of a mid-range standard mix. If the response factors and retention times vary by more than ±15 percent
or 0.10 minutes from the initial calibration, then recalibrate on freshly prepared working standards.

7.4 Analysis

7.4.1 Perform GC analysis on the extract.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range,
dilute the sample extract such that concentrations fall within the calibration range.

7.4.3 Check the retention values for each of the target constituents against the expected (calibration)
value. Qualify those results where the retention time does not fall within ± 0.05 minutes of the expected
value. Reject those results where the retention time does not fall with ± 0.10 minutes of the expected value.
Take corrective action if the results continue to fall outside of the proper range.

7.4.4 Use a retention time marker as an indicator of the reliability of each sample injection and GC
run. The retention time marker should fall within the same windows as the target constituents and should
be within ±15 percent area counts of its initial calibration value. If these criteria are not met, re-evaluate
the data using relative retention times. Reruns should occur to resolve data suspicions.

A x V x DF

Concentration in \ig/mL =

where: A = Amount of target constituent found in the extract in (ig/L,

Vt = Volume of solvent added to the reactor flask, 2.0 mL,

DF = Dilution factor, if required, and

Vs = Volume of the sample added to the reactor flask in mL.

8.0 QUALITY CONTROL

8.1 Quality control measures shall include as a minimum:

8.1.1 Daily mid-range calibration checks performed prior to the analysis of each day's lot of
samples or with each lot of 20 samples, whichever is more frequent.

8.1.2 Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day,
whichever is more frequent.

8.1.3 Analysis of laboratory blank samples at the same frequency. Should the results of the
laboratory blanks show contamination, the cause of the contamination should be investigated and corrective
action taken.

8.1.4 Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1/day, whichever is
more frequent.

FMC-S-001-4

-------
8.1.5	Analysis of mid-range matrix spike samples and a matrix spike duplicate at a frequency of
1 in 20 samples analyzed or 1/day, whichever is more frequent.

8.1.6	Use of the retention time marker during the analysis of all samples and standards.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-S-001-5

-------
NUS SOP Number 5.3
FIELD SCREENING OF TARGET SEMIVOLATILE ORGANIC COMPOUNDS

(AQUEOUS MATRIX)

1.0 SCOPE AND APPLICATION

1.1 The following methodology describes a modification of SW-846 preparative and EPA 600 series
analytical gas chromatographic procedures suitable for the determination of semivolatile contaminants in aqueous
matrix samples.

1.3 Table 1 provides a list of potential target compounds.

2.0 SUMMARY OF METHODS

In this methodology, a portion of neat sample is extracted using rapid field techniques. An aliquot of sample
extract is then directly injected onto an analytical column housed by a previously calibrated gas chromatograph (GC).
The semivolatile compounds are resolved by temperature-programmed GC and are detected by a flame ionization
detector (FID). The detector signals are processed and interpreted via a previously programmed integrator.

2.1 Low Level Analysis: Use of a 25-mL neat sample aliquot is suggested. Detection limits vary per each
compound sensitivity to the detector. Detection limits of approximately 100 (ig/L to 800 (ig/L are achievable.

2.2 Medium Level Analysis: Proportioned dilutions may be achieved by using a reduced sample aliquot.
For example, a 5-fold dilution can be simulated by extracting only 5 mL of neat sample while retaining the same
volume of extraction solvent.

3.0 INTERFERENCES

3.1 Interferences inherent to this procedure stem from 4 major sources: (1) impurities present in the solvents
used for extraction, (2) system artifacts caused by insufficient column conditioning, (3) residual contamination
remaining on improperly cleaned glassware, and (4) matrix interferences caused by coextracted organic matter.

3.2 Interferences in the analytical system are monitored by the analysis of method blanks. Method blanks
are analyzed under the same conditions and at the same time as standards and samples in order to establish average
background response.

3.3 Artifacts, which manifest themselves as carryover in the next analytical run, can also occur within the
analytical apparatus whenever a highly contaminated sample is introduced. To preclude this from occurring, injection
syringes are repeatedly flushed with solvent, and the analytical column is baked for a short period of time following
each direct injection analysis.

FMC-S-002-1

-------
Table 1

SUMMARY OF POTENTIAL TARGET COMPOUNDS

Semivolatile Organics Analysis

Acenaphthene

Hexachloroethane

Acenapthylene

Naphthalene

Anthracene

2-Chloronaphthalene

Benzo(a)anthracene

2-Methylnaphthalene

Benzo(a)pyrene

Phenanthrene

Total Benzo Fluoranthenes

Pyrene

Butylbenzylphthalate

1,2,4-Trichlorobenzene

Chrysene

Total Dichlorobenzenes

Diethyl phthalate

Phenol

Dimethyl phthalate

2-Chlorophenol

Di-n-butyl phthalate

2,4-Dichlorophenol

Di-n-octyl phthalate

2,4,5-Trichlorophenol

Fluoranthene

2,4,6-Trichlorophenol

Fluorene

2-Methylphenol

Hexachlorobenzene

4-Methylphenol

Hexachlorobutadiene

2,4-Dimethylphenol

Hexachlorocyclopentadiene

4-Chloro-3-methylphenol

4.0 APPARATUS AND MATERIALS

4.1	Gas Chromatograph: Hewlett-Packard 5890, or equivalent. The analytical system should be equipped
for packed or capillary column analysis with a temperature-programmable oven and on-column injection capabilities.

4.2	Detector: FID.

4.3	Analytical Column: Better resolution is achieved through use of a capillary column (such a DB-5, or
equivalent).	However, a packed column, such as 3% SP-2250 on 100/120 mesh Supelcoport, is more practical for
field use.

4.4	Syringes (assorted): 5-^L, 25-^L, 100-(iL, and 1-mL.

4.5	Analytical Balance: Capable of accurately weighing 0.0001 g.

FMC-S-002-2

-------
4.6 Vials: 40-mL septum-seal for extraction.

4.7 Vials: 2-dram septum-seal for extract storage.

4.8 Pipets (assorted): 1-mL, 5-mL, and 10-mL disposable glass.

4.9 Refrigerator: Separate for sample and standard storage. Capable of maintaining a temperature of 4°C.

4.10 Glass Marking Pen: For labeling vials.

4.11 Laboratory Timer: For use during the extraction process.

4.12 Hvdrion Paper: To measure pH.

5.0 REAGENTS

5.1 Methanol: Pesticide grade, or equivalent.

5.2 Methylene Chloride: Pesticide grade, or equivalent.

5.3 Sulfuric Acid: IN, reagent grade.

5.4 Neat Standards: 96 percent purity, or better, for each compound of interest.

5.5 Standards: Calibration standards containing the compounds of interest are prepared from commercially
purchased standard mixes or pure compounds. All standards are made and/or diluted using a 1:1 mixture of
methylene chloride and methanol, and are created for use via a 2-^L direct injection.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Samples awaiting analysis are stored at 4°C in a dedicated refrigerator. If, because of loading, it is not
possible to analyze all samples taken daily, the suggested holding time for the analysis of semivolatile organics in
aqueous matrix is 5 days prior to extraction, and analysis within 30 days. If holding times are exceeded, the affected
data should be qualified as suspect.

7.0 PROCEDURE

7.1 Sample Preparation: All samples must be extracted prior to chromatographic analysis. A suggested
protocol follows:

7.1.1 Pipet 25 mL of aqueous sample matrix each into 2 40-mL septum-seal vials; discard pipet.

7.1.2 Add exactly 2.5 mL of methylene chloride to one of the vials' contents.

7.1.3 Adjust the pH of the other vial's contents to a pH less than 2 using sulfuric acid.

7.1.4 Add exactly 2.5 mL methylene chloride to the adjusted contents of the second vial.

7.1.5 Cap the vials and shake vigorously for 2 full minutes.

FMC-S-002-3

-------
7.1.6 Set the vials aside and allow the contents to settle for 5 minutes.

7.1.7 Combine the extracts by pipetting exactly 1.5 mL each of the supernatant extracts into a
2-dram septum-seal vial.

7.1.8 Perform GC analysis by directly injecting 2 to 5 |±L of combined sample extract onto the GC's
analytical column.

7.2 Calibration: Calibrate the analytical system via the external standard method, in which response factors
(RF) for each compound are obtained by the analysis of a standard mix of known concentration. Following the
analysis of this known standard mix, create an electronic file establishing each peak's identity, retention time (RT),
RF, and known concentration. Determine the RF for each peak by dividing the known concentration by the peak
response (area or height units) of the associated peak. For initial calibration, determine each compound's average RF
by averaging the peak response results generated for the initial linearity study. Program these average RFs into the
integrator to allow for direct concentration reading of contaminants found in subsequent sample analyses.

7.2.1 Initial linearity:

7.2.1.1 Generate an initial 3-point calibration curve by the analysis of multiple aliquot
injections of calibration standard. For example, if the calibration standard is created such that a 2-
(iL spike yields results at the level of the reported detection limits, a 3-point calibration curve may
be achieved by the analysis of 2-, 5-, and 10-(iL aliquot spikes.

7.2.1.2 Compute the percent relative standard deviation (%RSD see 7.4.1) based on each
compound's RFs (see 7.5) to determine the acceptability (linearity) of the curve. The %RSD should
be less than 20 percent. Reanalyze standard runs yielding data that does not meet the %RSD
criterion.

7.2.2 Continuing calibration:

7.2.2.1 Update the calibration of the analytical system 3 times daily: (1) preceding the
daily analyses, (2) midday, and (3) after the daily analyses.

7.2.2.2 Analyze standards run for continuing calibration purposes at a level equal to the
reported detection limits. Continuing calibration RFs for each parameter should fall within 25
percent difference (%D, see 7.4.3) of the average RF calculated for that particular compound during
the initial linearity study. Qualify data associated with individual parameter not meeting the %D
criterion as suspect.

7.2.2.3 Conduct the continuing calibration at a concentration level equal to the reported
detection limits.

7.2.3 Peak identification: Compound identities may be substantiated by the analysis of each
individual component, thereby, documenting compound retention time.

7.3 Gas Chromatography

7.3.1 Analytical sequence: Conduct analyses in sets of 10, whenever possible, with 1 laboratory
duplicate spike analysis run per set. Bracket each set of sample analyses by the analysis of a standard, with
a method blank analysis following each standard run. The number of analyses per sample set and the
associated quality assurance/quality control (QA/QC) varies per contract. Consult the project work plan to
verify that all contractual obligations were met.

FMC-S-002-4

-------
7.3.2 First strip the sample contaminants from the matrix by means of methylene chloride
extraction (see 7.1). Introduce a 2- to 5-(iL aliquot of the sample extract onto the head of a previously
conditioned analytical column by means of direct injection technique. The semivolatile contaminants are
then resolved by temperature-programmed GC in which the action of carrier gas flow, elevated temperatures,
and the affinity each semivolatile compound has for the phases of the column packing cause the
contaminants to separate into bands. As the bands of contaminants elute from the column, they are
recognized by an FID. Detector signals are then processed by a previously programmed integrator. As long
as analytical conditions remain constant, each semivolatile compound will elute at a characteristic RT. In
this manner, sample contaminants are identified and quantified by comparison to a run of standard mix of
known concentration.

7.3.3 Under the following run conditions, most compounds of interest will elute within 32 minutes:

Run Parameter

Setting

Initial Column Temperature

100°C

Initial Hold Time

1 min

Rate

10°C/min

Final Column Temperature

300°C

Carrier Gas Flow

20 mL/min

Adjust these conditions as necessary in order to optimize the resolution of the specific compounds of interest.
7.4 Calculations

7.4.1 Calculate %RSD using the following equation:

ST)

%RSD = — x 100
X

where:

A (x - x)2
SD = >

M N - 1

and X is the mean of initial RFs (per compound).

7.4.2 Calculate relative percent difference (RPD) values using the following equation:

D1 ~ D2
RPD = i — x 100

+ g2>

where: D[ = First sample value, and

D2 = Second sample value.

7.4.3 Calculate %D using the following equation:

FMC-S-002-5

-------
%D = —	— x 100

where: X[ =	RF of first result, and

X2 =	RF of second result.

7.4.4 Calculate percent recovery (%R) using the following equation:

= SSR ~ SR x 100

s

where: SSR =	Spike sample results,

SR =	Sample result, and

S	=	Amount of spike added.

7.5 Sample Quantitation: Appropriate quantitation of sample contaminants is based upon the following

formula:

Concentration (]ig/L) = target peak response{sample) x RF x DF

where: RF =	Target analvte concentration in std (\ieAS)

Target peak response in std
DF =	Dilution factor used, when applicable.

8.0 QUALITY CONTROL

8.1 Overview

8.1.1	Field screening generates Level II data. As Level II data, the concurrent analysis of
laboratory duplicates and matrix spike analyses and the use of surrogate spike compounds is not required.
However, beyond the maintenance of practical Standard Operating Procedures (SOPs), certain elements of
QC (if opted) can greatly enhance the interpretation of and the confidence in the data generated. These
traditional elements of QC are discussed here as to how they are adapted to meet the demands of a
successfully applied field screening QA/QC program.

8.1.2	The primary purposes of an appropriate QA/QC program are to: (1) substantiate system
performance and give credence to the accuracy of the results generated, (2) to define aberrations and give
guidance to the interpretation of data, and (3) to achieve these goals through realistic efforts that do not
impede the forward progress of the analytical set.

8.1.3	The discussion presented here deals with only direct analytical QC. Additional elements of
QA/QC, such as field duplicate sample submissions, blind spike analysis, and external audits are not
discussed. Also not discussed are elements of QA/QC that are inherent to good chromatographic technique.
Examples of these accepted laboratory practices include (but are not limited to) the following: (1) the proper
conditioning of analytical columns and traps, (2) use of the solvent flush technique for the creation of
standards and for direct injections, and (3) the appropriate maintenance of selected detectors. Details
regarding these accepted practices are given in the referenced methodologies.

FMC-S-002-6

-------
8.2 Laboratory Duplicates: One laboratory duplicate should be analyzed per sample set. Laboratory
duplicate analyses should generate results of RPD within 30 percent (see 7.4.2).

8.4 Surrogate Spikes: The use of at least 1 surrogate spike compound is highly recommended. The identity,
concentration and addition of the appropriate surrogate spike varies with the procedure being used. Each associated
referenced methodology should be consulted for guidance. Surrogate spike recoveries should fall within ±30 percent
(see 7.4.4). Sample analyses yielding %R values outside this 30 percent window should be reanalyzed or the
associated data should be qualified as suspect.

8.5 Method Blanks: Method blanks are prepared and analyzed in exactly the same manner as sample
matrices. A method blank analysis should follow every standard run and sample of high concentration. Ideally,
method blank results should yield no interferences to the chromatographic analysis and interpretation of target
compounds. If interferences are present, associated data should be qualified as suspect and/or target detection limits
should be adjusted accordingly.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-S-002-7

-------
CSL Method

SV/SOIL/MECL EXT/GC-FID

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of soil samples for semivolatile hydrocarbon parameters that are
indicative of contamination at the site. It is presented as a means to rapidly characterize contamination in soil
samples. The method is semiqualitative and semiquantitative for the list of target constituents listed in Table 1. Other
compounds may be added as data become available.

1.2 Application of this method is limited to the screening analysis of soil for the target constituents. The
chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of soil contamination associated with other non-targeted compounds in the sample extracts. Positive identification
and quantification of specific constituents, such as these constituents and other organic priority pollutants, can be
supported by analyses of duplicate and other composited samples at a remote Contract Laboratory Program (CLP)
laboratory employing EPA approved testing protocols.

1.3 Preliminary method validation data indicate analysis recoveries of upwards of 90 percent for the styrene
and acid extractables.

1.4 The method detection limit (MDL) for the target constituents are estimated to be 1 ppm (^g/g) for these
acid extractables. These estimates are the result of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The methods presented here are loosely based on EPA Method 3550, Sonification Extraction, and EPA
method 8040, Analysis of Acid Extractables by Gas Chromatography (GC), found in the EPA SW-846, Test Methods
for Evaluating Solid Waste. 3rd ed., November 1986. In brief, the pH of the sample is determined and, if necessary,
adjusted to below pH 7. Methylene chloride is used in conjunction with sonification to effect extraction of the sample
for the target compounds. The extract is subsequently analyzed by capillary GC using a flame ionization detector
(FID).

3.0 INTERFERENCES

3.1 Samples containing compounds that coelute with the target constituents may cause a positive bias in the

results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples
having high levels of background organics or other interferences.

3.4 The response factors for uncalibrated peaks that are significantly different from those of the target
constituents may produce errors in the estimation of the total target constituent contamination.

FMC-S-003-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Soil (ng/kg)

o-Chlorophenol

2,4-Dichlorophenol

Pentachlorophenol

Phenol

Styrene

2,4,6-Trichlorophenol

4.0 APPARATUS AND MATERIALS

4.1 VOA Sample Vials: 40-mL capacity with septum screw caps; precleaned as purchased from a vender.

4.2 Balance: Sartorius; top loading electronic with 1500 g capacity with 0.01 g sensitivity.

4.3 pH Meter: Chemtrix; meter with combination electrode and purchased pH 4.0, 7.0, and 10.0 buffer
solutions.

4.4 Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation
of dilutions, and spiking of samples.

4.5 Sonifier: Heat Systems Ultrasonic Sonicator with variable control up to 375 watt output and water-
cooled cup horn.

4.6 Gas Chromatograph: Hewlett-Packard Model 5890A; temperature-programmable, electronic
integration, multilevel calibration, report annotation, automatic sampler, 30 m megabore capillary column (DB-5, 0.25
l^m film thickness), and FID.

5.0 REAGENTS

5.1 Solvents

5.1.2 Methylene chloride: Reagent grade, 99.9 percent.

5.1.3 Sodium sulfate: Reagent grade, anhydrous powder form.

5.2 Miscellaneous Reagents

5.2.1 Acidified sodium sulfate: Add 0.1 mL concentrated sulfuric acid to 100 g of sodium sulfate
slurried with enough ethyl ether to cover the salt. Remove the ethyl ether by vacuum drying. Test for
acidification by mixing 1 g of the treated salt in 5 mL of deionized water and measuring the pH. If the pH
is not less than 4, repeat the process. Exercise extreme caution in using sulfuric acid (burns) and ethyl ether
(flammable); prepared beforehand at a remote laboratory.

FMC-S-003-2

-------
5.3 Gases

5.3.1 Nitrogen: Carrier gas, prepurified grade.

5.3.2 Hydrogen: FID gas, prepurified grade.

5.3.3 Air: FID gas, zero grade.

5.4 Stock Standards: Prepared from purchased pure standard materials at approximately 1000 mg/L in
MeCl; prepared beforehand at a remote laboratory.

5.5 Working Standards: Prepared from stock standards by precise dilution; prepared beforehand at a remote
laboratory.

5.6 Retention Time Marker: 2,4,6-tribromophenol in MeCl at approximately 40.0 mg/L; prepared
beforehand at a remote laboratory.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1 The target constituents are either identified as or suspected of being carcinogens. All samples
are assumed to be hazardous. All stock and working calibration standards, as well as all samples, shall be
handled with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all
times when preparing and handling standards and field and laboratory samples.

7.1.3 Standards and samples shall be prepared in a fume hood.

7.1.4 Methylene chloride (MeCl), used in the preparation of sample extracts, is regulated by OSHA
and described in NIOSH/OSHA manual, Occupational Health Guidelines for Chemical Hazards. 1981. The
MeCl permissible exposure level (PEL) is 500 ppm in air over an 8-hour period. Its odor threshold is
between 25 and 50 ppm. Exposure pathways are oral, dermal, and airway. Effects of short-term exposure
are reported to be mental confusion, light-headedness, nausea, vomiting, and headache. High concentrations
may cause irritation of the eyes and respiratory tract. Prolonged exposure may cause skin burns. MeCl is
nonflammable.

7.1.5 Phenols and the various chlorophenols (mono-, di-, tri-, and penta-) have PELs that range
from 0.1 to 5.0 ppm. The odor threshold for phenol is between 0.3 and 3.0 ppm. The odor thresholds for
the various chlorophenols is not reported in the NIOSH/OSHA manual. NIOSH does report that con-
centrations of pentachlorophenol of about 0.5 mg/m3 (0.05 ppm) can cause irritation of the nose and eyes.
Exposure pathways are oral, dermal, eyes, and airway. Effects of short-term exposure include irritation of
the eyes and respiratory tract. Repeated or prolonged exposure may result in chronic poisoning with ensuing
vomiting, diarrhea, lack of appetite, headache, fainting, dizziness, dark urine, and possible skin rash. On
direct contact, these compounds can cause severe damage to the eyes and skin. Systemic effects result from
either a large exposure or repeated smaller exposures through any of the exposure routes, especially skin
contact.

FMC-S-003-3

-------
7.1.6 Styrene has a PEL above 10 ppm which is significantly higher than that for phenol and the
chlorophenols. The exposure pathways are oral, dermal, eyes, and airway. Despite higher PELS, short and
long term exposure may result in symptoms similar to those identified for the chlorophenolic constituents.

7.1.7 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Any situation which leads to or causes noticeable odors or produces any physical symptoms in
the workers shall be investigated immediately followed by appropriate corrective action.

7.1.8 The ultrasonic sonicator used for sample extractions emits a high frequency sound. When
in use,the sonicator horn shall be inside the sound chamber with the door closed.

7.1.9 Safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
cleanup kit shall be available for use at all times.

7.1.10 Laboratory wastes shall be separated and properly disposed. The wastes include: the original
sample, any aliquots thereof, initial wash water, chemical wastes generated in the analysis, and disposables
used in the preparation of the samples. These wastes shall be collected and deposited in a drum clearly
marked as "CSL Lab Wastes Only-Hazardous." Water used for final rinsing of glassware will be considered
nonhazardous and will be released into the laboratory sewer system at the site.

7.2 Sample Preparation and Extraction

7.2.1 Determine the sample pH.

7.2.2 In a labeled VOA vial, accurately weigh out approximately 5 to 10 grams of soil, recording
the weight to the nearest 0.01 g.

7.2.3 Volumetrically pipet 5.0 mL of MeCl containing the retention time marker to the VOA vial
and record the volume added. This should be done immediately after weighing to avoid potential loss of
analytes.

7.2.4 Sample treatment: If the pH of the sample is less than 7 and the sample is dry, then proceed
to step 7.2.5. If the pH of the sample is less than 7 and the sample is wet or a highly consolidated material,
then add about 2 g of sodium sulfate, mix, and proceed to step 7.2.5. If the pH of the sample is greater than
7, regardless of its wetness and consistency, then add about 2 g of acidified sodium sulfate, mix, and proceed
to step 7.2.5.

7.2.5 With the VOA vial cap tightly in place, sonicate at an output setting of 30 percent for approxi-
mately 5 minutes. The resulting sonified sample should be dispersed throughout the MeCl solvent and have
a grain-like appearance. If not, then add an additional 1 g of sodium sulfate and resonify. Repetitions of this
process may be needed to properly extract some samples.

7.2.6 After sonification, let the VOA vial stand until the solids have settled. Using a Pasteur pipet,
transfer a suitable aliquot of the MeCl solvent (extract) from the vial into a labeled GC autosampler vial and
cap immediately. If expecting a delay in the GC analysis, refrigerate the sample extracts until use.

7.3 Calibration

7.3.1 External calibration: Perform a three-level calibration at approximately 100, 10, and 1.0 (ig/g
for the target constituents.

7.3.2 Working calibration: Perform working calibrations with the analysis of each working day's
lot of samples or with each lot of 20 samples, whichever is more frequent. Verify working calibrations by

FMC-S-003-4

-------
use of a midrange standard mix. If the response factors vary by more than ±15 percent from the initial
calibration, then perform recalibration on freshly prepared working standards.

7.4 Instrumental Analysis

7.4.1 Perform GC analysis on the extract.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range,
dilute the sample extract so that concentrations fall within the calibration range.

7.4.3 Check the retention values for each of the target constituents against the expected (calibration)
value. Qualify those results where the retention time does not fall within ±0.05 minutes of the expected
value. Reject those results where the retention time does not fall within ±0.10 minutes of the expected value.
Take corrective action if the results continue to fall outside of the proper ranges.

7.4.4 Use the retention time marker as an indicator of the reliability of each sample injection and
GC run. The retention time marker should fall within the same windows as the target constituents and
should be within ±15 percent area counts of its initial calibration value. If these criteria are not met,
re-evaluate the data using relative retention times. Reruns should occur only as a last resort in resolving data
suspicions.

7.5 Calculations: Quantification of the target compounds is based on the integrated areas of the samples
in comparison to the integrated areas of the calibration standards for each analyte. The integrator reports the
concentrations in ng/mL in the extracts. Calculation of the concentration for each target constituent in the original
sample is as follows:

A x V x DF

Concentration (\ig/g) =

where: A

Vt
DF
Ws

8.0 QUALITY CONTROL

Quality control measures shall include as a minimum:

8.1 Daily midrange calibration checks performed prior to the analysis of each day's lot of samples or with
each lot of 20 samples, whichever is more frequent.

8.2 Analysis of field blank samples at a frequency of 1 in 20 samples analyzed.

8.3 Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory blanks
show contamination, the cause of the contamination should be investigated and corrective action taken.

8.4 Analysis of field duplicate samples at a frequency of 1 in 20 samples.

8.5 Analysis of laboratory duplicate samples at a frequency of 1 in 20 samples analyzed.

8.6 Analysis of midrange matrix spike samples at a frequency of 1 in 20 samples analyzed.

Amount of target constituent found m the extract m (ig/mL,
Volume of MeCl added to the VOA vial, 5.0 mL,

Dilution factor, if required, and

Weight of the sample added to the VOA vial in grams.

FMC-S-003-5

-------
8.7 Use of 2,4,6-tribromophenol as a retention time marker during the analysis of all samples and standards.
9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

Information not available.

FMC-S-003-6

-------
NUS SOP Number 5.4
FIELD SCREENING OF TARGET SEMIVOLATILE ORGANIC COMPOUNDS

fSOLID MATRIX)

1.0 SCOPE AND APPLICATION

1.1 The following methodology describes a modification of SW-846 analytical gas chromatographic
procedures suitable for the determination of semivolatile organic contaminants in solid matrix samples.

1.3 Table 1 provides a list of potential target compounds.

2.0 SUMMARY OF METHODS

In this methodology, a 2 g portion of a solid sample is extracted using rapid field techniques. An aliquot
of the sample extract is then directly injected onto an analytical column for analyses by temperature-programmed gas
chromatography (GC). The semivolatile contaminants are subsequently analyzed by a flame ionization detector
(FID). The detector signals are processed by a previously programmed integrator.

2.1 Low Level Analysis: The extraction of a 2 g sample portion is suggested to achieve analytical results
comparable to approximately 50 mg/kg reportable detection limits.

2.2 Medium Level Analysis: Sample dilutions are achieved by diluting a portion of the sample extract (as
above) in an appropriate volume of methylene chloride.

3.0 INTERFERENCES

3.3 Artifacts, which manifest themselves as carryover in the next analytical run, can also occur within the
analytical apparatus whenever a highly contaminated sample is introduced. To preclude this from occurring, injection
syringes are repeatedly flushed with solvent, and the analytical column is baked for a short period of time following
each direct injection analysis.

FMC-S-004-1

-------
Table 1

SUMMARY OF POTENTIAL TARGET COMPOUNDS

Semivolatile Organics Analysis

Acenaphthene

Hexachloroethane

Acenapthylene

Naphthalene

Anthracene

2-Chloronaphthalene

Benzo(a)anthracene

2-Methylnaphthalene

Benzo(a)pyrene

Phenanthrene

Total Benzo Fluoranthenes

Pyrene

Butylbenzylphthalate

1,2,4-Trichlorobenzene

Chrysene

Total Dichlorobenzenes

Diethyl phthalate

Phenol

Dimethyl phthalate

2-Chlorophenol

Di-n-butyl phthalate

2,4-Dichlorophenol

Di-n-octyl phthalate

2,4,5-Trichlorophenol

Fluoranthene

2,4,6-Trichlorophenol

Fluorene

2-Methylphenol

Hexachlorobenzene

4-Methylphenol

Hexachlorobutadiene

2,4-Dimethylphenol

Hexachlorocyclopentadiene

4-Chloro-3-methylphenol

4.0 APPARATUS AND MATERIALS

4.1	Gas Chromatograph: Hewlett-Packard 5890, or equivalent. The analytical system should be equipped
for packed or capillary column analysis with a temperature-programmable oven and on-column injection capabilities.

4.2	Detector: FID.

4.3	Analytical Column: Better resolution is achieved through the use of a capillary column (such a DB-5,
or equivalent). However, a packed column, such as 3% SP-2250 on 100/120 mesh Supelcoport, is more practical for
field use.

4.4	Syringes (assorted): 5-^L, 25-^L, 100-(iL, and 1-mL.

4.5	Analytical Balance: Capable of accurately weighing 0.0001 g.

FMC-S-004-2

-------
4.6 Vials: 40-mL septum-seal for extraction.

4.7 Vials: 2-dram septum-seal for extract storage.

4.8 Pipets (assorted): 1-mL, 5-mL, and 10-mL disposable glass.

4.9 Refrigerator: Separate for sample and standard storage. Capable of maintaining a temperature of 4°C.

4.10 Oven: Constant temperature; for use in the determination of moisture content.

4.11 Glass Marking Pen: For labeling vials.

4.12 Laboratory Timer: For use during the extraction process.

4.13 Hvdrion Paper: To measure pH.

5.0 REAGENTS

5.1 Methanol: Pesticide grade, or equivalent.

5.2 Methylene Chloride: Pesticide grade, or equivalent.

5.3 Sulfuric Acid: IN, reagent grade.

5.4 Anhydrous Sodium Sulfate: Used to remove moisture content.

5.5 Neat Standards: 96 percent purity, or better, for each compound of interest.

5.6 Standards: Calibration standards containing the compounds of interest are prepared from commercially
purchased standard mixes or pure compound. All standards are made and/or diluted using a 1:1 mixture of methylene
chloride and methanol, and are created for use via a 2-^L direct injection.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Samples awaiting analysis are stored at 4°C in a dedicated refrigerator. If, because of loading, it is not
possible to analyze all samples taken daily, the suggested holding time for the analysis of semivolatile organics in
solid matrix is 5 days prior to extraction and analysis within 30 days. If holding times are exceeded, the affected data
should be qualified as suspect.

7.0 PROCEDURE

7.1 Sample Preparation: Extract all samples prior to chromatographic analysis. A suggested protocol

follows:

7.1.1 Weigh and tare 2 40-mL septum-seal vials using an analytical balance.

7.1.2 Add 2.0 g of sample matrix (each) to the 2 vials. Record both sample weights.

FMC-S-004-3

-------
7.1.3 Add approximately 2 g of anhydrous sodium sulfate to each vial. Mix the vial contents
thoroughly using a clean spatula.

7.1.4 Add exactly 10 mL of methylene chloride to each vial.

7.1.5 Invert 1 vial several times to mix. Adjust the pH of this vial's contents to a pH less than 2
using sulfuric acid.

7.1.6 Cap the vial and shake vigorously for 2 full minutes (alternatively, vial contents may be
sonicated).

7.1.7 Set the vials aside and allow the contents to settle for 5 minutes.

7.1.8 Combine the extracts by pipetting off exactly 1.5 mL each of the supernatant extracts into a
labeled 2-dram septum-seal vial.

7.1.9 Perform GC analysis by directly injecting a 2- to 5-|±L aliquot of the combined sample extract
onto the GC's analytical column.

7.2 Percent Moisture (% moisture') Determination: Use a moisture correction factor (MCF) to adjust the
value generated for the amount of contaminant present in a solid matrix sample so that the value reflects the true (dry
weight) concentration of contaminant. Determine moisture content gravimetrically. The following protocol is
suggested for determining % moisture:

7.2.1 Mark and weigh an aluminum weighing pan using an analytical balance. Record weight; tare

balance.

7.2.2 Place 5 to 10 g of matrix (free from unrepresentative pebbles and organic matter) into the pan;
record weight.

7.2.3 Place the pan and its contents into a drying oven heated to 103°C.

7.2.4 Dry the matrix for a period of 4 to 6 hours (or until weight is constant).

7.2.5 Remove the pan from the oven and allow to cool to room temperature.

7.2.6 Weigh the pan and record the weight.

7.2.7 Calculate the % moisture and the MCF (see 7.6)

7.3 Calibration: Calibrate the analytical system via the external standard method, in which response factors
(RF) for each compound are obtained by the analysis of a standard mix of known concentration. Following the
analysis of this known standard mix, create an electronic file establishing each peak's identity, retention time (RT),
RF, and known concentration. Determine the RF for each peak by dividing the known concentration by the peak
response (area or height units) of the associated peak. For initial calibration, determine each compound's average RF
by averaging the peak response results generated for the initial linearity study. Program these average RFs into the
integrator to allow for direct concentration reading of contaminants found in subsequent sample analyses.

7.3.1 Initial linearity:

7.3.1.1 Generate an initial 3-point calibration curve by the analysis of multiple aliquot

injections of calibration standard. For example, if the calibration standard is created such that a 2-

FMC-S-004-4

-------
(iL spike yields results at the level of the reported detection limits, a 3-point calibration curve may
be achieved by the analysis of 2 |iL, 5 |iL, and 10 (iL aliquot spikes.

7.3.1.2 Compute the percent relative standard deviation (%RSD see 7.5.1) based on each
compound's RFs (see 7.6) to determine the acceptability (linearity) of the curve. The %RSD should
be less than 20 percent. Reanalyze standard runs yielding data that does not meet the %RSD
criterion.

7.3.2 Continuing calibration:

7.3.2.1 Update the calibration of the analytical system 3 times daily: (1) preceding the
daily analyses, (2) midday, and (3) after the daily analyses.

7.3.2.2 Analyze standards run for continuing calibration purposes at a level equal to the
reported detection limits. Continuing calibration RFs for each parameter should fall within 25
percent difference (%D, see 7.5.3) of the average RF calculated for that particular compound during
the initial linearity study. Qualify data associated with individual parameter not meeting the %D
criterion as suspect.

7.3.2.3 Conduct continuing calibration at a concentration level equal to the reported
detection limits.

7.3.3 Peak identification: Compound identities may be substantiated by the analysis of each
individual component, thereby, documenting compound retention time.

7.4 Gas Chromatography

7.4.1 Analytical sequence: Conduct analyses in sets of 10, whenever possible, with 1 laboratory
duplicate spike analysis run per set. Bracket each set of sample analyses by the analysis of a standard, with
a method blank analysis following each standard run. The number of analyses per sample set and the
associated quality assurance/quality control (QA/QC) varies per contract. Consult the project work plan to
verify that all contractual obligations were met.

7.4.2 First strip sample contaminants from the matrix by means of methylene chloride extraction
(see 7.1). Introduce a 2- to 5-(iL aliquot of the sample extract onto the head of a previously conditioned
analytical column by means of direct injection technique. The semivolatile contaminants are then resolved
by temperature-programmed gas chromatography in which the action of carrier gas flow, elevated
temperatures, and the affinity each semivolatile compound has for the phases of the column packing cause
the contaminants to separate into bands. As the bands of contaminants elute from the column, they are
recognized by an FID. Detector signals are then processed by a previously programmed integrator. As long
as analytical conditions remain constant, each semivolatile compound will elute at a characteristic RT. In
this manner, sample contaminants are identified and quantified by comparison to a run of standard mix of
known concentration.

7.4.3 Under the following run conditions, most compounds of interest will elute within 32 minutes:

Run Parameter

Setting

Initial Column Temperature

100°C

Initial Hold Time

1 min

FMC-S-004-5

-------
Rate

10°C/min

Final Column Temperature

300°C

Carrier Gas Flow

20 mL/min

These conditions will need to be adjusted as necessary in order to optimize the resolution of the specific
compounds of interest.

7.5 Calculations

7.5.1	Calculate %RSD using the following equation:

ST)

%RSD = — x 100
X

where:

A (x - x)2
SD = > 			

M N - 1

and X is the mean of initial RFs (per compound).

7.5.2	Calculate relative percent difference (RPD) values using the following equation:

D1 ~ D2
RPD = 	i	— x 100

+ g2>

2

where: D[ =	First sample value, and

D2 =	Second sample value.

7.5.3 Calculate the %D using the following equation:

X, - X„

%D =

Xi

where: X[ =	RF of first result, and

X2 =	RF of second result.

7.5.4 Calculate percent recovery (%R) using the following equation:

%* = SSR ~ SR x 100

s

where: SSR =	Spike sample results,

SR =	Sample result, and

S	=	Amount of spike added.

FMC-S-004-6

-------
7.6 Sample Quantitation: Due to the process and the need to correct the final value for moisture content,
the quantitation of semivolatile contaminants in solid matrix sample is based upon the following formula:

Concentration (]ig/kg)

target peak response^sample) x RF x DF x final volume (mL)

wt of sample extract (g) x % solids

where: RF

Target analvte concentration in std (\ieAS)
Target analyte peak response in std

% solids

100 - % moisture

% moisture

wet wt - Dry wt x 100
wet wt

8.0 QUALITY CONTROL

8.1 Overview

8.1.1 Field screening generates Level II data. As Level II data, the concurrent analysis of
laboratory duplicates and matrix spike analyses and the use of surrogate spike compounds is not required.
However, beyond the maintenance of practical Standard Operating Procedures (SOPs), certain elements of
QC (if opted) can greatly enhance the interpretation of and the confidence in the data generated. These
traditional elements of QC are discussed here as to how they are adapted to meet the demands of a
successfully applied field screening QA/QC program.

8.1.2 The primary purposes of an appropriate QA/QC program are to: (1) substantiate system
performance and give credence to the accuracy of the results generated, (2) to define aberrations and give
guidance to the interpretation of data, and (3) to achieve these goals through realistic efforts that do not
impede the forward progress of the analytical set.

8.1.3 The discussion presented here deals with only direct analytical QC. Additional elements of
QA/QC, such as field duplicate sample submissions, blind spike analysis, and external audits are not
discussed. Also not discussed are elements of QA/QC that are inherent to good chromatographic technique.
Examples of these accepted laboratory practices include (but are not limited to) the following: (1) the proper
conditioning of analytical columns and traps, (2) use of the solvent flush technique for the creation of
standards and for direct injections, and (3) the appropriate maintenance of selected detectors. Details
regarding these accepted practices are given in the referenced methodologies.

8.2 Laboratory Duplicates: One laboratory duplicate should be analyzed per sample set. Laboratory
duplicate analyses should generate results of RPD within 30 percent (see 7.5.2).

FMC-S-004-7

-------
8.5 Method Blanks: Method blanks are prepared and analyzed in exactly the same manner as sample
matrices. A method blank analysis should follow every standard run and sample of high concentration. Ideally,
method blank results should yield no interferences to the chromatographic analysis and interpretation of target
compounds. If interferences are present, associated data should be qualified as suspect and/or target detection limits
should be adjusted accordingly.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-S-004-8

-------
FASP Method Number F050.001

CHLORINATED PESTICIDES IN SOIL

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various organochloride pesticides in soil and sediment samples.

1.2 This method yields tentative identification and estimated quantitation of the analytes listed in Table 1.
Approximate quantitation limits are also listed in Table 1. Reported values are on an "as-received" basis; no dry
weights are used.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil or sediment is placed in a screw-cap culture tube. A small amount of
methanol is added to bind the water in the sample. The sample is extracted with a measured volume of hexane. An
optional cleanup involves treating an aliquot of the hexane extract with concentrated sulfuric acid. The use of sulfuric
acid as a cleanup step may not be appropriate in all cases. Many chlorinated pesticides are sensitive to acid and are
rapidly degraded (see Table 2). The cleanup step for these pesticides should use an alternate method such as Florisil.
Analysis is performed with a gas chromatograph (GC) equipped with an electron capture detector (ECD) and either
a packed glass column or a wide-bore capillary column under either isothermal or temperature-programmed oven
conditions. Identification is based on comparison of retention times between samples and standards. Quantitation
is by the external standard method.

3.0 INTERFERENCES

3.1 Phthalate esters are common interferents encountered in pesticide analyses. Interference may be
minimized by use of pesticide grade or ultrapure reagents, exhaustive cleanup of glassware, and avoidance of plastic
materials in laboratory operations. Phthalate interferences may be avoided through the use of selective detectors such
as Hall electrolytic conductivity detectors (ELCD).

3.2 The use of phenolic caps without Teflon liners should be avoided. Phenolic caps may deteriorate when
exposed to solvents and concentrated acid, causing interfering peaks in a chromatogram. The analytical system must
be demonstrated to be free from contamination under conditions of the analysis by running laboratory reagent blanks.

3.3 GC interference by sample carryover may be minimized by use of disposable glassware during sample
preparation and by use of the maximum possible number of rinse cycles on automatic injection systems or by
thoroughly rinsing syringes used in manual injections.

FMC-P-001-1

-------
Table 1

FASP Method F050.001 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Chlorinate
Pesticides

CAS Number

Quantitation Limits
Soil/Sediment**
(Hg/kg)

a-BHC

319-84-6

25

fl-BHC

319-85-7

25

S-BHC

319-86-8

25

y-BHC (Lindane)

58-89-9

25

Heptachlor

76-44-8

25

Aldrin

309-00-2

25

Heptachlor Epoxide

1024-57-3

25

Endosulfan I

959-98-8

25

Dieldrin

60-57-1

50

4,4'-DDE

72-55-9

50

Endrin

72-20-8

50

Endosulfan II

33212-65-9

50

4,4'-DDD

72-54-8

50

Endosulfan Sulfate

1031-07-8

50

4,4'-DDT

50-29-3

50

Endrin Ketone

53494-70-5

50

Methoxychlor

72-43-5

250

a-Chlordane

57-74-9

250

T oxaphene

8001-35-2

500

*	Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided

for guidance and may not always be achievable.

** Quantitation limits listed for soil and sediment are based on wet weight.

FMC-P-001-2

-------
Table 2

CHLORINATED PESTICIDE DEGRADATION WITH TIME AFTER
TREATMENT WITH CONCENTRATED SULFURIC ACID

Chlorinated Pesticides

CAS Number

Approximate* Percent Loss**

24 hours

48 hours

168 hrs

a-BHC

319-84-6

None***

None

None

fl-BHC

319-85-7

None

None

None

S-BHC

319-86-8

None

None

None

y-BHC (Lindane)

58-89-9

None

None

None

Heptachlor

75-44-8

10

15

20

Aldrin

309-00-2

30

50

75

Heptachlor Epoxide

1024-57-3

25

40

70

Endosulfan I

959-98-8

	

	

100

Dieldrin

60-57-1

100

100

100

4,4'-DDE

72-55-9

None

None

None

Endrin

72-20-8

100

100

100

Endosulfan II

33212-65-9

	

	

100

4,4'-DDD

72-54-8

None

None

None

Endosulfan Sulfate

1031-07-8

None

None

None

4,4'-DDT

50-29-3

None

None

None

Endrin Ketone

53494-70-5

	

	

	

Methoxychlor

72-43-5

	

	

	

Chlordane

57-74-9

None

None

None

T oxaphene

8001-35-2

None

None

None

Highly variable/matrix dependent. Should be verified by the analyst before routine use.

After treatment with H2S04 over the specified period of time.

No significant loss.

Not measured.

FMC-P-001-3

-------
3.4 Soap residues remaining on improperly rinsed glassware may degrade aldrin, heptachlor, and
organophosphorus pesticides.

3.5 Many interfering organic compounds can be eliminated using the sulfuric acid cleanup listed in this
method. However, if a sample contains percent-level concentrations of hydrocarbon-based oils, acid cleanup will not
remove all 4 contaminants. It is possible that a significant shift in retention times will occur when narrow-bore (0.25
and 0.32 mm) capillary columns are used in the GC analysis. Therefore, wide-bore (0.53 mm or greater) capillary
columns should be used.

3.6 Samples containing free sulfur or hexane-soluble organosulfur compounds may yield interfering GC
peaks. Cleanup of the extract can be made using copper turnings or filings. Mercury metal is sometimes used for
this purpose, but should be avoided in mobile laboratory operations.

3.7 Interferences coextracted from samples are matrix and site specific. It is possible that cleanups used
in either FASP or Regular Analytical Services (RAS) CLP methods may fail to eliminate interferences. Highly
specialized CLP Special Analytical Services (SAS) techniques may be required to produce acceptable analytical
results.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are two GC options that meet the requirements of this method. Other
configurations, not described herein, may also meet the method requirements.

4.1.1. Gas chromatograph. option 1: An analytical system complete with an isothermal GC capable
of operation at elevated temperatures and all necessary accessories including injector and detector systems
designed or modified to accept packed analytical columns is required. The system shall have a data handling
system attached to the detector that is capable of retention time labeling, relative retention time comparisons,
and peak height and peak area measurements.

4.1.1.1 Column 1: 1.8 m x 3.0 mm I.D. glass column packed with GP 1.5%
SP-2250/1.95% SP-2401 on 100/120 Supelcoport (Supelco), or equivalent.

4.1.1.2 Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco), or equivalent.

4.1.1.3 Detector: Linearized ECD with optional makeup gas supply at the detector's inlet.

4.1.1.4 Gas supply: The carrier gas and makeup gas (if required) should be ultrapure 5
percent methane in argon, or equivalent. All gases should pass through oxygen traps prior to the
GC to prevent degradation of the column's analytical coating and detector foil.

4.1.2 Gas chromatograph. option 2: An analytical system complete with a
temperature-programmable GC and all necessary accessories including injector and detector systems
designed or modified to accept megabore capillary analytical columns is required. The system shall have
a data handling system attached to the detector that is capable of retention time labeling, relative retention
time comparisons and peak height and peak area measurements.

4.1.2.1 Column: 15 m x 0.53 mm I.D. DB-608 fused silica capillary column (FSCC)
(J&W Scientific), or equivalent.

4.1.2.2 Detector: Linearized ECD using a system with makeup gas supply at the detector's
capillary inlet.

FMC-P-001-4

-------
4.1.2.3 Gas supply: The carrier gas should be ultrapure helium. The makeup gas should
be ultrapure 5 percent methane in argon, or equivalent. All gases should pass through oxygen traps
prior to the GC to prevent degradation of the column's analytical coating and detector foil.

4.2	Other Laboratory Equipment

4.2.1	Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps, for extraction; disposable 16 mm x 100 mm borosilicate glass culture tubes with
Teflon-lined caps, for acid cleanup.

4.2.2	Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3	Spatulas: Stainless steel, micro and semi-micro.

4.2.4	Microsvringe: 10-(iL.

4.2.5	Balance: Top-loading, capable of weighing to 0.01 g for weighing samples.

4.2.6	Micropipets: 10- to 1,000-^L.

4.2.7	Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and 25-mL.

4.2.8	Volumetric flasks: 10-, 25-, 50-, 100-mL.

4.2.9	Vortex mixer: Vortex Genie or equivalent.

4.2.10	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.11	Amber storage bottles: 100- and 500-mL.

4.2.12	Autosampler vials: 1- or 2-mL with Teflon-lined screw caps.

4.2.13	Graduated centrifuge tubes: 10-mL with ground glass stoppers.

4.2.14	Oxygen traps: Supelpure-O-Trap and OMJ-1 Indicating Tube or equivalent.

4.2.15	Leak detector: Snoop Liquid or equivalent for packed column operations or GOW-MAC
gas leak detector or equivalent for megabore capillary operations.

4.2.16	Timer: 0 to 10 minute range.

4.2.17	Teflon wash bottles: 500-mL.

4.2.18	Laboratory oven: Capable of maintaining temperatures of greater than or equal to 200°C.

4.2.19	Chromatographic data stamps: Used to record instrument operating conditions.

4.3	Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

FMC-P-001-5

-------
5.1 Solvents

5.1.1 Methanol: Pesticide quality, or equivalent.

5.1.2 Hexane: Pesticide quality, or equivalent.

5.1.3 Acetone: Pesticide quality, or equivalent.

5.1.4 Isooctane: Pesticide quality, or equivalent.

5.2 Miscellaneous Reagents

5.2.1 Reagent water: Reagent water is defined as water in which an interferent is not observed at
the quantitation limit (QL) of the analyte of interest. Reagent water may be generated using a carbon filter
bed containing activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent) or a water purification
system (Milli-Q Plus with Organex Q cartridge, Barnstead Water-1 system [provided with Base Support
Facilities], or equivalent), or purchased from commercial laboratory supply houses.

5.2.2 Sodium sulfate: Reagent, anhydrous, granular. Preconditioned by heating for 24 hours at
200°C and storing in clean glass containers with Teflon liners.

5.2.3 Nitric acid: 10 percent volume/volume.

5.2.4 Sulfuric acid: Concentrated; reagent quality.

5.2.5 Copper turnings or filings: Remove oxides by treating with dilute nitric acid, rinse with
distilled water to remove all traces of acid, rinse with acetone, and dry under a stream of nitrogen.

5.3 Gases

5.3.1 Five percent methane in argon: Ultrapure or chromatographic grade (always used in
conjunction with oxygen trap).

5.3.2 Helium: Ultrapure or chromatographic grade (always used in conjunction with oxygen trap).

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as
manufacturer-certified solutions. These standards are viable for 1 year unless otherwise noted by the supplier.
Single-pesticide standards may be used; however, standard mixtures (excluding chlordane and toxaphene) of
pesticides are recommended. Multicomponent pesticides such as chlordane and toxaphene should be prepared in
unique standard solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of three concentration levels for each
analyte of interest. This procedure is done through volumetric dilution of the stock standards with isooctane. The
lowest concentration standard should be approximately two times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

FMC-P-001-6

-------
5.7 Matrix Spike Solutions: Matrix spike solutions should be prepared by dilution of stock standard
solutions so that no more than 250 (iL of spike solution is required to provide a final sample spike level within the
advised quality control (QC) limits.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Soil samples should be shipped in 4-ounce, wide-mouthed
glass jars with Teflon-lined caps.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1)
December 1988, is required for sample tracking. The maximum holding times for soil chlorinated pesticide samples
are 7 days between collection and extraction, and 40 days between extraction and analysis.

7.0 PROCEDURE

7.1 Extraction

The sample extraction technique for chlorinated pesticides in soil or sediment is as follows:

7.1.1 Add 2 to 3 grams of well-homogenized sample to a tared and labeled 150-mm culture tube,
reweigh to the nearest 0.01 g. Record weights.

7.1.2 Optional: Add approximately 1 g of sodium sulfate. Recommended for samples of high
moisture content.

7.1.3 Add 1.0 mL of nanograde methanol by repipet to the culture tube and cap.

7.1.4 Vortex at maximum speed for 30 seconds.

7.1.5 Add 10.0 mL of nanograde hexane by repipet to the culture tube and recap.

7.1.6 Vortex at maximum speed for 60 seconds.

7.1.7 Transfer a 6 to 8 mL aliquot of the hexane layer to a labeled 100-mm culture tube using a
disposable pasteur pipet.

7.1.8 Add 1.0 mL of concentrated sulfuric acid by repipet to the aliquot and recap. (This cleanup
step should not be used initially when analyzing for heptachlor, heptachlor epoxide, dieldrin, endrin, endrin
aldehyde, endosulfan I, endosulfan II, and endosulfan sulfate. Degradation of these compounds is significant
on contact with sulfuric acid. See Table 2)

7.1.9 Vortex at maximum speed for 60 seconds.

7.1.10 Centrifuge for 5 minutes.

7.1.11 Transfer approximately 1 mL of extract into a Teflon-lined screw-cap autosampler vial,
using a disposable Pasteur pipet. Avoid transfer of any of the acid layer.

7.1.12 Optional: Enhanced sensitivity may be achieved by transferring 5.00 mL of hexane extract
to a 10-mL graduated centrifuge tube and reducing the solvent volume to between 0.2 and 0.4 mL by

FMC-P-001-7

-------
standard low-temperature N2 blowdown techniques, and making the final sample extract volume 0.50 mL
by rinsing tube walls with hexane.

7.1.13 The sample extract is now ready for GC injection.

7.2 Cleanup

7.2.1 General extract cleanup: The use of sulfuric acid in a routine cleanup step may not be
appropriate in all cases. Many chlorinated pesticides are sensitive to acid and are rapidly degraded. The
effect of concentrated sulfuric acid on chlorinated pesticides is shown in Table 2. Both positive and negative
effects of acid treatment on a sample may be used as an aid in the identification of specific chlorinated
pesticides.

7.2.2 Sulfur removal

7.2.2.1 Sulfur interference: Elemental sulfur may be encountered in many sediment
samples, marine algae, and some industrial wastes. The solubility of sulfur in various solvents is
very similar to that of chlorinated pesticides; therefore, the sulfur interference follows the pesticides
through the normal extraction and cleanup techniques. Sulfur will be quite evident in gas
chromatograms obtained from ECDs. If the GC is operated at the normal conditions for chlorinated
pesticide analysis, the sulfur interference can completely mask a large region of the chromatogram.
One technique for the elimination of sulfur follows.

7.2.2.2 Summary of method: The sample extract is combined with clean copper. The
mixture is shaken, and the extract is removed from the sulfur cleanup reagent.

7.2.2.3 Procedure for sulfur cleanup:

7.2.2.3.1 The copper must be reactive; therefore, all oxides of copper must be
removed so that the copper has a shiny, bright appearance (see Section 5.2).

7.2.2.3.2 Transfer 5 mL of final extract described in Section 7.1 (Step 7.1.10) to
a 16 mm x 100 mm screw cap culture tube with a Teflon-lined cap.

7.2.2.3.3 Add approximately 2 g of cleaned copper to the tube. Mix for at least
1 minute on the vortex mixer. This step may be repeated if sulfur removal is incomplete.

7.2.2.3.4 Resume the procedure described in Section 7.1 at Step 7.1.11.

7.2.2.3.5 The effect of copper on chlorinated pesticide recovery is shown in Table

7.2.3 Solid phase extraction technology: Solid phase extraction (SPE) technology (e.g., Sep-Pak)
or mini-Florisil columns may provide an acceptable alternative to acid cleanup for chlorinated pesticide
extracts.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
GC system is functioning properly; that is, conditions exist such that resolution, retention times,

FMC-P-001-8

-------
response reporting, and interpretation of GC spectra are within acceptable quality control limits
(Section 7.5). Using at least 3 calibration standards for each chlorinated pesticide or pesticide
mixture prepared as described in Section 5.0, generate initial calibration curves (response versus
mass of standard injected) for each target analyte chlorinated pesticide (see Section 7.4 for
chromatographic procedures).

7.3.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.5) based
on each pesticide's 3 calibration factors (CFs, see Section 7.5) to determine the acceptability
(linearity) of the curve. Unless otherwise specified, the %RSD must be less than or equal to 25
percent or the calibration is invalid and must be repeated. Establish a new initial calibration curve
anytime the GC system is altered (e.g., new column, change in gas supply, or change in oven
temperature) or shut down.

7.3.2 Continuing calibration:

7.3.2.1 Recheck the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing
calibration validation. This single point analysis follows the same analytical procedures used in
the initial calibration. Instrument response is used to compute the CF, which is then compared to
the mean initialcalibration factor (CF), and a relative percent difference (RPD, see Section 7.5) is
calculated. Unless otherwise specified, the RPD must be less than or equal to 25 percent for the
continuing calibration to be considered valid. Otherwise, the calibration must be repeated. A
continuing calibration remains valid for a maximum of 24 hours providing the GC system remains
unaltered during that time.

7.3.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

7.3.3 Final calibration: Obtain the final calibration at the end of each batch of samples analyzed.
The allowable RPD between the mean initial calibration and final calibration factors for each analyte must
be less than or equal to 50 percent. A final calibration that achieves less than or equal to 25 percent RPD
for all target analytes may be used as an ongoing continuing calibration.

7.4 Instrumental Analysis

7.4.1 Instrument parameters: Table 4 summarizes an example of acceptable instrument operating
conditions for the GC. Other instruments, columns, and chromatographic conditions may be used if this
method's QC criteria are met.

FMC-P-001-9

-------
Table 3

EFFECT OF COPPER TREATMENT ON CHLORINATED PESTICIDE RECOVERY*

Pesticide

Copper**

Lindane

94.8

Heptachlor

5.4

Aldrin

93.3

Heptachlor Epoxide

96.6

DDE

102.9

DDT

85.1

BHC

98.1

Dieldrin

94.9

Endrin

89.3

Table from EPA SW-846 Method 3660.

** Percent recoveries cited are averages based on duplicate analyses for all compounds other than for Aldrin
and BHC. For Aldrin, 3 determinations were averaged to obtain the result. Recovery of BHC is based on one
analysis.

7.4.2 Chromatograms:

7.4.2.1	Computer reproductions of chromatograms that are attenuated to ensure all peaks
are on scale up to a 100-fold range are acceptable. However, this can be no greater than a 100-fold
range. This is to prevent retention time shifts by column or detector overload. Generally, peak
response should be greater than 25 percent and less than 100 percent of full-scale deflection to
allow visual recognition of the chlorinated pesticides.

7.4.2.2	The following information must be recorded on each chromatogram:

•	Instrument and detector identification;

•	Column packing coating, length, and I.D.;

•	Oven temperature;

•	Injector/detector temperature;

•	Gases and flow rates;

•	Site name;

•	Sample number;

•	Date and time; and

•	GC operator initials.

FMC-P-001-10

-------
Table 4

EXAMPLE FASP PACKED COLUMN
ISOTHERMAL GC OPERATING CONDITIONS

Instrument:	Shimadzu GC Mini-2 equipped with Linearized ECD

Integrator:	Shimadzu Chromatopac C-R3A Data Processor

Column:	1.8 m x 3 mm glass column packed with 1.5% SP-2250/1.95%

SP-2401 on 100/120 Supelcoport

Carrier Gas:	Ultrapure 5 percent methane in Argon at a flow rate of

40 mL/min

Column (Oven) Temperature:	Dependent on specific chlorinated pesticide; isothermal, range

190°C to 225°C

250°C

Dependent on specific chlorinated pesticides and matrix, range
approximately 15 to 30 min

Solvent flush manual injection or automated sample injection
is recommended for chlorinated pesticide analysis. For the
solvent flush technique, the syringe barrel plus 1 (iL of
nanograde hexane, 0.5 (iL of air, and 2.0 to 3.0 (iL (measured
to the nearest 0.05 |±L) of sample extract are sequentially drawn
into a 10-(iL syringe and immediately injected into the GC.
Extreme care must be taken to avoid contamination of the
syringe needle with sulfuric acid when loading the syringe.
Injection of acid will damage the analytical column and
detector.

7.4.3 Chlorinated pesticide identification:

7.4.3.1	Qualitative identification of chlorinated pesticides is based on retention time, as
compared to standards on a single column and to a lesser extent on ECD selectivity. Qualitative
identification of multicomponent mixtures (chlordane and toxaphene) is based on both retention
time and relative peak intensity matching of sample with standard chromatograms. Chlordane and
toxaphene are multiple component mixtures of compounds that produce characteristic spectral
patterns with relatively constant proportions. Except in cases where the mixture has suffered severe
weathering, the chromatographic fingerprint is easily recognized by an experienced chemist.
Because chlordane and toxaphene are relatively inert, their identification is further confirmed by
their presence after digestion of interferences with concentrated sulfuric acid.

7.4.3.2	Qualitative identification of chlordane and toxaphene is based in part on ECD
selectivity, but primarily on retention time and spectral pattern as compared to known standards on
a single selected column. A second dissimilar column (e.g., 3% SP-2100 or 3% OV-1 on 100/120
Supelcoport) may be used for confirmation.

FMC-P-001-11

Detector/Injector Temperature:
G.C. Analysis Time:

Standard/Sample Injection:

-------
7.4.3.3 Generally, individual peak retention time windows should be less than or equal
to 5 percent for packed column analyses and less than or equal to 2 percent for megabore capillary
columns.

7.4.3.4 For the purpose of FASP analyses, relative peak intensity (height or area) matching
for positive identification is based on the chemist's best professional judgment in consultation with
more experienced spectral data interpretation specialists, when required. It is possible that
interferences may preclude positive identification of an analyte. In such case, the chemist should
report the presence of the interferents with a maximum possible pesticide concentration (see section
7.5.4).

7.4.4 System Performance: Degradation of chlorinated pesticides may occur in the GC system,
especially if the injector or column inlet is dirty. System performance is tested by analysis of a
4,4'-DDT/endrin mixture and quantifying the percent breakdown of these compounds (see section 7.5.5).

7.4.5 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided in Appendix B of this method.

7.4.6 Analytical sequence:

7.4.6.1 Instrument blank.

7.4.6.2 Initial calibration.

7.4.6.3 Check standard and/or performance evaluation sample (if available).

7.4.6.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.6.5 Associated QC lot method blank.

7.4.6.6 Twenty samples and associated QC lot spike and duplicate.

7.4.6.7 Repeat sequence beginning at step 7.4.6.6 until all sample analyses are completed
or another continuing calibration is required.

7.4.6.8 Final calibration when all sample analyses are complete.

7.5 Calculations

7.5.1 Initial calibration

7.5.1.1 GC response to single component chlorinated pesticides is measured by
determining calibration factors (CFs). They are the ratio of the response (peak area or height) to
the mass injected. For multicomponent mixtures such as chlordane and toxaphene, calculations are
normally based on 3 to 5 major peaks identified as resulting primarily from a single pesticide. The
chemist may select from any of the major peaks free of interferences so long as the same peaks are
used for both standard and sample calculations.

7.5.1.2 Calculate the calibration factor for each individual peak, or in the case of chlordane
and toxaphene, the summed area of 3 to 5 peaks for each chlorinated pesticide in the initial
calibration. The integrator may be employed to make all of these computations.

FMC-P-001-12

-------
CF

Area of Peak

Mass Injected (nanograms)

7.5.1.3 Using the calibration factors, calculate the %RSD for each chlorinated pesticide
at the 3 concentration levels using the following equation:

ST)

hRSD = — x 100

where SD, the standard deviation, is given by

SD

\

(X. - X):

i

N-l

where: X; =	Individual calibration factor (per analyte),

X =	Mean of initial 3 calibration factors (per analyte),

N =	Number of calibration standards.

7.5.1.4 The %RSD must be less than or equal to 25.0 percent.

7.5.2 Continuing calibration:

7.5.2.1	Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations. Midrange standards for all initial calibration analytes must be analyzed as
continuing calibration standards at specified intervals (less than or equal to 24 hours).

7.5.2.2	The RPD calculated using the following equation for each analyte must be less
than or equal to 25 percent.

\~ - CF J
RPD = 				— x 100

CFx + CFc
2

where: CF, =	Mean CF from the initial calibration for each analyte

CFc =	Measured CF from the continuing calibration for the same analyte.

7.5.3 Final calibration:

7.5.3.1 The final calibration is obtained at the end of any batch of samples analyzed.

FMC-P-001-13

-------
7.5.3.2 The RPD between the mean initial calibration and final calibration factors for each
analyte must be less than or equal to 50 percent. A final calibration that achieves less than or equal
to 25 percent RPD may be used as an ongoing continuing calibration.

| CF - CF |
RPD = -	-	— x 100

cft + cff
2

where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.4 Sample quantitation:

7.5.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations.

Concentration	^t1 (D)

(Wet weight) ^g g	(A ) (V.) {W )

\	s /	\	j_ /	\	s /

where: Ax	=	Response for the analyte to be measured

As	=	Response for the external standard

Is	=	Amount of standard injected (ng)

V;	=	Volume of extract injected (|iL)

Vt	=	Volume of total extract (nL)

Ws	=	Weight of sample extracted (g)

E	=	Enhanced sensitivity factor (if Section 7.1 extract concentration is used,

E = 10; if no enhancement, E= 1)

D	=	Dilution factor, if used.

7.5.4.2	Report results in micrograms per kilogram (ng/kg) without correction for blank,
spike recovery, or percent moisture.

7.5.4.3	Compute single-component chlorinated pesticide sample concentrations from
individual peak responses. Sample concentrations of multicomponent mixtures (chlordane and
toxaphene) are based on the summed response (peak areas) of the peaks identified in Section 7.5.1.

7.5.4.4	Weathering of chlordane and toxaphene often results in the uneven loss of different
components, so that sample spectra rarely match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum
possible concentration (qualified as less than the numerical value) that allows the data user to
determine if additional (e.g., CLP, RAS, or SAS) work is required or if the reported concentration
is below action levels and project objectives and DQOs have been met, to forego further analysis.

FMC-P-001-14

-------
7.5.4.5 Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) that allows the data
user to determine if additional (e.g., CLP, RAS, or SAS) work is required or, if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

7.5.5 System performance:

7.5.5.1 Evaluate the GC system by measuring DDT and Endrin breakdown. A standard
must be prepared containing only 4,4' -DDT and endrin at the same concentration as the mid-level
standard.

7.5.5.2 Degradation is measured by injecting the standard, quantitating the degradation
products of 4,4'-DDT (4,4'-DDE and 4,4'-DDD) and endrin (endrin ketone and endrin aldehyde),
and calculating the percent breakdown as follows:

o , , , Peak Area of DDE + DDD

%DDT breakdown = x 100

Peak Area of DDT + DDE + DDD

Peak Area of Endrin Aldehyde

+ Endrin Ketone

iEndrm breakdown = x 100

Peak Area of Endrin + Endrin

Aldehyde + Endrin Ketone

7.5.5.3 System performance must be checked after each continuing calibration. The
maximum allowable percent breakdown for either DDT or Endrin or the sum of both the DDT +
Endrin percent breakdowns is less than or equal to 25 percent. System performance criteria must
be met before analyses may proceed.

8.0 QUALITY CONTROL

Quality Control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 5. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-P-001-15

-------
Table 5

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F050.001 (Chlorinated Pesticides in Soil)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD
(%)

Alpha-BHC

30 to 200

+ 100

Beta-BHC

30 to 200

+ 100

Delta-BHC

30 to 200

+ 100

Gamma-BHC (Lindane)

30 to 200

+ 100

Heptachlor

30 to 200

+ 100

Aldrin

30 to 200

+ 100

Heptachlor Epoxide

30 to 200

+ 100

Endosulfan I

30 to 200

+ 100

Dieldrin

30 to 200

+ 100

4,4'-DDE

30 to 200

+ 100

Endrin

30 to 200

+ 100

Endosulfan II

30 to 200

+ 100

4,4'-DDD

30 to 200

+ 100

Endosulfan Sulfate

30 to 200

+ 100

4,4'-DDT

30 to 200

+ 100

Endrin Ketone

30 to 200

+ 100

Methoxychlor

30 to 200

+ 100

Chlordane

30 to 200

+ 100

T oxaphene

30 to 200

+ 100

*	Before acid cleanup: If the concentration of an analyte is less than 5 times the QL, advisory control limits

for duplicate RPD values becomes ±3 times the QL for that individual analyte.

FMC-P-001-16

-------
9.0 METHOD PERFORMANCE

9.1 The following is an example of a gas chromatogram for several commonly encountered chlorinated
pesticides using an ECD.

Figure 1

Gas Chromatogram - Chlorinated Pesticides

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-P-001-17

-------
9.2 Method F050.001 examples of QA/QC results: Spike and duplicate sample results are presented as
examples of FASP Method F050.001 empirical data (see Tables 6 and 7).

Table 6

FASP METHOD F050.001
CHLORINATED PESTICIDE SOIL MATRIX SPIKE PERCENT RECOVERY

Compound

Amount
Spiked
Og/kg)

Sample
Og/kg)

Sample
with
Spike
Og/kg)

Percent
Recovery
(%)

CLP
Matrix
Spike
Percent
Recovery
Limits
(%)

a-BHC

50

0

43.5

87



y-BHC (Lindane)

50

0

44

88

46-127

fl-BHC

50

0

37

74



Heptachlor

50

0

41

82

35-130

S-BHC

50

0

42

84



Aldrin

50

0

42

84

34-139

Heptachlor Epoxide

50

0

69

138



Endosulfan I

100

0

108

108



4,4'-DDE

100

0

92

92



Dieldrin

100

0

157

157

31-134

Endrin

100

0

102

102

42-139

4,4'-DDD

300

0

360

120



Endosulfan II

100

0

325

108



4,4'-DDT

300

0

386

129

23-134

Endrin Aldehyde

300

0

385

128



Endosulfan Sulfate

300

0

502

67



FMC-P-001-18

-------
Table 7

FASP METHOD F050.001
CHLORINATED PESTICIDE SOIL SPIKE TRIPLICATE PRECISION



Mean Percent

Standard

Compound

Recovery

Deviation



(%)

(%)

a-BHC

64

18

y-BHC (Lindane)

62

19

fl-BHC

74

39

Heptachlor

61

16

6-BHC

49

25

Aldrin

70

13

Heptachlor Epoxide

88

36

Endosulfan I

76

24

4,4'-DDE

74

16

Dieldrin

91

47

Endrin

77

18

4,4'-DDD

71

35

Endosulfan II

56

37

4,4'-DDT

81

35

Endrin Aldehyde

60

48

Endosulfan Sulfate

79

62

FMC-P-001-19

-------
10.0 REFERENCES

Information not available.

FMC-P-001-20

-------
APPENDIX A

FASP Method F050.001

Instrument Options:
GC System 1:

GC System 2:

GC System 3:

Data Handling System 1:
Data Handling System 2:
Data Handling System 3:

Shimadzu GC Mini-2 with linearized Electron Capture Detector (ECD), used for
isothermal, packed column analyses.

Shimadzu GC-mini 2 with linearized ECD modified with a Direct Conversion
and Makeup Gas Adapter for megabore capillary column operations and equipped
with a Shimadzu TP-M2R Temperature Programmer, used for
temperature-programmed megabore capillary column analyses.

Shimadzu GC-14A with linearized ECD, used for temperature-programmed
megabore capillary column analyses.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit and
Shimadzu FDD-1A Floppy Disk Drive.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-P-001-21

-------
APPENDIX B

FASP Method F050.001

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature:

Shimadzu GC Mini-2 equipped with linearized ECD.

Shimadzu Chromatopac C-R3A Data Processor.

1.8 m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401 on
100/120 Supelcoport.

Ultrapure 5 percent Methane in Argon at a flow rate of 30 to 40 mL/min.
Dependent on specific Aroclor, isothermal range 190°C to 225°C.

250oC.

FMC-P-001-22

-------
NUS SOP Number 5.6
FIELD SCREENING OF ORGANOCHLORINE PESTICIDES

fSOLID MATRIX)

1.0 SCOPE AND APPLICATION

1.1 The following methodology describes a modification of SW-846 analytical gas chromatographic
procedures suitable for the determination of organochlorine pesticide contaminants in solid matrix samples.

1.3 Table 1 provides a list of potential target compounds.

2.0 SUMMARY OF METHODS

In this methodology, a 5 g portion of solid sample is extracted using rapid field techniques. A 2- to 5-(iL
aliquot of sample extract is then directly injected onto an analytical column for the isothermal resolution of target
compounds. The organochlorine pesticide contaminants are detected by an electron capture detector (ECD). Detector
signals are processed and interpreted via a previously programmed integrator.

2.1 Low Level Analysis: Use of a 5 g portion of sample is suggested to achieve method detection limits
of approximately 25 Hg/kg.

2.2 Medium Level Analysis: Sample dilutions are achieved by diluting a portion of the sample extract (as
above) in an appropriate volume of isooctane.

3.0 INTERFERENCES

3.3 Artifacts, which manifest themselves as carryover in the next analytical run, can also occur within the
analytical apparatus whenever a highly contaminated sample is introduced. To preclude this, injection syringes are
repeatedly flushed with solvent, and the analytical column is baked for a short period of time following each direct
injection analysis.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph: Hewlett-Packard 5890, or equivalent. The analytical system should be equipped
for packed or capillary column analysis with isothermal oven and on-column injection capabilities.

FMC-P-002-1

-------
Table 1

SUMMARY OF POTENTIAL TARGET COMPOUNDS

Organochlorine Pesticide Analysis

	alpha-BHC	

	beta-BHC	

	delta-BHC	

	gamma-BHC	

	Aldrin	

	Chlordane	

	Dieldrin	

	Endosulfan I	

	Endosulfan II	

	Endosulfan sulfate	

	Endrin	

	Heptachlor	

	Heptachlor epoxide	

	4,4'-DDD	

	4,4'-DDE	

	4,4'-DDT	

4.2	Detector: ECD.

4.3	Analytical Column: Glass or stainless steel packed with 1.5% SP-2250/1.95% SP-2401 on 100/120
mesh Supelcoport. Alternatively, a 3% OV-1 on 80/100 mesh Supelcoport packed column or a suitable capillary
column may be used.

4.4	Syringes (assorted): 5-(iL, 25-(iL, 100-(iL, and 1-mL.

4.5	Analytical Balance: Capable of accurately weighing 0.0001 g.

4.6	Vials: 40-mL septum-seal for extraction.

4.7	Vials: 2-dram septum-seal for extract storage.

4.8	Glass Marking Pen: For labeling vials.

FMC-P-002-2

-------
4.9 Laboratory Timer: To use during the extraction process.

4.10 Pipets (assorted): 1-mL, 5-mL, and 10-mL disposable glass.

4.11 Refrigerator: Separate for sample and standard storage. Capable of maintaining a temperature of 4°C.

4.12 Oven: Constant temperature; for use in the determination of moisture content.

5.0 REAGENTS

5.1 Hexane: Pesticide grade, or equivalent.

5.2 Isooctane: Distilled in glass.

5.3 Neat Standards: 96 percent purity, or better, for each compound of interest.

5.4 Zero-grade Nitrogen: As carrier gas for the GC.

5.5 Anhydrous Sodium Sulfate: Used to remove moisture from the portion of soil prior to extraction.

5.6 Standards: Calibration standards containing the compounds of interest are prepared from commercially
purchased standard mixes or pure compounds. All standards are made and/or diluted using isooctane and are created
for use via a 2-^L direct injection. An example of a working calibration standard within a practical concentration
range follows:

Compound

Concentration (ng/^L)

Lindane

0.0125

Aldrin

0.0250

4,4'-DDT

0.0625

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Samples awaiting analysis are stored at 4°C in a dedicated refrigerator. If, because of loading, it is not
possible to analyze all samples taken daily, the suggested holding time for the analysis of organochlorine pesticides
in solid matrix is 5 days prior to extraction, and analysis within 30 days. If holding times are exceeded, the affected
data should be qualified as suspect.

7.0 PROCEDURE

7.1 Sample Preparation: Extract all samples prior to chromatographic analysis. A suggested extraction
protocol follows:

FMC-P-002-3

-------
7.1.1 Weigh and tare a 40-mL septum-seal vial using an analytical balance.

7.1.2 Add 5.0 g of sample matrix to the vial; record weight.

7.1.3 Add approximately 3 g of anhydrous sodium sulfate; mix thoroughly using a clean spatula.

7.1.4 Pipet exactly 8.0 mL of hexane into the vial.

7.1.5 Cap the vial and shake vigorously for 2 full minutes (alternatively, vial contents may be
sonicated).

7.1.6 Set the vial aside and allow the contents to settle for 5 minutes.

7.1.7 Pipet off the supernatant extract into a labeled 2-dram septum-seal vial.

7.1.8 Perform GC analysis by directly injecting 2 to 5 (iL of sample extract onto the GC's analytical

column.

7.2 Percent Moisture (% moisture') Determination: Use a moisture correction factor (MCF) to adjust the
value generated for the amount of contaminant present in a solid matrix sample so that the value reflects the true (dry
weight) concentration of contaminant. Determine moisture content gravimetrically. The following protocol is
suggested for determining % moisture:

7.2.1 Mark and weigh an aluminum weighing pan using an analytical balance. Record weight; tare

balance.

7.2.2 Place 5 to 10 g of matrix (free from unrepresentative pebbles and organic matter) into the pan;

record weight.

7.2.3 Place the pan and its contents into a drying oven heated to 103°C.

7.2.4 Dry the matrix for a period of 4 to 6 hours (or until weight is constant).

7.2.5 Remove the pan from the oven and allow to cool to room temperature.

7.2.6 Weigh the pan and record the weight.

7.2.7 Calculate the % moisture and the MCF (see 7.6)

7.3 Calibration: Calibrate the analytical system via the external standard method, in which response factors
(RF) for each compound are obtained by the analysis of a standard mix of known concentration. Following the
analysis of this known standard mix, create an electronic file establishing each peak's identity, retention time (RT),
RF, and known concentration. Determine the RF for each peak by dividing the known concentration by the peak
response (area or height units) of the associated peak. For initial calibration, determine each compound's average RF
by averaging the peak response results generated for the initial linearity study. Program these average RFs are
programmed into the integrator to allow for direct concentration reading of contaminants found in subsequent sample
analyses.

7.3.1 Initial linearity:

7.3.1.1 Generate an initial 3-point calibration curve by the analysis of multiple aliquot
injections of calibration standard. For example, if the calibration standard is created such that a 2-

FMC-P-002-4

-------
(iL spike yields results at the level of the reported detection limits, a 3-point calibration curve may
be achieved by the analysis of 2-\xL, 5-^L, and 10-(iL aliquot spikes.

7.3.1.2 Compute the percent relative standard deviation (%RSD see 7.5.1) based on each
compound's RFs (see 7.6) to determine the acceptability (linearity) of the curve. The %RSD should
be less than 20 percent. Reanalyze standard runs yielding data that does not meet the %RSD
criterion.

7.3.2 Continuing calibration:

7.3.2.1 Update the calibration of the analytical system 3 times daily: (1) preceding the
daily analyses, (2) midday, and (3) after the daily analyses.

7.3.2.2 Analyze standards run for continuing calibration purposes at a level equal to the
reported detection limits. Continuing calibration RFs for each parameter should fall within 25
percent difference (%D, see 7.5.3) of the average RF calculated for that particular compound during
the initial linearity study. Qualify data associated with individual parameter not meeting the %D
criterion as suspect.

7.3.2.3 Conduct the continuing calibration at a concentration level equal to the reported
detection limits.

7.3.3 Peak identification: Compound identities may be substantiated by the analysis of each
individual component, thereby documenting compound retention time.

7.4 Gas Chromatography

7.4.1 Analytical sequence: Conduct analyses in sets of 10, whenever possible, with 1 laboratory
duplicate spike analysis run per set. Bracket each set of sample analyses by the analysis of a standard, with
a method blank analysis following each standard run. The number of analyses per sample set and the
associated quality assurance/quality control (QA/QC) varies per contract. Consult the project work plan to
verify that all contractual obligations were met.

7.4.2 First strip the sample contaminants from the matrix by means of hexane extraction (see 7.1).
Introduce a 2- to 5-(iL aliquot of the sample extract onto the head of a previously conditioned analytical
column by means of direct injection technique. The organochlorine pesticide compounds are resolved
isothermally due to the affinity each compound has for the phases of the column packing as they migrate
(under flow) through the analytical column. As the contaminants elute from the column, they are recognized
by an ECD. Detector signals are then processed by a previously programmed integrator. As long as
analytical conditions remain constant, each type of organochlorine compound will elute at a characteristic
RT. In this manner, sample contaminants are identified and quantified by comparison to a run of standard
mix of known concentration.

7.4.3 Under the following run conditions, all commonly targeted organochlorine pesticides will
elute within 15 minutes:

Run Parameter

Setting

Injector Port Temperature

300°C

Isothermal Oven Temperature

215°C

FMC-P-002-5

-------
Detector Temperature

350°C

Carrier Gas Flow

70 mL/min

7.5 Calculations

7.5.1 Calculate %RSD using the following equation:

ST)

%RSD = — x 100
X

where:

A (x - x)2
SD = > 			

JV - 1

and X is the mean of initial RFs (per compound).

7.5.2 Calculate relative percent difference (RPD) values using the following equation:

D1 ~ D2
RPD = 	i	— x 100

+ g2>

2

where: D[ =	First sample value, and

D2 =	Second sample value.

7.5.3 Calculate the %D using the following equation:

X, - X„

bD =

Xi

where: X[ =	RF of first result, and

X2 =	RF of second result.

7.5.4 Calculate percent recovery (%R) using the following equation:

%* = SSR ~ SR x 100

s

where: SSR =	Spike sample results,

SR =	Sample result, and

S	=	Amount of spike added.

7.6 Sample Quantitation: Due to the need to correct the final value for moisture content, the quantitation
of pesticide contaminants in solid matrix is calculated based upon the following formula:

mcentration (]ig/kg)

target analyte peak responseisample) x RF x final volume (ml
wt of sample (g) x % solids

FMC-P-002-6

-------
where: RF

Target analvte concentration in std (\ieAS)
Target analyte peak response in std

% solids

100 - % moisture

% moisture

wet wt - dry wt x 100
wet wt

8.0 QUALITY CONTROL

8.1 Overview

8.1.1 Field screening generates Level II data. As Level II data, the concurrent analysis of
laboratory duplicates and matrix spike analyses and the use of surrogate spike compounds is not required.
However, beyond the maintenance of practical Standard Operating Procedures (SOPs), certain elements of
QC (if opted) can greatly enhance the interpretation of and the confidence in the data generated. These
traditional elements of QC are discussed here as to how they are adapted to meet the demands of a
successfully applied field screening QA/QC program.

8.1.2 The primary purposes of an appropriate QA/QC program are to: (1) substantiate system
performance and give credence to the accuracy of the results generated, (2) to define aberations and give
guidance to the interpretation of data, and (3) to achieve these goals through realistic efforts that do not
impede the forward progress of the analytical set.

8.1.3 The discussion presented here deals with only direct analytical QC. Additional elements of
QA/QC, such as field duplicate sample submissions, blind spike analysis, and external audits are not
discussed. Also not discussed are elements of QA/QC that are inherent to good chromatographic technique.
Examples of these accepted laboratory practices include (but are not limited to) the following: (1) the proper
conditioning of analytical columns and traps, (2) use of the solvent flush technique for the creation of
standards and for direct injections, and (3) the appropriate maintenance of selected detectors. Details
regarding these accepted practices are given in the referenced methodologies.

8.2 Laboratory Duplicates: One laboratory duplicate should be analyzed per sample set. Laboratory
duplicate analyses should generate results of RPD within 30 percent (see 7.5.2).

8.5 Method Blanks: Method blanks are prepared and analyzed in exactly the same manner as sample
matrices. A method blank analysis should follow every standard run and sample of high concentration. Ideally,
method blank results should yield no interferences to the chromatographic analysis and interpretation of target
compounds. If interferences are present, associated data should be qualified as suspect and/or target detection limits
should be adjusted accordingly.

FMC-P-002-7

-------
9.0 METHOD PERFORMANCE
Information not available.
10.0 REFERENCES

Information not available.

FMC-P-002-8

-------
FASP Method F050.002
CHLORINATED PESTICIDES IN WATER

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various organochloride pesticides in water samples.

1.2 Table 1 lists the compounds that may be determined by this method and approximate method
quantitation limits.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 This method yields tentative identification and estimated quantitation of the analytes listed in Table 1.
Report values are on an "as-received" basis.

1.5 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 A measured amount of water is placed in a volumetric flask. The sample is extracted with a measured
volume of hexane. An optional cleanup involves treating an aliquot of the hexane extract with concentrated sulfuric
acid. The use of sulfuric acid as a cleanup step may not be appropriate in all cases. Many chlorinated pesticides are
sensitive to acid and are rapidly degraded (see Table 2). The cleanup step for these pesticides should use an alternate
method such as Florisil. Analysis is performed with a gas chromatograph (GC) equipped with an electron capture
detector (ECD) and either a packed glass column or a wide-bore capillary column under either isothermal or
temperature-programmed oven conditions. Identification is based on comparison of retention times between samples
and standards. Quantitation is by the external standard method.

3.0 INTERFERENCES

3.2 The use of phenolic caps not containing Teflon liners should be avoided. Phenolic caps may deteriorate
when exposed to solvents and concentrated acid, causing interfering peaks in a chromatogram. The analytical system
must be demonstrated to be free from contamination under conditions of the analysis

by running laboratory reagent blanks.

FMC-P-003-1

-------
Table 1

FASP METHOD F050.002 TARGET COMPOUND LIST AND
QUANTITATION LIMITS (QL)*

Chlorinated
Pesticides

CAS Number

Quantitation Limits
In Water**
(M-R/L)

Alpha-BHC

319-84-6

0.05

Beta-BHC

319-85-7

0.05

Delta-BHC

319-86-8

0.05

Gamma-BHC (Lindane)

58-89-9

0.05

Heptachlor

76-44-8

0.05

Aldrin

309-00-2

0.05

Heptachlor Epoxide

1024-57-3

0.05

Endosulfan I

959-98-8

0.05

Dieldrin

60-57-1

0.10

4,4'-DDE

72-55-9

0.10

Endrin

72-20-8

0.10

Endosulfan II

33212-65-9

0.10

4,4'-DDD

72-54-8

0.10

Endosulfan Sulfate

1031-07-8

0.10

4,4'-DDT

50-29-3

0.10

Endrin Ketone

53494-70-5

0.10

Methoxychlor

72-43-5

0.50

a-Chlordane

57-74-9

0.50

T oxaphene

8001-35-2

1.00

*	Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided

for guidance and may not always be achievable.

** Quantitation limits listed for water are on an "as-received" basis.

FMC-P-003-2

-------
Table 2

CHLORINATED PESTICIDE DEGRADATION WITH TIME AFTER
TREATMENT WITH CONCENTRATED SULFURIC ACID

Chlorinated Pesticides

CAS Number

Approximate* Percent Loss**

24 hours

48 hours

168 hrs

a-BHC

319-84-6

None***

None

None

fl-BHC

319-85-7

None

None

None

S-BHC

319-86-8

None

None

None

y-BHC (Lindane)

58-89-9

None

None

None

Heptachlor

75-44-8

10

15

20

Aldrin

309-00-2

30

50

75

Heptachlor Epoxide

1024-57-3

25

40

70

Endosulfan I

959-98-8

	

	

100

Dieldrin

60-57-1

100

100

100

4,4'-DDE

72-55-9

None

None

None

Endrin

72-20-8

100

100

100

Endosulfan II

33212-65-9

	

	

100

4,4'-DDD

72-54-8

None

None

None

Endosulfan Sulfate

1031-07-8

None

None

None

4,4'-DDT

50-29-3

None

None

None

Endrin Ketone

53494-70-5

	

	

	

Methoxychlor

72-43-5

	

	

	

Chlordane

57-74-9

None

None

None

T oxaphene

8001-35-2

None

None

None

Highly variable/matrix dependent. Should be verified by the analyst before routine use.

After treatment with H2S04 over the specified period of time.

No significant loss.

Not measured.

FMC-P-003-3

*
**

-------
3.4 Soap residues remaining on improperly rinsed glassware may degrade aldrin, heptachlor, and
organophosphorus pesticides.

3.5 Many interfering organic compounds can be eliminated using the sulfuric acid cleanup listed in this
method. However, if a sample contains percent-level concentrations of hydrocarbon-based oils, acid cleanup will not
remove all contaminants. It is possible that a significant shift in retention times will occur when narrow-bore (0.25-
and 0.32-mm) capillary columns are used in the GC analysis. Therefore, wide-bore (0.53-mm or greater) capillary
columns should be used.

4.0 APPARATUS AND MATERIALS
4.1 Analytical Systems

4.1.1.1 Column 1: 1.8 m x 3.0 mm I.D. glass column packed with GP 1.5%
SP-2250/1.95% SP-2401 on 100/120 Supelcoport (Supelco), or equivalent.

4.1.1.2 Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco), or equivalent.

4.1.1.3 Detector: Linearized ECD with optional makeup gas supply at the detector's inlet.

4.1.2.1 Column: 15 m x 0.53 mm I.D. DB-608 fused silica capillary column (FSCC)
(J&W Scientific), or equivalent.

4.1.2.2 Detector: Linearized ECD using a system with makeup gas supply at the detector's
capillary inlet.

FMC-P-003-4

-------
4.1.2.3 Gas supply: The carrier gas should be ultrapure helium. The makeup gas should
be ultrapure 5% methane in argon, or equivalent. All gases should pass through oxygen traps prior
to the GC to prevent degradation of the column analytical coating and detector foil.

4.2	Other Laboratory Equipment

4.2.1	Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps, for extraction; disposable 16 mm x 100 mm borosilicate glass culture tubes with
Teflon-lined caps, for acid cleanup.

4.2.2	Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3	Spatulas: Stainless steel, micro and semi-micro.

4.2.4	Microsvringe: 10-(iL.

4.2.5	Balance: Top-loading, capable of weighing to 0.01 g for weighing samples.

4.2.6	Micropipets: 10-1,000 (iL.

4.2.7	Volumetric pipets/repipets: 0.5-, 1.0-, 5-, 10-, and 25-mL.

4.2.8	Volumetric flasks: 10-, 25-, 50-, 100-mL.

4.2.9	Vortex mixer: Vortex Genie or equivalent.

4.2.10	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.11	Amber storage bottles: 100- and 500-mL.

4.2.12	Autosampler vials: 1- or 2-mL with Teflon-lined screw caps.

4.2.13	Graduated centrifuge tubes: 10-mL with ground glass stoppers.

4.2.14	Oxygen traps: Supelpure-O-Trap and OMJ-1 Indicating Tube or equivalent.

4.2.15	Leak detector: Snoop Liquid or equivalent for packed column operations or GOW-MAC
gas leak detector or equivalent for megabore capillary operations.

4.2.16	Timer: 0 to 10 minute range.

4.2.17	Teflon wash bottles: 500-mL.

4.2.18	Laboratory oven: Capable of maintaining temperatures of greater than or equal to 200°C.

4.2.19	Chromatographic data stamps: Used to record instrument operating conditions.

4.3	Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1 Solvents

FMC-P-003-5

-------
5.1.1 Methanol: Pesticide quality, or equivalent.

5.1.2 Hexane: Pesticide quality, or equivalent.

5.1.3 Acetone: Pesticide quality, or equivalent.

5.1.4 Isooctane: Pesticide quality, or equivalent.

5.2 Miscellaneous Reagents

5.2.1 Reagent water: Reagent water is defined as water in which an interferent is not observed at
the FASP quantitation limit (FQL) of the analyte of interest. Reagent water may be generated using a carbon
filter bed containing activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent) or a water
purification system (Milli-Q Plus with Organex Q cartridge, Barnstead Water-1 system [provided with Base
Support Facilities], or equivalent), or purchased from commercial laboratory supply houses.

5.2.2 Sodium sulfate: Reagent, anhydrous, granular. Preconditioned by heating for 24 hours at
200°C and storing in clean glass containers with Teflon liners.

5.2.3 Nitric acid: 10 percent volume/volume.

5.2.4 Sulfuric acid: Concentrated; reagent quality.

5.2.5 Copper turnings or filings: Remove oxides by treating with dilute nitric acid, rinse with
distilled water to remove all traces of acid, rinse with acetone and dry under a stream of nitrogen.

5.3 Gases

5.3.1 5 percent methane in argon: Ultrapure or chromatographic grade (always used in conjunction
with oxygen trap).

5.3.2 Helium: Ultrapure or chromatographic grade (always used in conjunction with oxygen trap).

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as
manufacturer-certified solutions. These standards are viable for 1 year unless otherwise noted by the supplier.
Single-pesticide standards may be used; however, standard mixtures (excluding chlordane and toxaphene) of
pesticides are recommended. Multicomponent pesticides such as, chlordane and toxaphene should be prepared in
unique standard solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of three concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with isooctane. The lowest
concentration standard should be approximately two times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

FMC-P-003-6

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Water samples should be shipped in 1-liter narrow-mouthed
glass jars with Teflon-lined caps.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1)
December 1988, is required for sample tracking. The maximum holding times for water chlorinated pesticide samples
are 7 days between collection and extraction, and 40 days between extraction and analysis.

7.0 PROCEDURE

7.1 Extraction

The sample extraction technique for chlorinated pesticides in water is as follows:
7.1.1 Add 100 mL of water to a clean 100-mL volumetric flasks

pipet.

7.1.2 Add 1.0 mL of hexane by repipet to the flask and shake vigorously for 2 minutes.

7.1.3 Allow the layers to separate.

7.1.4 Transfer the hexane layer to a 10-mL graduated centrifuge tube using a disposable pasteur

7.1.5 Repeat steps 7.1.2 through 7.1.5 twice and combine the extracts.

7.1.6 Add 1.0 mL of concentrated sulfuric acid by repipet to the hexane extract. This cleanup step
should not be used initially when analyzing for heptachlor, heptachlor epoxide, dieldrin, Endrin, endrin
aldehyde, endosulfan I, endosulfan II, and endosulfan sulfate. Degradation of these compounds is significant
on contact with sulfuric acid (see Table 2).

7.1.7 Vortex at maximum speed for 60 seconds.

7.1.8 Centrifuge for 5 minutes.

7.1.9 Transfer approximately 1 mL of extract into a Teflon-lined screw cap autosampler vial, using
a disposable pasteur pipet. Avoid transfer of any of the acid layer.

7.1.10 The sample extract is now ready for GC injection.

7.2 Cleanup

7.2.2 Sulfur removal

FMC-P-003-7

-------
7.2.2.1 Sulfur interference: Elemental sulfur may be encountered in many sediment
samples, marine algae, and some industrial wastes. The solubility of sulfur in various solvents is
very similar to that of chlorinated pesticides; therefore, the sulfur interference follows the pesticides
through the normal extraction and cleanup techniques. Sulfur will be quite evident in gas
chromatograms obtained from ECDs. If the GC is operated at the normal conditions for chlorinated
pesticide analysis, the sulfur interference can completely mask a large region of the chromatogram.
One technique for the elimination of sulfur follows.

7.2.2.2 Summary of method: The sample extract is combined with clean copper. The
mixture is shaken and the extract is removed from the sulfur cleanup reagent.

7.2.2.3 Procedure for sulfur cleanup

7.2.2.3.1 The copper must be reactive; therefore, all oxides of copper must be
removed so that the copper has a shiny, bright appearance (see Section 5.2).

7.2.2.3.2 Transfer 5 mL of final extract described in Section 7.1 (Step 7.1.10) to
a 16 mm x 100 mm screw cap culture tube with a Teflon-lined cap.

7.2.2.3.3 Add approximately 2 g of cleaned copper to the tube. Mix for at least
1 minute on the vortex mixer. This step may be repeated if sulfur removal is incomplete.

7.2.2.3.4 Resume the procedure described in Section 7.1 at Step 7.1.11.

7.2.2.3.5 The effect of copper on chlorinated pesticide recovery is shown in Table

7.3 Calibration

7.3.1 Initial calibration

7.3.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
GC system is functioning properly; that is, conditions exist such that resolution, retention times,
response reporting, and interpretation of GC spectra are within acceptable quality control limits
(Section 7.5). Using at least three calibration standards for each chlorinated pesticide or pesticide
mixture prepared as described in Section 5.0, generate initial calibration curves (response versus
mass of standard injected) for each target analyte chlorinated pesticide (see Section 7.4 for
chromatographic procedures).

7.3.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.5) based
on each pesticide's three calibration factors (CFs, see Section 7.5) to determine the acceptability
(linearity) of the curve. Unless otherwise specified, the %RSD must be less than or equal to 25
percent or the calibration is invalid and must be repeated. Establish a new initial calibration curve
any time the GC system is altered (e.g., new column, change in gas supply, or change in oven
temperature) or shut down.

7.3.2 Continuing calibration

FMC-P-003-8

-------
7.3.2.1 Recheck the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing
calibration validation. This single point analysis follows the same analytical procedures used in
the initial calibration. Use instrument response to compute the CF, which is then compared to the
mean initial calibration factor (CF) and a relative percent difference (RPD, see Section 7.5) is
calculated. Unless otherwise specified, the RPD must be less than or equal to 25 percent for the
continuing calibration to be considered valid. Otherwise, the calibration must be repeated. A
continuing calibration remains valid for a maximum of 24 hours providing the GC system remains
unaltered during that time.

7.3.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

7.4 Instrumental Analysis

7.4.2 Chromatograms

7.4.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks
are on scale up to a 100-fold range are acceptable. However, this can be no greater than a 100-fold
range. This is to prevent retention time shifts by column or detector overload. Generally, peak
response should be greater than 25 percent and less than 100 percent of full-scale deflection to
allow visual recognition of the chlorinated pesticides.

7.4.2.2 The following information must be recorded on each chromatogram.

• Instrument and detector identification;

• Column packing coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

FMC-P-003-9

-------
Table 3

EFFECT OF COPPER TREATMENT ON CHLORINATED PESTICIDE RECOVERY*

Pesticide

Copper**

Lindane

94.8

Heptachlor

5.4

Aldrin

93.3

Heptachlor Epoxide

96.6

DDE

102.9

DDT

85.1

BHC

98.1

Dieldrin

94.9

Endrin

89.3

Table from EPA SW846 Method 3660.

** Percent recoveries cited are averages based on duplicate analyses for all compounds other than for Aldrin
and BHC. For Aldrin, three determinations were averaged to obtain the result. Recovery of BHC is based on one
analysis.

7.4.3 Chlorinated pesticide identification

7.4.3.1 Qualitative identification of chlorinated pesticides is based on retention time, as
compared to standards on a single column and to a lesser extent on ECD selectivity. Qualitative
identification of multicomponent mixtures (chlordane and toxaphene) is based on both retention
time and relative peak intensity matching of sample with standard chromatograms. Chlordane and
toxaphene are multiple component mixtures of compounds that produce characteristic spectral
patterns with relatively constant proportions. Except in cases where the mixture has suffered severe
weathering, the chromatographic fingerprint is easily recognized by an experienced chemist.
Because chlordane and toxaphene are relatively inert, their identification is further confirmed by
their presence after digestion of interferences with concentrated sulfuric acid.

7.4.3.2 Qualitative identification of chlordane and toxaphene is based in part on ECD
selectivity, but primarily on retention time and spectral pattern as compared to known standards on
a single selected column. A second dissimilar column (e.g., 3% SP-2100 or 3% OV-1 on 100/120
Supelcoport) may be used for confirmation.

FMC-P-003-10

-------
Table 4

EXAMPLE FASP PACKED COLUMN
ISOTHERMAL GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:

Detector/Injector Temperature:
G.C. Analysis Time:

Standard/Sample Injection:

Shimadzu GC Mini-2 equipped with Linearized ECD

Shimadzu Chromatopac C-R3A Data Processor

1.8 m x 3 mm glass column packed with 1.5% SP-2250/1.95%
SP-2401 on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of
40 mL/min

Dependent on specific chlorinated pesticide; isothermal, range
190°C to 225°C

250°C

Dependent on specific chlorinated pesticides and matrix, range
approximately 15 to 30 min

Solvent flush manual injection or automated sample injection
is recommended for chlorinated pesticide analysis. For the
solvent flush technique, the syringe barrel plus 1 (iL of
nanograde hexane, 0.5 (iL of air, and 2.0 to 3.0 (iL (measured
to the nearest 0.05 |±L) of sample extract are sequentially drawn
into a 10-(iL syringe and immediately injected into the GC.
Extreme care must be taken to avoid contamination of the
syringe needle with sulfuric acid when loading the syringe.
Injection of acid will damage the analytical column and
detector.

FMC-P-003-11

7.4.4 System performance: Degradation of chlorinated pesticides may occur in the GC system,
especially if the injector or column inlet is dirty. System performance is tested by analysis of a
4,4'-DDT/Endrin mixture and quantifying the percent breakdown of these compounds (see section 7.5.5).

7.4.5 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided in Appendix B of this method.

7.4.6 Analytical sequence

7.4.6.1 Instrument blank.

7.4.6.2 Initial calibration.

7.4.6.3 Check standard and/or performance evaluation sample (if available).

7.4.6.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.6.5 Associated QC lot method blank.

7.4.6.6 Twenty samples and associated QC lot spike and duplicate.

7.4.6.7 Repeat sequence beginning at step 7.4.6.6 until all sample analyses are completed
or another continuing calibration is required.

7.4.6.8 Final calibration when all sample analyses are complete.

7.5 Calculations

7.5.1 Initial calibration

7.5.1.1 GC response to single component chlorinated pesticides is measured by
determining calibration factors (CFs). They are the ratio of the response (peak area or height) to
the mass injected. For multicomponent mixtures such as chlordane and toxaphene, calculations are
normally based on three to five major peaks identified as resulting primarily from a single pesticide.
The chemist may select from any of the major peaks free of interferences so long as the same peaks
are used for both standard and sample calculations.

7.5.1.2 Calculate the calibration factor for each individual peak, or in the case of chlordane
and toxaphene, the summed area of three to five peaks for each chlorinated pesticide in the initial
calibration. The integrator may be employed to make all of these computations.

FMC-P-003-12

-------
Area of Peak

Cr

Mass Injected (nanograms)

7.5.1.3 Using the calibration factors, calculate the percent relative standard deviation
(%RSD) for each chlorinated pesticide at the three concentration levels using the following
equation.

ST)

%RSD = 4=r x 100
x

where SD, the standard deviation, is given by

SD

(x. - x):

jn

where: X;	=	Individual calibration factor (per analyte)

x	=	Mean of initial three calibration factors (per analyte),

N =	Number of calibration standards.

7.5.1.4 The %RSD must be less than or equal to 25.0 percent.

7.5.2 Continuing calibration

7.5.2.1	Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations. Midrange standards for all initial calibration analytes must be analyzed as
continuing calibration standards at specified intervals (less than or equal to 24 hours).

7.5.2.2	The relative percent difference (RPD) calculated using the following equation for
each analyte must be less than or equal to 25 percent.

| CF - CF J
RPD = -	-	— x 100

CFx + CFc

2

where: CF, =	Mean CF from the initial calibration for each analyte

CFc =	Measured CF from the continuing calibration for the same analyte.

7.5.3 Final calibration

7.5.3.1	The final calibration is obtained at the end of any batch of samples analyzed.

7.5.3.2	The RPD between the mean initial calibration and final calibration factors for each
analyte must be less than or equal to 50 precent. A final calibration that achieves less than or equal
to 25 percent RPD may be used as an ongoing continuing calibration.

FMC-P-003-13

-------
\CFt - CFr
RPD = 1

CFI + CFp

where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.4 Sample quantitation

7.5.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations.

Concentration	_ ^y)	(D)

(Wet weight) ^g	(CF ) {V.) {V )

\ c' ^ 1 ' x s'

where: Ax	=	Response for the analyte to be measured

CFc	=	CF from the continuing calibration for the same analyte

V;	=	Volume of extract injected (|iL)

Vt	=	Volume of total extract (nL)

Vs	=	Volume of water extracted (mL)

D	=	Dilution factor, if employed.

7.5.4.2	Report results in micrograms per liter (ng/L) without correction for blank, spike
recovery, or percent moisture.

7.5.4.3	Single-component chlorinated pesticide sample concentrations are computed from
individual peak responses. Sample concentrations of multicomponent mixtures (chlordane and
toxaphene) are based on the summed response (peak areas) of the peaks identified in Section 7.5.1.

7.5.4.4 Weathering of chlordane and toxaphene often results in the uneven loss of different
components, so that sample spectra rarely match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum
possible concentration (qualified as less than the numerical value) that allows the data user to
determine if additional (e.g., CLP, RAS, or SAS) work is required or if the reported concentration
is below action levels and project objectives and DQOs have been met, to forego further analysis.

7.5.4.5 Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) that allows the data
user to determine if additional (e.g., CLP, RAS, or SAS) work is required or, if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

7.5.5 System performance

FMC-P-003-14

-------
7.5.5.1	The GC system is evaluated by measuring DDT and Endrin breakdown. A
standard must be prepared containing only 4,4' -DDT and Endrin at the same concentration as the
mid-level standard.

7.5.5.2	Degradation is measured by injecting the standard, quantitating the degradation
products of 4,4'-DDT (4,4'-DDE and 4,4'-DDD) and Endrin (endrin ketone and endrin aldehyde),
and calculating the percent breakdown as follows:

o , , ,	Peak Area of DDE + DDD

%DDT breakdown = 	 x 100

Peak Area of DDT + DDE + DDD

Peak Area of Endrin Aldehyde

+ Endrin Ketone

iEndrm breakdown = 	 x 100

Peak Area of Endrin + Endrin

Aldehyde + Endrin Ketone

7.5.5.3 System performance must be checked after each continuing calibration. The
maximum allowable percent breakdown for either DDT or Endrin or the sum of both the DDT +
Endrin percent breakdowns is less than or equal to 25 percent. System performance criteria must
be met before analyses may proceed.

8.0 QUALITY CONTROL

Quality Control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 5. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-P-003-15

-------
Table 5

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F050.002 (Chlorinated Pesticides in Water)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD
(%)

Alpha-BHC

40 to 150

±50

Beta-BHC

40 to 150

±50

Delta-BHC

40 to 150

±50

Gamma-BHC (Lindane)

40 to 150

±50

Heptachlor

40 to 150

±50

Aldrin

40 to 150

±50

Heptachlor Epoxide

40 to 150

±50

Endosulfan I

40 to 150

±50

Dieldrin

40 to 150

±50

4,4'-DDE

40 to 150

±50

Endrin

40 to 150

±50

Endosulfan II

40 to 150

±50

4,4'-DDD

40 to 150

±50

Endosulfan Sulfate

40 to 150

±50

4,4'-DDT

40 to 150

±50

Endrin Ketone

40 to 150

±50

Methoxychlor

40 to 150

±50

Chlordane

40 to 150

±50

T oxaphene

40 to 150

±50

*	Before acid cleanup: If the concentration of an analyte is less than 5 times the QL, advisory control limits

for duplicate RPD values becomes ±3 times the QL for that individual analyte.

FMC-P-003-16

-------
9.0 METHOD PERFORMANCE

9.1 The following is an example of a gas chromatogram for several commonly encountered chlorinated
pesticides using an ECD.

Figure 1

Gas Chromatogram - Chlorinated Pesticides

Column: 1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-P-003-17

-------
9.2 Method F050.002 examples of QA/QC results: Spike and duplicate sample results are presented as
examples of FASP Method F050.002 empirical data(see Tables 6 and 7).

Table 6

FASP METHOD F050.002
CHLORINATED PESTICIDE WATER MATRIX SPIKE PERCENT RECOVERY

Compound

Amount
Spiked
(Hg/L)

Sample
(Hg/L)

Sample
with
Spike
(Hg/L)

Percent
Recovery
(%)

CLP
Matrix
Spike
Percent
Recovery
Limits
(%)

a-BHC

0.3

0

0.19

63



y-BHC (Lindane)

0.3

0

0.19

63

56-123

fl-BHC

00.3

0

0.20

67



Heptachlor

0.3

0

0.21

70

40-131

S-BHC

0.3

0

0.23

77



Aldrin

0.3

0

0.21

70

40-120

Heptachlor Epoxide

0.3

0

0.22

73



Endosulfan I

0.6

0

0.48

80



4,4'-DDE

0.6

0

0.48

80



Dieldrin

0.6

0

0.47

78

52-126

Endrin

0.6

0

0.39

65

56-121

4,4'-DDD

1.8

0

1.34

74



Endosulfan II

0.6

0

0.47

78



4,4'-DDT

1.8

0

1.31

73

38-127

Endrin Aldehyde

1.8

0

1.22

67



Endosulfan Sulfate

1.8

0

1.22

67



FMC-P-003-18

-------
Table 7

FASP METHOD F050.002
CHLORINATED PESTICIDE WATER SPIKE TRIPLICATE PRECISION



Mean Percent

Standard

Compound

Recovery

Deviation



(%)

(%)

a-BHC

60

8.4

y-BHC (Lindane)

65

5.3

fl-BHC

65

4.5

Heptachlor

61

4.5

6-BHC

69

4.8

Aldrin

67

2.6

Heptachlor Epoxide

71

4.8

Endosulfan I

75

3.5

4,4'-DDE

71

4.2

Dieldrin

70

5.3

Endrin

63

8.0

4,4'-DDD

69

4.4

Endosulfan II

72

3.7

4,4'-DDT

69

5.5

Endrin Aldehyde

55

9.3

Endosulfan Sulfate

62

6.1

FMC-P-003-19

-------
10.0 REFERENCES

Information not available.

FMC-P-003-20

-------
APPENDIX A

FASP Method F050.002

Instrument Options:
GC System 1:

GC System 2:

GC System 3:

Data Handling System 1:
Data Handling System 2:
Data Handling System 3:

Shimadzu GC Mini-2 with linearized Electron Capture Detector (ECD), used for
isothermal, packed column analyses.

Shimadzu GC-mini 2 with linearized ECD modified with a Direct Conversion
and Makeup Gas Adapter for megabore capillary column operations and equipped
with a Shimadzu TP-M2R Temperature Programmer, used for
temperature-programmed megabore capillary column analyses.

Shimadzu GC-14A with linearized ECD, used for temperature-programmed
megabore capillary column analyses.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit and
Shimadzu FDD-1A Floppy Disk Drive.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-P-003-21

-------
APPENDIX B

FASP Method F050.002

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector Temperature:

Injector Temperature:

Shimadzu GC Mini-2 equipped with linearized ECD

Shimadzu Chromatopac C-R3A Data Processor

1.8 m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent Methane in Argon at a flow rate of 30 to 40 mL/min
Dependent on specific Aroclor, isothermal range 190°C to 225°C
250oC
250°C

FMC-P-003-22

-------
NUS SOP Number 5.5
FIELD SCREENING OF ORGANOCHLORINE PESTICIDES

(AQUEOUS MATRIX)

1.0 SCOPE AND APPLICATION

1.1 The following methodology describes a modification of EPA Method 608. This methodology is suitable
for the determination of organochlorine pesticide contaminants in aqueous matrix samples.

1.3 Table 1 provides a list of potential target compounds.

2.0 SUMMARY OF METHODS

In this methodology, a portion of neat sample is extracted using rapid field techniques. An aliquot of sample
extract is then directly injected onto an analytical column housed in a previously calibrated gas chromatograph (GC).
The pesticide contaminants are resolved isothermally and are detected by an electron capture detector (ECD).
Detector signals are processed and interpreted via a previously programmed integrator.

2.1 Low Level Analysis: A 20-mL neat sample aliquot is suggested to achieve method detection limits of
approximately 0.5 (ig/L.

2.2 Medium Level Analysis: Proportioned dilutions may be achieved by using a reduced sample aliquot.
For example, a 5-fold dilution can be simulated by extracting only 4 mL of neat sample while retaining the same
volume of extraction solvent.

3.0 INTERFERENCES

3.3 Artifacts, which manifest themselves as carryover in the next analytical run, can also occur within the
analytical apparatus whenever a highly contaminated sample is introduced. To preclude this, injection syringes are
repeatedly flushed with solvent, and the analytical column is baked for a short period of time following each direct
injection analysis.

FMC-P-004-1

-------
Table 1

SUMMARY OF POTENTIAL TARGET COMPOUNDS

Organochlorine Pesticide Analysis

	alpha-BHC	

	beta-BHC	

	delta-BHC	

	gamma-BHC	

	Aldrin	

	Chlordane	

	Dieldrin	

	Endosulfan I	

	Endosulfan II	

	Endosulfan sulfate	

	Endrin	

	Heptachlor	

	Heptachlor epoxide	

	4,4'-DDD	

	4,4'-DDE	

	4,4'-DDT	

4.0 APPARATUS AND MATERIALS

4.1	Gas Chromatograph: Hewlett-Packard 5890, or equivalent. The analytical system should be equipped
for packed or capillary column analysis with isothermal oven and on-column injection capabilities.

4.2	Detector: ECD.

4.3	Analytical Column: Glass or stainless steel packed with 1.5% SP-2250/1.95% SP-2401 on 100/120
mesh Supelcoport. Alternatively, a 3% OV-1 on 80/100 mesh Supelcoport packed column or a suitable capillary
column may be used.

4.4	Syringes (assorted): 5-(iL, 25-(iL, 100-(iL, and 1-mL.

4.5	Analytical Balance: Capable of accurately weighing 0.0001 g.

FMC-P-004-2

-------
4.6 Vials: 40-mL septum-seal for extraction.

4.7 Vials: 2-dram septum-seal for extract storage.

4.8 Glass Marking Pen: For labeling vials.

4.9 Laboratory Timer: For use during the extraction process.

4.10 Pipets (assorted): 1-mL, 5-mL, and 10-mL disposable glass.

4.11 Refrigerator: Separate for sample and standard storage. Capable of maintaining a temperature of 4°C.
5.0 REAGENTS

5.1 Hexane: Pesticide grade, or equivalent.

5.2 Isooctane: Distilled in glass.

5.3 Neat Standards: 96 percent purity, or better, for each compound of interest.

5.4 Zero-grade Nitrogen: As carrier gas for the GC.

5.5 Standards: Calibration standards containing the compounds of interest are prepared from commercially
purchased standard mixes or pure compounds. All standards are made and/or diluted using isooctane and are created
for use via a 2-\xL direct injection. An example of a working calibration standard within a practical concentration
range follows:

Compound

Concentration (ng/^L)

Lindane

0.0125

Aldrin

0.0250

4,4'-DDT

0.0625

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Samples awaiting analysis are stored at 4°C in a dedicated refrigerator. If, because of loading, it is not
possible to analyze all samples taken daily, the suggested holding time for the analysis of organochlorine pesticides
in aqueous matrix is 5 days prior to extraction, and analysis within 30 days. If holding times are exceeded, the
affected data should be qualified as suspect.

7.0 PROCEDURE

FMC-P-004-3

-------
7.1 Sample Preparation: Extract all samples in hexane prior to chromatographic analysis according to the
following suggested protocol:

7.1.1 Pipet 20 mL of aqueous sample matrix each into a 40-mL septum-seal vial; discard pipet.

7.1.2 Add exactly 2.0 mL of hexane to the measured matrix aliquot.

7.1.3 Cap the vial and shake vigorously for 2 full minutes.

7.1.4 Set the vial aside and allow the contents to settle for 5 minutes.

7.1.5 Pipet off the supernatant extract into a labeled 2-dram septum-seal vial.

7.1.6 Perform GC analysis by directly injecting 2 to 5 |±L of combined sample extract onto the GC's
analytical column.

7.2 Calibration: Calibrate the analytical system via the external standard method, in which response factors
(RF) for each compound are obtained by the analysis of a standard mix of known concentration. Following the
analysis of this known standard mix, create an electronic file establishing each peak's identity, retention time (RT),
RF, and known concentration. The RF for each peak is determined by dividing the known concentration by the peak
response (area or height units) of the associated peak. For initial calibration, determine each compound's average RF
by averaging the peak response results generated for the initial linearity study. Program these average RFs into the
integrator to allow for direct concentration reading of contaminants found in subsequent sample analyses.

7.2.1 Initial linearity:

7.2.1.2 Compute the percent relative standard deviation (%RSD see 7.4.1) based on each
compound's RFs (see 7.5) to determine the acceptability (linearity) of the curve. The %RSD should
be less than 20 percent. Reanalyze standard runs yielding data that does not meet the %RSD
criterion.

7.2.2 Continuing calibration:

7.2.2.1 Update the calibration of the analytical system 3 times daily: (1) preceding the
daily analyses, (2) midday, and (3) after the daily analyses.

7.2.2.2 Analyze standards run for continuing calibration purposes at a level equal to the
reported detection limits. Continuing calibration RFs for each parameter should fall within 25
percent difference (%D, see 7.4.3) of the average RF calculated for that particular compound during
the initial linearity study. Qualify data associated with individual parameter not meeting the %D
criterion as suspect.

7.2.2.3 Conduct continuing calibration at a concentration level equal to the reported
detection limits.

7.2.3 Peak identification: Compound identities may be substantiated by the analysis of each
individual component, thereby, documenting compound retention time.

FMC-P-004-4

-------
7.3 Gas Chromatography

7.3.1 Analytical sequence: Conduct analyses in sets of 10, whenever possible, with 1 laboratory
duplicate spike analysis run per set. Bracket each set of sample analyses by the analysis of a standard, with
a method blank analysis following each standard run. The number of analyses per sample set and the
associated quality assurance/quality control (QA/QC) varies per contract. Consult the project work plan to
verify that all contractual obligations were met.

7.3.2 First strip the sample contaminants from the matrix by means of hexane extraction (see 7.1).
Introduce a 2- to 5-(iL aliquot of the sample extract onto the head of a previously conditioned analytical
column by means of direct injection technique. The organochlorine pesticide compounds are resolved
isothermally due to the affinity each compound has for the phases of the column packing as they migrate
(under flow) through the analytical column. As the contaminants elute from the column, they are recognized
by an ECD. Detector signals are then processed by a previously programmed integrator. As long as
analytical conditions remain constant, each type of organochlorine compound will elute at a characteristic
RT. In this manner, sample contaminants are identified and quantified by comparison to a run of standard
mix of known concentration.

7.3.3 Under the following run conditions, all commonly targeted organochlorine pesticides will
elute within 15 minutes:

Run Parameter

Setting

Injector Port Temperature

300°C

Isothermal Oven Temperature

215°C

Detector Temperature

350°C

Carrier Gas Flow

70 mL/min

7.4 Calculations

7.4.1 Calculate %RSD using the following equation:

%RSD = x 100

where:

A (x - x)2
SD = >

M N - 1

and X is the mean of initial RFs (per compound).

7.4.2 Calculate relative percent difference (RPD) values using the following equation:

D1 ~ D2
RPD = i — x 100

(D1 + D2)

FMC-P-004-5

-------
where:	D[ =	First sample value, and

D2 =	Second sample value.

7.4.3 Calculate the %D using the following equation:

X, - X„

%D =

Xi

where:	X[ =	RF of first result, and

X2 =	RF of second result.

7.4.4 Calculate percent recovery (%R) using the following equation:

i* = SSR ~ SR x 100
s

where:	SSR =	Spike sample results,

SR =	Sample result, and

S	=	Amount of spike added.

7.5 Sample Quantitation: Appropriate quantitation of sample contaminants is based upon the following

formula:

Concentration (]ig/L) = target analyte peak response{sample) x RF x DF

where:	RF =	Target analvte concentration in std ffig/L)

Target analyte peak response in std
DF =	Dilution factor used, when applicable.

8.0 QUALITY CONTROL

8.1 Overview

8.1.1	Field screening generates Level II data. As Level II data, the concurrent analysis of
laboratory duplicates and matrix spike analyses and the use of surrogate spike compounds is not required.
However, beyond the maintenance of practical Standard Operating Procedures (SOPs), certain elements of
QC (if opted) can greatly enhance the interpretation of and the confidence in the data generated. These
traditional elements of QC are discussed here as to how they are adapted to meet the demands of a
successfully applied field screening QA/QC program.

8.1.2	The primary purposes of an appropriate QA/QC program are to: (1) substantiate system
performance and give credence to the accuracy of the results generated, (2) to define aberrations and give
guidance to the interpretation of data, and (3) to achieve these goals through realistic efforts that do not
impede the forward progress of the analytical set.

8.1.3	The discussion presented here deals with only direct analytical QC. Additional elements of
QA/QC, such as field duplicate sample submissions, blind spike analysis, and external audits are not
discussed. Also not discussed are elements of QA/QC that are inherent to good chromatographic technique.
Examples of these accepted laboratory practices include (but are not limited to) the following: (1) the proper
conditioning of analytical columns and traps, (2) use of the solvent flush technique for the creation of

FMC-P-004-6

-------
standards and for direct injections, and (3) the appropriate maintenance of selected detectors. Details
regarding these accepted practices are given in the referenced methodologies.

8.2 Laboratory Duplicates: One laboratory duplicate should be analyzed per sample set. Laboratory
duplicate analyses should generate results of RPD within 30 percent (see 7.4.2).

8.4 Surrogate Spikes: The use of at least 1 surrogate spike compound is highly recommended. The identity,
concentration and addition of the appropriate surrogate spike varies with the procedure being used. Each associated
referenced methodology should be consulted for guidance. Surrogate spike recoveries should fall within ±30 percent
(see 7.4.4). Sample analyses yielding %R values outside this 30 percent window should be reanalyzed or the
associated data should be qualified as suspect.

8.5 Method Blanks: Method blanks are prepared and analyzed in exactly the same manner as sample
matrices. A method blank analysis should follow every standard run and sample of high concentration. Ideally,
method blank results should yield no interferences to the chromatographic analysis and interpretation of target
compounds. If interferences are present, associated data should be qualified as suspect and/or target detection limits
should be adjusted accordingly.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-P-004-7

-------
FASP Method Number F050.004

ORGANOPHOSPHORUS PESTICIDES IN WATER

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various organophosphorus pesticides in water samples using gas chromatographic (GC) techniques
with Flame Thermionic Detectors (FTD) or Flame Photometric Detectors (FPD).

1.2 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.3 This method yields tentative identification and estimated quantitation of the analytes listed in Table 1.
Approximate method quantitation limits (QL) are also listed in Table 1. Reported values are on an "as-received"
basis.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 A measured aliquot of water is placed in a volumetric flask. The sample is extracted with a measured
volume of hexane. Analysis is performed with a GC equipped with an FTD or FPD and either a packed glass column
or a megabore capillary column under temperature-programmed oven conditions. Identification is based on
comparison of retention times between samples and standards. Quantitation is by the external standard method.

3.0 INTERFERENCES

3.1 GC interference by sample carryover may be minimized by use of disposable glassware during sample
preparation and employing the maximum number of rinse cycles in automatic injection systems or by thoroughly
rinsing syringes employed in manual injections.

3.2 Soap residues remaining on improperly rinsed glassware may degrade organophosphorus pesticides.

3.3 Samples containing free sulfur or hexane-soluble organosulfur compounds may yield interfering GC
peaks when the FPD is employed. However, cleanup of the extract using copper (and mercury, another metal often
used for cleanup) causes degradation of organophosphorus pesticides.

3.4 Interferences coextracted from samples are matrix and site specific. It is possible that cleanups
employed in either FASP or Regular Analytical Services (RAS) CLP methods may fail to eliminate interferences.
Highly specialized CLP Special Analytical Services (SAS) techniques may be required to produce acceptable
analytical results.

FMC-P-005-1

-------
Table 1

FASP METHOD F050.004 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Organophosphorus
Pesticides

CAS Number

Quantitation Limits
Water**
(M-R/L)

Phorate

298-02-2

0.50

Dimethoate

60-51-5

0.50

Diazinon

333-41-5

0.50

Disulfoton

298-04-4

0.50

Malathion

121-75-5

0.50

Methyl Parathion

298-00-0

0.50

Merphos

150-50-5

0.50

DEF

78-48-8

0.50

Ethion

563-12-2

0.25

EPN

2104-64-5

1.00

Azinphos Methyl

86-50-0

1.00

Ronnel

299-84-3

0.50

Parathion Ethyl

56-38-2

0.50

C arbophenothion

7173-84-4

0.75

Azinphos Ethyl

2642-71-9

0.25

Coumaphos

56-72-4

0.50

Dichlorvos

62-73-7

2.50

Dioxathion

78-34-2

1.50

Phosphamidon

13171-21-6

1.50

F enthion

55-38-9

5.00

*	Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided

for guidance and may not always be achievable.

** Quantitation limits for organophosphorus pesticides in water are on "as-received" basis.

FMC-P-005-2

-------
3.5 Organophosphorus pesticides are light sensitive and will degrade upon exposure. All standards and
samples should be contained in amber bottles and stored in a dark environment.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems

4.1.1 Gas chromatograph: An analytical system, complete with a temperature-programmable GC
and all necessary accessories such as injector and detector systems designed or modified to accept packed
or megabore capillary analytical columns, is required. The system shall have a data handling system
attached to the detector that is capable of retention time labeling, relative retention time comparisons, and
providing peak height and/or peak area measurements. The system may include an autosampler.

4.1.2 Column 1: Packed column, 1.8 m x 3.0 mm I.D. glass column packed with GP 1.5%
SP-2250/1.95% SP-2401 on 100/120 Supelcoport (Supelco), or equivalent.

4.1.3 Column 2: Megabore capillary column; J&W 15 m x 0.53 mm DB-5 or DB-1301 fused

silica.

4.1.4 Detector: FTD [also known as Nitrogen/Phosphorus (N/P) detector or a thermionic emission
detector], or an FPD.

4.1.5 Gas supply: The carrier gas should be ultrapure helium. The makeup gas should also be
ultrapure helium. The helium should pass through an oxygen trap prior to the GC to prevent degradation of
the column's analytical coating. The FTD and FPD both require ultrapure hydrogen and ultrapure air.

4.2 Other Laboratory Equipment

4.2.1 Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction.

4.2.2 Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3 Spatulas: Stainless steel, micro and semi-micro.

4.2.4 Microsvringe: 10-(iL.

4.2.5 Balance: Top loading, capable of weighing to 0.01 g, used to weigh samples.

4.2.6 Analytical balance (optional'): Accuracy to 0.1 mg; used to weigh analytical standards. (Used
only if commercially prepared standards are not available.)

4.2.7 Micropipets: 10- to 1,000-^L.

4.2.8 Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and 25-mL.

4.2.9 Volumetric flasks: 10-, 25-, 50-, and 100-mL, with glass or Teflon stoppers.

4.2.10 Vortex mixer: Vortex Genie, or equivalent.

4.2.11 Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

FMC-P-005-3

-------
4.2.12 Amber storage bottles: 100-mL and 500-mL.

4.2.13	Autosampler vials: 1-mL or 2-mL clear or amber vials with Teflon-lined screw caps.

4.2.14	Graduated centrifuge tubes: 10-mL, with ground glass stoppers.

4.2.15	Oxygen traps: Supelpure-O-Trap and OMJ-1 indicating tube, or equivalent.

4.2.16	Leak detector: Snoop liquid, or equivalent, for packed column operations or GOW-MAC
gas leak detector, or equivalent, for megabore capillary operations.

4.2.17	Timer: 0 to 10 minute range.

4.2.18	Teflon wash bottles: 500-mL.

4.2.19	Laboratory oven: Capable of maintaining temperatures greater than or equal to 200°C.

4.2.20	Nitrogen blowdown apparatus (optional'): N-Evap, or equivalent.

4.2.21	Chromatographic data stamps: Used to record instrument operating conditions, if not
provided by data handling systems.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Methanol: Pesticide quality, or equivalent.

5.1.2	Hexane: Pesticide quality, or equivalent.

5.1.3	Isooctane: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

5.2.1	Reagent water: Reagent water is defined as water in which an interferent is not observed at
the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent), a water purification system (Milli-Q
Plus with Organex Q cartridge, Barnstead Water-1 Systems [provided with the Base Support Facilities], or
equivalent), or purchased from commercial laboratory supply houses.

5.2.2	Sodium sulfate: Reagent, anhydrous, granular. Pre-conditioned by heating for 24 hours at
200°C and storing in clean glass containers with Teflon liners.

5.3	Gases

5.3.1 Air: Ultrapure or chromatographic grade, always used in conjunction with an oxygen trap.

FMC-P-005-4

-------
5.3.2 Hydrogen: Ultrapure or chromatographic grade, always used in conjunction with an oxygen

trap.

5.3.3 Helium: Ultrapure or chromatographic grade, always used in conjunction with an oxygen

trap.

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as
manufacturer-certified solutions. These standards are viable for 1 year unless otherwise noted by the supplier.
Organophosphorus single pesticide standards may be used; however, standard mixtures of pesticides are
recommended, if available. Stock standards should be stored in amber bottles, in a dark environment.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with isooctane. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining concentrations
should define the approximate working range of the GC: one level at the upper linear range and the other midway
between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed amber glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

5.7 Matrix Spike Solution: Matrix spike solutions should be prepared by dilution of stock standard solutions
so that no more than 250 (iL of spike solution is required to provide a final sample spike level within this method's
QC limits.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Water samples should be shipped in 1-liter narrow-mouth
glass jars with Teflon-lined caps.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum recommended holding time for water
organophosphorus pesticide samples is 24 hours between collection and extraction, and 14 days between extraction
and analysis.

7.0 PROCEDURE

7.1 Extraction: The sample extraction technique for organophosphorus pesticides in water is as follows:

7.1.1 Add 100 mL of water sample to a clean 100-mL volumetric flask.

7.1.2 Add 1.0 mL of hexane by repipet to the flask and shake vigorously for 2 minutes.

7.1.3 Allow the layers to separate.

7.1.4 Transfer the hexane layer to a 10-mL graduated centrifuge tube using a disposable Pasteur

pipet.

7.1.5 Repeat steps 7.1.3 through 7.1.5 twice and combine the extracts.

FMC-P-005-5

-------
7.1.6 Add approximately 1 g of sodium sulfate.

7.1.7 Vortex at maximum speed for 60 seconds.

7.1.8 Centrifuge for 5 minutes.

7.1.9 When appropriate, transfer approximately 1 mL of extract into a Teflon-lined screw-cap
autosampler vial using a disposable Pasteur pipet.

7.1.10 The sample extract is now ready for GC injection.

7.2 Cleanup: Both detector options for organophosphorus pesticide determination are very specific to
phosphorus compounds. Their use eliminates the need for extensive cleanup procedures. Direct analysis of the
extract, without cleanup, is recommended for screening analysis.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly, that is, conditions exist such that resolution,
retention times, response reporting, and interpretation of chromatograms are within acceptable
quality control (QC) limits (Section 7.5). Using at least 3 calibration standards for each
organophosphorus pesticide or pesticide mixture prepared as described in Section 5, generate initial
calibration curves (response versus mass of standard injected) for each target organophosphorus
pesticide (refer to Section 7.4 for chromatographic procedures).

7.3.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.5) based
on each pesticide's 3 calibration factors (CFs, see Section 7.5) to determine the acceptability
(linearity) of the curve. Unless otherwise specified, the %RSD must be less than or equal to 25
percent, or the calibration is invalid and must be repeated. Establish a new initial calibration curve
any time the GC system is modified (e.g., new column, change in gas supply, change in oven
temperature) or shut down.

7.3.2 Continuing calibration:

7.3.2.1 Recheck the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing
calibration validation. This single-point analysis follows the same analytical procedures used in
the initial calibration. Use instrument response to compute the CF which is then compared to the
mean initial calibration factor (CF), and calculate a relative percent difference (RPD, see Section
7.5). Unless otherwise specified, the RPD must be less than or equal to 25 percent for the
continuing calibration to be considered valid. Otherwise, the calibration must be repeated. A
continuing calibration remains valid for a maximum of 24 hours providing the GC system remains
unaltered during that time.

7.3.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

FMC-P-005-6

-------
less than or equal to 50 percent. A final calibration that achieves an RPD less than or equal to 25 percent
may be used as an ongoing continuing calibration.

7.4 Instrumental Analysis

7.4.2 Chromatograms:

7.4.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks
are on scale over a 100-fold range are acceptable. However, this can not be greater than a 100-fold
range. This is to prevent retention time shifts by column or detector overload. Generally, peak
response should be greater than 25 percent and less than 100 percent of full scale deflection to allow
visual recognition of the organophosphorus pesticides.

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature program;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.4.3 Organophosphorus pesticide identification:

7.4.3.1 Qualitative identification of organophosphorus pesticides is based on retention
time, as compared to standards on a single column and to a lesser extent on the detector selectivity.
A second, dissimilar column may be used to assist in identification.

7.4.3.2 Generally, individual peak retention time windows should be less than or equal
to 5 percent for packed column analyses, and less than or equal to 2 percent for megabore capillary
columns.

7.4.3.3 For the purpose of FASP analyses, peak intensity (height or area) matching for
positive identification is based on the chemist's best professional judgement in consultation with
more experienced chromatographic data interpretation specialists, when required. It is possible that
interferences may preclude positive identification of an analyte.

FMC-P-005-7

-------
Table 2

EXAMPLE GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Makeup Gas:

Detector Gases:

Column Temperature Program:

Injector Temperature:
Detector Temperature:
G.C. Analysis Time:
Standard/Sample Injection:

Shimadzu GC 14A equipped with FTD

Nelson Analytical PC Integrator with a dual-channel interface and
20-MB hard disk drive for data storage

J&W 15 m x 0.53 mm DB-5 orDB-1301 fused silica megabore column.

Ultrapure helium at a flow rate of 10 mL/min.

Ultrapure helium at a flow rate of 40 mL/min.

Ultrapure hydrogen at a flow rate of 30 to 40 mL/min and ultrapure air at a flow
rate of 150 to 200 mL/min.

Initial temperature: 130°C;

Initial time: 2 mins
Ramp rate 1: 2.5°C/min
Final temperature 1: 155°C
Ramp rate 2: 5°C/min
Final temperature 2: 245°C
Final time: 6 mins

250oC

300oC

36 mins

Solvent flush manual injection or automated sample injection is
recommended for organophosphorus pesticide analysis. For the solvent
flush technique, the syringe barrel volume plus 1 (iL of nanograde
hexane, 0.5 (iL of air, and 2.0 to 3.0 (iL (measured to the nearest 0.05
HL) of sample extract are sequentially drawn into a 10-(iL syringe and
immediately injected into the GC.

FMC-P-005-8

-------
In such cases, the chemist should report the presence of the interferents with a maximum pesticide
concentration possible (see Section 7.5.4).

7.4.4 System performance: Degradation of organophosphorus pesticides may occur in the GC
system especially if the injector column inlet is contaminated.

7.4.5 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided in Appendix B of this method.

7.4.6 Analytical sequence:

7.4.6.1 Instrument blank.

7.4.6.2 Initial calibration.

7.4.6.3 Check standard solution and performance evaluation sample (if available).

7.4.6.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.6.5 Associated QC lot method blank.

7.4.6.6 Twenty samples and associated QC lot spike and duplicate.

7.4.6.7 Repeat sequence beginning at Step 7.4.6.5 until all sample analyses are completed
or another continuing calibration is required.

7.4.6.8 Final calibration when all sample analyses are complete.

7.5 Calculations

7.5.1 Initial calibration:

7.5.1.1 Measure the GC response to single-component organophosphorus pesticides by
determining CFs, the ratio of the response peak area or height to the mass injected.

7.5.1.2 Calculate the CF for each individual organophosphorus pesticide in the initial
calibration. The integrator may be used to make all of these computations.

CF = Area of Peak

Mass Injected (nanograms)

7.5.2 Using the CF values, calculate the %RSD for each organophosphorus pesticide at the 3
concentration levels using the following equation:

ST)

hRSD = 4=r x 100
X

where SD, the standard deviation, is given by

FMC-P-005-9

-------
sd = \ it-

\ i" i

Xi - X) 2

N - 1

where: X;
X
N

Individual calibration factor (per analyte),

Mean of initial 3 calibration factors (per analyte),
Number of calibration standards.

7.5.2.1 The %RSD must be less than or equal to 25 percent.

7.5.3 Continuing calibration:

7.5.3.1	Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations. Midrange standards for all initial calibration analytes must be analyzed at
specified intervals (less than or equal to 24 hours).

7.5.3.2	The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

7.5.4 Final calibration:

7.5.4.1	Obtain the final calibration at the end of any batch of samples analyzed.

7.5.4.2	The maximum allowable RPD between the mean initial calibration and final
calibration factors for each analyte must be less than or equal to 50 percent. A final calibration
which achieves an RPD less than or equal to 25 percent may be used as an ongoing continuing
calibration.

| CF - CF \

RPD = -	-	— x 100

CFX + CFc

2

where: CF,

CFc

Mean CF from the initial calibration for each analyte
Measured CF from the continuing calibration for the same analyte.

| CF - CF |
RPD = -	-	— x 100

cft + cff

2

where: CF,
CFf

Mean CF from the initial calibration for each analyte
Final CF for the same analyte.

7.5.5 Sample quantitation:

FMC-P-005-10

-------
7.5.5.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations:

[A ) [V ) (E) (D)

Concentration (]ig/L) =

(CF ) (V,) (V)

where: Ax =

Response for the analyte to be measured.

CFc =

CF from the continuing calibration for the same analyte.

V;

Volume of extract injected (|iL).

Vt

Volume of total extract (|iL).

Vs

Volume of sample extracted (mL).

E

Enhanced sensitivity factor (if Section 7.1 extract concentration is used,



E = 10; if no enhancement, E = 1)

D

Dilution factor, if used.

7.5.5.2	Compute organophosphorus pesticide sample concentrations from individual peak
responses.

7.5.5.3	Report results in micrograms per liter (|ig/L) without correction for blank, spike
recovery, or percent moisture.

7.5.5.4	Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) which allows the
data user to determine if additional (e.g., CLP analyses) work is required, or, if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 3. This method should be used in conjunction with quality assurance and control
(QA/QC) section of this catalog.

FMC-P-005-11

-------
Table 3

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F050.004 (Organophosphorus Pesticides in Water)

Fasp Advisory Quality Control Limits*



Spike Recovery

Duplicate RPD

Analyte

(%R)

(%)

Phorate

30 to 150

±75

Dimethoate

30 to 150

±75

Diazinon

30 to 150

±75

Disulfoton

30 to 150

±75

Malathion

30 to 150

±75

Methyl Parathion

30 to 150

±75

Merphos

30 to 150

±75

DEF

30 to 150

±75

Ethion

30 to 150

±75

EPN

30 to 150

±75

Azinphos Methyl

30 to 150

±75

Ronnel

30 to 150

±75

Parathion Ethyl

30 to 150

±75

C arbophenothion

30 to 150

±75

Azinphos Ethyl

30 to 150

±75

Coumaphos

30 to 150

±75

Dichlorvos

30 to 150

±75

Diozathion

30 to 150

±75

Phosphamidon

30 to 150

±75

F enthion

30 to 150

±75

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ±3 times the quantitation limit for that individual analyte.

FMC-P-005-12

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatogram is an example of a gas chromatogram for several commonly encountered
organophosphorus pesticides.

Figure 1

Gas Chromatogram - Organophosphorus Pesticides

Column:

J&W 15 m x 0.53 mm DB-5 or DB-1301 fused silica megabore column.

Injector Temperature: 250°C
Detector Temperature: 300°C

Gas: Carrier: Ultrapure helium at a flow rate of 10 mL/min.

Makeup gas: Ultrapure helium at a flow rate of 40 mL/min.
Reaction gas: Ultrapure hydrogen at a flow rate of 30 to 40 mL/min.
Reaction gas: Ultrapure air at a flow rate of 150 to 200 mL/min.

Detector: FTD

FMC-P-005-13

-------
9.2 Method F050.003 spike and duplicate samples: Spike and duplicate sample results are presented as
examples of FASP Method F050.004 empirical data (see Tables 4 and 5).

Table 4

FASP METHOD F050.004
ORGANOPHOSPHORUS PESTICIDE WATER MATRIX SPIKE PERCENT RECOVERY (%R)

Compound

Amount
Spiked
(M-R/L)

Sample
(M-R/L)

Sample
with spike
(M-R/L)

Percent
Recovery
(%)

Phorate

6.48

0.50UF

10.51

162

Diazinon

5.19

0.05UF

6.61

127

Disulfoton

6.66

0.05UF

10.40

156

Methyl Parathion

9.36

0.50UF

6.45

69

DEF/Merphos

6.57

0.50UF

0.56

8

EPN

16.02

1.00UF

9.02

56

Azinphos Methyl

16.26

1.00UF

20.31

125

U - The material was analyzed for but was not detected. The associated numerical value is a FASP
quantitation limit, adjusted for sample weight, extract volume, and sample dilution.

F - Data has been generated using FASP methodologies. Analytes are tentatively identified and
concentrations are quantitative estimates.

FMC-P-005-14

-------
Table 5

FASP METHOD F050.004
ORGANOPHOSPHORUS PESTICIDE WATER
DUPLICATE ANALYSIS RELATIVE PERCENT DIFFERENCE

Compound

Sample
Result
(M-R/L)

Duplicate
Result
(M-R/L)

Relative Percent
Difference
(%)

Phorate

0.50UF

0.50UF

0

Dimethoate

0.50UF

0.50UF

0

Diazinon

0.50UF

0.50UF

0

Disulfoton

0.50UF

0.50UF

0

Malathion

0.50UF

0.50UF

0

Methyl Parathion

0.50UF

0.50UF

0

DEF/Merphos

0.50UF

0.50UF

0

Ethion

0.25UF

0.25UF

0

EPN

1.00UF

1.00UF

0

Methyl Azinphos

1.00UF

1.00UF

0

Ronnel

0.50UF

0.50UF

0

Ethyl Parathion

0.50UF

0.50UF

0

Carbophenotion

0.75UF

0.75UF

0

Ethyl Azinphos

0.25UF

0.25UF

0

Coumaphos

0.50UF

0.50UF

0

Dichlorvos

2.50UF

2.50UF

0

Dioxathion

1.50UF

1.50UF

0

Phosphamidon

1.50UF

1.50UF

0

F enthion

5.00UF

5.00UF

0

U - The material was analyzed for but was not detected. The associated numerical value is a FASP
quantitation limit, adjusted for sample weight, extract volume, and sample dilution.

F - Data has been generated using FASP methodologies. Analytes are tentatively identified and
concentrations are quantitative estimates.

FMC-P-005-15

-------
10.0 REFERENCES

Information not available.

FMC-P-005-16

-------
APPENDIX A

FASP Method F050.004

Instrument Options:

GC System 3:	Shimadzu GC 14A with FTD or FPD, used for temperature-programmed

megabore capillary column analyses.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-P-005-17

-------
Specific Instrument Parameters:

Instrument:

Integrator:

Column:

Carrier Gas:

Makeup Gas:

Detector Gases:

APPENDIX B

FASP Method F050.004

Shimadzu GC 14A equipped with FTD

Nelson Analytical PC Integrator with a dual-channel interface and
20-MB hard disk drive for data storage

J&W 15 m x 0.53 mm DB-5 or DB-1301 fused silica megabore column

Ultrapure helium at a flow rate of 10 mL/min.

Ultrapure helium at a flow rate of 40 mL/min.

Ultrapure hydrogen at a flow rate of 30 to 40 mL/min and ultrapure air at a flow
rate of 150 to 200 mL/min

Column Temperature Program:

Injector Temperature:
Detector Temperature:

Initial temperature: 130°C;
Initial time: 2 mins
Ramp rate 1: 2.5°C/min
Final temperature 1: 155°C
Ramp rate 2: 5°C/min
Final temperature 2: 245°C
Final time: 6 mins

250oC

300oC

FMC-P-005-18

-------
FASP Method Number F050.003
ORGANOPHOSPHORUS PESTICIDES IN SOIL/SEDIMENT

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various organophosphorus pesticides in soil and sediment samples using gas chromatographic (GC)
techniques with either a Flame Thermionic Detector (FTD) or Flame Photometric Detector (FPD) system.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil or sediment is placed in a screw-cap culture tube. A small amount of
methanol is added to bind the water in the sample. The sample is extracted with a measured volume of hexane.
Analysis is performed with a GC equipped with an FTD or FPD and either a packed glass column or a megabore
capillary column under temperature-programmed oven conditions. Identification is based on comparison of retention
times between samples and standards. Quantitation is by the external standard method.

3.0 INTERFERENCES

3.1 GC interference by sample carryover may be minimized by use of disposable glassware during sample
preparation and employing the maximum number of rinse cycles on automatic injection systems or by thoroughly
rinsing syringes employed in manual injections.

3.2 Soap residues remaining on improperly rinsed glassware may degrade organophosphorus pesticides.

FMC-P-006-1

-------
Table 1

FASP METHOD F050.003 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Organophosphorus
Pesticides

CAS Number

Quantitation Limits
Soil/Sediment**
(Hg/kg)

Phorate

298-02-2

100

Dimethoate

60-51-5

100

Diazinon

333-41-5

100

Disulfoton

298-04-4

100

Malathion

121-75-5

100

Methyl Parathion

298-00-0

100

Merphos

150-50-5

100

DEF

78-48-8

100

Ethion

563-12-2

50

EPN

2104-64-5

200

Azinphos Methyl

86-50-0

200

Ronnel

299-84-3

100

Parathion Ethyl

56-38-2

100

C arbophenothion

7173-84-4

150

Azinphos Ethyl

2642-71-9

50

Coumaphos

56-72-4

100

Dichlorvos

62-73-7

350

Dioxathion

78-34-2

500

Phosphamidon

13171-21-6

300

F enthion

55-38-9

1000

*	Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided

for guidance and may not always be achievable.

** Quantitation limits listed for soil or sediment are based on an "as-received" basis.

FMC-P-006-2

-------
3.5 Organophosphorus pesticides are light sensitive and will degrade upon exposure. All standards and
samples should be contained in amber bottles and stored in a dark environment.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems

4.1.1 Gas chromatograph: An analytical system, complete with a temperature programmable GC
and all necessary accessories including injector and detector systems designed or modified to accept packed
or megabore capillary analytical columns, is required. The system shall have a data handling system
attached to the detector that is capable of retention time labeling, relative retention time comparisons, and
providing peak height and/or peak area measurements. The system may include an autosampler.

4.1.2 Column 1: Packed column, 1.8 m x 3.0 mm I.D. glass column packed with GP 1.5%
SP-2250/1.95% SP-2401 Supelcoport (Supelco), or equivalent.

4.1.3 Column 2: Megabore capillary column; J&W 15 m x 0.5 mm DB-5 or DB-1301 fused silica.

4.1.4 Detector: FTD [also known as Nitrogen/Phosphorus (N/P) detector or a Thermionic Emission
Detector], or an FPD.

4.2 Other Laboratory Equipment

4.2.1 Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction.

4.2.2 Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3 Spatulas: Stainless steel, micro and semi-micro.

4.2.4 Microsvringe: 10-(iL.

4.2.5 Balance: Top loading, capable of weighing to 0.01 g, used to weigh samples.

4.2.6 Analytical balance (optional'): Accuracy to 0.1 mg; used to weigh analytical standards. (Used
only if commercially prepared standards are not available.)

4.2.7 Micropipets: 10- to 1,000-^L.

4.2.8 Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and 25-mL.

4.2.9 Volumetric flasks: 10-, 25-, 50-, and 100-mL, with glass or Teflon-lined stoppers.

4.2.10 Vortex mixer: Vortex Genie, or equivalent.

4.2.11 Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.12 Amber storage bottles: 100-mL and 500-mL.

FMC-P-006-3

-------
4.2.13 Autosampler vials: 1-mL or 2-mL, clear or amber vials with Teflon-lined screw caps.

4.2.14	Graduated centrifuge tubes: 10-mL, with ground glass stoppers.

4.2.15	Oxygen traps: Supelpure-O-Trap and OMJ-1 indicating tube, or equivalent.

4.2.16	Leak detector: Snoop liquid, or equivalent, for packed column operations or GOW-MAC
gas leak detector, or equivalent, for megabore capillary operations.

4.2.17	Timer: 0 to 10 minute range.

4.2.18	Teflon wash bottles: 500-mL.

4.2.19	Laboratory oven: Capable of maintaining temperatures greater than or equal to 200°C.

4.2.20	Nitrogen blowdown apparatus (optional'): N-Evap, or equivalent.

4.2.21	Chromatographic data stamps: Used to record instrument operating conditions, if not
provided by data handling systems.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Methanol: Pesticide quality, or equivalent.

5.1.2	Hexane: Pesticide quality, or equivalent.

5.1.3	Isooctane: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

5.2.1	Reagent water: Reagent water is defined as water in which an interferent is not observed at
the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent), a water purification system (Milli-Q
Plus with Organex Q cartridge, Barnstead Water-1 Systems [provided with the Base Support Facilities], or
equivalent), or purchased from commercial laboratory supply houses.

5.2.2	Sodium sulfate: Reagent, anhydrous, granular. Pre-conditioned by heating for 24 hours at
200°C and storing in clean glass containers with Teflon-lined caps.

5.3	Gases

5.3.1	Air: Ultrapure or chromatographic grade (always used in conjunction with an oxygen trap).

5.3.2	Hydrogen: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

FMC-P-006-4

-------
5.3.3 Helium: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as
manufacturer-certified solutions. These standards are viable for 1 year unless otherwise noted by the supplier.
Organophosphorus single pesticide standards may be employed; however, standard mixtures of pesticides are
recommended, if available. Stock standards should be stored in amber bottles, in a dark environment.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with isooctane. The lowest
concentration standard should be equal to 2 times the QL as listed in Table 1. The remaining concentration levels
should define the approximate working range of the GC: one at the upper linear range and the other midway between
it and the standard. All standards must be stored at 4°C in Teflon-sealed amber glass bottles. Calibration solutions
must be replaced after 6 months, or whenever comparison with check standards indicates a problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

5.7 Matrix Spike Solutions: Matrix spike solutions should be prepared by dilution of stock standard
solutions so that no more than 250 (iL of spike solution are required to provide a final sample spike level within
quality control (QC) limits.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Soil and sediment samples should be shipped in 4-ounce
wide-mouth glass jars with Teflon-lined caps.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum recommended holding time for soil
organophosphorus pesticide samples is 24 hours between collection and extraction, and 14 days between extraction
and analysis.

7.0 PROCEDURE

7.1 Extraction: The sample extraction technique for organophosphorus pesticides in soil or sediment is as

follows:

7.1.1 Add 2 to 3 grams of well-homogenized sample to a tared and labeled 150 mm culture tube;
weigh again to the nearest 0.01 g. Record weights.

7.1.2 Optional: Add approximately 1 g of sodium sulfate (recommended for samples of high
moisture content).

7.1.3 Add 1 mL of nanograde methanol by repipet to the culture tube and cap.

7.1.4 Vortex at maximum speed for 30 seconds.

7.1.5 Add 10 mL nanograde hexane by repipet to the culture tube and recap.

7.1.6 Vortex at maximum speed for 60 seconds.

FMC-P-006-5

-------
7.1.7 Transfer a 6 to 8-mL aliquot of the hexane layer to a labeled 100 mm culture tube using a
disposable Pasteur pipet.

7.1.8 Centrifuge for 5 minutes.

7.1.9 For autosampler analysis, transfer approximately 1 mL of extract into a Teflon-lined screw-
cap autosampler vial, using a disposable Pasteur pipet.

7.1.10 Enhanced sensitivity may be achieved by transferring 5 mL of hexane extract to a 10-mL
graduated centrifuge tube, reducing the solvent volume to between 0.2 and 0.4 mL by standard low
temperature N2 blowdown techniques, and making the final sample extract volume 0.5 mL by rinsing the
tube walls with hexane.

7.1.11 The sample extract is now ready for GC injection.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly, that is, conditions exist such that resolution,
retention times, response reporting, and interpretation of chromatograms are within acceptable QC
limits (Section 7.5). Using at least 3 calibration standards for each organophosphorus pesticide or
pesticide mixture prepared as described in Section 5, generate initial calibration curves (response
versus mass of standard injected) for each target organophosphorus pesticide (refer to Section 7.4
for chromatographic procedures).

7.3.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.5) based
on each pesticide's 3 Calibration Factors (CFs, see Section 7.5) to determine the acceptability
(linearity) of the curve. Unless otherwise specified, the %RSD must be less than or equal to 25
percent, or the calibration is invalid and must be repeated. Establish a new initial calibration curve
any time the GC system is modified (e.g., new column, change in gas supply, change in oven
temperature, etc.) or shut down.

7.3.2 Continuing calibration:

7.3.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing
calibration validation. This single-point analysis follows the same analytical procedures used in
the initial calibration. Use instrument response to compute the CF which is then compared to the
mean initial calibration factor (CF), and calculate a relative percent difference (RPD, see Section
7.5). Unless otherwise specified, the RPD must be less than or equal to 25 percent for the
continuing calibration to be considered valid, or the calibration must be repeated. A continuing
calibration remains valid for a maximum of 24 hours provided the GC system remains unaltered
during that time.

7.3.2.2 Employ the continuing calibration in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

FMC-P-006-6

-------
7.3.3 Final calibration: Obtain the final calibration at the end of each batch of samples analyzed.
The allowable RPD between the mean initial calibration and final calibration CF s for each analyte must be
less than or equal to 50 percent. A final calibration that achieves an RPD less than or equal to 25 percent
may be used as an ongoing continuing calibration.

7.4 Instrumental Analysis

7.4.2 Chromatograms:

7.4.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks
are on scale over a 100-fold range are acceptable. However, this can be no greater than a 100-fold
range. This is to prevent retention time shifts by column or detector overload. Generally, peak
response should be greater than 25 percent and less than 100 percent of full scale deflection to allow
visual recognition of the organophosphorus pesticides.

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature program;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.4.3 Organophosphorus pesticide identification:

7.4.3.2 Generally, individual peak retention time windows should be less than or equal
to 5 percent for packed column analyses and less than or equal to 2 percent for megabore capillary
columns.

FMC-P-006-7

-------
Table 2

EXAMPLE GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Makeup Gas:

Detector Gases:

Column Temperature Program:

Injector Temperature:
Detector Temperature:
G.C. Analysis Time:
Standard/Sample Injection:

Shimadzu GC 14A equipped with an FTD.

Nelson Analytical PC Integrator with a dual-channel interface and
20-MB hard disk drive for data storage.

J&W 15 m x 0.53 mm DB-5 orDB-1301 fused silica megabore column.

Ultrapure helium at a flow rate of 10 mL/min.

Ultrapure helium at a flow rate of 40 mL/min.

Ultrapure hydrogen at a flow rate of 30 to 40 mL/min and ultrapure air at a flow
rate of 150 to 200 mL/min.

Initial temperature: 130°C;

Initial time: 2 mins
Ramp rate 1: 2.5°C/min
Final temperature 1: 155°C
Ramp rate 2: 5°C/min
Final temperature 2: 245°C
Final time: 6 mins

250oC

300oC

36 mins

Solvent flush manual injection or automated sample injection is
recommended for organophosphorus pesticide analysis. For the solvent
flush technique, the syringe barrel volume plus 1 (iL of nanograde
hexane, 0.5 (iL of air, and 2.0 to 3.0 (iL (measured to the nearest 0.05
HL) of sample extract are sequentially drawn into a 10-(iL syringe and
immediately injected into the GC.

FMC-P-006-8

-------
7.4.3.3 For the purpose of FASP analyses, peak intensity (height or area) matching for
positive identification is based on the chemist's best professional judgement in consultation with
more experienced chromatographic spectral data interpretation specialists, when required. It is
possible that interferences may preclude positive identification of an analyte. In such cases, the
chemist should report the presence of the interferents with a maximum pesticide concentration
possible (see Section 7.5.4).

7.4.4 System performance: Degradation of organophosphorus pesticides may occur in the GC
system especially if the injector column inlet is contaminated.

7.4.5 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided in Appendix B of this method.

7.4.6 Analytical sequence:

7.4.6.1 Instrument blank.

7.4.6.2 Initial calibration.

7.4.6.3 Check standard solution and performance evaluation sample (if available).

7.4.6.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.6.5 Associated QC lot method blank.

7.4.6.6 Twenty samples and associated QC lot spike and duplicate.

7.4.6.7 Repeat sequence beginning at Step 7.4.6.5 until all sample analyses are completed
or another continuing calibration is required.

7.4.6.8 Final calibration when all sample analyses are complete.

7.5 Calculations

7.5.1 Initial calibration:

7.5.1.1 Measure the GC response to single-component organophosphorus pesticides by
determining CFs, the ratio of the response peak area or height to the mass injected.

7.5.1.2 Calculate the CF for each individual organophosphorus pesticide in the initial
calibration. The integrator may be used to make all of these computations.

_ Area of Peak

Mass of Injected (nanograms)

7.5.2 Using the CF values, calculate the %RSD for each organophosphorus pesticide at the 3
concentration levels using the following equation:

FMC-P-006-9

-------
%RSD = — x 100
X

where SD, the standard deviation, is given by

sd = \ it-

\ i" i

Xi - X) 2

N - 1

where: X;
X
N

Individual calibration factor (per analyte),

Mean of initial 3 calibration factors (per analyte),
Number of calibration standards.

7.5.2.1 The %RSD must be less than or equal to 25 percent.

7.5.3 Continuing calibration:

7.5.3.1	Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations. Midrange standards for all initial calibration analytes must be analyzed at
specified intervals (less than or equal to 24 hours).

7.5.3.2	The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

7.5.4 Final calibration:

7.5.4.1	Obtain the final calibration at the end of any batch of samples analyzed.

7.5.4.2	The maximum allowable RPD between the mean initial calibration and final
calibration factors for each analyte must be less than or equal to 50 percent. A final calibration
which achieves an RPD less than or equal to 25 percent may be used as an ongoing continuing
calibration.

| CF - CF \

RPD = -	-	— x 100

CFX + CFc

2

where: CF,

CFc

Mean CF from the initial calibration for each analyte
Measured CF from the continuing calibration for the same analyte.

| CF - CF |
RPD = -	-	— x 100

cft + cff

2

FMC-P-006-10

-------
where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.5 Sample quantitation:

7.5.5.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations:

(A) (V ) (E) (D)

Concentration (]ig/L) =

(CF) (V,) (W)

where: Ax =

Response for the analyte to be measured.

CFc =

CF from the continuing calibration for the same analyte.

V;

Volume of extract injected (|iL).

Vt

Volume of total extract (|iL).

Ws

Weight of sample extracted (g).

E

Enhanced sensitivity factor (if Section 7.1 extract concentration is used,



E = 10; if no enhancement, E = 1)

D

Dilution factor, if used.

7.5.5.2	Compute organophosphorus pesticide sample concentrations from individual peak
responses.

7.5.5.3	Report results in micrograms per kilogramr ((ig/kg) without correction for blank,
spike recovery, or percent moisture.

7.5.5.4	Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) which allows the
data user to determine if additional (e.g., CLP analyses) work is required, or, if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 3. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-P-006-11

-------
Table 3

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F050.003 (Organophosphorus Pesticides in Soil)

Advisory Quality Control Limits*

Analyte

Spike Recovery (%R)

Duplicate RPD
(%)

Phorate

30 to 200

± 100

Dimethoate

30 to 200

± 100

Diazinon

30 to 200

± 100

Disulfoton

30 to 200

± 100

Malathion

30 to 200

± 100

Methyl Parathion

30 to 200

± 100

Merphos

30 to 200

± 100

DEF

30 to 200

± 100

Ethion

30 to 200

± 100

EPN

30 to 200

± 100

Azinphos Methyl

30 to 200

± 100

Ronnel

30 to 200

± 100

Parathion Ethyl

30 to 200

± 100

C arbophenothion

30 to 200

± 100

Azinphos Ethyl

30 to 200

± 100

Coumaphos

30 to 200

± 100

Dichlorvos

30 to 200

± 100

Diozathion

30 to 200

± 100

Phosphamidon

30 to 200

± 100

F enthion

30 to 200

± 100

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ±3 times the quantitation limit for that individual analyte.

FMC-P-006-12

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatogram is an example of a gas chromatogram for several commonly encountered
organophosphorus pesticides.

Figure 1

Gas Chromatogram - Organophosphorus Pesticides

Column:

J&W 15 m x 0.53 mm DB-5 or DB-1301 fused silica megabore column.

Injector Temperature: 250°C
Detector Temperature: 300°C

Gas: Carrier: Ultrapure helium at a flow rate of 10 mL/min.

Makeup gas: Ultrapure helium at a flow rate of 40 mL/min.
Reaction gas: Ultrapure hydrogen at a flow rate of 30 to 40 mL/min.
Reaction gas: Ultrapure air at a flow rate of 150 to 200 mL/min.

Detector:

FTD

FMC-P-006-13

-------
9.2 Method F050.003 spike and duplicate samples: Spike and duplicate sample results are presented as
examples of FASP Method F050.003 empirical data (see Tables 4 and 5).

Table 4

FASP METHOD F050.003
ORGANOPHOSPHORUS PESTICIDE SOIL MATRIX SPIKE PERCENT RECOVERY (%R)



Amount



Sample

Percent



Spiked

Sample

with spike

Recovery

Compound

(Hg/kg)

(Hg/kg)

(Hg/kg)

(%)

Phorate

970

100UF

1216

125

Diazinon

865

100UF

840

97

Disulfoton

1000

100UF

843

84

Methyl Parathion

1170

100UF

100UF

0

DEF/Merphos

985

100UF

504

51

EPN

2670

200UF

1548

58

Azinphos Methyl

2710

200UF

2035

75

U - The material was analyzed for but was not detected. The associated numerical value is a FASP
quantitation limit, adjusted for sample weight, extract volume, and sample dilution.

F - Data has been generated using FASP methodologies. Analytes are tentatively identified and
concentrations are quantitiative estimates.

FMC-P-006-14

-------
Table 5

FASP METHOD F050.003
ORGANOPHOSPHORUS PESTICIDE SOIL
DUPLICATE ANALYSIS RELATIVE PERCENT DIFFERENCE

Compound

Sample
Result
(Hg/kg)

Duplicate
Result
(Hg/kg)

Relative Percent
Difference
(%)

Phorate

100UF

100UF

0

Dimethoate

100UF

100UF

0

Diazinon

100UF

100UF

0

Disulfoton

100UF

100UF

0

Malathion

100UF

100UF

0

Methyl Parathion

100UF

100UF

0

DEF/Merphos

100UF

100UF

0

Ethion

50UF

50UF

0

EPN

200UF

200UF

0

Methyl Azinphos

200UF

200UF

0

Ronnel

100UF

100UF

0

Ethyl Parathion

235

283

18

Carbophenotion

150UF

150UF

0

Ethyl Azinphos

50UF

50UF

0

Coumaphos

100UF

100UF

0

Dichlorvos

350UF

350UF

0

Dioxathion

500UF

500UF

0

Phosphamidon

300UF

300UF

0

F enthion

1000UF

1000UF

0

U - The material was analyzed for but was not detected. The associated numerical value is a FASP
quantitation limit, adjusted for sample weight, extract volume, and sample dilution.

F - Data has been generated using FASP methodologies. Analytes are tentatively identified and
concentrations are quantitative estimates.

FMC-P-006-15

-------
10.0 REFERENCES

Information not available.

FMC-P-006-16

-------
APPENDIX A

FASP Method F050.003

Instrument Options:

GC System 3:	Shimadzu GC 14A with FTD or FPD, used for temperature-programmed

megabore capillary column analyses.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-P-006-17

-------
Specific Instrument Parameters:

Instrument:

Integrator:

Column:

Carrier Gas:

Makeup Gas:

Detector Gases:

APPENDIX B

FASP Method F050.003

Shimadzu GC 14A equipped with an FTD.

Nelson Analytical PC Integrator with a dual-channel interface and
20-MB hard disk drive for data storage.

J&W 15 m x 0.53 mm DB-5 orDB-1301 fused silica megabore column.

Ultrapure helium at a flow rate of 10 mL/min.

Ultrapure helium at a flow rate of 40 mL/min.

Ultrapure hydrogen at a flow rate of 30 to 40 mL/min and ultrapure air at a flow
rate of 150 to 200 mL/min.

Column Temperature Program:

Injector Temperature:
Detector Temperature:

Initial temperature: 130°C;
Initial time: 2 mins
Ramp rate 1: 2.5°C/min
Final temperature 1: 155°C
Ramp rate 2: 5°C/min
Final temperature 2: 245°C
Final time: 6 mins

250oC

300oC

FMC-P-006-18

-------
FASP Method Number F050.005

PHENOXYHERBICIDES IN SOIL/SEDIMENT

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various phenoxyherbicides in soil and sediment samples using gas chromatographic (GC) techniques
with an electron capture detector (ECD).

1.2 This method yields tentative identification and estimated quantitation of the analytes listed in Table 1.
Approximate method quantitation limits (QL) are also in Table 1. Reported values are on "as-received" basis; no dry
weights are used.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 To begin sample analysis, a measured amount of soil or sediment is placed in a screw-cap culture tube.
The soil is acidified and extracted with acetone, diethyl ether, and petroleum ether. The extract is back-extracted into
a measured volume of a potassium hydroxide (KOH) solution, and the ether is evaporated. The extract is cleaned up
with diethyl ether and petroleum ether, then acidified and back-extracted into diethyl ether and petroleum ether. The
extract is dried with sodium sulfate, then derivatized (esterified) with diazomethane. The derivatized extract is
solvent exchanged into isooctane for analysis. Analysis is performed using a temperature-programmed or isothermal
GC with an ECD. A megabore capillary column or a packed glass column is used under temperature-programmed
oven conditions. Identification is based on comparison of retention times and relative peak intensities between
samples and standards. Quantitation is based on the external standard method.

3.0 INTERFERENCES

3.1 Phthalate esters are common interferents encountered in ECD analyses. Interference may be minimized
by use of pesticide grade or ultrapure reagents, exhaustive cleanup of glassware, and avoidance of plastic materials
in laboratory operations. Phthalate interferences may be avoided through the use of selective detectors such as Hall
electrolytic conductivity detectors (ELCD).

3.2 The use of phenolic caps without Teflon liners should be avoided. Phenolic caps may deteriorate when
exposed to solvents and concentrated acid, causing interfering peaks in an ECD chromatogram. The analytical system
must be demonstrated to be free from contamination under conditions of the analysis by running laboratory reagent
blanks.

FMC-P-007-1

-------
Table 1

FASP METHOD F050.005 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Phenoxyherbicide

CAS Number

Quantitation Limit
in Soil/Sediment**
(Hg/kg)

Dicamba

1918-00-9

100

2,4-D

94-75-7

500

Silvex

93-72-1

100

Bromoxynil

100

2,4,5-T

93-76-5

100

2,4,5-TB

100

Dinoseb

88-85-7

250

Ioxynil

1000

2,4-DB

5000

* Specific quantitation limit values are highly matrix dependent. The quantitation limits listed herein are

provided for guidance and may not always be achievable.

** Quantitation limits listed for soil or sediment are on "as-received" basis.

3.3 GC interference by sample carryover may be minimized by use of disposable glassware during sample
preparation and by use of the maximum possible rinse cycle on automatic injection systems, or by thoroughly rinsing
syringes used in manual injections.

3.4 Interferences coextracted from samples are matrix and site specific. It is possible that techniques used
in either FASP or Routine Analytical Services (RAS) CLP methods may fail to eliminate interferences. Highly
specialized CLP Special Analytical Services (SAS) techniques may be required to produce acceptable analytical
results.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are 2 GC options that meet the requirements of this method. Other
GC configurations may be substituted if they also meet the method requirements.

4.1.1 Gas chromatograph. option 1: An analytical system complete with an isothermal GC capable
of operation at elevated temperatures and all necessary accessories including injector and detector systems
designed or modified to accept packed analytical columns is required. The system shall have a data handling
system attached to the detector that is capable of retention time labeling, relative retention time comparisons,
and providing peak height and peak area measurements.

FMC-P-007-2

-------
4.1.1.1	Column 1: 1.8 m x 3.0 mm I.D. glass column packed with GP 1.5%
SP-2250/1.95% SP-2401 on 100/120 Supelcoport (Supelco), or equivalent.

4.1.1.2	Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco), or equivalent.

4.1.1.3	Detector: Linearized ECD with optional makeup gas supply at the detector's inlet.

4.1.1.4	Gas supply: The carrier gas and makeup gas (if required) should be ultrapure 5
percent methane in argon, or equivalent. All gases should pass through oxygen traps prior to the
GC to prevent degradation of the column's analytical coating and detector foil.

4.1.2 Gas chromatograph. option 2: An analytical system, complete with a temperature
programmable GC and all necessary accessories including injector and detector systems designed or
modified to accept megabore capillary analytical columns, is required. The system shall have a data
handling system attached to the detector that is capable of retention time labeling, relative retention time
comparisons, and providing peak height and peak area measurements.

4.1.2.1	Column: 15 m x 0.53 mm I.D. DB-608 fused silica capillary column (FSCC; J&W
Scientific), or equivalent.

4.1.2.2	Detector: Linearized ECD using a system with makeup gas supply at the detector's
capillary inlet.

4.1.2.3	Gas supply: The carrier gas should be ultrapure helium. The makeup gas should
be ultrapure 5 percent methane in argon, or equivalent. All gases should pass through oxygen traps
prior to the GC to prevent degradation of the column's analytical coating and detector foil.

4.2 Other laboratory equipment

4.2.1	Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction; disposable 16 mm x 100 mm borosilicate glass culture tubes with
Teflon-lined caps for acid cleanup.

4.2.2	Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3	Spatulas: Stainless steel, micro and semi-micro.

4.2.4	Microsvringe: 10-(iL.

4.2.5	Balance: Top loading, capable of weighing to 0.01 g, used to weigh samples.

4.2.6	Micropipets: 10- to 1,000-^L.

4.2.7	Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and 25-mL.

4.2.8	Volumetric flasks: 10-, 25-, 50-, 100-mL.

4.2.9	Vortex mixer: Vortex Genie, or equivalent.

4.2.10	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

FMC-P-007-3

-------
4.2.11	Amber storage bottles: 100- and 500-mL.

4.2.12	Autosampler: 1- or 2- mL with Teflon-lined screw caps.

4.2.13	Graduated centrifuge: 10-mL, with ground glass stoppers.

4.2.14	Oxygen traps: Supelpure-O-Trap and OMJ-1 indicating tube, or equivalent.

4.2.15	Leak detector: Snoop liquid, or equivalent, for packed column operations or GOW-MAC
gas leak detector, or equivalent, for megabore capillary operations.

4.2.16	Timer: 0 to 10 minute range.

4.2.17	Teflon wash bottles: 500-mL.

4.2.18	Laboratory oven: Capable of maintaining temperature of greater than or equal to 200°C.

4.2.19	Nitrogen blowdown apparatus: N-Evap, or equivalent.

4.2.20	Chromatographic data stamps: Used to record instrument operating conditions.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Hexane: Pesticide quality, or equivalent.

5.1.2	Acetone: Pesticide quality, or equivalent.

5.1.3	Isooctane: Pesticide quality, or equivalent.

5.1.4	Petroleum ether: Pesticide quality, or equivalent

5.1.5	Diethyl ether: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

5.2.1	Reagent water: Reagent water is defined as water in which an interferent is not observed
at the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent), a water purification system (Milli-Q
Plus with Organex Q cartridge, Barnstead Water-1 Systems [provided with the Base Support Facilities], or
equivalent), or purchased from commercial laboratory supply houses.

5.2.2	Sodium sulfate: Reagent, anhydrous, granular. Pre-conditioned by heating for 24 hours at
200°C and storing in clean glass containers with Teflon-lined caps.

5.3	Gases

FMC-P-007-4

-------
5.3.1 Five percent methane in argon: Ultrapure or chromatographic grade (always used in

conjunction with an oxygen trap).

5.3.2 Helium: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as manufacturer
certified solutions. Phenoxyherbicide single standards may be used; however, standard mixtures of herbicides are
recommended, if available.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with isooctane. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for soil or sediment phenoxyherbicide
samples are 7 days between collection and extraction and 24 hours between derivatization and analysis.

7.0 PROCEDURE

7.1 Extraction: The sample extraction technique for phenoxyherbicides in soil or sediment is as follows:

7.1.1 Add 2 to 3 g of well-homogenized sample to a tared and labeled 150 mm culture tube; weigh

again to the nearest 0.01 g. Record weights.

7.1.2 Acidify the soil with approximately 1 mL of concentrated hydrochloric acid (HC1).

7.1.3 Add 1.0 mL of acetone to the acidified soil; vortex 1 minute.

7.1.4 Add 3.0 mL of diethyl ether; vortex 1 minute.

7.1.5 Transfer the solvent layer to a second labeled 150 mm culture tube.

7.1.6 Repeat steps 7.1.3 through 7.1.5; Add the second extract to the first.

FMC-P-007-5

-------
7.1.7 Concentrate the ether layer using nitrogen blowdown techniques on an N-Evap, if necessary
(total volume should be one-third the total culture tube volume available, or less); the nitrogen blowdown
apparatus should be set up in the fume hood.

7.1.8 Add 5.0 mL of aqueous 5 percent acidified sodium sulfate solution to the extract.

7.1.9 Check the pH of the water. If the water pH is greater than 2.0, add concentrated HC1 until the
pH is less than or equal to 2.0.

7.1.10 Vortex the extract for 1 minute.

7.1.11 Transfer the ether layer to a new labeled 150 mm culture tube.

7.1.12 Add 2.0 mL of petroleum ether to the water; vortex 1 minute.

7.1.13 Add the petroleum ether layer to the extract; discard the water layer.

7.1.14 Add 5.0 mL of deionized water and 0.5 mL of aqueous 37 percent KOH solution to the

7.1.15 Evaporate the ether using a water bath at 65°C (the water bath should be set up in the fume

7.1.16 Allow the sample to heat for an additional 60 minutes.

7.1.17 The extract is ready for cleanup.

7.2 Cleanup

7.2.1 General extract cleanup:

7.2.1.1 Check the pH of the water, which should be greater than or equal to 12.0. If the
pH is less than 12.0, add 37 percent KOH solution to adjust the pH.

7.2.1.2 Add 5.0 mL of diethyl ether to the water; vortex for 60 seconds. Discard the ether

layer.

7.2.1.3 Repeat step 7.2.1.2

7.2.1.4 Add 2.0 mL of petroleum ether to the sample; vortex for 60 seconds. Discard the
ether layer.

7.2.1.5 Acidify the sample to a pH of less than 2.0 with concentrated sulfuric acid.

7.2.1.6 Add 5.0 mL of diethyl ether to the sample; vortex for 1 minute.

7.2.1.7 Transfer the ether layer to a labeled, 150 mm culture tube.

7.2.1.8 Add 2.0 mL of diethyl ether to the water; vortex for 1 minute.

7.2.1.9 Transfer the ether layer to the culture tube containing the extract.

FMC-P-007-6

extract.

hood).

-------
7.2.1.10 Add 2 mL of petroleum ether to the water; vortex for 1 minute.

7.2.1.11 Transfer the ether to the culture tube containing the extract.

7.2.1.12 Add approximately 2 g of acidified sodium sulfate to the extract. Allow the
extract to stay in contact with the sodium sulfate for at least 2 hours.

7.2.1.13 The sample is ready to be derivatized in accordance with Section 7.3.

7.3 Derivatization

7.3.1 Conduct phenoxyherbicide analyses utilizing batch technique. Each batch (approximately 20
samples) has unique continuing calibrations, final calibrations, matrix spikes, duplicates, and blanks
derivatized at the same time and under the exact same conditions as the samples in the batch. Outside
intercomparison of continuing calibration calibration factors (CFs, see section 7.6) to the mean initial
calibration (CF) apply only to the batch of samples with which the QC samples were derivatized.

7.3.2 The derivatization procedure for the phenoxyherbicide extract is as follows:

7.3.2.1 Assemble the diazomethane bubbler.

7.3.2.2 Add 5 mL of diethyl ether to the first test tube. Add 1 mL of diethyl ether, 1 mL
of carbitol, 1.5 mL of 37 percent KOH, and 0.1 to 0.2 g Diazald to the second test tube.
Immediately place the exit tube into the culture tube containing the sample extract.

7.3.2.3 Apply nitrogen flow (10 mL/min) to bubble diazomethane through the extract for
10 minutes, or until the yellow color of diazomethane persists. The amount of Diazald used is
sufficient for esterification of approximately 3 sample extracts. An additional 0.1 to 0.2 g of
Diazald may be added (after the initial Diazald is consumed) to extend the generation of the
diazomethane. There is sufficient KOH present in the original solution to perform a maximum of
approximately 20 minutes of total esterification.

7.3.2.4 Remove the culture tube and cap. Store at room temperature in a hood for 20

minutes.

7.3.2.5 Solvent exchange the extract into isooctane to a final volume of 3 mL.

7.3.2.6 Sample is ready for injection.

7.4 Calibration

7.4.1 Initial calibration:

7.4.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution,
retention times, response reporting, and interpretation of chromatographic spectra are within
acceptable QC limits (Section 7.6). Using at least 3 calibration standards for each
phenoxyherbicide prepared as described in Section 5.5, generate initial calibration curves (response
versus mass of standard injected) for each phenoxyherbicide (refer to Section 7.5 for
chromatographic procedures).

FMC-P-007-7

-------
7.4.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.6) based
on the 3 calibration factors for each analyte to determine the acceptability (linearity) of the curve.
Unless otherwise specified, the %RSD must be less than or equal to 25 percent, or the calibration
is invalid and must be repeated. Establish a new initial calibration curve anytime the GC system
is altered (e.g., new column, change in gas supply, or change in oven temperature) or shut down.

7.4.2 Continuing calibration:

7.4.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing
calibration validation. This single point analysis follows the same analytical procedures used in
the initial calibration. Use instrument response to compute the CF which is then compared to the CF
and calculate a relative percent difference (RPD, see Section 7.6). Unless otherwise specified, the
RPD must be less than or equal to 25 percent for the continuing calibration to be considered valid.
Otherwise, the calibration must be repeated. A continuing calibration remains valid for a maximum
of 24 hours provided the GC system remains unaltered during that time.

7.4.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.6) for the period over which the calibration has been validated.

7.4.3 Final calibration: Obtain a final calibration at the end of each batch of sample analyses. The
allowable RPD between the mean initial calibration and final calibration CFs for each analyte must be less
than or equal to 50 percent. Use a final calibration that achieves an RPD less than or equal to 25 percent as
an ongoing continuing calibration.

7.5 Instrumental Analysis

7.5.1 Instrument parameters: Table 2 summarizes an example of acceptable instrument operating
conditions for the GC. Other instruments, columns, and chromatographic conditions may be used if this
method's QC criteria are met.

7.5.2 Chromatograms:

7.5.2.1 Computer reproduction of chromatograms that are attenuated to ensure all peaks
are on scale over a 100-fold range are acceptable. However, this can be no greater than a 100-fold
range. This is to prevent retention time shifts by column or detector overload. Generally, peak
response should be greater than 25 percent and less than 100 percent of full-scale deflection to
allow visual pattern recognition of phenoxyherbicides.

7.5.2.2 The following information must be recorded to each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.5.3 Phenoxvherbicide identification:

FMC-P-007-8

-------
7.5.3.1 Qualitative identification of phenoxyherbicides is based in part on ECD selectivity,
but primarily on retention time of spectral pattern as compared to known standards on a single
selected column. A second dissimilar column (e.g., 3% SP-2100 or 3% OV-1 on 100/120
Supelcoport) may be used for confirmation.

7.5.3.2 Generally, individual peak retention time windows should be less than or equal
to 5 percent for packed column analyses and less than or equal to 2 percent for megabore capillary
columns.

7.5.3.3 For the purposes of FASP analyses, relative peak intensity (height or area)
matching for positive phenoxyherbicide identification is based on the chemist's best professional
judgement in consultation with more experienced spectral data interpretation specialists, when
required. It is possible that interferences may preclude positive identification of an analyte. In
such cases, the chemist should report the presence of the interferents with a maximum possible
phenoxyherbicide concentration (see Section 7.6.4).

7.5.4 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided in Appendix B of this method.

7.5.5 Analytical sequence:

7.5.5.1 Instrument blank.

7.5.5.2 Initial calibration.

7.5.5.3 Check standard solution and/or performance evaluation sample (if available).

7.5.5.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.5.5.5 Associated QC lot method blank.

7.5.5.6 Twenty samples and associated QC lot spike and duplicate.

7.5.5.7 Repeat sequence beginning at step 7.5.5.5 until all sample analyses are complete
or another continuing calibration is required.

7.5.5.8 Final calibration when sample analyses are complete.

FMC-P-007-9

-------
Table 2

EXAMPLE FASP ISOTHERMAL GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature:
G.C. Analysis Time:
Standard/Sample Injection:

Shimadzu GC Mini-2 equipped with Linearized ECD

Shimadzu Chromatopac C-R3A Data Processor

1.8m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent methane in argon at a flow rate of 40 mL/min
160°C, isothermal
260°C
50 minutes

Solvent flush manual injection or automated sample injection is
recommended for phenoxyherbicide analysis. For the solvent flush
technique, the syringe barrel plus 2 (iL of nanograde hexane, 0.5 (iL of
air, and 2.0 (iL (measured to the nearest 0.05 (iL) of sample extract are
sequentially drawn into a 10-(iL syringe and immediately injected into
the GC.

7.6 Calculations

7.6.1 Initial calibration:

7.6.1.1	Measure the GC response to single-component phenxyherbicide by determining
CFs, the ratio of the response peak area or height to the mass injected.

7.6.1.2	Calculate the CF for each individual phenxyherbicide in the initial calibration. The
integrator may be used to make all of these computations.

CF

Area of Peak

Mass of Injected (nanograms)

7.6.2 Using the CF values, calculate the %RSD for each organophosphorus pesticide at the 3
concentration levels using the following equation:

ST)

hRSD = 4=- x 100
X

where SD, the standard deviation, is given by

FMC-P-007-10

-------
sd = \ it-

\ i" i

Xi - X) 2

N - 1

where: X;
X
N

Individual calibration factor (per analyte),

Mean of initial 3 calibration factors (per analyte),
Number of calibration standards.

7.6.2.1 The %RSD must be less than or equal to 25 percent.

7.6.3 Continuing calibration:

7.6.3.1	Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations. Midrange standards for all initial calibration analytes must be analyzed at
specified intervals (less than or equal to 24 hours).

7.6.3.2	The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

7.6.4 Final calibration:

7.6.4.1	Obtain the final calibration at the end of any batch of samples analyzed.

7.6.4.2	The maximum allowable RPD between the mean initial calibration and final
calibration factors for each analyte must be less than or equal to 50 percent. A final calibration
which achieves an RPD less than or equal to 25 percent may be used as an ongoing continuing
calibration.

| CF - CF \

RPD = -	-	— x 100

CFX + CFc

2

where: CF,

CFc

Mean CF from the initial calibration for each analyte
Measured CF from the continuing calibration for the same analyte.

| CF - CF |
RPD = -	-	— x 100

cft + cff

2

where: CF,
CFf

Mean CF from the initial calibration for each analyte
Final CF for the same analyte.

FMC-P-007-11

-------
7.6.5 Sample quantitation:

7.6.5.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations:

[A ) [V ) (E) (D)

Concentration (]ig/L) =

( CF ) ( V.) (W)

Ax

Response for the analyte to be measured.

CFc =

CF from the continuing calibration for the same analyte.

V;

Volume of extract injected (|iL).

Vt

Volume of total extract (|iL).

Ws

Weight of sample extracted (g).

E

Enhanced sensitivity factor (if Section 7.1 extract concentration is used,



E = 10; if no enhancement, E = 1)

D

Dilution factor, if used.

7.6.5.2	Compute phenoxyherbicide sample concentrations from individual peak responses.

7.6.5.3	Report results in micrograms per kilograms ((ig/kg) without correction for blank,
spike recovery, or percent moisture.

7.6.5.4	Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) which allows the
data user to determine if additional (e.g., CLP analyses) work is required, or, if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 3. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-P-007-12

-------
Table 3

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F050.005 (Phenoxyherbicides in Soil)

Advisory Quality Control Limits*



Spike

Duplicate RPD

Analyte

(%R)

(%)

Dicamba

30 to 200

± 100

2,4-D

30 to 200

± 100

Silvex

30 to 200

± 100

Bromoxynil

30 to 200

± 100

2,4,5-T

30 to 200

± 100

2,4,5-TB

30 to 200

± 100

Dinoseb

30 to 200

± 100

Ioxynil

30 to 200

± 100

2,4-DB

30 to 200

± 100

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ±3 times the quantitation limit for that individual analyte.

FMC-P-007-13

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatograms are examples of GC chromatograms for several commonly encountered
phenoxyherbicides, using an ECD.

Figure 1

Gas Chromatogram-Phenoxyherbicides

Column: 1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 160°C

Detector/Injector Temperature: 260°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-P-007-14

-------
9.2 Method F050.005 examples of sample OA/OC results: Spike and duplicate sample results are presented
as examples of FASP Method F050.005 empirical data (see Tables 4 and 5).

Table 4

FASP METHOD F050.005
SOIL MATRIX SPIKE PERCENT RECOVERY (%R)

Og/kg)

Analyte

Amount
Spiked

Sample

Sample
with Spike

Percent
Recovery

Boromoxynil

800 F

100 UF

114 F

14

Dinoseb

1765 F

250 UF

171 F

10

2,4,5-TB

560 F

100 UF

835 F

149

Table 5

FASP METHOD F050.005
SOIL DUPLICATE SAMPLE RELATIVE PERCENT DIFFERENCE (RPD)

Analyte

Sample

Duplicate
Sample

Relative Percent
Difference

Dicamba

3300 F

3000 F

10

2,4-D

100 UF

200 UF

0

Silvex

100 UF

100 UF

0

Bromoxynil

130 UF

130 F

0

2,4,5-T

100 F

180 F

200

2,4,-DB

210 F

150 F

33

Dinoseb

130 F

140 F

7

U - The material was analyzed for but was not detected. The associated numerical value is a FASP quantitation
limit, adjusted for sample weight, extract volume, and sample dilution.

F - Data has been generated using FASP methodologies. Analytes are tentatively identified and concentrations are
quantitative estimates.

FMC-P-007-15

-------
10.0 REFERENCES

Information not available.

FMC-P-007-16

-------
APPENDIX A

FASP Method F050.005

Instrument Options:
GC System 1:

GC System 2:

GC System 3:

Data Handling System 1:
Data Handling System 2:
Data Handling System 3:

Shimadzu GC Mini-2 with linearized ECD, used for isothermal packed column
analyses.

Shimadzu GC Mini-2 with linearized ECD modified with a direct conversion and
makeup gas adapter for megabore capillary column operations and equipped with
a Shimadzu TP-M2R temperature programmer, used for temperature-programmed
megabore capillary column analyses.

Shimadzu GC-14A with linearized ECD, used for temperature-programmed
megabore capillary column analyses.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit and
Shimadzu FDD-1A Floppy Disk Drive.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-P-007-17

-------
APPENDIX B

FASP Method F050.005

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Injector Temperature:

Detector Temperature:

Shimadzu GC Mini-2 equipped with linearized ECD.

Shimadzu Chromatopac C-R3A Data Processor.

1.8 m x 3 mm glass column packed with 1.5% SP-2250/ 1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of 30 to 40 mL/min.

160°C, isothermal.

260°C.

260°C.

FMC-P-007-18

-------
FASP Method Number F050.006

PHENOXYHERBICIDES IN WATER

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various phenoxyherbicides in water samples using gas chromatographic (GC) techniques with an
electron capture detector (ECD).

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 To begin sample analysis, a 100-mL volumetric flask is filled with the sample. The water is acidified
and extracted with diethyl ether and petroleum ether. The extract is back-extracted into a measured volume of a
potassium hydroxide (KOH) solution, and the ether is evaporated. The extract is cleaned up with diethyl ether and
petroleum ether, then acidified and back-extracted into diethyl ether and petroleum ether. The extract is dried with
sodium sulfate, then derivatized (esterified) with diazomethane. The derivatized extract is solvent exchanged into
isooctane for analysis. Analysis is performed using a temperature-programmed or isothermal GC with an ECD. A
megabore capillary column or a packed glass column is used under temperature-programmed oven conditions.
Identification is based on comparison of retention times and relative peak intensities between samples and standards.
Quantitation is based on the external standard method.

3.0 INTERFERENCES

3.1 Phthalate esters are common interferents encountered in ECD analyses. Interference may be minimized
by use of pesticide grade or ultrapure reagents, exhaustive cleanup of glassware, and avoidance of plastic materials
in lab operations. Phthalate interferences may be avoided through the use of selective detectors such as Hall
electrolytic conductivity detectors (ELCD).

3.2 The use of phenolic caps not containing Teflon liners should be avoided. Phenolic caps may deteriorate
when exposed to solvents and concentrated acid, causing interfering peaks in an ECD chromatogram. The analytical
system must be demonstrated to be free from contamination under conditions of the analysis by running laboratory
reagent blanks.

FMC-P-008-1

-------
Table 1

FASP METHOD F050.006 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Phenoxyherbicide

CAS Number

Quantitation Limit
in W ater
(M-R/L)

Dicamba

1918-00-9

1.0

2,4-D

94-75-7

Silvex

93-72-1

1.0

Bromoxynil

1.0

5-T

93-76-5

1.0

2,4,5-TB

1.0

Dinoseb

88-85-7

5.0

Ioxynil

2,4-DB

* Specific quantitation limit values are highly matrix dependent. The quantitation limits listed herein are

provided for guidance and may not always be achievable.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are 2 GC options that meet the requirements of this method. Other
GC configurations may be substituted if they also meet the method requirements.

4.1.1 Gas chromatograph. option 1: An analytical system, complete with an isothermal GC capable
of operation at elevated temperatures and all necessary accessories including injector and detector systems
designed or modified to accept packed analytical columns, is required. The system shall have a data handling
system attached to the detector that is capable of retention time labeling, relative retention time comparisons,
and providing peak height and peak area measurements.

4.1.1.1 Column 1: 1.8 m x 3.0 mm I.D. glass column packed with GP 1.5%
SP-2250/1.95% SP-2401 on 100/120 Supelcoport (Supelco), or equivalent.

FMC-P-008-2

-------
4.1.1.2 Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco), or equivalent.

4.1.1.3 Detector: Linearized ECD with optional makeup gas supply at the detector's inlet.

4.1.2 Gas chromatograph. option 2: An analytical system, complete with a temperature
programmable GC and all necessary accessories including injector and detector systems designed or
modified to accept megabore capillary analytical columns, is required. The system shall have a data
handling system attached to the detector that is capable of retention time labeling, relative retention time
comparisons, and providing peak height and peak area measurements.

4.1.2.1 Column: 15 m x 0.53 mm I.D. DB-608 fused silica capillary column (FSCC; J&W
Scientific), or equivalent.

4.1.2.2 Detector: Linearized ECD using a system with makeup gas supply at the detector's
capillary inlet.

4.1.2.3 Gas supply: The carrier gas should be ultrapure helium. The makeup gas should
be ultrapure 5 percent methane in argon, or equivalent. All gases should pass through oxygen traps
prior to the GC to prevent degradation of the column's analytical coating and detector foil.

4.2 Other Laboratory Equipment

4.2.1 Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction; disposable 16 mm x 100 mm borosilicate glass culture tubes with
Teflon-lined caps, for acid cleanup.

4.2.2 Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3 Spatulas: Stainless steel, micro and semi-micro.

4.2.4 Microsvringe: 10-(iL.

4.2.5 Balance: Top loading, capable of weighing to 0.01 g, used to weigh samples.

4.2.6 Micropipets: 10- to 1,000-^L.

4.2.7 Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and 25-mL.

4.2.8 Volumetric flasks: 10-, 25-, 50-, and 100-mL.

4.2.9 Vortex mixer: Vortex Genie, or equivalent.

4.2.10 Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

FMC-P-008-3

-------
4.2.11 Amber storage bottles: 100- and 500-mL.

4.2.12	Autosampler: 1- or 2-mL, with Teflon-lined screw caps.

4.2.13	Graduated centrifuge: 10-mL, with ground glass stoppers.

4.2.14	Oxygen traps: Supelpure-O-Trap and OMJ-1 indicating tube, or equivalent.

4.2.15	Leak detector: Snoop liquid, or equivalent, for packed column operations or GOW-MAC
Gas Leak Detector, or equivalent, for megabore capillary operations.

4.2.16	Timer: 0 to 10 minute range.

4.2.17	Teflon wash bottles: 500-mL.

4.2.18	Laboratory oven: Capable of maintaining temperatures greater than or equal to 200°C.

4.2.19	Nitrogen blowdown apparatus: N-Evap, or equivalent.

4.2.20	Chromatographic data stamps: Used to record instrument operating conditions.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Hexane: Pesticide quality, or equivalent.

5.1.2	Acetone: Pesticide quality, or equivalent.

5.1.3	Isooctane: Pesticide quality, or equivalent.

5.1.4	Diethyl ether: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

5.2.1	Reagent water: Reagent water is defined as water in which an interferent is not observed
at the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent), a water purification system (Milli-Q
Plus with Organex Q cartridge, Barnstead Water-1 Systems [provided with the Base Support Facilities], or
equivalent), or purchased from commercial laboratory supply houses.

5.2.2	Sodium sulfate: Reagent, anhydrous, granular. Pre-conditioned by heating for 24 hours at
200°C and storing in clean glass containers with Teflon-lined caps.

5.3	Gases

5.3.1 Five percent methane in argon: Ultrapure or chromatographic grade (always used in
conjunction with an oxygen trap).

FMC-P-008-4

-------
5.3.2 Helium: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with isooctane. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for water phenoxyherbicide samples
are 7 days between collection and extraction and 24 hours between derivatization and analysis.

7.0 PROCEDURE

7.1 Extraction: The sample extraction technique for phenoxyherbicides in water is as follows:

7.1.1 Overfill a 100-mL volumetric flask with sample.

7.1.2 Bring the volume to 100 mL by removing excess sample with a pipet.

7.1.3 Remove 10 mL of sample from the volumetric flask.

7.1.4 Acidify the sample with sulfuric acid to a pH of less than or equal to 2.

7.1.5 Add 12 mL of diethyl ether; shake vigorously for 2 minutes.

7.1.6 Transfer the ether layer to a labeled 150 mm culture tube.

7.1.7 Add 2 to 3 mL of ethyl ether to the volumetric flask.

7.1.8 Transfer the ether layer to the 150 mm culture tube containing the extract.

FMC-P-008-5

-------
7.1.9 Add 2.0 mL of petroleum ether to the volumetric flask and shake vigorously for 2 minutes.

7.1.10 Transfer the ether layer to the 150 mm culture tube containing the extract.

7.1.11 Add 5.0 mL of deionized water and 0.5 mL of aqueous 37 percent KOH solution to the

extract.

7.1.12 Evaporate the ether using a water bath at 65°C (the water bath should be set up in the fume

hood).

7.1.13 Allow the sample to heat for an additional 60 minutes.

7.1.14 The extract is ready for cleanup.

7.2 Cleanup

7.2.1 General extract cleanup

7.2.1.1 Check the pH of the water, which should be greater than or equal to 12.0. If the
pH is less than 12.0, add 37 percent KOH solution to adjust the pH.

7.2.1.2 Add 5.0 mL of diethyl ether to the water; vortex for 60 seconds. Discard the ether

layer.

7.2.1.3 Repeat step 7.2.1.2

7.2.1.4 Add 2.0 mL of petroleum ether to the sample; vortex for 60 seconds. Discard the
ether layer.

7.2.1.5 Acidify the sample to a pH of less than 2.0 with concentrated sulfuric acid.

7.2.1.6 Add 5.0 mL of diethyl ether to the sample; vortex for 1 minute.

7.2.1.7 Transfer the ether layer to a labeled 150 mm culture tube.

7.2.1.8 Add 2.0 mL of diethyl ether to the water; vortex for 1 minute.

7.2.1.9 Transfer the ether layer to the culture tube containing the extract.

7.2.1.10 Add 2 mL of petroleum ether to the water; vortex for 1 minute.

7.2.1.11 Transfer the ether to the culture tube containing the extract.

7.2.1.12 Add approximately 2 g of acidified sodium sulfate to the extract. Allow the
extract to stay in contact with the sodium sulfate for at least 2 hours.

7.2.1.13 The sample is ready to be derivatized in accordance with Section 7.3.

7.3 Derivatization

7.3.1 Conduct phenoxyherbicide analyses utilizing batch technique. Each batch (approximately 20
samples) has unique continuing calibrations, final calibrations, matrix spikes, duplicates, and blanks

FMC-P-008-6

-------
derivatized at the same time and under the exact same conditions as the samples in the batch. Outside
intercomparison of continuing calibration factors (CFs, see section 7.6) to the mean initial calibration factor
(CF) apply only to the batch of samples with which the QC samples were derivatized.

7.3.2 The derivatization procedure for the phenoxyherbicide extract is as follows:

7.3.2.1 Assemble the diazomethane bubbler.

7.3.2.4 Remove the culture tube and cap. Store at room temperature in a hood for 20

minutes.

7.3.2.5 Solvent exchange the extract into isooctane to a final volume of 3 mL.

7.3.2.6 Sample is ready for injection.

7.4 Calibration

7.4.1 Initial calibration:

7.4.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.6) based
on the 3 CFs for each analyte to determine the acceptability (linearity) of the curve. Unless
otherwise specified, the %RSD must be less than or equal to 25 percent or the calibration is invalid
and must be repeated. Establish a new initial calibration curve any time the GC system is altered
(e.g., new column, change in gas supply, or change in oven temperature) or shut down, curve.

7.4.2 Continuing calibration:

FMC-P-008-7

-------
Otherwise, the calibration must be repeated. A continuing calibration remains valid for a maximum
of 24 hours provided the GC system remains unaltered during that time.

7.4.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.6) for the period over which the calibration has been validated.

7.5 Instrumental Analysis

7.5.2 Chromatograms:

7.5.2.2 The following information must be recorded to each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

FMC-P-008-8

-------
Table 2

EXAMPLE ISOTHERMAL GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature
G.C. Analysis Time:
Standard/Sample Injection:

Shimadzu GC Mini-2 equipped with linearized ECD

Shimadzu Chromatopac C-R3A Data Processor

1.8 m x 3 mm glass column packed with 1.5% SP-2250/1.95%
SP-2401 on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of
40 mL/min

160°C, isothermal

260°C

50 minutes

Solvent flush manual injection or automated sample injection
is recommended for phenoxyherbicide analysis. For the
solvent flush technique, the syringe barrel plus 2 (iL of
nanograde hexane, 0.5 (iL of air, and 2.0 (iL (measured to the
nearest 0.05 (iL) of sample extract are sequentially drawn into
a 10-(iL syringe and immediately injected into the GC.

FMC-P-008-9

-------
7.5.2.3 Phenoxvherbicide identification:

7.5.2.4 Qualitative identification of phenoxyherbicides is based in part on ECD selectivity,
but primarily on retention time of spectral pattern as compared to known standards on a single
selected column. A second dissimilar column (e.g., 3% SP-2100 or 3% OV-1 on 100/120
Supelcoport) may be used for confirmation.

7.5.2.5 Generally, individual peak retention time windows should be less than or equal
to 5 percent for packed column analyses and less than or equal to 2 percent for megabore capillary
columns.

7.5.2.6 For the purposes of FASP analyses, relative peak intensity (height or area)
matching for positive phenoxyherbicide identification is based on the chemist's best professional
judgement in consultation with more experienced spectral data interpretation specialists, when
required. It is possible that interferences may preclude positive identification of an analyte. In such
cases, the chemist should report the presence of the interferents with a maximum possible
phenoxyherbicide concentration (see Section 7.6.4).

7.5.3 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided in Appendix B of this method.

7.5.4 Analytical sequence:

7.5.4.1 Instrument blank.

7.5.4.2 Initial calibration.

7.5.4.3 Check standard solution and/or performance evaluation sample (if available).

7.5.4.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.5.4.5 Associated QC lot method blank.

7.5.4.6 Twenty samples and associated QC lot spike and duplicate.

7.5.4.7 Repeat sequence beginning at step 7.5.5.5 until all sample analyses are complete
or another continuing calibration is required.

7.5.4.8 Final calibration when sample analyses are complete.

7.6 Calculations

7.6.1 Initial calibration:

7.6.1.1 Measure the GC response to single-component phenxyherbicide is measured by
determining CFs, the ratio of the response (peak area or height) to the mass injected.

7.6.1.2 Calculate the CF for each individual phenxyherbicide in the initial calibration. The
integrator may be used to make all of these computations.

FMC-P-008-10

-------
Area of Peak

Cr

Mass of Injected (nanograms)

7.6.1.3 Using the CF values, calculate the %RSD for each organophosphorus pesticide at
the 3 concentration levels using the following equation:

ST)

hRSD = 4=r x 100
X

where SD, the standard deviation, is given by

SD

(X. - X)'
N ~ 1

where: X; =	Individual calibration factor (per analyte),

X =	Mean of initial 3 calibration factors (per analyte),

N =	Number of calibration standards.

7.6.1.4 The %RSD must be less than or equal to 25 percent.

7.6.2 Continuing calibration:

7.6.2.1	Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations. Midrange standards for all initial calibration analytes must be analyzed at
specified intervals (less than or equal to 24 hours).

7.6.2.2	The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

| CF - CF \
RPD = -			— x 100

CFx + CFc

2

where: CF, =	Mean CF from the initial calibration for each analyte

CFc =	Measured CF from the continuing calibration for the same analyte.

7.6.3 Final calibration:

7.6.3.1	Obtain the final calibration at the end of any batch of samples analyzed.

7.6.3.2	The maximum allowable RPD between the mean initial calibration and final
calibration factors for each analyte must be less than or equal to 50 percent. A final calibration

FMC-P-008-11

-------
which achieves an RPD less than or equal to 25 percent may be used as an ongoing continuing
calibration.

\CFt - CF„
RPD = 		—

cft + cff

where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.6.4 Sample quantitation:

7.6.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations:

(A ) (V ) (E) (D)

Concentration (]ig/L) =

(CF ) (V,) (V)

where: Ax =

Response for the analyte to be measured.

CFc =

CF from the continuing calibration for the same analyte.

V;

Volume of extract injected (|iL).

Vt

Volume of total extract (|iL).

Vs

Volume of sample extracted (mL).

E

Enhanced sensitivity factor (if Section 7.1 extract concentration is used,



E = 10; if no enhancement, E = 1)

D

Dilution factor, if used.

7.6.4.2	Compute phenoxyherbicide sample concentrations from individual peak responses.

7.6.4.3	Report results in micrograms per liter (|ig/L) without correction for blank, spike
recovery, or percent moisture.

7.6.4.4	Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) which allows the
data user to determine if additional (e.g., CLP analyses) work is required, or, if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

8.0 QUALITY CONTROL

8.1 Quality Control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R)
and duplicate RPD are presented in Table 3. This method should be used in conjunction with the quality assurance
and control (QA/QC) section of this catalog.

FMC-P-008-12

-------
Table 3

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F050.006 (Phenoxyherbicides in Water)

ADVISORY QUALITY CONTROL LIMITS*



Spike

Duplicate RPD

Analyte

(%R)

(%)

Dicamba

30 to 200

+ 50

2,4-D

30 to 200

+ 50

Silvex

30 to 200

+ 50

Bromoxynil

30 to 200

+ 50

2,4,5-T

30 to 200

+ 50

2,4,5-TB

30 to 200

+ 50

Dinoseb

30 to 200

+ 50

Ioxynil

30 to 200

+ 50

2,4-DB

30 to 200

+ 50

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ±3 times the quantitation limit for that individual analyte.

FMC-P-008-13

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatograms are examples of GC chromatograms for several commonly encountered
phenoxyherbicides, using an ECD.

Figure 1

Gas Chromatogram - Phenoxyherbicides

Column: 1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 160°C

Detector/Injector Temperature: 260°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-P-008-14

-------
9.2 Method F050.006 examples of sample QA/QC results: Spike and duplicate sample results are presented
as examples of FASP Method F050.006 empirical data (see Tables 4 and 5).

Table 4

FASP METHOD F050.006
WATER MATRIX SPIKE PERCENT RECOVERY (%R)

(Hg/L)

Analyte

Sample

Duplicate
Sample

Sample
with Spike

Percent
Recovery

Bromoxynil

7.1 F

1.0 UF

3.0 F

42

Dinoseb

15.7 F

5.0 UF

5.0 F

32

2,4,5-DB

7.5 F

1.0 UF

8.0 F

107

Table 5

FASP METHOD F050.006
WATER DUPLICATE SAMPLE RELATIVE PERCENT DIFFERENCE (RPD)

(Hg/L)







Relative

Analyte

Sample

Duplicate

Percent





Sample

Difference

Dicamba

1.0 UF

1.0 UF

0

2,4-D

10 UF

10 UF

0

Silvex

1.0 UF

1.0 UF

0

Bromoxynil

1.0 UF

1.0 UF

0

2,4,5-T

1.0 UF

1.0 Uf

0

2,4-DB

50 UF

50 UF

0

Dinoseb

5 UF

5 UF

0

U - The material was analyzed for but was not detected. The associated numerical value is a FASP quantitation
limit, adjusted for sample weight, extract volume, and sample dilution.

F - Data has been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

FMC-P-008-15

-------
10.0 REFERENCES

Information not available.

FMC-P-008-16

-------
APPENDIX A

FASP Method F050.006

Instrument Options:
GC System 1:
GC System 2:

GC System 3:

Data Handling System 1:
Data Handling System 2:
Data Handling System 3:

Data Handling System 4:

Shimadzu GC Mini-2 with linearized ECD, used for isothermal packed
column analyses.

Shimadzu GC Mini-2 with linearized ECD modified with a direct
conversion and makeup gas adapter for megabore capillary column
operations and equipped with a Shimadzu TP-M2R Temperature
Programmer, used for temperature-programmed megabore capillary
column analyses.

Shimadzu GC-14A with linearized ECD, used for
temperature-programmed megabore capillary column analyses.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit
and Shimadzu FDD-1A floppy disk drive.

P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai
80286 computer, and Epson LX800 printer.

FMC-P-008-17

-------
APPENDIX B

FASP Method F050.006

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature:

Shimadzu GC Mini-2 equipped with linearized ECD.

Shimadzu Chromatopac C-R3A Data Processor.

1.8 m x 3 mm glass column packed with 1.5% SP-2250/ 1.95%
SP-2401 on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of 30 to
40 mL/min.

160°C, isothermal.

260°C.

FMC-P-008-18

-------
FASP Method F93006
CLP PESTICIDE/PCB ANALYSIS OF WATER. SEDIMENT

AND SOIL BY GAS CHROMATOGRAPHY

1.0 SCOPE AND APPLICATION

1.1 This method covers the determination of organochlorine pesticides in water, sediment and soil by a
method of gas chromatography with electron capture detection (ECD) adapted for use by the Field Analytical Services
Program (FASP) mobile laboratory. This FASP method is intended to provide rapid turnaround analyses in the field.
FASP data are not considered to be a substitute for analyses performed within the Contract Laboratory Program.
FASP data are not intended to be legally defensible. Table 1 list the traget constituents.

2.0 SUMMARY OF METHOD

2.1 Soil, sediment and water sample extracts, prepared following FASP SOP F93005 "Preparation of
Sediment, Soil and Water Samples for Pesticide Analysis", are analyzed by gas chromatography with electron capture
detection following Contract Laboratory Programs Protocols.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph (GC): Varian 3400 GC with an electron capture detector (ECD).

4.2 Autosampler: Varian 8100.

4.3 Data System: PE Nelson Chromoatographic software.

5.0 REAGENTS

5.1 Iso-octane: Pesticide Residue Analysis Grade.

5.2 Hexane: Pesticide Residue Analysis Grade.

5.3 Resolution Check Mixture in iso-octane:

Compounds

ng/mL

gamma-Chlordane
Endosulfan I
4,4'-DDE
Dieldrin

Endosulfan sulfate
Endrin ketone
Methoxychlor
T etrachloro-m-xylene
Decachlorobiphenyl

10.0

20.0

100.0

20.0

FMC-P-009-1

-------
Table 1

FASP METHOD F93005 TARGET COMPOUND LIST

Method Analvtes

alpha-BHC

beta-BHC

gamma-BHC

delta-BHC

Heptachlor

Aldrin

Heptachlor epoxide
Endosulfan I
Dieldrin
4,4'-DDE
Endrin

Endosulfan II

4,4'-DDD

Endosulfan sulfate

4,4'-DDT

Methoxychlor

Endrin ketone

Endrin aldehyde

alpha-Chlordane

gamma-Chlordane

T oxaphene

Aroclor-1016

Aroclor-1221

Aroclor-1232

Aroclor-1242

Aroclor-1248

Aroclor-1254

Aroclor-1260

5.4 Performance Evaluation Mixture fPEA/D in Iso-octane:

Compounds

ng/mL

gamma-BHC

10.0

alpha-BHC

10.0

4,4'-DDT

100.0

beta-BHC

10.0

Endrin

50.0

Methoxychlor

250.0

T etrachloro-m-xylene

20.0

Decachlorobiphenyl

20.0

5.5 Individual Standard Mixtures A and B in Iso-octane:

FMC-P-009-2

-------


Low Point

Midpoint

High Point

Mixture A Compounds

ng/mL

ng/mL

ng/mL

alpha-BHC

5.0

50.0

150.0

gamma-BHC

5.0

50.0

150.0

Heptachlor

5.0

50.0

150.0

Endosulfan I

5.0

50.0

150.0

Dieldrin

10.0

100.0

300.0

Endrin

10.0

100.0

300.0

4,4'-DDD

10.0

100.0

300.0

4,4'-DDT

10.0

100.0

300.0

Methoxychlor

50.0

500.0

1500.0

T etrachloro-m-xylene

20.0

20.0

20.0

Decachlorobiphenyl

20.0

20.0

20.0



Low Point

Midpoint

High Point

Mixture B Compounds

ng/mL

ng/mL

ng/mL

beta-BHC

5.0

50.0

150.0

delta-BHC

5.0

50.0

150.0

Aldrin

5.0

50.0

150.0

Heptachlor epoxide

5.0

50.0

150.0

alpha-Chlordane 5.0

50.0

150.0



gamma-Chlordane

5.0

50.0

150.0

4,4'-DDE

10.0

100.0

300.0

Endosulfan sulfate

10.0

100.0

300.0

Endrin aldehyde 10.0

100.0

300.0



Endrin ketone

10.0

100.0

300.0

Endosulfan II

10.0

100.0

300.0

T etrachloro-m-xylene

20.0

200.0

600.0

Decachlorobiphenyl

20.0

200.0

600.0

5.6 Multicomponent Standards, each prepared individually in iso-octane with surrogates added:

Compounds

ng/mL

Aroclor-1016/1260

100.0

Aroclor-1221

200.0

Aroclor-1232

100.0

Aroclor-1242

100.0

Aroclor-1248

100.0

Aroclor-1254

100.0

T oxaphene

500.0

T etrachloro-m-xylene

20.0

Decachlorobiphenyl

20.0

5.7	Helium: Carrier gas, ultra pure or equivalent.

5.8	Nitrogen: Make-up gas ultra pure or equivalent.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not available.

FMC-P-009-3

-------
7.0 PROCEDURE

7.1	Sample Preparation: The samples are prepared following FASP SOP F93005 for the extraction of soil,
sediment and water samples for pesticide/PCB analyses.

7.2	Gas Chromatograph Operating Conditions:

•	Carrier Gas

•	Column Flow

•	Make-up Gas

•	Make-up Gas Flow

•	Initial Temperature

•	Initial Time

•	Ramp

•	Final Temperature

•	Final Hold

•	Primary Analytical Column

•	Confirmation Column

•	Injector Temperature

•	Detector Temperature

7.3 Analytical Sequence:

7.3.1	Resolution Check.

7.3.2	Performance Evaluation Mixture.

7.3.3	Aroclor-1016/1260.

7.3.4	Aroclor-1221.

7.3.5	Aroclor-1232.

7.3.6	Aroclor-1242.

7.3.7	Aroclor-1248.

7.3.8	Aroclor-1254.

7.3.9	Toxaphene.

7.3.10	Low Point Standard A.

7.3.11	Low Point Standard B.

7.3.12	Midpoint Standard A.

7.3.13	Midpoint Standard B.

7.3.14	High Point Standard A.

Helium
5 mL/minute

N2

30 mL/minute

140°C

0.5 minutes

6°C/min

280°C

10 minutes

DB-608, 30 meters, 0.53 mm ID, fused silica

megabore capillary column
DB-1701, 0.53 mm ID, fused silica
megabore capillary column
250°C
300°C

FMC-P-009-4

-------
7.3.15 High Point Standard B.

7.3.16 Instrument Blank.

7.3.17 Performance Evaluation Mixture.

7.4 Sample Analysis

7.4.1 1 mL sample vials containing the sample extracts are placed on the autosampler following
the standards outlined in the analytical sequence in Section 7.3.

7.4.2 The instrument blank indicated in Section 7.3 is a hexane solution containing 20.0 ng/mL of
the surrogates.

7.5 Compound Identification

7.5.1 Single Component Pesticide Identification:

7.5.1.1 Single component pesticides are identified by retention time.

7.5.1.2 On-scale chromatograms are required for identification.

7.5.2 Multicomponent Pesticide Identification:

7.5.2.1 Mulitcomponent pesticides are identified both by pattern recognition and retention

time.

7.6 Compound Quantitation

7.6.1 Single Component Pesticide Quantitation:

7.6.1.1 Quantitation is performed on both columns.

7.6.1.2 The detector response of all single component target analytes must be within the
linear range of the initial calibration for quantitation.

7.6.1.3 The concentrations of target pesticides are calculated following the equations
outlined in USEPA CLP SOW 3/90, Section 13.5, page D-52/PEST.

7.6.2 Multicomponent Pesticide Quantitation:

7.6.2.1 A summation of the heights or areas of three to five of the major peaks are used
for the quantitation of toxaphene and Aroclors.

8.0 QUALITY CONTROL

8.1 Initial Calibration

8.1.1 The initial calibration sequence outlined in Section 7.3 is analyzed prior to sample analysis.

8.1.2 Calibration factors for each of the single component pesticides are calculated.

FMC-P-009-5

-------
8.1.3 Absolute retention times are determined for all single response pesticides, the surrogates and
at least three major peaks of each multicomponent analyte.

8.1.4 Resolution Check Acceptance Criteria:

8.1.4.1 The height of the valley between two adjacent peaks (4,4'-DDE/dieldrin,
methoxychlor/endrin ketone, endosulfan I/gamma-chlordane) in the Resolution Check Mixture must
be < 60% of the height of the shorter peak.

8.1.4.2 The retention time of each of the single component pesticides in the Resolution
Check must be within ± 0.02 minutes of the mean retention time.

8.1.5 PEM Acceptance Criteria:

8.1.5.1 The breakdown of 4,4'-DDT and endrin must be < 20% and the combined
breakdown of 4,4'-DDT and endrin must be < 30% on both columns.

8.1.5.2 All peaks must be 100% resolved on both columns.

8.1.5.3 The absolute retention time of each of the single component pesticides and
surrogates must be within ± 0.02 minutes of the mean established in the three-point initial
calibration; ± 0.025 minutes for methoxychlor.

8.1.5.4 The relative percent difference of the calculated and true amount for each single
component pesticide and surrogate must be < 25%.

8.1.6 Individual Standard Acceptance Criteria:

8.1.6.1 The percent relative standard deviation (%RSD) of the calibration factors from the
three-point calibration must be < 15% for alpha-BHC, beta-BHC, gamma-BHC, DDT, endrin and
methoxychlor and < 10% for all other single component pesticides.

8.1.6.2 One chromatogram from each of the two Individual Standard Mixtures A and B
must yield peaks of 50-100% of full scale.

8.1.6.3 The retention time of each of the single component pesticides in the Individual
Standard Mixtures must be within ± 0.02 minutes of the mean retention time.

8.1.6.4 The resolution between adjacent peaks in the midpoint Individual Standard
Mixtures A and B must be ^ 90%.

8.2 Calibration Verification

8.2.1 Sample analyses must be bracketed in 12-hour periods by acceptable analyses of and
instrument blank and PEM at the beginning and instrument blank and midpoint Individual Standard Mixtures
A and B at the end of the sequence.

8.2.1.1 After a break in sample analyses, an instrument blank and PEM must be analyzed.

8.2.2 PEM Acceptance Criteria:

FMC-P-009-6

-------
8.2.2.1 Follow criteria outlined in Sections 8.1.4.1, 8.1.4.2, 8.1.4.3 and 8.1.4.4.

8.2.3 Individual Standard Acceptance Criteria:

8.2.3.1 Follow criteria outlined in Sections 8.1.5.3 and 8.1.5.4

8.2.3.2 The relative percent difference between the midpoint concentration of the Individual
Standard Mixtures and true amount for each single component pesticide and surrogate
must be < 25%.

8.3	Instrument Blank Acceptance Criteria

8.3.1 The instrument blank must not contain any target pesticide at a concentration >0.5 times the
quantitation limit.

8.4	Surrogate Recovery Acceptance Criteria

8.4.1 The advisory QC limits for surrogate recovery are 60-150%.

8.5	Matrix Spike Recovery Acceptance Criteria

8.5.1 The percent recoveries (%R) and the relative percent difference (RPD) between the recoveries
of the matrix spike compounds must meet the following criteria:

Water/Soil

Compound

%R

RPD

gamma-BHC
Heptachlor

50-130
30-130
30-130
30-130
40-140
20-130

50
30
40
40
40
40

Aldrin

Dieldrin

Endrin

4,4'-DDT

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

1. CLP, EPA Contract Laboratory Program Statement of Work for Organic Analyses

2. EPA Method 8080, Organochlorine Pesticides and PCBs

FMC-P-009-7

-------
FASP Method F93005

PREPARATION OF SEDIMENT. SOIL AND WATER SAMPLES FOR PESTICIDE ANALYSIS

1.0 SCOPE AND APPLICATION

1.1 This method covers the preparation of water, sediment and soil samples for organochlorine pesticide
analysis by the Field Analytical Services Program (FASP) mobile laboratory. This FASP method is intended to
provide rapid turnaround analyses in the field. FASP data are not considered to be a substitute for analyses performed
within the Contract Laboratory Program. FASP data are not intended to be legally defensible.

2.0 SUMMARY OF METHOD

2.1 Sediment and soil samples are prepared by sonication and water samples are prepared using solid phase
extraction (SPE) for pesticide analysis by gas chromatography with electron capture detection. Procedures for Data
Quality Level II and Level III are included in this S.O.P. For soil samples, a 20 gram sample of soil is mixed with
powdered anhydrous sodium sulfate and extracted with a 10 mL portion of acetone using a sonication bath. Four
milliliters of hexane are added followed by 10 mL of water to partition the phases. The hexane layer is collected and
run through a Florisil column, dried with anhydrous sodium sulfate and reduced in volume using a a nitrogen
blowdown procedure to yield a 1 mL final extract volume. For water samples, a 100 mL water sample is extracted
three times with 3 mL of hexane. Extracts are dried with anhydrous sodium sulfate, solvent exchanged to hexane
using a nitrogen blowdown procedure to yield a 1 mL final extract volume.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Vacuum Manifold: Varian Vac-Elute.

4.2 Vacuum Pressure Gauge.

4.3 Solid Phase Extraction Cartridges: Varian Bond Elute-C8, 500 mg.

4.4 Leur Stopcocks.

4.5 Sample Reservoirs: Varian, 75 mL.

4.6 Sonicator: Branson 3200 Sonicator Bath, 25°C.

4.7 Analytical Balance.

4.8 Centrifuge.

4.9 Florisil Cartridges.

4.10 Nitrogen Evaporator.

5.0 REAGENTS

5.1 Surrogate Solution in hexane:

FMC-P-010-1

-------
Compound	fig/mL

Tetrachloro-m-xylene	0.2

Decachlorobiphenyl	0.2

5.2	Pesticide Matrix Spiking Solution in hexane:

Pesticide	fig/mL

gamma-BHC	1.0

Heptachlor	1.0

Aldrin	1.0

Dieldrin	4.0

Endrin	4.0

4,4'-DDT	4.0

5.3	Florisil Cartridge Check Solution in hexane:

Compound	fig/mL

2,4,5-Trichlorophenol	0.1

Mid-point pesticide calibration mixture

5.4	Acetone: Pesticide Residue Analysis Grade.

5.5	Deionized water.

5.6	Hexane: Pesticide Residue Analysis Grade.

5.7	Methanol: Pesticide Residue Analysis Grade.

5.8	Sodium Hydroxide. 0.5 N.

5.9	Sulfuric Acid. 0.5 N.

5.10	Cleaned Copper Powder.

5.11	Anhydrous Sodium Sulfate.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Sample Preparation

7.1.1 Soil Samples:

FMC-P-010-2

-------
7.1.1.1 Twenty grams of sediment or soil are weighed on an analytical balance into a 40-
mL VOA vial. The sample weight is recorded in the Pesticide/PCB Extraction Log Book.
Anhydrous sodium sulfate is added to the sample to remove moisture.

7.1.1.2 The surrogate solution (2.0 mL) is added to the sample along with 10 mL of
acetone. The volume of the surrogates and Standard Log identification numbers are recorded in the
Pesticide/PCB Extraction Log Book.

7.1.1.3 The vial is placed in the sonicator bath. The sonicator bath is turned on for ten

minutes.

7.1.1.4 Four milliliters of hexane are added and the mixture is shaken for an additional

minute.

7.1.1.5 Ten milliliters of water are added and the phases are allowed to separate. The
hexane layer is drawn of and collected.

7.1.1.5.1 For Level II screening, proceed with the florisil clean up of the sample

extract.

7.1.1.5.2 For Level III, extract the soil/acetone/water mixture two more times,
using a 4 mL aliquot of hexane each time.

7.1.1.6 The sample extract is passed through a Florisil cartridge for cleanup.

7.1.1.6.1 A Pasteur pipette is packed with a small wad of glass wool. Enough
Florisil is added to make a 1 inch column. The Florisil column is washed with 5 mL of
90:10 hexane/acetone, making sure to keep the cartridge bed from drying out.

7.1.1.6.2 The sample is added to the Florisil column, and the pesticide are eluted
with 5 mL of 90:10 hexane/acetone and collected in a vial containing 2-5 grams of
anhydrous sodium sulfate.

7.1.1.7 The sample extract is transferred to a 2 mL conical sample tube and concentrated
with the nitrogen evaporator to a 1 mL final sample volume.

7.1.1.7.1 The sample extract volume is reduced to below 1 mL and brought to a
final volume of 1 mL with hexane. The sample extract is transferred to a 1 mL vial.

7.1.1.7.2 Sample extracts which require sulfur removal are cleaned up with
granular copper as outlined in section 14.4.6 of QTM for organochlorine pesticides, page
D-37-PEST-Q.

7.1.1.8 Sample extracts are stored at 4°C if necessary.

7.1.2 Water Samples

7.1.2.1 A 100 mL water sample is poured into a 125 mL separatory funnel. The sample
volume is recorded in the Pesticide/PCB Extraction Log Book.

FMC-P-010-3

-------
7.1.2.2 The pH of the sample is adjusted to 5.0-7.0 using NaOH or H2S04.

7.1.2.3 The surrogate solution (2.0 mL) is added along with 5 mL of methanol and the
sample is shaken vigorously. The volume of the surrogates and Standard Log identification
numbers are recorded in the Pesticide/PCB Extraction Log Book.

7.1.2.4 The sample is extracted three times with 3 mL portions of hexane.

7.1.2.5 The combined extracts are dried with 2-5 grams of sodium sulfate.

7.1.2.6 The sample is concentrated following section 7.1.1.7.

7.1.2.7 Sample extracts which require sulfur removal are cleaned up with granular copper
as outlined in section 14.4.6 of QTM for organochlorine pesticides, page D-37-PEST-Q.

7.1.2.8 Sample extracts are stored at 4°C if necessary.

8.0 QUALITY CONTROL

8.1 Method Blanks

8.1.1 Method blanks are prepared for each type of matrix and with each set of samples.

8.1.2 For water samples, the method blank is prepared using 100 mL of reagent water and following
the procedure from section 7.1.2.

8.1.3 For sediment/soil samples, the method blank is prepared using clean sand and following the
procedure from section 7.1.1.

8.2 Matrix Spikes

8.2.1 For Level II, no matrix spike analyses are performed.

8.2.2 For Level III analyses, matrix spikes and spike duplicates are prepared.

8.2.2.1 One set of matrix spike and spike duplicate are prepared for each batch or 20

samples.

8.2.2.2 Matrix spike samples are spiked with 1.0 mL of matrix spike solution, see section
5 for target analytes and concentrations.

9.0 METHOD PERFORMANCE

Information not available.

10. REFERENCES

1. USEPA CLP Draft SOW for Quick Turnaround Analysis (3/27/92)

2. USEPA Contract Laboratory Program Statement of Work for Organic Analyses (3/90)

FMC-P-010-4

-------
ESAT Region 10 Method
FIELD EXTRACTION AND ANALYSIS OF CHLORINATED PESTICIDES IN SOIL BY ECD

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining estimated
quantities of certain organochlorine pesticides in soil and sediment samples. Target compounds and the method
quantitation limits are listed in Table 1. This method may be modified at the discretion of the analyst in order to meet
project specific goals (i.e. detection limit modifications, larger or smaller analyte lists, optimization of
chromatographic conditions for specific target compounds, etc.)

1.2 This method is intended for use by, or under the supervision of, analysts experienced in gas
chromatography (GC) and in the interpretation of GC chromatograms.

1.3 It is strongly recommended that 10% of the samples submitted for analysis by this method be split and
submitted for confirmational analysis using an EPA regulated method. Confirmational analyses are recommended
for Level II field analysis per Data Quality Objectives for Remedial Response Activities (EPA/540/G-87/003) and
are required for QA2 analyses (not required for QA1 analyses) per Quality Assurance/Quality Control Guidance
for Removal Activities (EPA/540/G-90/004). Any site specific information pertaining to the required analysis would
greatly enhance the support capabilities of the FASP team (i.e., action levels, known interferences, etc.)

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil is placed in a disposable screw-cap vial and extracted with acetone.
Compounds are detected by an Electron Capture Detector (ECD). Identification is based on comparison of retention
times and relative peak intensities between samples and standards.

3.0 INTERFERENCES

3.1 Method interferences may be caused by contaminants in solvents, reagents, glassware, as well as other
sample processing equipment and may lead to discrete artifacts or elevated baselines in the GC chromato grams. All
reagents and apparatus must be routinely demonstrated to be free from interferences under the conditions of the
analysis by running method and instrument blanks.

3.2 Interferences due to sample carryover may be eliminated by the use of disposable glassware during
sample prep and thoroughly rinsing syringes used in manual injections.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System: The following option meets the requirements of this method. Other GC
configurations may be used if they meet method requirements.

4.1.1 Gas Chromatogram: The system may perform either isothermal or temperature programs
and contain necessary accessories including injector and detector systems capable of accepting an analytical
column.

4.1.1.1 Column: DB-5; 15m x ,548mm; 1.5 (im film

FMC-P-011-1

-------
Table 1

TARGET COMPOUNDS AND QUANTITATION LIMITS

CHLORINATED PESTICIDES

QUANTITATION
LIMITS

SOIL/SEDIMENT
(ug/Kg)*

CAS #

A-BHC

50

319-84-6

B-BHC

50

319-85-7

D-BHC

50

319-86-8

LINDANE

50

58-89-9

HEPTACHLOR

50

76-44-8

ALDRIN

50

309-00-2

HEPTACHLOR EPOXIDE

50

1024-57-3

ENDOSULFAN I

50

959-98-8

DIELDRIN

200

60-57-1

4,4'-DDE

200

72-55-9

ENDRIN

100

72-20-8

ENDOSULFAN II

100

33213-65-9

4,4'-DDD

100

72-54-8

ENDOSULFAN SULFATE

100

1031-07-8

4,4'-DDT

100

50-29-3

ENDRIN KETONE

100

53494-70-5

METHOXYCHLOR

500

72-43-5

ENDRIN ALDEHYDE

100

7421-93-4

CHLORDANE

2500

57-74-9

TOXAPHENE

10000

8001-35-2

*	Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided

for guidance and may not always be achievable.

Quantitation limits for soil and sediment are based on wet weight.

Column used: DB-5; 15m x ,548mm; 1.5(im film.

FMC-P-011-2

-------
4.1.1.2	Detectors: Linearized ECD

4.1.1.3	Gas Supply: The carrier gas should be ultra-pure helium. The makeup gas should
be ultra-pure nitrogen, or equivalent. All gases should pass through oxygen traps prior to the GC
to prevent degradation of the column's analytical coating and the detector foil.

4.1.1.4	Data System: Capable of retention time labeling, relative retention time
comparisons, and providing peak height and peak area measurements. The current system uses PE
Nelson and Turbochrome.

4.2 Laboratory Equipment

4.2.1	Screw-cap culture tubes: Disposable 16mm X 125mm borosilicate glass with teflon-lined
phenolic caps.

4.2.2	Disposable pipets: Pasteur, 6 and 9 in. long.

4.2.3	Spatulas: Stainless steel.

4.2.4	Balance: Top-loading, capable of weighing to 0.1 g.

4.2.5	Syringes: 10(iL, 25(iL, 100|iL, and 1000(iL.

4.2.6	Vortex Mixer: Vortex Genie or equivalent.

4.2.7	Centrifuge: Capable of holding 16 mm X 125 mm culture tubes.

4.2.8	Autosampler Vials: 1 or 2mL with Teflon-lined caps.

4.2.9	Volumetric Flasks: lOmL, 25mL, and lOOmL.

4.2.10	N-Evaporator: Variable temperature water bath with multi-sample nitrogen purge
capability.

4.2.11	Leak Detector: "Snoop" liquid or equivalent.

4.2.12	Amber Storage Bottles: lOmL with Teflon-lined screw-caps.

4.2.13	Graduated Centrifuge Tubes: lOmL with ground glass stoppers.

4.2.14	Polv Wash Bottles: 500mL

5.0 REAGENTS

5.1	Solvents

5.1.1	Methanol: Pesticide quality, or equivalent.

5.1.2	Acetone: Pesticide quality, or equivalent.

5.1.3	Isooctane: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

FMC-P-011-3

-------
5.2.1 Sodium Sulfate: Reagent grade, anhydrous, granular; preconditioned by heating for 24 hours
at 200°C and storing in clean glass containers with Teflon-lined caps.

5.2.2 Sulfuric Acid: Concentrated; reagent quality.

5.3 Gases

5.3.1 Nitrogen: Ultra-pure chromatographic grade.

5.3.2 Helium: Ultra-pure chromatographic grade.

5.4 Stock Standard Solutions: Stock standards for each analyte listed in Table 1, section 11.0, should be
prepared from A2LA certified neat standards. Stock standard solutions must be replaced after one year.

5.5 Calibration Standards: Calibration standards at a minimum of three concentration levels ranging from
5.0 - 200 pg/(iL should be prepared through iso-octane dilution of the stock standards. One concentration level should
be near, but not above, the method detection limit. The remaining concentration levels should define the working
range of the instrument. The calibration standards must also contain the surrogate. Calibration standards must be
protected from light and stored in teflon sealed screw-cap bottles at 4 ± 2°C. Calibration standards must be replaced
after six months, or sooner if comparison with check standards indicate a problem.

5.6 Surrogate Standards: The analyst will monitor the performance of the extraction and analytical system
by spiking each sample, blank and matrix spike with one or two surrogates not expected to be present in the sample.
Suggested surrogates include Tetrachloro-m-xylene (TCMX) and/or Decachlorobiphenyl (DCB).

5.7 Matrix Spikes: Matrix spike solutions may be prepared by the dilution of stock standard solutions. The
spiking level should be approximately 5X (five times) the analyte concentration in the native sample.

5.8 Check Standards: Standards prepared by an analyst other than the analyst who prepared the calibration
standards. The check standards must also come from a different source than the calibration standards and should also
contain the surrogate.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Soil and sediment samples should be collected in four ounce wide mouthed glass jars with Teflon-lined
caps. Collected samples should be kept refrigerated at 4 ± 2°C until analysis has been completed.

7.0 PROCEDURE

7.1 Safety

7.1.1 The toxicity and carcinogenicity of each reagent has not been precisely defined; however,
each chemical compound must be treated as a potential health hazard. Accordingly, exposure to these
chemicals must be reduced to the lowest possible level.

7.1.2 The analysts should be familiar with the location and proper use of the fume hoods, eye
washes, safety showers, and fire extinguishers. In addition, the analysts must wear protective clothing and
safety glasses at all times. Contact lenses may not be worn while working in the laboratory.

7.1.3 Fume hoods must be utilized whenever possible to avoid potential exposure to organic

solvents.

7.1.4 Work with solvents or chemicals may be performed only when at least one other chemist is
in the area.

FMC-P-011-4

-------
7.1.5 Waste must be disposed of by placing it in an appropriately marked container beneath the
fume hoods, which are located in the extraction rooms or other designated areas. All waste containers must
be labeled with the start date, end date, and type of waste (i.e. halogenated or non-halogenated solvents.)

7.2 Extraction

7.2.1 Add 1.0 ± 0.1 g of well-homogenized sample to a tared and labeled 125mm culture tube.
Record weights in the extraction log.

7.2.2 Add appropriate surrogate and matrix spikes at this time. Allow solutions to reach room
temperature before spiking. The final concentration of the surrogates and matrix spike target compounds
should be 100 pg/^iL.

7.2.3 Optional: Add approximately 1 g of sodium sulfate to samples with a high moisture content.

7.2.4 Add 1.0 mL of methanol to the culture tube and cap.

7.2.5 Vortex at maximum speed for 30 seconds.

7.2.6 Add 10.0 mL of acetone to the culture tube and recap.

7.2.7 Vortex at maximum speed for 60 seconds.

7.2.8 Transfer approximately 5 mL of extract to a labeled culture tube. Mark the meniscus of
culture tube. Save the remainder of the original extract for cleanup procedures if necessary.

7.2.9 Solvent exchange to isooctane by using N-evap. The extract is now ready for analysis.

7.3 Clean-up f Optional)

7.3.1 Add 1.0 mL of concentrated sulfuric acid to the extract and recap. NOTE: This cleanup step
should not be used initially when analyzing for Heptachlor, Heptachlor epoxide, Dieldrin, Endrin, Endrin
aldehyde, Endosulfan I, Endosulfan II, and Ensosulfan sulfate. Degradation of these compounds is
significant on contact with sulfuric acid.

7.3.2 Vortex at maximum speed for 60 seconds.

7.3.3 Centrifuge for 5 minutes.

7.3.4 Transfer approximately 1 mL of extract into a Teflon-lined screw-cap autosampler vial using
a disposable pipet. Do not transfer the acid layer. The acid will destroy the column and may cause
permanent damage to the detector. The sample is now ready for analysis.

7.4 Recommended GC Conditions

7.4.1 The recommended analytical column is a 15 meter megabore DB-5. The carrier gas should
be helium with a flow rate of approximately 7 mL/min. The makeup gas to the detector should be nitrogen
with a flow rate of approximately 45-55 mL/min. The injection volume should be approximately 1 (iL
directly on column.

7.4.2 The following temperature program has proven to provide adequate separation for all target
compounds using the column mentioned above. The injector temperature was set at 225 °C and the detector
temperature was set at 320°C.

FMC-P-011-5

-------
Initial Temperature Rate (deg/min) Temperature °C Hold Time (min)

140°C

2
0
0
5

5
2
5

200 °C
230°C
280°C

7.5 Instrument Performance/Calibration

7.5.1 Degradation Check:

7.5.1.1 Prepare a standard containing only 4,4'-DDT and Endrin at the same concentration
as the mid-level standard. Calculate percent degradation for each compound. The maximum
individual allowable percent breakdown for either DDT or Endrin is 20%, and the combined of the
two should be less than or equal to 30%. System degradation must be checked prior to any analysis
and be performed as the last analysis of the day. Note: It is only necessary to perform a
degradation check if one of the following compounds is being analyzed for: DDE, DDD, DDT,
Endrin, Endrin Ketone, or Endrin Aldehyde.

7.5.2 Initial Calibration

7.5.2.1 Generate initial calibration curves using at least three calibration standards for each
target compound as described in section 5.5.

7.5.2.2 Correlation coefficients (r2) for each calibration curve must be greater than 0.95,
or the relative standard deviation (RSD) of the response factors must be less than ± 25% for the
curve to be valid. A new initial calibration curve must be generated whenever the GC is altered or
shut down for long periods of time or if comparison with a continuing calibration standard indicates
a problem.

7.5.3 Continuing Calibration

7.5.3.1 A continuing calibration check must be performed at the beginning and end of
every analytical sequence and after every 10 samples. The midrange initial calibration standard
may be used for continuing calibration validation. For a continuing calibration to be valid, the
percent difference (%DIF) must be less than or equal to ± 25%. If this criteria is not met, reshoot
the continuing calibration standard. If the standard is still outside the acceptance criteria, a new
initial calibration curve must be generated.

7.5.3.2 For megabore capillary columns, retention times must be within two percent
difference of the days first continuing calibration standard.

7.6 Pesticide Identification

7.5.2.2.1 Relative Standard Deviation

ST)

RSD = x 100

aRF

where: SD
aRF

Standard deviation

Average response factor (cone/area)

FMC-P-011-6

-------
7.6.1	Qualitative identification of target compounds is based on retention time matching of the
sample with standard chromatograms.

7.6.2	Individual retention time windows should be less than a two percent difference based on the
first continuing calibration check of the day.

8.0 QUALITY CONTROL

8.1 Quality assurance guidelines must be met for all analyses. Limits for matrix spike and matrix spike
duplicate recoveries must fall between 50-150% REC. Percent recoveries for the surrogates must also meet the above
requirements. Refer to DOC# ESAT-10A-5188 "Quality Assurance Guidelines for Field Analysis" for specific
criteria.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

1.	Fasp Method Number F050.002.

2.	Fasp Method Number F050.001.

3.	CSL Method FMC-P-004-1.

FMC-P-011-7

-------
FASP Method Number F040.003
POLYCHLORINATED BIPHENYLS fPCBS) IN OIL

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various Aroclors, also known as polychlorinated biphenyls (PCBs), in oil samples.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 To begin sample analysis, a measured amount of oil is placed in a screw cap culture tube. The sample
is extracted with a measured volume of hexane. An optional cleanup involves treating an aliquot of the hexane extract
with concentrated sulfuric acid. Analysis is performed using either a temperature- programmed/isothermal gas
chromatograph (GC) with a megabore capillary column, or isothermal GC with a packed column and electron capture
detector (ECD). Identification is based on comparison of retention times and relative peak intensities between
samples and standards. Quantitation is based on the external standard method.

3.0 INTERFERENCES

3.1 Phthalate esters are common interferents encountered in PCB analyses. Interference may be minimized
by use of pesticide grade or ultrapure reagents, exhaustive cleanup of glassware, and avoidance of plastic materials
in laboratory operations. Phthalate interferences may be avoided through the use of selective detectors such as Hall
electrolytic conductivity detectors.

3.3 GC interference by sample carryover may be minimized by use of disposable glassware during sample
preparation and by use of the maximum number of rinse cycles on automatic injection systems, or by thoroughly
rinsing syringes used in manual injections.

FMC-PCB-001-1

-------
Table 1

FASP METHOD F040.003 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

PCB

CAS Number

Quantitation Limit in Oil**
(mg/kg)

Aroclor-1016

12674-11-2

2.5

Aroclor-1221

11104-28-2

2.5

Aroclor-1232

11141-16-5

2.5

Aroclor-1242

53469-21-9

2.5

Aroclor-1248

12672-29-6

2.5

Aroclor-1254

11097-69-1

5.0

Aroclor-1260

11096-82-5

5.0

Aroclor-1262

37324-23-5

10.0

* Specific quantitation limit values are highly matrix dependent. The quantitation limits listed herein are

provided for guidance and may not always be achievable.

** Quantitation limits listed for oil are on an "as-received" basis.

3.4 Many interfering organic compounds can be eliminated using the sulfuric acid cleanup method listed
in this method. If a sample contains percent-level concentrations of hydrocarbon-based oils, acid cleanup will not
remove all contaminants. It is possible that a significant shift in retention times will occur when narrow-bore (0.25
mm and 0.32 mm) capillary columns are used in the GC analysis. It is advised that wide-bore (0.53 mm or greater)
capillary columns be used.

3.5 Samples containing free sulfur or hexane-soluble organosulfur compounds may yield interfering GC
peaks. Cleanup of the extract can be made using copper turnings or filings. Mercury metal is also commonly used
for this purpose; however, its use is to be avoided in field applications because of disposal requirements and its
hazardous properties.

3.6 Interferences coextracted from samples are matrix and site specific. It is possible that techniques used
in either FASP or Routine Analytical Services (RAS) CLP methods may fail to eliminate interferences. Highly
specialized CLP Special Analytical Services (SAS) techniques may be required to produce acceptable analytical
results.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are 2 GC options that meet the requirements of this method. Other
GC configurations may be substituted if they also meet the method requirements.

4.1.1 Gas chromatograph. option 1: An analytical system complete with an isothermal GC capable

of operation at elevated temperatures and all necessary accessories including injector and detector systems

FMC-PCB-001-2

-------
designed or modified to accept packed analytical columns is required. The system shall have a data handling
system attached to the detector that is capable of retention time labeling, relative retention time comparisons,
and providing peak height and peak area measurements.

4.1.1.1 Column 1: 1.8 m x 3.0 mm I.D. glass column packed with GP 1.5%
SP-2250/1.95% SP-2401 on 100/120 Supelcoport (Supelco) or equivalent.

4.1.1.2 Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco) or equivalent.

4.1.1.3 Detector: Linearized ECD with optional makeup gas supply at the detector's inlet.

4.1.2.1 Column: 15 m x 0.53 mm I.D. DB-608 fused silica capillary column (FSCC)
(J&W Scientific) or equivalent.

4.1.2.2 Detector: Linearized ECD using a system with makeup gas supply at the detector's
capillary inlet.

4.2 Other laboratory equipment

4.2.1 Screw cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction.

4.2.2 Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3 Spatulas: Stainless steel, micro and semimicro.

4.2.4 Microsvringe: 10-(iL.

4.2.5 Balance: Top loading, capable of weighing to 0.01 g.

4.2.6 Micropipets: 10- to 1,000-^L.

FMC-PCB-001-3

-------
4.2.7 Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and

25-mL.

4.2.8	Volumetric flasks: 10-, 25-, 50-, 100-mL.

4.2.9	Vortex mixer: Vortex Genie or equivalent.

4.2.10	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.11	Amber storage bottles: 100- and 500-mL.

4.2.12	Autosampler vials: 1- or 2-mL with Teflon-lined screw caps.

4.2.13	Graduated centrifuge tubes: 10-mL with ground glass stoppers.

4.2.14	Oxygen traps: Supelpure-O-Trap and OMJ-1 Indicating Tube, or equivalent.

4.2.15	Leak detector: Snoop liquid or equivalent for packed column operations or GOW-MAC Gas
Leak Detector, or equivalent, for megabore capillary operations.

4.2.16	Timer: 0 to 10 minute range.

4.2.17	Teflon wash bottles: 500-mL.

4.2.18	Laboratory oven: Capable of maintaining temperature of greater than or equal to 200°C.

4.2.19	Chromatographic data stamp: Used to record instrument operating conditions.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Methanol: Pesticide quality, or equivalent.

5.1.2	Hexane: Pesticide quality, or equivalent.

5.1.3	Acetone: Pesticide quality, or equivalent.

5.1.4	Isooctane: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

5.2.1 Reagent water: Reagent water is defined as water in which an interferent is not observed at
the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent), a water purification system (Milli-Q
Plus with Organex Q cartridge, Barnstead Water-1 Systems [provided with the Base Support Facilities], or
equivalent), or purchased from commercial laboratory supply houses.

FMC-PCB-001-4

-------
5.2.2 Sodium sulfate: Reagent, anhydrous, granular. Pre-conditioned by heating for 24 hours at

200°C and storing in clean glass containers with Teflon liners.

5.2.3 Nitric acid: 10 percent vol./vol.

5.2.4 Sulfuric acid: Concentrated.

5.2.5 Copper turnings or filings: Remove oxides by treating with dilute nitric acid, rinse with

distilled water to remove all traces of acid, rinse with acetone, and dry under a stream of nitrogen.

5.3 Gases

5.3.1 Five percent methane in argon: Ultrapure or chromatographic grade (always used in

conjunction with an oxygen trap).

5.3.2 Helium: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as manufacturer
certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This procedure is done through volumetric dilution of the stock standards with isooctane. The
lowest concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be handled, preserved, and shipped maintaining a chainof-custody following current
EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this rule are
the sample volumes required by the laboratory. Oil samples should be shipped in 1-L narrow-mouth glass containers
with Teflon-lined caps.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for oil PCB samples are 7 days
between collection and extraction and 40 days between extraction and analysis.

7.0 PROCEDURE

7.1 Extraction: The sample extraction technique for PCBs in oil is as follows:

FMC-PCB-001-5

-------
7.1.1 Add 0.2 to 0.3 grams of well-homogenized sample to a tared and labeled 150-mm culture
tube; weigh again to the nearest 0.01 gram. Record weights.

7.1.2 Add 10.0 mL of nanaograde hexane by repipet to the culture tube and recap.

7.1.3 Vortex at the maximum speed for 60 seconds.

7.1.4 Centrifuge for 5 minutes.

7.1.5 Transfer a 6 to 8 mL aliquot of the hexane layer to a 100-mm culture tube using a disposable
Pasteur pipet.

7.1.6 Add 1.0 mL of concentrated sulfuric acid by repipet to the aliquot and recap.

7.1.7 Vortex at maximum speed for 60 seconds.

7.1.8 Centrifuge for 5 minutes.

7.1.9 Transfer approximately 1 mL of extract into a Teflon-lined screw cap autosampler vial using
a disposable Pasteur pipet. Avoid transfer of any of the acid layer.

7.1.10 Enhanced sensitivity may be achieved by transferring 5.00 mL of acid-treated hexane extract
to a 10-mL graduated centrifuge tube and reducing the solvent volume to between 0.2 and 0.4 mL by
standard low-temperature N2 blowdown techniques and making the final sample extract volume 0.50 mL by
rinsing tube walls with hexane.

7.1.11 The sample extract is now ready for GC injection.

7.2 Cleanup

7.2.1 General extract cleanup:

7.2.1.1 Use of sulfuric acid as a routine cleanup procedure (Section 7.1) may not be
necessary in all cases but is required for all samples as a general precaution. Clean extracts extend
both column and detector life and provide more accurate and precise data.

7.2.1.2 Interferences resulting from extracts containing elevated levels of hydrocarbons
are not completely eliminated by this technique. High levels of hydrocarbons may cause
suppression of detector response leading to quantitative underestimates (generally by less than or
equal to 10 percent, based on experience) of PCB concentrations. Small shifts in retention times,
which the analyst must be aware of, may also be caused by hydrocarbons in the extract. The effect
of concentrated sulfuric acid on PCBs is shown in Table 2.

7.2.2 Sulfur removal:

7.2.2.1 Sulfur interference: Elemental sulfur may be encountered in some oils. The
solubility of sulfur in various solvents is very similar to that of PCBs; therefore, the sulfur
interference follows along with the PCBs through the normal extraction and cleanup techniques.
Sulfur will be quite evident in gas chromatograms obtained from ECDs. If the GC is operated at
the normal conditions for PCB analysis, the sulfur interference can completely mask a large region
of the chromatogram. The recommended technique for the elimination of sulfur follows.

FMC-PCB-001-6

-------
7.2.2.2 Summary of method: The sample extract is combined with clean copper. The
mixture is shaken, and the extract is removed from the sulfur cleanup reagent.

7.2.2.3 Procedure for sulfur cleanup:

7.2.2.3.1 The copper used must be reactive; therefore, all oxides of copper must
be removed so that the copper has a shiny, bright appearance.

7.2.2.3.2 Transfer 5 mL of the final extract described in Section 7 (Step 7.1.9)
to a 16 mm x 100 mm screw cap culture tube with a Teflon-lined cap.

7.2.2.3.3 Add approximately 2 g of cleaned copper to the tube. Mix for at least
1 minute on the vortex mixer. This step may be repeated if sulfur removal is incomplete.

7.2.2.3.4 Resume the procedure described in Section

7.1.8.

7.2.2.3.5 The effect of copper on PCB recovery is shown in Table 3.

7.2.3 Solid phase extraction technology: Solid phase extraction (SPE) technology (e.g., Sep-Pak)
may provide an acceptable alternative to acid cleanup for PCB extracts.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 After an experienced chromatographer has ensured that the entire chromatographic
system is functioning properly; that is, conditions exist such that resolution, retention times,
response reporting, and interpretation of chromatograms are within acceptable QC limits, the GC
may be calibrated (Section 7.5). Using at least 3 calibration standards for each Aroclor prepared
as described in Section 5.5, generate initial calibration curves (response versus mass of standard
injected) for each Aroclor (refer to Section 7.4 for chromatographic procedures).

7.3.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.5) based
on each Aroclor's 3 calibration factors (CFs, see Section 7.5) to determine the acceptability (linear-
ity) of the curve. Unless otherwise specified, the %RSD must be less than or equal to 25 percent,
or the calibration is invalid and must be repeated. Anytime the GC system is altered (e.g., new
column, change in gas supply, or change in oven temperature) or shut down, a new initial
calibration curve must be established.

FMC-PCB-001-7

-------
Table 2

PCB DEGRADATION WITH TIME
AFTER TREATMENT WITH CONCENTRATED SULFURIC ACID

PCB

CAS Number

Approximate Percent Loss*

24 hours

48 hours

168 hours (1 week)

Aroclor-1016

12674-11-2

None**

None

Aroclor-1221

11104-28-2

None

Aroclor-1232

11141-16-5

None

Aroclor-1242

53469-21-9

None

Aroclor-1248

12672-29-6

None

Aroclor-1254

11097-69-1

None

Aroclor-1260

11096-82-5

None

Aroclor-1262

37324-23-5

Not Tested

After treatment with H2S04over the specified period of time.

No significant loss.

7.3.1.3 It is acceptable to provide an initial calibration for a single Aroclor (e.g., A-1248)
to establish system linearity and extrapolate the acceptable linearity for other Aroclors. However,
an initial calibration must be provided for every detected target analyte.

7.3.2 Continuing calibration:

7.3.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing calibra-
tion validation. This single point analysis follows the same analytical procedures used in the initial
calibration. Instrument response is used to compute the CF which is then compared to the mean
initial calibration factor (CF), and a relative percent difference (RPD, see Section 7.5) is calculated.
Unless otherwise specified, the RPD must be less than or equal to 25 percent for the continuing
calibration to be considered valid. Otherwise, the calibration must be repeated. A continuing
calibration remains valid for a maximum of 24 hours provided the GC system remains unaltered
during that time.

7.3.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

FMC-PCB-001-8

-------
Table 3

EFFECT OF COPPER TREATMENT ON
PCB RECOVERY

PCB

CAS Number

Average Percent
Recovery After
Treatment with Cu*

Aroclor-1242

53469-21-9

112

Aroclor-1248

12672-29-6

100

Aroclor-1254

11097-69-1

Aroclor-1260

11096-82-5

Aroclor-1262

37324-23-5

Percent recoveries cited are averages based on duplicate analyses.

7.3.3 Final calibration: Obtain a final calibration at the end of each batch of sample analyses. The
allowable RPD between the mean initial calibration and final calibration factors for each analyte must be
less than or equal to 50 percent. A final calibration that achieves an RPD of less than or equal to 25 percent
may be used as an ongoing continuing calibration.

7.4 Instrumental Analysis

7.4.2 Chromatograms:

7.4.2.1 Computer reproductions of chromatograms that are attenuated to ensure all peaks
are on scale over a 100-fold range are acceptable. To prevent retention time shifts by column or
detector overload, however, they can be no greater than a 100-fold range. Generally, peak response
should be greater than 25 percent and less than 100 percent of full-scale deflection to allow visual
pattern recognition of various Aroclors.

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

FMC-PCB-001-9

-------
Table 4

EXAMPLE ISOTHERMAL GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature
G.C. Analysis Time:

Standard/Sample Injection:

Shimadzu GC Mini-2 equipped with Linearized ECD

Shimadzu Chromatopac C-R3A Data Processor

1.8m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of 40 mL/min
Dependent on specific Aroclor, isothermal, range 190°C to 225°C
250oC

Dependent on specific Aroclors and matrix, range approximately 15 to
30 minutes

Solvent flush manual injection or automated sample injection is recom-
mended for PCB analysis. For the solvent flush technique, the syringe
barrel plus 1 (iL of nanograde hexane, 0.5 (iL of air, and 2.0 to 3.0 (iL
(measured to the nearest 0.05 (iL) of sample extract are sequentially
drawn into a 10-(iL syringe and immediately injected into the GC. Ex-
treme care must be taken to avoid contamination of the syringe needle
with sulfuric acid when loading the syringe. Injection of acid will
damage the analytical column and detector.

FMC-PCB-001-10

-------
• Date and time; and

• GC operator initials.

7.4.3 Aroclor identification:

7.4.3.1 Qualitative identification of PCBs is based on both retention time and relative peak
intensity matching of sample with standard chromatograms. PCBs are multiple component
mixtures of compounds which produce characteristic spectral patterns with relatively constant
proportions (Figures 1 through 5). Except cases where the mixture has suffered severe weathering,
the chromatographic fingerprint is easily recognized by an experienced chemist. Because PCBs are
extremely inert, their identification is further confirmed by their presence after digestion of inter-
ferences with concentrated sulfuric acid.

7.4.3.2 Qualitative identification of PCBs is based in part on ECD selectivity, but
primarily on retention time and spectral pattern as compared to known standards on a single
selected column. A second dissimilar column (e.g., 3% SP-2100 or 3% OV-1 on 100/120
Supelcoport) may be used for confirmation.

7.4.3.3 Generally, individual peak retention time windows should be less than or equal
to 5 percent for packed column analyses and less than or equal to 2 percent for megabore capillary
columns.

7.4.3.4 For the purposes of field analyses, relative peak intensity (height or area) matching
for positive Aroclor identification is based on the chemist's best professional judgment in consulta-
tion with more experienced spectral data interpretation specialists, when required. It is possible that
interferences may preclude positive identification of an analyte. In such cases, the chemist should
report the presence of the interferents with a maximum possible PCB concentration (see Section
7.5.4).

7.4.4 Specific instrument parameters: Specific instrument operating parameters that have been
followed are provided as "Specific Instrument Parameters" in Appendix B of this method.

7.4.5 Analytical sequence:

7.4.5.1 Instrument blank.

7.4.5.2 Initial calibration.

7.4.5.3 Check standard solution and/or performance evaluation sample (if available).

7.4.5.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.5.5 Associated QC lot method blank.

7.4.5.6 Twenty samples and associated QC lot spike and duplicate.

7.4.5.7 Repeat sequence beginning at step 5 until all sample analyses are complete or
another continuing calibration is required.

7.4.5.8 Final calibration when all sample analyses are complete.

FMC-PCB-001-11

-------
7.5 Calculations

7.5.1 Initial calibration: For multicomponent mixtures such as PCBs, calculations are normally
based on a minimum of 5 major peaks identified as resulting primarily from a single Aroclor. The chemist
may select any 5 major peaks free from interferences so long as the same peaks are used for both standard
and sample calculations.

7.5.1.1 Calculate the calibration factor (CF) for each individual peak and the summed area
of all 5 peaks for each Aroclor in the initial calibration. The integrator may be used to make all of
these computations.

_ Area of Peak

Mass of Injected (nanograms)

7.5.1.2 Using the calibration factors, calculate the %RSD for each Aroclor at a minimum
of 3 concentration levels using the following equation.

ST)

%RSD = 4=r x 100
X

where SD, the Standard Deviation, is given by

[X.-X):
(N-l)

where: X; = Individual calibration factor (per analyte),

X = Mean of initial 3 calibration factors (per analyte),

N = Number of calibration standards.

7.5.13 The %RSD must be less than or equal to 25.0 percent.

7.5.2 Continuing calibration:

7.5.2.1 Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations. Midrange standards for all initial calibration analytes must be analyzed as
continuing calibration standards at specified intervals (less than or equal to 24 hours).

7.5.2.2 The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

\CF -CFJ
RPD = - 1 — x 100

CFj+CFc

FMC-PCB-001-12

-------
Mean CF from the initial calibration for each analyte
Measured CF from the continuing calibration for the same analyte.

7.5.3 Final calibration:

7.5.3.1	The final calibration is obtained at the end of any batch of samples analyzed.

7.5.3.2	The maximum allowable RPD between the mean initial calibration and final
calibration factors for each analyte must be less than or equal to 50 percent. A final calibration that
achieves an RPD of less than or equal to 25 percent may be used as an ongoing continuing
calibration.

\~-CF |

RPD = -	1	— x 100

cfi+cff
2

where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.4 Sample quantitation:

7.5.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations.

[A ) [V ) (E) (D)

Concentrationluq/kq) = 	

(CFJ (V.) (Wg)

where: Ax =

Response for the analyte to be measured.

CFc =

CF from the continuing calibration for the same analyte.

V;

Volume of extract injected (|iL).

Vt

Volume of total extract (|iL).

Ws

Weight of sample extracted (g).

E

Enhanced sensitivity factor (if Section 8 extract concentration is used,



E = 10; if no enhancement, E = 1)

D

Dilution factor, if used.

7.5.4.2	Report results in micrograms per kilogram (ng/kg) without correction for blank
or spike recovery.

7.5.4.3	Compute sample concentrations for individual peaks, as well as total area (a total
of 6 values), to provide the analyst with data sufficient to identify interferences or unique chromato-
graphic responses. If concentrations based on individual peak quantitations do not fail a Student's
t-test, then the results calculated based on total peak areas should be reported as the sample
concentration. However, samples have been encountered in which certain of the chromatogram

FMC-PCB-001-13

-------
peaks have yielded concentrations outside the expected range based on relative peak intensity
matching with standards. This outcome is generally the result of interferences, which cause higher
than true concentrations to be calculated, or of matrix-dependent factors leading to unique chroma-
tography. In such cases, an experienced chemist using t-test results may eliminate questionable
peaks from calculations and quantitate on fewer than 5 peaks. An average concentration from
calculations based on matching fewer than 5, but no less than 3 independent standard and sample
peaks may be reported.

7.5.4.4 Weathering of Aroclors often results in loss of the lower molecular weight PCBs,
and sample spectra rarely match identically with those of analytical standards. When positive
identification is questionable, the chemist may calculate and report a maximum possible
concentration (qualified as less than the numerical value), which allows the data user to determine
if additional (e.g., CLP analyses) work is required, or, if the reported concentration is below action
levels and project objectives and DQOs have been met, to forego further analysis.

7.5.4.5 Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) that allows the data
user to determine if additional (e.g., CLP analyses) work is required, or, if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 5. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-PCB-001-14

-------
Table 5

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F040.003 (PCBs in Oil)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD
(%)

A-1016

50 to 150

±50

A-1221

50 to 150

±50

A-1232

50 to 150

±50

A-1242

50 to 150

±50

A-1248

50 to 150

±50

A-1254

50 to 150

±50

A-1260

50 to 150

±50

A-1262

50 to 150

±50

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-PCB-001-15

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatograms are examples of GC chromatograms for several commonly encountered
Aroclors, using an ECD.

Figure 1
Gas chromatogram A-1242

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-001-16

-------
Figure 2
Gas chromatogram A-1248

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-001-17

-------
Figure 3
Gas chromatogram A-1254

Column: 1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-001-18

-------
Figure 4
Gas chromatogram A-1260

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-001-19

-------
Figure 5
Gas chromatogram A-1262

Column: 1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-001 -20

-------
10.0 REFERENCES

Information not available.

FMC-PCB-001-21

-------
APPENDIX A

FASP Method F040.003

Instrument Options:
GC System 1:

GC System 2:

GC System 3:

Data Handling System 1:
Data Handling System 2:
Data Handling System 3:

Shimadzu GC-mini 2 with linearized Electron Capture Detector (ECD), used for
isothermal, packed column analyses.

Shimadzu GC-mini 2 with linearized ECD modified with a Direct Conversion
and Makeup Gas Adapter for megabore capillary column operations and equipped
with a Shimadzu TP-M2R Temperature Programmer, used for
temperature-programmed megabore capillary column analyses.

Shimadzu GC-14A with linearized ECD, used for temperature-programmed
megabore capillary column analyses.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit and
Shimadzu FDD-1A Floppy Disk Drive.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-PCB-001 -22

-------
APPENDIX B

FASP Method F040.003

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature:

Shimadzu GC Mini-2 equipped with linearized ECD.

Shimadzu Chromatopac C-R3A Data Processor.

1.8 m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of 30 to 40 mL/min.
Dependent on specific Aroclor, isothermal, range 190°C to 225°C.
250oC.

FMC-PCB-001 -23

-------
NUS SOP Number 5.8
FIELD SCREENING OF POLYCHLORINATED BIPHENYL (PCB1 COMPOUNDS

fSOLID MATRIX)

1.0 SCOPE AND APPLICATION

1.1 The following methodology describes a modification of SW-846 Methods suitable for the determination
of polychlorinated biphenyl (PCB) contaminants in solid matrix samples.

1.3 Table 1 provides a list of potential target compounds.

2.0 SUMMARY OF METHODS

In this methodology, a 5 g portion of solid sample is extracted using rapid field techniques. A (iL aliquot
of sample extract is then directly injected onto an analytical column for the isothermal resolution of target
components. The PCB pattern is recognized by an electron capture detector (ECD) with detector signals processed
by a previously programmed integrator.

2.1 Low Level Analysis: Use of a 5 g portion of sample matrix is suggested to achieve method detection
limits of approximately 100 Hg/kg.

2.2 Medium Level Analysis: Sample dilutions are achieved by diluting a portion of the sample extract (as
above) in an appropriate volume of hexane.

3.0 INTERFERENCES

3.2 Interferences in the analytical system are monitored by the analyses of method blanks. Method blanks
are analyzed under the same conditions and at the same time as standards and samples, in order to establish average
background response.

3.3 Artifacts, which manifest themselves as carryover in the next analytical run, can also occur within the
analytical apparatus whenever a highly contaminated sample is introduced. To preclude this, injection syringes are
repeatedly flushed with solvent, and the analytical column is baked for a short period of time following each direct
injection analysis.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph: Hewlett-Packard 5890, or equivalent. The analytical system should be equipped
for packed or capillary column analysis with isothermal oven and on-column injection capabilities.

FMC-PCB-002-1

-------
Table 1

SUMMARY OF POTENTIAL TARGET COMPOUNDS

PCB Analysis
Aroclor 1016

	Aroclor 1221	

	Aroclor 1242	

	Aroclor 1248	

	Aroclor 1254	

	Aroclor 1260	

4.2	Detector: ECD.

4.3	Analytical Column: Glass or stainless steel column packed with 1.5% SP-2250/1.95% SP-2401 on
100/120 mesh Supelcoport, or equivalent. Alternatively, a suitable capillary column may be used.

4.4	Syringes (assorted): 5-^L, 25-^L, 100-|iL, and 1-mL.

4.5	Analytical Balance: Capable of accurately weighing 0.0001 g.

4.6	Vials: 40-mL septum-seal for sample extraction.

4.7	Glass Marking Pen: For labeling vials.

4.8	Laboratory Timer: For use during the extraction process.

4.9	Vials: 2-dram septum-seal for extract storage.

4.10	Pipets (assorted) : 1-mL, 5-mL, and 10-mL disposable glass.

4.11	Refrigerator: Separate for sample and standard storage. Capable of maintaining a stable temperature

of 4°C.

4.12	Oven: Constant temperature for use in the determination of moisture content.

5.0 REAGENTS

5.1	Methanol: Pesticide grade, or equivalent.

5.2	Hexane: Pesticide grade, or equivalent.

5.3	Neat Compounds: 96 percent purity, or better, for each Aroclor of interest.

FMC-PCB-002-2

-------
5.4 Organic-free Water: Laboratory supplied or purchased.

5.5 Zero-grade Nitrogen: As carrier gas for the GC.

5.6 Standards: A singular calibration standard for each PCB compound is prepared from commercially
purchased standards or pure compound. All standards are made and/or diluted using hexane and are created for use
via a 2-\xL injection. A working calibration standard concentration of 0.375 ng/^L for each Aroclor is usually
practical.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Samples awaiting analysis are stored at 4°C in a dedicated refrigerator. If, because of loading, it is not
possible to analyze all samples taken daily, the suggested holding time for the analysis of PCBs in solid matrix is 5
days prior to extraction, and analysis within 30 days. If holding times are exceeded, the affected data should be
qualified as suspect.

7.0 PROCEDURE

7.1 Sample Preparation: Extract all samples prior to chromatographic analysis. A suggested protocol for
hexane extraction follows:

7.1.1 Weigh and tare a 40-mL septum-seal vial using an analytical balance.

7.1.2 Add 5.0 g of sample matrix to the vial; record weight.

7.1.3 Pipet approximately 1.5 mL of organic-free water into the vial. (The water serves as a
wetting agent thus facilitating the transference of the PCB compounds from the soil matrix into the
methanol.)

7.1.4 Pipet approximately 2 mL of methanol into the vial.

7.1.5 Pipet exactly 2.5 mL of hexane into the vial. (By preference, the PCB compounds almost
exclusively partition into the hexane.)

7.1.6 Cap the vial and shake vigorously for 2 full minutes (alternatively, vial contents may be
sonicated).

7.1.7 Pipet off the supernatant extract into a labeled 2-dram septum-seal vial.

7.1.8 Perform GC analysis by directly injecting 2 to 5 (iL of sample extract onto the GC's analytical

column.

7.2 Percent Moisture (% moisture') Determination: Use a moisture correction factor (MCF) to adjust the
value generated for the amount of contaminant present in a solid matrix sample so that the value reflects the true (dry
weight) concentration of contaminant. Determine moisture content gravimetrically. The following protocol is
suggested for determining % moisture:

FMC-PCB-002-3

-------
7.2.1 Mark and weigh an aluminum weighing pan using an analytical balance. Record weight; tare

balance.

7.2.2 Place 5 to 10 g of matrix (free from unrepresentative pebbles and organic matter) into the pan;
record weight.

7.2.3 Place the pan and its contents into a drying oven heated to 103°C.

7.2.4 Dry the matrix for a period of 4 to 6 hours (or until weight is constant).

7.2.5 Remove the pan from the oven and allow to cool to room temperature.

7.2.6 Weigh the pan and record the weight.

7.2.7 Calculate the % moisture and the MCF (see 7.6)

7.3 Calibration: Calibrate the analytical system via the external standard method in which response factors
(RF) for each individual Aroclor are obtained by the analysis of a standard of known concentration. For each Aroclor
analyzed, sum the responses of several peaks characteristic to that particular Aroclor. Following the analysis of this
known standard, create a file noting each Aroclor's pattern (i.e., the retention times (RT) of each characteristic peak),
the appropriate RF, and known concentration. Determine the RF for each Aroclor by dividing the Aroclor's known
concentration by the summated peak responses (area or height units) which were taken from the associated pattern.
The concentration of PCB contaminants in samples is usually hand-calculated by manually summating the responses
of the characteristic peaks and comparing them to the analogous summated peaks designated in the Aroclor standard.

7.3.1 Continuing calibration:

7.3.1.1 Calibrate the analytical system 3 times daily: (1) preceding the daily analyses, (2)
midday, and (3) after the daily analyses.

7.3.1.2 Analyze standards run for continuing calibration purposes at a level equal to the
reported detection limits. Continuing calibration RFs for each parameter should fall within 25
percent difference (%D, see 7.5.3) of the average RF calculated for that particular compound during
the initial linearity study. Qualify data associated with individual parameter not meeting the %D
criterion as suspect.

7.3.1.3 Conduct the continuing calibration at a concentration level equal to the reported
detection limits.

7.3.2 Peak identification: Identify each PCB compound by its unique pattern (fingerprint). The
identity of each target Aroclor is substantiated by the singular analysis of each individual Aroclor.

7.4 Gas chromatography

7.4.1 Analytical sequence: Conduct analyses in sets of 10, whenever possible, with 1 laboratory
duplicate spike analysis run per set. Bracket each set of sample analyses by the analysis of a standard, with
a method blank analysis following each standard run. The number of analyses per sample set and the
associated quality assurance/quality control (QA/QC) varies per contract. Consult the project work plan to
verify that all contractual obligations were met.

FMC-PCB-002-4

-------
column by means of direct injection technique. The PCB compounds are resolved isothermally due to the
affinity the PCB components have for the phases of the column's packing as they migrate (under flow)
through the analytical column. As the contaminants elute from the column, they are recognized by an ECD.
Detector signals are then processed by an integrator. As long as analytical conditions remain constant, each
PCB pattern will elute at characteristic RT. In this manner, sample contaminants are identified and
quantified by comparison to a run of standards of known concentration.

7.4.3 The following run conditions have been found to be practical for the analysis of PCB
compounds analyzed by field screening techniques:

Run Parameter

Setting

Injector Port Temperature

280°C

Isothermal Oven Temperature

215°C

Detector Temperature

300°C

Carrier Gas Flow

30 mL/min

Under these conditions, Aroclor 1260 will elute within 35 minutes.
7.5 Calculations

7.5.1 Calculate %RSD using the following equation:

ST)

%RSD = — x 100
X

where:

k (x. - x)2

SD = ^

N - 1

and X is the mean of initial RFs (per compound).

7.5.2 Calculate relative percent difference (RPD) values using the following equation:

D1 ~ D2
RPD = 	i	— x 100

(D1 + D2)

where: D[ =	First sample value, and

D2 =	Second sample value.

7.5.3 Calculate the %D using the following equation:

FMC-PCB-002-5

-------
%D = —	— x 100

where: X[ =	RF of first result, and

X2 =	RF of second result.

7.5.4 Calculate percent recovery (%R) using the following equation:

= SSR ~ SR x 100

where: SSR =	Spike sample results,

SR =	Sample result, and

S	=	Amount of spike added.

7.6 Sample Quantitation: Appropriate quantitation of PCB contaminants is based upon the following

formula:

, /, , y designated peak response (spl) x RF x DF x final volume (

centration (]ig/kg) = 			—	—	—		-

wt of sample extract (g) x % solids

where: RF =	standard concentration

£ designated peak responses (std)
% solids	=	100 - % moisture

% moisture =	wet wt - dry wt x 100

wet wt

8.0 QUALITY CONTROL

8.1 Overview

8.1.1 Field screening generates Level II data. As Level II data, the concurrent analysis of
laboratory duplicates and matrix spike analyses and the use of surrogate spike compounds is not required.
However, beyond the maintenance of practical Standard Operating Procedures (SOPs), certain elements of
QC (if opted) can greatly enhance the interpretation of and the confidence in the data generated. These
traditional elements of QC are discussed here as to how they are adapted to meet the demands of a
successfully applied field screening QA/QC program.

8.1.2 The primary purposes of an appropriate QA/QC program are to: (1) substantiate system
performance and give credence to the accuracy of the results generated, (2) to define aberrations and give
guidance to the interpretation of data, and (3) to achieve these goals through realistic efforts that do not
impede the forward progress of the analytical set.

8.1.3 The discussion presented here deals with only direct analytical QC. Additional elements of
QA/QC, such as field duplicate sample submissions, blind spike analysis, and external audits are not
discussed. Also not discussed are elements of QA/QC that are inherent to good chromatographic technique.
Examples of these accepted laboratory practices include (but are not limited to) the following: (1) the proper
conditioning of analytical columns and traps, (2) use of the solvent flush technique for the creation of

FMC-PCB-002-6

-------
standards and for direct injections, and (3) the appropriate maintenance of selected detectors. Details
regarding these accepted practices are given in the referenced methodologies.

8.2 Laboratory Duplicates: One laboratory duplicate should be analyzed per sample set. Laboratory
duplicate analyses should generate results of RPD within 30 percent (see 7.5.2).

8.5 Method Blanks: Method blanks are prepared and analyzed in exactly the same manner as sample
matrices. A method blank analysis should follow every standard run and sample of high concentration. Ideally,
method blank results should yield no interferences to the chromatographic analysis and interpretation of target
compounds. If interferences are present, associated data should be qualified as suspect and/or target detection limits
should be adjusted accordingly.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-PCB-002-7

-------
FASP Method Number F040.002

POLYCHLORINATED BIPHENYLS fPCBS) IN WATER

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various Aroclors, also known as polychlorinated biphenyls (PCBs), in water samples.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 To begin sample analysis, a measured amount of water is placed in a volumetric flask. The sample is
extracted with a measured volume of hexane. An optional cleanup involves treating an aliquot of the hexane extract
with concentrated sulfuric acid. Analysis is performed using either a temperature- programmed/isothermal gas
chromatograph (GC) with a megabore capillary column, or isothermal GC with a packed column and electron capture
detector (ECD). Identification is based on comparison of retention times and relative peak intensities between
samples and standards. Quantitation is based on the external standard method.

3.0 INTERFERENCES

FMC-PCB-003-1

-------
Table 1

FASP METHOD F040.002 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

PCB

CAS Number

Quantitation Limit in
Water** (ng/L)

Aroclor-1016

12674-11-2

250

Aroclor-1221

11104-28-2

250

Aroclor-1232

11141-16-5

250

Aroclor-1242

53469-21-9

250

Aroclor-1248

12672-29-6

250

Aroclor-1254

11097-69-1

500

Aroclor-1260

11096-82-5

500

Aroclor-1262

37324-23-5

1000

* Specific quantitation limit values are highly matrix dependent. The quantitation limits listed herein are

provided for guidance and may not always be achievable.

** Quantitation limits listed for water are on an "as-received" basis.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are 2 GC options that meet the requirements of this method. Other
GC configurations may be substituted if they also meet the method requirements.

4.1.1 Gas chromatograph. option 1: An analytical system complete with an isothermal GC capable

of operation at elevated temperatures and all necessary accessories including injector and detector systems

FMC-PCB-003-2

4.1.1.1 Column 1: 1.8 m x 3.0 mm I.D. glass column packed with GP 1.5%
SP-2250/1.95% SP-2401 on 100/120 Supelcoport (Supelco) or equivalent.

4.1.1.2 Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco) or equivalent.

4.1.1.3 Detector: Linearized ECD with optional makeup gas supply at the detector's inlet.

4.1.2.1 Column: 15 m x 0.53 mm I.D. DB-608 fused silica capillary column (FSCC)
(J&W Scientific) or equivalent.

4.1.2.2 Detector: Linearized ECD using a system with makeup gas supply at the detector's
capillary inlet.

4.2 Other Laboratory Equipment

4.2.1 Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction.

4.2.2 Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3 Spatulas: Stainless steel, micro and semimicro.

4.2.4 Microsvringe: 10-(iL.

4.2.5 Balance: Top loading, capable of weighing to 0.01 g.

4.2.6 Micropipets: 10- to 1,000-^L.

FMC-PCB-003-3

-------
4.2.7	Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and

25-mL.

4.2.8	Volumetric flasks: 10-, 25-, 50-, 100-mL.

4.2.9	Vortex mixer: Vortex Genie or equivalent.

4.2.10	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.11	Amber storage bottles: 100- and 500-mL.

4.2.12	Autosampler vials: 1- or 2-mL with Teflon-lined screw caps.

4.2.13	Graduated centrifuge tubes: 10-mL with ground glass stoppers.

4.2.14	Oxygen traps: Supelpure-O-Trap and OMJ-1 indicating tube, or equivalent.

4.2.15	Leak detector: Snoop liquid or equivalent for packed column operations or GOW-MAC gas
leak detector, or equivalent, for megabore capillary operations.

4.2.16	Timer: 0 to 10 minute range.

4.2.17	Teflon wash bottles: 500-mL.

4.2.18	Laboratory oven: Capable of maintaining temperatures greater than or equal to 200°C.

4.2.19	Chromatographic data stamp: Used to record instrument operating conditions.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Methanol: Pesticide quality, or equivalent.

5.1.2	Hexane: Pesticide quality, or equivalent.

5.1.3	Acetone: Pesticide quality, or equivalent.

5.1.4	Isooctane: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

5.2.1 Reagent water: Reagent water is defined as water in which an interferent is not observed at
the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent), a water purification system (Milli-Q
Plus with Organex Q cartridge, Barnstead Water-1 Systems [provided with the Base Support Facilities], or
equivalent), or purchased from commercial laboratory supply houses.

FMC-PCB-003-4

-------
5.2.2 Sodium sulfate: Reagent, anhydrous, granular. Pre-conditioned by heating for 24 hours at

200°C and storing in clean glass containers with Teflon liners.

5.2.3 Nitric acid: 10 percent vol./vol.

5.2.4 Sulfuric acid: Concentrated.

5.2.5 Copper turnings or filings: Remove oxides by treating with dilute nitric acid, rinse with

distilled water to remove all traces of acid, rinse with acetone, and dry under a stream of nitrogen.

5.3 Gases

5.3.1 Five percent methane in argon: Ultrapure or chromatographic grade (always used in

conjunction with an oxygen trap).

5.3.2 Helium: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as manufacturer
certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This procedure is done through volumetric dilution of the stock standards with isooctane. The
lowest concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be handled, preserved, and shipped maintaining a chainof-custody following current
EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this rule are
the sample volumes required by the laboratory. Water samples should be shipped in 1-liter narrow-mouth glass jars
with Teflon-lined caps.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for water PCB samples are 7 days
between collection and extraction and 40 days between extraction and analysis.

7.0 PROCEDURE

7.1 Extraction: The sample extraction technique for PCBs in water is as follows:

FMC-PCB-003-5

-------
7.1.1 Add 100 mL of water to a clean 100 mL volumetric flask.

7.1.2 Add 1.0 mL hexane by repipet to the flask and shake vigorously for 2 minutes.

7.1.3 Allow the layers to separate.

7.1.4 Transfer the hexane layer to a 10-mL graduated centrifuge tube using a disposable Pasteur

pipet.

7.1.5 Repeat steps 7.1.2 through 7.1.4 twice and combine the extracts.

7.1.6 Add 1.0 mL of concentrated sulfuric acid by repipet to the hexane extract.

7.1.7 Vortex at maximum speed for 60 seconds.

7.1.8 Centrifuge for 5 minutes.

7.1.9 Transfer approximately 1 mL of extract into a Teflon-lined screw cap autosampler vial using
a disposable Pasteur pipet. Avoid transfer of any of the acid layer.

7.1.10 The sample extract is now ready for GC injection.

7.2 Cleanup

7.2.1 General extract cleanup:

7.2.2 Sulfur removal:

7.2.2.1 Sulfur interference: Elemental sulfur may be encountered in water samples,
marine algae, and some industrial wastes. The solubility of sulfur in various solvents is very
similar to that of PCBs; therefore, the sulfur interference follows along with the PCBs through the
normal extraction and cleanup techniques. Sulfur will be quite evident in gas chromatograms
obtained from ECDs. If the GC is operated at the normal conditions for PCB analysis, the sulfur
interference can completely mask a large region of the chromatogram. The recommended technique
for the elimination of sulfur follows.

7.2.2.2 Summary of method: The sample extract is combined with clean copper. The
mixture is shaken, and the extract is removed from the sulfur cleanup reagent.

7.2.2.3 Procedure for sulfur cleanup:

FMC-PCB-003-6

-------
7.2.2.3.1 The copper used must be reactive; therefore, all oxides of copper must
be removed so that the copper has a shiny, bright appearance.

7.2.2.3.2 Transfer all of the final extract described in Section 7 (Step 7.1.9) to a
16 mm x 100 mm screw-cap culture tube with a Teflon-lined cap.

7.2.2.3.3 Add approximately 2 g of cleaned copper to the tube. Mix for at least
1 minute on the vortex mixer. This step may be repeated if sulfur removal is incomplete.

7.2.2.3.4 Resume the procedure described in Section

7.1.10.

7.2.2.3.5 The effect of copper on PCB recovery is shown in Table 3.

7.2.3 Solid phase extraction technology: Solid phase extraction (SPE) technology (e.g., Sep-Pak)
may provide an acceptable alternative to acid cleanup for PCB extracts.

7.3 Calibration

7.3.1 Initial calibration:

FMC-PCB-003-7

-------
Table 2

PCB DEGRADATION WITH TIME
AFTER TREATMENT WITH CONCENTRATED SULFURIC ACID

PCB

CAS Number

Approximate Percent Loss*

24 hours

48 hours

168 hours (1 week)

Aroclor-1016

12674-11-2

None**

None

None

Aroclor-1221

11104-28-2

None

None

None

Aroclor-1232

11141-16-5

None

None

None

Aroclor-1242

53469-21-9

None

None

None

Aroclor-1248

12672-29-6

None

None

None

Aroclor-1254

11097-69-1

None

None

None

Aroclor-1260

11096-82-5

None

None

None

Aroclor-1262

37324-23-5

Not Tested

Not Tested

Not Tested

After treatment with H2S04over the specified period of time.

No significant loss.

7.3.2 Continuing calibration:

7.3.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing calibra-
tion validation. This single point analysis follows the same analytical procedures used in the initial
calibration. Instrument response is used to compute the CF which is then compared to the mean
initial calibration factor (CF), and a relative percent difference (RPD, see Section 7.5) is calculated.
Unless otherwise specified, the RPD must be less than or equal to 25 percent for the continuing
calibration to be considered valid. Otherwise, the calibration must be repeated. A continuing
calibration remains valid for a maximum of 24 hours provided the GC system remains unaltered
during that time.

FMC-PCB-003-8

-------
Table 3

EFFECT OF COPPER TREATMENT ON
PCB RECOVERY

PCB

CAS Number

Average Percent
Recovery After
Treatment with Cu*

Aroclor-1242

53469-21-9

112

Aroclor-1248

12672-29-6

100

Aroclor-1254

11097-69-1

Aroclor-1260

11096-82-5

Aroclor-1262

37324-23-5

Percent recoveries cited are averages based on duplicate analyses.

7.3.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

7.4 Instrumental Analysis

7.4.2 Chromatograms:

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

FMC-PCB-003-9

-------
• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.4.3 Aroclor identification:

7.4.3.3 Generally, individual peak retention time windows should be less than or equal
to 5 percent for packed column analyses and less than or equal to 2 percent for megabore capillary
columns.

7.4.4 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided as "Specific Instrument Parameters" in Appendix B of this method.

7.4.5 Analytical sequence:

7.4.5.1 Instrument blank.

7.4.5.2 Initial calibration.

7.4.5.3 Check standard solution and/or performance evaluation sample (if available).

7.4.5.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.5.5 Associated QC lot method blank.

7.4.5.6 Twenty samples and associated QC lot spike and duplicate.

FMC-PCB-003-10

-------
Table 4

EXAMPLE ISOTHERMAL GC OPERATING CONDITIONS

Shimadzu GC Mini-2 equipped with Linearized ECD

Shimadzu Chromatopac C-R3A Data Processor

1.8m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of 40 mL/min
Dependent on specific Aroclor, isothermal, range 190°C to 225°C
250°C

Dependent on specific Aroclors and matrix, range approximately 15 to
30 minutes

Solvent flush manual injection or automated sample injection is recom-
mended for PCB analysis. For the solvent flush technique, the syringe
barrel plus 1 (iL of nanograde hexane, 0.5 (iL of air, and 2.0 to 3.0 (iL
(measured to the nearest 0.05 (iL) of sample extract are sequentially
drawn into a 10-(iL syringe and immediately injected into the GC. Ex-
treme care must be taken to avoid contamination of the syringe needle
with sulfuric acid when loading the syringe. Injection of acid will
damage the analytical column and detector.

7.4.5.7 Repeat sequence beginning at step 7.4.5.5 until all sample analyses are complete
or another continuing calibration is required.

7.4.5.8 Final calibration when all sample analyses are complete.

7.5 Calculations

_ Area of Peak

Mass of Injected (nanograms)

FMC-PCB-003-11

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature:
G.C. Analysis Time:

Standard/Sample Injection:

-------
7.5.1.2 Using the calibration factors, calculate the %RSD for each Aroclor at a minimum
of 3 concentration levels using the following equation.

%RSD = — x 100
X

where SD, the Standard Deviation, is given by

A (X-X)2

SD = \ 2^ —1

\ / AT "1 \

(N-l)

where: X;
X
N

Individual calibration factor (per analyte),

Mean of initial 3 calibration factors (per analyte),
Number of calibration standards.

7.5.13 The %RSD must be less than or equal to 25.0 percent.

7.5.2 Continuing calibration:

7.5.2.2 The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

7.5.3 Final calibration:

7.5.3.1 The final calibration is obtained at the end of any batch of samples analyzed.

7.5.3.2 The maximum allowable RPD between the mean initial calibration and final
calibration factors for each analyte must be less than or equal to 50 percent. A final calibration that
achieves an RPD of less than or equal to 25 percent may be used as an ongoing continuing
calibration.

\CF -CFJ

RPD = - 1 — x 100

CFI+CFc

where: CF,

CFc

Mean CF from the initial calibration for each analyte
Measured CF from the continuing calibration for the same analyte.

FMC-PCB-003-12

-------
\CF -CF \
RPD = -	1	— x 100

cfi+cff

where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.4 Sample quantitation:

7.5.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations.

[A ) [V ) (E) (D)

Concentrationluq/kq) = 	

(CFJ (V.) (Vg)

where: Ax =	Response for the analyte to be measured.

CFc	=	CF from the continuing calibration for the same analyte.

V;	=	Volume of extract injected (|iL).

Vt	=	Volume of total extract (|iL).

Vs	=	Volume of sample extracted (mL).

E	=	Enhanced sensitivity factor (if Section 8 extract concentration is used,

E = 10; if no enhancement, E = 1)

D	=	Dilution factor, if used.

7.5.4.2	Report results in micrograms per literm (ng/L) without correction for blank or
spike recovery.

7.5.4.3	Compute sample concentrations for individual peaks, as well as total area (a total
of 6 values), to provide the analyst with data sufficient to identify interferences or unique chromato-
graphic responses. If concentrations based on individual peak quantitations do not fail a Student's
t-test, then the results calculated based on total peak areas should be reported as the sample
concentration. However, samples have been encountered in which certain of the chromatogram
peaks have yielded concentrations outside the expected range based on relative peak intensity
matching with standards. This outcome is generally the result of interferences, which cause higher
than true concentrations to be calculated, or of matrix-dependent factors leading to unique chroma-
tography. In such cases, an experienced chemist using t-test results may eliminate questionable
peaks from calculations and quantitate on fewer than 5 peaks. An average concentration from
calculations based on matching fewer than 5, but no less than 3 independent standard and sample
peaks may be reported.

7.5.4.4	Weathering of Aroclors often results in loss of the lower molecular weight PCBs,
and sample spectra rarely match identically with those of analytical standards. When positive
identification is questionable, the chemist may calculate and report a maximum possible
concentration (qualified as less than the numerical value), which allows the data user to determine

FMC-PCB-003-13

-------
if additional (e.g., CLP analyses) work is required, or, if the reported concentration is below action
levels and project objectives and DQOs have been met, to forego further analysis.

7.5.4.5 Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) that allows the data
user to determine if additional (e.g., CLP analyses) work is required, or, if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 5. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-PCB-003-14

-------
Table 5

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F040.002 (PCBs in Water)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD
(%)

A-1016

50 to 150

±50

A-1221

50 to 150

±50

A-1232

50 to 150

±50

A-1242

50 to 150

±50

A-1248

50 to 150

±50

A-1254

50 to 150

±50

A-1260

50 to 150

±50

A-1262

50 to 150

±50

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-PCB-003-15

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatograms are examples of GC chromatograms for several commonly encountered
Aroclors, using an ECD.

Figure 1
Gas chromatogram A-1242

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-003-16

-------
Figure 2
Gas chromatogram A-1248

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-003-17

-------
Figure 3
Gas chromatogram A-1254

Column: 1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-003-18

-------
Figure 4
Gas chromatogram A-1260

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-003-19

-------
Figure 5
Gas chromatogram A-1262

Column: 1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-003-20

-------
9.2 Method F040.002 examples of sample QA/QC results: Spike triplicate, and split sample results are
presented as examples of FASP Method F040.002 empirical data (see Tables 6 and 7).

Table 6

FASP METHOD F040.002
WATER MATRIX SPIKE PERCENT RECOVERY (%R)

Analyte

Number of Samples

Mean %R

Standard
Deviation of %R

Aroclor-1248

2

59.8

N/A

Aroclor-1254

17

98.8

27.9

Table 7

FASP METHOD F040.002
WATER DUPLICATE SAMPLE RELATIVE PERCENT DIFFERENCE (RPD)



Number of



Standard

Analyte

Duplicate Sample

Mean RPD

Deviation of RPD



Pairs





Aroclor-1248

1

3.01

N/A

Aroclor-1254

7

7.09

5.25

FMC-PCB-003-21

-------
10.0 REFERENCES

Information not available.

FMC-PCB-003-22

-------
APPENDIX A

FASP Method F040.002

Instrument Options:
GC System 1:

GC System 2:

GC System 3:

Data Handling System 1:
Data Handling System 2:
Data Handling System 3:

Shimadzu GC-mini 2 with linearized Electron Capture Detector (ECD), used for
isothermal, packed column analyses.

Shimadzu GC-mini 2 with linearized ECD modified with a Direct Conversion
and Makeup Gas Adapter for megabore capillary column operations and equipped
with a Shimadzu TP-M2R Temperature Programmer, used for
temperature-programmed megabore capillary column analyses.

Shimadzu GC-14A with linearized ECD, used for temperature-programmed
megabore capillary column analyses.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit and
Shimadzu FDD-1A Floppy Disk Drive.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-PCB-003-23

-------
APPENDIX B

FASP Method F040.002

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature:

Shimadzu GC Mini-2 equipped with linearized ECD.

Shimadzu Chromatopac C-R3A Data Processor.

1.8 m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of 30 to 40 mL/min.
Dependent on specific Aroclor, isothermal, range 190°C to 225°C.
250oC.

FMC-PCB-003-24

-------
FMC-PCB-003-1

-------
CSL Method

PCB. PEST/SOIL/HEXANE EXTRACTION/GC-ECD

1.0 SCOPE AND APPLICATION

1.1 This method uses capillary gas Chromatography with electron capture detection (GC/ECD) to analyze
soil samples for the presence of dieldrin, and PCBs 1254 and 1260.

1.2 Application of this method is limited to dieldrin, PCB aroclor 1254, and PCB aroclor 1260.

1.3 The method detection limits (MDL) are estimated to be 50 Mg/kg for dieldrin, and 500 Mg/kg for the PCB
aroclors 1254 and 1260.

2.0 SUMMARY OF THE METHODS

2.1 The soil extraction is based on EPA Method 3580, Waste Dilution. The analysis is based on EPA
Method 8080, Organochlorine Pesticides and PCBs, both found in EPA SW846, Test Methods for Evaluating Solid
Waste, 3rd Edition, November 1986.

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute or overlap with the target constituents may cause a positive
bias in the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDL's for the target constituents may be suppressed by baseline noise associated with samples
having high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 Sample Bottles: 40-mL VOA vials with teflon caps; precleaned as purchased from Eagle Pitcher.

4.2 Glassware: Class A volumetric pipets and flasks; beakers, vials, pasteur pipets, and miscellaneous
glassware as necessary for preparation and handling of samples and standards.

4.3 Lab ware: Necessary for preparation and handling of samples and standards.

4.4 Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation
of dilutions, and spiking of samples.

4.5 Gas Chromatograph: Hewlett Packard Model 5890 Series II GC with temperature programmable
oven-operated from 150°C to 280°C with a 530 /iM 30 M SPB-5 1.5 /iM capillary column, split/spitless inlet, and
ECD.

4.6 Autosampler: Hewlett Packard 7673 Autosampler.

FMC-PCB-005-1

-------
4.7 Integrator: Hewlett Packard 3396 Series II Integrator.

4.8 Laboratory Fume Hood.

4.9 Top-Loading Analytical Balance.

5.0 REAGENTS

5.1 Stock Standards: Prepare or purchase standard materials at approximately 2 mg/mL in methanol.

5.2 Working Standards: Prepared from stock standards by precise dilution in hexane.

5.3 Sodium Sulfate: Anhydrous, powder.

5.4 Ultra Pure Carrier Nitrogen: For use as makeup gas.

5.5 Ultra Pure Carrier Grade Helium: For use as carrier gas.

5.6 Hexane: Pesticide residue grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.4 Safety equipment, including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit, shall be available for use at all times.

7.1.5 Lab wastes shall be separated and properly disposed. The wastes include: used sample
aliquots in headspace vials or disposable purge chambers, unused soil and water samples, and small
quantities of alcohol waste generated by standard preparations and syringe rinsing. Used headspace vials
are placed in waste drums clearly labeled for water vials. Unused water samples are poured out of the VOA
vials into specifically labeled drums labeled CSL waste water and the empty vials are deposited into the
water vials drums. Unused soil samples are placed in CSL waste drums labeled specifically for soil jars.
Unused samples are held by the CSL for seven days before disposal. Water used for final rinsing of
glassware will be considered nonhazardous and will be released down the sanitary sewer.

7.2 Sample Preparation and Extraction

FMC-PCB-005-2

-------
7.2.1 Accurately weigh approximately 2 g of soil into an empty 40 milliliter volatile organic sample
bottle. Add approximately 1 g of sodium sulfate, conditioned at 400°C for 4 hours.

7.2.2 Add 5 mL of pesticide grade hexane, surrogate, and sonicate for 1 minute.

7.2.3 If necessary, centrifuge the sample for 2 minutes at 2,000 rpm.

7.2.4 Transfer as much of the 5 mL aliquot as possible to a 10-mL volumetric.

7.2.5 Repeat the 5 mL extract a second time, again transferring the hexane to the 10-mL volumetric.
Bring the volumetric to volume with hexane.

7.2.6 If the sample is obviously contaminated, and experience has shown similar extracts to contain
high levels of contamination, it is recommended that a preliminary dilution be prepared to avoid grossly
contaminating the gas chromatograph.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 Five-level calibration at approximately 10, 20, 50, 100, and 150 fxgfL of dieldrin,
and approximately 100, 200, 500, 1,000, and 2,000 /ig/L for the PCBs. These concentrations define
the linear calibration range of the instrument, this linear range must be determined before the
analysis of any samples. The instrument must be calibrated using the same instrument conditions
that are used to analyze the samples.

7.3.1.2 The validity of the calibration curve is further validated by the analysis of a QC
check sample. The QC check sample must be obtained from EPA or another certified vendor. The
QC check sample verifies the validity of the concentration of the standards used to obtain the initial
calibration. All parameters in the QC check standard must be recovered within 70 to 110 percent.
If any parameter exceeds this criterion, then a new calibration curve must be established. All
sample results for a target analyte can only be reported from valid initial calibrations.

7.3.2 Continuing Calibration

7.3.2.1 The continuing calibration standard should be selected from the initial calibration
standards, and it should be the standard that is closest to the midpoint of the calibration range. The
working calibration curve for each analyte must be verified daily by the analysis of a continuing
calibration standard. A day is defined as 24 hours from the start run time of the last valid
continuing calibration. The ongoing daily continuing calibration must be compared to the initial
calibration curve to verify that the operation of the measurement system is in control.

7.3.2.2 For each analyte, calculate the percent difference of the continuing calibration
standard RRF from the corresponding standard from the initial calibration curve using the following

equation:

% D =

[ RRF - RRF ] x 100

L IT? J

RRF

IT?

Where: RRFm
RRF

The mean response from the initial calibration curve.
The daily response from the continuing calibration point.

FMC-PCB-005-3

-------
7.3.3 Surrogate Recovery: Tetrachlorometaxylene shall be used as a surrogate. Recovery shall be
80 to 120 percent. Prepare secondary dilutions of the surrogate compound. This spiking solution must be
added to all standards, blanks, and samples. The surrogates and internal standards must be at a concentration
that provides a response similar to the response of the target analytes in the midpoint standard used for con-
tinuing calibration.

7.3.4 Quality Control fOC) Check Sample Solutions: The QC check standards are obtained from
EPA or an independent certified vendor. The QC check standards must be prepared independently from the
standards used for initial and continuing calibration standards.

7.4 Sample Analysis

7.4.1 Perform GC analysis on the extract using the instrument conditions, which were determined
during method development.

7.4.2 If the analysis indicates that the results are greater than the calibration range, prepare a
dilution of the sample to yield concentrations that fall within the calibration range.

7.4.3 Check the retention times for each of the reference peaks against the expected (calibration)
value. Reject those results where the retention time does not fall with ± 0.05 minute of the expected value.

7.5 Calculations

7.5.1 Quantification of the target compounds is based on the integrated areas of the samples in
comparison to the integrated areas of the calibration standards for each analysis. The integrator reports the
concentrations in PPB in the extracts. Calculation of the concentration for each target constituent in the
original sample is as follows:

A x v x DF
Cone, in ]ig/kg =

Where: A = Amount of target constituent found in/ig/L (from integrator);

Vt = Volume of the hexane in liters;

Ws = Weight of the sample added in kilograms; and

DF = Dilution factor if required.

8.0 QUALITY CONTROL

8.1 The linear calibration range of the instrument must be determined before the analysis of any samples.
The instrument must be calibrated using the same instrument conditions that are used to analyze the samples.

8.2 Daily analysis of a laborlatory blank, performed before the analysis of each day's sample. Should the
results of the laboratory blanks show contamination, the cause of the contamination should be investigated and
corrective action taken.

8.3 Analysis of field duplicate samples at a frequency of one in 20 samples of the same matrix.

8.4 Analysis of a surrogate with every sample. The surrogate solution must be added to all standards,
blanks, and samples. The surrogates and internal standards must be at a concentration that provides a response similar
to the response of the target analytes in the midpoint standard used for continuing calibration.

FMC-PCB-005-4

-------
8.5 Analysis of a midrange matrix spike sample at a frequency of one in 20 samples of the same matrix.
9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERNCES

Information not available.

FMC-PCB-005-5

-------
CSL Method

PCB/SOIL/SOLVENT EXTRACTION/PERCHLORINATION/GC-ECD

1.0 SCOPE AND APPLICATION

1.1 This method uses capillary gas chromatography with electron capture detection (GC/ECD) to analyze
soil samples for the presence of PCBs. PCBs are all biphenyls whose exhaustive chlorination products is
decachlorobiphenyl.

1.2 Application of this method is limited to the screening analysis of samples for total PCB concentration.
Positive identification and quantification of specific constituents, such as individual aroclors, should be supported
by analyses of duplicate and other composited samples at a laboratory employing agency-approved or published
testing protocols.

1.3 Preliminary method validation data indicate analysis recoveries of 90 percent.

1.4 The method detection limits (MDL) are estimated to be 100 Mg/kg for PCBs.

2.0 SUMMARY OF THE METHODS

2.1 The soil extraction is based on EPA Method 3580, Waste Dilution. The analysis is based on P & CAM
253, NIOSH 2nd Edition.

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute or overlap with the target constituents may cause a positive
bias in the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDL's for the target constituents may be suppressed by baseline noise associated with samples
having high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 Glassware: Class A volumetric pipets and flasks; beakers, vials, pasteur pipets, and miscellaneous
glassware as necessary for preparation and handling of samples and standards.

4.2 Lab ware: Necessary for preparation and handling of samples and standards.

4.3 Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation
of dilutions, and spiking of samples.

4.4 Gas Chromatograph: Hewlett Packard Model 5890 Series II GC with temperature programmable
oven-operated from 150°C to 280°C with a 530 /iM 30 M SPB-5 1.5 /iM capillary column, split/spitless inlet, and
ECD.

4.5 Autosampler: Hewlett Packard 7673 Autosampler.

4.6 Integrator: Hewlett Packard 3396 Series II Integrator.

FMC-PCB-006-1

-------
4.7 Laboratory Fume Hood: Absorbing type is acceptable.

4.8 Top-Loading Analytical Balance.

5.0 REAGENTS

5.1 Stock Standards: Prepare or purchase standard materials at approximately 2 mg/mL in methanol.

5.2 Working Standards: Prepared from stock standards by precise dilution in hexane.

5.3 Ultra Pure Carrier Grade Nitrogen: For use as makeup gas.

5.4 Ultra Pure Carrier Grade Helium: For use as carrier gas.

5.5 Hexane: Pesticide residue grade.

5.6 Antimony Pentachloride: Perchlorination reagent, distilled under vacuum.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.3 Sample preparation should be performed in a fume hood.

7.1.4 Safety equipment, including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit, shall be available for use at all times.

7.1.5 Hazardous lab wastes will be disposed of according to the CSL Chemical Hygiene Plan.

7.1.6 n-Hexane (C6H14) regulated by NIOSH. The suggested threshold limit value (TLV) is 50
ppm, and the permissible exposure level (8-hour PEL) is 50 ppm. Exposure pathways are oral, dermal, and
airway. Exposure is harmful and may be fatal. Overexposure may be irritating to the respiratory tract and,
in high concentrations, narcotic. Hexane has a faint, peculiar odor. Hexane is highly flammable and is
incompatible with active metals and strong alkaline solutions.

7.2 Sample Preparation and Extraction

7.2.1 Accurately weigh approximately 1 g of soil into a centrifuge tube containing 1 g of sodium
sulfate, conditioned at 400°C for 4 hours.

FMC-PCB-006-2

-------
7.2.2 Add 10 mL of pesticide grade hexane, surrogate, and vortex for 1 minute. Centrifuge for 2
minutes at 2,000 rpm.

7.2.3 Transfer a 300 fxL aliquot to a 13 mm x 100 mm tube and reduce under dry nitrogen to
approximately 10 /jL.

7.2.4 Immediately, and rapidly add 0.2 mL of distilled antimony pentachloride and cap the tube.
The sample should remain light yellow after this addition, but if the sample turns dark brown or black, it
must be discarded and another aliquot of that sample used. A sample of decachlorobiphenyl is treated in a
manner similar to the samples.

7.2.5 Place the samples in a 160°C sand bath for three hours. Remove from the bath and cool to
room temperature.

7.2.6 To each sample add dropwise 0.5 mL of 20 percent hydrochloric acid. This mixture is then
extracted four times with 1 to 2 mL of n-hexane. Each extract is passed through a funnel containing
approximately 0.5 g of anhydrous sodium sulfate into a 10 mL volumetric flask.

7.2.7 If the sample is obviously contaminated, and experience has shown similar extracts to contain
high levels of contamination, it is recommended that a preliminary dilution be prepared to avoid grossly
contaminating the gas chromatograph.

7.3 Calibration

7.3.1 Calibration: Five-level calibration at approximately 2, 4, 10, 20, 60 jj,g/L for
decachlorobiphenyl.

7.3.2 Working Calibration: Daily working calibration.

7.3.3 Calibration Criteria: A point to point linear plot, through the origin.

7.3.4 Retention Time Marker: Hexabromobiphenyl shall be used as a retention time marker.
Retention shifts greater than 0.2 minutes shall require corrective action.

7.4 Sample Analysis

7.4.1 Perform GC analysis on the extract using the instrument conditions, which were determined
during method development.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range,
prepare a dilution of the sample to yield concentrations that fall within the calibration range.

7.4.3 Check the retention times for each of the reference peaks against the expected (calibration)
value. Reject those results where the retention time does not fall within ± 5 percent of the expected value.

7.5 Calculations

7.5.1 Quantification of the target compounds is based on the integrated areas of the samples in
comparison to the integrated areas of the calibration standards for each analysis. The integrator reports the
concentrations in parts per billion (ppb) in the extracts. Calculation of the concentration for total PCBs in
the original sample is as follows:

FMC-PCB-006-3

-------
A x V x 33.33 x DF
Cone, in ]ig/kg = 	

Where: A

Vt
Ws
DF
33.33

8.0 QUALITY CONTROL

8.1	Daily five point calibration performed before the analysis of each day's samples.

8.2	Analysis of laboratory blanks before samples. Should the results of the laboratory blanks show
contamination, the cause of the contamination should be investigated and corrective action taken.

8.3	Analysis of field duplicate samples at a frequency of one in 10 samples or 1/day which ever is more

frequent.

8.4	Analysis of a retention time marker with every sample.

8.5	Perchlorination of a sample of decachlorobiphenyl with every sample batch.

8.6	Analysis of a mid-range matrix spike sample before beginning analysis of any given matrix.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-PCB-006-4

Amount of target constituent found m /ig/L;

Volume of the hexane in liters;

Weight of the sample added in kilograms;

Dilution factor, if required; and

Dilution factor of 0.3 mL aliquot brought to 10 mL.

-------
FASP Method F93007

PREPARATION AND ANALYSIS OF SAMPLES FOR POLYCHLORINATED BIPHENYLS

1.0 SCOPE AND APPLICATION

1.1 This method covers the preparation and analysis of water, soil/solid, oil and wipe samples for PCBs by
the Field Analytical Services Program (FASP) mobile laboratory. This FASP method is intended to provide rapid
turnaround analyses in the field. FASP data are not considered to be a substitute for analyses performed within the
Contract Laboratory Program. FASP data are not intended to be legally defensible.

2.0 SUMMARY OF METHOD

2.1 Soil/solid and wipe samples are prepared by sonication and water samples are prepared using solid phase
extraction (SPE) for PCB analysis by gas chromatography with electron capture detection. Procedures for Data
Quality Level II and Level III are included in this S.O.P. For soil samples, a 20 gram sample of soil is mixed with
powdered anhydrous sodium sulfate and extracted with a 10 mL portion of acetone using a sonication bath. Four
milliliters of hexane are added followed by 10 mL of water to partition the phases. The hexane layer is collected and
run through a Florisil column, dried with anhydrous sodium sulfate and reduced in volume using a a nitrogen
blowdown procedure to yield a 1 mL final extract volume. For water samples, a 100 mL water sample is extracted
three times with 3 mL of hexane. Extracts are dried with anhydrous sodium sulfate, solvent exchanged to hexane
using a nitrogen blowdown procedure to yield a 1 mL final extract volume.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Sonicator: Branson 3200 Sonicator Bath, 25°C.

4.2 Analytical Balance.

4.3 Centrifuge.

4.4 Florisil Cartridges.

4.5 Nitrogen Evaporator.

4.6 Gas Chromatograph fGCl: Varian 3400 GC with an electron capture detector (ECD).

4.7 Autosampler: Varian 8100.

4.8 Data System: PE Nelson Chromoatographic software.

5.0 REAGENTS

5.1 Acetone: Pesticide Residue Analysis Grade.

5.2 Deionized Water.

5.3 Hexane: Pesticide Residue Analysis Grade.

FMC-PCB-007-1

-------
5.4	Methanol: Pesticide Residue Analysis Grade.

5.5	Sodium Hydroxide. 0.5 N.

5.6	Sulfuric Acid. 0.5 N.

5.7	Concentrated Sulfuric Acid.

5.8	Anhydrous Sodium Sulfate.

5.9	Cleaned Copper Powder.

5.10	Standards

5.10.1	Aroclor-1026/1260: 100 ng/mL, 500 ng/mL, 2500 ng/mL.

5.10.2	Aroclor-1221: 200 ng/mL.

5.10.3	Aroclor-1232: 100 ng/mL.

5.10.4	Aroclor-1242: 100 ng/mL.

5.10.5	Aroclor-1248: 100 ng/mL.

5.10.6	Aroclor-1254: 100 ng/mL.

5.10.7	Toxaphene: 500 ng/mL.

5.10.8	Decachlorobiphenvl: 2 ng/mL.

5.11	Helium: Carrier gas, ultra pure or equivalent.

5.12	Nitrogen: Make-up gas, ultra pure or equivalent.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Sample Preparation

7.1.1 Soil Samples:

7.1.1.1	Twenty grams of sediment or soil are weighed on an analytical balance into a 40-
mL VOA vial. The sample weight is recorded in the Pesticide/PCB Extraction Log Book.
Anhydrous sodium sulfate is added to the sample to remove moisture.

7.1.1.2	The surrogate solution (2.0 mL) is added to the sample along with 10 mL of
acetone. The volume of the surrogates and Standard Log identification numbers are recorded in the
Pesticide/PCB Extraction Log Book.

FMC-PCB-007-2

-------
7.1.1.3 The vial is placed in the sonicator bath. The sonicator bath is turned on for ten

minutes.

7.1.1.4 Four milliliters of hexane are added and the mixture is shaken for an additional

minute.

7.1.1.5 Ten milliliters of water are added and the phases are allowed to separate. The
hexane layer is drawn of and collected.

7.1.1.5.1 For Level II screening, proceed with the florisil clean up of the sample

extract.

7.1.1.5.2 For Level III, extract the soil/acetone/water mixture two more times,
using a 4 mL aliquot of hexane each time.

7.1.1.6 The sample extrat is transfered to a 20-mL vial and 5 mL of concentrated sulfuric
acid are added and the vial capped.

7.1.1.7 The sample is shaken/vortexed for one minute and the phases are allowed to

separate.

7.1.1.7.1 If a clean phase separation is not achieved, remove the sulfuric acid
layer from the vial, add another 5 mL of concentrated sulfuric acid, shake the sample and
allow the phases to separate.

7.1.1.8 The hexane layer is transfered to a clean 20-mL vial.

7.1.1.9 An additional 1 mL of hexane is shaken with the sulfuric acid layer and then the
separated hexane is added to the clean 20-mL vial.

7.1.1.10 One milliliter of reagent water is added to remove excess sulfuric acid, the extract
is shaken, the phases are allowed to separate and the hexane layer is collected in a clean 20-mL
vial.

7.1.1.11 The sample extract is passed through a Florisil cartridge for cleanup.

7.1.1.11.1 A Pasteur pipette is packed with a small wad of glass wool. Enough
Florisil is added to make a 1 inch column. The Florisil column is washed with 5 mL of
90:10 hexane/acetone, making sure to keep the cartridge bed from drying out.

7.1.1.11.2 The sample is added to the Florisil column, and the pesticide are
eluted with 9 mL of hexane and collected in a vial containing 2-5 grams of anhydrous
sodium sulfate.

7.1.1.12 The sample extract is transferred to a 2 mL conical sample tube and concentrated
with the nitrogen evaporator to a 1 mL final sample volume.

7.1.1.12.1 The sample extract volume is reduced to below 1 mL and brought to
a final volume of 1 mL with hexane. The sample extract is transferred to a 1 mL vial.

7.1.1.12.2 Sample extracts which require sulfur removal are cleaned up with
granular copper as outlined in section 14.4.6 of QTM for organochlorine pesticides, page
D-37-PEST-Q.

FMC-PCB-007-3

-------
7.1.1.13 Sample extracts are stored at 4°C if necessary.

7.1.2 Water Samples

7.1.2.1	A 100 mL water sample is poured into a 125 mL separatory funnel. The sample
volume is recorded in the Pesticide/PCB Extraction Log Book.

7.1.2.2	The pH of the sample is adjusted to 5.0-7.0 using NaOH or H2S04.

7.1.2.3	The surrogate solution (2.0 mL) is added along with 5 mL of methanol and the
sample is shaken vigorously. The volume of the surrogates and Standard Log identification
numbers are recorded in the Pesticide/PCB Extraction Log Book.

7.1.2.4	The sample is extracted three times with 3 mL portions of hexane.

7.1.2.5	The combined extracts are dried with 2-5 grams of sodium sulfate.

7.1.2.6	The sample extract is cleaned up and concentrated following section 7.1.1.6.-

7.1.1.12

7.1.2.7	Sample extracts are stored at 4°C if necessary.

7.2	Analytical Sequence

7.2.1	Low Point Standard Aroclor-1016/1260.

7.2.2	Midpoint Standard Aroclor-1016/1260.

7.2.3	High Point Standard Aroclor-1016/1260.

7.2.4	Aroclor-1221.

7.2.5	Aroclor-1232.

7.2.6	Aroclor-1242.

7.2.7	Aroclor-1248.

7.2.8	Aroclor-1254.

7.2.9	Toxaphene.

7.2.10	Instrument Blank.

7.3	Gas Chromatograph Operating Conditions

•	Carrier Gas

•	Column Flow

•	Make-up Gas

•	Make-up Gas Flow

•	Initial Temperature

•	Initial Time

FMC-PCB-007-4

Helium
5 mL/minute

N2

30 mL/minute
140°C
1 minutes

-------
•	Ramp	10°C/min

•	Final Temperature	280°C

•	Final Hold	10 minutes

•	Primary Analytical Column	DB-608, 30 meters, 0.53 mm ID, fused silica

megabore capillary column

•	Injector Temperature	250°C

•	Detector Temperature	300°C

7.4	Sample Analysis

7.4.1 1 mL sample vials containing the sample extracts are placed on the autosampler following
the standards outlined in the analytical sequence in Section 7.2.

7.5	Compound Identification

7.5.1 Aroclors and toxaphene are identified both by pattern recognition and retention time.

7.6	Compound Quantitation

7.6.1	An average of the concentration of three to five of the major peaks are used for the
quantitation of toxaphene and aroclors.

7.6.2	The concentration of three to five individual peaks for the target aroclors and toxaphene are
calculated following the equations outlined in the 3/90 Statement of Work (SOW), Section III, page D-
52/PEST. The average of these values is determined and reported on Form I.

7.6.2.1 Water:

A x v x DF

concentration ( uq/L ) = 	

CF x v x v.

O	1

Where: A	=	Area of peak to be measured;

CF	=	Calibration factor for the mid point concentration external standard (area per ng);

V0	=	Volume of water extracted in milliliters (mL);

V;	=	Volume of extract injected in microliters (/iL);

Vt	=	Volume of the concentrated extract in microliters (/iL); and

DF	=	Dilution factor.

7.6.2.2 Soil:

A x v x DF

concentration ( \ig/Kg ) =

CF x w x v. x d

where: A, CF, V;, Vt, and DF are as given for water;

Ws =	Weight of sample extracted in grams (g); and

D =	(100 - percent moisture)/l00.

8.0 QUALITY CONTROL

FMC-PCB-007-5

-------
8.1 Initial Calibration

8.1.1 The initial calibration sequence outlined in Section 7.2 is analyzed prior to sample analysis.

8.1.2 Calibration factors for each of Aroclor and toxaphene are calculated using the summation of
the areas of three to five of the major peaks.

8.1.3 Initial Calibration Acceptance Criteria:

8.1.3.1 The percent relative standard deviation (%RSD) of the calibration factors from the
three-point calibration Aroclor-1016/1260 and decachlorobiphenyl must be < 25%.

8.2 Continuing Calibration

8.2.1 The percent difference (%D) between the calibration factor from the calibration check
standard and the average calibration factor from the initial calibration for Aroclor-1016/1260 must be ± 35%

8.2.2 The retention time of decachlorobiphenyl in the calibration check standard must be within
± 2.0%i of the mean retention time from the initial calibration.

8.3 Method Blanks

8.3.1 Method blanks are prepared for each type of matrix and with each set of samples.

8.3.2 For water samples, the method blank is prepared using 100 mL of reagent water and following
the procedure from section 7.1.2.

8.3.3 For sediment/soil samples, the method blank is prepared using clean sand and following the
procedure from section 7.1.1.

8.4 Blank Spikes

8.4.1 For Level II, no blank spike analyses are performed.

8.4.2 For Level III analyses, blank spikes are prepared.

8.4.2.1 One blank spike is prepared for each batch or 20 samples.

8.4.2.2 Blank spikes are prepared by spiking reagent water or clean sand with a solution
of Aroclor-1016/1260 at the midpoint calibration concentration and 10 (iL of 2 (ig/L
decachlorobiphenyl.

8.4.2.3 QC Acceptance Criteria

Compound

% Recovery

Aroclor-1016/1260

30-130%
50-150%

Decachlorobiphenyl

8.5 Surrogate Recovery Acceptance Criteria

8.5.1 The advisory QC limits for sample surrogate recovery are 60-150%.

FMC-PCB-007-6

-------
9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERNCES

1.	USEPA CLP Draft SOW for Quick Turnaround Analysis (3/27/92)

2.	USEPA Contract Laboratory Program Statement of Work for Organic Analyses (3/90)

3.	EPA Method 8080, Organochlorine Pesticides and PCBs

FMC-PCB-007-7

-------
ESAT Region 10 Method
FIELD ANALYSIS OF PCBS

1.0 SCOPE AND APPLICATION

1.1 These guidelines are proposed for the determination of PCBs in soils and sediments at various
concentrations. This method yields tentative identification and estimated quantitation of PCBs and should only be
performed by trained analysts. The primary objective is to provide analytical data in a timely manner for guidance
of ongoing work at a site which has been previously characterized.

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil or sediment is placed in a screw culture tube. A small amount of methanol
is added to bind the water in the sample. The sample is then extracted with a measured volume of hexane. An
optional cleanup involves treating an aliquot of the hexane extract with concentrated sulfuric acid. Analysis is
performed using either a temperature programmed/isothermal gas chromatograph (GC) with a megabore capillary
column or isothermal GC with a packed column and electron capture detector. Identification is based on comparison
of retention times and relative peak intensities between samples and standards. Quantitation is based on the external
standard method.

3.0 INTERFERENCES

3.2 Samples containing free sulfur or hexane-soluble organosulfur compounds may yield interfering GC
peaks. Cleanup of the extract can be made using copper turnings or filings.

4.0 APPARATUS AND MATERIALS

4.1 GC/ECD Isothermal or Temperature Programmable.

4.2 Megabore or Packed Column: Capable of adequately resolving multicomponent PCBs.

4.3 Data System: Capable of retention time labeling, relative retention time comparisons, and providing
peak height and peak area measurements.

4.4 Analytical Balance: Capable of measuring to 0.01 grams.

4.5 A Vortex Mixer. Centrifuge. Laboratory Oven, and Nitrogen Evaporator.

4.6 Disposable Glass Screw Cap Vials and Pipets.

5.0 REAGENTS

FMC-PCB-008-1

-------
5.1 Hexane. Methanol. Acetone, and Iso-octane: Pesticide grade or equivalent

5.2 Bright Copper Filings or Turnings.

5.3 Reagent Grade Water.

5.4 Nitric and Sulfuric Acid: Concentrated, reagent grade.

5.5 Ultrapure or Chromatographic Grade Gases.

5.6 Calibration and Check Standards.

5.7 Calibration Standards: Prepare calibration standards at a minimum of three concentration levels for each
analyte of interest. The lowest standard should be approximately 2X (two times) the quantitation level. The
remaining standards should define the linear range of the detector. Calibration standards must be replaced after six
months, or whenever comparison with check standards indicates a problem.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 The maximum holding times for soil and sediment PCB samples are 7 days between collection and
extraction and 40 days between extraction and analysis.

6.2 Samples should be shipped and stored in glass jars with Teflon lined caps. Samples should remained
refrigerated until extracted.

7.0 PROCEDURE

7.1 Add 2-3 grams of well homogenized sample to a tared and labeled concentrator tube. Weigh again to
the nearest 0.01 gram. Record the weights.

7.2 Optional: Add ~1 gram of sodium sulfate. Recommended for samples with high moisture content.

7.3 Add 1.0 mL of methanol to the tube and cap. Vortex at maximum speed for one minute.

7.4 Transfer 6-8 mL of hexane to the tube and cap. Vortex for one minute.

7.5 Add 1 mL of concentrated sulfuric acid to the tube and cap. Vortex for one minute.

7.6 Centrifuge for five minutes. Then transfer 1 mL of extract into an autosampler vial. Avoid transferring
any of the acid into the vial.

7.7 Enhanced sensitivity may be achieved by transferring a larger portion of the acid treated hexane and
reducing the volume via nitrogen blowdown.

7.8 The sample is now ready for GC injection.

7.9 Cleanup

7.9.1 Use of sulfuric acid may not be needed in all cases but should be used for all samples as a
general precaution as it will extend both column and detector life. Interferences resulting from a high level
of hydrocarbons may not be completely eliminated by this technique. High levels of hydrocarbons may also
have a suppression effect leading to quantitative underestimates.

FMC-PCB-008-2

-------
7.9.2 Bright copper may be used to remove elemental sulfur from sample extracts.

7.9.3 Solid phase extraction columns may also be employed to remove interferences from the
sample extract.

7.10 Initial Calibration

7.10.1 Use at least three calibration standards to generate curves for each of the analytes of interest.
Compute the percent relative standard deviation based on each on the calibration factors or the correlation
coefficient.

7.10.2 The %RSD should be less than or equal to 25% and the correlation coefficient should be
greater than or equal to 0.995.

7.10.3 The initial calibration should be rerun anytime instrument conditions are altered.

7.10.4 Once acceptable linearity has been established for one PCB it is reasonable to assume
acceptable linearity for all PCBs. However, an initial calibration must be provided for every detected target
analyte.

7.11 Continuing Calibration

7.11.1 The system should be rechecked on a regular basis using the midpoint calibration. The
standard should have a percent difference of less than or equal to 25% from the initial calibration.

7.12 Instrumental Analysis

7.12.1 The peak response should be greater than 25% and less than 100% of full scale deflection
in order to allow visual pattern recognition and to prevent retention time shifts due to detector overload.

7.12.2 The following information should be recorded in the instrument logbook:

7.12.2.1 Instrument and Detector identification

7.12.2.2 Column packing, coating, length, and ID

7.12.2.3 Oven, Injector, Detector temperatures

7.12.2.4 Gases and flows

7.12.2.5 Site name and sample number

7.12.2.6 Date, time, and GC operator initials

7.12.3 Qualitative identification of PCBs is based on retention time and pattern recognition as
compared to a known standard on a single column. A second dissimilar column may be used for
confirmation.

7.12.4 Individual peak retention time windows should be less than or equal to 2% for megabore
columns and less than or equal to 5% for packed columns.

7.12.5 For the purposes of field analysis positive identification is based on the chemist's best
professional judgement. It is possible that interferences may preclude positive identification of the analyte.

FMC-PCB-008-3

-------
In that case, the analyst should report the presence of the interferents with a maximum possible PCB
concentration.

7.12.6 Calculations should normally be reported based on a minimum of five major peaks for each
PCB. The same major peaks must be used for both the sample and the standard. Compute sample
concentrations for individual peaks and average. Sample results are reported on an "as is" basis in order to
eliminate drying time.

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

1. FASP Method F040.001

FMC-PCB-008-4

-------
FASP Method Number F040.001

POLYCHLORINATED BIPHENYLS fPCBS) IN SOIL

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various Aroclors, also known as poly chlorinated biphenyls (PCBs), in soil, and sediment samples.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 To begin sample analysis, a measured amount of soil or sediment is placed in a screw cap culture tube.
A small amount of methanol is added to bind the water. The sample is extracted with a measured volume of hexane.
An optional cleanup involves treating an aliquot of the hexane extract with concentrated sulfuric acid. Analysis is
performed using either a temperature- programmed/isothermal gas chromatograph (GC) with a megabore capillary
column, or isothermal GC with a packed column and electron capture detector (ECD). Identification is based on
comparison of retention times and relative peak intensities between samples and standards. Quantitation is based on
the external standard method.

3.0 INTERFERENCES

FMC-PCB-009-1

-------
Table 1

FASP METHOD F040.001 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

PCB

CAS Number

QuarShMSfflibiiHiitlit (/ig/kg)

Aroclor-1016

12674-11-2

250

Aroclor-1221

11104-28-2

250

Aroclor-1232

11141-16-5

250

Aroclor-1242

53469-21-9

250

Aroclor-1248

12672-29-6

250

Aroclor-1254

11097-69-1

500

Aroclor-1260

11096-82-5

500

Aroclor-1262

37324-23-5

1000

* Specific quantitation limit values are highly matrix dependent. The quantitation limits listed herein are

provided for guidance and may not always be achievable.

** Quantitation limits listed for oil are on an "as-received" basis.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are 2 GC options that meet the requirements of this method. Other
GC configurations may be substituted if they also meet the method requirements.

4.1.1 Gas chromatograph. option 1: An analytical system complete with an isothermal GC capable

of operation at elevated temperatures and all necessary accessories including injector and detector systems

FMC-PCB-009-2

4.1.1.1 Column 1: 1.8 m x 3.0 mm I.D. glass column packed with GP 1.5%
SP-2250/1.95% SP-2401 on 100/120 Supelcoport (Supelco) or equivalent.

4.1.1.2 Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco) or equivalent.

4.1.1.3 Detector: Linearized ECD with optional makeup gas supply at the detector's inlet.

4.1.2.1 Column: 15 m x 0.53 mm I.D. DB-608 fused silica capillary column (FSCC)
(J&W Scientific) or equivalent.

4.1.2.2 Detector: Linearized ECD using a system with makeup gas supply at the detector's
capillary inlet.

4.2 Other Laboratory Equipment

4.2.1 Screw cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction.

4.2.2 Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3 Spatulas: Stainless steel, micro and semimicro.

4.2.4 Microsvringe: 10-(iL.

4.2.5 Balance: Top loading, capable of weighing to 0.01 g.

4.2.6 Micropipets: 10- to 1,000-^L.

FMC-PCB-009-3

-------
4.2.7 Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and

25-mL.

4.2.8	Volumetric flasks: 10-, 25-, 50-, 100-mL.

4.2.9	Vortex mixer: Vortex Genie or equivalent.

4.2.10	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.11	Amber storage bottles: 100- and 500-mL.

4.2.12	Autosampler vials: 1- or 2-mL with Teflon-lined screw caps.

4.2.13	Graduated centrifuge tubes: 10-mL with ground glass stoppers.

4.2.14	Oxygen traps: Supelpure-O-Trap and OMJ-1 Indicating Tube, or equivalent.

4.2.15	Leak detector: Snoop liquid or equivalent for packed column operations or GOW-MAC Gas
Leak Detector, or equivalent, for megabore capillary operations.

4.2.16	Timer: 0 to 10 minute range.

4.2.17	Teflon wash bottles: 500-mL.

4.2.18	Laboratory oven: Capable of maintaining temperature of greater than or equal to 200°C.

4.2.19	Chromatographic data stamp: Used to record instrument operating conditions.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Methanol: Pesticide quality, or equivalent.

5.1.2	Hexane: Pesticide quality, or equivalent.

5.1.3	Acetone: Pesticide quality, or equivalent.

5.1.4	Isooctane: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

5.2.1 Reagent water: Reagent water is defined as water in which an interferent is not observed at
the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent), a water purification system (Milli-Q
Plus with Organex Q cartridge, Barnstead Water-1 Systems [provided with the Base Support Facilities], or
equivalent), or purchased from commercial laboratory supply houses.

FMC-PCB-009-4

-------
5.2.2 Sodium sulfate: Reagent, anhydrous, granular. Pre-conditioned by heating for 24 hours at

200°C and storing in clean glass containers with Teflon liners.

5.2.3 Nitric acid: 10 percent vol./vol.

5.2.4 Sulfuric acid: Concentrated.

5.2.5 Copper turnings or filings: Remove oxides by treating with dilute nitric acid, rinse with

distilled water to remove all traces of acid, rinse with acetone, and dry under a stream of nitrogen.

5.3 Gases

5.3.1 Five percent methane in argon: Ultrapure or chromatographic grade (always used in

conjunction with an oxygen trap).

5.3.2 Helium: Ultrapure or chromatographic grade (always used in conjunction with an oxygen

trap).

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as manufacturer
certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This procedure is done through volumetric dilution of the stock standards with isooctane. The
lowest concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

7.0 PROCEDURE

7.1 Extraction: The sample extraction technique for PCBs in oil is as follows:

FMC-PCB-009-5

-------
7.1.1 Add 2 to 3 grams of well-homogenized sample to a tared and labeled 150-mm culture tube;
weigh again to the nearest 0.01 gram. Record weights.

7.1.2 Optional: Add approximately 1 gram of sodium sulfate. Recommended for samples of high
moisture content.

7.1.3 Add 10 mL of nanograde methanol via repitet to the culture tube and cap.

7.1.4 Vortex at maximum speed for 30 seconds.

7.1.5 Add 10.0 mL of nanaograde hexane by repipet to the culture tube and recap.

7.1.6 Vortex at the maximum speed for 60 seconds.

7.1.7 Transfer a 6 to 8 mL aliquot of the hexane layer to a 100-mm culture tube using a disposable
Pasteur pipet.

7.1.8 Add 1.0 mL of concentrated sulfuric acid by repipet to the aliquot and recap.

7.1.9 Vortex at the maximum speed for 60 seconds.

7.1.10 Centrifuge for 5 minutes.

7.1.11 Transfer approximately 1 mL of extract into a Teflon-lined screw cap autosampler vial using
a disposable Pasteur pipet. Avoid transfer of any of the acid layer.

7.1.12 Enhanced sensitivity may be achieved by transferring 5.00 mL of acid-treated hexane extract
to a 10-mL graduated centrifuge tube and reducing the solvent volume to between 0.2 and 0.4 mL by
standard low-temperature N2 blowdown techniques and making the final sample extract volume 0.50 mL by
rinsing tube walls with hexane.

7.1.13 The sample extract is now ready for GC injection.

7.2 Cleanup

7.2.1 General extract cleanup:

7.2.2 Sulfur removal:

FMC-PCB-009-6

-------
7.2.2.1 Sulfur interference: Elemental sulfur may be encountered in some oils. The
solubility of sulfur in various solvents is very similar to that of PCBs; therefore, the sulfur
interference follows along with the PCBs through the normal extraction and cleanup techniques.
Sulfur will be quite evident in gas chromatograms obtained from ECDs. If the GC is operated at
the normal conditions for PCB analysis, the sulfur interference can completely mask a large region
of the chromatogram. The recommended technique for the elimination of sulfur follows.

7.2.2.2 Summary of method: The sample extract is combined with clean copper. The
mixture is shaken, and the extract is removed from the sulfur cleanup reagent.

7.2.2.3 Procedure for sulfur cleanup:

7.2.2.3.1 The copper used must be reactive; therefore, all oxides of copper must
be removed so that the copper has a shiny, bright appearance.

7.2.2.3.2 Transfer 5 mL of the final extract described in Section 7 (Step 7.1.9)
to a 16 mm x 100 mm screw cap culture tube with a Teflon-lined cap.

7.2.2.3.3 Add approximately 2 g of cleaned copper to the tube. Mix for at least
1 minute on the vortex mixer. This step may be repeated if sulfur removal is incomplete.

7.2.2.3.4 Resume the procedure described in Section

7.1.8.

7.2.2.3.5 The effect of copper on PCB recovery is shown in Table 3.

7.2.3 Solid phase extraction technology: Solid phase extraction (SPE) technology (e.g., Sep-Pak)
may provide an acceptable alternative to acid cleanup for PCB extracts.

7.3 Calibration

7.3.1 Initial calibration:

Table 2

PCB DEGRADATION WITH TIME
AFTER TREATMENT WITH CONCENTRATED SULFURIC ACID

FMC-PCB-009-7

-------
PCB

CAS Number

Approximate Percent Loss*

24 hours

48 hours

168(howeek)

Aroclor-1016

12674-11-2

None**

None

Aroclor-1221

11104-28-2

None

Aroclor-1232

11141-16-5

None

Aroclor-1242

53469-21-9

None

Aroclor-1248

12672-29-6

None

Aroclor-1254

11097-69-1

None

Aroclor-1260

11096-82-5

None

Aroclor-1262

37324-23-5

Not Tested

After treatment with H2S04over the specified period of time.

No significant loss.

or equal to 25 percent, or the calibration is invalid and must be repeated. Anytime the GC system
is altered (e.g., new column, change in gas supply, or change in oven temperature) or shut down,
a new initial calibration curve must be established.

7.3.2 Continuing calibration:

7.3.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing calibra-
tion validation. This single point analysis follows the same analytical procedures used in the initial
calibration. Instrument response is used to compute the CF which is then compared to the mean
initial calibration factor (CF), and a relative percent difference (RPD, see Section 7.5) is calculated.
Unless otherwise specified, the RPD must be less than or equal to 25 percent for the continuing
calibration to be considered valid. Otherwise, the calibration must be repeated. A continuing
calibration remains valid for a maximum of 24 hours provided the GC system remains unaltered
during that time.

FMC-PCB-009-8

-------
Table 3

EFFECT OF COPPER TREATMENT ON
PCB RECOVERY

PCB

CAS Number

Average Percent
Recovery After
Treatment with Cu*

Aroclor-1242

53469-21-9

112

Aroclor-1248

12672-29-6

100

Aroclor-1254

11097-69-1

Aroclor-1260

11096-82-5

Aroclor-1262

37324-23-5

Percent recoveries cited are averages based on duplicate analyses.

7.3.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

7.4 Instrumental Analysis

7.4.2 Chromatograms:

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D;

• Oven temperature;

• Injector/detector temperature;

FMC-PCB-009-9

-------
Table 4

EXAMPLE ISOTHERMAL GC OPERATING CONDITIONS

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature
G.C. Analysis Time:

Standard/Sample Injection:

Shimadzu GC Mini-2 equipped with Linearized ECD

Shimadzu Chromatopac C-R3A Data Processor

1.8m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of 40 mL/min
Dependent on specific Aroclor, isothermal, range 190°C to 225°C
250oC

Dependent on specific Aroclors and matrix, range approximately 15 to
30 minutes

Solvent flush manual injection or automated sample injection is recom-
mended for PCB analysis. For the solvent flush technique, the syringe
barrel plus 1 (iL of nanograde hexane, 0.5 (iL of air, and 2.0 to 3.0 (iL
(measured to the nearest 0.05 (iL) of sample extract are sequentially
drawn into a 10-(iL syringe and immediately injected into the GC. Ex-
treme care must be taken to avoid contamination of the syringe needle
with sulfuric acid when loading the syringe. Injection of acid will
damage the analytical column and detector.

FMC-PCB-009-10

-------
• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.4.3 Aroclor identification:

7.4.3.3 Generally, individual peak retention time windows should be less than or equal
to 5 percent for packed column analyses and less than or equal to 2 percent for megabore capillary
columns.

7.4.4 Specific instrument parameters: Specific instrument operating parameters that have been
followed are provided as "Specific Instrument Parameters" in Appendix B of this method.

7.4.5 Analytical sequence:

7.4.5.1 Instrument blank.

7.4.5.2 Initial calibration.

7.4.5.3 Check standard solution and/or performance evaluation sample (if available).

7.4.5.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.5.5 Associated QC lot method blank.

7.4.5.6 Twenty samples and associated QC lot spike and duplicate.

FMC-PCB-009-11

-------
7.4.5.7 Repeat sequence beginning at step 5 until all sample analyses are complete or
another continuing calibration is required.

7.4.5.8 Final calibration when all sample analyses are complete.

7.5 Calculations

_ Area of Peak

Mass of Injected (nanograms)

7.5.1.2 Using the calibration factors, calculate the %RSD for each Aroclor at a minimum
of 3 concentration levels using the following equation.

ST)

%RSD = 4=r x 100
X

where SD, the Standard Deviation, is given by

SD = .

(X.-X)2
(N-l)

where: X; = Individual calibration factor (per analyte),

X = Mean of initial 3 calibration factors (per analyte),

N = Number of calibration standards.

7.5.13 The %RSD must be less than or equal to 25.0 percent.

7.5.2 Continuing calibration:

7.5.2.2 The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

FMC-PCB-009-12

-------
\CF -CFJ
RPD = -	1	— x 100

CFj+CFc

2

where: CF, =	Mean CF from the initial calibration for each analyte

CFc =	Measured CF from the continuing calibration for the same analyte.

7.5.3 Final calibration:

7.5.3.1	The final calibration is obtained at the end of any batch of samples analyzed.

7.5.3.2	The maximum allowable RPD between the mean initial calibration and final
calibration factors for each analyte must be less than or equal to 50 percent. A final calibration that
achieves an RPD of less than or equal to 25 percent may be used as an ongoing continuing
calibration.

\~-CF |

RPD = -	1	— x 100

cfi+cff
2

where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.4 Sample quantitation:

7.5.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations.

[A ) [V ) (E) (D)

Concentrationluq/kq) = 	

(CFJ (V.) (Wg)

where: Ax =

Response for the analyte to be measured.

CFc =

CF from the continuing calibration for the same analyte.

V;

Volume of extract injected (nL).

Vt

Volume of total extract (nL).

Ws

Weight of sample extracted (g).

E

Enhanced sensitivity factor (if Section 8 extract concentration is used,



E = 10; if no enhancement, E = 1)

D

Dilution factor, if used.

7.5.4.2 Report results in micrograms per kilogram ((ig/kg) without correction for blank
or spike recovery.

FMC-PCB-009-13

-------
7.5.4.3 Compute sample concentrations for individual peaks, as well as total area (a total
of 6 values), to provide the analyst with data sufficient to identify interferences or unique chromato-
graphic responses. If concentrations based on individual peak quantitations do not fail a Student's
t-test, then the results calculated based on total peak areas should be reported as the sample
concentration. However, samples have been encountered in which certain of the chromatogram
peaks have yielded concentrations outside the expected range based on relative peak intensity
matching with standards. This outcome is generally the result of interferences, which cause higher
than true concentrations to be calculated, or of matrix-dependent factors leading to unique chroma-
tography. In such cases, an experienced chemist using t-test results may eliminate questionable
peaks from calculations and quantitate on fewer than 5 peaks. An average concentration from
calculations based on matching fewer than 5, but no less than 3 independent standard and sample
peaks may be reported.

8.0 QUALITY CONTROL

FMC-PCB-009-14

-------
Table 5

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F040.001 (PCBs in Soil)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD
(%)

A-1016

50 to 150

±50

A-1221

50 to 150

±50

A-1232

50 to 150

±50

A-1242

50 to 150

±50

A-1248

50 to 150

±50

A-1254

50 to 150

±50

A-1260

50 to 150

±50

A-1262

50 to 150

±50

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

FMC-PCB-009-15

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatograms are examples of GC chromatograms for several commonly encountered
Aroclors, using an ECD.

Figure 1
Gas chromatogram A-1242

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-009-16

-------
Figure 2
Gas chromatogram A-1248

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-009-17

-------
Figure 3
Gas chromatogram A-1254

Column: 1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-009-18

-------
Figure 4
Gas chromatogram A-1260

Column:	1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-009-19

-------
Figure 5
Gas chromatogram A-1262

Column: 1.8 m x 3.0 mm (1.5% SP-2250/1.95% SP-2401 on 100/120 Supelcoport)

Column Temperature: 210°C

Detector/Injector Temperature: 250°C

Gas: 5 percent Methane in Argon at 40 mL/min

Detector: ECD

FMC-PCB-009-20

-------
9.2 Method F040.001 examples of sample QA/QC results: Spike triplicate, and split sample results are
presented as examples of FASP Method F040.002 empirical data (see Tables 6 and 7).

Table 6

FASP METHOD F040.002
SOIL MATRIX SPIKE PERCENT RECOVERY (%R)

Analyte

Number of Samples

Mean %R

Standard
Deviation of %R

Aroclor-1248

9

108

19.0

Aroclor-1254

8

103

12.1

Table 7

FASP METHOD F040.002
WATER DUPLICATE SAMPLE RELATIVE PERCENT DIFFERENCE (RPD)

Analyte

Number of
Duplicate Sample
Pairs

Mean RPD

Standard
Deviation of RPD

Aroclor-1248

9

12.0

8.94

Aroclor-1254

7

10.0

13.7

Aroclor-1260

7

9.04

5.62

FMC-PCB-009-21

-------
Table 8

FASP METHOD F040.001 STATISTICAL COMPARISON OF FASP/CLP
	METHOD SPLIT SAMPLE ANALYSES	

Analyte:	A-1248

Number of Samples:	17

Range of Measured Concentration:	420 to 620,000 Mg/kg

Linear Regressio Slope:	0.867

Linear Regression Intercept:	0.133

Linear Regression Coefficient:	0.999

10.0 REFERENCES

Information not available.

FMC-PCB-009-22

-------
APPENDIX A

FASP Method F040.002

Instrument Options:
GC System 1:

GC System 2:

GC System 3:

Data Handling System 1:
Data Handling System 2:
Data Handling System 3:

Shimadzu GC-mini 2 with linearized Electron Capture Detector (ECD), used for
isothermal, packed column analyses.

Shimadzu GC-mini 2 with linearized ECD modified with a Direct Conversion
and Makeup Gas Adapter for megabore capillary column operations and equipped
with a Shimadzu TP-M2R Temperature Programmer, used for
temperature-programmed megabore capillary column analyses.

Shimadzu GC-14A with linearized ECD, used for temperature-programmed
megabore capillary column analyses.

Shimadzu Data Processor Chromatopac C-R1B.

Shimadzu Data Processor Chromatopac C-R3A.

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit and
Shimadzu FDD-1A Floppy Disk Drive.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-PCB-009-23

-------
APPENDIX B

FASP Method F040.002

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature:

Shimadzu GC Mini-2 equipped with linearized ECD.

Shimadzu Chromatopac C-R3A Data Processor.

1.8 m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent methane in Argon at a flow rate of 30 to 40 mL/min.
Dependent on specific Aroclor, isothermal, range 190°C to 225°C.
250oC.

FMC-PCB-009-24

-------
EMSL METHOD 8101

FIELD GAS CHROMATOGRAPHIC
ANALYSIS FOR POLYNUCLEAR AROMATIC HYDROCARBONS

1.0 SCOPE AND APPLICATION

1.1 Method 8101 is used to determine the concentration of certain polynuclear aromatic hydrocarbons
(PAHs) in water and soil matrices. Table 1 lists compounds that have been determined by this method, with typical
retention times and method detection limits. The field gas chromatographic procedures described are designed with
an emphasis on quick turnaround time for sample analysis. Method sensitivity and performance may be affected by
the level of interferences and the matrix being analyzed. Specifically, Method 8101 has been used to detect and
quantitate the following compounds:

Naphthalene Benzo(a)anthracene
Acenaphthylene Chrysene

Acenaphthene Benzo(b)fluoranthene

Fluorene Benzo(k)fluoranthene

Phenanthrene Benzo(a)pyrene

Anthracene Indeno(l ,2,3-cd)pyrene

Fluoranthene Dibenzo(a,h)anthracene

Pyrene Benzo(g,h,i)perylene

1.2 This method is recommended for use by, or under the close supervision of, analysts experienced in
the operation of gas chromatographic instrumentation.

1.3 Benzo(b)fluoranthene and benzo(k)fluoranthene co-elute when the temperature program given in
Table 2 is used.

2.0 SUMMARY OF METHOD

2.1 Sample Preparation: Semivolatile PAHs are quantitatively extracted from water samples and soil sample
extracts using the solid-phase extraction method (Method 35XX).

2.2 Sample Analysis: Aliquots of the liquid extracts are analyzed by gas chromatography using direct
injection. The components are separated by a wide-bore, fused-silica capillary column using temperature
programming, and detected using a detector appropriate for the target analytes. This method describes the use of the
flame ionization detector (FID).

3.0 INTERFERENCES

3.1 Contamination of the sampling and extraction apparatus can cause interferences. Care should be taken
to ensure that all field sampling equipment has been thoroughly cleaned and stored in a clean area. All extraction
apparatus must be rinsed 3 times with methanol between each extraction. A method blank prepared from reagent
water and carried through the entire sample preparation procedure should be performed with each set of extractions.

3.2 Solvents, reagents, glassware, and other sample processing hardware may yield discrete artifacts and/or
elevated baselines. All of these materials must be demonstrated to be free from interferences, under the condition
of the analysis, by analyzing method blanks.

FMC-PAH-001-1

-------
Table 1

METHOD DETECTION LIMIT FOR POLYNUCLEAR AROMATIC HYDROCARBONS

Compound

CAS Number

Retention time
(min)

Method Detection
Limits, Water*
Cug/mL)

Method
Detection Limits,
Soil* (jug/g)

Naphthalene

91-20-3

4.47

0.02

0.7

Acenaphthylene

208-96-8

8.24

0.02

0.7

Acenaphthene

83-32-9

7.86

0.02

0.7

Fluorene

86-73-7

9.22

0.02

0.7

Phenanthrene

85-01-8

10.96

0.02

0.7

Anthracene

120-12-7

11.04

0.02

0.7

Fluoanthene

206-44-0

13.17

0.02

0.7

Pyrene

129-00-0

13.53

0.02

0.7

Benz(a)anthracene

56-55-3

15.84

0.02

0.7

Chrysene

218-01-9

15.91

0.02

0.7

Benzo(b)fluoanthene

205-99-2

17.77"

0.02

0.7

B enzo (k)fluo anthene

207-08-9

17.77"

0.02

0.7

Benzo(a)pyrene

50-32-8

18.20

0.02

0.7

Indeno(l ,2,3-cd)pyrene

193-39-5

20.01

0.04

1.4

Dibenz(a,h)anthracene

53-70-3

20.15

0.04

1.4

Benzo(g,h,i)perylene

191-24-2

20.48

0.04

1.4

Method Detection Limit values taken from Method performance Data Obtaines During Development of Quick
Turnaround Methods for Polvcvclic Aromatic Hydrocarbons. Phenol, and Pesticides/PCBs (Reference 1)

Compound co-elute

Note: Compound retention time were determined using the column and analytical conditions given in Table 2.

FMC -PAH-001 -2

-------
Table 2

CHROMATOGRAPHIC CONDITIONS FOR POLYNUCLEAR AROMATIC HYDROCARBONS

Detector

Column

Carrier Gas

Carrier Gas Flow
(cm3/min)

T emperature
Program

FID 300°C

(1)

Helium

12-15

70°C for 3 min
then to 260 °C at
12°C/min hold for
2 min

(1) 15-m by 0.53-mm I.D., fused-silica, capillary column with a 0.5-^m film thickness (J&W DB-5, Supelco SPB-5,
or equivalent)

3.2.1 Instrumentation should be located away from any contamination source.

3.2.2 In a field laboratory, standards preparation and sample analyses are frequently performed in
close proximity. Minimum method quality assurance demands that standards, solvents, and wastes are
handled and stored away from the instruments. Ovens and gas chromatographic detectors should be vented.

3.2.3 To maintain a clean operating environment, the analyst may not be assigned to take field

samples.

3.2.4 The use of high-purity gases, appropriate gas traps, and high-quality solvents is required to
reduce potential interferences.

3.3 Contamination by carryover can occur whenever high-level samples are analyzed before low-level
samples. Carryover can be reduced by solvent-rinsing the syringes and sample containers at least 3 times with hexane
between samples. As a cross-contamination check, a blank sample of the solvent rinse should be analyzed whenever
high-level samples are analyzed.

4.0 APPARATUS AND MATERIALS

4.1 Extraction Apparatus: Two different solid phase extraction media can be used according to Method

35XX.

4.1.1 Option 1 - Extraction Cartridges: Non-polar, C-8, 500-mg, disposable, solid-phase, glass
extraction cartridges (Analytichem, J.T. Baker, or equivalent) are used in conjunction with a vacuum
manifold that allows adjustment of the solvent flow through the individual cartridges. Cartridges must be
equipped with either stainless steel or Teflon frits. (Note: Each lot of cartridges must be tested for
contamination prior to use with this method.) The vacuum manifold must have a calibrated vacuum gauge
and a maximum pressure of at least 15 inches of mercury. Disposable, polyethylene, 75-mL graduated
sample reservoirs are required for each sample and blank.

4.1.2 Option 2 - extraction Disks: Non-polar, C-8, 25-mm or 47-mm diameter, solid-phase,
extraction disks which fit standard glass filtering apparatus (3M Empore C-8 disks, or equivalent).

(Note: Each lot of disks must be tested for contamination prior to use with this method.)

FMC -PAH-001-3

-------
4.1.3 Ultrasonic Call Disrupter (Sonicator): The sonicator must have a minimum output of 375
watts with pulsing capability (Heat Systems Ultrasonics, Inc., W-385, or equivalent). A 1/8" microtip is
used for sonication of all soil samples.

4.2 Gas Chromatograph

4.2.1 Gas Chromatograph System: A complete analytical system consisting of a gas
chromatograph capable of temperature programming, stable flow control, suitable for direct injections, and
possessing all required accessories, including detector, columns, column supplies, gases,syringes, and data
system. Carrier gas lines should be constructed of stainless steel or copper tubing.

4.2.2 Gas Chromatographic Column: 15-m x 0.53-mm I.D., fused-silica, capillary column with
a 0.25-1.0 (im film thickness (J&W DB-5, Supelco SPB-5 or an equivalent which meets the criteria given
in Section 8.0). The use of a fused-silica, guard column is recommended when highly contaminated matrices
are analyzed.

4.2.3 Detector: Flame ionization detector *(FID).

4.2.4 Data System: A data system capable of measuring peak heights and peak areas is
recommended.

5.0 REAGENTS

5.1 Reagent Water: ASTM Type II water.

5.2 Solvents: Methanol, hexane (pesticide quality or equivalent).

5.3 Sulfuric Acid: 0.5N H2S04 (Reagent grade).

5.4 Sodium Hydroxide: 0.5N NAOH, (Reagent grade).

5.5 Stock Standards: Stock standards may be prepared from pure standard materials or purchased as
certified solutions of known concentrations (e.g., EPA-traceable methanolic stock solutions). Prepare all standards
in a solvent appropriate for the detector being used.

5.5.1 When using pure materials, prepare stock solutions at a concentration of 1.0 Hg/^L by
dissolving 0.10 g of the standard in the appropriate solvent and diluting to volume in a 100-mL volumetric
flask. Transfer the stock solutions to reagent bottles and seal with Teflon-lined screw caps prior to
refrigeration.

5.5.2 Standards should be checked frequently for signs of degradation or evaporation, especially
just prior to the preparation of working standards.

5.6 Secondary-Dilution Standards: May be prepared for single or multiple components. Prepare by dilution
of stock solutions of known concentrations in hexane in 10-mL or 25-mL volumetric flasks. Transfer the
secondary-dilution standard to a small-volume septum-capped container, such as an autosampler vial. Store, with
minimal headspace, at 4°C ± 2°C and protect from light.

5.7 Surrogate/Retention-Time Standard: A surrogate standard may be used to monitor the performance
of the analytical procedures and the effectiveness of the method for each sample matrix. This standard can also
be used to detect shifts in chromatographic retention times. The compound 2-bromonaphthalene, C10H7Br, is
recommended for these purposes. Prepare a solution in methanol at a concentration of 2 mg/mL. Add 10 (iL of
the surrogate/retention-time standard to each 100-mL water sample or blank. Add 20 (iL of this standard to each

FMC -PAH-001 -4

-------
6-g soil sample or blank. Appropriate concentrations of this standard should also be added to each calibration
standard.

6.0 SAMPLE COLLECTION AND HANDLING

6.1 Sample Collection: Samples must be collected in glass containers. Conventional sampling practices
should be followed, except that the bottle must not be prewashed with sample before collection.

6.2 Field replicates should be collected to validate the precision of the sampling technique.

6.3 Sample Handling: Samples should be maintained at 4°C and allowed to warm to ambient temperature
just prior to analysis. Samples must be extracted and analyzed within 7 days of collection.

6.3.1 Sediment/Soil Samples: Mix sample thoroughly, especially consolidated samples. Discard
any foreign objects such as sticks, leaves, and rocks.

6.3.2 Water Samples: Collect water samples in widemouth, glass containers.

7.0 PROCEDURE

7.1 Sample Preparation

7.1.1 Sediment/Soil Samples: Weigh 6 g of undried sediment/soil into a 40-mL test tube. Add 9
mL methanol and sonicate at maximum power output for the microtip; cool the sample during sonication.
The sonicator must be set for 50% pulse action. Sonicate the sample for 2 min. The power output may have
to be adjusted to ensure that the sample extract does not splash excessively; loss of sample during sonication
is not acceptable. Rinse the sonicator tip after each sample extraction with 1 mL methanol. Combine the
rinse liquid with the sample extract.

7.1.1.1 Centrifuge the test tube containing the sample and extract for approximately 5
minutes at 1000 to 2000 rpm.

7.1.1.2 Pipet 5.0 mL of the sample extract into 100 mL of reagent water. Swirl sample
vigorously to mix thoroughly.

7.1.1.3 Pass the aqueous solution through the solid-phase extraction medium according
to the disk or cartridge procedures described in Method 35XX.

7.1.2 Water Samples: Add 5 mL of methanol to a 100-mL water sample, mix thoroughly, and pass
it through the solid-phase extraction medium according to the disk or cartridge procedures described in
Method 35XX.

7.1.3 Blanks: Prepare a minimum of one method blank for each matrix type and for each set of
samples prepared during a 24-hour period.

7.2 Instrument Preparation: Instruments must be set up and stabilized in the field analytical facility prior

to use.

7.2.1 Set up the instruments following the recommended chromatographic conditions listed in Table

FMC -PAH-001-5

-------
7.2.2 Attach the column to the injector only, and set the oven temperature to 270°C, with 5-mL/min
carrier gas flow, to bake out any contaminants that may have been acquired during shipping. Continue until
baseline is stabilized.

7.2.3 Cool the oven to the recommended starting temperature and attach the free column end to the
detector. Turn on the detector and allow the instrument to stabilize until the oven and detector temperatures
are stable.

7.3 Instrument Calibration

7.3.1 Baseline Check: Check for baseline noise. The response of any analyte which is used for
calibration or quantitation must exceed the baseline noise by at least a factor of six.

7.3.2 Calibration must be performed using the same sample introduction method that will be used
to analyze actual samples.

7.3.3 Calibration Procedure: The procedure for external standard calibration should be used. For
each analyte of interest, prepare calibration standards at a minimum of 3 concentration levels as described
in Section 5.6 of this Method. One of the external standards should be at a concentration near, but above,
the method detection limit. The other concentrations should correspond to the expected range of
concentrations found in real samples or should encompass the working range of the detector.

7.3.3.1 Refer to Section 7.4.2 of Method 8000 for calculation of calibration factors and

curves.

7.3.3.2 If the percent relative standard deviation (%RSD) of the calibration factor is less
than 25% over the working range, linearity through the origin can be assumed, and the average
calibration factor may be used for quantitation. If the %RSD is greater than 25%, calibration curves
must be constructed for each analyte.

7.3.4 Retention-Time Windows: Before establishing retention-time windows, ensure that the GC
system is working within optimum operating conditions. Retention-time windows are established using the
three levels of standards injected during the initial calibration.

7.3.4.1 Calculate the standard deviation of the three absolute retention times for each
single component analyzed in the initial calibration curve. Plus or minus three times the standard
deviation of the response for each component in the standard will be used to define the
retention-time window. If the retention-time window is less than ± 0.01 min., a ± 3% window may
be used.

7.3.4.2 An experienced analyst should interpret the chromatograms. In those cases
where the retention-time deviation for a particular analyte is greater than the retention-time
window, the daily calibration-check standard should be evaluated to determine if the
chromatographic system is operating properly.

7.4 Daily Calibration Check: The working calibration curve or calibration factors must be verified on
each day of analysis by the injection of the mid-point calibration standard. The daily calibration check is
performed prior to analyzing the first samples of the day, at mid-day, and following the last sample of the day. A
calibration check must also be performed whenever operating conditions are changed (e.g., carrier gas is replaced
or septum is replaced), or whenever a change in instrument performance is suspected. (The frequency of
calibration verification depends on the detector. Detectors such as the electron capture and photoionization
detectors are more susceptible to changes in detector response than less sensitive detectors, such as flame
ionization detectors.)

FMC -PAH-001 -6

-------
7.4.1 The retention times of the target analytes in the first daily check standard must fall within
the retention-time windows established during the initial calibration.

7.4.1.1 If the retention times are outside of the established windows, corrective action
must be taken (refer to Section 7.5 of this method).

7.4.1.2 Establish daily retention-time windows using the analyte retention times from
the first daily check standard and the standard deviations determined in the initial calibration.

7.4.2 If the response for any analyte in the first daily calibration-check standard varies from the
predicted response by more than ± 35%, a new calibration curve must be prepared for that analyte.

R ~ R

% difference =— x 100

R-,

where: R[ = Calibration Factor from initial calibration curve or calibration factor from first

daily calibration-check standard.

R2 = Calibration Factor from daily calibration-check standard.

7.4.3 If the mid-point or final calibration-check standard exceeds the ± 35% difference criterion,
the calibration-check standard must be reanalyzed. If the calibration factor still does not meet the given
criterion, the target analytes in the samples analyzed since the last acceptable calibration check must be
flagged. A new initial calibration should be performed if more samples are to be analyzed that day.

7.5 Suggested Chromatographic System Maintenance for Capillary Columns: Corrective measures may
involve one or more of the following remedial actions. Clean and deactivate the glass injection port insert or replace
with a clean and deactivated insert. Cut off the first few inches, up to one foot, of the injection port side of the
column (Note: Non-perpendicular cuts of the column may degrade system performance). Remove the column and
backflush with solvent according to the manufacturer's instructions. If these procedures fail to eliminate degradation
problems, it may be necessary to deactivate the metal injector body and/or replace the column. (Section 7.7.3, Method
8000). If samples are known to be problematic a fused-silica guard column can be installed at the injection-port end
of the analytical column.

7.6 Gas Chromatographic Analysis: Refer to Section 7.6 of Method 8000 for analytical procedures.
Samples must be analyzed using the same sample introduction procedures used far instrument calibration.

7.7 Calculations: The concentration of each analyte in the samples may be determined using a computing
integrator programmed with calibration standard data, or may be calculated by hand. Refer to Section 7.8.1 of Method
8000 for calculation of sample concentrations. Take into account the dilution of the soil sample introduced by using
only 5 mL of the 10-mL methanol extract.

8.0 QUALITY CONTROL
8.1 Sampling OC

8.1.1 Before collecting samples, any potential sources of interference from the sampling apparatus
should be eliminated. Any sampling train components that could come in contact with samples should be
thoroughly cleaned.

FMC -PAH-001 -7

-------
8.1.1.1 Sampling at locations with heavy soil contamination may require that the sampling
apparatus be washed with hot soapy water and then solvent-rinsed. Field-collection blank samples
should be prepared to verify the cleanliness of the sampling system. Fieldcollection blanks are
samples of clean water and soil collected and analyzed in the same manner and with the same
apparatus as samples from areas of suspected contamination.

8.1.1.2 When budget and scheduling permit, samples should be collected in duplicate. If
two or more samples are analyzed, the difference between the sample results should be within
±20% of the initial results, or the point should be resampled.

8.2 Field Laboratory OC

8.2.1 Each laboratory that uses these methods is required to operate a quality control program. The
minimum requirement of this program consists of an initial demonstration of laboratory capability. The
laboratory must maintain records to document the quality of the data generated. Ongoing data quality checks
are compared with established performance criteria to determine if the results of analyses meet the
performance characteristics of this method.

8.2.2 Before processing any samples, the analyst should demonstrate, through analysis of an
instrument blank, that interferences from the analytical system are not present.

8.2.3 During sample processing, the analyst must demonstrate, through the ongoing analysis of
method blanks, that all sample and standard containers and reagents are free of interferents. In addition to
the method blanks specified in Section 7.1.3, blanks should be prepared when reagent water, solvent lots,
or extraction cartridge or disk lots are changed.

8.3 Required Instrument OC

8.3.1 Section 7.3.1 requires that the response of any analyte used for calibration or quantitation must exceed
the baseline noise by at least a factor of six.

8.3.2 Section 7.3.3.2 requires that the %RSD of the calibration factors from the initial standards be less than
25% in order to use the average calibration factor for quantitation.

8.3.3 Each day analyses are performed, daily calibration checks (Section 7.4) should be evaluated to
determine if the chromatographic system is operating properly. Refer to Section 8.4 of Method 8000 for
additional procedures which may be used as diagnostic checks on instrument performance.

8.3.3.1 Section 7.4.2 sets a limit of ±35% difference when comparing the first daily check standard
response of a given analyte against the response in the initial calibration. If the limit is exceeded, a new
standard curve must be prepared.

8.3.3.2 Section 7.4.3 specifies that the differences of the mid-day and final calibration-check
analyte responses be less than ±35% of the first daily calibration check analyte response. If, after two
analyses of a calibration-check standard, these criteria are not met, all results for the outlying analytes are
to be flagged.

8.3.4 Sections 7.3.4 and 7.4.1 require the establishment of initial calibration and retention-time windows.

8.4 To establish the ability to generate acceptable precision, replicates of the daily mid-range calibration
check standard should be analyzed on the first day analyses are preformed.

FMC -PAH-001-8

-------
8.4.1 Analyze four aliquots of the check standard by the same procedures used to analyze actual

samples.

8.4.2 Calculate the average concentration and the standard deviation for each analyte of interest
using the four results. Calculate the percent relative standard deviation.

8.4.3 Results from the replicate analyses should be included in all reports.

9.0 METHOD PERFORMANCE

9.1 Method Detection Limit data were determined during method-development laboratory studies. All other
performance data were generated during field studies. Method detection limits are highly matrix-dependent. The
detection limits listed here were determined using spiked reagent water and clean sand, and may not always be
achievable.

9.2 Linearity: Examples of the calibration factors *(CFs) from a three-point, field, initial calibration, the
mean CFs, and the %RSDs are presented in Table 3. Linearity values were taken from Laboratory and Field
Evaluation of a Quick Turnaround Method for the Analysis of Polvnuclear Aromatic Hydrocarbons (Reference 2).

9.3 Precision and Accuracy: Tables 4 and 5 give method precision and accuracy data as a function of the
concentration of the analytes of interest. Table 4 presents recovery values from replicate injections of a mid-range
calibration standard. The standard solution, containing each compound at a concentration of 50 (ig/mL, was analyzed
at a frequency of once per four hours of sample analysis. The %RSD was determined for the four days of field
analysis. Table 5 gives the averaged results for triplicate daily analyses of a marine sediment reference material
(HS-3, National Research Council of Canada Marine Analytical Chemistry Standards Program). These data are taken
from the reference 2.

10.0 REFERENCES

1. Lockheed Engineering and Sciences Co., Method Performance Data Obtained During Development of Quick
Turnaround Methods for Poly cyclic Aromatic Hydrocarbons, Phenols and Pesticides/PCBs. 1990. Report for EPA
Contract 68-03-3249.

2. Amick, E.N., Munslow, W.D., Pierett, S.L., Laboratory and Field Evaluation of a Quick Turnaround Method
for the Analysis of Polynuclear Aromatic Hydrocarbons. Report for EPA Contract 6803-3249. (In preparation.)

FMC -PAH-001-9

-------
Table 3

PAH STANDRAD LINEARITY

Compound

CF LOW

CF MED

CF HIGH

CF MEAN

% RSD

Naphthalene

1.94

2.05

2.01

2.00

3.0

Acenaphthylene

1.71

1.85

1.71

1.76

4.4

Acenaphthene

2.06

2.09

2.10

2.09

1.1

Fluorene

1.86

1.86

1.87

1.86

0.3

Phenanthrene

1.42

1.54

1.68

1.54

8.4

Anthracene

2.33

2.03

1.89

2.09

11.0

Fluoanthene

1.74

1.60

1.55

1.63

6.1

Pyrene

1.67

1.64

1.54

1.62

4.4

Benz(a)anthracene

9.17

1.05

1.22

1.06

14.0

Chrysene

1.50

1.51

1.64

1.55

5.3

Benzo(b&k)fluoanthene

1.16

1.15

1.21

1.17

2.8

Benzo(a)pyrene

1.57

1.03

1.09

1.23

24.0

Indeno(l ,2,3-cd)pyrene

1.31

0.89

0.79

0.99

28.0

Dibenz(a,h)anthracene

1.54

1.09

1.05

1.23

22.0

Benzo(g,h,i)perylene

1.63

0.98

0.90

1.17

34.0

FMC -PAH-001-10

-------
Table 4

METHOD DETECTION LIMIT FOR POLYNUCLEAR AROMATIC HYDROCARBONS

Compound









% RECC
INJECT

)VERY
ION#



1A

IB

2A

2B

3A

3B

4

MEAN

%RSD

Naphthalene

109

112

130

125

133

95

104

116

11

Acenaphthylene

109

107

132

127

134

97

107

116

12

Acenaphthene

110

106

126

120

135

96

105

114

11

Fluorene

115

114

123

127

99

133

109

117

9

Phenanthrene

118

121

128

125

99

130

111

119

9

Anthracene

120

los

123

120

119

97

115

115

7

Fluoanthene

112

114

115

122

91

124

115

113

9

Pyrene

106

102

137

116

87

119

122

113

13

Benz(a)anthracene

94

104

125

122

149

101

116

116

15

Chrysene

106

98

122

144

83

122

120

114

16

Benzo(b&k)fluoanthene

103

100

115

111

96

134

107

109

11

Benzo(a)pyrene

110

103

106

103

131

91

100

106

11

Indeno(l ,2,3-cd)pyrene

144

185

117

118

77

116

68

118

31

Dibenz(a,h)anthracene

150

138

116

112

80

116

82

113

21

Benzo(g,h,i)perylene

107

113

117

114

0

...

67

86

49

FMC-PAH-001-11

-------
Table 5

ANALYTICAL RESULTS FOR STANDARD REFERENCES MATERAILS

Cnrrmmirirl

DAY 1

DA Y ?

DAY "!

DAY 4

CERTIFIED
VAT TTF

Naphthalene

2.3

3.0

2.0

1.2

0.9

Acenaphthylene

0.5

0.6

ND

ND

0.3

Acenaphthene

1.6

2.0

1.4

0.9

4.5

Fluorene

3.0

3.9

2.8

1.9

13.6

Phenanthrene

38.1

43.5

32.9

22.9

85.0

Anthracene

1.1

ND

ND

ND

13.4

Fluoanthene

27.1

25.8

23.6

18.3

60.0

Pyrene

15.0

16.3

14.6

12.2

39.0

Benz(a)anthracene

5.7

7.0

9.4

9.0

14.6

Chrysene

7.8

7.7

7.8

7.4

14.1

Benzo(b&k)fluoanthene

26.1

19.6

29.4

22.1

10.5

Benzo(a)pyrene

21.0

00
00

16.0

13.5

7.4

Indeno(l ,2,3-cd)pyrene

ND

ND

4.6*

2.9

5.4

Dibenz(a,h)anthracene

ND

ND

5.0

5.3

1.3

Benzo(g,h,i)perylene

ND

ND

2.3

0.9

5.0

Note: All results are given in /j,g/g. Values represent the average concentration for triplicate analyses.
Value represents the average concentration from two analyses.

FMC -PAH-001-12

-------
CSL Method

PAH/WATER/HEXANE EXT/GC-FID

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of water for selective polynuclear aromatic hydrocarbons (PAH).
The list of target constituents is in Table 1. Other compounds may be added as data become available.

1.2 Application of this method is limited to the screening analysis of water for the target constituents. The
chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of water contamination associated with other nontargeted compounds in the sample extracts. Positive identification
and quantification of specific constituents, such as these constituents and other organic priority pollutants, should be
supported by analyses of duplicate and other composited samples at a remote CLP laboratory employing EPA
approved testing protocols.

1.3 Preliminary method validation data indicate analysis recoveries of upwards of 80 percent.

1.4 The method detection limit (MDL) for the target constituents are 20 Hg/kg. These detection limits are
the result of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The method presented here is based on EPA Method 610 Polvnuclear Aromatic Hydrocarbons. EPA-
EMSL, Cincinnati, Ohio, EPA-600/4-82-057, July, 1983. In brief, hexane is used to effect extraction of the target
constituents from the sample matrix. The extract is subsequently analyzed on a capillary gas chromatograph using
a flame ionization detector (FID).

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target constituents may cause a positive bias in
the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples
having high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 Reacti-Flasks: 25-mL capacity with screw cap and septum liner.

4.2 Sample Syringe: Glass, 20-mL with Teflon plunger.

FMC-PAH-002-1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Water (ng/kg)

Naphthalene

20

Acenaphthylene

20

Acenaphthene

20

Fluorene

20

Phenanthrene

20

Anthracene

20

Fluoranthene

20

Pyrene

20

Benzo(a)anthracene

20

Cyrysene

20

Benzo(b)fluoranthene

20

Benzo(k)fluoranthene

20

Benzo(a)pyrene

20

Indeno(l ,2,3-cd)pyrene

20

Dibenzo(a,h,i)perylene

20

4.3	Glassware: Class A volumetric pipets and flasks; beakers, vials, Pasteur pipets, and miscellaneous
glassware as necessary for the preparation and handling of samples and standards.

4.4	Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation
of dilutions, and spiking of samples.

4.5	Gas Chromatograph fGCl: Hewlett-Packard Model 5890A; temperature programming, electronic
integration, report annotation, automatic sampler, 30-meter capillary column (DB-5, 0.25 micron film thickness, 0.323
bore), and FID.

5.0 REAGENTS

5.1	Hexane: Spectro grade, 99.9 percent.

5.2	Stock Standards: Prepare or purchase standard materials at approximately 1000 mg/L in methanol or
other suitable solvent.

5.3	Working Standards: Prepared from stock standards by precise dilution in hexane or methanol.

FMC-PAH-002-2

-------
5.4 Gases:

5.4.1 Hydrogen: Carrier gas, Grade 5.

5.4.2 Nitrogen: Makeup gas, prepurified grade.

5.4.3 Zero grade air: Less than 0.1 ppm hydrocarbons.

5.5 Retention Time Marker and Surrogate Compounds: Hexamethylbutadiene, dibutyl phthalate, and 0,P-

DDE.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.1 The target constituents are either identified as or suspected of being carcinogens. All samples
are assumed to be hazardous. Handle all stock and working calibration standards, as well as all samples,
with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all
times when preparing and handling standards and field and laboratory samples.

7.1.3 Prepare standards and samples in a fume hood.

7.1.4 Hexane (CgH14) is regulated by NIOSH. The suggested permissible exposure level (PEL) is
50 ppm with a ceiling level of 180 ppm. Exposure pathways are oral, dermal, and airway. Effects of
short-term exposure are drowsiness and irritation of eyes and nose, large doses may cause unconsciousness.
Prolonged overexposure may cause

irritation of the skin. The odor threshold of hexane is reported as 2.0 ppm. Hexane is highly flammable and
is incompatible with strong oxidizing agents.

7.1.5 Store sample extracts and standards prepared in flammable solvents in an explosion-proof
refrigerator or cooler (outside the laboratory).

7.1.6 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Any situation which leads to or causes noticeable odors or produces any physical symptoms in
the workers shall be investigated immediately followed by appropriate corrective action.

7.1.7 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical
spill clean-up kit available for use at all times.

7.1.8 Separate and dispose of lab wastes properly. The wastes include: used sample aliquots, initial
wash water, chemical wastes generated in the analysis, and disposables used in the preparation of the
samples. Collect and deposit these wastes in a drum clearly marked as "CSL Lab Wastes Only—Hazardous".
Consider water used for final rinsing of glassware hazardous, and release it into a 50 gallon drum outside
the lab trailer. Dispose of these wastes in accordance with the appropriate and relevant disposal methods.

7.2 Sample Preparation and Extraction

FMC-PAH-002-3

-------
7.2.1 To a precleaned 25-mL reacti-flask, volumetrically pipet 2 mL of hexane containing the
retention time marker. Transfer 20 mL of the water sample from the VOA vial into the barrel of the 20-mL
syringe. Insert the plunger into the syringe, invert and waste away the trapped air and excess sample until
the desired sample aliquot is contained in the syringe.

7.2.2 Transfer the sample aliquot to the reacti-flask, cap the flask, and vigorously shake for 2
minutes to achieve extraction of the sample. Following the extraction, leave the flask undisturbed for 1
minute to permit separation of the hexane and sample. Using a Pasteur pipet, transfer a suitable aliquot of
the hexane solvent extract from the flask.

7.2.3 If the sample is obviously contaminated and past experience has shown similar extracts to
contain high levels of contamination, it is recommended that a preliminary dilution be made to avoid grossly
contaminating the gas chromatograph.

7.3 Calibration

7.3.1 External calibration: Use four-level calibration with standards at approximately 10.0, 1.0,
0.1, and 0.01 ng/mL for the target constituents in hexane.

7.3.2 Working calibration: Perform working calibration with the analysis of each working day's
lot of samples or with each lot of 20 samples, whichever is more frequent. Verify working calibration by
use of a mid-range standard mix. If the response factors and retention times vary by more than ±15 percent
or 0.15 minutes from the initial calibration, then recalibrate on freshly prepared working standards.

7.4 Analysis

7.4.1 Perform GC analysis on the extract using the instrument conditions similar to those listed in
Attachment 1.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range,
dilute the sample extract such that concentrations fall within the calibration range.

7.4.3 Check the retention values for each of the reference constituents against the expected
(calibration) value. Flag those results where the retention time does not fall within ± 0.15 minutes of the
expected value.

7.4.4 Use a retention time marker as an indicator of the reliability of each sample injection and GC
run. The retention time marker should fall within the same windows as the target constituents and should
be within ±15 percent area counts of its initial calibration value. If these criteria are not met, re-evaluate
the data using relative retention times. Reruns should occur to resolve data suspicions.

7.5 Calculations

7.5.1 Base quantification of the target compounds on the integrated areas of the samples in
comparison to the integrated areas of the calibration standards for each analyte. The integrator reports the
concentrations in ng/mL in the extracts. Calculate the concentration for each target constituent in the
original sample as follows:

A x v x DF

Concentration (]ig/L) = x 100

FMC-PAH-002-4

-------
where: A

Amount of target constituent found in the extract in ng/L,

Volume of solvent added to the reactor flask, 2.0 mL,

Dilution factor, if required,

Dimensional correction factor, and

Volume of the sample added to the reactor flask in mL.

Vt
DF
1000
Vs

8.0 QUALITY CONTROL

Quality control measures shall include as a minimum:

8.1	Daily mid-range calibration checks performed prior to the analysis of each day's lot of samples or with
each lot of 20 samples, whichever is more frequent.

8.2	Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day, whichever is more

frequent.

8.3	Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory blanks
show contamination, the cause of the contamination should be investigated and corrective action taken.

8.4	Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1/day, whichever is more

frequent.

8.5	Analysis of mid-range matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1/day, whichever is more frequent.

8.6	Use of the retention time marker during the analysis of all samples and standards.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-PAH-002-5

-------
CSL Method

PAH/SOIL/HEXANE EXT/GC-FID

1.0 SCOPE AND APPLICATION

1.1 This method uses capillary gas chromatography with flame ionization detection (GC/FID) to screen
samples for the presence of selected polynuclear aromatic hydrocarbons (PAH). Target constituents are listed in
Table 1.

1.2 Application of this method is limited to the screening analysis of samples for the target constituents.
The chromatographic record produced in the analyses allows the site investigation team to examine the relative degree
of soil contamination associated with other nontargeted compounds in the sample extracts. Positive identification
and quantification of specific constituents, such as these constituents and other organic priority pollutants, should be
supported by analyses of duplicate and other composited samples at a remote CLP laboratory employing EPA
approved testing protocols.

1.3 Preliminary method validation data indicate analysis recoveries of upwards of 80 percent.

1.4 The method detection limits (MDL) for the target constituents are 1 mg/kg. These limits are the result
of previous method development work.

2.0 SUMMARY OF METHOD

2.1 The methods presented here are loosely based on EPA Method 3550, sonification extraction, and EPA
Method 8100, "Polynuclear Aromatic Hydrocarbons", found in the EPA SW-846, Test Methods for Evaluating Solid
Waste. 3rd ed., November 1986. In brief, hexane is used in conjunction with sonification to effect extraction of the
target compounds from the sample matrix. The extract is subsequently analyzed by capillary gas chromatography
using a flame ionization detector.

3.0 INTERFERENCES

3.1 Samples containing compounds that co-elute with the target compounds may cause a positive bias in
the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples
having high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 VOA Sample Vials: 40-mL capacity with septum screw caps.

4.2 Balance: Sartorius; top loading electronic with 1500 g capacity and 0.01 g sensitivity.

FMC -PAH-003 -1

-------
Table 1

CSL METHOD TARGET COMPOUND LIST AND
QUANTITATION LIMITS

Analyte

Quantitation Limit in Soil (mg/kg)

Naphthalene

1

Acenaphthylene

1

Acenaphthene

1

Fluorene

1

Phenanthrene

1

Anthracene

1

Fluoranthene

1

Pyrene

1

Benzo(a)anthracene

1

Chrysene

1

Benzo(b)fluoranthene

1

Benzo(k)fluoranthene

1

Benzo(a)pyrene

1

Indeno(l ,2,3-cd)pyrene

1

Dibenzo(a,h)anthracene

1

Benzo(g,h,i)perylene

1

4.3 Glassware: Class A volumetric pipets and flasks; beakers, vials, Pasteur pipets, and miscellaneous
glassware as necessary for the preparation and handling of samples and standards.

4.4 Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation
of dilutions, and spiking of samples.

cup horn.

4.5 Sonifier: Heat Systems Ultrasonic Sonicator with variable control up to 375 watt output and watercooled

4.6 Gas Chromatograph: Hewlett-Packard Model 5890A; temperature programming, electronic integration,
multilevel calibration, report annotation, automatic sampler, 30 meter capillary column (DB-5, 0.25 micron film
thickness, 0.323 mm bore), and FID.

5.0 REAGENTS

FMC -PAH-003 -2

-------
5.1 Solvents:

5.1.1 Hexane: Spectro grade, 99.9 percent.

5.1.2 Distilled water: Adjusted to pH 12 with 5N NaOH.

5.2 Sodium Sulfate: Reagent grade, anhydrous powder form.

5.3 Stock Standards: Prepared from purchased pure standard materials at approximately 1000 mg/L in
methanol or other suitable solvent.

5.4 Working Standards: Prepared from stock standards by precise dilution in hexane or methanol

5.5 Retention Time Marker and Surrogate Compounds: Hexamethylbutadiene, dibutyl phthalate, and 0,P-

DDE.

5.6 Gases:

5.6.1 Hydrogen: Carrier gas, Grade 5.

5.6.2 Nitrogen: Makeup gas, prepurified grade.

5.6.3 Zero grade air: <0.1 ppm Hydrocarbons.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1 The target constituents are either identified as or suspected of being carcinogens. All samples
are assumed to be hazardous. Handle all stock and working calibration standards, as well as all samples,
with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all
times when preparing and handling standards and field and laboratory samples.

7.1.3 Prepare standards and samples in a fume hood.

7.1.4 Hexane (C5H12) is regulated by NIOSH. The suggested permissible exposure level (PEL) is
50 ppm with a ceiling level of 180 ppm. Exposure path ways are oral, dermal, and airway. Effects of
short-term exposure are drowsiness and irritation of eyes and nose; large doses may cause unconsciousness.
Prolonged overexposure may cause irritation of the skin. The odor threshold of n-hexane is reported as 2.0
ppm. Hexane is highly flammable and is incompatible with strong oxidizing agents.

7.1.5 Store sample extracts and standards prepared in flammable solvents in an explosion-proof
refrigerator or in a cooler (outside the laboratory).

FMC-PAH-003-3

-------
7.1.6 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Investigate any situation which leads to or causes noticeable odors or produces any physical
symptoms in the workers and follow immediately with appropriate corrective action.

7.1.7 The ultrasonic sonicator used for sample extractions emits a high frequency sound. When
in use, the sonicator horn shall be inside the sound chamber with the door closed.

7.1.8 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical
spill clean-up kit available for use at all times.

7.1.9 Separate and dispose of laboratory wastes properly. The wastes include: the original sample,
any aliquots thereof, initial wash water, chemical wastes generated in the analysis, and disposables used in
the preparation of the samples. Collect and deposit these wastes in a drum clearly marked as "CSL Lab
Wastes Only-Hazardous". Consider water used for final rinsing of glassware nonhazardous, and release it
into the laboratory sewer system at the site.

7.2 Sample Preparation and Extraction

7.2.1 In a labeled VOA vial, add an aliquot of soil, approximately 5 to 10 grams to the vial and
accurately record the soil sample weight to the nearest .01 grams. Place the vial on the top loading balance
and record its tare weight. Using a lOO-^L syringe, add 0.1 mL of the surrogate spike mix. Volumetrically
pipet 10.0 mL of hexane containing the retention time marker.

7.2.2 Sample treatment: If the sample is wet or a highly consolidated material (i.e., clay), add about
2 g of sodium sulfate and mix. It may be necessary to integrate the sodium sulfate into the sample using a
spatula or other appropriate utensil.

7.2.3 With the VOA vial cap tightly in place, sonicate at an output setting of 30 percent for approxi-
mately 5 minutes. The resulting sonified sample should be dispersed throughout the hexane solvent and have
a grain-like appearance. If not, then add an additional 1 g of sodium sulfate and resonify. Repetitions of this
process may be needed to properly extract some samples.

7.2.5 After sonification, let the VOA vial stand until the solids have settled. Using a Pasteur pipet,
transfer a suitable aliquot of the hexane solvent (extract) from the vial into a labeled GC autosampler vial
and cap immediately with septum crimp seals. Refrigerate the sample extracts until analyzed.

7.2.6 If the extract is noticeably colored, turbid, or otherwise indicates a dirty sample, it may be
advantageous to do some cleanup by adding approximately 10 mL of pH 12 water and shaking vigorously.
This will remove phenolic compounds and results in a cleaner extract. If the sample is obviously
contaminated and past experience has shown similar extracts to contain high levels of contamination, it is
recommended that a preliminary dilution be made to avoid grossly contaminating the gas chromatograph.

7.3 Calibration

7.3.1 External calibration: Perform four-level calibration at approximately 100, 10.0, 1.0, and 0.1
(ig/mL for the target constituents in hexane.

7.3.2 Working calibration: Perform working calibration with the analysis of each working day's
lot of samples or with each lot of 20 samples, whichever is more frequent. Verify working calibration by
use of a mid-range standard mix. If the response factors and retention times vary by more than ±15 percent
or 0.15 minutes from the initial calibration, then recalibrate on freshly prepared working standards.

FMC -PAH-003 -4

-------
7.4 Analysis

7.4.1 Perform GC analysis on the extract using the instrument conditions similar to those listed in
Attachment 1.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range,
dilute the sample extract such that concentrations fall within the calibration range.

7.4.3 Check the retention values for each of the target constituents against the expected (calibration)
value. Reject those results where the retention time does not fall with ± 0.15 minutes of the expected value.

7.4.5 If a grossly contaminated sample is injected, it may be necessary to run a solvent blank
several times afterward to clean residual contamination from the injection port and column. If this does not
work, and blank runs still contain contamination, it will be necessary to change the injection port liner.
Following the change of the liner, several blank runs will be needed to obtain a stable baseline.

7.5 Calculations

7.5.1 Base quantification of the target compounds on the integrated areas of the samples in
comparison to the integrated areas of the calibration standards for each analyte. The integrator reports the
concentrations in ng/mL in the extracts. Calculate the concentration for each target constituent in the
original sample as follows:

A x v x DF

Concentration (]ig/L) = x 100

where: A
Vt
DF
1000
Ws

Amount of target constituent found in the extract in ng/M,

Volume of solvent MeCl added to the VOA vial, 5.0 mL,

Dilution factor, if required,

Dimensional correction factor, and

Weight of the sample added to the VOA vial in grams.

,0 QUALITY CONTROL

Quality control measures shall include as a minimum:

8.1 Daily mid-range calibration checks performed prior to the analysis of each day's lot of samples or with
each lot of 20 samples, whichever is more frequent.

8.2 Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1/day, whichever is more

frequent.

8.4 Analysis of field duplicate samples at a frequency of 1 in 20 samples, or 1/day, whichever is more

frequent.

FMC-PAH-003-5

-------
8.5	Analysis of a mid-range matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1/day, whichever is more frequent.

8.6	Use of the retention time marker during the analysis of all samples and standards is required.

8.7	Use of surrogate spikes during the analysis of all samples is required. Analysis of laboratory duplicate
samples is at a frequency of 1 in 20 samples analyzed.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC -PAH-003 -6

-------
Region 10 Laboratory Method

RAPID UV SCREENING OF TOTAL POLYNUCLEAR AROMATIC HYDROCARBONS (PAH)

IN SOIL AND SEDIMENT SAMPLES

1.0 SCOPE AND APPLICATION

1.1 The following method is the standard operating procedure (SOP) for rapid UV screening of total
polynuclear aromatic hydrocarbons (PAHS) in soil and sediment samples. It has been optimized to correlate with
total identifiable PAHs as measured by high pressure liquid chromatography (HPLC).

1.2 The concentrations measured by this method should be considered estimates for screening and trending
purposes only. The screening data should be backed up with HPLC and/or gas chromatography/mass spectrometry
(GC/MS) data. For an official PAH analysis, the EPA-regulated methodology must be used.

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 UV Spectrophotometer: Capable of reading at 252 and 272 nm wavelengths. The readout should be
in absorbance units.

4.2 Quartz UV-spectrophotometer Cells.

4.3 Syringes: Positive displacement, 1.00- and 0.100-mL.

4.4 Volumetric Flasks: Three 5- and/or 10-mL.

4.5 Centrifuge: Capable of holding 50-mL tubes.

4.6 Plastic Centrifuge Tubes: 50-mL.

4.7 Analytical Balance.

4.8 Silica Gel TLC Slides: With fluorescent indicator. Commercially available slides with flexible
backing work well. The slides should be at least 10 cm long, and wide enough to spot at least 2 spots.

4.9 Capillary Tubes: 25- and 2-/iL, calibrated.

4.10 Developing Chamber: Small size which fits one slide (e.g., 10 cm high by 5 cm long by 5 cm

wide).

4.11 UV Lights: Shortwave (254 nm) and longwave (360 nm).

5.0 REAGENTS

FMC-PAH-004-1

-------
5.1

Deionized Water.

5.2	Cvclohexane: UV-spectroscopic grade.

5.3	Methanol: UV-spectroscopic grade.

5.4	Potassium Bromide: Reagent grade.

5.5	Phenanthrene: For preparation of standards (purity of 98 percent, or better).

5.6	Reagent Preparation:

5.6.1	Prepare a solution that is 20 percent deionized water and 80 percent methanol. Add 10 g
of KBr for each 100 mL of solution to saturate it.

5.6.2	Prepare a KBr-saturated aqueous solution. Add 15 g of KBr to every 100 mL of
deionized water.

5.7	Pentane: Spectroscopic grade.

5.8 A set of PAH standard solutions, and a standard solution which contains 3 or 4 commonly appearing
PAHS. For good visibility on the developed slide, each PAH should be at a concentration of about 1 mg/mL
when spotting with 2-/iL capillaries.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1	Calibration

7.1.1	Prepare the following phenanthrene solutions in UV-spectroscopic grade cyclohexane to 2
significant figures: 0.6, 1.2, 1.8, 2.4, and 3.0 /ig/ml.

7.1.2	Obtain the absorbance of these solutions at 252 nm using the UV-spectroscopic grade
cyclohexane as the blank.

7.1.3	Plot the absorbance at 252 versus the phenanthrene concentration. Use a calculator to do
a linear regression for this plot which should have a correlation coefficient greater than 0.99. The average
slope of this plot, in mL/mg, is the absorption coefficient, (a), or proportionality constant between the
absorbance and the concentration.

7.2	Extraction of PAHs From Soil

7.2.1	Take 2 g of well-mixed sediment, and place in a centrifuge tube.

7.2.2	Add 10 mL of the KBr-saturated, water/methanol solution.

7.2.3	Secure the vial's cap and shake vigorously for 15 seconds.

7.2.4	Add 10 mL of cyclohexane, resecure the cap, and shake vigorously for 45 seconds.

FMC-PAH-004-2

-------
7.2.5 Centrifuge the sample for 2 minutes to break the emulsion.

7.3 Determination of Sample Concentration

7.3.1	Compare the color of the cyclohexane layer with previously extracted soil solutions to
determine what dilution may be necessary to obtain on-scale UV-absorbance readings.

7.3.2	Determine the UV absorbances at 252 and 272 nm.

7.3.3	Use the following formulas to calculate the concentration of total PAHs in the soil:

ec = 0.47 - 0.3 ( —- 1.1)
a

272

where: ec =	Empirical coefficient; if eccalculated is less than 0.14, then ec = 0.14

A252 = Absorbance at 252 nm
A272 = Absorbance at 272 nm

x d x ev x ec

[PAH] = —^	

a x m

where: [PAH] =	Estimate of total PAH concnetration (mg/kg sample)

d	=	Dilution factor (dilution necessary to obtain an on-scale UV-absorbance)

ev =	Extract volume (mL of cyclohexane)

a	=	Absorbance/phenanthrene, calibration curve slope (mL/mg), see section 7.1

m =	Mass of sample used

7.4 OPTION: Tentative Identification of PAHS
7.4.1 Method:

7.4.1.1	Prepare the developing chamber as follows:

7.4.1.1.1	Cover the bottom 5 mm with pentane.

7.4.1.1.2	Place a piece of filter paper along 1 side to act as a wick.

7.4.1.1.3	Cover the chamber, and let it sit for about 10 minutes to equilibrate.

7.4.1.2	Spot each slide with 25 fxL of extract (this amount works well for samples
where the [PAH] is less than 100 /ig/Kg sample; smaller amounts can be spotted for
higher-level samples), and 2 fxL of the common-PAH standard solution. Be sure to mark the
center of the application spot in pencil.

7.4.1.3	After the spots have dried, place the TLC slide in the developing chamber, and
be sure to replace its lid.

7.4.1.4	When the solvent front nears the top of the slide (the solvent front must not go
beyond the top of the slide), remove the slide from the chamber, and immediately mark the
solvent front.

7.4.1.5	Allow the slide to dry, and then view under the UV light.

FMC-PAH-004-3

-------
7.4.1.6 Determine the Rf value of each spot on the developed slide.

Distance a spot has moved
Distance the solvent front has moved

7.4.2 Tentative Identification of PAHS: Tentative identification of PAHs can be made by
comparing the Rf values and appearances of the spots from the extracts to the predetermined results of
the co-developed, common-PAH standard. Generally, this will be done for selected samples that have a
total *PAH concentration below 100 /ig/Kg of sample.

8.0 QUALITY CONTROL

8.1 Reagents and Glassware: All reagents and glassware will be checked for interferences at 252 and
272 nm. The volumetric flasks will be rinsed with cyclohexane, and the cyclohexane will be checked for
absorbances. One disposable centrifuge tube from each lot will be rinsed with 10 mL each of KBr-saturated,
methanol/water solution and cyclohexane, and each rinse will be checked for absorbances. Matched covets will
be filled with deionized water, and checked against each other for absorption at the wavelengths of interest.

8.2 Calibration: Calibration of the spectrophotometer with standard phenanthrene solutions is to be
carried out daily.

8.3 Control Sample: A laboratory control sample that has been homogenized, extracted, and analyzed
by HPLC, and whose absorbances at 252 and 272 nm have been previously determined, will be analyzed daily.
This sample will consist of sediment and soil from the site of interest.

8.4 Reagent Blanks: Reagent blanks will be run daily or with each batch of samples, whichever is more
frequent. Follow the procedure for extraction of PAHs from the soil (with the exclusion of 7.2.1), and the procedure
for the determination of sample concentration.

8.5 Duplicate Analysis: For 5 percent of the samples (1 in 20), a duplicate analysis will be run.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-PAH-004-4

-------
FASP Method Number F060.001

POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) IN SOIL

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various poly cyclic aromatic hydrocarbons (PAHs) in soil and sediment samples.

1.3 This method should be used only by trained analysts under the super-vision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 To begin sample analysis, a measured amount of soil is placed in a screw-cap culture tube. The sample
is extracted twice with a measured volume of methylene chloride. Isolation of target analytes is accomplished by
silica gel cleanup of the extract to eliminate interferences (primarily aliphatic hydrocarbons). Analysis is performed
using a temperature-programmed gas chromatograph (GC) with a megabore capillary column or a packed column,
and a flame ionization detector (FID). Identification is based on comparison of retention times between samples and
standards. Quantitation is by the external standard method.

3.0 INTERFERENCES

3.1 Interferences may be minimized by use of pesticide grade or ultrapure reagents, exhaustive cleanup of
glassware, and avoidance of plastic materials in laboratory operations. The analytical system must be demonstrated
to be free from contamination under conditions of the analysis by running laboratory reagent blanks.

3.2 GC interference by sample carryover may be minimized by use of disposable glassware during sample
preparation and by use of the maximum possible number of rinse cycles on automatic injection systems, or by
thoroughly rinsing syringes used in manual injections.

3.3 Interferences coextracted from samples are matrix and site specific. It is possible that cleanups used
in either FASP or Regular Analytical Services (RAS) CLP methods may fail to eliminate interferences. Highly
specialized CLP Special Analytical Services (SAS) techniques may be required to produce acceptable analytical
results.

FMC -PAH-005 -1

-------
Table 1

FASP METHOD F060.001 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

PAH

CAS Number

Quantitation Limit in
Soil/Sediment** (ng/kg)

Naphthalene

91-20-3

1000

Acenaphthylene

208-96-8

1000

Acenaphthene

83-32-0

1000

Fluorene

86-73-7

1000

Phenanthrene

85-01-8

1000

Anthracene

120-12-7

1000

Fluoranthene

206-44-0

1000

Pyrene

129-00-0

1000

Chrysene

218-01-9

1000

Benzo(a)anthracene

56-55-3

1000

Benzo(b)fluoranthene* * *

205-00-2

1000

Benzo(k)fluoranthene* * *

207-08-9

1000

Benzo(a)pyrene

52-32-8

1000

Indeno( 1,2,3 -cd)pyrene* * * *

193-39-5

1000

Dibenzo(a,h)
anthracene****

53-70-3

1000

Benzo(g,h,i)perylene

191-24-2

1000

*	Specific quantitaion limit values are highly matrix dependent. The quantitation limits herein are provided

for guidance and may not always be achievable.

** Quantitation limits listed for soil/sediment are on an "as-received" basis.

*** These compounds coelute.

**** These compounds coelute.

FMC -PAH-005 -2

-------
4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are 2 GC options that meet the requirements of this method. Other
GC configurations, not described herein, may be substituted if they meet the method requirements.

4.1.1 Gas chromatograph. option 1: An analytical system complete with a temperature-
programmable GC and all necessary accessories including detector and injector systems designed or
modified to accept megabore capillary analytical columns is required. The system shall have a data handling
system attached to the detector that is capable of retention time labeling, relative retention time comparisons,
and providing peak height and peak area measurements.

4.1.1.1 Column 1: 1.8 m x 3.0 mm I.D. glass column packed with 3% SP-2250 on
100/120 Supelcoport (Supelco), or equivalent.

4.1.1.2 Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco), or equivalent.

4.1.1.3 Detector: FID with optional makeup gas supply at the detector's inlet.

4.1.1.4 Gas supply: The carrier gas and makeup gas (if required) should be ultrapure
helium or nitrogen. The flame gases are zero air and ultrapure hydrogen, or equivalent. All gases
should pass through hydrocarbon traps prior to the GC.

4.1.2 Gas chromatograph. option 2: An analytical system complete with a temperature-
programmable GC and all necessary accessories including injector and detector systems designed or
modified to accept megabore capillary analytical columns is required. The system shall have a data handling
system attached to the detector that is capable of retention time labeling, relative retention time comparisons,
and providing peak height and peak area measurements.

4.1.2.1 Column: 15 m x 0.53 mm I.D. DB-5 fused silica capillary column (FSCC) (J&W
Scientific), or equivalent.

4.1.2.2 Detector: FID using a system with makeup gas supply at the detector's capillary

inlet.

4.1.2.3 Gas supply: The carrier gas and makeup gas should be ultrapure helium or
nitrogen. The flame gases are zero air and ultrapure hydrogen, or equivalent. All gases should pass
through hydrocarbon traps prior to the GC.

4.2 Other Laboratory Equipment

4.2.1 Glass wool: Heat at 200°C for 24 hours and store in glass jars with Teflon-lined caps.

4.2.2 Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction.

4.2.3 Disposable pipets: Pasteur, 6 and 9 inches long. Giant, 10 mm O.D. x 6 inches long.

4.2.4 Spatulas: Stainless steel, micro and semimicro.

4.2.5 Microsvringe: 10-(iL.

FMC-PAH-005-3

-------
4.2.6	Balance: Top loading, capable of weighing to 0.01 g, used to weight samples.

4.2.7	Micropipets: 10- to 1,000-^L.

4.2.8	Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and 25-mL.

4.2.9	Volumetric flasks: 10-, 25-, 50-, and 100-mL.

4.2.10	Vortex mixer: Vortex Genie, or equivalent.

4.2.11	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.12	Amber storage bottles: 100- and 500-mL.

4.2.13	Autosampler vials: 1- or 2-mL with Teflon-lined screw-caps.

4.2.14	Graduated centrifuge tubes: 15-mL with ground glass stoppers.

4.2.15	Hydrocarbon traps: Supelpure-HC-Trap, or equivalent.

4.2.16	Leak detector: Snoop liquid, or equivalent, for packed-column operations, and GOW-MAC
gas leak detector, or equivalent, for megabore capillary operations.

4.2.17	Timer: 0 to 10 minute range.

4.2.18	Teflon wash bottles: 500-mL.

4.2.19	Chromatographic data stamp: Used to record instrument operating conditions.

4.2.20	Nitrogen evaporation system: N-Evap, or equivalent.

4.2.21	Laboratory oven: Capable of maintaining temperatures of 200°C.

4.3 Instrument Options: Specific instrument options that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Petroleum ether: Pesticide quality, or equivalent.

5.1.2	Methylene chloride: Pesticide quality, or equivalent.

5.1.3	Isooctane: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

5.2.1 Reagent water: Reagent water is defined as water in which an interferent is not observed at
the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300 or equivalent) or a water purification system (Milli-Q
Plus with Organex Q cartridge or equivalent).

FMC -PAH-005 -4

-------
5.2.2 Sodium sulfate: Reagent, anhydrous, granular. The sodium sulfate is reconditioned by
heating for 24 hours at 200°C and storing in clean glass containers with Teflon-lined covers.

5.2.3 Silica gel: Grade 923, mesh 100/200. Activate the gel for 16 hours at 130°C in a shallow
glass tray loosely covered with foil. The gel may be stored for up to 1 week in glass jars with Teflon-lined
covers.

5.3 Gases

5.3.1 Helium: Ultrapure or chromatographic grade (always used in conjunction with a hydrocarbon

trap).

5.3.2 Nitrogen: Ultrapure or chromatographic grade (always used in conjunction with a
hydrocarbon trap).

5.3.3 Zero air: Zero grade or chromatographic grade (always used in conjunction with a
hydrocarbon trap).

5.3.4 Hydrogen: Ultrapure or chromatographic grade (always used in conjunction with a
hydrocarbon trap).

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as manufacturer-
certified solutions. Single PAH standards may be used; however, standard mixtures of PAHs are recommended.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with isooctane. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Soil samples should be shipped in 4-ounce, wide-mouthed
glass jars with Teflon-lined caps.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for soil PAH samples are 7 days
between collection and extraction, and 40 days between extraction and analysis.

7.0 PROCEDURE

FMC-PAH-005-5

-------
7.1 Extraction: The sample extraction technique for PAHs in soil or sediment is as follows:

7.1.1 Add 2 to 3 grams of well-homogenized sample to a tared and labeled 150 mm culture tube;
reweigh to the nearest 0.01 g. Record weights.

7.1.2 Add 6 mL of methylene chloride by repipet to the culture tube and cap.

7.1.3 Vortex at maximum speed for 2 minutes.

7.1.4 Centrifuge sample for 5 minutes.

7.1.5 Quantitatively decant the solvent using a disposable Pasteur pipet into a clean 150 mm culture

tube.

7.1.6 Repeat steps 7.1.2 through 7.1.5, combining the extracts.

7.1.7 Add a small quantity of anhydrous sodium sulfate to the extract and vortex for 30 seconds.

7.1.8 Add 2 mL of isooctane and vortex for 10 seconds.

7.1.9 Reduce the solvent volume to approximately 1.0 mL with gentle heat under a N2 stream.

7.1.10 The extract is now ready for cleanup.

7.2 Cleanup

7.2.1 General extract cleanup: The use of a silica gel chromatography column as part of a routine
cleanup procedure may not be necessary in all cases, but is required for all samples as a general precaution.
Clean extracts extend both column and detector life, and provide more accurate and precise data. Technique
gained through experience is critical in column chromatography. Columns must not be allowed to lose their
slurry characteristics, or channeling may significantly reduce cleanup effectiveness. Mixing between
solvents must be minimized to avoid poor chromatographic separations.

7.2.2 Silica gel column preparation:

7.2.2.1 Place a small slug of muffle-furnaced glass wool into a 10 mm O.D. (4-mL) giant

pipet.

7.2.2.2 Add 1.8 g of activated silica gel to the column.

7.2.2.3 Add a 1 cm layer of anhydrous sodium sulfate on top of the silica gel.

7.2.2.4 Rinse the column with 10 mL of methylene chloride and discard the rinsate. From
this point on, the column must not be allowed to go dry until the cleanup is completed.

7.2.2.5 Rinse the column with 10 mL of petroleum ether and discard the rinsate.

7.2.3 Procedure for cleanup:

7.2.3.1 Add the concentrated sample extract (Section 7.1) to the column using a small
disposable pipet.

FMC -PAH-005 -6

-------
7.2.3.2 Rinse the extract culture tube with 2 0.5-mL aliquots of isooctane and add the
rinsate to the column.

7.2.3.3 Elute the column with 6.0 mL of petroleum ether and discard the solvent.

7.2.3.4 Elute the column with 10 mL of methylene chloride. Collect the first 10 mL of
eluted solvent in a graduated centrifuge tube.

7.2.3.5 For highly contaminated samples, the extract is now ready for GC injection.
However, in most cases, greater sensitivity is required and is achieved by proceeding as follows:

7.2.3.6 Reduce the solvent volume to less than 1 mL with low heat under a nitrogen

stream.

7.2.3.7 Stopper the centrifuge tube and allow to cool. Record the volume.

7.2.3.8 The sample extract is now ready for GC injection.

7.2.4 Solid phase extraction technology: Solid phase extraction (SPE) technology (e.g., Sep-Pak)
may provide an acceptable alternative to acid cleanup for PAH extracts.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 After an experienced chromatographer has ensured that the entire chromatographic
system is functioning properly; that is, conditions exist such that resolution, retention times,
response reporting, and interpretation of chromatographic spectra are within acceptable QC limits,
the GC may be calibrated (Section 7.5). Using at least 3 calibration standards for each PAH target
analyte prepared as described in Section 5.5, generate initial calibration curves (response versus
mass of standard injected) for each PAH target analyte (refer to Section 7.4 for chromatographic
procedures).

7.3.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.5) based
on each PAH target analyte's 3 calibration factors (CFs, see Section 7.5) to determine the acceptabi-
lity (linearity) of the curve. Unless otherwise specified the %RSD must be less than or equal to
25 percent, or the calibration is invalid and must be repeated. Any time the GC system is altered
(e.g., new column, or change in gas supply, change in oven temperature) or shut down, a new initial
calibration curve must be established.

7.3.2 Continuing calibration:

7.3.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing calibra-
tion validation. This single point analysis follows the same analytical procedures used in the initial
calibration. Instrument response is used to compute the CF, which is then compared to the mean
initial calibration factor (CF), and a relative percent difference (RPD, see Section 7.5) is calculated.
Unless otherwise specified, the RPD must be less than or equal to 25 percent for the continuing
calibration to be considered valid. Otherwise, the calibration must be repeated. A continuing
calibration remains valid for a maximum of 24 hours providing the GC system remains unaltered
during that time.

FMC -PAH-005 -7

-------
7.3.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

7.3.3 Final calibration: Obtain the final calibration at the end of each batch of sample analyses.
The maximum allowable RPD between the mean initial calibration and the final calibration factors for each
analyte must be less than or equal to 50 percent. A final calibration that achieves less than or equal to 25
percent RPD may be used as an ongoing continuing calibration.

7.4 Instrumental Analysis

7.4.1 Instrument parameters: Table 2 summarizes an example of acceptable instrument operating
conditions for the GC. Other instruments, columns, and chromatographic conditions may be employed if
this method's QC criteria are met.

7.4.2 Chromatograms:

7.4.2.1 Computer reproduction of chromatograms that are attenuated to ensure all peaks
are on scale over a 100-fold range are acceptable. To prevent retention time shifts by column or
detector overload, however, they can be no greater than a 100-fold range. Generally, peak response
should be greater than 25 percent and less than 100 percent of full-scale deflection to allow visual
recognition of the various PAH compounds.

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gas and flow;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

FMC-PAH-005-8

-------
Table 2

EXAMPLE TEMPERATURE-PROGRAMMED GC OPERATING CONDITIONS

Instrument:

Integrator:
Column:
Carrier Gas:
Detector Gas:

Column (oven)
Temperature Program:

Injector Temperature:
Detector Temperature:
GC Analysis Time:
Standard/Sample Injection:

Shimadzu GC Mini-2 equipped with FID modified to accept megabore
capillary columns and a Shimadzu TP-M2R temperature programmer

Shimadzu Chromatopac C-R3A Data Processor

J&W 15 m x 0.53 mm DB-5 fused silica megabore capillary column

Ultrapure Helium or Nitrogen, at a flowrate of 10 mL/min

Zero air at a flowrate of 300 mL/min; ultrapure hydrogen at a flowrate
of 40 mL/min

Initial temperature: 75°Cfor2mins
Ramp: 15°C/min

Final temperature: 310°C for 7 mins

330oC

330oC

Approximately 25 mins

Solvent flush manual injection or automated sample injection is
recommended for PAH analysis. Two microliters of nanograde
methylene chloride, 0.5 (iL of air, and 2.0 to 3.0 (iL (measured to the
nearest 0.05 (iL) of sample extract are sequentially drawn into a 10-(iL
syringe and immediately injected into the GC.

7.4.3	PAH identification:

7.4.3.1	Qualitative identification of PAHs is based on retention time as compared to
standards on a single column. A second, dissimilar column may be used to assist in identification.

7.4.3.2	Generally, individual peak retention time windows should be less than or equal
to 2 percent for megabore capillary columns (less than or equal to 5 percent for packed columns).

7.4.3.3	It may not be possible or practical to separate all target analyte PAHs on a single
column. In such cases these target analytes should be denoted as the appropriate combination of
PAHs.

7.4.3.4	It is possible that interferences may preclude positive identification of an analyte.
In such cases, the chemists should report the presence of the interferents with the maximum
possible PAH concentration (see Section 7.5).

7.4.4	Specific instrument parameters: Specific instrument operating parameters that have been used
are provided as "Specific Instrument Parameters" in Appendix B of this method.

FMC-PAH-005-9

-------
7.4.5 Analytical sequence:

7.4.5.1	Instrument blank.

7.4.5.2	Initial calibration.

7.4.5.3	Check standard solution and/or performance evaluation sample (if available).

7.4.5.4	Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.5.5	Associated QC lot method blank.

7.4.5.6	Twenty samples and associated QC lot spike and duplicate.

7.4.5.7	Repeat sequence beginning at 7.4.5.5 until all sample analyses are completed or
another continuing calibration is required.

7.4.5.8	Final calibration when all sample analyses are complete.

7.5 Calculations

7.5.1 Initial calibration: Chromatographic response to PAH target analytes is measured by
determining CFs. In the case of coeluted analytes, the summed areas and masses should be employed to
generate a combined CF for the target analyte PAHs.

7.5.1.1 Calculate the calibration factor (CF) for each PAH target anlyte in the initial
standard. The integrator may be used to make all of these computations.

7.5.1.2 Using the calibration factors, calculate the %RSD for each Aroclor at a minimum
of 3 concentration levels using the following equation.

ST)

%RSD = 4=r x 100
X

where SD, the Standard Deviation, is given by

CF =

Area of Peak

Mass of Injected (nanograms)

A (X-X)2

SD = \ 2^ —1	

\	/ AT	"1 \

(N-l)

where: X;
X
N

Individual calibration factor (per analyte),

Mean of initial 3 calibration factors (per analyte),
Number of calibration standards.

FMC-PAH-005-10

-------
7.5.13 The %RSD must be less than or equal to 25.0 percent.

7.5.2 Continuing calibration:

7.5.2.2 The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

\~-CF J
RPD = - 1 — x 100

CFj+CFc

where: CF, = Mean CF from the initial calibration for each analyte

CFc = Measured CF from the continuing calibration for the same analyte.

7.5.3 Final calibration:

7.5.3.1 The final calibration is obtained at the end of any batch of samples analyzed.

\CF-CFr
RPD =

cfi+cff

where: CF, = Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.4 Sample quantitation:

7.5.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations.

{A ) (V ) (D)

Concentration{\ig/ kg) ~ x

(CF) (V,) (W)

FMC-PAH-005-11

-------
where: Ax

Response for the analyte to be measured.

CF from the continuing calibration for the same analyte.

Volume of extract injected (|iL).

Volume of total extract (|iL).

Weight of sample extracted (g).

Dilution factor, if used.

CFc
V;
Vt
Ws

7.5.4.2 Report results in micrograms per kilogram (ng/kg) without correction for blank, spike
recovery, or percent moisture.

7.5.4.3 Coeluted analytes should be quantitated and reported as the combination of the unseparated
PAH target analytes.

7.5.4.4 Sample spectra may not match identically with those of analytical standards. When positive
identification is questionable, the chemist may calculate and report a maximum possible concentration
(qualified as less than the numerical value) that allows the data user to determine if additional (e.g., CLP
RAS or SAS) work is required, or, if the reported concentration is below action levels and project objectives
and DQOs have been met, to forego further analysis.

7.5.4.5 Similarly, when sample concentration exceeds the linear range, the analyst may report a
probable minimum level (qualified as greater than the numerical value) which allows the data user to
determine if additional (e.g., CLP RAS or SAS) work is required, or, if the reported concentration is above
action levels and project objectives and DQOs have been met, to forego further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 3. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-PAH-005-12

-------
Table 3

MATRIX SPIKE RECOVERY (%R) AND DUPLICATE
RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F060.001 (PAHs in Soil)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD
(%)

Naphthalene

30 to 200

± 100

Acenapthylene

30 to 200

± 100

Acenaphthene

30 to 200

± 100

Fluorene

30 to 200

± 100

Phenanthrene

30 to 200

± 100

Anthracene

30 to 200

± 100

Fluoranthene

30 to 200

± 100

Pyrene

30 to 200

± 100

Benzo(a)anthracene

30 to 200

± 100

Chrysene

30 to 200

± 100

Benzo(b)fluoranthene**/
B enzo (k)fluoranthene * *

30 to 200

± 100

Benzo(a)pyrene

30 to 200

± 100

Indeno(l ,2,3-cd)pyrene***/
Dibenzo(a,h)anthracene***

30 to 200

± 100

Benzo(g,h,i)perylene

30 to 200

± 100

*	If the concentration of an analyte is less than 5 times the quantitation limits, advisory control limits for

duplicate RPD values become ± 3 times the quantitation limits for that individual analyte.

** Coeluting analytes.

*** Coeluting analytes.

FMC-PAH-005-13

-------
9.0 METHOD PERFORMANCE

9.1 The following is an example of a GC spectra for several commonly encountered PAHs.

Figure 1

Gas chromatogram - PAH compounds

Column: 15 m x 0.53 mm DB-5 fused silica megabore capillary

Column Temperature Program: Initial: 75°C - 2 mins;

Ramp: 15°C per minute;

Final: 310°C - 7 mins.

Detector/Injector Temperature: 330°C

Carrier Gas: Helium at 10 mL/min

Detector: FID

9.2 Method F060.001 examples of QA/QC results: Spike triplicate, and split sample results are
presented as examples of FASP Method F060.001 empirical data (see Tables 4, 5, and 6).

FMC-PAH-005-14

-------
Table 4

FASP METHOD F060.001
PAH SOIL MATRIX SPIKE PERCENT RECOVERY (%R)

Analyte

Number of
Samples

Mean %R

Standard Deviation of
%R

Naphthalene

5

65

20

Acenaphthylene

9

76

19

Acenaphthene

5

51

7

Fluorene

5

87

14

Phenanthrene

9

65

19

Anthracene

5

88

12

Fluoranthene

9

70

15

Pyrene

5

87

12

Benzo(a)anthracene

5

77

13

Chrysene

5

80

21

Benzo(b)fluoranthene/
Benzo(k)fluoranthene

5

93

16

Benzo(a)pyrene

9

90

16

Indeno (1,2,3 -cd)py rene/
Dibenz(a,h)anthracene

5

80

12

Benzo(g,h,i)perylene

9

91

22

Q

FMC-PAH-005-15

-------
Table 5

FASP METHOD F060.001
PAH SOIL TRIPLICATE SAMPLE PRECISION

Analyte

Number of Triplicate Sample
Groups

Mean %RSD

Naphthalene

3

ND

Acenapthylene

3

ND

Acenaphthene

3

ND

Fluorene

3

ND

Phenanthrene

3

49

Anthracene

3

45

Fluoranthene

3

40

Pyrene

3

44

Benzo(a)anthracene

3

46

Chrysene

3

46

Benzo(b)fluoranthene/
Benzo(k)fluoranthene

3

42

Benzo(a)pyrene

3

47

Indeno (1,2,3 -cd)py rene/
Dibenzo(a,h)anthracene

3

10

Benzo(g,h,i)perylene

3

30

ND - Not detected in any sample

FMC-PAH-005-16

-------
Table 6

FASP METHOD F060.001
STATISTICAL COMPARISON OF FASP/CLP
METHOD SPLIT SAMPLE ANALYSES

Analyte

Number of
Samples

Linear Regression
Coefficient

Phenanthrene

6

-0.23

Anthracene

6

0.997

Fluoranthene

6

0.994

Pyrene

6

0.991

Chrysene/
Benzo(a)anthracene

6

0.995

Benzo(b)fluoranthene/
Benzo(k)fluoranthene

6

0.923

Benzo(a)pyrene

6

0.977

Indeno (1,2,3 -cd)py rene/
Dibenz(a,h)anthracene

3

0.48

Benzo(g,h,i)perylene

6

0.997

FMC-PAH-005-17

-------
10.0 REFERENCES

Information not available.

FMC-PAH-005-18

-------
APPENDIX A

FASP Method F060.001

Instrument Options:

GC System:	Shimadzu GC-mini 2 with FID modified with a direct conversion and Makeup

Gas Adapter for megabore capillary column operations.

Temperature Programmer:	Shimadzu TP-M2R for temperature-programmed megabore capillary column

analyses.

Data Handling System 1: Shimadzu Data Processor Chromatopac C-R1B.

Data Handling System 2: Shimadzu Data Processor Chromatopac C-R3A.

Data Handling System 3: Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT display unit and

Shimadzu FDD-1A Floppy Disk Drive.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-PAH-005-19

-------
APPENDIX B

FASP Method F060.001

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Columns:

Carrier Gas:

Detector Gas:

Column (Oven) Temperature:

Injector Temperature:

Detector Temperature:

Shimadzu GC Mini-2 equipped with FID modified to accept megabore
capillary columns and Shimadzu TP-M2R temperature programmer.

Shimadzu Chromatopac C-R3A Data Processor.

J&W 15 m x 0.53 mm DB-5 fused silica megabore capillary column or
Supelco 30 m x 0.75 mm SPB-5 borosilicate megabore capillary
column.

Ultrapure helium or nitrogen, 10 mL/min.

Zero air, 300 mL/min; ultrapure hydrogen, 40° mL/min.

Initial temperature: 75°C for 2 min.

Ramp: 15°C/min.

Final temperature: 310°C for 7 min.

330°C

330°C

FMC-PAH-005-20

-------
FASP Method Number F060.002

POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) IN WATER

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various poly cyclic aromatic hydrocarbons (PAHs) in water samples.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 To begin sample analysis, a measured amount of water is placed in a volumetric flask. The sample is
extracted twice with a measured volume of methylene chloride. Isolation of target analytes is accomplished by silica
gel cleanup of the extract to eliminate interferences (primarily aliphatic hydrocarbons). Analysis is performed using
a temperature-programmed gas chromatograph (GC) with a megabore capillary column or a packed column, and a
flame ionization detector (FID). Identification is based on comparison of retention times between samples and
standards. Quantitation is based on the external standard method.

3.0 INTERFERENCES

FMC-PAH-006-1

-------
Table 1

FASP METHOD F060.002 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

PAH

CAS Number

Quantitation Limit in Water

(m-r/L)

Naphthalene

91-20-3

20

Acenaphthylene

208-96-8

20

Acenaphthene

83-32-0

20

Fluorene

86-73-7

20

Phenanthrene

85-01-8

20

Anthracene

120-12-7

20

Fluoranthene

206-44-0

20

Pyrene

129-00-0

20

Chrysene

218-01-9

20

Benzo(a)anthracene

56-55-3

20

Benzo(b)fluoranthene**

205-00-2

20

B enzo (k)fluoranthene * *

207-08-9

20

Benzo(a)pyrene

52-32-8

20

Indeno( 1,2,3 -cd)py rene * * *

193-39-5

20

Dibenzo(a,h)anthracene***

53-70-3

20

Benzo(g,h,i)perylene

191-24-2

20

*	Specific quantitaion limit values are highly matrix dependent. The quantitation limits herein are provided

for guidence and may not always be achievable.

** These compounds coelute.

*** These compounds coelute.

FMC-PAH-006-2

-------
4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are 2 GC options that meet the requirements of this method. Other
GC configurations may be substituted if they meet the method requirements.

4.1.1.1 Column 1: 1.8 m x 3.0 mm I.D. glass column packed with 3% SP-2250 on
100/120 Supelcoport (Supelco) or equivalent.

4.1.1.2 Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco) or equivalent.

4.1.1.3 Detector: Flame ionization detector (FID) with optional makeup gas supply at the
detector's inlet.

4.1.1.4 Gas supply: The carrier gas and makeup gas (if required) should be ultrapure
helium or nitrogen. The flame gases are zero air and ultrapure hydrogen or equivalent. All gases
should pass through hydrocarbon traps prior to the GC.

4.1.2 Gas chromatograph. option 2: An analytical system complete with a temperature-
programmable GC and all necessary accessories including injector and detector systems designed or
modified to accept megabore capillary analytical columns is required. The system shall have a data handling
system attached to the detector that is capable of retention time labeling, relative retention time comparisons,
and providing peak height and/or peak area measurements.

4.1.2.1 Column: 15 m x 0.53 mm I.D. DB-5 fused silica capillary column (FSCC) (J&W
Scientific) or equivalent.

4.1.2.2 Detector: FID using a system with makeup gas supply at the detector's capillary

inlet.

4.1.2.3 Gas supply: The carrier gas and makeup gas should be ultrapure helium or
nitrogen. The flame gases are zero air and ultrapure hydrogen or equivalent. All gases should pass
through hydrocarbon traps prior to the GC.

4.2 Other Laboratory Equipment

4.2.1 Glass wool: Heat at 200°C for 24 hours and store in glass jars with Teflon-lined caps.

4.2.2 Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction.

4.2.3 Disposable pipets: Pasteur, 6 and 9 inches long. Giant, 10 mm O.D. x 6 inches long.

4.2.4 Spatulas: Stainless steel, micro and semimicro.

4.2.5 Microsvringe: 10-(iL.

FMC-PAH-006-3

-------
4.2.6	Balance: Top loading, capable of weighing to 0.01 g, used to weight samples.

4.2.7	Micropipets: 1 0-jj.L to 1,000-^L.

4.2.8	Volumetric pipets/repipets: 0.5-, 1.0-, 5-, 10-, and

25-mL.

4.2.9	Volumetric flasks: 10-, 25-, 50-, and 100-mL.

4.2.10	Vortex mixer: Vortex Genie or equivalent.

4.2.11	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.12	Amber storage bottles: 100- and 500-mL.

4.2.13	Autosampler vials: 1- or 2-mL with Teflon-lined screw caps.

4.2.14	Graduated centrifuge tubes: 15-mL with ground glass stoppers.

4.2.15	Hydrocarbon traps: Supelpure-HC-Trap or equivalent.

4.2.16	Leak detector: Snoop liquid, or equivalent, for packed-column operations, and GOW-MAC
gas leak detector, or equivalent, for megabore capillary operations.

4.2.17	Timer: 0 to 10 minute range.

4.2.18	Teflon wash bottles: 500-mL.

4.2.19	Chromatographic data stamp: Used to record instrument operating conditions.

4.2.20	Nitrogen evaporation system: N-Evap, or equivalent.

4.2.21	Laboratory oven: Capable of maintaining temperatures of 200°C.

4.3 Instrument Options: Specific instrument options that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Petroleum ether: Pesticide quality, or equivalent.

5.1.2	Methylene chloride: Pesticide quality, or equivalent.

5.1.3	Isooctane: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

FMC-PAH-006-4

-------
5.2.1 Reagent water: Reagent water is defined as water in which an interferent is not observed at
the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300 or equivalent) or a water purification system (Milli-Q
Plus with Organex Q cartridge or equivalent).

5.2.2 Sodium sulfate: Reagent, anhydrous, granular. The sodium sulfate is reconditioned by
heating for 24 hours at 200°C and storing in clean glass containers with Teflon-lined covers.

5.3 Gases

5.3.1 Helium: Ultrapure or chromatographic grade (always used in conjunction with a hydrocarbon

trap).

5.3.2 Nitrogen: Ultrapure or chromatograhic grade (always used in conjunction with a hydrocarbon

trap).

5.3.3 Zero Air: Zero grade or chromatographic grade (always used in conjunction with a
hydrocarbon trap).

5.3.4 Hydrogen: Ultrapure or chromatographic grade (always used in conjunction with a
hydrocarbon trap).

5.4 Stock Standard Solutions: Stock standard solutions of analytes should be purchased as manufacturer
certified solutions. Single PAH standards may be used; however, standard mixtures of PAHs are recommended.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with isooctane. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Water samples should be shipped in 1-liter narrow-mouthed
glass containers with Teflon-lined caps.

FMC-PAH-006-5

-------
6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for water PAH samples are 7 days
between collection and extraction, and 40 days between extraction and analysis.

7.0 PROCEDURE

7.1 Extraction: The sample extraction technique for PAHs in water is as follows:

7.1.1 Add 100 mL of water to a clean 100-mL volumetric flask.

7.1.2 Add 3.0 mL methylene chloride by repipet to the flask and shake vigorously for 2 minutes.

7.1.3 Allow the layers to separate.

7.1.4 Transfer the organic layer to a 10-mL graduated centrifuge tube using a disposable Pasteur

pipet.

7.1.5 Repeat steps 7.1.2 through 7.1.4 twice and combine the extracts.

7.1.6 Add a small quantity of anhydrous sodium sulfate to the extract and vortex for 30 seconds.

7.1.7 Add 2 mL of isooctane and vortex for 10 seconds.

7.1.8 Reduce the solvent volume to approximately 1.0 mL with gentle heat under a N2 stream.

7.1.9 The sample extract is now ready for cleanup.

7.2 Cleanup

7.2.1 The use of a silica gel chromatography column as part of a routine cleanup procedure may
not be necessary in all cases, but is required for all samples as a general precaution. Clean extracts extend
both column and detector life and provide more accurate and precise data. Technique gained through
experience is critical in column chromatography. Columns must not be allowed to lose their slurry
characteristics, or channeling may significantly reduce cleanup effectiveness. Mixing between solvents must
be minimized to avoid poor chromatographic separations.

7.2.2 Silica gel column preparation:

7.2.2.1 Place a small slug of muffle-furnaced glass wool into a 10 mm O.D. (4-mL) giant

pipet.

7.2.2.2 Add 1.8 g of activated silica gel to the column.

7.2.2.3 Add a 1 cm layer of anhydrous sodium sulfate on top of the silica gel.

7.2.2.4 Rinse the column with 10 mL of methylene chloride and discard the rinsate. From
this point on, the column must not be allowed to go dry until the cleanup is completed.

7.2.2.5 Rinse the column with 10 mL of petroleum ether and discard the rinsate.

FMC-PAH-006-6

-------
7.2.3 General extract cleanup:

7.2.3.1 Add the concentrated sample extract (Section 7.1) to the column using a small
disposable pipet.

7.2.3.2 Rinse the extract culture tube with 2 0.5-mL aliquots of isooctane and add the
rinsate to the column.

7.2.3.3 Elute the column with 6.0 mL of petroleum ether and discard the solvent.

7.2.3.4 Elute the column with 10 mL of methylene chloride. Collect the first 10 mL of
eluted solvent in a graduated centrifuge tube.

7.2.3.5 For highly contaminated samples, the extract is now ready for GC injection.
However, in most cases, greater sensitivity is required and is achieved by proceeding as follows:

7.2.3.6 Reduce the solvent volume to less than 1 mL with low heat under a nitrogen

stream.

7.2.3.7 Stopper the centrifuge tube and allow to cool. Record the volume.

7.2.3.8 The sample extract is now ready for GC injection.

7.2.4 Solid phase extraction technology: Solid phase extraction (SPE) technology (e.g., Sep-Pak)
may provide an acceptable alternative to acid cleanup for PAH extracts.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 After an experienced chromatographer has ensured that the entire chromatographic
system is functioning properly; that is, conditions exist such that resolution, retention times,
response reporting, and interpretation of chromatographic spectra are within acceptable QC limits,
the GC may be calibrated (Section 7.5). Using at least 3 calibration standards for each PAH target
analyte prepared as described in Section 5.5, generate initial calibration curves (response versus
mass of standard injected) for each PAH target analyte (refer to Section 7.4 for chromatographic
procedures).

7.3.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.5) based
on each PAH target analyte's 3 calibration factors (CFs, see Section 7.5) to determine the acceptabi-
lity (linearity) of the curve. Unless otherwise specified, the %RSD must be less than or equal to
25 percent, or the calibration is invalid and must be repeated. Any time the GC system is altered
(e.g., new column, or change in gas supply, change in oven temperature) or shut down, a new initial
calibration curve must be established.

7.3.2 Continuing calibration:

FMC-PAH-006-7

-------
initial calibration factor (CF), and a relative percent difference (RPD, see Section 7.5) is calculated.
Unless otherwise specified, the RPD must be less than or equal to 25 percent for the continuing
calibration to be considered valid. Otherwise, the calibration must be repeated. A continuing
calibration remains valid for a maximum of 24 hours providing the GC system remains unaltered
during that time.

7.3.2.2 The continuing calibration is used in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

7.3.3 Final calibration: The final calibration must be obtained at the end of each batch of sample
analyses. The maximum allowable RPD between the mean initial calibration and the final calibration factors
for each analyte must be less than or equal to 50 percent. A final calibration that achieves an RPD less than
or equal to 25 percent may be used as an ongoing continuing calibration.

7.4 Instrumental Analysis

7.4.2 Chromatograms:

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gas and flow;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

FMC-PAH-006-8

-------
Table 2

EXAMPLE TEMPERATURE-PROGRAMMED GC OPERATING CONDITIONS

Shimadzu GC Mini-2 equipped with FID modified to accept megabore
capillary columns and a Shimadzu TP-M2R temperature programmer.

Shimadzu Chromatopac C-R3A Data Processor.

J&W 15 m x 0.53 mm DB-5 fused silica megabore capillary column.

Ultrapure Helium or Nitrogen, at a flowrate of 10 mL/min.

Zero air at a flowrate of 300 mL/min; ultrapure hydrogen at a flowrate
of 40 mL/min.

Initial temperature: 75°C for 2 mins.

Ramp: 15°C/min.

Final temperature: 310°C for 7 mins.

330°C
330°C

Approximately 25 mins.

Solvent flush manual injection or automated sample injection is
recommended for PAH analysis. Two microliters of nanograde
methylene chloride, 0.5 (iL of air, and 2.0 to 3.0 (iL (measured to the
nearest 0.05 (iL) of sample extract are sequentially drawn into a 10-(iL
syringe and immediately injected into the GC.

7.4.3 PAH identification:

7.4.3.1 Qualitative identification of PAHs is based on retention time as compared to
standards on a single column. A second, dissimilar column may be used to assist in identification.

7.4.3.2 Generally, individual peak retention time windows should be less than or equal
to 2 percent for megabore capillary columns (less than or equal to 5 percent for packed columns).

7.4.3.3 It may not be possible or practical to separate all target analyte PAHs on a single
column. In such cases these target analytes should be denoted as the appropriate combination of
PAHs.

7.4.3.4 It is possible that interferences may preclude positive identification of an analyte.
In such cases, the chemists should report the presence of the interferents with the maximum
possible PAH concentration (see Section 7.5.4).

7.4.4 Region-specific instrument parameters: Specific instrument operating parameters that have
been followed are provided as "Specific Instrument Parameters" in Appendix B of this method.

Instrument:

Integrator:
Column:
Carrier Gas:
Detector Gas:

Column (oven)
Temperature Program:

Injector Temperature:
Detector Temperature:
GC Analysis Time:
Standard/Sample Injection:

FMC-PAH-006-9

-------
7.4.5 Analytical sequence:

7.4.5.1 Instrument blank.

7.4.5.2 Initial calibration.

7.4.5.3 Check standard solution and/or performance evaluation sample (if available).

7.4.5.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.5.5 Associated QC lot method blank.

7.4.5.6 Twenty samples and associated QC lot spike and duplicate.

7.4.5.7 Repeat sequence beginning at 7.4.5.5 until all sample analyses are completed or
another continuing calibration is required.

7.4.5.8 Final calibration when all sample analyses are complete.

7.5 Calculations

7.5.1 Initial calibration: Chromatographic response to PAH target analytes is measured by
determining CFs. In the case of coeluted analytes, the summed areas and masses should be employed to
generate a combined CF for the target analyte PAHs.

7.5.1.1 Calculate the calibration factor (CF) for each PAH target anlyte in the initial
standard. The integrator may be used to make all of these computations.

7.5.1.2 Using the calibration factors, calculate the %RSD for each Aroclor at a minimum
of 3 concentration levels using the following equation.

ST)

%RSD = 4=r x 100
X

where SD, the Standard Deviation, is given by

CF =

Area of Peak

Mass of Injected (nanograms)

A (X-X)2

SD = \ 2^ —1

\ / AT "1 \

(N-l)

where: X;
X
N

Individual calibration factor (per analyte),

Mean of initial 3 calibration factors (per analyte),
Number of calibration standards.

7.5.13 The %RSD must be less than or equal to 25.0 percent.

FMC -PAH-006-10

-------
7.5.2 Continuing calibration:

7.5.2.2 The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

\~-CF J
RPD = - 1 — x 100

CFj+CFc

where: CF, = Mean CF from the initial calibration for each analyte

CFc = Measured CF from the continuing calibration for the same analyte.

7.5.3 Final calibration:

7.5.3.1 The final calibration is obtained at the end of any batch of samples analyzed.

\CF-CFr
RPD =

cfi+cff

where: CF, = Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.4 Sample quantitation:

Concentration(]ig/ kg)

(AJ (Vt) (D)

TcfTTvTTvJ

where: Ax = Response for the analyte to be measured.

CFc = CF from the continuing calibration for the same analyte.

FMC-PAH-006-11

-------
D

V;
Vt
Vs

Volume of extract injected (|iL).
Volume of total extract (|iL).
Volume of sample extracted (jAS).
Dilution factor, if used.

7.5.4.2 Report results in micrograms per liter (ng/L) without correction for blank or spike
recovery.

7.5.4.3 Coeluted analytes should be quantitated and reported as the combination of the
unseparated PAH target analytes.

7.5.4.4 Sample spectra may not match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum
possible concentration (qualified as less than the numerical value) that allows the data user to
determine if additional (e.g., CLP RAS or SAS) work is required, or, if the reported concentration
is below action levels and project objectives and DQOs have been met, to forego further analysis.

7.5.4.5 Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) which allows the
data user to determine if additional (e.g., CLP RAS or SAS) work is required, or, if the reported
concentration is above action levels and project objectives and DQOs have been met to, forego
further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for spike %R and duplicate RPD are
presented in Table 3. This method should be used in conjunction with the quality assurance and control (QA/QC)
section of this catalog.

FMC -PAH-006-12

-------
Table 3

MATRIX SPIKE RECOVERY (%R) AND DUPLICATE
RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F060.002 (PAHs in Water)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD (%)

Naphthalene

30 to 200

± 100

Acenapthylene

30 to 200

± 100

Acenaphthene

30 to 200

± 100

Fluorene

30 to 200

± 100

Phenanthrene

30 to 200

± 100

Anthracene

30 to 200

± 100

Fluoranthene

30 to 200

± 100

Pyrene

30 to 200

± 100

Benzo(a)anthracene

30 to 200

± 100

Chrysene

30 to 200

± 100

Benzo(b)fluoranthene**/
B enzo (k)fluoranthene * *

30 to 200

± 100

Benzo(a)pyrene

30 to 200

± 100

Indeno(l ,2,3-cd)pyrene***/
Dibenzo(a,h)anthracene***

30 to 200

± 100

Benzo(g,h,i)perylene

30 to 200

± 100

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

** Coeluting analytes.

*** Coeluting analytes.

FMC -PAH-006-13

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatogram is an example of a chromatogram of several commonly encountered PAHs.

Figure 1

Gas chromatogram - PAH compounds

Column: 15 m x 0.53 mm DB-5 fused silica megabore capillary

Column Temperature Program: Initial 75°C - 2 mins; ramp 15°C per minute;

Final 310°C - 7 mins

Detector/Injector Temperature: 330°C

Carrier Gas: Helium at 10 mL/min

Detector: FID

FMC -PAH-006-14

-------
9.2 Method F060.002 examples of QA/QC results: Matrix spike sample results are presented as examples
of FASP Method F060.002 empirical data (see Table 4.

Table 4

FASP METHOD F060.002
WATER MATRIX SPIKE PERCENT RECOVERY (%R)

Analyte

Number of Samples

%R

Acenapthylene

1

57

Acenaphthene

1

55

Fluorene

1

86

Phenanthrene

1

112

Anthracene

1

141

Fluoranthene

1

64

Pyrene

1

32

Benzo(a)anthracene

1

113

Chrysene

1

113

Benzo(b)fluoranthene/
Benzo(k)fluoranthene

1

111

Benzo(a)pyrene

1

173

Indeno (1,2,3 -cd)py rene/
Dibenzo(a,h)anthracene

1

142

Benzo(g,h,i)perylene

1

107

FMC -PAH-006-15

-------
10.0 REFERENCES

Information not available.

FMC -PAH-006-16

-------
APPENDIX A

FASP Method F060.002

Instrument Options:

GC System:	Shimadzu GC-mini 2 with FID modified with a Direct Conversion and Makeup

Gas Adapter for megabore capillary column operations.

Temperature Programmer:	Shimadzu TP-M2R for temperature-programmed megabore capillary column

analyses.

Data

Handling

System 1:

Shimadzu Data Processor Chromatopac C-R1B.

Data

Handling

System 2:

Shimadzu Data Processor Chromatopac C-R3A.

Data

Handling

System 3:

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT
Shimadzu FDD-1A Floppy Disk Drive.

Data

Handling

System 4:

P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface,
computer, and Epson LX800 printer.

FMC -PAH-006-17

-------
APPENDIX B

FASP Method F060.002

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Columns:

Carrier Gas:

Detector Gas:

Column (Oven) Temperature:

Injector Temperature:

Detector Temperature:

Shimadzu GC Mini-2 equipped with FID modified to accept megabore
capillary columns and Shimadzu TP-M2R temperature programmer.

Shimadzu Chromatopac C-R3A Data Processor.

J&W 15 m x 0.53 mm DB-5 fused silica megabore capillary column or
Supelco 30 m x 0.75 mm SPB-5 borosilicate megabore capillary
column.

Ultrapure helium or nitrogen, 10 mL/min.

Zero air, 300 mL/min; ultrapure hydrogen, 40 mL/min.

Initial temperature: 75°C for 2 min.

Ramp: 15°C/min.

Final temperature: 310°C for 7 min.

330oC.

330oC.

FMC -PAH-006-18

-------
FASP Method Number F060.003

POLYCYCLIC AROMATIC HYDROCARBONS fPAHS1 IN OIL

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentrations of various poly cyclic aromatic hydrocarbons (PAHs) in oil samples.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 To begin sample analysis, a measured amount of oil is placed in a screw-cap culture tube. The sample
is extracted twice with a measured volume of methylene chloride. Isolation of target analytes is accomplished by
silica gel cleanup of the extract to eliminate interferences (primarily aliphatic hydrocarbons). Analysis is performed
using a temperature-programmed gas chromatograph (GC) with a megabore capillary column or a packed column,
and a flame ionization detector (FID). Identification is based on comparison of retention times between samples and
standards. Quantitation is by the external standard method.

3.0 INTERFERENCES

3.2 GC interference by sample carryover may be minimized by use of disposable glassware during sample
preparation and by use of the maximum possible rinse cycles on automatic injection systems, or by thoroughly rinsing
syringes used in manual injections.

FMC -PAH-007 -1

-------
Table 1

FASP METHOD F060.003 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

PAH

CAS Number

Quantitation Limit
in Oil** (ng/kg)

Naphthalene

91-20-3

1000

Acenaphthylene

208-96-8

1000

Acenaphthene

83-32-0

1000

Fluorene

86-73-7

1000

Phenanthrene

85-01-8

1000

Anthracene

120-12-7

1000

Fluoranthene

206-44-0

1000

Pyrene

129-00-0

1000

Chrysene

218-01-9

1000

Benzo(a)anthracene

56-55-3

1000

Benzo(b)fluoranthene* * *

205-00-2

1000

Benzo(k)fluoranthene* * *

207-08-9

1000

Benzo(a)pyrene

52-32-8

1000

Indeno( 1,2,3 -cd)pyrene* * * *

193-39-5

1000

Dibenzo(a,h)anthracene****

53-70-3

1000

Benzo(g,h,i)perylene

191-24-2

1000

*	Specific quantitation limit values are highly matrix dependent. The quantitation limits herein are provided

for guidance and may not always be achievable.

** Quantitation limits listed for oil are based on an "as-received" basis.

*** These compounds coelute.

**** These compounds coelute.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are two GC options that meet the requirements of this method. Other
GC configurations, not described herein, may be substituted if they meet the method requirements.

FMC -PAH-007 -2

-------
4.1.1 Gas chromatograph. option 1: An analytical system complete with a temperature-
programmable GC and all necessary accessories including detector and injector systems. The system shall
have a data handling system attached to the detector that is capable of retention time labeling, relative
retention time comparisons, and providing peak height and peak area measurements.

4.1.1.1 Column 1: 1.8 m x 3.0 mm I.D. glass column packed with 3% SP-2250 on
100/120 Supelcoport (Supelco), or equivalent.

4.1.1.2 Column 2: 1.8 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco), or equivalent.

4.1.1.3 Detector: FID with optional makeup gas supply at the detector's inlet.

4.1.2 Gas chromatograph. option 2: An analytical system complete with a temperature-
programmable GC and all necessary accessories including injector and detector systems designed or
modified to accept megabore capillary analytical columns is required. The system shall have a data handling
system attached to the detector that is capable of retention time labeling, relative retention time comparisons,
and providing peak height and/or peak area measurements.

4.1.2.1 Column: 15 m x 0.53 mm I.D. DB-5 fused silica capillary column (FSCC) (J&W
Scientific), or equivalent.

4.1.2.2 Detector: FID using a system with makeup gas supply at the detector's capillary

inlet.

4.2 Other Laboratory Equipment

4.2.1 Glass wool: Heat at 200°C for 24 hours and store in glass jars with Teflon-lined caps.

4.2.2 Screw cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined phenolic caps for extraction.

4.2.3 Disposable pipets: Pasteur, 6 and 9 inches long. Giant, 10 mm O.D. x 6 inches long.

4.2.4 Spatulas: Stainless steel, micro and semimicro.

4.2.5 Microsvringe: 10-(iL.

4.2.6 Balance: Top loading, capable of weighing to 0.01 g, used to weigh samples.

4.2.7 Micropipets: 10- to 1,000-^L.

4.2.8 Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and 25-mL.

FMC -PAH-007 -3

-------
4.2.9 Volumetric flasks: 10-, 25-, 50-, and 100-mL.

4.2.10	Vortex mixer: Vortex Genie, or equivalent.

4.2.11	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.12	Amber storage bottles: 100- and 500-mL.

4.2.13	Autosampler vials: 1- or 2-mL with Teflon-lined screw caps.

4.2.14	Graduated centrifuge tubes: 15-mL with ground glass stoppers.

4.2.15	Hydrocarbon traps: Supelpure-HC-Trap, or equivalent.

4.2.16	Leak detector: Snoop liquid, or equivalent, for packed-column operations, and GOW-MAC
gas leak detector, or equivalent, for megabore capillary operations.

4.2.17	Timer: 0 to 10 minute range.

4.2.18	Teflon wash bottles: 500-mL.

4.2.19	Chromatographic data stamp: Used to record instrument operating conditions.

4.2.20	Nitrogen evaporation system: N-Evap, or equivalent.

4.2.21	Laboratory oven: Capable of maintaining temperatures of 200°C.

4.3 Instrument Options: Specific instrument options that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1	Solvents

5.1.1	Petroleum ether: Pesticide quality, or equivalent.

5.1.2	Methylene chloride: Pesticide quality, or equivalent.

5.1.3	Isooctane: Pesticide quality, or equivalent.

5.2	Miscellaneous Reagents

5.2.1	Reagent water: Reagent water is defined as water in which an interferent is not observed at
the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed containing
activated carbon (Calgon Corporation, Filtrasorb-300 or equivalent) or a water purification system (Milli-Q
Plus with Organex Q cartridge or equivalent).

5.2.2	Sodium sulfate: Reagent, anhydrous, granular. The sodium sulfate is reconditioned by
heating for 24 hours at 200°C and storing in clean glass containers with Teflon-lined covers.

5.2.3	Silica gel: Grade 923, mesh 100/200. Activate the gel for 16 hours at 130°C in a shallow
glass tray loosely covered with foil. The gel may be stored for up to 1 week in glass jars with Teflon-lined
covers.

FMC -PAH-007 -4

-------
5.3 Gases

5.3.1 Helium: Ultrapure or chromatographic grade (always used in conjunction with a hydrocarbon

trap).

5.3.2 Nitrogen: Ultrapure or chromatographic grade (always used in conjunction with a
hydrocarbon trap).

5.3.3 Zero air: Zero grade or chromatographic grade (always used in conjunction with a
hydrocarbon trap).

5.3.4 Hydrogen: Ultrapure or chromatographic grade (always used in conjunction with a
hydrocarbon trap).

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for each
analyte of interest. This is done through volumetric dilution of the stock standards with isooctane. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining standard
concentrations should define the approximate working range of the GC: one at the upper linear range and the other
midway between it and the lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles.
Calibration solutions must be replaced after 6 months, or whenever comparison with check standards indicates a
problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Oil samples should be shipped in 100-mm glass culture tubes
with Teflon-lined caps.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding times for oil PAH samples are 7 days
between collection and extraction, and 40 days between extraction and analysis.

7.0 PROCEDURE

7.1 Extraction: The sample extraction technique for PAHs in oil is as follows:

7.1.1 Add 0.2 to 0.3 g of well-homogenized sample to a tared and labeled 150 mm culture tube;
reweigh to the nearest 0.01 g. Record weights.

7.1.2 Add 6 mL methylene chloride by repipet to the culture tube and cap.

FMC -PAH-007 -5

-------
7.1.3 Vortex at maximum speed for 2 minutes.

7.1.4 Centrifuge sample for 5 minutes.

7.1.5 Quantitatively decant the solvent using a disposable Pasteur pipet into a clean 150 mm culture

tube.

7.1.6 Repeat steps 7.1.2 through 7.1.5 and combine the extracts.

7.1.7 Add a small quantity of anhydrous sodium sulfate to the extract and vortex for 30 seconds.

7.1.8 Add 2 mL of isooctane and vortex for 10 seconds.

7.1.9 Reduce the solvent volume to approximately 1.0 mL with gentle heat under a N2 stream.

7.1.10 The sample extract is now ready for cleanup.

7.2 Cleanup

7.2.2 Silica gel column preparation:

7.2.2.1 Place a small piece of muffle-furnaced glass wool into a 10 mm O.D. (4-mL) giant

pipet.

7.2.2.2 Add 1.8 g of activated silica gel to the column.

7.2.2.3 Add a 1 cm layer of anhydrous sodium sulfate on top of the silica gel.

7.2.2.4 Rinse the column with 10 mL of methylene chloride and discard the rinsate. From
this point on, the column must not be allowed to go dry until the cleanup is completed.

7.2.2.5 Rinse the column with 10 mL of petroleum ether and discard the rinsate.

7.2.3 Procedure for cleanup:

7.2.3.1 Add the concentrated sample extract (Section 7.1) to the column using a small
disposable pipet.

7.2.3.2 Rinse the extract culture tube with two 0.5 mL aliquots of isooctane and add the
rinsate to the column.

7.2.3.3 Elute the column with 6.0 mL of petroleum ether and discard the solvent.

FMC -PAH-007 -6

-------
7.2.3.4 Elute the column with 10 mL of methylene chloride. Collect the first 10 mL of
eluted solvent in a graduated centrifuge tube.

7.2.3.5 For highly contaminated samples, the extract is now ready for GC injection.
However, in most cases, greater sensitivity is required and is achieved by proceeding as follows:

7.2.3.6 Reduce the solvent volume to less than 1 mL with low heat under a nitrogen

stream.

7.2.3.7 Stopper the centrifuge tube and allow to cool. Record the volume.

7.2.3.8 The sample extract is now ready for GC injection.

7.2.4 Solid phase extraction technology: Solid phase extraction (SPE) technology (e.g., Sep-Pak)
may provide an acceptable alternative to acid cleanup for PAH extracts.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 After an experienced chromatographer has ensured that the entire chromatographic
system is functioning properly; that is, conditions exist such that resolution, retention times,
response reporting, and interpretation of chromatographic spectra are within acceptable QC limits,
the GC may be calibrated (Section 7.5). Using at least 3 calibration standards for each PAH target
analyte prepared as described in Section 5.5, initial calibration curves (response versus mass of
standard injected) are generated for each PAH target analyte (refer to Section 7.4 for chromato-
graphic procedures).

7.3.2 Continuing calibration:

7.3.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing calibra-
tion validation. This single point analysis follows the same analytical procedures used in the initial
calibration. Instrument response is used to compute the CF, which is then compared to the mean
initial calibration factor (CF), and a relative percent difference (RPD, see Section 7.5) is calculated.
Unless otherwise specified, the RPD must be less than or equal to 25 percent for the continuing
calibration to be considered valid. Otherwise, the calibration must be repeated. A continuing
calibration remains valid for a maximum of 24 hours providing the GC system remains unaltered
during that time.

7.3.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.5) for the period over which the calibration has been validated.

FMC -PAH-007 -7

-------
7.3.3 Final calibration: The final calibration must be obtained at the end of each batch of sample
analyses. The maximum allowable RPD between the mean initial calibration and the final calibration factors
for each analyte must be less than or equal to 50 percent. A final calibration that achieves an RPD less than
or equal to 25 percent may be used as an ongoing continuing calibration.

7.4 Instrumental Analysis

7.4.2 Chromatograms:

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing, coating, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gas and flow;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

7.4.3 PAH identification:

7.4.3.1 Qualitative identification of PAHs is based on retention time as compared to
standards on a single column. A second, dissimilar column may be used to assist in identification.

7.4.3.2 Generally, individual peak retention time windows should be less than or equal
to 2 percent for megabore capillary columns (less than or equal to 5 percent for packed columns).

FMC -PAH-007 -8

-------
Table 2

EXAMPLE TEMPERATURE-PROGRAMMED GC OPERATING CONDITIONS

Shimadzu GC Mini-2 equipped with FID modified to accept megabore
capillary columns and a Shimadzu TP-M2R temperature programmer.

Shimadzu Chromatopac C-R3A Data Processor.

J&W 15 m x 0.53 mm DB-5 fused silica megabore capillary column.

Ultrapure Helium or Nitrogen, at a flowrate of 10 mL/min.

Zero air at a flowrate of 300 mL/min; ultrapure hydrogen at a flowrate
of 40 mL/min.

Initial temperature: 75°C for 2 mins.

Ramp: 15°C/min.

Final temperature: 310°C for 7 mins.

330°C
330°C.

Approximately 25 mins.

7.4.3.3 It may not be possible or practical to separate all target analyte PAHs on a single
column. In such cases these target analytes should be denoted as the appropriate combination of
PAHs.

7.4.4 Region-specific instrument parameters: Specific instrument operating parameters that have
been used are provided as "Specific Instrument Parameters" in Appendix B of this method.

7.4.5 Analytical sequence:

7.4.5.1 Instrument blank.

7.4.5.2 Initial calibration.

7.4.5.3 Check standard solution and/or performance evaluation sample (if available).

Instrument:

Integrator:
Column:
Carrier Gas:
Detector Gas:

Column (oven)
Temperature Program:

Injector Temperature:
Detector Temperature:
GC Analysis Time:
Standard/Sample Injection:

FMC -PAH-007 -9

-------
7.4.5.4 Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.5.5	Associated QC lot method blank.

7.4.5.6	Twenty samples and associated QC lot spike and duplicate.

7.4.5.7	Repeat sequence beginning at 7.4.5.5 until all sample analyses are completed or
another continuing calibration is required.

7.4.5.8	Final calibration when all sample analyses are complete.

7.5 Calculations

7.5.1 Initial calibration: Chromatographic response to PAH target analytes is measured by
determining CFs. In the case of coeluted analytes, the summed areas and masses should be employed to
generate a combined CF for the target analyte PAHs.

7.5.1.1 Calculate the calibration factor (CF) for each PAH target anlyte in the initial
standard. The integrator may be used to make all of these computations.

7.5.1.2 Using the calibration factors, calculate the %RSD for each Aroclor at a minimum
of 3 concentration levels using the following equation.

ST)

%RSD = 4=r x 100
X

where SD, the Standard Deviation, is given by

CF =

Area of Peak

Mass of Injected (nanograms)

A (X-X)2

SD = \ 2^ —1	

\	/ AT	"1 \

(N-l)

where: X;
X
N

Individual calibration factor (per analyte),

Mean of initial 3 calibration factors (per analyte),
Number of calibration standards.

7.5.13 The %RSD must be less than or equal to 25.0 percent.

7.5.2 Continuing calibration:

FMC -PAH-007-10

-------
7.5.2.1	Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations. Midrange standards for all initial calibration analytes must be analyzed as
continuing calibration standards at specified intervals (less than or equal to 24 hours).

7.5.2.2	The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

\~-CF J
RPD = -	1	— x 100

CFj+CFc

2

where: CF, =	Mean CF from the initial calibration for each analyte

CFc =	Measured CF from the continuing calibration for the same analyte.

7.5.3 Final calibration:

7.5.3.1	The final calibration is obtained at the end of any batch of samples analyzed.

7.5.3.2	The maximum allowable RPD between the mean initial calibration and final
calibration factors for each analyte must be less than or equal to 50 percent. A final calibration that
achieves an RPD of less than or equal to 25 percent may be used as an ongoing continuing
calibration.

\~-CF |

RPD = -	1	— x 100

cfi+cff
2

where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.4 Sample quantitation:

7.5.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations.

{A ) (V ) (D)

Concentrationluq/kq) = 			

(CFJ (V.) (Wg)

where: Ax	=	Response for the analyte to be measured.

CFc =	CF from the continuing calibration for the same analyte.

V;	=	Volume of extract injected (|iL).

Vt	=	Volume of total extract (|iL).

Ws	=	Weight of sample extracted (g).

FMC-PAH-007-11

-------
D	=	Dilution factor, if used.

7.5.4.2	Report results in micrograms per kilogram (ng/kg) without correction for blank
or spike recovery.

7.5.4.3	Coeluted analytes should be quantitated and reported as the combination of the
unseparated PAH target analytes.

7.5.4.4	Sample spectra may not match identically with those of analytical standards.
When positive identification is questionable, the chemist may calculate and report a maximum
possible concentration (qualified as less than the numerical value) that allows the data user to
determine if additional (e.g., CLP RAS or SAS) work is required, or, if the reported concentration
is below action levels and project objectives and DQOs have been met, to forego further analysis.

7.5.4.5	Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as less than the numerical value) which allows the data
user to determine if additional (e.g., CLP RAS or SAS) work is required, or, if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 3. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC -PAH-007-12

-------
Table 3

MATRIX SPIKE RECOVERY (%R) AND DUPLICATE
RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

Method F060.003 (PAHs in Oil)

Advisory Quality Control Limits*

Analyte

Spike %R

Duplicate RPD
(%)

Naphthalene

30 to 200

± 100

Acenapthylene

30 to 200

± 100

Acenaphthene

30 to 200

± 100

Fluorene

30 to 200

± 100

Phenanthrene

30 to 200

± 100

Anthracene

30 to 200

± 100

Fluoranthene

30 to 200

± 100

Pyrene

30 to 200

± 100

Benzo(a)anthracene

30 to 200

± 100

Chrysene

30 to 200

± 100

Benzo(b)fluoranthene**/
B enzo (k)fluoranthene * *

30 to 200

± 100

Benzo(a)pyrene

30 to 200

± 100

Indeno(l ,2,3-cd)pyrene***/
Dibenzo(a,h)anthracene***

30 to 200

± 100

Benzo(g,h,i)perylene

30 to 200

± 100

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory control limits for

duplicate RPD values become ± 3 times the quantitation limit for that individual analyte.

** Coeluting analytes.

*** Coeluting analytes.

FMC -PAH-007-13

-------
9.0 METHOD PERFORMANCE

9.1 The following is an example of a GC spectra for several commonly encountered PAHs.

Figure 1

Gas chromatogram - PAH compounds

Column: 15 m x 0.53 mm DB-5 fused silica megabore capillary

Column Temperature Program: Initial 75°C - 2 mins;

Ramp 15°C per minute;

Final 310°C - 7 mins.

Detector/Injector Temperature: 330°C

Carrier Gas: Helium at 10 mL/min

Detector: FID

FMC -PAH-007-14

-------
9.2 Method F060.003 examples of QA/QC results: Split sample results are presented as examples of
FASP Method F060.003 empirical data (see Table 4).

Table 4

FASP METHOD F060.003
COMPARISON OF FASP/EPA LABORATORY SPLIT SAMPLE ANALYSES

Analyte

EPA Lab Concentration (ng/kg)

FASP Analysis Concentration
(Hg/kg)

Naphthalene

1,100,000

13,000

Acenaphthene

2,000,000

44,000

Phenanthrene

9,200,000

8,600,000

Anthracene

630,000

100,000

Fluoranthene

5,300,000

1,800,000

Pyrene

1,900,000

1,500,000

Benzo(a)anthracene

1,200,000

1,400,000

Chrysene

500,000

1,400,000

Benzo(b)fluoranthene/
Benzo(k)fluoranthene

450,000

220,000

Benzo(a)pyrene

210,000

730,000

Indeno (1,2,3 -cd)py rene/
Dibenzo(a,h)anthracene

82,000

200,000

Benzo(g,h,i)perylene

89,000

200,000

FMC -PAH-007-15

-------
10.0 REFERENCES

Information not available.

FMC -PAH-007-16

-------
APPENDIX A

FASP Method F060.003

Instrument Options:

GC System:	Shimadzu GC-mini 2 with FID modified with a Direct Conversion and Makeup

Gas Adapter for megabore capillary column operations.

Temperature Programmer:	Shimadzu TP-M2R for temperature-programmed megabore capillary column

analyses.

Data

Handling

System 1:

Shimadzu Data Processor Chromatopac C-R1B.

Data

Handling

System 2:

Shimadzu Data Processor Chromatopac C-R3A.

Data

Handling

System 3:

Shimadzu Data Processor Chromatopac C-R3A equipped with a CRT
Shimadzu FDD-1A Floppy Disk Drive.

Data

Handling

System 4:

P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface,
computer, and Epson LX800 printer.

FMC -PAH-007-17

-------
APPENDIX B

FASP Method F060.003

Specific Instrument Parameters:

Option A

Instrument:

Integrator:

Columns:

Carrier Gas:

Detector Gas:

Column (Oven) Temperature:

Injector Temperature:

Detector Temperature:

Shimadzu GC Mini-2 equipped with FID modified to accept megabore
capillary columns and Shimadzu TP-M2R temperature programmer.

Shimadzu Chromatopac C-R3A Data Processor.

J&W 15 m x 0.53 mm DB-5 fused silica megabore capillary column or
Supelco 30 m x 0.75 mm SPB-5 borosilicate megabore capillary
column.

Ultrapure helium or nitrogen, 10 mL/min.

Zero air, 300 mL/min; ultrapure hydrogen, 40° mL/min.

Initial temperature: 75°C for 2 min.

Ramp: 15°C/min.

Final temperature: 310°C for 7 min.

330°C

330°C

FMC -PAH-007-18

-------
CSL Method

PAHS/SOIL/MEOH EXT/UV

1.0 SCOPE AND APPLICATION

1.1 This method is designed to be a quick screening method for determining relative concentration of
polynuclear aromatic hydrocarbons in soil and sediment samples.

1.2 Application of this method is limited to the screening analysis of soil and sediments for PAHs.
2.0 SUMMARY OF METHOD

2.1 This method is to determine PAHs present in soil or sediment samples relative to a selected calibration
standard. The sediment sample (wet) is mixed with methanol and sonicated in a water bath for 5 minutes to aid
dissolution of the compounds from the soil matrix. The particulate material is allowed to settle or the extract is
filtered to remove particulates. The methanol extract is then placed in a cuvette and the absorbance of the extract is
measured using a UV spectrophotometer at 254 nm. The concentration of the PAHs are reported relative to a
previously prepared calibration curve. Results are reported in units of Mg/kg (wet weight).

3.0 INTERFERENCES

3.1 Other compounds containing double bonds, aromatic rings or other substituent groups may cause a
positive response. This warning should be heeded and some samples should be submitted for more complete PAH
analysis to confirm results from this screening method.

4.0 APPARATUS AND MATERIALS

4.1 Vial: 40-mL glass vials with Teflon lined screw.

4.2 Balance: Top loading with ± 0.01-gm sensitivity.

4.3 Sonifier: Heat Systems Ultrasonic Sonicator with variable control up to 375-watt output and
water-cooled cup horn or equivalent.

4.4 Filter Paper.

4.5 UV Spectrophotometer.

4.6 Quartz UV Spectrophotometer Cell: 1-cm path lenght.

5.0 REAGENTS

5.1 Methanol: UV spectroscopy grade.

5.2 Anthracene: Reagent grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

FMC-PAH-008-1

-------
7.1 Safety

7.1.1 Samples contaminated with PAH constituents may be hazardous. Samples may include
flammables, explosives, and potentially carcinogenic compounds. All samples are assumed to be hazardous
and should be handled as such. All stock and working calibration standards, as well as all samples,
shall be handled with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2 Lab analysts shall wear lab coats, safety glasses, and surgical gloves at all times when
preparing and handling standards and field and labs amples.

7.1.3 Standards and samples shall be prepared in a fume hood.

7.1.4 Sample preparation should be performed in a fume hood.

7.1.5 The ultrasonic sonicator used for sample extractions emits a high frequency sound. When in
use, the sonicator horn shall be inside the sound chamber with the door closed, or another form of hearing
protection shall be used.

7.1.6 Safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
cleanup kit shall be available for use at all times.

7.1.7 Laboratory wastes shall be separated and properly disposed. The wastes include: used sample
aliquots, initial wash water, chemical wastes generated in the analysis, and disposables used in the prepara-
tion of the samples. These wastes shall be collected and deposited in a drum clearly marked as "CSL Lab
Wastes Only—Hazardous." Water used for final rinsing of glassware will be considered nonhazardous and
will be released into a 50-gallon drum outside the lab trailer. Save unused portions of samples and dispose
of as directed in the "STANDARD OPERATING PROCEDURES."

7.2 Sample Preparation and Extraction

7.2.1 Take 1 gram of wet sediment from a well mixed sample and place in a vial. Add 25 mL of
methanol and cap the vial. Place the vial in the sonic bath and sonicate vial for 5 minutes.

7.2.2 Remove vials from sonic bath and allow particulate matter to settle. Alternatively, the
methanol extract can be filtered to remove particulates.

7.3 Calibration

7.3.1 Prepare a series of 5 solutions of anthracene in methanol for calibrating the UV
spectrophotometer. These solutions should cover the range of absorbances expected for the samples or the
range of approximately 0 to 0.8 absorbance units.

7.3.2 Determine the absorbance reading of the 5 calibration solutions and plot the results as
concentration in /ig/mL versus absorbance. The correlation coefficient for the calibration curve should be
>0.99

7.4 Analysis

7.4.1 Measure the absorbance reading for each of the samples. Dilute the samples as necessary
to obtain a reading within the calibration range.

FMC-PAH-008-2

-------
7.5 Calculations

7.5.1 Calculate the concentration of PAHs in eqach sample based upon the calibration curve. After
accounting for any dilutions, calculate and report the sample results in Mg/kg (wet weight) relative to
anthracene.

[ ( uq/mL in extract ) x ( mL of ext ) ]

]ig/Kg ( wet wt. ) = —— 	¦			¦——

wt. of sample in Kg

8.0 QUALITY CONTROL

8.1	Daily midrange calibration checks performed prior to the analysis of each day's lot of samples or with
each lot of 20 samples, whichever is more frequent.

8.2	Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1 per day, whichever is
more frequent.

8.3	Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory blanks
show contamination. The cause of the contamination should be investigated and corrective action taken.

8.4	Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1 per day, whichever is more

frequent.

8.5	Analysis of a midrange matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1 per day, whichever is more frequent.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-PAH-008-3

-------
FASP Method F93009

ANALYSIS OF WATER. SEDIMENT AND SOIL FOR POLYNUCLEAR AROMATIC

HYDROCARBONS (TAH)BY GAS CHROMATOGRAPHY

1.0 SCOPE AND APPLICATION

1.1 This method covers the determination of polynuclear aromatic hydrocarbons in water, sediment and soil
by a method of gas chromatography with flame ionization detection (FID) and photoionization detection (PID)
adapted for use by the Field Analytical Services Program (FASP) mobile laboratory. This FASP method is intended
to provide rapid turnaround analyses in the field. FASP data are not considered to be a substitute for analyses
performed within the Contract Laboratory Program. FASP data are not intended to be legally defensible. Table 1
list the target analytes and their MDL.

2.0 SUMMARY OF METHOD

2.1 Soil, sediment and water sample extracts, prepared following FASP SOP F93008 "Preparation of
Sediment, Soil and Water Samples for Semivolatile Compounds: Polynuclear Aromatic Hydrocarbons and Phenols",
are analyzed by gas chromatography with flame ionization detection and photoionization detection following Contract
Laboratory Programs Protocols.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph fGCl: Varian 3400 GC with a flame ionization detector (FID) and a photoionization
detector (PID).

4.2 Autosampler: Varian 8100.

4.3 Data System: PE Nelson Chromatographic software.

5.0 REAGENTS

5.1 Hexane: Pesticide Residue Analysis Grade.

5.2 Calibration Check Standard: A daily one-point check of the Initial Calibration. The concentration of
the calibration check standard is the same as the mid level standard used in the initial calibration.

5.3 Performance Verification Standard (TVS'): This standard is analyzed at the end of every sequence. The
concentration of the PVS is the same as the low level standard used in the initial calibration.

5.4 Helium: Carrier gas, ultra pure or equivalent.

5.5 Hydrogen and Air: Make-up gas.

FMC-PAH-009-1

-------
Table 1

FASP METHOD F93009 TARGET COMPOUND LIST AND MDL

Compounds	MDL

Naphthalene	6.3

Acenaphthylene	6.7

Acenaphthene	5.5

Fluorene	31.3

Phenanthrene	11.4

Anthracene	11.2

Fluoranthene	5.0

Pyrene	2.7

Chrysene	13.1

Benzo(a)anthracene	22.9

Benzo(b)fluoranthene/Benzo(k)fluoranthene	8.7

Benzo(a)pyrene	3.6

Indeno( 1,2,3 -cd)pyrene/dibenzo(a,h)anthracene	27.7

Benzo(ghi)perylene	5.2

5.6 PAH calibration standard mix concentrations

Low Point Midpoint	High Point

Compounds

ug/mL

ug/mL

ug/mL

Naphthalene

10

50

100

Acenaphthylene 20

100

200



Acenaphthene

10

50

100

Fluorene

2

10

20

Phenanthrene

1

5

10

Anthracene

1

5

10

Fluoranthene

2

10

20

Pyrene

1

5

10

Chrysene

1

5

10

Benzo(a)anthracene

1

5

10

Benzo(b)fluoranthene

3

15

30

Benzo(k)fluoranthene

3

15

30

Benzo(a)pyrene

1

5

10

Indeno(l ,2,3-cd)pyrene

3

15

30

Dibenzo(a,h)anthracene

3

15

30

Benzo(ghi)perylene

2

10

20

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not available.

7.0 PROCEDURE

7.1 Sample Preparation: The samples are prepared following FASP SOP F93008 for the extraction of soil,
sediment and water samples for polynuclear aromatic hydrocarbon and phenol analyses.

7.2 Instrument Calibration

FMC-PAH-009-2

-------
7.2.1 Initial Calibration Analytical Sequence:

7.2.1.1 Low Point Standard.

7.2.1.2 Mid Point Standard.

7.2.1.3	High Point Standard.

7.2.1.4	Instrument Blank.

7.2.1.5	Laboratory Control Sample.

7.2.1.6	Method Blank.

7.2.1.7	Field Samples.

7.2.1.8	Instrument Blank.

7.2.1.9 Performance Verification Standard.
7.2.2 Daily Calibration Analytical Sequence:
7.2.2.1 Instrument Blank.

7.2.2.2 Calibration Check Standard.

7.2.2.3 Method Blank.

7.2.2.4	Laboratory Control Sample.

7.2.2.5	Field Samples.

7.2.2.6	Instrument Blank.

7.2.2.7	Performance Verification Standard.

Gas Chromato graph Operating Conditions

•	Carrier Gas

•	Column Flow

•	Make-up Gas

•	Make-up Gas Flow

•	Initial Temperature

•	Initial Time

•	Ramp

•	Final Temperature

•	Final Hold

•	Primary Analytical Column

Confirmation Column

Helium

5 mL/minute

Hydrogen and air

35 mL/minute Hydrogen

125°C

0.5 minutes

10°C/min

290°C

19 minutes

DB-5, 15 meters, 0.53 mm ID, fused silica
megabore capillary column with FID
detector

DB-608, 15 meters, 0.53 mm ID, fused silica
megabore capillary column with PID
detector

FMC-PAH-009-3

-------
• Injector Temperature 285°C

• Detector Temperature 300°C

7.4 Sample Analysis

7.4.1 1 mL sample vials containing the sample extracts are placed on the autosampler following
the standards outlined in the analytical sequence in Section 7.2.

7.4.2 The instrument blank indicated in Section 7.2 is a hexane solution containing 20.0 ug/mL of
the surrogates.

7.5 Compound Identification

7.5.1 Target analytes are identified by retention time.

7.5.2 On-scale chromatograms are required for identification.

7.6 Compound Quantitation

7.6.1 Quantitation is performed on the DB-5 column.

7.6.2 The detector response of all target analytes must be within the linear range of the initial
calibration for quantitation.

7.6.3 The concentrations of target analytes are calculated following the equations outlined in
USEPA CLP Draft SOW for Quick Turnaround Analysis 3/27/92, Section 18.3, page D-36-PAH-Q.

8.0 QUALITY CONTROL

8.1 Initial Calibration

8.1.1 The initial calibration sequence outlined in Section 7.2 is analyzed prior to sample analysis.

8.1.2 Calibration factors for each target analytes are calculated.

8.1.3 Absolute retention times are determined for all target analytes and the surrogates.

8.1.4 Initial Calibration Acceptance Criteria:

8.1.4.1 The percent relative standard deviation of the calibration factors from the three-
point calibration must be < 25 %.

8.1.4.2 The retention time of the surrogate or System Monitoring Compound (SMC) must
be within ± 20 % of the mean retention time calculated from the initial calibration standards.

8.1.5 Resolution Acceptance Criteria:

8.1.5.1 The percent valley between phenanthrene and anthracene, and indeno(l,2,3-
cd)pyrene and dibenzo(a,h)anthracene must be < 35.0% in the low standard.

8.2 Calibration Verification

FMC-PAH-009-4

-------
8.2.1	Sample analyses must be bracketed in 24-hour periods by acceptable analyses of and
instrument blank and a mid level Calibration Check Standard at the beginning and instrument blank and a
low level Performance Verification Standard at the end of the sequence.

8.2.2	Calibration Check Acceptance Criteria:

8.2.2.1 The percent valley between phenanthrene and anthracene, and indeno(l,2,3-
cd)pyrene and dibenzo(a,h)anthracene must be < 35.0% in the low standard.

8.2.3	Performance Verification Standard (TVS') Acceptance Criteria:

8.2.3.1	All PVS target analytes must have a concentration of 75 - 125% of the true
concentration.

8.2.3.2	The percent valley between phenanthrene and anthracene, and indeno(l,2,3-
cd)pyrene and dibenzo(a,h)anthracene must be < 45.0% in the low standard.

8.3	Instrument Blank Acceptance Criteria

8.3.1 The instrument blank must not contain any target analytes at a concentration >0.5 times the
response in the initial calibration low level standard.

8.4	Surrogate Recovery Acceptance Criteria

8.4.1 The advisory QC limits for surrogate recovery are 50-150%.

8.5	Laboratory Control Spike fLCS) Acceptance Criteria

8.5.1 All LCS compounds must have percent recoveries between 30 - 130%.

8.6	A second source QC Sample is extracted and analyzed for each batch or 20 samples. The percent
recoveries (%R) of the QC Sample must meet the following criteria:

Compounds

% Recoveries

Acenaphthylene

Phenanthrene

Fluoranthene

Benzo(a)anthracene

Benzo(b)fluoranthene/

D-139* (*D = Detected)
D-155
14-123
12-135
6-150

benzo(k)fluoranthene
Benzo(a)pyrene
Dibenzo(a,h)anthracene/
indeno( 1,2,3 -cd)pyrene
Benzo(ghi)perylene

D-110

D-128

D-116

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. USEPA CLP Draft SOW for Quick Turnaround Analysis (3/27/92)

FMC-PAH-009-5

-------
2. EPA Method 8100, Polynuclear Aromatic Hydrocarbons

FMC-PAH-009-6

-------
FASP Method F93008

PREPARATION OF SEDIMENT. SOIL AND WATER SAMPLES FOR SEMIVOLATILE

COMPOUNDS: POLYNUCLEAR AROMATIC HYDROCARBON AND PHENOL ANALYSIS

1.0 SCOPE AND APPLICATION

1.1 This method covers the preparation of water, sediment and soil samples for polynuclear aromatic
hydrocarbon (PAH) and phenol analysis by the Field Analytical Services Program (FASP) mobile laboratory. This
FASP method is intended to provide rapid turnaround analyses in the field. FASP data are not considered to be a
substitute for analyses performed within the Contract Laboratory Program. FASP data are not intended to be legally
defensible.

2.0 SUMMARY OF METHOD

2.1 Sediment and soil samples are prepared by sonication and water samples are prepared using separatory
funnel extraction for PAH analysis by gas chromatography with flame ionization detection (FID) and phenol analysis
with photoionization detection (PID). Procedures for Data Quality Level II and Level III are included in this S.O.P.

2.2 For soil samples, a 20 gram sample of soil is extracted with a 10 mL portion of acetone followed by a
10 mL portion of hexane using a sonication bath. Extracts are then decanted into a separatory funnel containing 100
mL of water which has been adjusted to pH >11. The mixture is shaken and the phases separated. The soil sample
is washed with an additional aliquot of hexane. The solvent fraction is partitioned with the water phase as above.
The combined solvent extracts are reduced in volume to 1 mL and analyzed for PAHs by gas chromatography. The
aqueous phase is then adjusted to pH < 2 and extracted sequentially with three aliquots of hexane. The combined
solvent extracts are reduced in volume to one mL and analyzed for phenols by gas chromatography.

2.3 For water samples, a 100 mL water sample is adjusted to pH >11 and extracted sequentially with three
3 mL aliquots of hexane. The combined solvent extracts are reduced in volume to 1 mL and analyzed for phenols
by gas chromatography. The pH of the sample is then adjusted to pH < 2, 20 grams of sodium chloride are added and
then extracted sequentially with three 3 mL aliquots of 1:1 methylene chloride:hexane. The combined solvent extracts
are reduced in volume to 1 mL and analyzed for PAHs by gas chromatography.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Sonicator: Branson 3200 Sonicator Bath, 25°C.

4.2 Analytical Balance.

4.3 125 mL Separatory Funnel.

4.4 Centrifuge.

4.5 Nitrogen Evaporator.

5.0 REAGENTS

5.1 Standards

FMC-PAH-010-1

-------
5.1.1	Surrogate Solution in hexane:

Compound

4,4'-Difluorobiphenyl
2,4,6-Tribromophenol
2-Fluorophenol

5.1.2	Quality Control fOP Sample for PAH Analysis:

Compound	fig/mL

100

lig/mL

20
50
50

Acenapththylene

Phenanthrene

Fluoranthene

Benzo(a)anthracene

Benzo(b)fluoranthene

Benzo(a)pyrene

Dibenzo(a,h)anthracene

Benzo(g,h,i)perylene

100

10

10

10

10

10

10

5.1.3 Quality Control fOP Sample for Phenol Analysis:

Compound

Hg/mL

Phenol

500

2-Chlorophenol

500

2,4-Dimethylphenol

500

2-Nitrophenol

500

2,4-Dichlorophenol

500

4-Chloro-3-methylphenol 500



2,4,6-Trichlorophenol

500

2,4-Dinitrophenol

500

4-Nitrophenol

500

2-Methyl-4,6-dinitrophenol

500

Pentachlorophenol

500

5.2	Acetone: Pesticide Residue Analysis Grade.

5.3	Deionized water.

5.4	Hexane: Pesticide Residue Analysis Grade.

5.5	Sodium Hydroxide. 10 M.

5.6	Sulfuric Acid. 1:1.

5.7	Sodium Chloride.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not available.

Analysis

PAHs

Phenols

Phenols

FMC-PAH-010-2

-------
7.0 PROCEDURE

7.1 Sample Preparation

7.1.1 Soil Samples:

7.1.1.1 Twenty grams of sediment or soil are weighed on an analytical balance into a 40
mL VOA vial. The sample weight is recorded in the Pesticide/PCB Extraction Log Book.

7.1.1.2 100 ul of the PAH surrogate and 25 ul of the phenol surrogate are added to the
sample along with 10 mL of acetone. The volume of the surrogates and Standard Log identification
numbers are recorded in the Pesticide/PCB Extraction Log Book.

7.1.1.3 The vial is placed in the sonicator bath. The sonicator bath is turned on for ten
minutes. Ten millilites of 1:1 methylene chloride:hexane is added to the mixture and shaken for
an additional minute.

7.1.1.4 The solvent layer is then decanted into a separatory funnel containing 100 mL of
water which had been adjusted to pH >11. The mixture is shaken and the phases separated.

7.1.1.5 The soil sample is washed with an additional aliquot of 1:1 methylene
chloride:hexane. The solvent fraction is partitioned with the water phase as above. The solvent
layer is removed and collected. The extracts are recombined, reduced in volume to 1 mL and
analyzed for PAHs.

7.1.1.6 The aqueous phase is then adjusted to pH < 2 with 1:1 sulfuric acid and 20 g of
sodium chloride.

7.1.1.7 This mixture is extracted sequentially with three 3 mL aliquots of 1:1 methylene
chloride:hexane. The extracts are recombined, reduced in volume to 1 mL and analyzed for
phenols.

7.1.1.8 Each of the sample extracts are transferred to a 2 mL conical sample tube and
concentrated with the nitrogen evaporator to a 1 mL final sample volume.

7.1.1.8.1 Each sample extract volume is reduced to below 1 mL and brought to

a final volume of 1 mL with hexane. The sample extracts are transferred to a 1 mL vial.

7.1.1.9 Sample extracts are stored at 4 C if necessary.

7.1.2 Water Samples:

7.1.2.1 A 100 mL water sample is poured into a 125 mL separtory funnel. The sample
volume is recorded in the Pesticide/PCB Extraction Log Book.

7.1.2.2 The pH of the sample is adjusted to > 11 using NaOH.

7.1.2.3 100 ul of the PAH surrogate and 25 ul of the phenol surrogate are added and the
sample is shaken vigorously. The volume of the surrogates and Standard Log identification
numbers are recorded in the Pesticide/PCB Extraction Log Book.

7.1.2.4 The sample is extracted using a separatory funnel.

FMC-PAH-010-3

-------
7.1.2.4.1 The mixture is extracted three times with 3 mL aliquots of hexane. The
extracts are combined and reduced in volume to 1 mL and analyzed for PAHs.

7.1.2.4.2 The pH is adjusted to < 2 using 1:1 H2S04 and 20 grams of sodium
chloride is added.

7.1.2.4.3 The mixture is extracted three times with 3 mL aliquots of hexane. The
extracts are reduced in volume to 1 mL and analyzed for phenols.

7.1.2.5 The sample extract is concentrated following section 7.1.1.8.

7.1.2.6 Sample extracts are stored at 4°C if necessary.

8.0 QUALITY CONTROL

8.1 Method Blanks

8.1.1 Method blanks are prepared for each type of matrix and with each set of samples.

8.1.2 For water samples, the method blank is prepared using 100 mL of reagent water and following
the procedure from section 7.1.2.

8.1.3 For sediment/soil samples, the method blank is prepared using clean sand and following the
procedure from section 7.1.1.

8.2 Matrix Spikes

8.2.1 For Level II, no matrix spike analyses are performed.

8.2.2 For Level III analyses, matrix spikes and spike duplicates are prepared.

8.2.2.1 One set of matrix spike and spike duplicate are prepared for each batch or 20

samples.

8.2.2.2 Matrix spike samples are spiked with 1.0 mL of matrix spike solution.

8.3 Quality Control fOP Sample

8.3.1 A QC sample is analyzed with each 20 samples. Reagent water is spiked with 100 uL of the
QC standard, see section 5 for target analytes and concentrations.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERNCES

1. USEPA CLP Draft SOW for Quick Turnaround Analysis (3/27/92)

FMC-PAH-010-4

-------
ESAT Region 10 Method
EXTRACTION AND ANALYSIS OF POLYNUCLEAR

AROMATIC HYDROCARBONS IN SOIL BY GC/FID

1.0 SCOPE AND APPLIACTION

1.2 This method is intended for use by or under the supervision of analysts experienced in gas
chromatography (GC) and in the interpretation of GC chromatograms.

1.3 It is strongly recommended that 10% of the samples submitted for analysis by this method be split and
submitted for confirmational analysis using an EPA regulated method. Confirmational analyses are recommended
for Level II field analysis per Data Quality Objectives for Remedial Response Activities (EPA/540/G-87/003) and
are required for QA2 analyses (not required for QA1 analyses) per Quality Assurance/Quality Control Guidance
for Removal Activities (EPA/540/G-90/004). Any site specific information pertaining to the requested analysis
would greatly enhance the support capabilities of the FASP team, i.e., action levels, known interferences, etc.

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil is placed in a disposable screw-cap vial and extracted using a measured
volume of acetone. Compounds are detected by a Flame Ionization Detector (FID). Identification is based on
comparison of retention times and relative peak intensities between samples and standards.

3.0 INTERFERENCES

3.1 Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample
processing equipment and may lead to discrete artifacts or elevated baselines in the HPLC chromato grams. All
reagents and apparatus must be routinely demonstrated to be free from interferences under the conditions of the
analysis by running method and instrument blanks.

3.2 Interferences due to sample carryover may be eliminated by the use of disposable glassware during
sample prep and thoroughly rinsing syringes used in manual injections.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System: The following option meets the requirements of this method. Other GC
configurations may be used if they meet method requirements.

4.1.1 Gas Chromatograph: The system must perform either isothermal or temperature programs

and contain necessary accessories, including injector and detector systems capable of accepting an analytical

column.

4.1.1.1 Column: 15 meter DB-5 (or equivalent) megabore with 0.25 film thickness

FMC-PAH-011-1

-------
Table 1

METHOD TARGET COMPOUNDS AND QUANTITATION LIMITS

TARGET COMPOUNDS

CAS
NUMBERS

QUANTITATION
LIMIT (mg/Kg)*

Naphthalene

91-20-3

2.0

Acenaphthylene

208-96-8

2.0

Acenaphthene

83-32-9

2.0

Flourene

86-73-7

2.0

Phenanthrene

85-01-8

2.0

Anthracene

120-12-7

2.0

Fluoranthene

206-44-0

2.0

Pyrene

129-00-0

2.0

Benzo(a)anthracene

56-55-3

2.0

Chrysene

218-01-9

2.0

Benzo(b)fluoranthene

205-99-2

2.0

Benzo(k)fluoranhtene

207-08-9

2.0

Benzo(a)pyrene

50-32-8

2.0

Dibenzo(a,h)anthracene

53-70-3

2.0

Benzo(g,h,i)perylene

191-24-2

2.0

Indeno(l,2,3-c,d)pyrene

193-39-5

2.0

* Quantitation limits based on 1.0 g sample and 2 mL final volume.

4.1.1.2	Detectors: Flame ionization detector.

4.1.1.3	Data System: Capable of retention time labeling, relative retention time
comparisons, and providing peak height and peak area measurements. The current system uses PE
Nelson and Turbochrome.

4.2 Laboratory Equipment

4.2.1	Screw-cap Culture Tubes: Disposable 16mm xl50mm borosilicate glass with teflon-lined
phenolic caps.

4.2.2	Disposable Pipets: Pasteur, 6 and 9 in. long.

4.2.3	Spatulas: Stainless steel

FMC-PAH-011-2

-------
4.2.4

Syringes: lO^L, 25|iL, lOO^L and 1000(iL.

4.2.5 Balance: Top loading, capable of weighing out to 0.01 g.

4.2.6 Volumetric Flasks: lOmL, 25mL and lOOmL.

4.2.7 Vortex Mixer:

4.2.8 Centrifuge: Capable of holding 16mm x 150mm culture tubes.

4.2.9 Amber Storage Bottles: lOmL with Teflon-lined screw-caps.

4.2.10 Graduated Centrifuge Tubes: lOmL with ground glass stoppers.

4.2.11 N-Evaporator: Variable temperature water bath with multi-sample nitrogen purge capability.

4.2.12 Leak Detector: "Snoop" liquid or equivalent.

4.2.13 Polv Wash Bottles: 500mL

5.0 REAGENTS

5.1 Solvents: Acetone, Iso-octane, Hexane, Methylene Chloride, and Petroleum ether Pesticide grade or

better.

5.2 Miscellaneous Reagents

5.2.1 Milli-0 deionized water or equivalent.

5.2.2 Anhydrous Sodium Sulfate.

5.2.3 Silica Gel.

5.3 Gases: Hydrogen, Helium, and Air Ultra-pure or chromatographic grade.

5.4 Stock Standard Solutions: Stock standards for each analyte listed in Table 1 should prepared from A2LA
certified neat standards. Stock standard solutions must be replaced after one year.

5.5 Calibration Standards: Calibration standards, at a minimum of three concentration levels ranging from
1.0 - 200 ng/uL, should be prepared through hexane dilution of the stock standards. One concentration level should
be near, but above, the method detection limit. The remaining concentration levels should define the working range
of the instrument. The calibration standards must also contain the surrogate. Calibration standards must be protected
from light and stored in teflon sealed screw-cap bottles at approximately 4°C. Calibration standards must be replaced
after six months, or sooner if comparison with check standards indicate a problem.

5.6 Check Standards: Standards prepared by a chemist other than the analyst who prepared the calibration
standards. The check standards must also come from a different source than the calibration standards and must also
contain the surrogate.

5.7 Surrogate Standards: The analyst will monitor the performance of the extraction and analytical system
by spiking each sample, blank, and matrix spike with a surrogate not expected to be present in the sample. A
suggested surrogate is p-Terphenyl-D-14 and/or 9,10-Diphenylanthracene.

FMC-PAH-011-3

-------
5.8 Matrix Spikes: Matrix spike solutions may be prepared by dilution of stock standard solutions. The
spiking level should be approximately five times the analyte concentration in the native sample.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Soil and sediment samples should be collected in four-ounce wide-mouthed glass jars with Teflon-lined
caps. Collected samples should be kept at 4°C ± 2 until analysis has been completed.

7.0 PROCEDURE

7.1 Safety

7.1.3 Fume hoods must be utilized whenever possible to avoid potential exposure to organic

solvents.

7.1.4 Work with solvents or chemicals may be performed only when at least one other chemist is
in the area.

7.1.5 Waste should be disposed of by placing it in an appropriately marked container beneath the
fume hoods in the extraction rooms or other designated area. All waste containers should be labeled with
the start date, end date, and type of waste (ie. halogenated or non-halogenated solvents).

7.2 Extraction

7.2.1 Add 1.0 + 0.1 g well homogenized soil sample to a tared and labeled culture tube.

7.2.2 Add appropriate surrogates. The final concentration of surrogate in the sample extract should
be 40 ng/(iL for p-Terphenyl.

7.2.3 Add 10 mL of acetone to the culture tube and cap.

7.2.4 Vortex for 1 minute

7.2.5 Centrifuge the culture tube for 10 minutes at half speed.

7.2.6 Transfer the 5 mL aliquot of acetonitrile to a labeled 10 mL graduated centrifuge tube via
Pasteur pipet.

7.2.7 Add sodium sulfate to remove any water residue.

7.2.8 Add 2 mL iso-octane and N-evap to 1 mL.

7.3 Clean-up: (Optional)

FMC-PAH-011-4

-------
7.3.1 Manufacture a silica gel column using a giant pipet. Plug the tip with glass wool, and add
1.8 grams of silica gel and top with 0.5 grams of sodium sulfate.

7.3.2 Rinse the column with 10 mL of methylene chloride. Do not let the column go dry.

7.3.3 Rinse the column with 10 mL of petroleum ether.

7.3.4 Add the sample extract to the top of the column. Rinse the column with 6 mL of petroleum
ether. Discard the eluant.

7.3.5 Rinse the column with 10 mL of methylene chloride. Collect a 10 mL sample volume. The
sample is now ready for analysis.

7.4 Recommended GC Conditions

7.4.1 The recommended analytical column is a 15 meter megabore DB-5. The carrier gas should
be helium with a flow rate of approximately 5mL/min. The injection volume should be approximately luL
directly on column.

7.4.2 The following temperature program has proven to provide separation for all target compounds
using the column mentioned above. The injector/detector block was set at 275 C.

Initial 60 C hold for 3 min

Ramp 8 C/min to 260 C

Final 260 C hold for 3 min

7.5 Calibration

7.5.1 Initial Calibration:

7.5.1.1 Generate initial calibration curves using at least three calibration concentrations
for each target compound as described in section 5.5.

7.5.1.2 Correlation coefficients (r2) for each calibration curve must be greater than 0.95,
or the relative standard deviation (RSD) of the response factors must be less than ± 25%, for the
curve to be valid. A new initial calibration curve must be generated whenever the HPLC is altered
or shut down for long periods of time or if comparison with a continuing calibration standard
indicates a problem.

7.5.1.2.1 Relative Standard Deviation

ST)

RSD = x 100

aRF

where: SD = Standard deviation

aRF = Average response factor (conc/area)

7.5.2 Check Standard: The accuracy of the initial calibration must be verified by running a check
standard immediately after the initial calibration. The calculated response of the check standard
must be within ± 25% difference of the expected concentration.

7.5.3 Continuing Calibration

FMC-PAH-011-5

-------
7.5.3.1 A continuing calibration check must be performed at the beginning and end of
every analytical sequence and after every 10 samples. The midrange initial calibration standard
may be used for continuing calibration validation. For a continuing calibration standard to be valid,
the percent difference (%DIF) must be less than or equal to ± 25%. If this criteria is not met,
reshoot the continuing calibration standard. If the standard is still outside the acceptance criteria,
a new initial calibration curve must be generated.

7.6 Polvnuclear Aromatic Hydrocarbon Identification

7.6.1	Qualitative identification of target compounds is based on retention time matching of the
sample with standard chromatograms.

7.6.2	Individual retention time windows should be less than 2% difference based on the first
continuing calibration of the day.

8.0 QUALITY CONTROL

8.1 Quality assurance guidelines must be met for all analyses. Matrix spike and matrix spike duplicate
recoveries must fall between 50-150 %REC. Percent recoveries for the surrogates must meet the same criteria as the
matrix spikes. Refer to DOC# ESAT 10A-5188 "Quality Assurance Guidleines for Field Analysis" for specific
criteria.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

1.	FASP Method Number F060.001

2.	FASP Method Number F060.003

3.	CSL Method FMC-PAH-003

FMC-PAH-011-6

-------
ESAT Region 10 Method
FASP EXTRACTION AND ANALYSIS OF PAH BY HPLC

1.0 SCOPE AND APPLIACTION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining estimated
quantities of polynuclear aromatic hydrocarbons (PAHs) in soil. Target compounds and the method quantitation
limits are listed in Table 1. This method may be modified at the discretion of the analyst in order to meet project
specific goals (ie. detection limit modifications, larger or smaller analyte lists, optimization of chromatographic
conditions for specific target compounds).

1.2 This method is intended for use by or under the supervision of analysts experienced in high performance
liquid chromatography (HPLC) and in the interpretation of HPLC chromatograms.

1.3 It is strongly recommended that 10% of the samples submitted for analysis by this method be split and
submitted for confirmational analysis using an EPA regulated method. Confirmational analyses are recommended
for Level II field analysis per Data Quality Objectives for Remedial Response Activities (EPA/540/G-87/003) and
are required for QA2 analyses (not required for QA1 analyses) per Quality Assurance/Quality Control Guidance
for Removal Activities (EPA/540/G-90/004). Any site specific information pertaining to the requested analysis
would greatly enhance the support capabilities of the FASP team, i.e., action levels, known interferences, etc.

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil is placed in a disposable screw-cap vial and extracted using two consecutive
measured volumes of acetonitrile. Analysis is performed using a gradient programmed HPLC with a C18 reverse
phase column. Compounds are detected by ultraviolet (UV) and fluorescence detectors. Identification is based on
comparison of retention times and relative peak intensities between samples and standards.

3.0 INTERFERENCES

3.2 Interferences due to sample carryover may be eliminated by the use of disposable glassware during
sample prep and thoroughly rinsing syringes used in manual injections.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System: The following option meets the requirements of this method. Other HPLC
configurations may be used if they meet method requirements.

4.1.1 High Performance Liquid Chromatograph: The system must perform gradient elution and

contain necessary accessories including injector and detector systems capable of accepting an analytical

column.

FMC-PAH-012-1

-------
Table 1

METHOD TARGET COMPOUNDS AND QUANTITATION LIMITS

TARGET COMPOUNDS

CAS
NUMBERS

QUANTITATION
LIMIT (mg/Kg)*

Naphthalene

91-20-3

1.0

Acenaphthylene

208-96-8

1.375

Acenaphthene

83-32-9

1.5

Flourene

86-73-7

0.15

Phenanthrene

85-01-8

0.125

Anthracene

120-12-7

0.0125

Fluoranthene

206-44-0

0.125

Pyrene

129-00-0

0.1875

Benzo(a)anthracene

56-55-3

0.05

Chrysene

218-01-9

0.10

Benzo(b)fluoranthene

205-99-2

0.025

Benzo(k)fluoranhtene

207-08-9

0.0125

Benzo(a)pyrene

50-32-8

0.025

Dibenzo(a,h)anthracene

53-70-3

0.25

Benzo(g,h,i)perylene

191-24-2

0.25

Indeno(l,2,3-c,d)pyrene

193-39-5

0.05

* Quantitation limits based on 1.0 g sample wet weight.

4.1.1.1	Column: Reverse phase CI8, 5 micron particle size diameter in a 250mm x 4.6mm
I.D. stainless steel column (Vydac No. 201TP64 or equivalent).

4.1.1.2	Detectors: Fluorescence and/or Ultraviolet (UV) detectors may be used.

4.1.1.2.1	Fluorescence Detector: For excitation at 254nm and emission greater
than 389nm cutoff (Spectra Physics SP8410 or equivalent).

4.1.1.2.2	UV Detector: 254nm, coupled to the fluorescence detector.

4.1.1.3	Data System: Capable of retention time labeling, relative retention time
comparisons, and providing peak height and peak area measurements. The current system uses PE
Nelson and Turbochrome.

FMC-PAH-012-2

-------
4.2 Laboratory Equipment

4.2.1 Screw-cap Culture Tubes: Disposable 16mm xl50mm borosilicate glass with teflon-lined

phenolic caps.

4.2.2 Disposable Pipets: Pasteur, 6 and 9 in. long.

4.2.3 Spatulas: Stainless steel

4.2.4 Syringes: lO^L, 25|iL, 100|iL and 1000(iL.

4.2.5 Balance: Top loading, capable of weighing out to 0.01 g.

4.2.6 Volumetric Flasks: lOmL, 25mL and lOOmL.

4.2.7 Vortex Mixer:

4.2.8 Centrifuge: Capable of holding 16mm x 150mm culture tubes.

4.2.9 Amber Storage Bottles: lOmL with Teflon-lined screw-caps.

4.2.10 Graduated Centrifuge Tubes: lOmL with ground glass stoppers.

4.2.11 N-Evaporator: Variable temperature water bath with multi-sample nitrogen purge capability.

4.2.12 Leak Detector: "Snoop" liquid or equivalent.

4.2.13 Polv Wash Bottles: 500mL

5.0 REAGENTS

5.1 Solvents: Acetonitrile, HPLC quality or better.

5.2 Miscellaneous Reagents: Milli-Q deionized water or equivalent.

5.3 Gases

5.3.1 Nitrogen: Ultra-pure or chromatographic grade.

5.3.2 Helium: Ultra-pure or chromatographic grade.

5.4 Stock Standard Solutions: Stock standards for each analyte listed in Table 1 should prepared from A2LA
certified neat standards. Stock standard solutions must be replaced after one year.

5.5 Calibration Standards: Calibration standards at a minimum of three concentration levels should be
prepared through acetonitrile dilution of the stock standards. One concentration level should be near, but above, the
method detection limit. The remaining concentration levels should define the working range of the instrument. The
calibration standards must also contain the surrogate. Calibration standards must be protected from light and stored
in teflon sealed screw-cap bottles at approximately 4°C. Calibration standards must be replaced after six months,
or sooner if comparison with check standards indicate a problem.

FMC-PAH-012-3

-------
5.6 Check Standards: Standards prepared by a chemist other than the analyst who prepared the calibration
standards. The check standards must also come from a different source than the calibration standards and must also
contain the surrogate.

5.8 Matrix Spikes: Matrix spike solutions may be prepared by dilution of stock standard solutions. The
spiking level should be approximately five times the analyte concentration in the native sample.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Soil and sediment samples should be collected in four-ounce wide-mouthed glass jars with Teflon-lined
caps. Collected samples should be kept refrigerated until analysis has been completed.

7.0 PROCEDURE

7.1 Safety

7.1.3 Fume hoods must be utilized whenever possible to avoid potential exposure to organic

solvents.

7.1.4 Work with solvents or chemicals may be performed only when at least one other chemist is
in the area.

7.2 Extraction

7.2.1 Add 1.0 + 0.1 g well homogenized soil sample to a tared and labeled culture tube.

7.2.2 Add appropriate surrogates. The final concentration of surrogate in the sample extract should
be 0.26 ng/(iL for p-Terphenyl and 0.06 ng/(iL for 9,10-Diphenylanthracene.

7.2.3 Add 5 mL of acetonitrile to the culture tube and cap.

7.2.4 Vortex for 1 minute.

7.2.5 Centrifuge the culture tube for 10 minutes at half speed.

7.2.6 Transfer the 5 mL aliquot of acetonitrile to a labeled 10 mL graduated centrifuge tube via
Pasteur pipet.

FMC-PAH-012-4

-------
7.2.7 Repeat steps 7.2.3 - 7.2.7 for a final volume of 10 mL.

7.2.8 Evaporate the sample to 1.0 mL under a gentle stream of nitrogen using the N-evap with a
water bath temperature of approximately 30°C.

7.2.9 The sample extract is ready for injection into the HPLC.

7.3 Recommended HPLC Conditions

7.3.1 The following parameters are recommended for use with the column described in paragraph
4.1.1.1: Isocratic elution for 1.0 min with 50:50 v/v acetonitrile:water, followed by a linear gradient elution
to 100% acetonitrile over 14.0 min then hold at 100% acetonitrile for 8.0 min. The flow rate is 1.5 mL/min
with a run time of 25 minutes.

7.4 Calibration

7.4.1 Initial Calibration:

7.4.1.1 Generate initial calibration curves using at least three calibration concentrations
for each target compound as described in section 6.5.

7.4.1.2 Correlation coefficients (r2) for each calibration curve must be greater than 0.95,
or the relative standard deviation (RSD) of the response factors must be less than ± 25%, for the
curve to be valid. A new initial calibration curve must be generated whenever the HPLC is altered
or shut down for long periods of time or if comparison with a continuing calibration standard
indicates a problem.

7.4.1.2.1 Relative Standard Deviation

ST)

RSD = x 100

aRF

where: SD = Standard deviation

aRF = Average response factor (conc/area)

7.4.2 Check Standard: The accuracy of the initial calibration must be verified by running a check
standard immediately after the initial calibration. The calculated response of the check standard
must be within ± 25% difference of the expected concentration.

7.4.3 Continuing Calibration

7.4.3.1 A continuing calibration check must be performed at the beginning and end of
every analytical sequence and after every 10 samples. The midrange initial calibration standard
may be used for continuing calibration validation. For a continuing calibration standard to be valid,
the percent difference (%DIF) must be less than or equal to ± 25%. If this criteria is not met,
reshoot the continuing calibration standard. If the standard is still outside the acceptance criteria,
a new initial calibration curve must be generated.

7.5 Polvnuclear Aromatic Hydrocarbon Identification

7.5.1 Qualitative identification of target compounds is based on retention time matching of the
sample with standard chromatograms.

FMC-PAH-012-5

-------
7.5.2 Quantitation of the samples may be based on results obtained from the UV/Vis and
fluoresence detectors either singly or combined depending on the quality of the chromatographs obtained
and the accuracy of the continuing calibration standards.

7.5.3 Retention time windows should be set at ± 2% difference from the first continuing calibration
of the day.

8.0 QUALITY CONTROL

8.1 Quality assurance guidelines must be met for all analyses. Matrix spike and matrix spike duplicate
recoveries must fall between 50-150 %REC. Percent recoveries for the surrogates must meet the same criteria as the
matrix spikes. Refer to DOC# ESAT 10A-5188 "Quality Assurance Guidleines for Field Analysis" for specific
criteria.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

1.	FASP Method Number F060.001

2.	FASP Method Number F060.003

FMC-PAH-012-6

-------
FASP Method Number F070.001

PENTACHLOROPHENOL IN SOIL/SEDIMENT

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the
concentration of pentachlorophenol in soil and sediment samples, using a batch extraction and derivatization
technique and gas chromatographic (GC) analysis.

1.3 This method should be used only by trained analysts under the supervision of an experienced chemist.

1.4 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target compounds and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP, encompassing the range of sample
concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil or sediment is placed in a screw-cap culture tube. The sample is extracted
with methanol. Derivatization reactant solution (pentafluorobenzyl bromide and hexacyclooctadecane in isooctane),
and potassium carbonate are added to the methanol extract, and the culture tube is capped and heated in an 80°C water
bath for 4 hours. The derivatized pentachlorophenol samples are extracted with hexane for analysis. Analysis is
performed using either a temperature-programmed or isothermal gas chromatograph (GC) with a megabore capillary
or packed column, and electron capture detector (ECD). Identification is based on comparison of retention times
between samples and standards. Quantitation is based on the external standard method.

3.0 INTERFERENCES

3.2 The use of phenolic caps not containing Teflon liners should be avoided. Phenolic caps may deteriorate
when exposed to solvents and concentrated acid, causing interfering peaks in an ECD chromatogram. The analytical
system must be demonstrated to be free from contamination under conditions of the analysis by running laboratory
reagent blanks.

3.3 GC interference by sample carryover may be minimized by use of disposable glassware during sample
preparation and employing the maximum possible rinse cycle on automatic injection systems or by thoroughly rinsing
syringes employed in manual injections.

FMC-O-OOl-1

-------
Table 1

FASP METHOD F070.001 TARGET COMPOUND LIST AND
QUANTITATION LIMIT*

Phenol

CAS Number

Quantitation Limit
in Soil/Sediment**
(Hg/kg)

Pentachlorophenol

87-86-5

100

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided

for guidance and may not always be achievable.

** Quantitation limits listed for soil or sediment are on an "as-received" basis.

4.0 APPARATUS AND MATERIALS

4.1 Analytical Systems: Listed below are 2 GC options that meet the requirements of this method. Other
GC configurations may be substituted if they also meet the method requirements.

4.1.1 Gas chromatograph. option 1: An analytical system, complete with an isothermal GC capable
of operation at elevated temperatures and all necessary accessories including injector and detector systems
designed or modified to accept packed analytical columns, is required. The system shall have a data
handling system attached to the detector that is capable of retention time labeling, relative retention time
comparisons, and providing peak height and/or peak area measurements.

4.1.1.1 Column 1: 1 m x 3.0 mm I.D. glass column packed with GP 1.5% SP-2250/1.95%
SP-2401 on 100/120 Supelcoport (Supelco), or equivalent.

4.1.1.2 Column 2: 1 m x 3.0 mm I.D. glass column packed with 3% OV-1 on 100/120
Supelcoport (Supelco), or equivalent.

4.1.1.3 Detector: Linearized ECD with optional makeup gas supply at the detector's inlet.

FMC-O-OOl-2

-------
4.1.2.1	Column: 15 m x 0.53 mm I.D. DB-608 fused silica capillary column (FSCC; J&W
scientific), or equivalent.

4.1.2.2	Detector: Linearized ECD employing a system with makeup gas supply at the
detector's capillary inlet.

4.1.2.3	Gas supply: The carrier gas should be ultrapure helium. The makeup gas should
be ultrapure 5 percent methane in argon, or equivalent. All gases should pass through oxygen traps
prior to the GC to prevent degradation of the column's analytical coating and detector foil.

4.2 Other Laboratory Equipment:

4.2.1	Screw-cap culture tubes: Disposable 16 mm x 150 mm borosilicate glass culture tubes with
Teflon-lined caps for extraction.

4.2.2	Disposable pipets: Pasteur, 6 and 9 inches long.

4.2.3	Spatulas: Stainless steel micro and semi-micro.

4.2.4	Microsvringe: 10-(iL.

4.2.5	Balance: Top loading, capable of weighing to 0.01 g used to weigh samples.

4.2.6	Micropipets: 10- to 1,000-^L.

4.2.7	Volumetric pipets and repipets: 0.5-, 1.0-, 5-, 10-, and 25-mL.

4.2.8	Volumetric flasks: 10-, 25-, 50-, and 100-mL.

4.2.9	Vortex mixer: Vortex genie, or equivalent.

4.2.10	Centrifuge: Capable of holding 16 mm x 150 mm culture tubes.

4.2.11	Amber storage bottles: 100- and 500-mL.

4.2.12	Autosampler vials: 1- or 2-mL with Teflon-lined screw caps.

4.2.13	Graduated centrifuge tubes: 10-mL with ground glass stoppers.

4.2.14	Oxygen traps: Supelpure-O-Trap and OMJ-1 indicating tube, or equivalent.

4.2.15	Leak detector: Snoop liquid, or equivalent, for packed column operations or GOW-MAC
gas leak detector, or equivalent, for megabore capillary operations.

4.2.16	Timer: 0 to 10 minute range.

4.2.17	Teflon wash bottles: 500-mL.

4.2.18	Laboratory oven: Capable of maintaining temperatures of greater than or equal to 200°C.

4.2.19	Water bath.

FMC-O-001-3

-------
4.2.20 Chromatographic data stamp: Used to record instrument operating conditions, if not
provided by the data handling system.

4.3 Instrument Options: Specific instrument systems that have been used are provided as "Instrument
Options" in Appendix A of this method.

5.0 REAGENTS

5.1 Solvents

5.1.1 Methanol: Pesticide quality, or equivalent.

5.1.2 Hexane: Pesticide quality, or equivalent.

5.1.3 Acetone: Pesticide quality, or equivalent.

5.1.4 Isooctane: Pesticide quality, or equivalent.

5.2 Miscellaneous Reagents

5.2.1 Reagent water (carbon free): Reagent water is defined as water in which an interferent is not
observed at the QL of the analyte of interest. Reagent water may be generated using a carbon filter bed
containing activated carbon (Calgon Corporation, Filtrasorb-300, or equivalent), a water purification system
(Milli-Q Plus with Organex Q cartridge, Barnstead Water-1 Systems [provided with the Base Support
Facilities], or equivalent), or purchased from commercial laboratory supply houses.

5.2.2 Sodium sulfate: Reagent, anhydrous, granular. Pre-conditioned by heating for 24 hours at
200°C and storing in clean glass containers with Teflon-lined caps.

5.2.3 Pentafluorobenzvl bromide

CAUTION: Lachrymator!

5.2.4 Hexacvclooctadecane (T8-crown-6 ether)

CAUTION: Toxic!

5.2.5 Potassium carbonate: Reagent grade, or equivalent.

5.3 Gases

5.3.1 Five percent methane in argon: Ultrapure or chromatographic grade (always used in
conjunction with oxygen trap).

5.3.2 Helium: Ultrapure or chromatographic grade (always used in conjunction with oxygen trap).

5.4 Stock Standard Solutions: Stock standard solutions of the analyte should be purchased as manufacturer
certified solutions.

5.5 Calibration Standards: Prepare calibration standards at a minimum of 3 concentration levels for
pentachlorophenol. This is done through volumetric dilution of the stock standards with methanol. The lowest
concentration standard should be approximately 2 times the QL as listed in Table 1. The remaining concentration
levels should define the approximate working range of the GC: one at the upper linear range and the other midway

FMC-O-OOl-4

-------
between it and lowest standard. All standards must be stored at 4°C in Teflon-sealed glass bottles. Calibration
solutions must be replaced after 6 months, or whenever comparison with check standards indicates a problem.

5.6 Check Standards: Check standards are calibration standards independently prepared by a chemist other
than the calibration standard preparer.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be collected, handled, preserved, and shipped maintaining a chain-of-custody following
current EPA regulations and recommendations in force at the time of sample collection. The sole exceptions to this
rule are the sample volumes required by the laboratory. Soil samples should be shipped in 4-ounce wide-mouth glass
jars with Teflon-lined caps.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for soil pentachlorophenol samples is
7 days between collection and extraction, and 24 hours between derivatization and analysis.

7.0 PROCEDURE

7.1 Extraction and Derivatization: Pentachlorophenol analyses are conducted utilizing a batch technique.
Each batch (approximately 20 samples) has unique continuing calibrations, final calibrations, matrix spikes,
duplicates, and blanks derivatized at the same time and under the exact same conditions as the samples in the batch.
Outside intercomparison of continuing calibration factors (CFs, see section 7.4) to the mean initial calibration factors
(CF) apply only to the batch of samples with which the QC samples were derivatized.

7.1.1 Sample preparation method:

7.1.1.1 Add 2 to 3 g of well homogenized sample to a tared and labeled 150 mm culture
tube; weigh again to the nearest 0.01 g. Record weights.

7.1.1.2 Add approximately 0.5 g of sodium sulfate.

7.1.1.3 Add 10 mL of methanol and mix for 2 minutes on a vortex mixer.

7.1.1.4 Centrifuge the sample for 5 minutes.

7.1.1.5 Place 5 mL of the extract into a clean tube.

7.1.2 Derivatization reactant solution preparation:

7.1.2.1 Add 1 mL of pentafluorobenzyl bromide to a 50-mL volumetric flask.

7.1.2.2 Add 1 g of hexacyclooctadecane (18-crown-6 ether; CAUTION: Toxic!).

7.1.2.3 Dilute to 50 mL with 2-propanol.

FMC-O-001-5

-------
7.1.2.4 This solution remains active for approximately 1 week. It should be refrigerated
and stored in the dark.

7.1.2.5 One mL of derivatization solution will react with up to 0.3 mg of total phenols.
7.1.3 Sample derivatization:

7.1.3.1 Add 1 mL of derivatization solution to 5 mL of sample extract in the culture tube.

7.1.3.2 Add approximately 3 mg of potassium carbonate and gently shake to mix.

7.1.3.3 Cap the culture tube and place in a hot water bath at 80°C for 4 hours (CAUTION:
High pressure!).

7.1.3.4 After 4 hours, remove culture tube from bath and allow to cool.

7.1.3.5 Add 5 mL of hexane and vortex mix for 1 minute.

7.1.3.6 Add 5 mL of organic-free water and vortex mix for 1 minute.

7.1.3.7 Transfer the hexane layer to a clean culture tube and add 1 g of sodium sulfate.
The sample is now ready for analysis.

7.2 Sample Analysis: The solvent flush injection technique is used for this analysis. Two (iL of nanograde
hexane, 1 (iL of air, and 2 (iL of sample are drawn into a 10-(iL syringe and immediately injected into the GC
equipped with an ECD.

7.3 Calibration

7.3.1 Initial calibration:

7.3.1.1 Calibrate the GC after an experienced chromatographer has ensured that the entire
chromatographic system is functioning properly; that is, conditions exist such that resolution,
retention times, response reporting, and interpretation of chromatograms are within acceptable QC
limits (Section 7.4). Using at least 3 calibration standards for pentachlorophenol as described in
Section 5.5, generate the initial calibration curve (response versus mass of standard injected). Refer
to Section 7.4 for chromatographic procedures.

7.3.1.2 Compute the percent relative standard deviation (%RSD, see Section 7.4) based
on pentachlorophenol's 3 CFs to determine the acceptability (linearity) of the curve. Unless
otherwise specified the %RSD must be less than or equal to 30 percent or the calibration is invalid
and must be repeated. Establish a new initial calibration curve any time the GC system is altered
(e.g., new column, change in gas supply, change in oven temperature) or shut down.

7.3.2 Continuing calibration:

7.3.2.1 Re-check the GC system on a regular basis through the continuing calibration. The
midrange initial calibration standard is generally the most appropriate choice for continuing
calibration validation. This single-point analysis follows the same analytical procedures used in
the initial calibration. Use instrument response to compute the CF which is then compared to the
CF, and calculate a relative percent difference (RPD, see Section 7.4). Unless otherwise specified,
the RPD must be less than or equal to 30 percent for the continuing calibration to be considered

FMC-O-OOl-6

-------
valid or the calibration must be repeated. A continuing calibration is valid for the batch of samples,
blanks, and spiked samples extracted and derivatized with the calibrating standard.

7.3.2.2 Use the continuing calibration in all target analyte sample concentration
calculations (Section 7.4) for the batch associated with the calibration standard.

7.3.3 Final calibration: Obtain the final calibration at the end of each batch of sample analyses.
The allowable RPD between the initial calibration and final calibration CF s for each analyte must be less
than or equal to 60 percent. A final calibration that achieves an RPD less than or equal to 30 percent may
be used as an ongoing continuing calibration.

7.4 Instrumental Analysis

7.4.2 Chromatograms:

7.4.2.2 The following information must be recorded on each chromatogram:

• Instrument and detector identification;

• Column packing and coating program, length, and I.D.;

• Oven temperature;

• Injector/detector temperature;

• Gases and flow rates;

• Site name;

• Sample number;

• Date and time; and

• GC operator initials.

FMC-O-OOl-7

-------
Table 2

EXAMPLE ISOTHERMAL GC OPERATING CONDITIONS

Shimadzu GC Mini-2 equipped with an ECD

Shimadzu Chromatopac C-R3A Data Processor

1 m x 3 mm glass column packed with 1.5% SP-2250/1.95%
SP-2401 on 100/120 Supelcoport

Ultrapure 5 percent methane in argon at a flow rate of
40 mL/min

Range 190oC to 225°C
250°C

Approximately 15 mins

Solvent flush manual injection or automated sample injection
is recommended for pentachlorophenol analysis. For the
solvent flush technique, the syringe barrel plus 1 (iL of
nanograde hexane, 0.5 (iL of air, and 2.0 to 3.0 (iL (measured
to the nearest 0.05 |±L) of sample extract are sequentially drawn
into a 10-(iL syringe and immediately injected into the GC.

7.4.3 Pentachlorophenol identification:

7.4.3.1 Qualitative identification of pentachlorophenol is based on retention time as
compared to standards on a single column and to a lesser extent on the detector selectivity. A
second dissimilar column may be used to assist in identification.

7.4.3.2 Generally, individual peak retention time windows should be less than or equal
to 5 percent of the initial calibration mean retention time for packed column analyses and less than
or equal to 2 percent for megabore capillary columns.

7.4.3.3 It is possible that interferences may preclude positive identification of an analyte.
In such cases, the chemist should report the presence of the interferent(s) with a maximum pesticide
concentration possible (see Section 7.4.4).

7.4.4 System performance: Degradation of pentachlorophenol may occur in the GC system
especially if the injector and/or column inlet is contaminated.

7.4.5 Specific instrument parameters: Specific instrument operating parameters that have been used
are provided in Appendix B of this method.

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector/Injector Temperature:
G.C. Analysis Time:
Standard/Sample Injection:

7.4.6 Analytical sequence:

7.4.6.1 Instrument blank.

FMC-O-OOl-8

-------
7.4.6.2

7.4.6.3

7.4.6.4

Initial calibration.

Check standard solution and performance evaluation sample if available.
Continuing calibration; repeat within 24 hours of previous continuing calibration.

7.4.6.5	Associated QC batch method blank.

7.4.6.6	Twenty samples and associated QC batch spike and duplicate.

7.4.6.7	Repeat sequence beginning at step 7.3.6.5 until all sample (batch) analyses are
completed or another continuing calibration is required.

7.4.6.8	Final calibration when all sample analyses are complete.

7.5.1 Initial calibrations:

7.5.1.1	Gas chromatographic response to single component pentachlorophenol is measured
by determining CFs. They are the ratio of the response (peak area or height) to the mass injected.

7.5.1.2	Calculate the CF for pentachlorophenol in the initial calibration. The integrator
may be employed to make all of these computations.

7.5.1.3 Using the CFs calculated above, calculate the % RSD for pentachlorophenol at the
3 concentration levels using the equation below:

ST)

% RSD = 4=r x 100
X

where SD, the Standard Deviation, is given by

7.5 Calculations

CF =

Area of Peak

Mass of Injected (nanograms)

A (X-X)2

SD = \ 2^ —1	

\	/ AT	"1 \

(N-l)

where: X;
X
N

Individual calibration factor (per analyte),

Mean of initial 3 calibration factors (per analyte),
Number of calibration standards.

7.5.1.4 The %RSD must be less than or equal to 25.0 percent.

FMC-O-OOl-9

-------
7.5.2 Continuing calibration:

7.5.2.1	Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations. Midrange standards for all initial calibration analytes must be analyzed as
continuing calibration standards at specified intervals (less than or equal to 24 hours).

7.5.2.2	The maximum allowable RPD calculated using the equation below for each analyte
must be less than or equal to 25 percent.

\~-CF J
RPD = -	1	— x 100

CFj+CFc

2

where: CF, =	Mean CF from the initial calibration for each analyte

CFc =	Measured CF from the continuing calibration for the same analyte.

7.5.3 Final calibration:

7.5.3.1	The final calibration is obtained at the end of any batch of samples analyzed.

7.5.3.2	The maximum allowable RPD between the mean initial calibration and final
calibration factors for each analyte must be less than or equal to 50 percent. A final calibration that
achieves an RPD of less than or equal to 25 percent may be used as an ongoing continuing
calibration.

\~-CF |

RPD = -	1	— x 100

cfi+cff
2

where: CF, =	Mean CF from the initial calibration for each analyte

CFf = Final CF for the same analyte.

7.5.4 Sample quantitation:

7.5.4.1 Calculate the concentration in the sample using the following equation for external
standards. The response can be measured by automated peak height or peak area measurements
from an integrator. Sample quantitation is based on analyte calibration factors calculated from
continuing calibrations.

[A ) [V ) (E) (D)

Concentrationluq/kq) = 	

(CFJ (V.) (Wg)

where: Ax =	Response for the analyte to be measured.

CFc =	CF from the continuing calibration for the same analyte.

V; =	Volume of extract injected (|iL).

FMC-O-001-10

-------
D

E

Vt
Ws

Volume of total extract (|iL).

Weight of sample extracted (g).

Enhanced sensitivity factor (if Section 8 extract concentration is used,
E = 10; if no enhancement, E = 1)

Dilution factor, if used.

7.5.4.2	Pentachlorophenolic sample concentrations are computed from individual peak
responses.

7.5.4.3	Report results in micrograms per kilogram (ng/kg) without correction for blank,
spike recovery, or percent moisture.

7.5.4.4	Similarly, when sample concentration exceeds the linear range, the analyst may
report a probable minimum level (qualified as greater than the numerical value) which allows the
data user to determine if additional (e.g., CLP analyses) work is required, or if the reported
concentration is above action levels and project objectives and DQOs have been met, to forego
further analysis.

8.0 QUALITY CONTROL

Quality control criteria must be met for all analyses. Advisory limits for spike percent recovery (%R) and
duplicate RPD are presented in Table 3. This method should be used in conjunction with the quality assurance and
control (QA/QC) section of this catalog.

FMC-O-OOl-11

-------
Table 3

MATRIX SPIKE PERCENT RECOVERY (%R) AND
DUPLICATE RELATIVE PERCENT DIFFERENCE (RPD) ADVISORY LIMITS

FASP Method F070.001 (Pentachlorophenol in Soil)



Advisory Quality Control Limits*





Spike

Duplicate Relative

Analyte

(%R)

Percent Difference





(%)

Pentachlorophenol

30-200

± 100

*	If the concentration of an analyte is less than 5 times the quantitation limit, advisory quality control limits

for duplicate RPD become ±3 times the quantitation limit for that individual analyte.

FMC-O-OOl-12

-------
9.0 METHOD PERFORMANCE

9.1 The following chromatogram is an example of a GC chromatogram for pentachlorophenol using an ECD

detector.

Figure 1

Gas Chromatogram - Pentachlorophenol

Column:	1 m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401 on 100/120 Supelco port

Detector/Injector Temperature: 250°C

Carrier Gas: Ultrapure 5 percent methane in argon at a flow rate of 40 mL/min.

Detector: ECD

FMC-O-001-13

-------
9.2 Method F070.001 examples of sample OA/OC results: Spike and duplicate sample results are presented
as examples of FASP Method F070.001 empirical data (see Tables 4 and 5).

Table 4

FASP METHOD F070.001
PENTACHLOROPHENOL SOIL MATRIX SPIKE PERCENT RECOVERY (%R)



Spiked

Sample

Sample

Spike Amount

Sample

Result

Result

Added

Percent

Number

Og/kg)

Og/kg)

Og/kg)

Recovery









(%)

AB-1

5.08 F

4.42 F

0.433 F

152

AC-2

136 F

133 F

0.418 F

NC

AE-1

6.42 F

1.01 F

5.56 F

97

AE-2

12.5 F

0.672F

3.61 F

328

AG-2

13.2 F

3.94 F

5.29 F

175

BKG-1

0.266F

0.050F

0.429 F

62

U - The material was analyzed for but was not detected. The associated numerical value is an instrumental
detection limit, adjusted for sample volume.

F - Data have been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

NC - Not calculated. The concentration of the analyte in the sample exceeds the amount of spike added by more
than a factor of 10.

FMC-O-OOl-14

-------
Table 5

FASP METHOD F070.001
PENTACHLOROPHENOL SOIL DUPLICATE ANALYSIS RELATIVE PERCENT DIFFERENCE



Sample

Duplicate

Relative Percent

Sample

Results

Results

Difference

Number

(Hg/kg)

(Hg/kg)

(%)

AB-1

4.42 F

5.08 F

13.9

AC-2

133 F

48.0 F

93.9

AD-5

27.4 F

8.84 F

102

AE-3

109 F

75.4 F

36.4

AF-4

17.6 F

11.6 F

41.1

AH-4

1.19 F

3.74 F

103

U - The material was analyzed for but was not detected. The associated numerical value is an instrumental
detection limit, adjusted for sample volume.

F - Data have been generated using FASP methodologies. Analytes are tentatively identified and concentrations
are quantitative estimates.

FMC-O-OOl-15

-------
10.0 REFERENCES

Information not available.

FMC-O-OOl-16

-------
APPENDIX A

FASP Method F070.001

Instrument Options:

GC System 3:	Shimadzu GC-14A with linearized ECD, used for temperature-programmed

megabore capillary column analyses.

Data Handling System 4: P.E. Nelson 2100 SW Integrator with 960 Series Intelligent Interface, Hyundai 80286

computer, and Epson LX800 printer.

FMC-O-OOl-17

-------
APPENDIX B

FASP Method F070.001

Specific Instrument Parameters:

Instrument:

Integrator:

Column:

Carrier Gas:

Column (Oven) Temperature:
Detector Temperature:

Injector Temperature:

Shimadzu GC Mini-2 equipped with linearized ECD

Shimadzu Chromatopac C-R3A Data Processor

1 m x 3 mm glass column packed with 1.5% SP-2250/1.95% SP-2401
on 100/120 Supelcoport

Ultrapure 5 percent methane in argon at a flow rate of 40 mL/min

Range 190 to 225°C

250oC

250°C

FMC-O-OOl-18

-------
CSL Method

TPH/SOIL/FREON EXT/IR

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of soil and solid samples for total petroleum hydrocarbons, such
as fuels and oils. It is presented as a means to rapidly characterize contamination in site investigation derived
samples. The method is sensitive to petroleum-based hydrocarbons and can be cross sensitive to other hydrocarbons.
The target contaminants for this method are gasoline, diesel, fuel oil, stoddard solvent, and mineral spirts.

1.2 Application of this method is limited to the screening analysis of soil and sediments for TPH. Results
are reported as TPH in milligrams per kilogram (ppm) based on quantification against a reference oil.

1.3 This TPH method utilizes a silica gel cleanup of the sample extract. Silica gel removes constituents such
as animal greases and vegetable oils.

1.4 Preliminary method validation indicates recoveries of upwards of 80 percent for TPH spikes are
achievable by this method.

1.5 The method detection limit (MDL) for TPH is estimated to be 15.0 mg/kg (ppm). This estimate is the
result of previous method development work and may vary in response to the complexity of the sample matrix.

2.0 SUMMARY OF METHOD

2.1 The method presented here is a modification of EPA Method 418.1, "Petroleum Hydrocarbons, Total
Recoverable," found in EPA-600/4-79-020, Methods for Chemical Analysis of Water and Wastes. A modification
of Method 418.1 is required to process soil samples. Specifically the sample extraction steps described by Method
418.1 are appropriate for water samples; this method requires modification for processing of soil samples. Sample
extraction by sonification has been chosen for extraction of soils.

2.2 The sonification extraction method included herein is based on method 3550 (EPA SW846 3rd ED).
In brief, an aliquot of sample is acidified to pH less than 2, immersed with freon, chemically dried with sodium
sulfate, silica gel is mixed in, extracted by sonification, and then analyzed by infrared spectrophotometry.

3.0 INTERFERENCES

3.1 This method will measure only freon extractables.

3.2 Impurities present in the freon solvent can adversely affect the measurement of low-level TPH. Use
redistilled freon if necessary.

3.3 Heavy molecular weight petroleum hydrocarbons, such as asphalt oils, are not reliably extracted by freon
and, therefore, will not be reliably quantified by the TPH analysis.

3.4 To the extent possible, sampling techniques, sample pretreatment, and analysis should be standardized
to ensure comparability in the final results.

4.0 APPARATUS AND MATERIALS

4.1 VOA Sample Vials: 40-mL capacity with septum screw caps; precleaned as purchased from Eagle
Pitcher, or equal.

FMC-O-002-1

-------
4.2 Balance: Sartorius; top loading electronic with 1,500-gm capacity with 0.01-gm sensitivity.

4.3 Glassware: Class A volumetric pipets and flasks; beakers, vials, pasteur pipets, and miscellaneous
glassware as necessary for preparation and handling of samples and standards.

4.4 Sonifier: Heat Systems Ultrasonic Sonicator with variable control up to 375-watt output and
water-cooled cup horn.

4.5 Infrared Spectrophotometer (TR): Fixed wavelenght, for measurement of absorbance at 2,390 cm"1.
Complete with quartz cells of 10-, 50-, and 100-mm cell path lenghts and appropriate cell holders.

4.6 pH Paper.

5.0 REAGENTS

5.1 Freon 113 n.l.2-trichloro-1.2.2-trifluoroethane'): Redistill if necessary.

5.2 Hydrochloric Acid. (!:!'): Mix equal volumes of the concentrated acid and distilled water.

5.3 Sodium Sulfate: Anhydrous crystal, powdered.

5.4 Silica Gel: 60-200 mesh, Davidson Grade 950 or equivalent.

5.5 n-Hexadecane: Reagent grade.

5.6 Isooctane: Reagent grade.

5.7 Chlorobenzene: Reagent grade.

5.8 Reference Oil: Pipet 15.0 mL n-hexadecane, 15.0 mL isooctane, and 10.0 mL chlorobenzene into a
50-mL glass stoppered bottle. This reference oil mixture is considered as TPH at a neat concentration (pure form).
Maintain the integrity of the mixture by keeping stoppered, except when withdrawing aliquots.

5.9 Stock Standard: Pipet 1.0 mL referenced oil (5.8) into a tared 200-mL volumetric flask and immediately
stopper. Weigh and dilute to volume with fluorocarbon-113. Calculate TPH stock standard solution concentration
as milligrams per lifer (mg/L).

5.10 Working Standards: Pipet appropriate volumes of stock standard (5.8) into 100-mL volumetric flasks
according to the cell path length to be used. Dilute to volume with fluorocarbon- 1 13. Calculate concentration of
the TPH working standards from the stock standard, mg/L.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1 Samples contaminated with TPH constituents may be hazardous. Samples may include
flammables, explosives, and potentially carcinogenic compounds. All samples are assumed to be hazardous

FMC-0-002-2

-------
and should be handled as such. All stock and working calibration standards, as well as all samples, shall
be handled with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2 Lab analysts shall wear lab coats, safety glasses, and surgical gloves at all times when
preparing and handling standards and field and lab samples.

7.1.3 Standards and samples shall be prepared in a fume hood.

7.1.4 Freon 113 (l,l,2-trichloro-l,2,2-trifluoroethane) is regulated by OSHA. The permissible
exposure level is 1,000 ppm. Primary routes of exposure are: inhalation, skin or eye contact, and oral.
Effects of short-term exposure are light-headedness, giddiness, shortness of breath, and may lead to narcosis
and cardiac irregularities.

7.1.4.1 First Aid Measures:

• If inhaled, remove to fresh air;

• In case of eye contact, immediately flush eye with copious quantities of
water for 15 minutes; and

• In case of skin contact, immediately wash skin with copious quantities
of soap and water.

7.1.5 Sample extracts and standards prepared in flammable solvents shall be stored in an explosion-
proof refrigerator or a cooler (outside the laboratory).

7.1.6 Sample preparation should be performed in a fume hood with adequate skin, eye, and hearing
protection provided for and used by the analysts. Any situation creating odor levels should be immediately
corrected.

7.1.7 All of the target compounds have "good warning properties." Any situation that leads to or
causes noticeable odors or produces any physical symptoms in the workers shall be investigated immediately
followed by appropriate corrective action.

7.1.8 The ultrasonic sonicator used for sample extractions emits a high frequency sound. When in
use, the sonicator horn shall be inside the sound chamber with the door closed.

7.1.9 Safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
cleanup kit shall be available for use at all times.

7.1.10 Laboratory wastes shall be separated and properly disposed. The wastes include: used
sample aliquots, initial wash water, chemical wastes generated in the analysis, and disposables used in the
preparation of the samples. These wastes shall be collected and deposited in a drum clearly marked as "CSL
Lab Wastes Only—Hazardous." Water used for final rinsing of glassware will be considered nonhazardous
and will be released into a 50-gallon drum outside the lab trailer. Save unused portions of samples and
dispose of as directed in the "STANDARD OPERATING PROCEDURES."

7.2 Sample Preparation and Extraction

7.2.1 In a labeled VOA vial, accurately weigh approximately 5 grams of sample. Acidify the
sample aliquot with 1:1 HC1 to pH 2 or less by mixing the vial contents with a spatula and dropwise addition
of the acid.

FMC-0-002-3

-------
7.2.2 To the sample vial, volumetrically pipet 10.0 mL of freon.

7.2.3 To the sample vial, add about 2 gm of sodium sulfate and thoroughly mix with a spatula;
avoid loss of freon during the mixing. For samples that are wet or highly consolidated such as clays,
additional sodium sulfate may be needed to thoroughly chemically dry the sample. The end result of this
sample treatment step should be a sample having a dry, grainy appearance.

7.2.4 With the VOA vial cap tightly in place, set the vial in the sonifier cup horn. Sonify at an
output setting of 30 percent for approximately 5 minutes. The cup horn must have cold water passing
through it all times during the sonifying operation. If, after sonification, the sample isn't completely
interdispersed with the freon or doesn't have a loose, grainy appearance, then additional sample treatment
and sonification is required.

7.2.5 To the sample vial, add about 3 grams of silica gel and thoroughly mix with a spatula.
Transfer the extract into a clean quartz IR cell.

7.2.6 Let the VOA vial stand until the solids have settled.

7.2.7 Closely examine the extract for turbidity or the presence of suspended particulate. If turbidity
or suspended particulates exist go back to step 7.2.5 and filter the diluted extract through grease-free cotton
wool or filter paper into a clean flask. Once again examine the extract for turbidity and suspended particles
and if absent prepare the extract for analysis as described in 7.2.5 and 7.2.6.

7.3 Calibration

7.3.1 Plot the calibration absorbance verses concentration (milligrams per liter).

7.4 Analysis

7.4.1 Set up the IR analyzer in accordance with the manufacturer's specifications. Virgin freon
should be used in the sample cell to zero a single-beam instrument.

7.4.2 Calibrate the IR in accordance with the manufacturer's recommendations and by use of the
calibration procedure described in Section 7.3.

7.4.3 Deliver a suitable volume of the diluted extract to a quartz cell. Dilute if required, and
reanalyze extracts that fall outside the calibration range of the IR. Always zero the instrument with a cell
of same path length used in the analysis.

7.4.4 Record the maximum absorbance of the extract at a wavelength or peak of 2,930 cm"1. Using
the calibration curve, convert absorbance readings into milligrams per liter (mg/L) of TPH.

7.5 Calculations

7.5.1 Quantification of TPH is based on the maximum absorbance at 2,930 cm"1 as compared to
external calibration of the IR using reference oil. Absorbance readings of sample extracts can be converted
into milligrams per kilogram (ppm) of TPH in the original sample as follows:

M x V x DF
Cone TPH, mg/kg=

Where: M = Milligrams/liter (mg/L) of TPH from the calibration curve;

Vt = Original volume, in mL, of freon added to VOA vial;

FMC-0-002-4

-------
DF
W

v s

Dilution factor, if required; and

Weight, in grams, of the sample added to the VOA vial.

8.0 QUALITY CONTROL

8.1	Daily midrange calibration checks performed prior to the analysis of each day's lot of samples or with
each lot of 20 samples, whichever is more frequent.

8.2	Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1 per day, whichever is
more frequent.

8.3	Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory blanks
show contamination. The cause of the contamination should be investigated and corrective action taken.

8.4	Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1 per day, whichever is more

frequent.

8.5	Analysis of a midrange matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1 per day, whichever is more frequent.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-0-002-5

-------
CSL Method

TPH-G/SOIL/METHANOL EXT/GC-PID

1.0 SCOPE AND APPLICATION

1.2 Application of this method is limited to the screening analysis of soil.

2.0 SUMMARY OF METHOD

2.1 The methods presented here are based on EPA Method 5030 and 8020, found in EPA SW846, Test
Methods for Evaluating Solid Waste, 3rd Edition, November 1986, and Total Petroleum Hydrocarbons, Analytical
Methods, State of Oregon, Soil Matrix Rules for UndergroundStorage Tank Cleanup, OAR 340-122-350, December
1990. This method involves extracting the soil samples with methanol, combining a portion of the extract with
reagent water, pumping the aqueous mixture on a purge and trap instrument, and performing the analysis on the gas
chromatograph using a photoionization detector (PID). In brief, hexane is used in conjunction with sonification to
effect extraction of the target constituents from the sample matrix. The extract is subsequently analyzed.

3.0 INTERFERENCES

3.1 Samples containing compound such as petroleum hydrocarbons, that co-elute with the target constitents
may cause a positive bias in the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples
having high levels of background organics or other interferences.

3.4 The response factors for uncalibrated peaks that are significantly different than those of the target
conhtituents may produce errors in the estimation of the total target constituent contamination.

4.0 APPARATUS AND MATERIALS

4.1 VOA Sample Vials: 40-mL capacity with septum screw caps; precleaned as purchased from I-Chem.

4.2 Balance: Sartorius; top loading electronic with 1,500-gm capacity with 0.01-gm sensitivity.

4.3 Glassware: Class A volumetric pipets and flasks; beakers, vials, pasteur pipets, and miscellaneous
glassware as necessary for preparation and handling of samples and standards.

4.4 Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation
of dilutions, and spiking of samples.

4.5 Sonifier: Heat Systems Ultrasonic Sonicator with variable control up to 375-watt output and
water-cooled cup horn.

FMC-O-003-1

-------
4.6 Gas Chromatograph fGCl: Hewlett-Packard Model 5890 Series II; temperature programming, electronic
integration, report annotation, automatic sampler; Supelco 5 percent SP-1200, 1.75 percetn betone on 100/200
Supelcoport 6 feet x 1/8 inches; SS J & W DB-wax megabore 0.53 x 30 m capillary, or equivalent; liquid sample
concentrator, Tenax/silica gel/charcoal trap, and PID.

5.0 REAGENTS

5.1 Methanol: GC/purge and trap grade, 99.9 percent.

5.2 Stock Standards: Prepared from purchased pure standard materials.

5.3 Working Standards: Prepared from stock standards by precise dilution in methanol.

5.4 Nitrogen: Carrier gas, prepurified grade.

5.5 Hydrogen: PID gas, prepurified grade.

5.6 Air: PID gas, zero grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1 Samples contaminated with TPH constituents may be hazardous. Samples may include
flammables, explosives, and potentially carcinogenic compounds. All samples are assumed to be hazardous
and should be handled as such. All stock and working calibration standards, as well as all samples, shall
be handled with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2 Lab analysts shall wear lab coats, safety glasses, and surgical gloves at all times when
preparing and handling standards and field and lab samples.

7.1.3 Standards and samples shall be prepared in a fume hood.

7.1.4 Sample extracts and standards prepared in flammable solvents shall be stored in an explosion-
proof refrigerator or cooler (outside the laboratory).

7.1.5 Sample preparation should be performed in a fume hood with adequate skin, eye, and hearing
protection provided for and used by the analysts. Any situation creating odor levels should be immediately
corrected.

7.1.6 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Any situation that leads to or causes noticeable odors or produces any physical symptoms in
the workers shall be investigated immediately followed by appropriate corrective action.

7.1.7 The ultrasonic sonicator used for sample extractions emits a high frequency sound. When in
use, the sonicator horn shall be inside the sound chamber with the door closed.

7.1.8 Safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
cleanup kit shall be available for use at all times.

FMC-0-003-2

-------
7.1.9 Laboratory wastes shall be separated and properly disposed. The wastes include: used sample
aliquots, initial wash water, chemical wastes generated in the analysis, and disposables used in the prepara-
tion of the samples. These wastes shall be collected and deposited in a drum clearly marked as "CSL Lab
Wastes Only—Hazardous." Water used for final rinsing of glassware will be considered nonhazardous and
will be released into a 50-gallon drum outside the lab trailer. Save unused portions of samples and dispose
of as directed in the "STANDARD OPERATING PROCEDURES."

7.2 Sample Preparation and Extraction

7.2.1 In a labeled VOA vial, accurately weigh out approximately 20 grams of soil recording the
weight to the nearest 0.01 gm. Add 50 fxL of the 1,000 fxg/mL surrogate solution and add 10 mL of
methanol. Quickly cap the vial and shake for 2 minutes or sonicate for 2 minutes and allow the methanol
to separate.

7.2.2 A 100 /jL aliquot of the methanol extract is transferred to 5 mL of reagent water in the
adjustable 5-mL syringe. The sample is injected into the purging chamber of the purge and trap device. If
samples have elevated concentrations of volatiles, a smaller aliquot of the methanol extract may be selected.

7.3 Calibration

7.3.1 External Calibration: Use a five-level calibration.

7.3.2 Working Calibration: Working calibration shall be verified with the analysis of each working
day's lot of samples or with each lot of 20 samples, whichever is more frequent. Working calibration shall
be verified by use of a midrange standard mix. If the areas vary by more than ± 20 percent from the initial
calibration, then recalibration shall be performed on freshly prepared working standards.

7.3.3 Gasoline Stock Standard: Equal portions of three grades of nonoxygenated gasoline (regular,
unleaded regular, and unleaded supreme) from three different oil companies are mixed together to form a
composite gasoline. From this composite gasoline a stock standard is prepared accordingly. Place
approximately 9 mL of methanol in a 10-mL ground-glass stoppered volumetric flask. Allow the flask to
stand, unstoppered, until all alcohol wetted surfaces have dried (about 10 minutes). Tare flask and contents
unstoppered.

7.3.3.1 Add about 10 drops of the composite gasoline standard to the flask. The liquid

must fall directly into the alcohol without contacting the neck of the flask. Reweigh, dilute to

volume with methanol, stopper, and mix by inverting the flask several times.

7.3.3.2 Calculate the concentration as follows:

Stock Cone, ]ig/mL = { Final Wt' mg ] ~ ( Tared Wt' mg ] x ^00° ™

10 mL mg

FMC-0-003-3

-------
7.3.4	Second Dilution Standard: prepare a 10 mL, 2,500 /ig/mL gasoline standard by adding the
appropriate volume of stock standard, as calculated below, to a 10-mL volumetric flask and diluting to the
mark with methanol.

Stock Std, mL = (2, 500 VglmL ) x ( IQmL )

Stock Std Cone, ]ig/mL

7.3.5	Calibration Standard: The aquqous, purge gasoline standards are each prepared by adding
1-, 2-, 5-, and 10-juL of 2,500 /ig/mL of the dilution standard to 5 mL of organic free water by injecting each
aliquot into the end of the 5-mL syringe containing 5 mL of organic free water. The calibration standard
concentrations in the purged water are calculated as follows:

Calibration Std, Vg/mL = ( St°ck ] * ( °-°01 mL/]lL ] * ( 2'5°° ^g/mL >

5 mL

7.3.6	Stock Surrogate Standard: Make up a standard that is approximately 5,000 /ig/mL by
accurately weiging about 50 mg of the surrogate compound into a 10-mL volumetric flask and filling to the
mark with methanol.

7.3.6.1 Working Surrogate Spike. 1000 ug/mL: Add the appropriate volume of the stock

surrogate standard to a 10 mL volumetric flask and dilute to the mark with methanol.

7.4 Analysis

7.4.1	The volatile hydrocarbons (gasoline) in the sample are concentrated by the purge and trap
units onto the tenax/silica gel/charcoal trap. At completion of the purge cycle the purge and trap unit is
cycled to the desorb mode and the volatile hydrocarbons are swept onto the GC column. At the end of the
desorb mode, the GC run is started and the analysis completed. The chromatography time is 25 minutes but
the entire purge and trap/GC cycle time is approximately 45 minutes per sample.

7.4.2	If the analysis indicates that the results are more than 50 percent above the calibration range,
dilute the sample extract such that concentrations fall within the calibration range.

7.4.3	Suggested purge and trap operating parameters:

Purge ready temperature = 30°C
Purge temperature = 30°C for 11 minutes

Desorb preheat temperature = 125°C
Desorb temperature = 200 °C for 4 minutes
Bake temperature = 225°C for 12 minutes
Purge gas pressure = 20 psi
Purge gas flow = 40 mL/minute
Desorb gas flow = 20 mL/minute

7.4.4	Suggested GC parameters:

J & W DB-wax megabore 0.53 mn ID x 30 m capillary column
Starting column temperature = 35°C isothermal for 5 minutes
Ramp rate = 8°C/minute for 2.5 minutes
Final temperature = 140°C isothermal for 6.88 minutes
Injector temperature = 240°C
Detector temperature = 245 °C
Total run time = 25 minutes

FMC-0-003-4

-------
Injected sample volume = direct from P & T
Carrier flow = 20 mL/minute

7.5 Calculations

7.5.1 The area of the components from benzene to naphthalene is integrated as a group (valley to
valley) and compared to concentrations of the gasoline standards that are also integrated as a group. Sample
concentrations are to be reported on an as-received basis with no correction for moisture content. If a single
point calibration method is being used, linearity must be demonstrated in the working range.

, { A x R ) x 5 mL x D

Sample Cone, mq/qm =

E x Wf

Where: A
E
D
Wt

Group area of sample;

Volume methanol used, 0.1 mL;
Methanol extract volume, mL; and
Weight of the sample, g.

,0 QUALITY CONTROL

8.1 Daily midrange calibration checks performed prior to the analysis of each day's lot of samples or with
each lot of 20 samples, whichever is more frequent.

8.2 Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1 per day, whichever is
more frequent.

8.3 Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory blanks
show contamination. The cause of the contamination should be investigated and corrective action taken.

8.4 Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1 per day, whichever is more

frequent.

8.5 Analysis of a midrange matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1 per day, whichever is more frequent.

8.6 The selected surrogate compound should be nonpolar, purgeable from water and observable in a
petroleum matrix. Fifty /ig of this surrogate is to be added to the soil just before extraction with 10 mL methanol.
This will produce an extract concentration of 5 mg/mL, suggested surrogates include bromofluorobenzen,
chloroctadecane, and trifluorotoluene.

8.7 Addition of an appropriate surrogate extraction spike, just prior to extraction, is require. The recovery
of the surrogate must be between 50 percent and 150 percent and must be reported with the results. However, if the
percent recovery of the surrogate cannot be calculated because of a high level of contamination, a note to that effect
is acceptable.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-0-003-5

-------
CSL Method

TPH-HCID/SOIL/METHYLENE CHLORIDE EXT/GC-FID

1.0 SCOPE AND APPLICATION

1.2 Application of this method is limited to the screening analysis of soil and sediments for TPH. Results
are reported as TPH-HCID in milligrams per kilogram (ppm) based on quantification against a reference standard.

2.0 SUMMARY OF METHOD

2.1 The method presented here follows Total Petroleum Hydrocarbons, Analytical Methods, State of
Oregon, Soil Matrix Rules for Underground Storage Tank Cleanup, OAR 340-122-350, December 1990. In brief,
one aliquot of sample is immersed with methylene chloride, extracted by sonification, and analyzed by gas
chromatography.

3.0 INTERFERENCES

3.1 Samples containing compound such as petroleum hydrocarbons, that co-elute with the target constitents
may cause a positive bias in the results.

3.2 The presence of compounds that closely match the retention times of the target constituents may result
in false identifications.

3.3 The MDLs for the target constituents may be suppressed by baseline noise associated with samples
having high levels of background organics or other interferences.

4.0 APPARATUS AND MATERIALS

4.1 VOA Sample Vials: 40-mL capacity with septum screw caps; precleaned as purchased from I-Chem.

4.2 Balance: Sartorius; top loading electronic with 1,500-gm capacity with 0.01-gm sensitivity.

4.3 Glassware: Class A volumetric pipets and flasks; beakers, vials, pasteur pipets, and miscellaneous
glassware as necessary for preparation and handling of samples and standards.

4.4 Syringes: Hamilton glass type as required for injection of sample extracts and standards, preparation
of dilutions, and spiking of samples.

4.5 Sonifier: Heat Systems Ultrasonic Sonicator with variable control up to 375-watt output and
water-cooled cup horn.

4.6 Gas Chromatograph fGCl: Hewlett-Packard Model 5890 Series II; temperature programming, electronic
integration, report annotation, automatic sampler, fused silica capillary column, DB-1, 30 m x 0.25 mm or equivalent,
and FID.

FMC-O-004-1

-------
5.0 REAGENTS

5.1 Methylene Chloride: GC grade, 99.9 percent.

5.2 Methanol: GC/PT grade, 99.9 percent.

5.3 Sodium Sulfate: Reagent grade, anhydrous powder form.

5.4 Stock Standards: Prepared from purchased pure standard materials.

5.5 Working Standards: Prepared from stock standards by precise dilution in methanol.

5.6 Nitrogen: Carrier gas, prepurified grade.

5.7 Hydrogen: FID gas, prepurified grade.

5.8 Air: FID gas, zero grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE
7.1 Safety

7.1.1 Samples contaminated with TPH constituents may be hazardous. Samples may include
flammables, explosives, and potentially carcinogenic compounds. All samples are assumed to be hazardous
and should be handled as such. All stock and working calibration standards, as well as all samples,
shall be handled with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2 Lab analysts shall wear lab coats, safety glasses, and surgical gloves at all times when
preparing and handling standards and field and lab samples.

7.1.3 Standards and samples shall be prepared in a fume hood.

7.1.4 Methylene chloride (MeCl), used in the preparation of sample extracts, is regulated by OSHA
and described in NIOSH/OSHA manual, Occupational Health Guidelines for Chemical Hazards, 1981. The
MeCl permissible exposure level (PEL) is 500 ppm in air over an 8-hour period. Its odor threshold is
between 25 and 50 ppm. Exposure pathways are oral, dermal, and airway. Effects of short-term exposure
are reported to be mental confusion, light-headedness, nausea, vomiting, and headache. High concentrations
may cause irritation of the eyes and respiratory tract. Prolonged exposure may cause skin burns. MeCl is
nonflammable.

7.1.5 Sample extracts and standards prepared in flammable solvents shall be stored in an explosion-
proof refrigerator or a cooler (outside the laboratory).

FMC-0-004-2

-------
7.1.7 All of the target compounds are reported in the NIOSH manual as having "good warning
properties." Any situation that leads to or causes noticeable odors or produces any physical symptoms in
the workers shall be investigated immediately followed by appropriate corrective action.

7.1.8 The ultrasonic sonicator used for sample extractions emits a high frequency sound. When in
use, the sonicator horn shall be inside the sound chamber with the door closed.

7.1.9 Safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill
cleanup kit shall be available for use at all times.

7.2 Sample Preparation and Extraction

7.2.1 In a labeled VOA vial, accurately weigh out approximately 10 grams of soil recording the
weight to the nearest 0.01 gm. Combine with 2 grams anhydrous sodium sulfate, add 50 fxL of 200 fxg/mL
surrogate standard, 20-mL methylene chloride and seal with teflon lined cap.

7.2.2 With the VOA vial cap tightly in place, sonicate at an output setting of 30 percent for
approximately 5 minutes. The resulting sonified sample should be dispersed throughout the methylene
chloride and have a grain-like appearance. If not, then add an additional 1 gm of sodium sulfate and
resonify. Repetitions of this process may be needed to properly extract some samples.

7.2.3 After sonification, let the VOA vial stand until the solids have settled. Using a pasteur pipet,
transfer a suitable aliquot of the methylene chloride solvent (extract) from a vial into a labeled GC
auto-sampler vial and cap immediately with septum crimp seals. Refrigerate the sample extracts until use.

7.3 Calibration

7.3.1 External Calibration: Use a five-level calibration.

7.3.3 Retention Time Standard: Prepare a composite standard of n-alkane hydrocarbons from
pentane (C5) through triacontane (C30) plus tetra-contane (C40) at 25 fxg/mL per component.

7.3.4 Comparison Reference Standards: Individual petroleum products (i.e., gasoline, kerosene,
Fuel No.l, Fuel No. 2, etc.) at approximately 250 fxg/mL.

7.3.5 Gasoline Stock Standard: Equal portions of three grades of nonoxygenated gasoline (regular,
unleaded regular, and unleaded supreme) from three different oil companies are mixed together to form a
composite gasoline. From this composite gasoline a stock standard is prepared accordingly. Place
approximately 9 mL of methanol in a 10-ml ground-glass stoppered volumetric flask. Allow the flask to
stand, unstoppered, until all alcohol wetted surfaces have dried (about 10 minutes). Tare flask and contents
unstoppered.

FMC-0-004-3

-------
7.3.5.1 Add about 10 drops of the composite gasoline standard to the flask. The liquid
must fall directly into the alcohol without contacting the neck of the flask. Reweigh, dilute to
volume with methanol, stopper, and mix by inverting the flask several times.

7.3.5.2 Calculate the concentration as follows:

Stock Cone, vg/mL = ( Final Wt' mg ] ~ ( Tared Wt' mg ] x i'000 ™

10 mL mg

7.3.6 Diesel Stock Standard: Equal portions of diesel fuel from three different oil companies are
mixed together to form a composite diesel fuel. From this composite fuel a stock standard of approximately
5,000 /ig/mL is prepared by adding four drops of the diesel stock to an empty, tared 10-mL volumetric flask.
The flask is reweighed and then brought to volume with methylene chloride.

7.3.6.1 Calculate the concentration as follows:

Stock Cone, ]ig/mL = { Final Wt' mg ] ~ ( Tared Wt' mg ] x ^00° ™

10 mL mg

7.3.7 Composite Calibration Standard: Prepare a mixture that contains 10 /ig/mL gasoline and 25
/ig/mL diesel by adding an appropriate volume of gasoline stock standard and diesel stock standard to a
10-ml volumetric flask and diluting to the mark with methylene chloride.

( 10 iig/mL ) x ( 10 mL ) 1, 000 muL

Volume Gasoline Stock, ]iL

Volume Diesel Stock, pi

Gasoline Stock Cone, ]ig/mL mL

( 25 iig/mL ) x ( 10 mL ) 1, 000 muL
Diesel Stock Cone, ]ig/mL mL

7.3.7.1 This mixture corresponds to 20-mg/kg gasoline and 50-mg/kg diesel in soil,
following this method's extraction procedure.

7.3.8 Stock Surrogate Standard: Make up a standard that is approximately 5,000 /ig/mL by
accurately weiging about 50 mg of the surrogate compound into a 10-mL volumetric flask and filling to the
mark with methylene chloride.

7.3.8.1 Working Surrogate Spike. 400 ug/mL: Add the appropriate volume of the stock
surrogate standard to a 10 mL volumetric flask and dilute to the mark with methylene chloride.

Stock Vol, viL = ( 400 yg/mL ) x ( 10 mL ) x 1, 000 muL
Stock Std Cone, \ig/mL mL

7.4 Analysis

7.4.1 Perform GC analysis on the extract.

7.4.2 If the analysis indicates that the results are more than 50 percent above the calibration range,
dilute the sample extract such that concentrations fall within the calibration range.

FMC-0-004-4

-------
7.4.3 Petroleum products are to be identified as follows: If the petroleum product can be matched
to reference chromatograms, by pattern recognition, then the sample can be identified as such; otherwise,
identify as follows:

• Gasoline is indicated if compounds are detected between hexane (C6) and decane (C10);

• Diesel and related products are indicated if compounds are detected between decane (C10)
and octocosane (C28); and

• Bunker C and related products are indicated by the presence of a chromatographic
envelope extending beyond octocosane (C28).

7.5 Calculations

7.5.1 Gasoline: The calibration standard area of the components from hexane (C6) through decane
(C10) is integrated to the baseline as a group. The sample is integrated in the same manner and the grouped
areas are compared. If the sample area exceeds the calibration standard area, proceed with method TPH-G
for accurate quantitation. If the sample area does not exceed the calibration standard area, then report as
"gasoline not detected by TPH-HCID."

7.5.2 The area of the components from decane (C10) through octocosane (C28) is integrated to the
baseline as a group. The sample is integrated in the same manner and the grouped areas are compared. If
the sample area exceeds the calibration standard area, proceed with method TPH-D for accurate quantitation.
If the sample area does not exceed the calibration standard area, then report as "diesel not detected by
TPH-HCID."

NOTE: A large amount of diesel contamination will also calculate as gasoline contamination. If

it is obvious that gasoline is not present, TPH-G does not need to be performed.

7.5.3 Quantification of the target pounds is based on the integrated areas of the samples in
comparison to the integrated areas of the calibration standards for each analyte. The integrator reports the
concentrations in /ig/mL in the extracts. Calculation of the concentration for each target constituent in the
original sample on an as-received basis is as follows:

A x v x DF
Cone in \ig/gm =

Where: A = Amount of target consitiuents found in the extract in /ig/mL.

Vt = Volume of solvent added to the VOA vial, 5.0 mL.

DF = Dilution factor, if required.

Ws = Weight of the sample added to the VOA vial in grams.

8.0 QUALITY CONTROL

8.1 Daily midrange calibration checks performed prior to the analysis of each day's lot of samples or with
each lot of 20 samples, whichever is more frequent.

8.2 Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1 per day, whichever is
more frequent.

FMC-0-004-5

-------
8.3	Analysis of laboratory blank samples at the same frequency. Should the results of the laboratory blanks
show contamination. The cause of the contamination should be investigated and corrective action taken.

8.4	Analysis of field duplicate samples at a frequency of 1 in 20 samples or 1 per day, whichever is more

frequent.

8.5	Analysis of a midrange matrix spike samples and a matrix spike duplicate at a frequency of 1 in 20
samples analyzed or 1 per day, whichever is more frequent.

8.6	The selected surrogate compound should be nonpolar, neutral extractable, and observable in a petroleum
matrix. Twenty fxg of this surrogate is to be added to the soil just before extraction with 20 mL methylene chloride.
This will produce an extract concentration of 1/ig/mL, suggested surrogates are chloroctadecane and ortho-terphenyl.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-0-004-6

-------
FASP Method F93010

ANALYSIS OF WATER. SEDIMENT AND SOIL FOR PHENOLS BY GAS CHROMATOGRAPHY

1.0 SCOPE AND APPLICATION

1.1 This method covers the determination of phenols in water, sediment and soil by a method of gas
chromatography with photoionization detector (PID) and flame ionization detection (FID) adapted for use by the
Field Analytical Services Program (FASP) mobile laboratory. This FASP method is intended to provide rapid
turnaround analyses in the field. FASP data are not considered to be a substitute for analyses performed within the
Contract Laboratory Program. FASP data are not intended to be legally defensible. Table 1 list the target analytes
and their MDL.

2.0 SUMMARY OF METHOD

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph fGCl: Varian 3400 GC with a photoionization detector (PID) and a flame ionization
detector. (FID)

4.2 Autosampler: Varian 8100.

4.3 Data System: PE Nelson Chromatographic software.

5.0 REAGENTS

5.1 Hexane: Pesticide Residue Analysis Grade.

5.4 Helium: Carrier gas, ultra pure or equivalent.

5.5 Nitrogen: Make-up gas.

FMC-O-005-1

-------
Table 1

FASP METHOD F93010 TARGET COMPOUND LIST AND MDL

Compounds
Phenol

2-Chlorophenol

2,4-Dimethylphenol

2-Nitrophenol

2,4-Dichlorophenol

4-Chloro-3-methylphenol

2,4,6-Trichlorophenol

2,4-Dinitrophenol

4-Nitrophenol

2-Methyl-4,6-dinitrophenol

Pentachlorophenol

5.6 PAH calibration standard mix concentrations:

17

MDL

20.89
30.25
33.09
44.06
41.04

17

80.19
39.08
147.38
28

Compounds
Phenol

2-Chlorophenol

2,4-Dimethylphenol

2-Nitrophenol

2,4-Dichlorophenol

4-Chloro-3-methylphenol 5

2,4,6-Trichlorophenol

2,4-Dinitrophenol

4-Nitrophenol

2-Methyl-4,6-dinitro-phenol
Pentachlorophenol

Low Point
ug/mL

5
5
5
5
5

125

Midpoint
ug/mL

50
50
50
50
50

250

75

75

125

125

125

High Point
ug/mL

250
250
250
250
250

150
150
250
250
250

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1	Sample Preparation: The samples are prepared following FASP SOP F93008 for the extraction of soil,
sediment and water samples for polynuclear aromatic hydrocarbon and phenol analyses.

7.2	Instrument Calibration

7.2.1 Initial Calibration Analytical Sequence:

7.2.1.1	Low Point Standard.

7.2.1.2	Mid Point Standard.

7.2.1.3	High Point Standard.

FMC-0-005-2

-------
7.2.1.4	Instrument Blank.

7.2.1.5	Laboratory Control Sample.

7.2.1.6	Method Blank.

7.2.1.7	Field Samples.

7.2.1.8	Instrument Blank.

7.2.1.9	Performance Verification Standard.

7.2.2 Daily Calibration Analytical Sequence:

7.2.2.1	Instrument Blank.

7.2.2.2	Calibration Check Standard.

7.2.2.3	Method Blank.

7.2.2.4	Laboratory Control Sample.

7.2.2.5	Field Samples.

7.2.2.6	Instrument Blank.

7.2.2.7	Performance Verification Standard.

7.3 Gas Chromatograph Operating Conditions

Carrier Gas
Column Flow
Make-up Gas
Make-up Gas Flow
Initial Temperature
Initial Time
Ramp

Intermediate Temperature
Intermediate Time
Final Temperature
Final Hold

Primary Analytical Column

Confirmation Column

Injector Temperature
Detector Temperature

Helium
4 mL/minute
Nitrogen
35 mL/minute
90°C
1 minutes
10°C/min
115°C
3 minutes
220 °C
10 minutes

DB-608, 15 meters, 0.53 mm ID, fused silica

megabore capillary column with PID

DB-5, 15 meters, 0.53 mm ID, fused silica megabore

capillary column with FID

250°C

300°C

7.4 Sample Analysis

FMC-0-005-3

-------
7.4.1 1 mL sample vials containing the sample extracts are placed on the autosampler following
the standards outlined in the analytical sequence in Section 7.2.

7.4.2 The instrument blank indicated in Section 7.2.1 and 7.2.2 is a hexane solution containing 20.0
ug/mL of the surrogates.

7.5 Compound Identification

7.5.1 Target analytes are identified by retention time.

7.5.2 On-scale chromatograms are required for identification.

7.6 Compound Quantitation

7.6.1 Quantitation is performed on both columns.

7.6.2 The detector response of all target analytes must be within the linear range of the initial
calibration for quantitation.

7.6.3 The concentrations of target analytes are calculated following the equations outlined in
USEPA CLP Draft SOW for Quick Turnaround Analysis 3/27/92, Section 21.3, page D-49-PHEN-Q.

8.0 QUALITY CONTROL

8.1 Initial Calibration

8.1.1 The initial calibration sequence outlined in Section 7.2 is analyzed prior to sample analysis.

8.1.2 Calibration factors for each target analytes are calculated.

8.1.3 Absolute retention times are determined for all target analytes and the surrogates.

8.1.4 Initial Calibration Acceptance Criteria:

8.1.4.1 The percent relative standard deviation of the calibration factors from the three-
point calibration must be < 25%.

8.1.4.2 The retention time of the surrogate or System Monitoring Compound (SMC) must
be within ± 2.0 percent of the mean retention time calculated from the initial calibration standards.

8.2 Calibration Verification

8.2.1 Sample analyses must be bracketed in 24-hour periods by acceptable analyses of and
instrument blank and a mid level Calibration Check Standard at the beginning and instrument blank and a
low level Performance Verification Standard at the end of the sequence.

8.2.2 Calibration Check Acceptance Criteria:

8.2.2.1 Follow criteria outlined in Sections 9.1 through 9.5.

8.2.2.2 Percent Differences (%D) must be ± 35%.

FMC-0-005-4

-------
8.2.3 Performance Verification Standard (PVS) Acceptance Criteria

8.2.3.1	Follow criteria outlined in Sections 10.1 through 10.5.

8.2.3.2	All PVS target analytes must have a concentration of 75 - 125% of the true
concentration.

8.3	Instrument Blank Acceptance Criteria

8.3.1 The instrument blank must not contain any target analytes at a concentration >0.5 times the
response in the initial calibration low level standard.

8.4	Surrogate Recovery Acceptance Criteria

8.4.1 The advisory QC limits for surrogate recovery are 50-150%.

8.5	Laboratory Control Spike fLCS) Acceptance Criteria

8.5.1 All LCS compounds must have percent recoveries between 30 - 130%.

8.6	Quality Control fOC) Sample

8.6.1 A second source QC Sample is extracted and analyzed for each batch or 20 samples. The
percent recoveries (%R) of the QC Sample must meet the following criteria:

Compounds

% Recovery

Phenol

23-108

2-Chlorophenol

38-126

2,4-Dimethylphenol

24-118

2-Nitrophenol

43-117

2,4-Dichlorophenol

43-119

4-Chloro-3-methylphenol

99-122

2,4,6-Trichlorophenol

53-119

2,4-Dinitrophenol

12-145

4-Nitrophenol

13-110

2-Methyl-4,6-dinitrophenol

30-136

Pentachlorophenol

36-134

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

1.	USEPA CLP Draft SOW for Quick Turnaround Analysis (3/27/92)

2.	EPA Method 8040, Phenols

FMC-0-005-5

-------
FASP Method F93002
ANALYSIS OF TOTAL PETROLEUM HYDROCARBONS

BY HEADSPACE GAS CHROMATOGRAPHY

1.0 SCOPE AND APPLICATION

1.1 This method covers the analysis of samples in the field by the Field Analytical Services Program (FASP)
Mobile Laboratory. This FASP method is based on modifications to approved EPA methods and is intended to supply
rapid turnaround analyses in the field. FASP data are not intended to be a substitute for analyses performed within
the Contract Laboratory Program. FASP data are not intended to be legally defensible. This method is suitable for
determination of gasoline and the low boiling hydrocarbon constituents of higher molecular weight petroleum
products, such as diesel.

2.0 SUMMARY OF METHOD

2.1 This method is a screening level method for the determination of total petroleum hydrocarbons by
headspace. The sample is analyzed by gas chromatography on a megabore capillary column with a flame ionization
detector (FID) and a photoionization detector (PID) operated in series.

3.0 INTERFERENCES

Infornmation not available.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph (GO: Varian 3400 GC with a FID and a PID installed in series.

4.2 Headspace Sampler: Tekmar Model 7000.

4.3 Data System: Nelson Analytical.

5.0 REAGENTS

5.1 Standards: A mixed diesel and gasoline standard will be prepared in acetone or other suitable water
soluble solvent.

5.2 Solvents: All solvents used as diluents will be HPLC grade or equivalent.

5.3 Reagent Organic Free Water: Prepared from distilled, deionized water by purging with an inert gas.

5.4 Reagent Gases

5.4.1 Hydrogen: Ultra pure or equivalent.

5.4.2 Helium: Ultra pure or equivalent.

5.4.3 Nitrogen: Ultra pure or equivalent.

5.4.4 Air: Zero air or equivalent.

FMC-O-006-1

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Analytical Sequence

7.1.1	Blank.

7.1.2	Initial Calibration.

5.0 mg/L
50 mg/L
100 mg/L
250 mg/L
500 mg/L

7.1.3	Blank.

7.1.4	Laboratory Control Sample (LCS).

7.1.5	Continuing Calibration Standard (CCS) (Not analyzed on day initial calibration performed).

7.1.6	10 samples.

7.1.7	LCS.

7.1.8	Continue with steps f. and g. until 24 hours have passed since last CC.

7.1.9	Blank.

7.1.10	CC.

7.1.11	Continue at step f.

7.2 Operating Conditions

7.2.1 Headspace Analyzer: Follow manufacturers recommendations.

Platen

Platen equilibrium

Sample equilibrium

Vial size

Mixer

Mix

Mix power

Stabilize

Pressurize

Pressure equilibrium

Loop fill

Loop equilibrium

Inject

Valve

85 °C
1 minute
20 minutes
20 mL

on

2 minutes
2

0.25 minutes
1 minute
0.05 minute
0.20 minute
0.05 minute
1 minute
85 °C

FMC-0-006-2

-------
Line

Injections per vial
GC cycle time
Parameter optimization
Sample loop size

45 minutes
on

85 °C

1 mL

7.2.2 Gas Chromatograph:

Initial temperature
Initial time

40 °C
4 minutes
10 °C/minute
275 °C
2 minutes

DB-5, 15 meters, 0.53 mm ID, fused silica
megabore capillary

Ramp

Final temperature
Final hold

Analytical column

7.2.3 Photoionization Detector Operating Conditions:

Base
Lamp

200 °C
10 ev

7.3 Compound Identification: Identification of total petroleum hydrocarbons is made by comparison of a
pattern of peaks within the same retention time range as a similar peak pattern in a hydrocarbon standard. Weathered
hydrocarbons may have patterns which are markedly different from newly prepared standards, but a qualified
identification may be made if, in the analysts opinion, there is strong evidence of an identifiable multiresponse
material. Otherwise, results will be reported as total petroleum hydrocarbons.

7.4 Compound Quantitation: A concentration factor is calculated from standard chromatograms as the
summation of the area beneath the hydrocarbon pattern within a specified retention time range. The quantitation of
unknowns is accomplished by summing the sample peak pattern area in the same retention time range as used for
calculation of concentration factors, and multiplying the summation of the sample peak pattern area by the standard
concentration factor. Quantitation limits are 1 mg/L for TPH in water and 10 mg/kg for TPH in soil and sediment.

7.5 Sample Analysis

7.5.1 Water Sample Analysis:

7.5.1.1 Water samples are poured into a capped 5-mL Luer lock syringe. Once the syringe
barrel is completely filled, the plunger is inserted and the volume adjusted to 5 mL. The plunger
is withdrawn slightly and 5 uL of the surrogate spiking solution is added through the Luer tip of the
syringe. The syringe is emptied into a 20-mL headspace vial and the vial is capped with a septum
cap. The cap is crimped such that it does not turn freely but the septum is not dimpled. The vial is
then placed in the headspace autosampler carousel.

7.5.2 Soil Samples

7.5.2.1 Five grams of the soil sample is weighed into a 20-mL septum vial. Two milliliters
of distilled water is added to the vial along with 5 uL of the surrogate spiking solution. The vial is
capped as described above and placed in the headspace autosampler carousel.

8.0 QUALITY CONTROL

FMC-0-006-3

-------
8.1 Blanks: Blanks are analyzed once each 24 hour period. There should be no hydrocarbons present in the
blank at a level greater than the reporting limit. If contamination is present in the blank, steps must be taken to
decontaminate the system prior to proceeding with analysis of samples.

8.2 Calibration

8.2.1 Initial Calibration: Five initial calibration levels are used. The percent relative standard
deviation for the response factors must be less than 30 %. If this criteron is not met, the system should be
recalibrated.

8.2.2 Continuing Calibration: A continuing calibration standard is analyzed once each 24 hour
period at a concentration equal to the midpoint of the calibration curve. The percent difference between the
response factor in the continuing calibration and the initial calibration must be less than 25%, or the system
must be recalibrated.

8.2.3 Laboratory Control Sample: A laboratory control sample is prepared at the same level as the
midpoint calibration standard using a second source normal hydrocarbon standard. The recovery of the
standard should be 70 to 135 percent. If the recovery is not within these limits, and is not corrected by
reanalysis, the data will be flagged as estimated.

8.2.4 Surrogate: A solution of 4-bromofluorobenzene will be added to each sample and blank at
a concentration near the midpoint of the calibration range. The advisory surrogate recovery limits are 50%
to 150%.

9.0 METHOD PERFORMANCE
Information not available.
10.0 REFERENCES

1. Leaking Underground Fuel Tank Field Manual:

Tank Closure. State of California, October 1989.

Guidelines for Site Assessment, Cleanup, and Underground

FMC-0-006-4

-------
ERT Method

LOW LEVEL METHANE ANALYSIS FOR SUMMA CANISTER GAS SAMPLES

1.0 SCOPE AND APPLICATION

1.1 This standard operating procedure (SOP) is intended for use when analyzing Summa canister gas
samples for low parts per million volume (ppmv) levels of methane.

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as
required, dependent on site conditions, equipment limitations or limitations imposed by the procedure or other
procedure limitations. In all instances, the ultimate procedures employed should be documented and associated
with the final report.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 A flame ionization detector (FID) gas chromatograph (GC) is used to separate and quantitate methane
in gas samples. The sample is introduced into the carrier gas as a plug and passes through a gas chromatography
column which then separates it into two peaks. The first peak is unresolved air; the second peak is resolved
methane. Peak areas are used in conjunction with calibration plots for quantitative measurements. This
separation is completed in five (5) minutes.

3.0 INTERFERENCES

3.1 This section is not applicable to this SOP as interferences have not been studied.

4.0 APPARATUS AND MATERIALS

4.1 Gas Chromatograph: Varian 3400 gas chromatograph with flame ionization detector (or equivalent)
capable of operating at 225°C.

4.2 Carrier Gas Cylinder: Ultra high purity helium with a two stage regulator delivering a pressure of 90

psi.

4.3 Syringes: 1 mL and 0.1 mL precision gas-tight with needles for sample introduction.

4.4 Gas Chromatography Column: 10 ft. x 1/4 in. stainless steel column packed with Spherocarb,

100/120 mesh (or equivalent), capable of operating at 100°C, injection temperature of 200°C.

4.5 Electronic Integrator: Spectra-Physics SP4290 integrator (or equivalent).

4.6 Septum Port Adaptor: For Summa canister.

4.7 Soap Film Flow Meter: (or equivalent).

5.0 REAGENTS

5.1 Helium Gas: Ultra high purity grade helium (99.9999%).

FMC-O-007-1

-------
5.2 Hydrogen Gas: Ultra high purity grade hydrogen (99.9999%).

5.3 Air: Ultra zero grade air (<0.05 ppmv total hydrocarbon).

5.4 Methane Standards: Calibration standards (in the range of 5-100 ppmv), balance air.

6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING

6.1 Refer to USEPA Method TOM concerning Summa canister cleaning and sample collection. In
addition refer to ERT SOP #1703, Summa Canister Cleaning and ERT SOP #1704, Summa Canister Sampling.

6.2 Canisters are stored and analyzed at room temperature.

7.0 PROCEDURES

7.1 Gas Chromato graph

7.1.1 The carrier gas is turned on and the flow rate adjusted to 40 mL per minute. The air is turned on
and the flow rate adjusted to 150 mL per minute. The hydrogen is turned on and the flow rate is adjusted to
30 mL per minute. The flows are checked with a soap film flow meter. The flame ionization detector is
then ignited and allowed to equilibrate for ten minutes. The integrator is turned on and zeroed before
samples are introduced.

7.2 Calibration

7.2.1 Introduce, via 1 mL syringe, aliquots of the same size as will be used on the sample injections of
the standard calibration gas mixtures in the gas chromatograph injector. At least one injection each
standard gas mixture is required before starting to analyze samples. The very first calibration should be
performed in triplicate.

7.2.2 Verify the initial calibration by injection of a complete set of at least four standards (at least five
different concentrations of standards are routinely available from commercial suppliers) at the
commencement of each day's analytical activities. It is suggested that each sample injection be followed
systematically by a standard injection so that many injection areas are tabulated and averaged in the report.

7.3 Injection of Sample

7.3.1 A 1-mL sample is withdrawn from the Summa septum port using a 1-mL gas-tight syringe. The
sample is quickly injected, guarding against blow-back of the plunger. Simultaneously, the integrator is
activated and the sample run is labeled. The integrator run is ended in five minutes and rezeroed before the
next analysis.

7.3.2 Samples analyzed above the calibrated linear range can be reanalyzed by injecting a smaller
volume, or by diluting in ultra high purity zero air to acquire responses within the linear range. These
dilutions may be done by injecting a measured volume of the sample into Tedlar bag and adding a measured
volume of zero air. For instance, 100 mL of sample measured with a gas tight syringe, added to 900 mL of
zero air would be diluted by a factor 10. These volumes have to be recorded and taken into account in the
calculations.

7.4 Calculations

FMC-0-007-2

-------
7.4.1 A linear standard curve of ppmv versus peak area is prepared. The sample concentrations are
calculated using the formula y = mx + b; where y is the peak area, m is the slope (peak area/ppmv), b is the
y intercept (peak area), and x is the concentration (ppmv).

7.4.2 The above equation may be rearranged to:

where y is measured area, corresponding to a sample injection and x is the desired methane concentration
in the sample injection. If a dilution has been made then, of course, the concentration obtained must be
multiplied by the ratio of the final sample volume to the initial sample volume. Most integrator packages
will handle the above calculations but it is recommended that a commercial spreadsheet program be used
so that the final report preparation may be expedited.

7.5 Health and Safety

7.5.1 When working with potentially hazardous materials, refer to USEPA, OSHA or corporate health
and safety practices.

8.0 QUALITY CONTROL

8.1 The following quality assurance/quality control procedures are applicable:

9.0 METHOD PERFORMANCE

9.1 Precision

9.1.1 The precision of the method is monitored during the second lowest calibration standard from the
linear curve. A control range is established for the standard using three standard deviations from the mean
of ten independent analyses. The standard is analyzed periodically (at the beginning and end of a series of
samples or every 8 hours) and must respond within the range of three standard deviations for the system and
data precision to be considered under control. If the results of the standard analysis are out of range, the
system must be repaired and the standards rerun, for a new calibration curve must be performed.

9.2 Accuracy

9.2.1 The accuracy of the method is monitored by periodically analyzing blind performance evaluation
samples. These samples should not be prepared by the same outside source that the calibration standards
were obtained from.

10.0 REFERENCES

Information not available.

FMC-0-007-3

-------
ESAT Region 10 Method
EXTRACTION AND ANALYSIS OF PENTACHLOROPHENOL

IN SOILS BY ELECTRON CAPTURE

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed to determine estimated quantities of
Pentachlorophenol (PCP) in soil. Target compounds and the method quantitation limits are listed in Table 1.

1.2 This method is intended for, use by, or under the supervision of, analysts experienced in the use of gas
chromatography (GC) and in the interpretation of GC chromatograms.

2.0 SUMMARY OF METHOD

2.1 A measured amount of soil is placed in a disposable screw cap vial and extracted with a measured
volume of MTBE and methylated. Compounds are detected by an Electron Capture detector (ECD).

Identification is based on comparison of retention times and relative peak intensities between samples and
standards.

3.0 INTERFERENCES

3.1 Method interferences may be caused by contaminants in solvents, reagents, glassware, as well as other
sample processing equipment that can lead to discrete artifacts or elevated baselines in the GC chromatograms.
All reagents and apparatus must be routinely demonstrated to be free from interferences under the conditions of
the analysis by running method and instrument blanks.

3.2 Interferences due to sample carryover may be eliminated by the use of disposable glassware during
sample prep and by thoroughly rinsing syringes used in manual injections.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System: The following option meets the requirement of this method. Other GC
configurations may be used if they meet method requirements.

4.1.1 Gas Chromatograph: The system may perform either isothermal or temperature programs and
contain necessary accessories including injector and detector systems capable of accepting an analytical
column.

4.1.1.1 Column: 3% OV-1 and/or 1.50% SP-2250; 1.95% SP-2401 on a 100/120 mesh.

4.1.1.2 Detectors: Electron capture detector may be used.

4.1.1.3 Data System: Capable of retention time labeling, relative retention time comparisons, as well
as providing peak height and peak area measurements.

FMC-O-008-1

-------
Table 1

METHOD TARGET COMPOUNDS AND
QUANTITATION LIMITS

Pentachlorophenol data not yet available.

FMC-0-008-2

-------
4.2 Laboratory Equipment

4.2.1	Screw Cap Culture Tubes: Disposable 16mm xl50mm borosilicate glass with teflon-lined
phenolic caps.

4.2.2	Disposable Pipets: Pasteur, 6 and 9 in. long.

4.2.3	Spatulas: Stainless steel.

4.2.4	Syringes: lOul, 25ul, lOOul and lOOOul.

4.2.5	Balance: Top loading, capable of weights to 0.01 g.

4.2.6	Volumetric Flasks: 10ml, 25ml and 100ml.

4.2.7	Vortex Mixer:

4.2.8	Centrifuge: Capable of holding 16mm x 150mm culture tubes.

4.2.9	Amber Storage Bottles: 10ml with Teflon-lined screw caps.

4.2.10	Graduated Centrifuge Tubes: 10ml with ground glass stoppers.

4.2.11	N-Evaporator: Variable temperature water bath with multi-sample nitrogen purge capability.

4.2.12	Leak Detector: Snoop liquid or equivalent.

4.2.13	Polv Wash Bottles: 500ml.

5.0 REAGENTS

5.1	Solvents

5.1.1 Methvl-tert-butvlether fMTBE'). Methanol. Hexane. Diethyl ether (unpreserved'l: Pesticide grade
or better.

5.2	Miscellaneous Reagents

5.2.1	Reagent Water: Milli-Q deionized or equivalent.

5.2.2	N-Nitrosomethvl Urea: Crystalline form.

5.2.3	Potassium Hydroxide: 37% in deionized water.

5.2.4	Sulfuric Acid: Concentrated, reagent grade.

5.2.5	Bright Copper: Remove oxides by treating with dilute Nitric acid, rinse with distilled water to
remove all traces of acid, rinse with acetone, and dry under a stream of nitrogen.

5.2.6	Derivatizing Reagent: Weigh out 0.5 grams of N-Nitrosomethyl urea. Dissolve in 25 mL of
unpreserved diethyl ether. Add 1 mL of 37% KOH. Stopper and keep cold until ready for use. Solution
must be made fresh each day.

FMC-0-008-3

-------
5.3 Gases

5.3.1 Nitrogen: Ultra pure or chromatographic grade.

5.4 Stock Standard Solutions: Stock standards for each analyte listed in Table 1, Section 3.2 should be
purchased as manufacturer certified solutions. Stock standards must be replaced after 1 year.

5.5 Calibration Standards: Calibration standards at a minimum of three concentration levels should be
prepared through dilution of the stock standards with hexane. One concentration level should be near, but not
above, the method detection limit. The remaining concentration levels should define the working range of the
instrument. Calibration standards must be protected from light and stored in teflon sealed screw cap bottles at 4
C. Calibration standards must be replaced after 6 months, or sooner if comparison with check standards indicate
a problem.

5.6 Check Standards: Standards prepared by an analyst other than the analyst who prepared the calibration
standards. The check standards must also come from a different source than the calibration standards.

5.7 Surrogate Standards: The analyst will monitor the performance of the extraction and analytical system
by spiking each sample, blanks, and matrix spikes with one or two surrogates not expected to be present in the
sample. A suggested surrogate standard is 2,4,6-Tribromophenol.

5.8 Matrix Spikes: Matrix spike solutions can be made by dilution of stock standard solutions. The
spiking level should be approximately 5X (five times) the concentration of the native compound.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Soil and sediment samples should be collected in 4-ounce wide mouthed glass jars with Teflon-lined
caps.

7.0 PROCEDURE

7.1 Safety

7.1.1 The toxicity and carcinogenicity of each reagent has not been precisely defined; however, each
chemical compound must be treated as a potential health hazard.

7.1.2 The analysts should be familiar with the location and proper use of the fume hoods, eye washes
and fire extinguishers. In addition, the analysts must wear protective clothing and safety glasses at all
times. Contact lenses cannot be worn in the laboratory.

7.1.3 Fume hoods must be utilized whenever possible to avoid potential exposure to organic solvents.

7.2 Extraction

7.2.1 Add 1.0 + 0.01 g well homogenized soil sample to a tared and labeled culture tube.

7.2.2 Add appropriate surrogates.

7.2.3 Add 1 ml of acidified water to the culture tube and cap.

7.2.4 Vortex for 1 minute.

7.2.5 Add 10 mL of MTBE to the culture tube and cap.

FMC-0-008-4

-------
7.2.6 Vortex for one minute.

7.2.7 Centrifuge the culture tube for 1 minute at half speed.

7.2.8 Transfer a 3 ml aliquot of MTBE to a labeled 10 ml graduated centrifuge tube via Pasteur pipet.
Mark the meniscus.

7.3 Derivatization

7.3.1 Add 1 mL of derivatizing reagent to the 3 mL sample extract. Let react for 5-10 minutes.

7.3.2 Under a gentle stream of nitrogen evaporate the extract to 3 mL. Add 5ml hexane and N-evap
back to the original 3 ml volume.

7.3.3 Archive a portion of the extract for future dilutions.

7.4 Cleanup

7.4.1 Add 2 mL concentrated sulfuric acid to the sample extract.

7.4.2 Vortex for one minute. Let layers separate.

7.4.3 Transfer organic layer to an autosampler vial for storage.

7.5 Optional Cleanup for Sulfur

7.5.1 Add bright copper to the sample extract. Copper grains will turn black in the presence of sulfur.
The sample extract is now ready to shoot.

7.6 Recommended GC Conditions
Information not available.

7.7 Calibration

7.7.1 Initial Calibration:

7.7.1.1 Generate initial calibration curves using at least three calibration standards for each target
compound as described in Section 5.5.

7.7.1.2 Correlation coefficients (R) for each calibration curve must be greater than 0.95 to be valid.
A new initial calibration curve must be run anytime the GC is altered or shut down for long periods of
time.

7.7.2 Continuing Calibration: A continuing calibration must be performed on a regular basis. The
midrange initial calibration standard is used for continuing calibration validation. For a continuing
calibration to be valid, the percent difference (%D) must be less than or equal to 25%. If this criteria is not
met, a new initial calibration curve must be run.

7.8 Pentachlorophenol Identification:

7.8.1 Qualitive identification of PCP is based on retention time matching of the sample with standard
chromatograms.

FMC-0-008-5

-------
7.8.2 Individual retention time windows should be less than 2% PD based on the first continuing
calibration of the day.

7.9	Calculation

7.9.1 Sample Quantitation:

7.9.1.1 Use the following calculation to determine the concentration in the sample. The response can
be measured by automated peak area measurements or from an integrator. Sample quantitation is based
on a three point initial external calibration of all target analytes.

Concentration (ug/kg)= fAYBYlOOO')

(C)(D)

Where: A = Instrument peak area response (ng/ul)

B = Total volume of extract (ml)

C = Dry weight of sample (g)

D = Percent solids in sample

7.10	Matrix Spike Recovery:

7.10.1	To calculate the percent recovery for the matrix spike and matrix spike duplicate use:

% Matrix Spike Recovery = E x 100
F

Where E is the instrument peak area response (ng/ul) from the sample and F is the known concentration
spiked into the sample (ng/ul).

7.10.2	Relative percent difference (RPD) is calculated using:

RPD = (L -K) x 100
fL + K)

2

Where L and K is the value of the spiked concentration for the matrix spike and matrix spike duplicate
respectively.

7.10.3	Surrogate Recovery:

7.10.3.1 The calculation for surrogate recovery is as follows:

% Surrogate Recovery = G x 100
H

Where G is the raw peak area response in the sample and H is the raw peak area response determined from
a standard.

7.10.4	Continuing Calibration:

7.10.4.1 The percent difference (%D) is calculated using:

FMC-0-008-6

-------
%D = LJ.x 100
I

Where I is the known concentration of each compound and J is the peak area response in ng/ul.

7.10.5 Retention Times:

7.10.5.1 The percent difference (%D) is calculated using:

%D = M - N x 100
M

Where M is the average retention time from the initial calibration and N is the sample retention time.

8.0 QUALITY CONTROL

8.1 Quality control must be met for all analyses. Limits for matrix spike and matrix spike duplicate must
fall between 50%-150% RPD. Percent recoveries for the surrogates must also meet the same criteria as the
matrix spikes. Refer to DOC# ESAT-10A-5188 Quality Assurance Guidelines for Field Analysis for specific
criteria.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES
1. Fasp Method Number F070.001

FMC-0-008-7

-------
ESAT Region 10 Method
FIELD EXTRACTION AND ANALYSIS OF TOTAL PETROLEUM HYDROCARBONS

IN SOIL BY FID

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in identifying petroleum
products containing components ranging from C7 to C30 as well as heavier oils with specific product
confirmation by pattern matching in soils. Target compounds and the method quantitation limits are listed in
Table 1. This method may be modified at the discretion of the analyst in order to meet project specific goals (i.e.
detection limit modifications, larger or smaller analyte lists, optimization of chromatographic conditions for
specific target compounds).

1.2 While this method is intended to be qualitative, it can be used to eliminate the need for further analyses
for those samples which demonstrate TPH levels significantly below the regulatory limits. If the sample contains
C7 through C12 (gasoline range), C12 through C24 (diesel range), or an unresolved chromatographic envelope
>C24 (motor oils) above the reporting limits of this method, then final quantitation must be performed using the
SOP specific to each range.

1.3 This method is intended for, or under the supervision of, analysts experienced in gas chromatography
(GC) and the interpretation of GC chromatograms.

1.4 It is strongly recommended that 10% of the samples submitted for analysis by this method be split and
submitted for confirmational analysis using an EPA regulated method. Confirmational analyses are
recommended for Level II field analysis per Data Quality Objectives for Remedial Response Activities
(EPA/540/G-87/003) and are required for QA2 analyses (not required for QA1 analyses) per Quality
Assurance/Quality Control Guidance for Removal Activities (EPA/540/G-90/004). Any site specific
information pertaining to the requested analysis could greatly enhance the support capabilities of the FASP team,
i.e., action levels, known interferences, etc.

2.0 SUMMARY OF METHOD

Approximately two grams of sample is extracted with methylene chloride using a vortex and centrifuge. A
portion of the extract is injected into a gas chromatograph equipped with a flame ionization detector (FID).

2.1 Gasoline is indicated if compounds are detected from toluene through dodecane (C12). The lower
reporting limit is 84 ppm for gasoline in soil.

2.2 Diesel and related products are indicated if compounds are detected eluting after dodecane (CI2)
through tetracosane (C24). The lower reporting limit is 50 ppm for diesel in soil.

2.3 Lube oil is indicated by an unresolved chromatographic envelope eluting after tetracosane (C24).
Quantitation is accomplished by integrating the unresolved chromatographic envelope. The lower reporting limit
is 160 ppm for motor oil in soil.

FMC-O-009-1

-------
Table 1

TARGET COMPOUND LIST AND QUANTITATION LIST

Compound

Practical Quantitation Limit*

Gasoline
Diesel
Motor oil

84 mg/Kg (ppm)

50 mg/Kg (ppm)
160 mg/Kg (ppm)

* Based on 2 gram sample and 2 mL final volume.

3.0 INTERFERENCES

3.1 Method interferences may be caused by contaminants in solvents, reagents, glassware, and other
sample processing apparatus that lead to discrete artifacts or elevated baselines in gas chromatograms.

3.2 Contamination by carryover can occur whenever high-concentration and low-concentration samples are
analyzed in sequence. To reduce the potential for carryover, the sample syringe or purging device must be rinsed
out between samples with an appropriate solvent. Whenever an unusually concentrated sample is encountered, it
should be followed by injection of a solvent blank to check for cross contamination.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System: The following option meets the requirement of this method. Other GC
configurations may be used if they meet method requirements.

4.1.1 Gas chromatograph: The system must perform a temperature program and contain necessary
accessories including injector and detector systems capable of accepting an analytical column.

4.1.1.1 Column: 30 meter DB-5 (or equivalent) megabore with 1.5 (im film thickness.

4.1.1.2 Detectors: Flame ionization detector.

4.1.1.3 Data System: Capable of retention time labeling, relative retention time comparisons, and
providing peak height and peak area measurements. The current system uses PE Nelson and
Turbochrome.

4.2 Laboratory Equipment:

4.2.1 Screw-cap Culture Tubes: Disposable 16mm x 125mm borosilicate glass with teflon-lined
phenolic caps.

4.2.2 Disposable Pipets: Pasteur, 6 and 9 inch long and pipet bulbs.

4.2.3 Scoopulas: Stainless steel.

4.2.4 Syringes: Gastight syringe, 10(iL, 25(iL, lOO^L, and lOOO^L.

4.2.5 Balance: Top loading, capable of weighing out to 0.1 g.

4.2.6 Volumetric Flasks: lOmL, 25mL, and lOOmL, ground glass stoppered.

FMC-0-009-2

-------
4.2.7 Vortex mixer

4.2.8 Centrifuge: Capable of holding 16mm x 125mm culture tubes.

4.2.9 Amber Storage Bottles: lOmL with Teflon-lined screw caps.

4.2.10 Vials: 1.8mL with teflon-lined septa.

4.2.11 Graduated Centrifuge Tubes: lOmL with ground glass stoppers.

4.2.12 N-Evaporator: Variable temperature water bath with multi-sample nitrogen purge capability.

4.2.13 Leak Detector: "Snoop" liquid or equivalent.

4.2.14 Polv Wash Bottles: 500mL
5.0 REAGENTS

5.1 Solvents: Methylene chloride and Methanol, pesticide grade or equivalent

5.2 Miscellaneous Reagents

5.2.1 Sodium Sulfate. Anhydrous

5.2.2 Silica Gel: Activated, stored at 130°C for 24 hours before use.

5.2.3 Reagent Water: Milli-Q deionized or equivalent.

5.3 Gases: Hydrogen, Helium and Air, Ultra-pure or chromatographic grade.

5.4 Stock Standard Solutions

5.4.1 Motor oil stock standards are prepared by adding approximately 4 drops of 30 weight motor oil
(Pennzoil or equivalent) to a tared 10 mL volumetric flask. Reweigh and bring to volume with methylene
chloride, stopper and mix by inverting the flask several times. Stock standard solutions must be replaced
after one year.

5.4.2 Diesel stock standards are prepared equal portions of #2 diesel oil from at least two different oil
companies are mixed together to form a composite diesel fuel. From this composite fuel a stock standard is
prepared by adding approximately 4 drops of diesel stock to a tared 10 mL volumetric flask to about 0.1 g.
Then bring to volume with methylene chloride, stopper and mix by inverting the flask several times. Stock
standard solutions must be replaced after one year.

5.4.3 Gasoline stock standards are prepared using equal portions of three grades of non-oxygenated
gasoline (regular, unleaded regular, and unleaded supreme) mixed together to form a composite gasoline
standard. From this composite fuel a stock standard is prepared by adding approximately 8 drops of
gasoline stock to a tared 10 mL volumetric flask to about 0.1 g. Then bring to volume with methanol,
stopper and mix by inverting the flask several times. Stock standard solutions must be replaced after one
year.

Calculate the concentration as follows:

Stock conc., ng/mL = (final wt.. mg) - ftare wt.. mg) x 1000 fig

FMC-0-009-3

-------
10 mL

5.5 Calibration Standards: Calibration standards at a minimum of three concentration levels ranging from
160 - 1600 (ig/mL for motor oil, 39 - 1700 ng/mL for diesel, 84 - 1600 ng/mL for gasoline should be prepared
through methylene chloride dilutions of stock standards. One concentration level should be near, but above, the
method detection limit. The remaining concentration levels should define the working range of the instrument.
The calibration standards must also contain the surrogate. Calibration standards must be protected from light and
stored in teflon sealed screw cap bottles at approximately 4±2°C. Calibration standards must be replaced after
six months, or sooner if comparison with check standards indicate a problem.

5.7 Surrogate Standards: The analyst will monitor the performance of the extraction and analytical system
by spiking each sample, blank and matrix spike with one or two surrogates not expected to be present in the
sample. The use of additional surrogates or different surrogates is optional. The selected surrogate should be
non-polar, neutral extractable, and observable in a petroleum matrix. The suggested surrogate is tetracosane.

5.7.1 Make up a stock standard which contains approximately 5000 ng/mL by accurately weighing
about 50 mg of the chosen surrogate into a 10 mL volumetric flask and filling to volume with methylene
chloride.

5.8 Matrix Spikes: Matrix spike solutions can be prepared by dilution of stock standard solutions. The
spiking level should be approximately five times the analyte concentration in the native sample.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Soil and sediment samples should be collected in four-ounce wide-mouthed glass jars with Teflon-lined
caps. Collected samples should be kept refrigerated until analysis has been completed.

7.0 PROCEDURE

7.1 Safety

7.1.1 The toxicity and carcinogenicity of each reagent has not been precisely defined; however, each
chemical compound must be treated as a potential health hazard. Accordingly, exposure to these chemicals
must be reduced to the lowest possible level.

7.1.2 The analyst should be familiar with the location and proper use of the fume hoods, eye washes,
safety showers, and fire extinguishers. In addition, the analyst must wear protective clothing and safety
glasses at all times. Contact lenses may not be worn while working in laboratory.

7.1.3 Fume hoods must be utilized whenever possible to avoid potential exposure to organic solvents.

7.1.4 Work with solvents or chemicals may be performed only when at least one other chemist is in the
area.

7.1.5 Waste should be disposed of by placing it in an appropriately marked container beneath the fume
hoods in the extraction rooms or other designated area. All waste containers should be labeled with the
start date, end date, and type of waste (i.e. halogenated or non-halogenated solvents).

7.2 Extraction

FMC-0-009-4

-------
7.2.1 Weigh out approximately 2.0 grams of soil into a tared culture tube.

7.2.2 Allow the spiking standards to come to room temperature and swirl to remix the standards before
adding them to the samples. Spike blanks, samples, and matrix spikes with appropriate spiking solution.

7.2.3 Add 10.0 mL of methylene chloride.

7.2.4 Approximately 1 gram of silica gel and 1 gram of sodium sulfate, anhydrous, is added to the
culture tube.

7.2.5 Vortex each sample for 1 minute.

7.2.6 Centrifuge each sample for 5 minutes at half speed.

7.2.7 Transfer a 5 mL aliquot to a graduated centrifuge tube via Pasteur pipet and bring to 1 mL under a
gentle stream of nitrogen using the N-evap with a water bath temperature of approximately 30°C.

7.2.8 Store at 4±2°C until analysis.

7.2.9 Final volume of extract is 2 mL.

7.2.10 The sample is now ready for analysis.

7.3 Recommended GC Conditions

7.3.1 The recommended analytical column is a 15 meter megabore DB-5. The carrier gas should be
helium with a flow rate of approximately lOmL/min. The injection volume should be approximately l(iL
directly on column.

7.3.2 The following temperature program has proven to provide separation for all target compounds
using the column mentioned above. The injector/detector block was set at 275°C.

Initial 50 °C hold for 9 min

Ramp 10°C/min to 300°C

Final 300°C hold for 5 min

The following flows are suggested:

Hydrogen= 23 mL/min
Air= 230 mL/min

Helium= 10 mL/min

7.4 Calibration

7.4.1 Initial Calibration:

7.4.1.1 Generate initial calibration curves using at least three calibration standards for each target
compound as described in section 5.5.

7.4.1.2 Correlation coefficients (rA2) for each calibration curve must be greater than 0.95, or the
relative standard deviation (RSD) of the response factors must be less than ± 25% for the curve to be

FMC-0-009-5

-------
valid. A new initial calibration curve must be generated whenever the GC is altered or shut down for
long periods of time or if comparison with a continuing calibration standard indicates a problem.

7.4.1.2.1 Relative Standard Deviation

ST)

RSD = x 100

aRF

where: SD = Standard deviation

aRF = Average response factor (conc/area)

7.4.2 Check Standards: The accuracy of the initial calibration should be verified by running a check
standard immediately after the initial calibration. The calculated response of the check standard must be
within ± 25% difference of the expected concentration.

7.4.3 Continuing Calibration: A continuing calibration check must be performed at the beginning and
end of every analytical sequence and after every 10 samples. The midrange initial calibration standard may
be used for continuing calibration validation. For a continuing calibration to be valid, the percent difference
(%DIF) must be less than or equal to ± 25%. If this criteria is not met, reshoot the continuing calibration
standard. If the standard is still outside the acceptance criteria, a new initial calibration curve must be
generated.

7.5 Motor Oil Identification

7.5.1 Qualitative identification of target compound is indicated by an unresolved envelope that elutes
after tetracosane (C24). Quantitation is accomplished by integrating the unresolved envelope. If the sample
does not exceed the standard area, then report a "heavy oil concentration less than 160 mg/Kg by HCID."

7.6 Diesel Identification

7.6.1 Qualitative identification of target compound is accomplished by integrating as a group the area of
components to the baseline after tridecane through eicosane. If the sample area does not exceed the
calibration standard area, then report as "diesel concentration less than 39 mg/Kg by HCID."

7.7 Gasoline Identification:

7.7.1 Qualitative identification of target compound is accomplished by integrating as a group the area of
components to the baseline after toluene through 1,2,4-trimethylbenzene. If the sample area does not
exceed the calibration area, then report as "gasoline concentration less than 84 mg/Kg by HCID."

8.0 QUALITY CONTROL

8.1 Quality assurance guidelines must be met for all analyses. Recoveries for matrix spike and matrix spike
duplicate must fall between 50%-150%. Recoveries for the surrogates must also meet the same criteria as the
matrix spikes. Refer to DOC# ESAT-10A-5188 "Quality Assurance Guidelines for Field Analysis" for specific
criteria.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

FMC-0-009-6

-------
Information not available.

FMC-0-009-7

-------
FASP Method Number F 100.001
SELECTED METALS IN SOIL/SEDIMENT BY X-RAY FLUORESCENCE

1.0 SCOPE AND APPLICATION

1.1 This Field Analytical Support Project (FASP) method is proposed for use in determining the concentrations
of various elements in soil, sediment, and solid samples.

1.2 This method offers qualitative identification of elements with atomic numbers 11 through 92 and currently
quantitates the analytes listed in Table 1. Approximate quantitation limits are also listed in Table 1. A potential exists
for other elements to be quantitated besides those listed in Table 1.

1.3 This method should be used only by trained analysts under the super-
vision of an experienced chemist.

1.4 This method analyzes total elemental concentrations and cannot distinguish between valence or oxidation
states (i.e., total chromium versus hexavalent chromium). Liquids or oily wastes will not be analyzed by this method
due to the potential damage to the instrument.

1.5 The primary objective of FASP is to provide analytical data in a timely manner for guidance of ongoing
work in the field. Identification of specific target analytes and prior knowledge regarding potential matrix
interferences are prerequisites to successful use of FASP. FASP is not equivalent to or a replacement for Contract
Laboratory Program (CLP) analyses. Verification of data through the CLP or other laboratories, encompassing the
range of sample concentrations, is recommended.

2.0 SUMMARY OF METHOD

2.1 This method utilizes the X-ray fluorescence (XRF) technique to determine concentrations of elements in
soil or solid samples. It is written specifically for the Tracor Spectrace 6000 energy dispersive X-ray fluorescence
analyzer but can generally be used with a variety of XRF instruments. Only qualified chemists trained in the proper
use, theory, and safety of XRF analysis should operate this system.

2.2 The principle of XRF analysis is based on electron excitation. Elemental atoms in a soil sample are
irradiated with a beam of X-rays. Electrons in the atoms' lower lying energy levels are excited to higher energy
levels. The vacancies left in the inner electron orbitals make the atom unstable. Relaxation to the ground state
occurs, resulting in the emission of X-rays characteristic of the excited elements. Thus, by examining the energies
of the X-rays emitted by the irradiated soil sample, identification of elements present in the sample is possible.
Comparing the intensities of the X-rays emitted from a given sample to those emitted from reference standard with
known analyte concentrations allows quantitation of the elements present in the samples.

2.3 The Tracor Spectrace 6000 utilizes a variable energy X-ray tube with an electronically cooled
lithium/silicon detector. Dried and ground samples are irradiated in the X-ray chamber under specified excitation
conditions, and the resulting spectrum is stored and processed by an interfaced personal computer. The Tracor
software package utilizes certified standards files and pure elemental spectra to perform a least squares fit on the
sample spectrum. A "Fundamental Parameters" program applies calculated matrix coefficients to quantitate analyte
concentrations corrected for enhancement and absorption effects.

FMC-I-001-1

-------
Table 1

FASP METHOD F100.001 TARGET COMPOUND LIST AND
QUANTITATION LIMITS*

Element

CAS Number

Quantitation Limit
Soil/Sediment/Solid**
(ppm)

Antimony

7440-36-0

15

Arsenic

7440-38-2

15

Cadmium

7440-43-9

15

Calcium

7440-70-2

15

Chromium

7440-47-3

15

Copper

7440-50-8

15

Iron

7439-89-6

15

Lead

7439-92-1

15

Manganese

7439-96-5

15

Mercury

7439-97-6

15

Nickel

7440-02-0

15

Potassium

7440-09-7

15

Selenium

7782-49-2

15

Silver

7440-22-4

15

Thorium

7440-29-1

15

Tin

7440-31-5

15

Uranium

7440-61-1

15

Zinc

7440-66-6

15

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for
guidance and may be biased high or may not always be achievable.

** Quantitation limits listed for soil/sediment are based on an "as-received" basis.

3.0 INTERFERENCES

3.1 Some complex matrix effects will produce synergistic (enhancing) or antagonistic (masking) effects that
may artificially increase or decrease the resulting concentrations of various elements in the sample. The Tracor
Spectrace 6000 corrects for these effects by applying a mathematical computer program called "Fundamental
Parameters." Initially, spectra and corresponding elemental concentrations of certified standards are acquired. These

FMC-I-001-2

-------
standards are used to construct a calibration curve by plotting measured X-ray intensities against known elemental
concentrations. The program calculates values termed alpha coefficients using the hypothetical standards established
by the Fundamental Parameters' program, which mathematically describe the complex matrix effects.

3.2 Analysis of unknowns (samples) proceeds by an iterative computation. An estimate of the composition
of the unknown is made by comparison of the measured intensities to the pure element count-rate values and standard
calibration curve. The alpha coefficients are then applied to the estimated concentrations to make a new estimate of
the composition. The process is repeated with the program using the last calculated composition value and the alpha
coefficients to calculate a new composition. If the difference between the last calculated concentration and the
concentration determined from the new iteration is less than one percent relative, the program assumes convergence,
and the analysis procedure ends.

4.0 APPARATUS AND MATERIALS

4.1 Analytical System: Elemental identification and quantitation is obtained using the Tracor Spectrace 6000
energy dispersive XRF spectrometer in conjunction with the "Fundamental Parameters" Personal Computer (PC)
software program run on a NEC Powermate 2 PC. The Tracor Spectrace 6000 utilizes a variable voltage X-ray tube
with an electronically cooled silicon/lithium detector. The spectrometer is able to achieve detection limits of
approximately 15 ppm (parts per million) consistently and confidently without liquid nitrogen cooling of the XRF
detector. The detection limits are more than adequate for most elements in soil contamination investigations.

4.2 Other Laboratory Equipment

4.2.1 Glass Petri dishes: 150 mm or 25 mm.

4.2.2 Agate mortar and pestle.

4.2.3 Plastic X-rav sample containers: 31 mm.

4.2.4 Polypropylene (Mylar) window film: 0.2 mL.

4.2.5 Tweezers: Stainless steel or plastic.

4.2.6 Drying oven.

5.0 REAGENTS

5.1 Certified Calibration Standards: Certified soil, sediment, ores, or solid samples may be obtained through
the National Institute of Standards and Technology (NIST), the Environmental Protection Agency (EPA), or the
Canadian Centre for Mineral and Energy Technology (CANMET).

5.2 Pure Elemental Standards: These solid samples may be the oxides, chlorides, etc., of the element of
interest. Known concentration is not required, but the sample should be free of interfering constituents.

5.3 Reagent Water: Reagent water is defined as water in which an interferent is not observed at the quantitation
limit (QL) of the analyte of interest. Reagent water may be purchased from commercial laboratory supply houses.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

FMC-I-001-3

-------
avoiding large rocks and non-soil derived materials such as twigs or trash. The soil or sediment sample is collected
in a 1 to 2 ounce glass jar.

6.2 The use of chain-of-custody records as described in the U.S. EPA "CLP Users Guide" (9240.0-1),
December 1988, is required for sample tracking. The maximum holding time for solid samples is 6 months, but it
is recommended that all samples be analyzed as soon as possible.

6.3 Use of metal sampling tools should be avoided as much as possible. The sample is collected to fill a 1 to
2 ounce glass jar. If laboratory confirmation is required, additional sample must be collected to fulfill the laboratory
requirements.

7.0 PROCEDURE

7.1 Sample Preparation

7.1.1 Place the sample in a clean, labelled Petri dish or compatible apparatus for drying. Dry the sample
in an oven or air dry until moisture is removed.

7.1.2 Grind and homogenize the sample with a properly decontaminated agate mortar and pestle for at least
2 minutes, or until desired homogeneity has been obtained.

7.1.3 Place an aliquot of sample in an XRF sample cup and cover with polypropylene (Mylar) film.

7.1.4 The sample is now ready for analysis by XRF.

7.2 Calibration

7.2.1 Pure element spectra:

7.2.1.1 Begin calibration of the instrument with collection of pure element spectra which are of interest
for analysis or which may cause analytical interferences. Three sets of conditions are used to analyze for
elements from potassium (Z = 19) to uranium (Z = 92).

7.2.1.2 The first condition is termed "Mid Z Analysis", which includes the pure element spectra for
potassium, calcium, titanium, chromium, manganese, and iron. Titanium and iron are not analyzed under
these conditions but are used to correct for matrix interferences.

7.2.1.3 Irradiate pure elemental standards as unknown samples with the tube voltage and amperage
adjusted for each element so a dead time of 50 percent is achieved. Acquire the spectra until the peak of
interest count rate is above 20,000. Save the spectra as the elemental number, and label it as a reference (i.e.,
for potassium, the spectrum number is 19 and the label is "K - REF").

7.2.1.4 After the spectra are acquired, setup a spectrum processing reference file for the Mid Z Analysis.
List each pure element in the spectrum processing menu, and identify and store a region of interest.
Designate pure elements which are not analyzed by a in the reference file (i.e. titanium is designated as
" *Ti")

7.2.1.5 Follow this procedure for the "High Z Analysis", which includes the pure elements of manganese,
iron, nickel, copper, uranium, thorium, lead, mercury, zinc, selenium, arsenic, rubidium, zirconium,
strontium, and a lead interference peak.

FMC-I-001-4

-------
7.2.1.6 Also collect pure elemental spectra in the same way for the "Silver Analysis", which includes the
pure elements silver, cadmium, tin, and antimony.

7.2.1.7 The K-alpha emission lines define the regions of interest for all the above-mentioned elements
except for uranium, thorium, lead, and mercury which use the L-alpha emission lines.

7.2.2 Standards spectra:

7.2.2.1 After the pure elemental spectra are acquired and processed, irradiate the certified standard
samples. The standards should have matrices similar to the kinds of unknown samples expected for analysis.
They should also provide 2 to 3 or more elemental concentrations ranging over approximately 2 orders of
magnitude. For example, standards with percentage concentrations of elements such as zinc, copper, or iron
should be avoided if environmental samples are to be analyzed. Standard ore samples should be used if
unknown ore samples are primarily to be analyzed.

7.2.2.2 Create a standards file by using the analysis technique menu and the setup standards key. Enter
each standard with the corresponding certified elemental values in this file. Non-certified values should not
be used for standardization but may be entered into the file in parenthesis. For elemental concentrations
which are not known, no value should be entered.

7.2.2.3 Before the standard spectra are collected, change the analysis from "run unknowns" to
"standardize", and set the save on disk file number at an even hundreds number for each set of conditions
(i.e., Mid Z Analysis save on disk number is 200; High Z Analysis save on disk number is 300, etc.).

7.2.2.4 Irradiate the standards with the tube current and voltage adjusted so that the highest standard dead
time is approximately 50 percent for each analytical condition. These adjusted tube currents and voltages
must remain fixed for any subsequential unknown analysis.

7.2.2.5 Acquire and process the standards spectra by using the "Acquisition Parameter" and "Spectrum
Processing" menus in each Mid Z, High Z, and Silver Analysis Procedure Menu Pages. (See operators
manual for more detailed guidance.)

7.2.3 Fundamental parameters: After the standards have been irradiated under all 3 analytical conditions,
calculate the alpha coefficients from the fundamental parameters program. This is accomplished by entering
the "Combine" procedure through the setup function key. Set the "Analysis Techniques" menu conditions to
"standardize", "fundamental parameters", and save on disk file number 500. The Fundamental Parameters
program is initiated by hitting the F1 - "run" function key. Alpha coefficients should be calculated after
approximately 30 minutes.

7.3 Instrumental Analysis

7.3.1 Instrumental parameters: Table 2 summarizes current excitation conditions for the Mid Z, High Z,
and Silver Analyses. These conditions are approximate guidelines and may be changed in the future according
to analytical needs and certified standards used.

7.3.2 Unknown analysis: Analyze unknown samples by changing the "Analysis Techniques" menu
conditions in all of the procedures to "run unknowns" and "fundamental parameters" and the save on disk file
numbers to 250, 350, 450, and 550. The unknown analysis is initiated by hitting the F1 - "run" function key
from the "Combine" procedure.

7.4 Calculations: Contouring software (SURFER) is available which can generate concentration contours from
the XRF elemental data. Also available is the geostatistical technique called "kriging" that can be used to produce

FMC-I-001-5

-------
contour maps and concentration isopleths. This technique produces optimal estimation of nonsampled points or
blocks from known sample values. This program is also on the SURFER software package.

8.0 QUALITY CONTROL

8.1 Quality control criteria must be met for all analyses. This method should be used in conjunction with the
quality assurance and quality control (QA/QC) section of this catalog.

8.2 Energy Calibration: The instrument is energy calibrated with a pure copper standard at the beginning of
each shift and at least every five hours during the analysis. This calibration corrects the instrument for electronic
drift.

8.3 Initial and Continuing Calibration: NIST or CANMET certified standards are analyzed at the beginning
of each shift and at a 10 percent frequency rate to determine initial and continuing calibration of the instrument.
Percent differences (%D) are calculated by comparing the certified values to instrumental results. All elements for
associated samples for which %D is less than 80 percent or greater than 120 percent will be qualified as estimated
(J). If %D is less than 50 percent or greater than 150 percent for any element, the instrument is re-energy calibrated
and the standard and any associated samples are reanalyzed. If %D is still out of the control limits of 50 percent to
150 percent, the results for that element in associated samples are rejected and qualified "R". An exception to this
requirement exists for values below 30 ppm (2 times the QL).

%D = " true\ x 100%
true

FMC-I-001-6

-------
Table 2

EXAMPLE EXCITATION CONDITIONS

Procedure : Mid Z analysis Tube voltage : 16 kv
Filter used : Aluminum Tube current : 0.14 Ma

Atmosphere : Air Livetime : 200 sec

Analysis method: Fundamental parameters

Procedure : High Z analysis Tube voltage : 33 kv
Filter used : Five Tube current : 0.28 Ma

Atmosphere : Air Livetime : 200 sec

Analysis method: Fundamental parameters

Procedure : Silver analysis Tube voltage : 50 kv
Filter used : Six Tube current : 0.35 Ma

Atmosphere : Air Livetime : 200 sec

Analysis method: Fundamental parameters

Where,

kv = killivolts Aluminum = 0.127 mm thick aluminum filter
Ma = milliamperes Five = 0.127 mm thick rhodium filter
sec = seconds Six = 0.63 mm thick copper filter

8.4 Duplicate Analysis: Sample duplicates are analyzed at a 20 percent frequency rate or for each sample
group, whichever is more frequent. The samples are spilt for duplicate analysis during sample preparation. This
indicates the precision of the analysis as well as the homogeneity of the sample matrix. Relative percent differences
(%RPD) are calculated by comparing duplicate sample results. All elements for associated samples for which the
%RPD is greater than 35 percent will be estimated and qualified "J". An exception to this requirement exists for
values below 30 ppm (2 times the QL).

% RPD = X ~ Y x 100%

(X + Y) / 2

8.5 Confirmational Analysis: Sample splits shall be sent to other approved laboratories for confirmation of
analytical results at a recommended frequency of 20 percent. It is recommended that duplicate confirmation analyses
be as similar as possible (i.e. XRF vs. XRF rather than XRF vs. AA/ICP). If AA/ICAP analysis is performed as a
confirmation, a correlation between analytical results may be performed instead of a direct comparison.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-I-001-7

-------
CSL Method

INORGANICS/SOIL/ACID DIGESTION/AA-FLAME

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of soil. It is presented as a means to rapidly characterize
contamination from the site. This method is intended to analyze for inorganic compounds containing barium (Ba),
chromium (Cr), nickel (Ni), lead (Pb), and zinc (Zn). Other compounds may be added as data become available.

1.2 Application of this method is limited to the screening analysis of soil for this specific list of parameters.
The analytical data produced in the analyses allows the site investigation team to examine the relative degree of soil
contamination. Positive quantification of these specific parameters, and other inorganic priority pollutants, should
be supported by analyses of duplicate and other composited samples at a remote CLP laboratory employing EPA
approved testing protocols.

2.0 SUMMARY OF METHOD

2.1 This method is loosely based on EPA Method 3050, Acid Digestion of Sedimented Sludges and Soils,
followed by Method 7000, Atomic Absorption Methods, found in EPA SW-846, Test Methods for Evaluating Solid
Waste. 3rd ed., September 1986. A 1.0 g sample (wet weight) is digested in nitric acid (HN03) and hydrogen
peroxide (H^O^. The digestate is then digested for 60 minutes, filtered, and then brought to a 100-mL volume with
deionized water. The digestate is subsequently analyzed on an atomic absorption spectrophotometer using flame
aspiration techniques.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Sample Bottles: 8 oz. wide mouth pre-cleaned glass sample jars with Teflon lids.

4.2 Balance: Sartorius; top loading electronic with 1500 g capacity
with 0.01 g sensitivity.

4.3 Glassware: Class A volumetric pipets and flasks; beakers, vials, Pasteur pipets, and miscellaneous
glassware as necessary for the preparation and handling of samples and standards.

4.4 Griffin Beakers: 200-mL tall form with 100 mm watch glass for sample digestions.

4.5 Hot Plate: Variable temperature control.

4.6 Autoclave.

4.7 Strip Chart Recorder: Perkin Elmer Model RLOO-A; single pen.

4.8 Flame Atomic Absorption Spectrophotometer: Perkin Elmer Model 2380; digital gas controls,
background corrector, wavelength drive, and EDL power supply.

5.0 REAGENTS

FMC-I-002-1

-------
5.1 Solvents

5.1.1 Concentrated nitric acid. HNO:: Spectrograde.

5.1.2 Concentrated hydrochloric acid. HC1: Spectrograde.

5.1.3 Thirty percent hydrogen peroxide. H202: Spectrograde.

5.2 Stock Standards: Ba, Cr, Ni, Pb, Zn; purchased at 1,000 mg/L in water.

5.3 Working Standards: Prepared from stock standards by precise dilution with deionized water.

5.4 Gases

5.4.1 Acetylene. C2H2: Purity 99.6 percent.

5.4.2 Air: As supplied by compressor, filtered.

5.4.3 Nitrous oxide. N2Q: Prepurified grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.1 The target constituents are either identified as, or suspected of being, carcinogens. All
samples are assumed to be hazardous. All stock and working calibration standards, as well as all samples,
shall be handled with the utmost care using good laboratory techniques in order to avoid harmful exposure.

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all
times when preparing and handling standards and field and laboratory samples.

7.1.3 Prepare standards and samples in a fume hood.

7.1.4 Investigate any situation which leads to or causes noticeable odors or produces any physical
symptoms in the workers, and immediately follow with the appropriate corrective action.

7.1.5 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and a chemical
spill clean-up kit available for use at all times.

7.1.6 Separate and dispose of laboratory wastes properly. The wastes include: used sample
aliquots, initial wash water, chemical wastes generated in the analysis, and disposables used in the
preparation of the samples. Collect and deposit these wastes in a drum clearly marked as "CSL Lab Wastes
Only—Hazardous." Consider water used for final rinsing of glassware nonhazardous, and release it into a
50-gallon drum outside the laboratory trailer. Dispose of this waste in an appropriate manner along with
other investigation derived wastes from the site. Save unused portions of samples, and dispose of as directed
in the "STANDARD OPERATING PROCEDURES."

7.2 Digestion

FMC-I-002-2

-------
7.2.1 Weigh a measured quantity of soil, approximately 1 g, into a Griffin beaker with a watch
glass cover. Digest the sample by treatment with 10 mL of nitric acid and 5 mL of 30 percent hydrogen
peroxide, place on a hot plate, and cautiously heat to effect a gentle reflux action. Do not allow the sample
to evaporate to dryness; should this occur, discard the sample and reprepare. After 60 minutes of refluxing,
cool the beaker and add 10 mL of concentrated hydrochloric acid. Heat the sample on a hot plate until the
nitric acid fumes have dissipated and the sample is completely digested.

7.2.2 Cool the digestate to room temperature, transfer to a 100-mL volumetric flask, dilute to the
mark with deionized water, mix, and then filter through a Whatman 41 (or equivalent) filter paper.

7.2.3 Transfer the digestate to a disposable specimen container.

7.3 Calibration

7.3.1 Establish AA operating conditions including nebulizer, lamp, burner head, flame, and
analytical wave length to optimize absorbance for each target element.

7.3.2 Develop a working calibration curve from a reagent blank and a minimum of 3 concentration
levels within the normal linear range for the element. One of the standards shall be near the instrument
detection limit (IDL).

7.3.3 Autozeroing shall be performed both during the initial calibration, working calibrations, and
prior to each sample analysis.

7.3.4 Working calibration shall be established each time a lamp for an element is inserted or at the
start of each working day. Mid-range standards should be analyzed along with every lot of 10 samples. If
response varies by more than ±15 percent, the test shall be repeated with a fresh calibration standard, or a
new working calibration shall be performed using freshly prepared standards.

7.4 Instrumental Analysis

7.4.1 Analyze by atomic absorption using the parameters listed in Table 1.

7.4.2 Dilute the sample if required, such that the analysis is within the normal linear range for the

7.5 Calculations: Base quantitation of the target compounds on the peak height of the samples in
comparison to the peak height of the calibration standards for each analyte. The instrument reports the concentrations
in ng/mL in the extracts. Calculation of the concentration for each target constituent in the original sample, on a dry
basis, is as follows:

element.

Concentration (]ig/gm)

A x V, x DF

W x S

where: A

Amount of target constituent found in the digestate in (ig/mL (mg/L),

Final volume of digestate, mL,

Dilution factor, if required,

Weight of the sample added to the beaker, g, and

Fraction solids (percent solids/100)

v s

8.0 QUALITY CONTROL

FMC-I-002-3

-------
Advised quality control measures shall include as a minimum:

8.1	Daily mid-range calibration checks performed prior to the analysis of each lot of samples or with each
lot of 10 samples, whichever is more frequent.

8.2	Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1 per day, whichever is
more frequent. Should the results of the field blanks show contamination greater than that of the specified instrument
detection limit, the cause of the contamination should be investigated and corrective action taken.

8.3	Analysis of laboratory blank samples at a frequency of 1 in 20 samples analyzed or 1 per day, whichever
is more frequent. Should the results of the laboratory blanks show contamination greater than that of the specified
instrument detection limit, the cause of the contamination should be investigated and corrective action taken.

8.4	Analysis of field duplicate samples at a frequency of 1 in 10 samples or 1 per day, whichever is more

frequent.

8.5	Analysis of a mid-range matrix spike sample at a frequency of 1 in 10 samples analyzed or 1 per day,
whichever is more frequent.

FMC-I-002-4

-------
Table 1

AA SPECIFICATIONS FOR TARGET ANALYTES

Element

X (nm)

Slit

Flame

Flow

Flame Conditions





(nm)



(L/min)



Ba

553.6

0.4

C2H2

43

Rich, red







n7o

35



Cr

357.9

0.7

c2h2*

20

Rich, yellow







Air

45



Ni

232.0

0.2

C2H2*

20

Lean, blue







Air

45



Pb

283.3

0.7

C2H2*

20

Lean, blue







Air

45



Zn

213.9



C2H2*



Lean, blue







Air





If matrix interferences persist, a N20-C2H2 flame may be used to eliminate these interferences.

FMC-I-002-5

-------
CSL Method

HEXAVALENT CHROMIUM/SOIL/ALKALINE DIGESTION/SPECTROPHOTOMETER

1.0 SCOPE AND APPLICATION

1.1 This method is used to quantitatively determine the concentration of hexavalent chromium, Cr (VI), in
soil and sludge samples.

1.2 The method detection limit (MDL) for hexavalent chromium is estimated to be 5 mg/kg in the solid

sample.

2.0 SUMMARY OF METHOD

2.1 The method presented here is loosely based on EPA Method 3060, alkaline digestion, followed by EPA
Method 7196, colorimetric measurement, found in the EPA SW-846, Test Methods for Evaluating Solid Waste. 2nd,
ed., July 1982.

2.2 A 25 gram solid sample is extracted with a hot 3 percent sodium carbonate - 2 percent sodium hydroxide
solution to dissolve Cr (VI) and to protect it from reduction to trivalent chromium.

2.3 The digestate is subsequently filtered and diluted to 250 mL with deionized water. Cr (VI) is then
determined colorimetrically by reaction with

diphenylcarbazide in acid solution. A red-violet color of unknown composition is produced and it's absorbance is
measured photometrically at 540 nm.

3.0 INTERFERENCES

3.1 The chromium reaction with diphenylcarbazide is generally free from interferences except at relatively
low concentrations. Hexavalent molybdenum, mercury salts, and vanadium can cause interferences. Concentrations
up to 8,000 mg/kg for molybdenum and mercury, and for vanadium concentrations up to 10 times that of chromium,
can be tolerated.

3.2 Solid samples which have unusually high buffering capacity may require additional digestion solution
in order to achieve the correct digestion

conditions.

4.0 APPARATUS AND MATERIALS

4.1 Balance: Sartorius; top loading electronic with 1500 g capacity with
0.01 g sensitivity.

4.2 Griffin Beakers: 200-mL tall form with 100 mm watch glass for sample digestions.

4.3 Hot Plate Stirrer: Variable temperature and speed control.

4.4 Filtration Apparatus: High-pressure (75 psi) with high volume pre-filter and 0.45 (im final filter.

4.5 Spectrophotometer: Bausch and Lomb; with variable wave length and 1 cm path length.
5.0 REAGENTS

FMC-I-003-1

-------
5.1 Solvents

5.1.1 Deionized water: As provided by the laboratory purification system.

5.1.2 Nitric acid: Concentrated, spectrograde.

5.1.3 Sodium carbonate: Anhydrous, analytical reagent grade.

5.1.4 Sodium hydroxide: Analytical reagent grade.

5.1.5 Potassium dichromate: Analytical reagent grade.

5.1.6 Acetone: Spectrograde.

5.2 Miscellaneous Reagents

5.2.1 Sulfuric acid. 10 percent: Dilute 100 mL of spectrograde concentrated sulfuric acid to 1,000
mL with deionized water.

5.2.2 Diphenvlcarbazide solution: Dissolve 1.25 g 1,5-diphenyl-carabzide in 250 mL of acetone.
Store in a brown bottle, and discard it when the solution becomes discolored.

5.2.3 Digestion solution: In a 1,000-mL volumetric flask, dissolve 30.0 g sodium carbonate and
20.0 g sodium hydroxide in deionized water and dilute to the mark. Store in a plastic bottle and prepare fresh
monthly.

5.3 Potassium Dichromate Stock Solution: Dissolve 2.83 g of dried potassium dichromate (reagent grade)
in deionized water and dilute to 100 mL

(1 mL = 1.0 mg Cr).

5.4 Potassium Dichromate Standard Solution: Dilute 125 mL potassium dichromate stock solution to 1,000
mL with deionized water (1 mL = 125 (ig Cr).

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 To reduce the chemical activity of Cr (VI), the sample and digestate should be stored at 4°C until
analyzed.

6.2 Since the stability of Cr (VI) in soil and aqueous solutions is not fully understood, the samples should
be extracted and analyzed as soon as possible.

7.0 PROCEDURE

7.1 Safety

7.1.1 Laboratory coats, safety glasses, and surgical gloves shall be worn by laboratory analysts at
all times when preparing and handling standards and field and laboratory samples.

7.1.2 Prepare standards and samples in a fume hood.

7.1.3 Investigate any situation which leads to or causes noticeable odors or produces any physical
symptoms in the workers immediately, and follow with appropriate corrective action.

FMC-I-003-2

-------
7.1.4 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical
spill clean-up kit available for use at all times.

7.1.5 Separate and dispose of laboratory wastes properly. The wastes include: used sample
aliquots, initial wash water, chemical wastes generated in the analysis, and disposables used in the
preparation of the samples. Collect and deposit these wastes in a drum clearly marked as "CSL Lab Wastes
Only—Hazardous". Consider water used for final rinsing of glassware hazardous, and release it into a 50
gallon drum outside the laboratory trailer. Dispose of these wastes in accordance with the appropriate and
relevant disposal methods.

7.2 Digestion

7.2.1 Place 25 g of the solid sample into a 200-mL Griffin beaker.

7.2.2 Add 100 mL digestion solution. Cover the beaker with a watch glass, and heat on a hot plate
with constant mixing for 30 to 45 minutes. Do not allow to boil or to go to dryness.

7.2.3 Cool the solution and transfer it quantitatively to the filtration apparatus with deionized water
and filter. Quantitatively transfer the filtrate with deionized water to a 250-mL volumetric flask.

7.2.4 If the sample will not be immediately analyzed, refrigerate it at a high pH. Just prior to
analysis, place a magnetic stirring bar into the flask, and with constant stirring, add dropwise conc. nitric
acid. Bring the pH of the solution to between 7 and 8.

NOTE: Carbon dioxide will be evolved.

7.2.5 Remove the stirring bar, and dilute the contents of the flask to the mark with deionized water.

7.3 Preparation of Calibration Curve

7.3.1 To compensate for possible losses of chromium during digestion and color development, treat
the chromium standards by the same procedures as the samples. Pipet 1 mL and 10 mL each of the Cr (VI)
standard and 5 mL and 12.5 mL of the Cr (VI) stock solution into 200-mL Griffin beakers. Digest these
standards according to Section 7.2, and develop the color as in Section 7.4.

7.3.2 Read the absorbance of each standard at 540 nm and in a 1 cm cell. Construct a calibration
curve by plotting absorbance values of the standards against concentration (ng/mL Cr VI).

7.4 Color Development and Measurement: Transfer 95 mL of the extract to be tested to a 100-mL
volumetric flask. Add 2 mL diphenlycarbazide solution and mix. Add 10 percent sulfuric acid solution to give a pH
of 2 ± 0.5, dilute to 100 mL with deionized water, and let stand 5 to 10 minutes for full color development. Read
absorbance of the solution at 540 nm in a 1 cm cell. Use a reagent blank that has been carried through both the diges-
tion and color development methods to zero the spectrophotometer.

NOTE: If the solution is turbid after dilution to 100 mL, take an absorbance reading before adding the
diphenylcarbazide reagent, and correct the absorbance reading of the final colored solution by
subtracting the absorbance measured before the diphenylcarbazide was added.

7.5 Calculations: Determine the concentration of hexavalent chromium in the digestate directly from the
calibration curve. If the concentration of the digestate exceeds 50 percent of the maximum calibration value, then
dilute the digestate and reanalyze the sample. Once a satisfactory concentration has been determined for the digestate,
calculate the concentration of Cr (VI) in the sample on a dry basis as follows:

FMC-I-003-3

-------
Concentration (mg/kg)

C x v, x DF x 1000

W x S

where: C

Amount found in the digestate in (ig/mL,
Final volume of digestate, mL,

Dilution factor, if required,

Weight of the sample, g, and
Fraction solids (percent solids/100)

v s

8.0 QUALITY CONTROL

Quality control measures shall include as a minimum:

8.1 To verify that neither a reducing and/or an oxidizing condition exists in the sample matrix and that
chemical interferences are at a minimum, double spikes and duplicates will be run on at least 3 soil samples from the
site prior to analyzing actual field samples. If the recoveries of these spikes are within the specified limits, then the
following Quality Assurance (QA) Protocol will be followed. If the spike recoveries are not acceptable, double spikes
as frequent as 1 in 3 or 1 in 1 will be required. A decision concerning spiking frequencies will be made pending
review of the initial spike studies.

8.2 One sample from each batch of ten (10), or one each day, will be selected as a check sample.

8.3 The following spikes and duplicates will be run on individual aliquots of each check sample:

8.4 If the recoveries and relative percent differences are out of the limits specified in, the quality of the data
is suspect and the use of this data should be discussed with the project manager and the regional manager.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

8.3.1 One duplicate analysis.

8.3.2 One Cr (VI) spike at twice the concentration of that found in the sample.

8.3.3 One Cr (III) spike equal to the action level for that of

Cr (VI).

FMC-I-003-4

-------
CSL Method

INORGANICS/WATER/ACID DIGESTION/AA-FLAME

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of water. It is presented as a means to rapidly characterize
contamination from the site. This method is intended to analyze for inorganic compounds containing calcium (Ca),
magnesium (Mg), potassium (K), and sodium (Na). Other compounds may be added as data become available.

1.2 Application of this method is limited to the screening analysis of water for this specific list of
parameters. The analytical data produced in the analyses allows the site investigation team to examine the relative
degree of water contamination. Positive quantification of these specific parameters, and other inorganic priority
pollutants, should be supported by analyses of duplicate and other composited samples at a remote CLP laboratory
employing EPA approved testing protocols.

2.0 SUMMARY OF METHOD

2.1 The method presented here is loosely based on EPA Method 200.0, Acid Digestion of Water and Wastes
found in EPA-600 Methods For Chemical Analysis of Water and Wastes. March 1983. A 100-mL sample is digested
in nitric acid (HN03) and hydrogen peroxide (IJ Q ). The digestate is then brought to a 100-mL volume with
deionized water and filtered. The digestate is subsequently analyzed on an atomic absorption spectrophotometer (AA)
using flame aspiration techniques.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Cubitainers: 1-L.

4.2 Balance: Sartorius; top loading electronic with 1500 g capacity
with 0.01 g sensitivity.

4.3 Glassware: Class A volumetric pipets and flasks; beakers, vials, Pasteur pipets, and miscellaneous
glassware as necessary for the preparation and handling of samples and standards.

4.4 Griffin Beakers: 200-mL tall form with 100 mm watch glass for sample digestions.

4.5 Hot Plate: Variable temperature control.

4.6 Strip Chart Recorder: Perkin Elmer Model RIOO-A; single pen.

4.7 Flame Atomic Absorption Spectrophotometer: Perkin Elmer Model 2380; digital gas controls,
background corrector, wavelength drive, and EDL power supply.

5.0 REAGENTS

5.1 Solvents

FMC-I-004-1

-------
5.1.1 Concentrated nitric acid. HNO:: Spectrograde.

5.1.2 Concentrated hydrochloric acid. HC1: Spectrograde.

5.1.3 Thirty percent hydrogen peroxide. H202: Spectrograde.

5.2 Stock Standards: Ca, Mg, K, Na; purchased at 1,000 mg/L in water.

5.3 Working Standards: Prepared from stock standards by precise dilution with deionized water.

5.4 Gases

5.4.1 Acetylene. C2H2: Purity 99.6 percent.

5.4.2 Air: As supplied by compressor, filtered.

5.4.3 Nitrous oxide. N2Q: Prepurified grade.

5.4.4 Hydrogen: Prepurified.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.1 All samples are assumed to be hazardous. All stock and working calibration standards, as
well as all samples, shall be handled with the utmost care using good laboratory techniques in order to avoid
harmful exposure.

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves at all
times when preparing and handling standards and field and laboratory samples.

7.1.3 Prepare standards and samples in a fume hood.

7.1.4 Investigate any situation which leads to or causes noticeable odors or produces any physical
symptoms in the workers and immediately follow with appropriate corrective action.

7.1.5 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and a chemical
spill clean-up kit available for use at all times.

7.1.6 Separate and dispose of laboratory wastes properly. The wastes include: used sample
aliquots, initial wash water, chemical wastes generated in the analysis, and disposables used in the
preparation of the samples. Collect and deposit these wastes in a drum clearly marked as "CSL Lab Wastes
Only—Hazardous." Consider water used for final rinsing of glassware nonhazardous and dispose of it in an
appropriate manner along with other investigation derived wastes from the site. Save unused portions of
samples, and dispose of them as directed in the "STANDARD OPERATING PROCEDURES."

7.2 Digestion

FMC-I-004-2

-------
7.2.1 Measure 100 mL of water out into a Griffin beaker with a watch glass cover. Digest the
sample by treatment with 2 mL of nitric acid and 5 mL of 30 percent hydrogen peroxide, and place on a hot
plate for 2 hours. Add 5 mL of concentrated hydrochloric acid. Heat the sample on a hot plate until the
nitric acid fumes have dissipated and the sample is completely digested.

7.2.2 Cool the digestate to room temperature, transfer to a 100-mL volumetric flask, dilute to the
mark with deionized water, mix, and then filter through a Whatman 41 (or equivalent) filter paper.

7.2.3 Transfer the digestate to a disposable specimen container.

7.3 Calibration

7.3.1 Establish AA operating conditions including nebulizer, lamp, burner head, flame, and
analytical wave length to optimize absorbance for each target element.

7.3.3 Establish a working calibration curve each time a lamp for an element is inserted or at the
start of each working day. Analyze mid-range standards along with every lot of 10 samples. If response
varies by more than ±15 percent, repeat the test with a fresh calibration standard, or perform a new working
calibration using freshly prepared standards.

7.4 Sample Analysis

7.4.1 Analyze the sample by atomic absorption using the parameters listed in Table 1.

7.4.2 Dilute the sample if required, such that the analysis is within the normal linear range for the

element.

7.5 Calculations: Quantification of the target compounds is based on the peak height of the samples in
comparison to the peak height of the calibration standards for each analyte. The instrument reports the concentrations
in ng/mL in the extracts. Calculation of the concentration for each target constituent in the original sample, on a dry
basis, is as follows:

Concentration (]ig/mL) = A x Vd x DF

where: A = Amount of target constituent found in the digestate in ng/mL (mg/L),

Vd = Final volume of digestate, mL, and

DF = Dilution factor, if required.

8.0 QUALITY CONTROL

Quality control measures shall include as a minimum:

8.1 Daily mid-range calibration checks performed prior to the analysis of each lot of samples or with each
lot of 10 samples, whichever is more frequent.

8.2 Analysis of field blank samples at a frequency of 1 in 20 samples analyzed or 1 per day, whichever is
more frequent. Should the results of the field blanks show contamination greater than that of the specified instrument
detection limit, the cause of the contamination should be investigated and corrective action taken.

FMC-I-004-3

-------
8.3	Analysis of laboratory blank samples at a frequency of 1 in 20 samples analyzed or 1 per day, whichever
is more frequent. Should the results of the laboratory blanks show contamination greater than that of the specified
instrument detection limit, the cause of the contamination should be investigated and corrective action taken.

8.4	Analysis of field duplicate samples at a frequency of 1 in 10 samples, or 1 per day, whichever is more

frequent.

8.5	Analysis of a mid-range matrix spike sample at a frequency of 1 in 10 samples analyzed or 1 per day,
whichever is more frequent.

FMC-I-004-4

-------
Table 1

AA SPECIFICATIONS FOR TARGET ANALYTES

Element

X (nm)

Slit

Flame

Flow
(L/min)

Head

Comments

Ca

422.7

0.7

C2H2
Arr N20-C2H2

20
45

Nitrous
Oxide

Add 20' lanthanum
chloride to sample
standard and blank

Mg

285.2

1.4

c2h2

Arr N20-C2H2

20
45

Nitrous
Oxide

Add 20' lanthanum
chloride to sample
standard and blank

K

766.5

0.2

h2

Air

50
35

Nitrous
Oxide

Use the red filler and
EM-chop

Na

589.0

0.4

h2

Air

50
35

Nitrous
Oxide

Use EM-chop

9.0 METHOD PERFORMANCE
Information not available.
10.0 REFERENCES

Information not available.

FMC-I-004-5

-------
FASP Method F93004
MERCURY ANALYSIS OF MERCURY BY

COLD VAPOR ATOMIC ABSORPTION SPECTROSCOPY

1.0 SCOPE AND APPLICATION

1.1 This method covers the determination of mercury in water and soil by the cold vapor atomic absorption
technique adapted for use by the Field Analytical Services Program (FASP) mobile laboratory. This FASP method
is intended to provide rapid turnaround analyses in the field. FASP data are not considered to be a substitute for
analyses performed within the Contract Laboratory Program. FASP data are not intended to be legally defensible.
This method is appropriate for analysis of mercury only.

2.0 SUMMARY OF METHOD

2.1 Samples of both soil and water are prepared by an oxidative digestion to produce divalent mercury ions
which are reduced to elemental mercury by the addition of a reducing agent. The volatile elemental mercury is purged
from solution and detected in the vapor phase by absorbance at the 253.7 nm wavelength by using cold vapor atomic
absorption spectroscopy.

3.0 INTEREFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Atomic Absorption Spectrometer Equipped for Cold Vapor Operation.

4.2 Integrating Recorder or Data System.

4.3 Purging Vessels: 500-mL aspirator bottles, gas washing bottle, or other glassware which is suitable for
sample purging and introduction of reagents.

5.0 REAGENTS

All reagents must be certified for mercury analysis.

5.1 Concentrated Nitric and Sulfuric Acids: Ultrex or equivalent.

5.2 Dilute Sulfuric Acid. 0.5 N: 14 mL to 1 L water.

5.3 Stannous Chloride or Stannous Sulfate. 10% w/v in 0.5N Sulfuric Acid.

5.4 Hvdroxvlamine Hydrochloride. 12 % w/v.

5.5 Potassium Permanganate. 5% w/v.

5.6 Potassium Persulfate. 5% w/v.

5.7 Mercury Stock Standards: Purchased as 1000 ppm solutions.

5.8 Mercury Calibration Standards: Prepared by dilution of the mercury stock solutions with reagent water.

FMC-I-005-1

-------
5.9 Second Source Standards: Prepraed from mercuric acetate and used to prepare initial calibration
verification (ICV) standards and continuing calibration verification standards (CCVs).

5.10 Laboratory Control Samples: Prepared from SRM 8407 for soil analyses.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Daily Analytical Sequence

7.1.1 Instrument Blank.

7.1.2 STDA (At reporting limit).

7.1.3 STDB.

7.1.4 STDC.

7.1.5 STDD.

7.1.6 CCB (preparation blank).

7.1.7 SSS (soil or water).

7.1.8 Samples 1-10.

7.1.9 CCV (continuing calibration standard equal to STDC).

7.1.10 CCB (preparation blank).

7.1.11 Repeat with 8-10, i.e. sample 11-20, etc..

7.1.12 Sequence must end with a CCV and CCB.

7.2 The analytical procedure for waters is outlined in the flow chart in Figure 1.

7.3 The preparation procedure for soil uses microwave digestion. A 1-g soil sample is placed in the
digestion vessel and 5 mL of 5% potassium permanganate, 5 mL 5% potassium persulfate, and 10 mL concentrated
nitric acid.The power setting is dependent on the number of vessels in the microwave cavity. The power settings by
number of digestion vessels are as follows:

Number of Samples Power Setting Time (minutes')

12 100% 20

6 80% 20

3 80% 10

7.4 Each preparation batch of soil samples will consist of no more than 10 field samples and two QC
samples, a preparation blank prepared from clean sand and a SSS prepared from NIST SRM 8407.

FMC-I-005-2

-------
7.5 The analytical procedure for soils is outlined in the flow chart in Figure 2.

7.6 Calibration

7.6.1 For both soil and water, a blank and four point calibration curve which covers th instrument
linear range is prepared by analysis of spiked reagent water in a manner identical to samples on a daily basis.

7.6.2 An initial calibration check sample is prepared from a second source standard and is analyzed
each day following the initial calibration.

7.6.3 A continuing calibration check sample is prepared at the midpoint concentration and is run
after analysis of each 10 samples.

8.0 QUALITY CONTROL

8.1 Quality Control Guidelines

Quality Control Sample

Accuracy
Criteria

Precision
Criteria

Frequency

Other
Criteria

Blank

Daily

Mercury
<0.2 ppb

Initial Calibration

Daily

r>=0.995

Second Source Standard
(Percent Recovery)

80%-120%

Daily

Continuing Calibration Check (Percent
Difference)

80%-120%

1 per 10

Duplicate

(Relative Percent Difference)

Soils,RPD
±35%

Waters,RPD
+20%

1 per 20

8.2 Corrective Action: No sample analyses will be performed if blank contamination is present, the initial
calibration does not meet the 0.995, criteria or other unacceptable system performance problems are encountered, until
corrective action is performed.

8.3 Quantitation: The equation of a linear regression line is calculated by using the mercury response at four
standard concentration levels and the instrument blank. This equation is used to equate the mercury response in
samples to a concentration. The same procedure is used for all field and QC samples. Soil results will be reported
on a dry weight basis.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. EPA Method 245.1 CLP-M, EPA Contract Laboratory Program Statement of Work for Inorganic Analyses

FMC-I-005-3

-------
2.	EPA Method 7470, Mercury in Liquid Waste (Cold Vapor Technique) and EPA Method 7471, Mercury in Solid
or Semisolid Waste (Cold Vapor Technique), Test Methods for Evaluating Solid Wastes, SW-846, 3rd Edition.

3.	EPA Method 3015, Microwave Assisted Acid Digestion of Aqueous Samples and Extracts, Test Methods for
Evaluating Solid Wastes, SW-846, 1st Update.

4.	EPA Method 3051, Microwave Assisted Acid Digestion of Sediments, Sludges, Soils, and Oils, Test Methods for
Evaluating Solid Wastes, SW-846, 1st Update.

FMC-I-005-4

-------
ESAT Region 10 Method
FASP MERCURY COLD VAPOR ATOMIC ABSORPTION ANALYSIS

1.0 SCOPE AND APPLICATIONS

1.1 This SOP describes the Cold Vapor Atomic Absorption (C VAA) method used to determine the mercury
content of environmental samples. Specific details refer to the operation of the Perkin-Elmer 403 Atomic Absorption
Spectrophotometer.

1.2 It is strongly recommended that 10% of the samples submitted for analysis by this method be split and
submitted for confirmational analysis using an EPA regulated method. Confirmational anlyses are recommended for
Level II field analysis per Data Quality Objectives for Remedial Response Activities (EPA/540/G-90/004). Any
site specific information pertaining to the requested analysis would greatly enhance the support capabilities of the
FASP Team, i.e. action levels, known interferences, etc.

2.0 SUMMARY OF METHOD

2.1 This flameless AA procedure is a modification of that commonly used (USEPA SW-846 Methods 7470
and 7471) to quantify the acid-leachable mercury content of environmental samples. It has been adapted especially
for use as a field analytical technique.

2.2 Elemental mercury exhibits a strong atomic resonance transition in the ultraviolet spectral region at
253.7 nm. Absorption of radiation of this wavelength can be used to determine the amount of mercury present in a
given sample.

2.3 First, any organic or inorganic mercurial compounds must be reacted to convert the mercury present into
free Hg(II). To achieve this, the sample matrix is subjected to attack by a combination of concentrated nitric and
hydrochloric acids. The efficiency of this procedure is increased through microwave heating in sealed vessels.

2.4 Subsequent addition of stannous chloride results in the reduction of Hg(II) to Hg(0) by Sn(II). The
solution is then aerated and the mercury-enriched vapor stream passed through a quartz-windowed absorption cell
positioned in the light path of the atomic absorption spectrophotometer. The absorbance is measured and compared
to the absorbances of a set of calibration standards. Conversion of absorbance readings from the samples into
concentration values with the appropriate units is then accomplished using linear least squares data reduction.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Atomic Absorption Spectrophotometer

4.1.1 Any AA instrument having an appropriate sample presentation area in which an absorption

cell can be mounted. (Instrument settings described below).

4.2 Mercury Hollow Cathode Lamp: Westinghouse WL-22847, argon filled, or equivalent.

4.3 Strip Chart Recorder: Multi-range variable speed recorder electronically compatible with the
spectrometer's analog output port.

FMC-I-006-1

-------
4.4 Absorption Cell: Standard, spectrophotometry, 10-15cm in length, 2.5cm outside diameter, fitted with
SI grade quartz windows, having gas inlet and outlet ports 6mm OD not more than 2cm from the ends of the cell.

4.4.1 The cell is mounted on the burner head both for support and positioning ability.

4.4.2 The cell is aligned in the light path with the appropriate adjustments made to maximize light
transmittance.

4.5 Low-pressure Gas Regulator.

4.6 Flowmeter: Gas, capable of measuring up to 1 L/min flow rate.

4.7 Aeration Tubing.Tvgon: Mercury-free.

4.8 Drying Tube: "Perma-Pure®"

4.8.1 Sheath flow rate to be 1.5-2X that of the sample delivery flow.

4.9 Mercury Vapor Trap, either

4.9.1 Equal volumes of 0.1M KMn04 and 10% H2S04.

4.9.2 0.25% I2 in 3% aqueous KI .

4.10 Microwave Oven: MDS-81 or equivalent, with turntable

4.11 Digestion Vessels: Microwave 120 mL capacity, with pressure relief valve

4.12 Capping Station: Microwave vessel, for use with 4.11

4.13 Polyethylene Bottles: 250 mL, narrow-mouth, with Caps.

5.0 REAGENTS

5.1 Concentrated Nitric Acid: 6M, Reagent grade.

5.2 Concentrated Hydrochloric Acid: 12M. Reagent grade.

5.3 Stannous Chloride Dihvdrate fSnCl2-2H2Q').

5.3.1 In a capped, 1L polyethylene bottle carefully dissolve 40g of stannous chloride dihydrate in
lOOmL of concentrated (12M) hydrochloric acid. After the SnCl2 has dissolved, dilute to a final volume of
1L with type II deionized water. Store this solution for only short periods as it degrades upon exposure to
air.

5.4 Argon Gas: Standard cylinder

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 All water samples should be acidified with nitric acid to a pH of less than two. Sludges, sediments and
soils do not require drying before analysis; determination of percent solids may be required, however.

FMC-I-006-2

-------
6.2 Unless they are to be analyzed soon after collection, samples should be stored at 4°C. Samples must be
at ambient temperature prior to digestion or analysis.

7.0 PROCEDURE

7.1 Safety

7.1.1 The toxicity or carcinogenicity of each reagent used in this method has not been precisely
defined; however, each chemical compound must be treated as a potential health hazard. Exposure to these
chemicals must be maintained at the lowest possible level.

7.1.2 The analysts should be familiar with the location and proper use of the fume hood, eye
washes, safety showers and fire extinguishers. In addition, the analysts must wear protective clothing, acid-
resistant gloves and goggles or safety glasses at all times. For work with larger volumes of concentrated
acids, a laboratory apron and full-face shield should be worn. Contact lenses must not be worn while working
in the laboratory.

7.1.3 Laboratory work may be performed only when at least one other chemist is in the area.

7.1.4 Waste should be diposed of by placing it in designated collection containers. All containers
should be labelled with the start date, end date and type of waste.

7.2 Standard and Spike Preparation

7.2.1 Matrix spikes and duplicate matrix spikes are prepared at the rate of one pair for each 20
samples. Spikes are prepared by adding lmL of a 0.1 ug/mL stock solution to a lOOmL aliquot of sample.
The resulting spike concentration is then 0.1 ug Hg per lOOmL of sample (ie. lppb). Spike recovery is
calculated using the formula

apparent concentration-sample concentration

% recovery = £- x 100

final spike concentration

7.2.2 A series of six calibration standards, two reagent blanks, two quality control (QC) reference
sediments (for soils) and two QC reference waters (for soils and waters) are needed each time the analysis
is performed. Also, for each ten samples an additional reagent blank and QC reference water sample is to
be analyzed. The proper order of analysis is as follows:

7.2.2.1 Calibration.

7.2.2.2 Blank.

7.2.2.3 Water QC reference.

7.2.2.4 Soil QC reference (if required).

7.2.2.5 (ten samples).

7.2.2.6 Water QC reference.

7.2.2.7 (more samples).

7.2.2.8 Blank.

FMC-I-006-3

-------
7.2.2.9 Water QC reference.

7.2.2.10 Soil reference (if required).

7.3 Preparation of Standards

7.3.1 Transfer 0.2, 0.5, 1, 2, 3 and 4 mL of the 0.1 fxg Hg/mL stock solution to a series of digestion
containers. Add enough type II deionized water to each container to bring the final volume to 100 mL.
Prepare the standards and the procedural blanks (which are considered samples in the analysis) following
the procedure for water samples.

7.4 Preparation of OC Reference Standards

7.4.1 Prepare the sediment QC reference (if required), in duplicate, by accurately weighing 0.20
grams of NIST SRM 2704, 1646 or similar reference material into the digestion container. Prepare the QC
reference sediment following the digestion procedure for sediment samples. This QC reference materials
should contain 1.44 and 0.063 fxg Hg/g, respectively.

7.4.2 Prepare the water QC reference, where the number of required replicates are determined by
the total number of samples, by accurately weighing 2.0 mL of a 1:10 dilution of NIST 1641b into the
digestion container. Prepare the QC reference water following the digestion procedure for water samples.
This reference should contain 3.04 /ig Hg/mL.

7.5 Instrument Set-up

7.5.1 Turn-on the main power of the Perkin-Elmer 403. Using the knurled knob on the base of the
lamp holder and observing the meter behing the lamp, adjust the lamp current to the value recommended on
the lamp base (usually about 6mA). Allow the instrument to warm up for one hour or more.

7.5.2 Using the GAIN control, increase the PMT voltage until the needle on the energy meter (front
panel) is in the center of the dark red band. This adjustment will creep with time, requiring periodic
readjustment.

7.5.3 Adjust the sample cell position in the light path for maximum transmittance. With the
instrument operating in ABSORBANCE mode, the optimal cell position will correspond to a minimum
absorbance reading (as indicated by the Nixie tube display).

7.5.4 Check the control settings on the instrument. They should be set as follows:

POWER
FILTER

out

off

EMISSION CHOPPER

SLIT

RANGE

WAVELENGTH

(as set)
uv

253.7

(adjust slightly for max. energy)

OFF LINE
ABSORBANCE
10 AVERAGE
RECORDER FULL SCALE
RECORDER RESPONSE

0.5A
2 or 3

FMC-I-006-4

-------
7.5.5 At this point, it may be necessary to adjust the input voltage level which corresponds to full-
scale deflection ofthe chart recorder. Do this by analyzing a 4 ppb Hg solution with the chart gain set at 1
mV. Adjust the ATTENUATE control such that the pen deflection is 80% of the chart width. It may be
easier to note the (arbitrary) absorbance value of the 4ppb solution on the digitube readout, then use a card
to block the light path unti 1 a similar reading is obtained. The controls on the recorder can then be adjusted.

7.5.5.1 Note that adjusting the attenuation will cause the baseline position to shift. The

'zero' and 'attenuate' controls will have to be "walked" together in order to achieve the proper zero

level and full-scale pen deflection. Once set, this adjustment probably won't change much.

7.6 Digestion and Analysis of Samples

It is very important that the temperature of the reagents, standards and samples are all between 20-
25°C. Often the temperature inside the mobile unit is outside of this range. Use the appropriate
environmental control to bring the ambient temperature to within this range.

7.6.1 Transfer the sample to a digestion vessel.

7.6.1.1 For soils, use 0.5g.

7.6.1.2 For waters, use 50mL.

7.6.2 Add the appropriate amount of reagents.

7.6.2.1 For soils, add lOmL type II deionized water, 6mL of HCL and 2mL of HN03.

7.6.2.2 For waters, add 6mL of HCL and 2mL of HN03.

7.6.3 Place a safety valve and cap on the vessel and place the vessel in the capping station.

7.6.4 Tighten cap.

7.6.5 Place vessel in turntable and attach venting tube.

7.6.6 Repeat steps 7.6.1 - 7.6.5 until the turntable contains 12 vessels.

7.6.7 Turn the MDS-81D exhaust on to the maximum fan speed.

7.6.8 Activate the turntable so that it rotates.

7.6.9 For both waters and soils, program the instrument time as follows:

PROGRAM 1: 1 minute @ 30% power

PROGRAM 2: 4 minutes @ 80% power

PROGRAM 3: 10 minutes @ 100% power

7.6.10 Press START and allow the sample mixtures to heat.

7.6.11 Allow the sample solutions to cool to room temperature and manually vent each vessel.

7.6.12 Quantitatively transfer the solutions (filter if necessary) to preweighed 250mL poly bottles
and bring the total volume up to 100.OmL.

FMC-I-006-5

-------
7.6.13 Purge the headspace of the poly bottle and attach the poly bottle to the aeration apparatus.

7.6.14 Add 5mL of the stannous chloride solution to the separatory funnel.

7.6.15 Open the valve of the funnel and using a bulb, force the SnCl2 solution into the poly bottle.
Close the valve.

7.6.16 Open the argon valve to aerate the sample and to force the mercury vapor into the
absorbance cell.

7.6.17 After the absorbance reading reaches a maximum close the nitrogen valve and record this

value.

7.6.18 Purge the system of any remaining mercury vapor by attaching an empty bottle and allowing
argon to flow until the absorbance reading returns to zero.

7.7 Interpretation of Data

The data can be analyzed using either standard linear regression analysis provided with commercial
or scientific applications package or worked up manually. For instructions regarding regression, please see
the application's reference manual. A description of the manual method follows.

7.7.1 Determine the blank's absorption value in either absorbance units or millimeters, as measured
from the chart trace.

7.7.2 Calculate the conversion factor (CF):

concentration of standard

Conversion Factor {CF)

sample value-blank value

EXAMPLE: Calculate the conversion factor for the 0.2ppb standard with an absorbance of 500 units and
a blank absorbance of 68 units.

CF = 0 .

500-68
= 0. 00046

7.7.3 Calculate the conversion factors for each standard and determine the average. This average
CF value is used when calculating the mercury content of the samples.

7.7.4 Calculate the mercury content in water samples:

lag Hg/L = [ { sample-blank) x CF] x 10

EXAMPLE: Sample #1 had an absorbance of 1219 units, a blank absorbance of 68 units, and a CD of
0.00044. Calculate the mercury content of sample #1.

7.7.5 Calculate the mercury content in sediment samples:

EXAMPLE: Sample #2 had an absorbance of 1240 units, a blank absorbance of 68 units, and a conversion
factor of 0.00044. Calculate the mercury concentration in sample #2.

FMC-I-006-6

-------
lag Hg/g =[( 1240 -68 ) *0 . 00044 ] *1
= 0.52 ]ag Hg/ g

7.7.6 Calculate the spike recovery of a sample, when using a 0.1 ug Hg/lOOmL spike.

EXAMPLE: Sample #3 had an absorbance of 85 units. Sample #4 was a replicate of sample #3 which was
spiked to a level of lppb. Sample #4 had an absorbance of 300 units. The blank absorbance was 68 units and
the conversion factor was 0.00044. Calculate the spike recovery for sample #4.

>recovery =

( (300-68) - (85-68) ) *0.00044

0.1

*100

= 95i

7.8 Calculating Detection Limits

7.8.1 Mercury detection limits should be determined by analyzing ten replicates of a 0.01 ug
Hg/lOOmL solution. These standards are taken through the entire digestion process. The detection is based
upon a volume of lOOmL. Lower detection limits can be achieved by using a larger volume (effectively
diluting the solution). The detection limit is calculated by multiplying the standard deviation on the ten
standards by 2.82. This is the "student's t" value at the 99% confidence level for 10 replicates.

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

Information not available.

FMC-I-006-7

-------
CSL Method

ALKALINITY

1.0 SCOPE AND APPLICATION

1.1 This method is applicable to drinking, surface, and saline waters, domestic and industrial wastes.

1.2 The method is suitable for all concentration ranges of alkalinity; however, appropriate aliquots should
be used to avoid a titration volume greater than 50 mL.

1.3 Automated titrimetric analysis is equivalent.

2.0 SUMMARY OF METHOD

2.1 An unaltered sample is titrated to an electrometrically determined end point of pH 4.5. The sample must
not be filtered, diluted, concentrated, or altered in any was.

3.0 INTERFERNCES

3.1 Substances, such as salts of weak organic and inorganic acids present in large amounts, may cause
interference in the electrometric pH measurements.

3.2 For sample having high concentrations of mineral acids, such as mine wastes and associated receiving
waters, titrate to an electrometric endpoint of pH 3.9, using the procedure in Annual Book of ASTM Standards. Part
31. "Water", p 115. D-1067. Method D. CI9761.

3.3 Oil and grease, by coating the pH electrode, may also interfere, causing sluggish response.
4.0 APPARATUS AND MATERIALS

4.1 Electometric Titrator: pH meter or electrically operated titrator that uses a glass electrode and can be
read to 0.05 pH units. Standardize and calibrate according to manufacturer's instructions. If automatic temperature
compensation is not provided, titrate at 25 ± 2°C.

4.2 Titration Vessel: Use an appropriate sized vessel to keep the air space above the solution at a minimum.
Use a rubber stopper fitted with holes for the glass electrode, reference electrode (or combination electrode) and buret.

4.3 Magnetic Stirrer.

4.4 Pipets: Volumetric.

4.5 Flasks: Volumetric 100-, 200-, 1000-mL.

4.6 Burets: Pyrex 50, 25 and 10-mL.

5.0 REAGENTS

FMC-C-001-1

-------
5.1	Sodium Carbonate Solution, approximately 0.05 N: Place 2.5 ± 0.2 g (to nearest mg) Na2C03 (dried at
250°C for 4 hours and cooled in desiccator) into a 2 L volumetric flask and dilute to the mark with deionized distilled
water.

5.2	Standard Acid (sulfuric or hydrochloric'). 0.1 N: Dilute 3.0 mL cone H2S04 or 8.3 mL cone HCL to 1
L with deionized distilled water. Standardize versus 40.0 mL of 0.05 N Na2C03 solution with about 60 mL deionized
distilled water by titrating potentiometrically to pH of about 5. Lift electrode and rinse into beaker. Boil solution
gently for 3-5 minutes under a watch glass cover. Cool to room temperature. Rinse cover glass into beaker. Continue
titration to the pH inflection point. Calculate normality using:

53.00 x c

where: A =	g Na2C03 weighed into 1 L;

B = mL Na2C03 solution; and
C	=	mL acid used to inflection point.

5.3 Standard Acid (sulfuric or hydrochloric'). 0.02 N: Dilute 200.0 mL of 0.1000 N standard acid to 1 L with
deionized distilled water. Standardize by potentiometric titration of 15.0 mL and 0.05 N Na2C03 solution as above.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 The sample should be refrigerated at 4°C and run as soon as practical. Do not open sample bottle before

analysis.

7.0 PROCEDURE

7.1	Sample Size

7.1.1	Use a sufficiently large volume of titrant (>20 mL in a 50 mL buret) to obtain good precision
while keeping volume low enough to permit sharp end point.

7.1.2	For <1000 mg CaC03/L use 0.02 N titrant.

7.1.3	For>1000 mg CaC03/L use 0.1 N titrant.

7.1.4	A preliminary titration is helpful.

7.2	Potentiometric Titration

7.2.1	Place sample in flask by pipetting with pipet tip near bottom of flask.

7.2.2	Measure of pH of sample.

7.2.3	Add standard acid (5.2 or 5.3), being careful to stir thoroughly but gently to allow needle to
obtain equilibrium.

7.2.4	Titrate to pH 4.5. Record volume of titrant.

7.3	Potentiometric Titration of Low Alkalinity

7.3.1 For alkalinity of <20 mg/L titrate 100-200 mL as above (7.2) using a 10 mL microburet and
0.02N acid solution (5.3).

FMC-C-001-2

-------
7.3.2 Stop titration at pH in range of 4.3-4.7, record volume and exact pH. Very carefully add
titrant to lower pH exactly 0.3 pH units and record volume.

7.4 Calculations

7.4.1 Potentiometric titration to pH 4.5:

Alkalinity, mg/L CaC03 = A x N x 50.000

mL of sample

where: A	=	mL standard acid; and

N =	Normality standard acid.

7.4.2 Potentiometric titration of low alkalinity:

Total alkalinity, mg/L CaC03 = f2B -C)xNx 50.000

mL of sample

where: B	=	mL titrant to first recorded pH;

C	=	Total mL titrant to reach pH 0.3 unites lower; and

N =	Normality of acid.

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

1. Standard Methods for the Examination of Water and Wastewater, 15th Edition, p 270, Method 403, (1981).

FMC-C-001-3

-------
CSL Method

CHEMICAL OXYGEN DEMAND DETERMINATION. OPEN RFLUX

1.0 SCOPE AND APPLICATION

1.1 This method covers the determination of COD in surface waters and domestic and industrial wastes
titrimetrically and colorimetrically.

1.2 The applicable range of this method is 3 - 900 mg/L chemical oxygen demand.

2.0 SUMMARY OF METHOD

2.1 The samples are digested with a strong oxidizing agent at elevated temperature and reduced pH. The
samples are oxidized by a solution of potassium dichromate in 50 percent sulfuric acid. The excess dichromate is
titrated with standard ferrous ammonium sulfate using orthophenanthroline ferrous complex (ferroin) as an indicator.

3.0 INTERFERENCES

3.1 Chlorides are quantitatively oxidized by dichromate and represent a positive interference. Mercuric
sulfate is added to the digestion tubes to complex the chlorides.

4.0 APPARATUS AND MATERIALS

4.1 Reflux Apparatus: Glassware should consist of a 500-mL Erlenmeyer flask or a 300-mL round bottom
flask made of heat-resistant glass connected to a 12-inch Allihn condenser by means of a ground glass joint. Any
equivalent reflux apparatus may be substituted provided that a ground-glass connection is used between the flask and
the condenser.

5.0 REAGENTS

5.1 Potassium Acid Phthalate: Dissolve 425 mg of potassium acid phthalate (dried for two hours at 120°C)
in 800 mL of deionized distilled water and dilute to 1 L (1 mL = 500 /ig COD).

5.2 Standard Potassium Dichromate Solution. 0.25 N: Dissolve 12.2588 g of K2Cr207 (primary standard
grade, previously dried for two hours at 103°C) in water and dilute to 1 L. The addition of 0.12 g/L sulphamic acid
will eliminate interference due to nitrates in the sample at concentrations up to 6 mg/L.

5.2.1 Dilute Potassium Dichromate Solution. 0.025 N: Dilute 100 mL of standard potassium
dichromate solution (5.2) to 1 L with distilled water.

5.3 Standard Ferrous Ammonium Sulfate. 0.250 N: Dissolve 98 g of Fe(NH4)2(S04)2,6H20 in distilled
water. Add 20 mL of concentrated H2S04 with extreme caution, cool and dilute to 1 L. This solution must be
standardized against the standard potassium dichromate solution daily.

5.3.1 Standardization: Dilute 25.0 mL of standard dichromate solution to about 250 mL with
distilled water. Add 20 mL of concentrated sulfuric acid. Cool, then titrate with ferrous ammonium sulfate
titrant using 10 drops of ferroin indicator. Calculate the normality of the solution according to the following
equation:

FMC-C-002-1

-------
(mL K Cr 0 ) (0.25)

Normality = 	

mi Fe(iVH4)2(S04)2

5.3.2 Dilute Ferrous Ammonium Sulfate. 0.025 N: Dilute 100 mL of standard ferrous ammonium
sulfate (5.3) to 1 L with distilled water. This solution must be standardized daily against dilute potassium
dichromate solution (5.2.1) following the same procedure as the standardization of the ferrous ammonium
sulfate titrant (5.3.1).

5.4	Mercuric Sulfate. HgSO,: Powdered.

5.5	Phenanthroline Ferrous Sulfate Indicator Solution: Dissolve 1.48 g of l-lO-(ortho) phenanthroline
monohydrate together with 0.70 g of FeS04,7H20 in 100 mL of water. This indicator may be purchased already
prepared.

5.6	Sulfuric Acid. LLSO,: Concentrated, reagent grade.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1	Collect the samples in glass bottles if possible. Use of plastic containers is permissible if it is known
that no organic contaminants are present in the containers.

6.2	Samples should be preserved with sulfuric acid to pH < 2 and maintained at 4°C until analysis.
7.0 PROCEDURE

7.1	Place several boiling stones or glass beads in the reflux flask. Add 50 mL of sample or an aliquot diluted
to 50 mL. Add 0.4 g of HgS04 for sample concentrations < 50 mg/L or 1.0 g of HgS04 for sample concentrations
> 50 mg/L to the reflux flask and very slowly add 5.0 mL sulfuric acid reagent, with mixing to dissolve the HgS04.

7.2	Cool the reflux flask and slowly add 10 mL of 0.025 N K2Cr207 for concentrations < 50 mg/L or 25 mL
of 0.25 N K2Cr207 for concentrations > 50 mg/L and mix. Attach the flask to the condenser; start the cooling water.

7.3	Add remaining sulfuric acid reagent (70 mL) through open end of condenser. Continuing swirling and
mixing while adding the sulfuric acid reagent.

7.4	Cover open end of condenser with a small beaker to prevent foreign material from entering refluxing
mixture and reflux for two hours.

7.5	Allow the flask to cool and wash down the condenser with 30 mL of distilled water. When the sample
has reached room temperature, quantitatively transfer the sample solution to a 250-mL Erlenmeyer flask, washing
out the reflux flask three or four times with distilled water. Add 3 drops of ferroin indicator. Titrate the excess
dichromate with 0.025 N ferrous ammonium sulfate solution for concentrations < 50 mg/L or 0.25 N ferrous
ammonium sulfate solution for concentrations > 50 mg/L. The end point of the titration will be indicated by a sharp
color change from blue-green to reddish-brown.

7.6 Calculations

FMC-C-002-2

-------
7.6.1 Prepare a standard curve by plotting peak height or percent transmittance against the known
concentrations of the standards.

7.6.2 Compute concentration of samples by comparing sample response to standard curve. NOTE:
If the volume of sample was less than the method called for, the analyst is advised to divide the volume used
by the final volume of digestate and multiply by the concentration of the standard curve.

8.0 QUALITY CONTROL

8.1 A blank consisting of 20 mL of distilled water is to be processed as a sample to check for reagent
contamination.

9.0 METHOD PERFORMANCE

9.1 A set of synthetic samples containiung potassium hydrogen phthalate and NaCl was tested by 74
laboratory. At a COD of 200 mg/L in the absence of chloride, the standard deviation was ±13 mg/L (coefficient of
variation, 6.5%). At a COD of 160 mg/L and 100 mg/L of chloride, the standard deviation was ± 14 mg/L
(coefficient of variation, 10.8%).

10.0 REFERENCES

1.	Standard Methods for the Examination of Water and Wastewater, 15th Edition, Method 508, 1981.

COD, mg/ L

( A - B ) x N x 8000
S

where: A
B
N

Volume 0.25 N Fe(NH4)2(S04)2 for blank titration, mL;
Volume 0.25 N Fe(NH4)2(S04)2 for sample titration, mL;
Normality of the Fe(NH4)2(S04)2 solution;

Equivalent weight of oxygen, mg/eq;

Volume of sample used, mL;

8000
S

7.6.3 Convert results to (ig/L COD before reporting.

FMC-C-002-3

-------
CSL Method

ANIONS IN WATER BY ION CHROMATOGRAPHY

1.0 SCOPE AND APPLICATION

1.1 This method is applicable to the determination of chloride, fluoride, nitrate, nitrite, phosphate, and sulfate
in drinking, ground and surface waters, boiler and cooling waters, domestic and industrial wastes, and atmospheric
precipitation samples.

1.2 The range of the method may be varied through instrument and/or sample size. Using a 100 (iL sample
size and a sensitivity of 10-jUmho full scale, the following are approximate detection limits:

Approximate
Detection Limit
Anion mg/L

Chloride (CL) 0.1
Fluoride (F") 0.05

Nitrate (NO;) 0.1

Nitrite (N02") 0.1

Phosphate (P043) 0.1
Sulfate (S042) 0.1

If lower detection levels are required, the sensitivity may be improved by using a lower scale setting or a larger
sample injection.

1.3 This method is restricted to use by or under the supervision of analysts experienced in the use of ion
chromatography and in the interpretation of the resulting ion chromatogram.

2.0 SUMMARY OF METHOD

2.1 A small volume of sample, typically 0.1 to 3 mL, is introduced into an ion chromatograph. The anions
of interest are separated and measured using a system comprised of a guard column, separator column, suppressor
column, and conductivity detector.

2.2 The anions are identified on the basis of retention times as compared to standards. Quantitaion is by
measurement of peak area or height.

3.0 INTERFERENCES

3.1 Interferences can be caused by substances with retention times that are similar to and overlap those of the
anion of interest. Large amounts of an anion can interfere with the peak resolution of an adjacent anion.

3.2 Method interferences may be caused by contaminants in the reagent water, reagents, glassware, and other
sample processing apparatus that lead to discrete artifacts or elevated baseline in ion chromatograms.

3.3 Samples that contain particles larger than 0.45 microns and reagent solutions that contain particles larger
than 0.20 microns require filtration to prevent damage to instrument columns and flow systems.

FMC-C-003-1

-------
3.4 The use of concentrated sulfuric acid, in the preservation of the sample, can cause possible problems by
converting nitrite to nitrate. The analyst should beware of the type of preservative method used and take the
appropriate action.

3.5 Water peak inflection may cause washing out of fluoride, by use of an eluant spiking solution, this
problem can be corrected.

4.0 APPARATUS AND MATERIALS

4.1 Ion Chromatograph: Any analytical system complete with ion chromatograph and all required accessories
including analytical columns, detector, stripchart recorder and a data system for peak integration.

4.2 Anion Guard Column: 4 x 50mm.

4.3 Anion Separator Column: 4 x 250mm.

4.4 Anion Suppressor Column: fiber.

4.5 Detector: Conductivity cell, approximately 6 8,1 volume.

5.0 REAGENTS

5.1 Reagent Water: ASTM Type I water, free of anions of interest and containing no particles larger than 0.20
microns.

5.2 Eluent Solution: Sodium bicarbonate 0.003 M, sodium carbonate 0.0024 M. Dissolve 1.0080 g sodium
bicarbonate (NaHC03) and 1.0176 g of sodium carbonate (Na2C03) in reagent water and dilute to 4 L.

5.3 Regeneration Solution (Tiber suppressor): Sulfuric acid 0.025 N. Dilute 111 mL conc. sulfuric acid
(H2S04) to approximately 600 mL of deionized distilled water and dilute to 4 Ls with deionized distilled water.

5.4 Stock Standards. 1000 mg/L: Stock standard solutions may be purchased as certified solutions or prepared
from ACS reagent grade materials (dried at 105°C for 30 minutes) as listed below.

5.4.1 Chloride (CI") 1000 mg/L: Dissolve 1.6484 g of sodium chloride in deionized distilled water and dilute
to 1 L with deionized distilled water.

5.4.2 Fluoride (F") 1000 mg/L: Dissolve 2.2100 g of sodium fluoride (NaF) in deionized distilled water and
dilute to 1 L with deionized distilled water. Store in chemical resistant glass or polyethylene bottle.

5.4.3 Nitrate (NO) 1000 mg/L: Dissolve 1.3707 g of sodium nitrate (NaN03) in deionized distilled water
and dilute to 1 L with deionized distilled water.

5.4.4 Nitrite (NO) 1000 mg/L: Dissolve 1.4998 g sodium nitrite (NaN02) in deionized distilled water and
dilute to 1 L with deionized distilled water. Store in a sterilized glass bottle. Refrigerate and prepare fresh
monthly.

5.4.5 Phosphate (POJ 1000 mg/L: Dissolve 1.4330 g of potassium dihydrogen phosphate (KH2P04) in
deionized distilled water and dilute to 1 L with deionized distilled water.

5.4.6 Sulfate (SO^ 1000 mg/L: Dissolve 1.4790 g of sodium sulfate (Na2SO„) in deionized distilled water
and dilute to 1 L with deionized distilled water.

FMC-C-003-2

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 System Equilibration

7.1.1 Establish a stable baseline with working eluent running through the system and establish ion
chromatographic operating parameters. This requires at least 30 minutes.

7.2 Calibration

7.2.1 For the anions, prepare a combined calibration standard at a minimum of three concentration levels
and a blank by adding accurately measured volumes of the stock standards to a volumetric flask and diluting
to volume with reagent water. One of the standards must be at the MDL. The attenuator range settings must
be linear.

7.2.2 Using injections of 0.1 to 1.0 mL (determined by injection loop volume) of each calibration standard,
tabulate peak height or area responses against the concentration. The results are used to prepare a calibration
curve for each analyte. During this procedure, retention times must be recorded.

7.3 Sample Analysis:

7.3.1 Remove sample particulates, if necessary, by filtering through a prewashed 0.2 /im-pore-diameter
membrane filter.

7.3.2 Using a prewashed syringe of 1 to 10 mL capacity equipped with a male luer fitting inject sample or
standard.

7.3.3 Inject enough sample to flush sample loop several times: 0.1 mL sample loop inject at least 1 mL.

7.3.4 Swith ion chromatograph from load to inject modeand record peak heights or area and retention times
on strip chart recorder.

7.3.5 After the last peak has appeared and the conductivity signal has returned to base line, another sample
can be injected.

7.4 Calculations

7.4.1 Calculate concentration of each anion, in mg/L, by referring to the appropriate calibration curve.
Alternatively, when the response is shown to be linear, use th following equation:

C = H x F x D

Where: C = mg/L anion;

H = Peak area or height;

F = Response factor = concentration of standard/height (or area) of standard; and

D = Dilution factor.

,0 QUALITY CONTROL

FMC-C-003-3

-------
8.1	Matrix matching, with the samples, is mandatory for all blanks, standards, and quality control samples,
to avoid inaccurate concentration values due to possible standard curve deviations

8.2	The working calibration curve must be verified on each working day or whenever the anion eluent is
changed and after every 20 samples. If the response or retention time for any analyte varies from the expected values
by more than + 10%, the test must be repeated, using fresh calibration standards. If the results are still more than +
10%, an entire new calibration must be prepared for that analyte. Nonlinear response can result when the separator
column capacity is exceeded (overloading). Maximum loading (all anions) should not exceed 400 ppm.

8.3	The width of the retention time window used to make identifications must be based upon measurements
of actual retention time variations of standards run over three non-consecutive days. Three times the standard
deviation will be used to calculate the retention time windows. The retention time for fluoride, and nitrate-nitrite must
be within the retention time window established during the most recent initial calibration.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Standard Methods for the Examination of Water and Wastewater, 15th Edition, p. 483, Method 429, 1981.

FMC-C-003-4

-------
CSL Method

HARDNESS. TOTAL (mg/L as CaCCM

1.0 SCOPE AND APPLICATION

1.1 This automated method is applicable to drinking, surface, and saline waters. The applicable range is 10
to 400 mg/L as CaC03. Approximately 12 samples per hour can be analyzed.

2.0 SUMMARY OF METHOD

2.1 The magnesium EDTA exchanges magnesium on an equivalent basis for any calcium and/or other cations
to form a more stable EDTA chelate than magnesium. The free magnesium reacts with calmagite at a pH of 10 to
give a red-violent complex. Thus, by measuring only magnesium concentration in the final reaction stream, an
accurate measurement of total hardness is possible.

3.0 INTERFERENCES

3.1 No significant interferences.

4.0 APPARATUS AND MATERIALS

4.1 Technicon Auto Analyzer: Consisting of

4.1

.1

Sampler;

4.1

.2

Continuous filter;

4.1

.3

Manifold;

4.1

.4

Proportioning pump;

4.1.5 Colorimeter equipped with 15 mm tubular flow cell and 520 nm filters; and
4.1.6 Recorder equipped with range expander.

5.0 REAGENTS

5.1	Buffer: Dissolve 67.6 g NH4C1 in 572 mL of NH4OH and dilute to 1 L with deionized distilled water.

5.2	Calmagite Indicator: Dissolve 0.25 g in 500 mL of deionized distilled water by stirring approximately 30
minutes on a magnetic stirrer. Filter.

5.3	Monomagnesium Ethvlenediamine-tetraacetate (MeEDTA): Dissolve 0.2 g of MgEDTA in 1 L of
deionized distilled water.

5.4	Stock Solution: Weigh 1.000 g of calcium carbonate (pre-dried at 105°C) into 500 mL Erlenmeyer flask;
add 1:1 HCL until all CaC03 has dissolved. Add 200 mL of deionized distilled water and boil for a few minutes.
Cool, add a few drops of methyl red indicator, and adjust to the orange color with 3N NH4OH and dilute to 1 L with
deionized distilled water. (1.0 mL = 1.0 mg CaC03)

FMC-C-004-1

-------
5.4.1 Dilute each of the following volumes of stock solutions to 250 mL in a volumetric flask for appropriate
standards.

5.5 Ammonium Hydroxide. IN: Dilute 70 mL of concentrated NH4OH to 1 L with deionized distilled water.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Cool to 4°C, HN03 to pH<2.

7.0 PROCEDURE

7.1 Pretreatment

7.1.1 For drinking waters, surface waters, saline waters, and dilutions thereof, no pretreatment steps are
necessary.

7.1.2 For most wastewaters, and highly polluted waters, the sample must be digested as the cation
determination for use with the Atomic Absorption Spectrophotometer.

7.2 Neutralize 50.0 mL of sample with IN ammonium hydroxide and note volume of NH4OH used.

7.3 Due to the many variations of instruments, the analyzt is advised to set up the manifold and follow the
operational procedure according to the manufacturers instructions for there specific instruments.

7.4 Calculation

7.4.1 Prepare standard curve by plotting peak heights of processed standards against concentration values.
Compute concentration of samples by comparing sample peak heights with standard curve. Correct for amount
of NH4OH used in 7.2 as follows:

Stock Solution. mL

CaCO,. mg/L

2.5
5.0
10.0
15.0
25.0
35.0
50.0
75.0
100.0

10.0
20.0
40.0
60.0
100.0
140.0
200.0
300.0
400.0

mg/L = x B

where: A = Volume of sample plus volume of NH4OH; and
B = Concentration from standard curve.

8.0 QUALITY CONTROL

Information not available.

FMC-C-004-2

-------
9.0 METHOD PERFORMANCE

Infromation not avialable.

10.0 REFERENCES

1. Standard Methods for the Examination of Water and Wastewater, 15th Edition, p 210, Method 314, 1981.

FMC-C-004-3

-------
CSL Method

OIL AND GREASE. PARTITION GRAVIMETRIC

1.0 SCOPE AND APPLICATION

1.1 This method includes the measurement of fluorocarbon-113 extractable matter from surface and saline
waters, industrial and domestic wastes. It is applicable to the determination of relatively non-volatile hydrocarbons,
vegetable oils, animal fats, waxes, soaps, greases and related matter.

1.2 The method is not applicable to measurement of light hydrocarbons that volatilize at temperatures below

70°C.

1.3 Some crude oils and heavy fuel oils contain a significant percentage of residue-type materials that are not
soluble in fluorocarbon-113. Accordingly, recoveries of these materials will be low.

1.4 The method covers the range from 5 to 1000 mg/L of extractable material.

2.0 SUMMARY OF METHOD

2.1 The sample is acidified to a low pH (<2) and serially extracted with fluorocarbon-113 in a separatory
funnel. The solvent is evaporated from the extract and the residue weighed.

3.0 INTERFERENCES

3.1 Trichlorotrifluoroethane has the ability to dissolve not only oil ans grease but also other organic substances.
No known solvent will dissolve selectively only oil and grease. Solvent removal results in the loss of short-chain
hydrocarbond and simple aromatics byvolatilization. Petroleum fuels from gasoline through #2 fuel oils are
completely or partially lost in the solvent removal operation.

4.0 APPARATUS AND MATERIALS

4.1 Separatory Funnel: 2 L, with Teflon stopcock.

4.2 Distillating Flask: 125 mL.

4.3 Filter Paper: 11 cm.

4.4 Water Bath.

5.0 REAGENTS

5.1 Hydrochloric Acid. (!:!'): Mix equal volumes of conc. HC1 and deionized distilled water.

5.2 Fluorocarbon-113. (T.l-2-trichloro-1.2.2-trifluoroethane'): b.p. 48°C.

5.3 Sodium Sulfate: Anhydrous crystal.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

FMC-C-005-1

-------
6.1 A representative sample of 1 L volume should be collected in a glass bottle. If analysis is to be delayed
for more than a few hours, the sample is preserved by the addition of 5 mL HC1 (5.1) at the time of collection and
refrigerated at 4°C.

4.2 Because losses of grease will occur on sampling equipment, the collection of a composite sample is
impractical. Individual portions collected at prescribed time intervals must be analyzed separately to obtain the
average concentration over an extended period.

7.0 PROCEDURE

7.1 Mark the sample bottle at the water meniscus for later determination of sample volume. If the sample was
not acidified at time of collection, add 5 mL HC1 (5.1) to the sample bottle. After mixing the sample, check the pH
by touching pH-sensitive paper to the cap to insure that the pH is 2 or lower. Add more acid if necessary.

7.2 Pour the sample into a separatory funnel.

7.3 Tare a distilling flask (pre-dried in an oven at 103°C and stored in a desiccator).

7.4 Add 30 mL fluorocarbon-113 (5.2) to the sample bottle and rotate the bottle to rinse the sides. Transfer
the solvent into the separatory funnel. Extract by shaking vigorously for 2 minutes Allow the layers to separate, and
filter the solvent layer into the flask through a funnel containing solvent moistened filter paper.

NOTE: An emulsion that fails to dissipate can be broken by pouring about 1 g sodium sulfate (5.3) into the filter
paper cone and slowly draining the emulsion through the salt. Additional 1 g portions can be added to the cone as
required.

7.5 Repeat (7.4) twice more, with additional portions of fresh solvent, combining all solvent in the distilling

flask.

7.6 Rinse the tip of the separatory funnel, the filter paper, and then the funnel with a total of 10-20 mL solvent
and collect the rinsings in the flask.

7.7 Distill solvent from distilling flask in a water bath at 70°C.

7.8 Placeflask on a water bath at 70°C for 15 minutes and draw air through it with an aplied vacuum for the
final 1 minute.

7.9 Cool the boiling flask in a desiccator for 30 minutes and weigh.

7.10 Calculation

R ~ B

mg/L Total Oil and Grease =

where: R = Residue, gross weight of extraction flask minus the tare weight, in milligrams;

B = Blank determination, residue of equivalent volume of extraction solvent, in milligrams; and
V = Volume of sample, determined by refilling sample bottle to calibration line and correcting for acid
addition if necessary, in liters.

8.0 QUALITY CONTROL

Information not available.

FMC-C-005-2

-------
9.0 METHOD PERFORMANCE

9.1 The method was tested by a single laboratory on a sewage sample. By this method the oil and grease
concentration was 12.6 mg/L. When 1-L portions of sewage were dosed with 14.0 mg of a mixture of No. 2 fuel oil
and Wesson oil, recovery of added oils was 93% with a standard deviation of 0.9 mg.

10.0 REFERENCES

1. Standard Methods for the Examination of Water and Wastewater, 15th Edition, Method 503, (1981).

FMC-C-005-3

-------
CSL Method

TOTAL DISSOLVED SOLIDS DRIED AT 180°C

1.0 SCOPE AND APPLICATIONS

1.1 This method is applicable to drinking, surface, and saline waters, domestic and industrial wastes.

1.2 The practical range of the determination is 10 to 20,000 mg/L.

1.3 Filterable residue is defined as those solids capable of passing through a glass fiber filter and dried to
constant weight at 180°C.

2.0 SUMMARY OF METHOD

2.1 A well-mixed sample is filtered through a standard glass fiber filter. The filtrate is evaporated and
dried to constant weight at 180°C.

2.2 The filtrate from the total suspended solids determination method may be used for total dissolved

solids.

3.0 INTERFERENCES

3.1 Highly mineralized waters containing significant concentrations of calcium, magnesium, chloride
and/or sulfate may be hygroscopic and will require prolonged drying, desiccation and rapid weighing.

3.2 Samples containing high concentrations of bicarbonate will require careful and possibly prolonged
drying at 180°C to insure that all the bicarbonate is converted to carbonate.

3.3 Too much residue in the evaporating dish will crust over and entrap water that will not be driven off
during drying. Total residue should be limited to about 200 mg.

4.0 APPARATUS AND MATERIALS

4.1 Glass Fiber Filter Discs. Without Organic Binder.

4.2 Filtration Apparatus: One of the following suitable for filter disk selected.

4.2.1 Membrane filter funnel.

4.2.2 Gooch crucible, 25-mL to 40-mL capacity, with Gooch crucible adapter.

4.2.3 Filtration apparatus with reservoir and course(40- to 60-jUm) fritted disk as filter support.

4.3 Suction Flask.

4.4 Drying Oven: For operation at 180 ± 2°C.

4.5 Desiccator.

4.6 Analytical Balance: Capable of weighing to 0.1 mg.

FMC-C-006-1

-------
4.7 Evaporating Dishes: Porcelain, 90 mm diamter and 100 mL volume. Platinum dishes may be
substituted.

4.8 Muffle Furnace: For operation at 550 ± 50°KEYBOARD().

4.9 Steam bath.

5.0 REAGENTS

Information not required.

6.0 SAMPLE HANDLING AND PRESERVATIONS

6.1 Non-representative particulates such as leaves, sticks, fish, and lumps of fecal matter should be
excluded from the sample if it is determined that their inclusion is not desired in the final result.

6.2 Preservation of the sample is not practical; analysis should begin as soon as possible. Refrigeration
or icing to 4°C, to minimize microbiological decomposition of solids, is recommended.

7.0 PROCEDURE

7.1 Preparations of Glass Fiber Filter Disc

7.1.1 Insert disk with with wrinkled surface up in filtration apparatus. Apply vacuum and wash the
disc with three successive 20 mL volumes of deionized distilled water. Continue suction to remove all traces
of water.

7.2 Selection of Filter and Sample Size

7.3 Preparation of evaporating dishes:

7.3.1 If Volatile solids is also to be measured heat the clean dish to 550 ± 50°C) for one hour in a
muffle furnace. If only total dissolved soilds are to be measured heat the clean dish to 180 ± 2°C) for one
hour. Cool in desiccator and store until needed. Weigh immediately before use.

7.4 Sample Analysis

7.4.1 Filter measured volume of well mixed sample through the glass fiber filter, wash with three 10
mL porions of deionized distilled water and continue to apply vacuum for about 3 minutes after filtration is
complete to remove as much water as possible.

7.4.2 Transfer filtrate to a weighed evaporating dish and evaporate to dryness on a steam bath. If
filtrate volume exceeds dish capacity add successive portions to the same dish after evaporation.

7.4.3 Dry the evaporated sample for at least one hour at 180 ± 2°C. Cool in a desiccator and weigh.
Repeat the drying cycle until a constant weight is obtained or until weight loss is less than 0.5 mg.

7.5 Calculations

FMC-C-006-2

-------
7.5.1 Calculate total dissolved solids as follows:

mg/ L

(A - B) x1,000
C

where: A
B
C

Weight of dried residue - dish in mg;
Weight of dish in mg; and
mL of sample filtered

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

9.2 Single-laboratory duplicate analyses of 77 samples of a known of 293 mg/L prepared were made with
a standrad deviation of difference of 21.20 mg/L.

10.0 REFERENCES

1. Standard Methods for Examination of Water and Wastewater, 15th Edition, p. 95, Method 209 B, 1981.

FMC-C-006-3

-------
CSL SW-846 METHOD 9060

TOTAL ORGANIC CARBON

1.0 SCOPE AND APPLICATION

1.1 Method 9060 is used to determine the concentration of organic carbon in ground water, surface and
saline waters, and domestic and Industrial wastes. Some restrictions are noted in Sections 2.0 and 3.0.

1.2 Method 9060 is most applicable to measurement of organic carbon above 1 mg/L.

2.0 SUMMARY OF METHOD

2.1 Organic carbon is measured using a carbonaceous analyzer. This instrument converts the organic
carbon in a sample to carbon dioxide (C02) by either catalytic combustion or wet chemical oxidation. The C02
formed is then either measured directly by an infrared detector or converted to methane (CH4) and measured by a
flame Ionization detector. The amount of C02 or CH4 in a sample is directly proportional to the concentration of
carbonaceous material in the sample.

2.2 Carbonaceous analyzers are capable of measuring all forms of carbon In a sample. However,
because of various properties of carbon-containing compounds in liquid samples, the manner of preliminary
sample treatment as fell as the instrument settings will determine which forms of carbon are actually measured.
The forms of carbon that can be measured by Method 9060 are:

2.2.1 Soluble, nonvolatile organic carbon: e.g., natural sugars.

2.2.2 Soluble, volatile organic carbon: e.g., mercaptans, alkanes, low molecular weight alcohols.

2.2.3 Insoluble, partially volatile carbon: e.g., low molecular weight oils.

2.2.4 Insoluble, particulate carbonaceous materials: e.g., cellulose fibers.

2.2.5 Soluble or insoluble carbonaceous materials adsorbed or entrapped on insoluble inorganic

suspended matter: e.g., only matter adsorbed on silt particles.

2.3 Carbonate and bicarbonate are inorganic forms of carbon and must be separated from the total
organic carbon value. Depending on the instrument manufacturers instructions, this separation can be
accomplished by either a simple mathematical subtraction, or by removing the carbonate and bicarbonate by
converting them to C02 with degassing prior to analysis.

3.0 INTERFERENCES

3.1 Carbonate and bicarbonate carton represent an interference under the terms of this test and must be
removed or accounted for in the final calculation.

3.2 This procedure is applicable only to homogeneous samples which can be injected into the apparatus
reproducibly by means of a microliter-type syringe or pipet. The openings of the syringe or pipet limit the
maximum size of particle which may be included in the sample.

3.3 Removal of carbonate and bicarbonate by acidification and purging with nitrogen, or other inert gas,
can result in the loss of volatile organic substances.

FMC-C-007-1

-------
4.0 APPARATUS AND MATERIALS

4.1 Apparatus for Blending or Homogenizing Samples: Generally, a Waring-type blender is
satisfactory.

4.2 Apparatus for Total and Dissolved Organic Carbon

4.2.1 Several companies manufacture analyzers for measuring carbonaceous material in liquid
amples. The most appropriate system should be selected based on consideration of the types of samples
to be analyzed; the expected concentration range, and the forms of carbon to be measured.

4.2.2 No specific analyzer is recommended as superior. If the technique of chemical oxidation is
used, the laboratory must be certain that the instrument is capable of achieving good carbon recoveries in
samples containing particulates.

5.0 REAGENTS

5.1 ASTM Type II Water (ASTM D11931: Water should be monitored for impurities, and should be
boiled and cooled to remove C02.

5.2 Potassium Hydrogen Phthalate. Stock Solution. 1,000 mg/L carbon: Dissolve 0.2128 g of potassium
hydrogen phthalate (primary standard grade) in Type II water and dilute to 100.0 mL. NOTE: Sodium oxalate and
acetic acid are not recommended as stock solutions.

5.3 Potassium Hydrogen Phthalate. Standard Solutions: Prepare standard solutions from the stock solution
by dilution with Type II water.

5.4 Carbonate-bicarbonate. Stock Solution. 1,000 mg/L carbon: Weigh 0.3500 g of sodium bicarbonate an
0.4418g of sodium carbonate and transfer both to the same 100-mL volumetric flask. Dissolve with Type II water.

5.5 Carbonate-bicarbonate. Standard Solution: Prepare a series of standards similar to Step 5.3. NOTE: This
standard is not required by some instruments.

5.6 Blank Solution: Use the same Type II water as was used to prepare the standard solutions.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 All samples must be collected using a sampling plan that addresses the considerations discussed in
Chapter Nine of this manual.

6.2 Sampling and storage of samples in glass bottles is preferable. Sampling and storage in plastic bottles
such as conventional polyethylene and cubitainers Is permissible if it is established that the containers do not
contribute contaminating organics to the samples. NOTE: A brief study performed In the EPA Laboratory indicated
that Type II water stored in new, 1-qt cubitainers did not show any increase in organic carbon after 2 weeks' exposure.

6.3 Because of the possibility of oxidation or bacterial decomposition of some components of aqueous
samples, the time between sample collection and the start of analysis should be minimized. Also, samples should be
kept cool 4°C and protected from sunlight and atmospheric oxygen.

6.4 In instances where analysis cannot be performed within 2 hr from time of sampling, the sample is
acidified (pH < 2) with HC1 or H2S04.

7.0 PROCEDURE

FMC-C-007-2

-------
7.1 Homogenize the sample in a blender. NOTE: To avoid erroneously high resu*its, inorganic carbon
must be accounted for. The preferred method is to measure total carbon and Inorganic carbon and to obtain
the organic carbon by subtraction. If this is not possible, follow Steps 7.2 and 7.3 prior to analysis; however,
volatile organic carbon may *I)e lost.

7.2 Lower the pH of the sample to 2.

7.3 Purge the sample with nitrogen for 10 min.

7.4 Follow instrument manufacturer's instructions for calibration, procedure, and calculations.

7.5 For calibration of the instrument, a series of standards should be used that encompasses the expected
concentratior,range of the samples.

7.6 Quadruplicate analysis is required. Report both the average and the range.

8.0 QUALITY CONTROL

8.1 All quality control data should be maintained and available for easy reference or inspection.

8.2 Employ a minimum of one blank per sample batch to determine if contamination or any memory effects
are occurring.

8.3 Verify calibration with an independently prepared check standard every 15 samples.

8.4 Run one spike duplicate sample for every 10 samples. A duplicate sample is a sample brought through
the whole sample preparation and analytical process.

9.0 METHOD PERFORMANCE

9.1 Precision and accuracy data are available in Method 415.1 of Methods for Chemical Analysis of Water
and Wastes.

10.0 REFERENCES

1. Annual Book of ASTM Standards, Part 31, "Water,". Standard D 2574-79, p.469 (1976).

2. Standard Methods for the Examination of Water and Wastewater, 14th ed., p.532, Method 505 (1975).

FMC-C-007-3

-------
CSL Method

TOTAL SUSPENDED SOLIDS DRIED AT 103-105°C

1.0 SCOPE AND APPLICATIONS

1.1 This method is applicable to drinking, surface, and saline waters, domestic and industrial wastes.

1.2 The practical range of the determination is 4 to 20,000 mg/L.

1.3 Residue, non-filterable, is defined as those solids which are retained by a glass fiber filter and dried
to constant weight at 103-105°C.

2.0 SUMMARY OF METHOD

2.1 A well-mixed sample is filtered through a glass fiber filter, and the residue retained on the filter is dried
to constant weight at 103-105°C.

2.2 The filtrate from this method may be used for Residue, Filterable.

3.0 INTERFERENCES

3.1 Filtration apparatus, filter material, pre-washing, post-washing, and drying temperature are specified
because these variables have been shown to affect the results.

3.2 Samples high in Filterable Residue (dissolved solids), such as saline waters, brines and some wastes,
may be subject to a positive interference. Care must be taken in selecting the filtering apparatus so that washing of
the filter and any dissolved solids in the filter (7.5) minimizes this potential interference.

4.0 APPARATUS AND MATERIALS

4.1 Glass Fiber Filter Discs. Without Organic Binder.

4.2 Filtration Apparatus: One of the following suitable for filter disk selected.

4.2.1 Membrane filter funnel.

4.2.2 Gooch crucible, 25-mL to 40-mL capacity, with Gooch crucible adapter.

4.2.3 Filtration apparatus with reservoir and course(40- to 60-jUm) fritted disk as filter support.

4.3 Suction Flask.

4.4 Drying Oven: 103 - 105°C.

4.5 Desiccator.

4.6 Analytical Balance: Capable of weighing to 0.1 mg.

4.7 Planchet: Aluminum or stainless steel, 65-mm diameter.

5.0 REAGENTS

FMC-C-008-1

-------
Information not required.

6.0 SAMPLE HANDLING AND PRESERVATIONS

6.2 Preservation of the sample is not practical; analysis should begin as soon as possible. Refrigeration
or icing to 4°C, to minimize microbiological decomposition of solids, is recommended.

7.0 PROCEDURE

7.1 Preparations of Glass Fiber Filter Disc

7.1.2 Remove filter from filter apparatus and transfer to an aluminum or stainless steel planchet as
a support. Alternatively remove crucible and fliter combination if a Gooch crucible is used.

7.1.3 Dry in an oven at 103-105°C for one hour. Cool in desiccator to balance temperature and
weigh. Repeat the drying cycle until a constant weight is obtained (weight loss is less than 0.5 mg). Store
in a desiccator until neeeded. Weigh immediately before use.

7.2 Selection of Filter and Sample Size

7.2.1 Choose sample volume toyield between 2.5 and 200 mg dried residue. If more than 10
minutes are required to complete filtration, increase filter size or decrease sample volume but do not produce
less than 2.5 mg residue. For nonhomogeneous samples such as raw wastewater, use a large filter to permit
filtering a representative sample.

7.3 Sample Analysis

7.3.1 Assemble the filtering apparatus and begin suction. Wet the filter with a small volume of
deionized distilled water to seat it against the fitted support.

7.3.2 With suction on, wash the graduated cylinder, filter, non-filterable residue and filter funnel
wall with three portions of deionized distilled water allowing complete drainage between washing. Remove
all traces of water by continuing to apply vacuum after water has passed through.

7.3.2 Carefully remove the filter from the filter apparatus and transfer to an aluminum or stainless
steel planchet as a support. Alternatively, remove crucible and filter combination from crucible adapter if
a Gooch crucible is used. Dry at least one hour at 103-105°C. Cool in a desiccator and weigh. Repeat the
drying cycle until a constant weight is obtained (weight loss is less than 0.5 mg).

7.4 Calculations

7.4.1 Calculate total suspended solids as follows:

FMC-C-008-2

-------
where: A = Weight of filter - dried residue in mg;

B = Weight of filter in mg; and
C = mL of sample filtered

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

9.1	The standard deviation was 5.2 mg/L (coefficient of variation 33%) at 15 mg/L, 24 mg/L (10%) at 242
mg/L, and 13 mg/L (0.76%) at 1707 mg/L in studies by two analyses of four sets of 10 determinations each.

9.2	Single-laboratory duplicate analyses of 50 samples of water and wastewater were made with a standrad
deviation of difference of 2.8 mg/L.

10.0 REFERENCES

1. Standard Methods for Examination of Water and Wastewater, 15th Edition, p. 97, Method 209 C, 1981.

FMC-C-008-3

-------
ERT Method

10-DAY CHRONIC TOXICITY TEST USING
DAPHNIA MAGNA OR DAPHNIA PULEX

1.0 SCOPE AND APPLICATION

1.1 The procedure for conducting a 10-day chronic toxicity test using Daphnia magna or Daphnia pulex is
described below. This test is applicable to leachates, effluents, and liquid phases of sediments. Mortality,
reproduction and growth are used to assess the toxicity of the test media.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Larval daphnids are placed in individual containers and exposed to different concentrations of a test
media over a 10-day period. Concentrations are renewed every other day and mortality, reproduction and growth
are recorded.

3.0 INTERFERENCES AND POTENTIAL PROBLEMS

3.1 Non-target chemicals (i.e., residual chlorine) cause adverse effects to the organisms giving false
results.

3.2 Dissolved oxygen depletion due to biological oxygen demand, chemical oxygen demand and
metabolic wastes also is a potential problem.

3.3 Loss of a toxicant through volatilization and adsorption to exposure chambers also may occur (Peltier
and Weber, 1985).

3.4 The results of a static toxicity test do not reflect temporal fluctuation in test media toxicity (Peltier
and Weber, 1985). Also the effect of the toxicant is organism dependent.

4.0 APPARATUS AND MATERIALS

4.1 Apparatus

4.1.1 60 larval daphnids: Acclimated at least 24 hr. to dilution water.

4.1.2 60 exposure chambers: 100 mL volume, labeled.

4.1.3 Trav: To hold exposure chambers and glass covers.

4.1.4 Pipettes: Wide-bore, inside diameter 1.5 times the length of the daphnid.

4.1.5 Graduated cylinders: 250 mL and 1 L.

FMC-C-009-1

-------
4.1.6	Pipette: 1 mL.

4.1.7	Beakers: 250 mL.

4.1.8	Volumetric flasks: 500 mL.

4.1.9	Test media: 1 L/day.

4.1.10	Diluent: 3 L/day.

4.1.11	Waste containers.

4.1.12	Light table: To aid in counting the organisms.

4.1.13	Suitable food.

4.2	Washing Procedure

4.2.1	Wash with warm water and detergent.

4.2.2	Rinse with tap water.

4.2.3	Rinse with 10% nitric acid solution.

4.2.4	Rinse with deionized water.

4.2.5	Rinse with 100% acetone.

4.2.6	Rinse with deionized water.

4.2.7	Final rinse with dilution water.

4.3	Test Organisms

4.3.1 Test organisms may be reared inhouse or obtained from an outside source. Positive identification
of the species is required before beginning the test. Daphnids to be used must be less than 24 hours old and
from the second to the sixth brood of an healthy adult. Populations of healthy daphnids have large
individuals, have an absence of floaters, have an absence of ephippia, no parasites, individuals are dark
colored and produce large numbers of young. The optimum pH range for daphnids is 6.8-8.5; therefore,
the pH of the dilution water or the concentrations may have to be adjusted prior to the start of the test
(Briesinger et al. 1987).

4.4	Equipment for Chemical Analysis

4.4.1 Meters are needed to measure dissolved oxygen, temperature, pH and conductivity. Calibrate the
meters according to the manufacturers' instructions. Measure alkalinity and hardness according to a
standard method (APHA, 1985).

REAGENTS

FMC-C-009-2

-------
5.1 Dilution Water: Dilution water is reconstituted deionized water unless otherwise specified. See
Horning and Weber (1985) for the preparation of synthetic fresh water. Set up a laboratory or standard dilution
water control when reconstituted deionized water is used as the dilution water. The dilution water for a test is the
same as the water used to culture daphnids and the water used to acclimate daphnids before the beginning of the
test.

5.2 Test Media: If the test media is a liquid, dilutions may be made directly for the required
concentrations. If the test media is a sediment, preliminary filtration and dilutions are required to produce a
liquid phase.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 The selected environmental matrix will be sampled utilizing the methodology detailed in ERT
Standard Operating Procedures (SOPs) #2012, Soil Sampling; #2013, Surface Water Sampling; #2016, Sediment
Sampling, and any other procedure applicable for the media sampled.

6.2 Once collected, the samples will be placed in containers constructed from materials suitable for the
suspected contaminants. Because surrogate test species will be exposed to varying concentrations of the sample
material, no chemical preservative are to be used. The preservation and storage protocol is therefore limited to
holding the samples on ice at 4°C for the holding time specified by the analytical method. Prior to shipping, the
laboratory performing the toxicity tests will be notified of any potential hazards that may be associated with the
samples.

7.0 PROCEDURES

7.1 The test begins when half of the organisms are in the exposure chambers.

7.2 Destroy all test organisms at the completion of the test.

7.3 Choose a range of concentrations that span those causing zero mortality to those causing complete
mortality. The concentrations cited below are used as an example and may be adjusted to meet the criteria of the
specific situation. A geometric or logarithmic range of concentrations also may be used (Sprague, 1973).

7.4 The example below provides enough test media for five replicates containing 80 mL each and extra
for chemical analysis. Other ranges may be used according to needs of the analyses.

7.3 Rinse all exposure chambers, except the chamber containing 100% test media, in dilution water before
the start of the test.

7.4 Pipette 0.5 mL of the test media into a volumetric flask and dilute to 500 mL. Using a graduated
cylinder, pour 80 mL into each exposure chamber and pour the rest into a beaker for chemical measurements.

7.5 Continue these steps for all concentrations. Always work from the lowest concentration to the highest
in order to minimize the risk of cross contamination.

7.6 Using a wide bore pipette, randomly select and carefully place one daphnid into each exposure
chamber.

FMC-C-009-3

-------
Test Concentrations
test merlin

Example 1. Test Dilution

Volume (mL)

Diluent

Test Media

0.0
0.1
1.0
10.0
50.0
100.0

500.0
499.5
495.0
450.0
250.0
0.0

0.0
0.5
5.0
50.0
250.0
500.0

7.7 Place the pipette tip below the surface and gently expel the daphnid into the chamber.

7.8 Concentrations are renewed every other day for the duration of the test. However, if the test begins on
a Monday, then renewals may be done on Wednesday, Friday and the following Monday and Wednesday.

7.9 Measure and record mortality and survival at one (1) hour and then when test concentrations are
renewed.

7.10 Count the number of live or dead young produced by each female.

7.11 Temperature, dissolved oxygen, pH, conductivity, alkalinity and hardness should be measured on all
new concentrations. Conduct these measurements on old test concentrations at least three times during the test.

7.12 Prepare test media concentrations as done previously. Pour the concentrations into new exposure
chambers, reserving extra for chemical analyses.

7.13 Count the number of live or dead adults and young, using the light table if necessary.

7.14 Record these results and then carefully transfer the adult daphnid into the new concentrations.

7.15 Using a suitable food, feed daphnids once daily during the test.

7.16 After feeding the daphnids, cover the exposure chamber to reduce evaporation of the test
concentrations.

7.17 Calculations

7.17.1 The methods used to determine the EC50 differ depending on the results of the test. If there is
no partial mortality in any replicate (i.e. all alive or all dead), then the Moving-Average Method may be
used to determine the EC50. If there is partial mortality within a replicate, then the Probit Method should be
used to calculate the EC50. Also the Lowest Observable Effect Concentration (LOEC) is recorded and the
No Observable Effects Concentration (NOEC) is recorded (Peltier and Weber, 1985). Dunnett's many-one t
procedure or Bonferroni t procedure (Miller, 1966) may be used to determine comparisons between the
concentrations response to the test media as compared to the control. Other methods of estimating the
response values may be used if justified and an accepted reference is cited (Biesinger, et al. 1987).

7.18 Health and Safety

FMC-C-009-4

-------
7.18.1 When working with potentially hazardous materials, follow US EPA, OSHA and corporate
health and safety procedures.

8.0 QUALITY CONTROL

8.1 Quality control should encompass the following parameters to ensure a valid test. The guidelines in
this text and in Table 1 (Appendix A) should be followed to insure adequate QA/QC.

8.1.1 Test media sampling.

8.1.2 Test organisms.

8.1.3 Facilities equipment.

8.1.4 Test media/leachate preparation.

8.1.5 Dilution water.

8.1.6 Test conditions.

8.1.7 Standard reference toxicant.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. APHA. 1985. Standard Methods for the Examination of Water and Wastewater. 1971. American Public
Health Association, 16th ed.

2. Biesinger, K.E., L.R. Williams, and W.H. van der Schalie. 1987. Procedures for conducting Daphnia
Magna toxicity bioassays. EPA/600/8 - 87/011. Environmental Monitoring and Support Laboratory. Cincinnati,
OH. 57 pp.

3. Horning, W.B. and C. Weber. 1985. Short-term Methods for Estimating the Chronic Toxicity of Effluents
and Receiving Waters to Freshwater Organisms. EPA/600/4-85/014. Environmental Monitoring and Support
Laboratory, Cincinnati, OH. 162 pp.

4. Huston, Mark, SOP.I, 10 Day Chronic Toxicity Test Using Daphnia Magna or Daphnia Pulex. U.S. EPA
Environmental Response Team - Technical Assistance Team TDD: 11871206.

5. Miller, R.G. 1966. Simultaneous Statistical Inference. McGraw-Hill Book Company, New York, N.Y.

6. Peltier, William H. and Cornelius Weber. 1985. Methods for Measuring the Acute Toxicity of Effluents to
Freshwater and Marine Organisms. EPA/600/4-85/013. Environmental Monitoring and Support Laboratory,
Cincinnati, OH. 216 pp.

7. Spraque, J.B. 1973. The ABC's of Pollutant Bioassay Using Fish. pp. 6 - 13 in Biological Methods for the
Assessment of Water Quality. J. Cairns and K. Dickson (eds.). STP 528. American Society for Testing and
Materials, Phila. PA 256 pp.

FMC-C-009-5

-------
CSL Method

EXTRACTABLE ORGANICS/SOIL/GRAVIMETRIC

1.0 SCOPE AND APPLICATION

1.1 This method is used for field screening of soils and sediments for extractable organics as an indicator of
organic constituent contamination. It is presented here as a means of rapidly characterizing field samples as part of
a field sampling plan.

1.2 Application of this method is limited to the screening analysis for extractable organics (EO) in soils and
sediment.

1.3 This method measures semivolatile organic constituents present in a sample as a group parameter.
Characterization of specific organic contaminants in duplicate or similar composite samples should occur at remote
CLP laboratories employing EPA testing protocols.

1.4 The data produced in the analysis allows the site investigation team to examine the relative degree of
contamination associated with other sample constituents. The EO content can be compared between samples spatially
related to each other in vertical or horizontal planes and with background.

1.5 The method detection limit for this method is estimated to be 0.05 percent. The analytical range is
estimated to be from 0.05 percent to 95 percent (2,4,6-trimethylphenol).

2.0 SUMMARY OF METHOD

2.1 This method is a manual method adapted for field use from these sources: State of Washington Department
of Ecology, 1983, Chemical Testing Methods. Sample extraction for Halogenated and Poly cyclic Aromatic
Hydrocarbon Analysis; EPA SW-846, Method 9071, 1986, Test Methods for Evaluating Solid Waste. Oil and Grease
Extraction Method for Sludge Samples; EPA SW-846, Method 3550, 1986, Test Methodd for Evaluating Solid
Wastes. Sonification Extraction. In brief, a weighed and dried sample is extracted with solvent. The resultant
mixture is filtered and the solvent evaporated. The residue is then gravimetrically measured and related back to the
original dried sample weight; results are reported as %EO.

3.0 INTERFERENCES

3.1 Matrix interferences will likely be coextracted from the sample. The extent of these interferences will vary
from soil to soil, depending on the nature and diversity of the soil being analyzed. Naturally occurring organics, such
as humic acids, would act as chemical interferences, possibly causing positive bias. Even though inherently
empirical, the EO method provides the greatest utility when performed in a consistent manner.

4.0 APPARATUS AND MATERIALS

4.1 Glass Vials: 40-mL with vinyl-lined cap.

4.2 Culture Tubes: 20 mm x 150 mm Pyrex.

4.3 Aluminum Weighing Pans.

4.4 Berzelius Beaker: 200-mL Corning.

FMC-C-010-1

-------
4.5 Evap-O-Rac Apparatus: Cole-Parmer.

4.6 Buchner Funnels: 30-mL Pyrex with coarse porosity fritted disc.

4.7 Sonicator: Heat Systems.

5.0 REAGENTS

5.1 Petroleum Ether: Aldrich.

5.2 Sodium Sulfate: Anhydrous, Aldrich.

5.3 2.4.6-Trimethvlphenol: Aldrich.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.1 All samples are assumed to be hazardous from their constituents within the sample. They may contain
known or suspected carcinogens. Handle samples with the utmost care using good laboratory techniques in
order to avoid harmful exposure. Prepare samples in the fume hood.

7.1.2 Laboratory coats, safety glasses, and surgical gloves should be worn by laboratory analysts at all times
when preparing and handling standards and field and laboratory samples.

7.1.3 Make safety equipment including a fire extinguisher, first aid kit, eye wash, and chemical spill cleanup
kit available for use at all times.

7.1.4 Reduce exposure to chemicals by whatever means available. Analysts should read and observe
guidance from the Material Safety Data Sheets (MSDS) provided by suppliers on initial purchase of reagents.
While not as comprehensive as the MSDS, 7.1.5 describes some important safety information.

7.1.5 Petroleum ether is comprised of the low boiling fractions of petroleum which consists chiefly of
hydrocarbons of the methane series, principally pentanes and hexanes. Petroleum ether is a clear, colorless,
nonfluorescent, highly flammable, volatile liquid. The vapors mixed with air explode if ignited.

CAUTION: Store petroleum ether in a cool place and away from fire.

7.2 Sample Preparation and Analysis

7.2.1 All samples must be oven dried at 105°C prior to analysis. Percent moisture should be determined
in accordance with ASTM Method D 2216-80.

7.2.2 Once dried, weigh out 10 g of sample into a tared vial. Break any lumps into a uniformly small size
using a spatula. For high concentration samples, a 2 g sample may be used. Likewise, lower detection limits
can be achieved using a 30 g sample. A 2 g or 30 g sample aliquot offers an alternative which might be
warranted under certain circumstances.

FMC-C-010-2

-------
7.2.3 Add 25 mL of petroleum ether to the sample vial.

7.2.4	Add a small amount of sodium sulfate. The sodium sulfate is a drying agent which will adsorb water,
possibly freeing bound organics. The matrix should appear as a fine powder in liquid suspension.

7.2.5	Extract by sonification for 3 minutes.

7.2.6	Using a coarse fritted filter, filter the sample mixture into a weighed 25 mm x 150 mm Pyrex culture
tube.

7.2.7	Place the test tube into the Evap-O-Rac and evaporate off the solvent.

7.2.8	Reweigh the test tube and record any weight gain.

7.3 Calculations

7.3.1	Results are to be presented as percent extractable organics (%EO).

Wf ~ W.

%EO = —	i x 100

S

where: EO = Extractable organics,

Wf = Final weight of test tube,

W; = Initial weight of test tube, and
S = Initial dry weight of sample.

7.3.2	Relative percent difference (RPD) for duplicate analyses is calculated as follows.

D1 ~ D2
RPD = —i		 x 100

D1 + D2

2

where: D[ = First duplicate and
D2 = Second duplicate.

7.3.3 Spike percent recovery (%R) is calculated as follows.

= SSR ~ SR x 100
SA

where: SSR	= Spiked sample result,

SR = Sample result, and
SA = Spike added = spike fgl x 0.4 x 100
spike (g) + sample (g)

7.4 Analytical Sequence: The following is an analytical sequence, assuming a 20 sample/day workload.

FMC-C-010-3

-------
7.4.1 The sample lot is to be analyzed as a batch.

7.4.2 The following should be included in the sample batch: 1 lab blank, 1 standard, 1 matrix spike, 1 matrix
spike duplicate, and 1 laboratory duplicate. This makes for a total of 25 samples that should be processed as
a batch.

8.0 QUALITY CONTROL

8.1	Blanks should be analyzed at a frequency of 1 in 20 samples, with a %EO of less than 0.05 percent for silica

sand.

8.2	2,4,6-Trimethylphenol should be analyzed as a standard at a frequency of 1 in 20 samples. Recoveries
should be at least 80 percent.

8.3	Matrix spikes are administered in order to assess the accuracy of a method. For this method, 2,4,6-
trimethylphenol will be employed as the spike compound. Spikes should be analyzed at a frequency of 1 in 20
samples or 1/day, whichever is more frequent, with a recovery of 60 to 130 percent. A matrix spike duplicate (MSD)
is subsequently analyzed to assess the precision of the method.

8.4	Duplicates are performed as a means of monitoring the precision of a method. Perform duplicate analysis
of samples at a frequency of 1 in 20 samples or 1/day, whichever is more frequent.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-C-010-4

-------
CSL Method

MOISTURE/SOIL/DRYING OVEN

1.0 SCOPE AND APPLICATION

1.1 This quantitative method is used for field screening of soils, wastes, and mixtures of the same for moisture
for purposes of obtaining a factor for correcting the results of other analyses on the same sample to a "dry weight"
basis. This is necessary for sample data comparison.

1.2 Application of this method is limited to those samples having sufficient moisture to have a significant effect
on the values of the other constituents determined on an "as-received", or wet, basis.

1.3 This method measures all components which are volatile under conditions of the test as a group parameter.
Characterization of specific contaminants present in addition to water should occur at remote CLP laboratories
employing EPA approved testing protocols.

1.4 The data produced in the analysis allows the site investigation team to use this parameter in association with
other sample constituents to determine the relative degree of contamination.

1.5 The method detection limit for this method is estimated to be 0.2 percent.

2.0 SUMMARY OF METHOD

The method presented here is adapted for field use from EPA Method 9040 found in EPA SW-846, Test
Methods for Evaluating Solid Wastes. 2nd ed., July 1982. In brief, a well-mixed aliquot of a sample is quantitatively
transferred to a pre-weighed dish and evaporated to dryness at a temperature of 103°C to 105°C. The loss in the
weight of the sample is the moisture.

3.0 INTERFERENCES

3.1 Non-representative material, such as rocks or surface debris, should be excluded if it is determined that their
inclusion is not desired in the final result.

3.2 Non-moisture constituents which are volatile at or below 103°C to 105°C will be measured and reported
as moisture content.

4.0 APPARATUS AND MATERIALS

4.1 Evaporating Dishes: Aluminum weighing pans with a 40-mL capacity.

4.2 Balance: Sartorius, analytical electronic balance, 0.0001 g sensitivity, minimum 110 g capacity.

4.3 Drying Oven: Mechanical forced air or gravity convection for drying at 103 °C to 105°C having an
appropriate thermometer.

4.4 Desiccator.

4.5 Desiccant.

4.6 Mortar and Pestle.

FMC-C-011-1

-------
5.0 REAGENTS

Information not necessary.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.1 All samples are assumed to be hazardous from the constituents within the sample. They may contain
known or suspected carcinogens. The pH of the samples may represent a hazardous condition. Samples should
be handled with the utmost care using good laboratory techniques in order to avoid harmful exposure. Samples
should be prepared in a fume hood.

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves when preparing
and handling the samples.

7.1.3 Make safety equipment including a fire extinguisher, first-aid kit, eye wash, and chemical spill cleanup
kit available for use at all times.

7.1.4 The volatiles driven off the samples while heating are assumed to be hazardous. Inhalation should
be avoided. Place the drying oven inside a fume hood.

7.1.5 Investigate any situation that leads to physical evidence or physical symptoms of exposure
immediately and follow with appropriate corrective action.

7.2 Sample Preparation

7.2.1 Mix the sample in its container with a clean glass rod to obtain homogenous, representative sub-
samples. Perform this in a fume hood.

7.2.2 If necessary, break lumps into a uniformly small size using a mortar and pestle under a fume hood.

7.2.3 If rocks are present in the sample, remove them using forceps. Weigh the rocks and the remaining
sample and record both weights.

7.3 Analysis

7.3.1 Mark a clean aluminum pan on the handle or the bottom with a pencil in order to identify the samples.

7.3.2 Heat a clean aluminum pan to 103°C to 105°C for 1 hour. Remove from the oven with forceps, cool,
desiccate, weigh to the nearest 0.1 mg, and store in the desiccator until ready for use.

7.3.3 Transfer approximately 5 g of prepared sample to the pre-weighed aluminum pan. Weigh to the
nearest 0.1 mg.

7.3.4 Place the pan in the oven and evaporate to dryness. This will take approximately 2 hours.

7.3.5 Remove from the oven and weigh as in 7.3.2.

FMC-C-011-2

-------
7.3.6 Repeat 7.3.2 to 7.3.5 until a constant weight is obtained or until the loss of weight is less than 4
percent of the previous weight or 0.5 mg, whichever is less.

7.4 Calculations

7.4.1	Percent moisture is calculated by the following formula.

% Moisture = —	— x 100

A - B

where: A = Pan + wet sample,

B = Pan, and
C = Pan + dry sample.

7.4.2	Percent solids is calculated by the following formula.

% Solids = 100 - %Moisture

8.0 QUALITY CONTROL

8.1	Duplicate sample should be analyzed at a frequency of 1 in 10 samples or 1/day, whichever is more
frequent.

8.2	The balance should be checked with NBS class S-l weights at the start and end of the project or monthly,
whichever is more frequent.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-C-011-3

-------
CSL Method

PAINT FILTER TEST/SOIL/PAINT FILTERS

1.0 SCOPE AND APPLICATION

1.1 This method is used to determine the presence of free liquids in representative samples of waste and soils.

1.2 Application of this method is used to determine if free liquids are present, which is a criteria for
determining if ignitability and corrosivity shall be performed.

1.3 The method detection limit (MDL) for this method is estimated to be 2.0 percent Volume/Weight (2 mL
from 100 g sample).

2.0 SUMMARY OF METHOD

2.1 The method presented here is adapted for field use from EPA Method 9095 found in SW-846, Test Methods
for Evaluating Solid Wastes. 3rd ed., September 1986. In brief, a predetermined amount of material is placed on a
paint filter. If any portion of the material passes through and drops from the filter within the 5 minute test period,
the material is deemed to contain free liquids.

3.0 INTERFERENCES

3.1 Filter media was observed to separate from the filter cone on exposure to alkaline materials. This
development causes no problem if the sample is not disturbed.

4.0 APPARATUS AND MATERIALS

4.1 Conical Paint Filter: Mesh number 60, available at local paint stores having fine filters for automotive

paint.

4.2 Glass Funnel: Necessary if the paint filter containing the waste cannot sustain its weight on the ring stand;
fluted glass or mouth large enough to allow at least 1 inch of the filter mesh to protrude such as not to interfere with
the movement of material through the filter into the graduated cylinder.

4.3 Ring Stand.

4.4 Graduated Cylinder: 100-mL.

5.0 REAGENTS

None.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not available.

7.0 PROCEDURE

FMC-C-012-1

-------
7.1	Sample Preparation: A 100 mL or 100 g representative sample is required for the test. If it is not possible
to obtain that amount that is sufficiently representative of the waste, the analyst may use multiples of that amount.
However, in this instance, the analyst shall divide the sample into the proper amount and test each portion separately.
If any portion contains free liquids, the entire sample is considered to have free liquids. If the percent of free liquid
needs to be determined, it shall be the average of the sub-samples tested.

7.2	Analysis

7.2.1	Assemble the test apparatus as shown in Figure 1.

7.2.2	Place the sample in the filter. A funnel may be used to support the paint filter.

7.2.3	Allow the sample to drain for 5 minutes into the graduated cylinder.

7.2.4	Record the volume, if any, in mL.

7.3	Calculations

7.3.1 Percent free liquid:

mL X 100

Free Liquid

100 (g or mL)

7.3.2	Report as percent WW (volume/weight) if the sample is in g. Report as percent V/V (volume/volume)
if the sample is in mL.

7.3.3	Adjust values if tested as in 5.1.

8.0 QUALITY CONTROL

8.1 Duplicate samples shall be analyzed at afrequency of 1 in 10 samples or 1/day, whichever is more frequent.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-C-012-2

-------
CSL Method

pH/SOIL/pH METER

1.0 SCOPE AND APPLICATION

1.1 Application of this method is limited to field screening of soils, wastes, and mixtures of same for pH. It
is presented as a means of rapidly characterizing field samples and is used as an indicator of contamination at the site.

1.2 The method measures the pH produced by water soluble constituents from the sample. Further
characterization of specific contaminants in duplicate or similar composite samples should be supported by a remote
CLP laboratory employing EPA approved testing protocols.

1.3 The data produced in the analysis allows the site investigation team to examine the relative degree of
contamination associated with other sample constituents as found by the site team or remote CLP laboratory. The
pH can be compared between samples spatially related to each other in vertical or horizontal planes and with
background.

1.4 The precision/accuracy of the method is ± 0.1 pH units.

2.0 SUMMARY OF METHOD

2.1 The method presented here is adapted for field use from EPA Method 9040 found in EPA SW-846, Test
Methods for Evaluating Solid Wastes. 2nd ed., July, 1982. In brief, a well mixed, weighed aliquot of sample is mixed
with an equal weight of deionized water for a specified period of time. The suspension is allowed to settle. The pH
of the upper aqueous phase is measured electrometrically using a pH meter and combination electrode.

3.0 INTERFERENCES

3.1 The combination electrode, in general, is not subject to solution interferences from color, turbidity, colloidal
matter, oxidants, reductants, or high salinity.

3.2 Sodium error occurs at pH levels greater than pH 10.

3.3 Coatings of oily material or particulate matter can impair the electrode response. These coatings can
usually be removed by gentle wiping or detergent washing, followed by deionized water rinsing. Additional treatment
described in the electrode instructions may be necessary to restore electrode response.

3.4 Temperature affects the electrometric measurement of pH. For this work, measurement at room
temperature will be sufficient.

4.0 APPARATUS AND MATERIALS

4.1 Balance: Sartorius, top loading electronic with 1500 g capacity and 0.01 g sensitivity and taring feature.

4.2 pH Meter: Chemtrix model 600 meter with combination pH electrode.

4.3 Sample Cups: 3 oz capacity.

4.4 Wash Bottle.

FMC-C-013-1

-------
4.5 Magnetic Stirrer and Stir Bars.

4.6 Mortar and Pestle.

5.0 REAGENTS

pH Buffer Solutions: pH 4.0, 7.0, and 10.0, purchased from supplier.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Safety

7.1.1 The pH of the samples may represent a hazardous condition. Additionally, all samples are considered
to be hazardous from the constituents in the sample. They may contain known or suspected carcinogens.
Handle samples with utmost care using good laboratory techniques in order to avoid harmful exposure. Prepare
samples in a fume hood.

7.1.2 Laboratory analysts shall wear laboratory coats, safety glasses, and surgical gloves when preparing
and handling the samples.

7.1.3 Make safety equipment, including a fire extinguisher, first aid kit, eye wash, and chemical spill
clean-up kit available for use at all times.

7.1.4 Investigate any situation which leads to physical evidence or phvsical symptoms of exposure
immediately, and follow with appropriate corrective action.

7.2 Sample Preparation

7.2.1 Mix the sample in its container with a clean glass rod to obtain homogenous, representative sub-
samples. Perform this in the fume hood.

7.2.2 If necessary, break lumps into a uniformly small size using a mortar and pestle, under the fume hood.

7.2.3 If rocks are present in the sample, remove them using forceps. Weigh the rocks and remaining sample.
Record both weights.

7.3 Calibration

7.3.1 Standardize the pH/electrode system using 2 buffers in accordance with the manufacturer's
instructions. Use the pH 7.0 buffer and the pH 4.0 or pH 10.0 buffer, depending on whether the samples are
expected to be above or below pH 7.0. Recalibrate the system if the sample's pH is not on the same side of pH
7.0 that the instrument was calibrated.

7.3.2 Calibrate each day. Check calibration after all samples have been run.

7.4 Analysis

7.4.1 Allow the sample and pH buffers to come to room temperature and calibrate the system.

FMC-C-013-2

-------
7.4.2	Place a sample cup on the top loading balance. After the reading has stabilized, push the tare bar to
zero the balance.

7.4.3	Accurately weigh approximately 5 g of well mixed sample into the sample cup. Weigh to 0.01 g.
Record the weight. Push the tare bar to re-zero the balance.

7.4.4	While still on the balance, accurately add an equal weight of deionized water dispensed from a fine
tipped wash bottle.

7.4.5	Remove the cup from the balance. Add a stir bar, and place the cup on the magnetic stirrer. Observe
the stirred sample for dispersion of the sample in the water. If the sample is not mixing well, frequently stir
the water/sample extract with a glass rod over the entire mixing period. Mix for 10 minutes.

7.4.6	Let the solid phase settle in the cup.

7.4.7	Insert the pH electrode into the upper aqueous phase to a depth sufficient to cover its sensing element.

7.4.8	Gently swirl the cup until a drift free (0.1 pH) reading is observed. Record the pH to the nearest 0.1
units.

8.0 QUALITY CONTROL

8.1	Duplicate samples should be analyzed at a frequency of 1 in 10 samples or 1/day, whichever is more
frequent. The values should agree to 0.2 pH units.

8.2	The neutrality of the deionized water should be checked daily by using short range pH paper.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-C-013-3

-------
CSL Method

SPECIFIC GRAVITY OF SOILS

1.0 SCOPE AND APPLICATION

1.1 This method can be used to determine the specific gravity of soils by means of a pycnometer. The soil is
composed of particles larger than the Number 4 (4.75 mm) sieve. The specific gravity value for the soil shall be the
weighted average of the two values.

1.2 The values stated in acceptable metric units are to be regarded as the standard.

1.3 Specific gravity is the ratio of the mass of a unit volume of a material at a stated temperature to the mass
in air of the same volume of gas-free deionized distilled water at a stated temperature.

2.0 SUMMARY OF METHOD

2.1 The specific gravity of a soil is used in almost every equation expressimg the phase relationship of air,
water, and solids in a given volume.

2.2 The term "solid particles," as used in geotechnical engineering, is typically assumed to mean naturally
occurring mineral particles that are not very soluble in water. Therefore the specific gravity of materials containing
extraneous materials (such as cement, lime, etc.), water-soluble matter (such as sodium chloride), and soils containing
matter with a specific gravity of less than one, typically require special treatment of a qualified definition of specific
gravity.

3.0 INTEREFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Pvcnometer: Either a volumetric flask having a capacity of at least 100 ml or a stoppered bottle having a
capacity of at least 50 ml. The stopper shall be of the same material as the bottle, and of such size and shape that it
will be easily inserted to a fixed depth in the neck of the bottle and shall have a small hole through its center to permit
emission of air and surplus water.

5.0 REAGENTS

Information not available.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Place the sample in the pycnometer, taking care not to lose any of the soil in case the weight of the sample
has been determined. Add deionized distilled water to fill the volumetric flask about three-fourths full or the
stoppered bottle about half full.

7.2 Remove entrapped air by either of the following methods:

FMC-C-014-1

-------
7.2.1 Subject the contents to a partial vacuum (air pressure not exceeding 100 mmHg).

7.2.2 Boil gently for at least 10 minutes while occasionally rolling the pycnometer to assist in the removal
of air.

7.2.3 Subject the contents to reduced air pressure either by connecting the pycnometer directly to an
aspirator or vacuum pump, or by use of a bell jar. Some soils boil violently when subjected to reduced air
pressure. It will be necessary in those cases to reduce the air pressure at a slower rate or to use a larger flask.
Cool samples that are heated to room temperature.

7.3 Fill the pycnometer with deionized distilled water, clean the outside and dry with a clean, dry cloth.
Determine the weight of the pycnometer and contenst, Wb and the temperature in degrees Celsius, Tx, of the contents.

7.4 Calculation

7.7.1 Calculate the specific gravity of the soil, based on water at a temperature Tx, as follows:

VI.

Specific Gravity, T =

W + ( W - W )

where: W0 = Weight of sample of oven dry soil g;

Wa = Weight of pycnometer filled with water at temperature Tx, g;

Wb = Weight of pycnometer filled with water and soil at temperature Tx, g; and

Tx = Temperature of the contents of the pycnometer when weight Wb was determined, C°.

7.7.2 Unless otherwise required, specific gravity values reported shall be based on water at 20°C. The value
based on water at 20°C shall be calculated from the value based on water at the observed temperature Tx as
follows:

Specific gravity, TX/20°C = K x specific gravity, Tx/Tx

where: K = A number found by dividing the relative density of water at temperature T, by the relative
density of water at 20°C. Values for a range of tmeperatures are given in Table 1.

7.7.3 When it is desired to report the specific gravity value based on water at 4°C, such a specific gravity
value may be calculated by multiplying the specific gravity value at temperature Tx, by the relative density at
temperature Tx.

7.7.4 When any portion of the orginial sample of soil is eliminated in the preparation of the test sample, the
portion on which the test has been made shall be reported.

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

FMC-C-014-2

-------
1. Annual Book of ASTM Standards, "Specific Gravity of Soils", Standard D 854-83, Method D, p 156 (1983)

FMC-C-014-3

-------
CSL Method

TOTAL CARBON/SOIL/COMBUSTION TRAIN

I.0 SCOPE AND APPLICATION

1.1 This Close Support Laboratory (CSL) method is used for field screening soils, wastes, and mixtures of the
same for total carbon (TC) as an indicator of organic constituent contamination at the site.

1.2 Application of this method is limited to the screening analysis for TC in waste and soils.

1.3 This method measures volatile, semivolatile, and nonvolatile organic constituents present in a sample as
a group parameter. Characterization of specific organic contaminants in duplicate or similar composite samples may
occur at remote CLP laboratories employing EPA approved testing protocols.

1.4 The data produced in the analysis allows the site investigation team to examine the relative degree of
contamination associated with other sample constiuents. The TC content can be compared between samples spatially
related to each other in vertical or horizontal planes and with background.

1.5 This method does not distinguish carbon from mineral sources or humus sources in soil from carbon of
waste origin. Both calcium carbonate (CaC03) and ground pine needles, if present, would be measured as TC.
Inorganic carbon may be separately determined by other methods.

1.6 The method detection limit (MDL) for this method is estimated to be 0.02 percent. The analytical range
is estimated to be from 0.02 to 93 percent (for triphenylmethane). This method is not applicable to liquid samples,
such as water and wastewaters, having TC in the parts per million range.

2.0 SUMMARY OF METHOD

2.1 The method presented here is a manual method adapted for field use from these sources: EPA/CE-81-1,
EPA/Corps of Engineers Procedures for Handling and Chemical Analysis of Sediment and Water Samples, TOC
Procedure for Sediment Samples, May, 1981; American Society of Testing and Materials, ASTM E777-81, Vol.

II.04, 1986 edition; and Commercial Methods of Analysis, Snell and Biffen, p. 284-284, 1964.

2.2 In brief, a sample is ignited in a high temperature furnace in the presence of pure oxygen converting any
carbon present to its combustion product, carbon dioxide. The carbon dioxide is absorbed on ascarite, sodium
hydroxide impregnated mineral fibers. The carbon dioxide absorbed is determined gravimetrically using an analytical
balance. The carbon dioxide weight gain is calculated to the carbon concentration in the sample. The configuration
of the TC analysis train is shown in Figure 1.

3.0 INTERFERENCES

3.1 Carbon dioxide from the atmosphere and oxygen can be absorbed by the ascarite and weighed. A trap is
used to remove carbon dioxide prior to entering a furnace. An airtight system is maintained during the analysis to
prevent gain from or loss to the atmosphere.

3.2 Moisture can be absorbed by the ascarite and weighed. Traps are used for drying the oxygen supply to the
furnace and the combustion offgas from the furnace prior to ascarite absorption of carbon dioxide.

3.3 Sulfur dioxide from combustion can be absorbed by the ascarite and weighed. A chromic acid trap is used
to convert sulfur dioxide to sulfate and absorb it.

FMC-C-015-1

-------
3.4 Organics from equipment handling (fingerprints), airborne dust, cleaning residue, etc., can effect the results.
Care should be used in cleaning. Forceps and tongs will be used in handling equipment.

3.5 Traces of analysis chemicals on the outer surfaces of glassware can absorb carbon dioxide and/or water.
Outer surfaces should be clean and dry.

3.6 Sample drying or excessive handling may result in the loss of volatile organic constituents which contribute
to the TC. Whenever possible, sample analysis should be on a "as-received" basis, minimizing sampling handling
to obtain representative aliquots to analyze.

3.7 Delayed analysis may result in loss of volatiles, biodegradation, or other physical chemical changes
effecting the TC results. In the event that analysis is delayed to the next day, samples should be refrigerated.

4.0 APPARATUS AND MATERIALS

4.1 Tube Furnace: Lindberg, single heating zone, split furnace controlling temperatures at 1000°C to 1300°C.

4.2 Balance: Sartorius, top loading, electronic balance, 1500 g capacity with 0.01 g sensitivity for sample
preparation.

4.3 Balance: Sartorius, analytical electronic balance, 0.0001 g sensitivity, minimum 110 g capacity.

4.4 Furnace Combustion Tube: McDanel, one reduced end, 22 mm I.D. x 29 mm O.D. x 30 cm L, maximum
working temperature of 1400°C.

4.5 Combustion Boats: Fisher, heavy gauge nickel boats, minimum 2 in number, 89 mm L x 16 mm W x 9.5
mm D hole to facilitate removal at one end.

4.6 Combustion Boats: Fisher, ceramic disposable boats and boat covers essentially free of carbon, 95 mm L
x 13 mm W x 11 mm D, for use with oily samples.

4.7 Oxygen TCP Purifying Train: Between the 02 cylinder and the furnace.

4.7.1 Water Absorber: Gas drying cylinder containing indicating Drierite.

4.7.2 Carbon Dioxide fC02') Absorber: Drying tube or U-tube containing Ascarite.

4.7.3 Water Absorber: Drying tube containing Aquasorb.

4.8 Offgas Purifying Train: After the furnace.

4.8.1 Acid Trap: Fisher, bubble counter containing no reagent for preventing acid carryback into the
furnace.

4.8.2 Water Absorber/flow Rate Indicator: Fleming absorption bulb containing chromic acid.

4.8.3 Water Absorber: U-tube containing magnesium perchlorate, Mg(C104)2.

4.9 Carbon Dioxide Absorption Tower: Either a Nesbitt bulb for a 160 g capacity balance, or a Stetser-Norton
bulb for a 110 g capacity balance.

5.0 REAGENTS

FMC-C-015-2

-------
5.1 Oxygen: 99.99 percent pure, water less than 5 ppm, hydrocarbons less than 1 ppm, carbon monoxide less
than 0.2 ppm, and carbon dioxide less than 0.5 ppm, metal-oxide semi-conductor grade or better, complete with two
stage oxygen regulator or nitrogen regulator with an adapter.

5.2 Combustion Boat Reagents

5.2.1 Alundum: Reagent grade, 60 mesh, containing less than 0.0015 percent carbon.

5.2.2 Tin: Reagent grade, 20 mesh fine grain, containig less than 0.0015 percent carbon.

5.3 Absorber Reagents

5.3.1 Drierite: Self indicating, 10-20 mesh.

5.3.2 Ascarite: Self indicating, 20-30 mesh.

5.3.3 Aquasorb: Indicating phosphorous pentoxide, pre-packed in drying tubes.

5.3.4 Magnesium perchlorate: Reagent grade, anhydrous salt, granular.

5.3.5 Sulfuric acid: Reagent grade, concentrated acid at 95 to 98 percent composition.

5.3.6 Potassium dichromate: Reagent grade.

5.3.7 Chromic acid: Made in the laboratory by adding some potassium dichromate to the concentrated
sulfuric acid bottle and mixing in order to obtain a saturated solution having undissolved dichromate crystals
in the bottom.

5.4 Carbon Standards

5.4.1 Dextrose: Reagent grade, anhydrous powder, 40.0 percent carbon.

5.4.2 Potassium hydrogen phthalate fKHP): Reagent grade, primary standard 47.07 percent carbon.

5.4.3 Performance check: 5 percent w/w concentration made with 12.5 g dextrose and 87.5 g Bentonite,
20-200 mesh, well ground and mixed with a mortar and pestle.

5.4.4 Reference sample: National Bureau of Standards (NBS), Standard Reference Material (SRM), if
available.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not available.

7.0 PROCEDURE

7.1 Sample Preparation

7.1.1 Mix the sample in its container with a clean glass rod to obtain homogenous, representative
sub-samples. Perform this in the fumehood.

FMC-C-015-3

-------
7.1.2	If necessary, break lumps into uniformly small size using a mortar and pestle located in the fume hood.

7.1.3	If rocks are present in the sample, remove them using forceps. Weigh the rocks and remaining sample
and record the weights.

7.2	System Preparation

7.2.1	Connect copper tubing from the 2-stage oxygen regulator to the needle valve gas flow control near the
furnace.

7.2.2	Assemble the oxygen purifying train in the order listed in 4.7 using amber latex tubing from the needle
valve through the train to a glass tube in a rubber stopper which fits the open end of the combustion tube.

7.2.2.1 Use filter wool at each end of the absorbing tubes to prevent movement of the absorbents,
Ascarite or Drierite.

7.2.3	Assemble the combustion offgas purifying train in the order listed in 4.8 using amber latex tubing from
the reduced end of the combustion tube through the train to the carbon dioxide absorber.

7.2.3.1	Carefully pipet 20 mL of chromic acid into the Fleming absorption bulb.

7.2.3.2	Use filter wool at each end of the U-tube to prevent movement of the magnesium perchlorate.

7.2.4	Assemble the carbon dioxide absorption tower.

7.2.4.1	Place filter wool in the bottom 5 mm of the Nesbitt or Stetser-Norton bulb.

7.2.4.2	Using a glass funnel, add 5 mm depth of magnesium perchlorate on the top of the filter wool.

7.2.4.3	Mix the Ascarite by shaking in its original container. Using a glass funnel, add Ascarite on top
of the magnesium perchlorate. Add to a depth such that the final weight of the absorber will be at least 10
g less than the capacity of the analytical balance.

7.2.4.4	Using a glass funnel, add another 5 mm depth of magnesium perchlorate on top of the Ascarite.

7.2.4.5	Place 5 mm of filter wool on top of the magnesium perchlorate.

7.3	Analysis Preparation

7.3.1	Turn on furnace to allow it to warm up to 1000°C to 1300°C. Leave the furnace on all the time to
allow analysis without waiting for the furnace to warm up. Temperatures in excess of 1400°C may damage
the combustion tube.

7.3.2	Turn on the first stage oxygen cylinder valve to full tank pressure. Adjust the second stage reducing
valve to 20 psi. Replace the oxygen cylinder when the tank pressure falls below 25 psi.

7.3.3	Close the needle valve control and check for leaks in the system from the oxygen cylinder to the needle
valve.

FMC-C-015-4

-------
7.3.4 Adjust the overall system flow rate to approximately 100 mL/minute using the needle valve control;
the flow is indicated by a steady stream of bubbles in the chromic acid in the Fleming absorption bulb. Too
much oxygen flow (500 mL/min) is indicated by violent bubbling at the chromic acid surface.

7.3.5 Analyze consecutive blanks consisting of a boat containing alundum in accordance with 7.4. System
stability is shown by a carbon dioxide absorber weight difference of less than 0.0015 g, the detection limit for
a 2 g sample.

7.3.6 Analyze consecutive standards in accordance with the procedures in 7.4. Initial calibration shall be
indicated by 2 consecutive TC valves within 2 percent of the theoretical valve. Alternate dextrose and KHP
standards every other day. Two percent represents ± 0.80 percent for dextrose and ± 0.90 percent for KHP.

7.4 Analysis

7.4.1 Fill a boat with alundum. Use a nickel boat for routine determinations; use a disposable boat with
cover for oily samples.

7.4.2 Use a spatula tip to make a groove in the center of the alundum along the lenghth of the boat within
5 mm of each end.

7.4.3 Lay down a fine line of granular tin into the groove in such a manner that the tin particles touch each
other. To economize, weigh the tin for the first few analyses to determine the minimum amount of tin necessary
for the type of boat used.

7.4.4 Weigh an appropriate size sample into the prepared boat, distributing the sample along the length of
the fine line of tin. Use the balance taring feature and record the weight to the nearest 0.1 mg.

7.4.4.1 Appropriate size samples should yield less than 0.200 g of carbon dioxide. See Table 1 for data.

These sample sizes have been recommended for reasons of representativeness, absorption efficiency, and

absorber recharge minimization. Carbon dioxide yields greater than 0.200 g may provide data of equivalent

quality.

7.4.4.2 Samples may be weighed directly into the boat or into a weighing device (glassine or plastic boat)

if a quantitative transfer to the boat can be accomplished.

7.4.5 Lay down another line of granular tin on top of the sample in the same manner and amount as 7.4.3.
It is not necessary to cover the sample with tin. Take care to avoid having the tin contact the side of the boat.

7.4.6 Crack open the carbon dioxide absorption tower (absorber) for 10 seconds to allow the pressure to
equilibrate to atmospheric pressure. Close and weigh, recording the weight to the nearest 0.1 mg. Place the
absorber near the end of the combustion train.

7.4.7 Using forceps, place the boat in the cool portion of the furnace allowing sufficient clearance for the
rubber stopper.

7.4.8 Insert the rubber stopper into the combustion and adjust the flow rate as in 7.3.4.

7.4.9 After 30 seconds, open the carbon dioxide absorber. Connect the absorber to the tubing from the
combustion gas purifying train, taking care that the connection allows gas flow from the bottom of the absorber
and venting to the atmosphere at the top of the absorber.

7.4.10 Remove the stopper and push the entire boat into the red hot zone of the tube using the furnace tool.

FMC-C-015-5

-------
7.4.11 Insert the stopper, start the timer, and wait for combustion to occur. Generally, but not always, this
occurs with 2 or 3 minutes. Evidence of combustion is reduced oxygen bubbles in the chromic acid followed
by chromic acid rise in the Fleming bulb caused by rapid oxygen consumption during combustion.

7.4.12 It is imperative that a positive oxygen flow rate be maintained over the entire combustion period,
estimated to be 2 minutes in duration. From the first moment that reduced flow is observed, add increasing
amounts of oxygen by opening the needle control valve while trying to maintain a near constant bubble rate in
the chromic acid. Do not add so much oxygen as to cause violent bubbling.

7.4.12.1 Too little oxygen flow can result in chromic acid being pulled back into the tubing, safety trap,

and possibly, the combustion tube itself. This will render the data unusable. Additionally, a safety hazard

will occur should the acid crack the combustion tube and fill the laboratory with acid fumes.

7.4.12.2 Too much oxygen flow can result in breaking a seal in the system or poor carbon dioxide

absorption from the channelling in the Ascarite.

7.4.13 When combustion ceases as evidenced by increased bubbling, reduce the oxygen flow to around 100
mL/minute, as before.

7.4.14 Allow 5 minutes for complete carbon dioxide absorption.

7.4.15 Disconnect the carbon dioxide absorber, close its stopper, and place it by the analytical balance,
allowing 5 minutes for equilibration.

7.4.16 Remove the boat from the combustion tube using the furnace tool to slide it onto a heat resistant
plate.

7.4.17 Crack open the carbon dioxide absorber for 10 seconds, close, and weigh as in 7.4.6.

7.4.18 Remove most of the combustion residue from the boat using forceps. Traces of residue will not
interfere with the next test because they are essentially free of carbon.

7.5 Calculations

7.5.1 Percent carbon, on an "as-received" or wet basis, is calculated as follows.

where: A = Sample weight (g),

B = Final absorber weight (g),

C = Initial absorber weight (g), and
27.29 = 12.011 (molecular weight of CI
44.011 (molecular weight of C02)

7.5.2 Percent carbon, on a dry weight basis, is calculated as follows.

% Carbon (wet basis)

(B - C) x 27.29
A

% Carbon (dry basis)

FMC-C-015-6

-------
where: E = Percent carbon on a wet basis and
% Solids = 100 - % Moisture
100

7.5.3 Relative percent difference (RPD) for duplicate analyses is calculated as follows.

D1 ~ D2
RPD = —i		 x 100

D1 + D2

2

where: D[ = First duplicate and
D2 = Second duplicate

7.5.4 Spike percent recovery (%R) is calculated as follows.

= SSR ~ SR x 100
SA

where: SSR	= Spiked sample result,

SR = Sample result, and

SA = Spike added =	spike fgl x 0.4 x 100

spike (g) + sample (g)

7.6 Analytical Sequence: The following is a typical daily analytical sequence, assuming a 20 sample daily
workload:

7.6.1	Initial blank without tin.

7.6.2	Initial blank with tin (if needed).

7.6.3	Initial standard: Dextrose or KHP on alternating days.

7.6.4	Initial standard as in 7.6.3.

7.6.5	Field samples 1 through 10 (maximum).

7.6.6	Duplicate of 1 of the samples in 7.6.5.

7.6.7	Spike of the same sample in 7.6.6.

7.6.8	Daily performance check sample.

7.6.9	Reference sample (if available and if needed for 1 in 20 requirement).

7.6.10	Continuing blank with tin.

7.6.11	Field samples 11 through 20 (maximum).

FMC-C-015-7

-------
7.6.12 Duplicate of 1 of samples in 7.6.11.

7.6.13 Spike of the same sample in 7.6.12.

7.6.14 Continuing blank with tin.

7.6.15 Final standard: same as 7.6.3.

8.0 QUALITY CONTROL

8.1 Detection Limit: 0.02 percent carbon for 2 g sample. If using a smaller sample which has less than 0.0015
g of absorbed carbon dioxide, rerun the analysis with 2 g or larger sample.

8.2 Blanks: absorber weight gain of less than 0.0015 g.

8.2.1 Initial blanks: without tin.

8.2.2 Continuing blanks: normal proportion of tin performed at a frequency of 1 in 10 or 1 per day,
whichever is more frequent.

8.3 Calibration Standard: ±2 percent of theoretical value for initial calibration and final calibration
performed at the end of each day's analyses.

8.4 Precision: duplicates of ±20 percent RPD performed at a frequency of 1 in 10 field samples or 1 per day,
whichever is more frequent.

8.5 Accuracy: spikes of 75 to 125 percent spike recovery performed at a frequency of 1 in 10 field samples
or 1 per day, whichever is more frequent.

8.5.1 Reference sample of ±10 percent of NBS certified value performed at a rate of 1 in 20 field
samples analyzed (not per day), if the reference material is available.

8.5.2 Performance check sample of ±10 percent of the calculated value performed at the rate of
one per day.

8.6 If any or all parts of 8.2-8.7 are out of compliance, then the cause should be determined and corrective
action taken. Rerun all samples analyzed while the system was out of compliance.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-C-015-8

-------
CSL Method

TOTAL FIXED. AND VOLATILE SOLIDS IN SOLIDS AND SEMISOLIDS SAMPLES

1.0 SCOPE AND APPLICATIONS

1.1 This method is applicable to the detrminanation of total solids and its fixed and volatile fractions in such
soilds and semisolids samples as river and lake sediments, sludges separated from water and wastewater treatment
processes, and sludge cakes from vacuum filtration, centrifugation, or other sludge dewatering processes.

2.0 SUMMARY OF METHOD

2.1 The residue obtained from the determination of total, suspended or dissolved residue is ignited at 550°C
in a muffle furnace. The loss of weight on ignition is reported as mg/L volatile residue.

3.0 INTERFERENCES

3.1 The determination is subject to negative error due to loss of ammonium carbonate and volatile organic
matter during drying.

3.2 Carefully observe specified ignition time and temperature to control losses of volatile inorganic salts.

3.3 After drying or ignition, residues often are very hydroscopic and rapidly absorb moisture from the air.
4.0 APPARATUS AND MATERIALS

4.1 Drying Oven: For operation at 103 10 105°C.

4.2 Desiccator.

4.3 Analytical Balance: Capable of weighing to 10 mg.

4.4 Evaporating Dishes: Porcelain, 90 mm diamter and 100 mL volume. Platinum dishes may be
substituted.

4.5 Muffle Furnace: For operation at 550 ± 50°KEYBOARD().

4.6 Steam Bath.

5.0 REAGENTS

Information not required.

6.0 SAMPLE HANDLING AND PRESERVATIONS

6.1 Preservation of the sample is not practical; analysis should begin as soon as possible. Refrigeration or
icing to 4°C, to minimize microbiological decomposition of solids, is recommended.

7.0 PROCEDURE

7.1 Total Solids

FMC-C-016-1

-------
7.1.1 Preparation of evaporating dishes:

7.1.1.1 If Volatile solids is also to be measured, heat the clean dish to 550 ± 50°C) for one
hour in a muffle furnace. If only total dissolved soilds are to be measured heat the clean dish at 103
to 105°C for one hour. Cool in desiccator and store until needed. Weigh immediately before use.

7.1.2 Sample Analysis:

7.1.2.1 Fluid Samples: If the sample contains enough moisture to flow more or less
readily, stir to homogenize, place 25 to 50 g in a prepared evaporating dish, and weigh. Evaporate
to dryness on a water bath, dry at 103 to 105°C for 1 hour, cool to balance temperature in an
individual desiccator containing fresh desiccant and weigh.

7.1.2.2 Solid Samples: If the sample consists of discrete pieces of soil material, take cores
from each piece with a No. 7 cork borer or pulverize the entire sample coarsely on a clean surface
by hand, using rubber gloves. Place 25 to 50 g in a prepared evaporating dish, and weigh. Place in
an oven at 103 to 105°C overnight. Cool to balance temperature in an individual desiccator
containing fresh desiccant and weigh.

7.2 Fixed and Volatile Solids

7.2.1 Transfer to a cool muffle furnace, heat furnace to 550 ± 50°C, and ignite for 1 hour. (If the
residue from 7.1.2 above contains large amounts of organic matter, first ignite the residue over a gas burner
and under an exhaust hood in the presence of adequate air to lessen losses due to reducing conditions and
to avoid odors in the laboratory.) Cool in desiccator to balance temperature and weigh.

7.5 Calculations

7.5.1 Calculate percent total solids as follows:

% total solids = (A - B) x 1.000
C -B

7.5.2 Calculate percent volatile solids as follows:

% volatile solids = (A - D) x 1.000
A -B

7.5.3 Calculate percent fixed solids as follows:

% fixed solids = (D - B) x 1.000
A -B

where: A

Weight of dried residue + dish in mg;

Weight of dish in mg;

Weight of wet sample + dish in mg; and
Weight of residue + dish after ignition in mg.

B
C
D

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

FMC-C-016-2

-------
Information not available.

10.0 REFERENCES

1. Standard Methods for Examination of Water and Wastewater, 15th Edition, p. 99, Method 209 F, 1981.

FMC-C-016-3

-------
ERT Method

WATER LEVEL MEASUREMENT

1.0 SCOPE AND APPLICATION

1.1 The purpose of this Standard Operating Procedure (SOP) is to set guidelines for the determination of
the depth to water and floating chemical product (i.e., gasoline, kerosene) in an open borehole, cased borehole,
monitoring well or piezometer.

1.2 Generally, water level measurements taken in boreholes, piezometers, or monitoring wells are used to
construct water table or potentiometric surface maps and to determine flow direction as well as many other aquifer
characteristics. Therefore, all water level measurements at a given site should be collected within a 24-hour period
with a great deal of accuracy. Certain situations may necessitate that all water level measurements be taken within
a shorter time interval. These situations may include:

• The magnitude of the observed changes between wells appears too large;

• Atmospheric pressure changes;

• Aquifers which are tidally influenced;

• Aquifers affected by river stage, impoundments, and/or unlined ditches;

• Aquifers stressed by intermittent pumping of production wells;

• Aquifers being actively recharged due to precipitation event; and

• Occurrence of pumping.

1.3 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as
required, dependent on site conditions, equipment limitations or limitations imposed by the procedure or other
procedure limitations. In all instances, the ultimate procedures employed should be documented and associated with
the final report.

1.4 Mention of trade names or commercial products does not constitute US EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 A survey mark should be placed on the casing for use as a reference point for measurement. Generally,
the reference point is made at the top of casing or "stickup", but often the lip of the riser pipe is not flat. Another
measuring reference should be located on the grout apron. The measuring point should be documented in the site
logbook and on the groundwater level data form (Appendix A). Every attempt should be made to notify future field
personnel of such reference point in order to ensure comparable data and measurements.

2.2 Prior to measurement, water levels in piezometers and monitoring wells should be allowed to stabilize
for a minimum of 24 hours after well construction and development. In low yield situations, recovery may take
longer. All measurements should be made to an accuracy of 0.01 feet.In general, working with decontaminated
equipment, proceed from least to most contaminated wells. Where many wells are to be sampled (i.e., greater than
ten), measurements may be taken in a systematic manner to insure efficiency and accuracy. Open the well and
monitor headspace with the appropriate monitoring instrument to determine the presence of volatile organic

FMC-C-017-1

-------
compounds. Lower water level measurement device into well until water surface or bottom of casing at least twice
is encountered.

2.3 Measure distance from water surface to reference point on well casing at least twice and record in site
logbook and/or groundwater level data form. Remove all downhole equipment, decontaminate as necessary, and
replace casing cap. Note that if floating hydrocarbon product is present, a special dual liquid water level indicator
is required.

3.0 INTERFERENCES

3.1 The chalk used on steel tape may contaminate the well.

3.2 Cascading water may obscure the water mark or cause it to be inaccurate.

3.3 Many types of electric sounders use metal indicators at five-foot intervals around a conducting wire.
These intervals should be checked with a surveyor's tape (preferably with units divided in hundredths of a foot) to
insure accuracy.

3.4 If there is oil present on the water, it can insulate the contacts of the probe on an electric sounder or give
false readings due to thickness of the oil. It is recommended to determine the thickness and density of the oil layer
in order to determine the correct water level. A special liquid water level indicator is required.

3.5 Turbulence in the well and/or cascading water can make water level determination difficult with either
an electric sounder or steel tape.

3.6 An airline measures drawdown during pumping. It is only accurate to 0.5 foot unless it is calibrated for
various drawdowns.

4.0 APPARATUS AND MATERIALS

4.1 There are a number of devices which can be used to measure water levels. The device must be capable
of attaining an accuracy of 0.01 feet, and calibrated on a regular basis.

4.2 Air Monitoring Equipment.

4.3 Well Depth Measurement Device.

4.4 Electronic Water Level Indicator.

4.5 Metal Tape Measure.

4.6 Airline.

4.7 Chalk.

4.8 Ruler.

4.9 Logbook.

4.10 Paper Towels.

4.11 Groundwater Water Level Data Forms.

FMC-C-017-2

-------
4.12 pH Meter (optional).

4.13 Specific Conductivity Meter (optional).

4.14 Thermometer (optional).

5.0 REAGENTS

5.1 No chemical reagents are used in this procedure; however, decontamination solutions may be necessary.
If decontamination of equipment is required, refer to ERT SOP #2006, Sampling Equipment Decontamination, and
the site specific work plan.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 This section is not applicable to this standard operating procedure (SOP).

7.0 PROCEDURES

7.1 Preparation

7.1.1 Determine the extent of the sampling effort, the sampling methods to be employed, and the
types and amounts of equipment and supplies needed.

7.1.2 Obtain necessary sampling and monitoring equipment.

7.1.3 Decontaminate or pre-clean equipment, and ensure that it is in working order.

7.1.4 Prepare scheduling and coordinate with staff, clients, and regulatory agency, if appropriate.

7.1.5 Perform a general site survey prior to site entry in accordance with the site specific Health
and Safety Plan.

7.1.6 Identify and mark all sampling locations.

7.2 Procedures

7.2.1 Make sure water level measuring equipment is in good operating condition.

7.2.2 If possible and when applicable, start at those wells that are least contaminated and proceed
to those wells that are most contaminated.

7.2.3 Clean all equipment entering well by the following decontamination procedure:

7.2.3.1 Triple rinse equipment with deionized water;

7.2.3.2 Wash equipment with an Alconox solution which is followed by a deionized water

rinse;

7.2.3.3 Rinse with an approved solvent (e.g., methanol, isopropyl alcohol, acetone) as per
the work plan, if organic contamination is suspected; and

7.2.3.4 Place equipment on clean surface such as a teflon or polyethylene sheet.

FMC-C-017-3

-------
7.2.4 Remove locking well cap, note well ID, time of day, elevation (top of casing) and date in site
logbook or an appropriate groundwater level data form.

7.2.5 Remove well casing cap.

7.2.6 If required by site-specific condition, monitor headspace of well with a photoionization
detector (PID) or flame ionization detector (FID) to determine presence of volatile organic compounds, and
record in site logbook.

7.2.7 Lower electric water level measuring device or equivalent (i.e., permanently installed
transducers or airline) into the well until water surface is encountered.

7.2.8 Measure the distance from the water surface to the reference measuring point on the well
casing or protective barrier post and record in the site logbook. In addition, note that the water level
measurement was from the top of the steel casing, the top of the PVC riser pipe, the ground surface, or some
other position on the well head.

7.2.9 The groundwater level data forms (Form 1, Appendix A) should be completed.

7.2.10 Measure total depth of well (at least twice to confirm measurement) and record in site
logbook or on groundwater level data form.

7.2.11 Remove all downhole equipment, replace well casing cap and locking steel caps.

7.2.12 Rinse all downhole equipment and store for transport to next well. Decontaminate all
equipment as outlined in Step 3 above.

7.2.13 Note any physical changes, such as erosion or cracks in protective concrete pad or variation
in total depth of well, in field logbook and on groundwater level data form.

7.3 Calculations

7.3.1 To determine groundwater elevation above mean sea level, use the following equation:

7.4 Health and Safety

7.4.1 When working with potentially hazardous materials, follow USEPA, OSHA, or corporate
health and safety practices.

8.0 QUALITY CONTROL

8.1 All data must be documented on standard chain of custody forms, field data sheets, groundwater level
data forms, or within personal/site logbooks.

8.2 All instrumentation must be operated in accordance with operating instructions as supplied by the
manufacturer, unless otherwise specified in the work plan. Equipment checkout and calibration activities must occur
prior to sampling/operation, and they must be documented.

E = E - D

where: Ew
E
D

Elevation of water above mean sea level (ft) or local datum;

Elevation above sea level or local datum at point of measurement (ft); and

Depth to water (ft).

FMC-C-017-4

-------
8.3 Each well should be tested at least twice in order to compare results.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

1.	U.S. Environmental Protection Agency, 1986. RCRA Groundwater Monitoring Technical Enforcement
Guidance Document, pp. 207.

2.	U.S. Environmental Protection Agency, 1987, A Compendium of Superfund Field Operations Methods.
EPA/540/p-87/001 Office of Emergency and Remedial Response Washington, D.C. 20460.

FMC-C-017-5

-------
ERT Method

CONTROLLED PUMPING TEST

1.0 SCOPE AND APPLICATION

1.1 The most reliable and commonly used method of determining aquifer characteristics is by controlled
aquifer pumping tests. Groundwater flow varies in space and time and depends on the hydraulic properties of the
rocks and the boundary conditions imposed on the groundwater system. Pumping tests provide results that are more
representative of aquifer characteristics than those predicted by slug or bailer tests. Pumping tests require a greater
degree of activity and expense, however, and are not always justified for all levels of investigation. As an example,
slug tests may be acceptable at the reconnaissance level whereas pumping tests are usually performed as part of a
feasibility study in support of designs for aquifer remediation.

1.2 Aquifer characteristics which may be obtained from pumping tests include hydraulic conductivity (K),
transmissivity (T), specific yield (Sy) for unconfined aquifers, and storage coefficient (S) for confined aquifers. These
parameters can be determined by graphical solutions and computerized programs. The purpose of this standard
operating procedure (SOP) is to outline the protocol for conducting controlled pumping test.

1.4 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 It is desirable to monitor pre-test water levels at the test site for about one week prior to performance
of the pump test. This information allows for the determination of the barometric efficiency of the aquifer, as well
as noting changes in head, due to recharging or pumping in the area adjacent to the well. Prior to initiating the long
term pump test, a step test is conducted to estimate the greatest flow rate that may be sustained by the pump well.

2.2 After the pumping well has recovered from the step test, the long term pumping test begins. At the
beginning of the test, the discharge rate is set as quickly and accurately as possible. The water levels in the pumping
well and observation wells are recorded accordingly with a set schedule. Data is entered on the Pump/Recovery Test
Data Sheet (Appendix A). The duration of the test is determinated by project needs and aquifer properties, but rarely
goes beyond three days or until water levels become constant.

3.0 INTERFERENCES

3.1 Interferences and potential problems include: atmospheric conditions; impact of local potable wells; and
compression of the aquifer due to trains, heavy traffic, etc

4.0 APPARATUS AND MATERIALS

4.1 Tape Measure (subdivided into tenths of feet).

4.2 Submersible Pump.

FMC-C-018-1

-------
4.3	Water Pressure Transducer.

4.4	Electric Water Level Indicator.

4.5	Weighted Tapes.

4.6	Steel Tape (subdivided into tenths of feet).

4.7	Generator.

4.8	Electronic Data-logger (if transducer method is used).

4.9	Watch or Stopwatch with Second Hand.

4.10	Semi-log Graph Paper fif required).

4.11	Water Proof Ink Pen and Logbook.

4.12	Thermometer.

4.13	Appropriate References and Calculator.

4.14	A barometer or Recording Barograph (Tor tests conducted in confined aquifers').

4.15	Heat Shrinks.

4.16	Electrical Tape.

4.17	Flashlights and Lanterns.

4.18	pH Meter.

4.19	Conductivity Meter.

4.20	Discharge Pipe.

4.21	Flow Meter.

5.0 REAGENTS

5.1 No chemical reagents are used for this procedure; however, decontamination solutions may be necessary.
If decontamination of equipment is required, refer to ERT SOP #2006, Sampling Equipment Decontamination and
the site specific work plan.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

This section is not applicable to this SOP.

7.0 PROCEDURES

7.1 Preparation

FMC-C-018-2

-------
7.1.1 Determine the extent of the sampling effort, the sampling methods to be employed, and the
types and amounts of equipment and supplies needed.

7.1.2 Obtain necessary sampling and monitoring equipment.

7.1.3 Decontaminate or preclean equipment, and ensure that it is in working order.

7.1.4 Prepare scheduling and coordinate with staff, clients, and regulatory agency, if appropriate.

7.1.5 Perform a general site survey prior to site entry in accordance with the site specific Health
and Safety Plan.

7.1.6 Identify and mark all sampling locations.

7.2 Field Preparation

7.2.1 Review the site work plan and become familiar with information on the wells to be tested.

7.2.2 Check and ensure the proper operation of all field equipment. Ensure that the electronic
data-logger is fully charged, if appropriate. Test the electronic data-logger using a container of water.
Always bring additional transducers in case of malfunctions.

7.2.3 Assemble a sufficient number of field data forms to complete the field assignment.

7.2.4 The pumping well should be properly developed prior to testing per ERT SOP #2156,
W ellDevelopment.

7.2.5 An orifice, weir, flow meter, container or other type of water measuring device to accurately
measure and monitor the discharge from the pumping well shall be provided.

7.2.6 Sufficient pipe to transport the discharge from the pumping well to an area beyond the
expected cone of depression is needed. Conducting a pumping test in contaminated groundwater may require
treatment, special handling, or a discharge permit before the water can be discharged.

7.2.7 The discharge pipe must have a gate valve to control the pumping rate.

7.2.8 Determine if there is an outlet near the well head for water quality determination and
sampling.

7.3 Pre-Test Monitoring

7.3.1 It is desirable to monitor pretest water levels at the test site for about one week prior to
performance of the test. This can be accomplished by using a continuous-recording device such as a
Stevens Recorder. This information allows the determination of the barometric efficiency of the aquifer
when barometric records are available. It also helps determine if the aquifer is experiencing an increase or
decrease in head with time due to recharge or pumping in the nearby area, or diurnal effects of
evapotranspiration. Changes in barometric pressure are recorded during the test (preferably with an on-site
barograph) in order to correct water levels for any possible fluctuations which may occur due to changing
atmospheric conditions. Pretest water level trends are projected for the duration of the test. These trends

FMC-C-018-3

-------
and/or barometric changes are used to "correct" water levels during the test so they are representative of the
hydraulic response of the aquifer due to pumping of the test well.

7.4 Step Test

7.4.1 Prior to initiating a long term pumping test, a step test shall be conducted. The purpose of
a step test is to estimate the greatest flow rate that may be sustained during a long term test. The test shall
be performed by progressively increasing the flow rate on one hour intervals. The generated drawdown
versus time data is plotted on semilogarithmic graph paper, and the discharge rate is determined from this
graph.

7.5 Pump Test

7.5.1 Time Intervals: After the pumping well has fully recovered from the step test, the long term
pumping test may start. At the beginning of the test, the discharge rate should be set as quickly and
accurately as possible. The water levels in the pumping well and observation wells will be recorded
according to table 4 and 5.

7.5.2 Water Level Measurements: Water levels will be measured as specified in ERT SOP #2151,
Well Level Measurement. During the early part of the test, sufficient personnel should be available to have
at least one person at each observation well and at the pumping well. After the first two hours, two people
are usually sufficient to continue the test. It is not necessary that readings at the wells be taken
simultaneously. It is very important that depth to water readings be measured accurately and readings
recorded at the exact time measured. Alternately, individual pressure transducers and electronic data-loggers
may be used to reduce the number of field personnel hours required to complete the pumping test. A typical
aquifer pump test form is shown in Appendix A.

7.5.3 Test Duration: The duration of the test is determined by the needs of the project and
properties of the aquifer. One simple test for determining adequacy of data is when the log-time versus
drawdown for the most distant observation well begins to plot as a straight line on the semi-log graph paper.
There are several exceptions to this simple rule of thumb; therefore, it should be considered a minimum
criteria. Different hydrogeologic conditions can produce straight line trends on log-gtime versus drawdown
plots. In general, longer tests produce more definitive results. A duration of one to three days is desirable,
followed by a similar period of monitoring the recovery of the water level. Unconfined aquifers and partially
penetrating wells may have shorter test durations. Knowledge of the local hydrogeology, combined with
a clear understanding of the overall project objectives is necessary in interpreting just how long the test
should be conducted. There is no need to continue the test if the water level becomes constant with time.
This normally indicates that a hydrogeologic source has been intercepted and that additional useful
information will not be collected by continued pumping.

FMC-C-018-4

-------
TABLE 4

Time Intervals for Measuring Drawdown in the Pumped Well

Elapsed Time From Start of Test (Minutes)

Interval between Measurements (Minutes)

0 - 10

0.5 - 1

10 - 15

1

15-60

5

60 - 30

30

300- 1440

60

1440 - termination

480

TABLE 5

Time Interval for Measuring Drawndown in an Observation Well

Elapsed Time From Start of Test (Minutes)

Interval between Measurements (Minutes)

0-60

2

60 - 120

5

120 - 240

10

240 - 360

30

360 - 1440

60

1440 - termination

480

7.6 Post Operation

7.6.1	Decontaminate and/or dispose of equipment as per ERT SOP #2006 Sampling Equipment
Decontamination.

7.6.2	When using an electronic data-logger, use the following procedures.

7.6.2.1	Stop logging sequence; and

7.6.2.2	Print data, or save memory and disconnect battery at the end of the day's activities.

7.6.3	Replace testing equipment in storage containers.

7.6.4	Check sampling equipment and supplies. Repair or replace all broken or damaged equipment.

7.6.5	Review field forms for completeness.

7.6.6	Interpret pumping/recovery test field results.

FMC-C-018-5

-------
7.7 Calcualtions

7.7.1 There are several accepted methods for determining aquifer properties such as transmissivity,
storativity, and conductivity. However, the method to use is dependent on the characteristics of the aquifer
being tested (confined, unconfined, leaky confining layer etc.). When reviewing pump test data the
following texts may be used to determine the method most appropriate to your case. Applied Hydrogeology
(Fetter, 1980). Groundwater and Wells (Driscoll, 1986). Groundwater (Freeze & Cherry, 1979).

7.8 Health and Safety

7.8.1 When working with potentially hazardous materials, following USEPA, OSHA, and corporate
health and safety practices.

8.0 QUALITY CONTROL

8.1 All gauges, transducers, flow meters, and other equipment used in conducting pumping tests shall be
calibrated before use at the site.

8.2 Copies of the documentation of instrumentation calibration should be obtained and filed with the test
data records. The calibration records will consist of laboratory measurements and, if necessary, any on-site zero
adjustment and/or calibration will be performed. Where possible, all flow and measurement meters will be checked
on-site using a container of measured volume and stopwatch; the accuracy of the meters must be verified before
testing proceeds.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

1. Boulton, N.S., 1954. The Drawdown of the Water-Table under Non-Steady Conditions Near a Pumped Well
in an Unconfined Formation", Paper 5979 in Proceedings of the Institution of Civil Engineers, Vol. 3, p. 564.

2. Boulton, N.S., 1963. Analysis of Data from Non-Equilibrium Pumping Tests Allowing for Delayed Yield
from Storage", Paper 6693 in Proceedings of the Institution of Civil Engineers, Vol. 26, pp. 469-82.

3. Bower, H., 1978. Groundwater Hydrology, McGraw-Hill Book Company, New York, New York.

4. Bower, H. and R.C. Rice, 1976. A Slug Test for Determining Hydraulic Conductivity of Unconfined
Aquifers with Completely or Partially Penetrating Wells", Water Resources Research, Vol. 12, No. 3.

5. Bredehoeft, J.D. and S.S. Papadopulos, 1980. A Method of Determining the Hydraulic Properties of tight
Formations", Water Resources Research, Vol. 16, No. 1, pp. 233-238.

6. Cooper, Jr. H.H., J.D., Bredehoeft, and S.S. Papadopulos, 1967. "Response of a Finite-Diameter Well to
an Instantaneous Charge of Water", Water Resources Research, Vol. 13, No. 1.

7. Cooper, Jr., H.H., and C.E., Jacob, 1946. "A Generalized Graphical Method for Evaluating Formation
Constants and Summarizing Well-Field History", American Geophysical Union Transactions, Vol. 27, No. 4, pp.
526-534.

8. Earlougher, R.C., 1977. Advances in Well Test Analysis, Society of Petroleum Engineers of AIME.

FMC-C-018-6

-------
9. Ferris, J.G., and D.B., Knowles, 1954. "The Slug Test for Estimating Transmissivity", U.S. Geological
Survey Ground Water Note 26.

FMC-C-018-7

-------
ERT Method

SLUG TESTS

1.0 SCOPE AND APPLICATION

1.1 This procedure is applicable to determine the horizontal hydraulic conductivity of distinct geologic
horizons under in-situ conditions. The hydraulic conductivity (K) is an important parameter for modeling the flow
of groundwater in an aquifer.

2.0 SUMMARY OF METHOD

2.1 A slug test involves the instantaneous injection or withdrawal of a volume or slug of water or solid
cylinder of known volume. This is accomplished by displacing a known volume of water from a well and measuring
the artificial fluctuation of the groundwater level.

2.2 The primary advantages of using slug tests to estimate hydraulic conductivities are numerous. First,
estimates can be made in-situ, thereby avoiding errors incurred in laboratory testing of disturbed soil samples.
Second, tests can be performed quickly at relatively low costs because pumping and observation wells are not
required. And lastly, the hydraulic conductivity of small discrete portions of an aquifer can be estimated (e.g., sand
layers in a clay).

3.0 INTERFERENCES

3.1 Limitations of slug testing include: 1) only the hydraulic conductivity of the area immediately
surrounding the well is estimated which may not be representative of the average hydraulic conductivity of the area,
and 2) the storage coefficient, S, usually cannot be determined by this method.

4.0 APPARATUS AN MATERIALS

4.1 Tape Measure (subdivided into tenths of feet).

4.2 Water Pressure Transducer.

4.3 Electric Water Level Indicator.

4.4 Weighted Tapes.

4.5 Steel Tape (subdivided into tenths of feet).

4.6 Electronic Data-logger (if transducer method is used).

4.7 Stainless Steel Slug of a Known Volume.

4.8 Watch or Stopwatch with Second Hand.

4.9 Semi-log Graph Paper (if required).

4.10 Water Proof Ink Pen and Logbook.

4.11 Thermometer.

FMC-C-019-1

-------
4.12 Appropriate References and Calculator.

4.13 Electrical Tape.

4.14 2IX Micro logger.

4.15 Compaq Portable Computer or Equivalent with Grapher Installed on The Hard Disk.
5.0 REAGENTS

5.1 No chemical reagents are used in this procedure; however, decontamination solvents may be necessary.
If decontamination of the slug or equipment is required, refer to ERT/REAC Standard Operating Procedure (SOP)
#2006, Sampling Equipment Decontamination and the site specific work plan.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

This section is not applicable to this standard operating procedure (SOP).

7.0 PROCEDURES

7.1 F ield Procedures

The following general procedures may be used to collect and report slug test data. These procedures may
be modified to reflect site specific conditions:

7.1.1 When the slug test is performed using an electronic data-logger and pressure transducer, all
data will be stored internally or on computer diskettes or tape. The information will be transferred directly
to the main computer and analyzed. A computer printout of the data shall be maintained in the files as
documentation.

7.1.2 If the slug test data is collected and recorded manually, the slug test data form (Figure 1,
Appendix A) will be used to record observations. The slug test data form shall be completed as follows:

• Site ID - Identification number assigned to the site;

• Location ID - Identification of location being tested;

• Date - The date when the test data was collected in this order: year, month, day (e.g.,
900131 for Januaiy 31, 1990);

• Slug volume (ft3) - Manufacturers specification for the known volume or displacement of
the slug device;

• Logger - identifies the company or person responsible for performing the field
measurements;

• Test method - The slug device is either injected or lowered into the well or withdrawn or
pulled-out from the monitor well. Check the method that is applicable to the test situation
being run;

• Comments - Appropriate observations or information for which no other blanks are
provided;

FMC-C-019-2

-------
• Elapsed time (min) - Cumulative time readings from beginning of test to end of test, in
minutes; and

• Depth to water (ft) - Depth to water recorded in tenths of feet.

7.1.3 Decontaminate the transducer and cable.

7.1.4 Make initial water level measurements on monitor wells in an upgradient to downgradient
sequence, if possible.

7.1.5 Before beginning the slug test, information will be recorded and entered into the electronic
data-logger. The type of information may vary depending on the model used. When using different models,
consult the operator's manual for the proper data entry sequence to be used.

7.1.6 Test wells from least contaminated to most contaminated, if possible.

7.1.7 Determine the static water level in the well by measuring the depth to water periodically for
several minutes and taking the average of the readings, (see SOP #2151, Water Level Measurements).

7.1.8 Cover sharp edges of the well casing with duct tape to protect the transducer cables.

7.1.9 Install the transducer and cable in the well to a depth below the target drawdown estimated
for the test but at least two feet from the bottom of the well. Be sure the depth of submergence is within the
design range stamped on the transducer. Temporarily tape the transducer cable to the well to keep the
transducer at a constant depth.

7.1.10 Connect the transducer cable to the electronic data-logger.

7.1.11 Enter the initial water level and transducer design range into the recording device according
to manufacturers instructions (the transducer design range will be stamped on the side of the transducer).
Record the initial water level on the recording device.

7.1.12 "Instantaneously" introduce or remove a known volume or slug of water to the well. Another
method is to introduce a solid cylinder of known volume to displace and raise the water level, allow the
water level to restabilize and remove the cylinder. It is important to remove or add the volumes as quickly
as possible because the analysis assumes an "instantaneous" change in volume is created in the well.

7.1.13 With the moment of volume addition or removal assigned time zero, measure and record
the depth to water and the time at each reading. Depths should be measured to the nearest 0.01 foot. The
number of depth-time measurements necessary to complete the test are variable. It is critical to make as
many measurements as possible in the early part of the test. The number and intervals between
measurements will be determined from earlier previous aquifer tests or evaluations.

7.1.14 Continue measuring and recording depth-time measurements until the water level returns
to equilibrium conditions or a sufficient number of readings have been made to clearly show a trend on a
semi-log plot of time versus depth.

7.1.15 Retrieve slug (if applicable).

Note: The time required for a slug test to be completed is a function of the volume of the slug, the hydraulic
conductivity of the formation and the type of well completion. The slug volume should be large enough that
a sufficient number of water level measurements can be made before the water level returns to equilibrium
conditions. The length of the test may range from less than a minute to several hours.If the well is to be

FMC-C-019-3

-------
used as a monitoring well, precautions should be taken that the wells are not contaminated by material
introduced into the well. If water is added to the monitoring well, it should be from an uncontaminated
source and transported in a cleancontainer. Bailers or measuring devices should be cleaned prior to the test.
If tests are performed on more than one monitor well, care must be taken to avoid cross contamination of
the wells. Slug tests shall be conducted on relatively undisturbed wells. If a test is conducted on a well that
has recently been pumped for water sampling purposes, the measured water level must be within 0.1 foot
of the water level prior to sampling. At least one week should elapse between the drilling of a well and the
performance of a slug test.

7.2 Post Operations

7.2.1 When using an electronic data-logger use the following procedure:

7.2.1

.1

Stop logging sequence.

7.2.1

.2

Print data.

7.2.1

.3

Send data to computer by telephone.

7.2.1

.4

Save memory and disconnect battery at the end of the day's activities.

7.2.1

.5

Review field forms for completeness.

7.3 Calcualtions

7.3.1 The simplest interpretation of piezometer recovery is that of Hvorslev (1951). The analysis
assumes a homogenous, isotropic medium in which soil and water are incompressible. Hvorslev's expression
for hydraulic conductivity (K) is:

K= r2ln ( L/R) forL/R>8
2 LT0

where: K	=	hydraulic conductivity [ft/sec]

r	=	casing radius [ft]

L	=	length of open screen (or borehole) [ft]

R	=	filter pack (borehole) radius [ft]

T0	=	Basic Time Lag [sec]; value of t on semi-logarithmic plot of H-h/H-JI vs. t,

where H-h/H-H0 = 0.37

H	=	initial water level prior to removal of slug

H0	=	water level at t = 0

h	=	recorded water level at t > 0

(Hvorslev, 1951; Freeze and Cherry, 1979)

The Bower and Rice method is also commonly used for K calculations. However, it is much more time
consuming than the Hvorslev method. Refer to Freeze and Cherry or Applied Hydrogeology (Fetter) for a
discussion of these methods.

7.3 Health and Safety

7.3 Standard health and safety practices will be followed as per the site specific Health and Safety

Plan.

FMC-C-019-4

-------
8.0 QUALITY CONTROL

8.1 The following general quality assurance procedures apply:

8.1.1	All data must be documented on standard chain-of-custody forms, field data sheets, or within
personal/site logbooks.

8.1.2	All instrumentation must be operated in accordance with operating instructions as supplied
by the manufacturer, unless otherwise specified in the work plan. Equipment checkout and calibration
activities must occur prior to sampling/operation, and they must be documented.

8.1.3	Each well should be tested at least twice in order to compare results.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1.	Bower, H., 1978. Groundwater Hydrology, McGraw-Hill Book Company, New York, New York.

2.	Bower, H., and R.C. Rice, 1980. "A Slug Test for Determining the Hydraulic Properties of Tight
Formations", Water Resources Research, Vol. 16, No. 1 pp. 233-238.

3.	Cooper, Jr. H.H., J.D., Bredehoeft, and S.S. Papadopulos, 1967. "Response of a Finite-Diameter
Well to an Instantaneous Charge of Water", Water Resources Research, Vol. 13, No. 1.

4.	DOI (U.S. Department of the Interior), Ground Water Manual, U.S. Government Printing Office,
New York, New York, Washington, D.C.

5.	Earlougher, R.C., 1977. Advances in Well Test Analysis, Society of Petroleum Engineers of AIME.

6.	Ferris, J.G., and D.B., Knowles, 1954. "The Slug Test for Estimating Transmissivity", U.S. Geological
Survey Ground Water Note 26.

7.	Freeze, R. Allen and John A. Cherry, 1979. Groundwater, Prentice-Hall, Inc., Englewood Cliffs, New
Jersey.

8.	Hvorslev, 1951. "Time Lag and Soil Permeability in Ground Water Observations", Bulletin No. 36, U.S.
Army Corps of Engineers p. 50.

9.	Johnson Division, UOP, Inc., 1966. Ground Water and Wells, Johnson Division, UOP, Inc., St. Paul,
Minnesota.

10.	Lohman, S.W., 1982. "Ground Water Hydraulics", U.S. Geological Survey, Paper 708, p. 70. Neuman, S.P.,
1972. "Theory of Flow in Unconfined Aquifers Considering Delayed Response of the Water Table", Water
Resources Research, Vol. 8, No. 4, p. 1031.

11.	Papadopulos, S.S., J.D., Bredehoeft, H.H., Cooper, Jr., 1973. "On the Analysis of Slug Test Data", Water
Resources Research, Vol. 9, No. 4.

12.	Todd, David K., 1980. Ground Water Hydrology, 2nd ed. John Wiley & Sons.

FMC-C-019-5

-------
ERT Method

GENERAL SURFACE GEOPHYSICS

1.0 SCOPE AND APPLICATION

1.1 The purpose of this standard operating procedure (SOP) is to describe the general procedures used to
acquire surface geophysical data that facilitates waste delineation, and geologic,hydrogeologic or other interpretation
related to hazardous waste site characterization. This procedure provides a means of consistently performing the
various surface geophysical methods.

1.2 The media pertinent to these surface geophysical methods are soil/rock and groundwater. The sensitivity
or minimum response of a given method depends on the comparison of the object or area of study to that of its
background (i.e., what the media's response would be like without the object of study). Therefore, the suitability of
surface geophysical methods for a given investigation must be judged on the object's ability to be measured and, the
extent to which the specific setting of the study interferes with the measurement.

1.3 The surface geophysical method(s) selected for application at a site are dependent on site conditions,
such as depth to bedrock, depth to target, urban disturbances (fences, power lines,surface debris, etc.) and atmospheric
conditions. Detectability of the target is dependent on the sensitivity of the instrument and the variation of the field
measurement from the ambient noise.Ambient noise is the pervasive noise associated with an environment.
Therefore, the applicability of geophysical methods at a given site is dependent on the specific setting at that site.

1.4 Five geophysical methods may be utilized in hazardous waste site characterization: magnetometry,
electromagnetics, resistivity, seismology and ground penetrating radar (GPR). Magnetometers maybe used to locate
buried ferrous metallic objects and geologic information. Electromagnetic method scan be used to determine the
presence of metals, electrical conductivity of the terrain, and geologic information. Resistivity methods are used to
determine the electrical resistivity of the terrain and geologic information. Seismic methods are useful in determining
geologic stratigraphy and structure. GPR may be used to locate disturbance in the soil (i.e., trenches, buried utilities
and fill boundaries)and some near surface geologic information.

1.5 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as
required, dependent on site conditions, equipment limitations or limitations imposed by the procedure or other
procedure limitations. In all instances, the ultimate procedures employed should be documented and associated with
the final report.

1.6 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Magnetics

2.1.1 A magnetometer is an instrument which measures magnetic field strength in units of gammas
(nanoteslas). Local variations, or anomalies, in the earth's magnetic field are the result of disturbances
caused mostly by variations in concentrations of ferromagnetic material in the vicinity of the magnetometer's
sensor. A buried ferrous object, such as a steel drum or tank, locally distorts the earth's magnetic field and
results in a magnetic anomaly. The objective of conducting a magnetic survey at a hazardous waste or
groundwater pollution site is to map these anomalies and delineate the area of burial of the sources of these
anomalies.

FMC-C-020-1

-------
2.1.2 Analysis of magnetic data can allow an experienced geophysicist to estimate the areal extent
of buried ferrous targets, such as a steel tank or drum. Often, areas of burial can be prioritized upon
examination of the data, with high priority areas indicating a near certainty of buried ferrous material. In
some instances, estimates of depth of burial can be made from the data. Most of these depth estimates are
graphical methods of interpretation, such as slope techniques and half-width rules, as described by Nettleton
(1976). The accuracy of these methods is dependent upon the quality of the data and the skill of the
interpreting geophysicist. An accuracy of 10 to 20 percent is considered acceptable. The magnetic method
may also be used to map certain geologic measures, such as igneous intrusions,which may play an important
role in the hydrogeology of a groundwater pollution site.

2.1.3 Advantages:

2.1.3.1 Advantages of using the magnetic method for the initial assessment of hazardous
waste sites are the relatively low costs of conducting the survey and the relative ease of completing
a survey in a short amount of time. Little, if any, site preparation is necessary. Surveying
requirements are not as stringent as for other methods and may be completed with a transit or
Brunton-type picket transit and non-metallic measuring tape. Often, a magnetic investigation is a
very cost-effective method for initial assessment of a hazardous waste site where steel drums or
tanks are suspected of being buried.

2.2 Electromagnetics

2.2.1 The electromagnetic method is a geophysical technique based on the physical principles of
inducing and detecting electrical current flow within geologic strata. A receiver detects these induced
currents by measuring the resulting time-varying magnetic field. The electromagnetic method measures bulk
conductivity (the inverse of resistivity) of geologic materials beneath the transmitter and receiver coils.
Electromagnetics should not be confused with the electrical resistivity method. The difference between the
two techniques is in the way that the electrical currents are forced to flow in the earth. In the
electromagnetic method, currents are induced by the application of time-varying magnetic fields,whereas
in the electrical resistivity method, current is injected into the ground through surface electrodes.

2.2.2 Electromagnetics can be used to locate pipes, utility lines, cables, buried steel drums,trenches,
buried waste, and concentrated contaminant plumes. The method can also be used to map shallow geologic
features such as lithologic changes and fault zones.

2.2.3 Advantages:

2.2.3.1 Electromagnetic measurements can be collected rapidly and with a minimum
number of field personnel. Most electromagnetic equipment used in groundwater pollution
investigations is lightweight and easily portable. The electromagnetic method is one of the more
commonly used geophysical techniques applied to groundwater pollution investigations.

2.3 Electrical Resistivity

2.3.1 The electrical resistivity method is used to map subsurface electrical resistivity
structure,which is in turn interpreted by the geophysicist to determine the geologic structure and/or physical
properties of the geologic materials. Electrical resistivities of geologic materials are measured in
ohm-meters, and are functions of porosity, permeability, water saturation and the concentration of dissolved
solids in the pore fluids.

2.3.2 Resistivity methods measure the bulk resistivity of the subsurface as do the electromagnetic
methods. The difference between the two methods is in the way that electrical currents are forced to flow
in the earth. In the electrical resistivity method, current is injected into the ground through surface

FMC-C-020-2

-------
electrodes, whereas in electromagnetic methods currents are induced by application of time-varying magnetic
fields.

2.3.3 Advantages:

2.3.3.1 The principal advantage of the electrical resistivity method is that quantitative
modeling is possible using either computer software or published master curves. The resulting
model scan provide accurate estimates of depths, thicknesses and resistivities of subsurface
layers. The layer resistivities can then be used to estimate the resistivity of the saturating fluid,which
is related to the total concentration of dissolved solids in the fluid.

2.4 Seismic

2.4.1 Surface seismic techniques used in groundwater pollution site investigations are largely
restricted to seismic refraction and seismic reflection methods. The equipment used for both methods is
fundamentally the same and both methods measure the travel-time of acoustic waves propagating through
the subsurface. In the refraction method, the travel-time of waves refracted along an acoustic interface is
measured, and in the reflection method, the travel-time of a wave which reflects or echoes off an interface
is measured. The interpretation of seismic data will yield subsurface velocity information, which is
dependent upon the acoustic properties of the subsurface material. Various geologic materials can be
categorized by their acoustic properties or velocities. Depth to geologic interfaces can be calculated using
the velocities obtained from a seismic investigation. The geologic information gained from a seismic
investigation can then be used in the hydrogeologic assessment of a groundwater pollution site and the
surrounding area.

2.4.2 The interpretation of seismic data can indicate changes in lithology or stratigraphy, geologic
structure, or water saturation (water table). Seismic methods are commonly used to determine the depth and
structure of geologic and hydrogeologic units, to estimate hydraulic conductivity, to detect cavities or voids,
to determine structure stability, to detect fractures and fault zones, and to estimate ripability. The choice of
method depends upon the information needed and the nature of the study area. This decision must be made
by a geophysicist who is experienced in both methods, is aware of the geologic information needed by the
hydrogeologist, and is also aware of the environment of the study area. There fraction technique has been
used more often than the reflection technique for hazardous waste site investigations.

2.4.3 Seismic Refraction Method: Seismic refraction is most commonly used at sites where bedrock
is less than 500 feet below the ground surface. Seismic refraction is simply the travel path of a sound wave
through an upper medium and along an interface and then back to the surface. A detailed discussion of the
seismic refraction technique can be found in Dobrin (1976), Telford and others (1985), and Musgrave (1967).

2.4.3.1 Advantages:

2.4.3.1.1 Seismic refraction surveys generally predominate over reflection
surveys for site investigations. The velocities of each layer can be determined from
refraction data, and a relatively precise estimate of the depth to different interfaces can be
calculated.

2.4.3.1.1 Refraction surveys can be useful to obtain depth information at
locations between bore holes. Subsurface information can be obtained between bore holes
at a fraction of the cost of drilling. Refraction data can be used to determine the depth to
the water table or bedrock. Refraction surveys are useful in buried valley areas to map the
depth to bedrock. The velocity information obtained from a refraction survey can be

FMC-C-020-3

-------
related to various physical properties of the bedrock. Rock types have certain ranges of
velocities and these velocities are not always unique to a particular rock type. However,
they can allow a geophysicist to differentiate between certain units, such as shales and
granites.

2.4.4 Seismic Reflection Method: The seismic reflection method has not been as commonly used
on groundwater pollution site investigations as seismic refraction. In the seismic reflection method, a sound
wave travels down to a geologic interface and reflects back to the surface. Reflections occur at an interface
where there is a change in the acoustic properties of the subsurface material.

2.4.4.1 Advantages:

2.4.4.1.1 The seismic reflection method yields information that allows the
interpreter to discern between fairly discrete layers. The reflection method has been used
to map stratigraphy. Reflection data is usually presented in profile form, and depths to
interfaces are represented as a function of time. Depth information can be obtained by
converting time sections into depth from velocities obtained from seismic refraction data,
sonic logs, or velocity logs. The reflection technique requires much less space than
refraction surveys. The long offsets of the seismic source from the geophones, common
in refraction surveys are not required in the reflection method. In some geologic
environments reflection data can yield acceptable depth estimates.

2.5 Ground Penetrating Radar

2.5.1	The ground penetrating radar (GPR) method has been used for a variety of civil engineering,
groundwater evaluation and hazardous waste site applications. The success of this geophysical method is
the most site specific of all geophysical techniques, providing subsurface information ranging in depth from
several tens of meters to only a fraction of a meter. A basic understanding of the function of the GPR
instrument, together with a knowledge of the geology and mineralogy of the site can help determine if GPR
will be successful in the site assessment. When possible, the GPR technique should be integrated with other
geophysical and geologic data to provide the most comprehensive site assessment.

2.5.2	The GPR method uses a transmitter that emits pulses of high-frequency electromagnetic
waves into the subsurface. The transmitter is either moved slowly across the ground surface or moved at
fixed station intervals. The penetrating electromagnetic waves are scattered at changes in the complex
dielectric permitivity, which is a property of the subsurface material dependent primarily upon the bulk
density, clay content and water content of the subsurface (Olhoeft, 1984). The electromagnetic energy back
scattered to the surface receiving antenna is recorded as a function of time.

2.5.3	Depth penetration is severely limited by attenuation of the transmitted electromagnetic waves
into the ground. Attenuation is caused by the sum of electrical conductivity,dielectric relaxation, and
geometric scattering losses in the subsurface. Generally,penetration of radar frequencies is minimized by
a shallow water table, an increase in the clay content of the subsurface, and in environments where the
electrical resistivity of the subsurface is less than 30 ohm-meters (Olhoeft, 1986). Ground penetrating radar
works best in dry sandy soil above the water table. At applicable sites, depth resolution should be expected
to be between one and ten meters (Benson, 1982).

2.5.4	The analog plot produced by a continuous recording GPR system is analogous to a seismic
reflection profile, that is, data is represented as a function of horizontal distance versus time. This
representation should not be confused with a geologic cross section which represents data as a function of
horizontal distance versus depth. Because very high-frequency electromagnetic waves in the megahertz
range are used by radar systems, and time delays are measured in nanoseconds (10-9 seconds), very high
resolution of the subsurface is possible using GPR. This resolution can be as high as 0.1 meter. For depth

FMC-C-020-4

-------
determinations, it is necessary to correlate the recorded features with actual depth measurements from bore
holes or from the results of other geophysical investigations.When properly interpreted, GPR data can
optimally resolve changes in soil horizons,fractures, water insoluble contaminants, geological features,
man-made buried objects, and hydrologic features such as water table depth and wetting fronts.

2.5.5 Advantages: Most GPR systems can provide a continuous display of data along a traverse
which can often be interpreted qualitatively in the field. GPR is capable of providing high resolution data
under favorable site conditions. The real-time capability of GPR results in a rapid turnaround, and allows
the geophysicist to quickly evaluate subsurface site conditions.

3.0 INTERFERENCES

3.1 Magnetics Limitations

3.1.1 There are certain limitations in the magnetic method. One limitation is the problem
of"cultural noise" in certain areas. Man-made structures that are constructed using ferrous material, such
as steel, have a detrimental effect on the quality of the data. Features to be avoided include steel structures,
power lines, metal fences, steel reinforced concrete,pipelines and underground utilities. When these features
cannot be avoided, their locations should be noted in a field notebook and on the site map.

3.1.2 Another limitation of the magnetic method is the inability of the interpretation methods to
differentiate between various steel objects. For instance, it is not possible to determine if an anomaly is the
result of a steel tank or a group of steel drums or old washing machines. Also, the magnetic method in no
way allows the interpreter to determine the contents of a buried tank or drum.

3.2 Electromagnetic Limitations

3.2.1 The main limitation of the electromagnetic method is "cultural noise". Sources of "cultural
noise" can include: large metal objects, buried cables, pipes, buildings, and metal fences. Lateral variability
in the geology can cause conductivity anomalies or lineations. These features can easily be misinterpreted
as a contaminant plume.

3.3 Resistivity Limitations

3.3.1 The limitations of using the resistivity method in groundwater pollution site investigations
are largely due to site characteristics, rather than in any inherent limitations of the method.Typically,
pollution sites are located in industrial areas that contain an abundance of broad spectrum electrical noise.
In conducting a resistivity survey, the voltages are relayed to the receiver over long wires that are grounded
at each end. These wires act as antennae receiving the radiated electrical noise that in turn degrades the
quality of the measured voltages.

3.3.2 Resistivity surveys require a fairly large area, far removed from pore lines and grounded
metallic structures such as metal fences, pipelines and railroad tracks. This requirement precludes using
resistivity on many pollution sites. However, the resistivity method can often be used successfully off-site
to map the stratigraphy of the area surrounding the site. A general "rule of thumb" for resistivity surveying
is that grounded structures be at least half of the maximum electrode spacing away from the axis of the
survey line.

3.3.3 Another consideration in the resistivity method is that the fieldwork tends to be more labor
intensive than some other geophysical techniques. A minimum of two to three crew members are required
for the fieldwork.

3.4 Seismic Limitations

FMC-C-020-5

-------
3.4.1 Seismic Refraction Method Limitations:

3.4.1.1 The seismic refraction method is based on several assumptions. To successfully
resolve the subsurface using the refraction method, the conditions of the geologic environment must
approximate these assumptions. They include the following: 1) the velocities of the layers increase
with depth, 2) the velocity contrasts between layers is sufficient to resolve the interface, and 3) the
geometry of the geophones in relation to the refracting layers will permit the detection of thin
layers. If these conditions are not met, accurate depth information will not be obtained.

3.4.1.2 There are several disadvantages to collecting and interpreting seismic refraction
data. Data collection can be labor intensive. Also, large line lengths are needed, therefore, as a
general rule, the distance from the shot, or seismic source, to the first geophone station must be at
least three times the desired depth of exploration.

3.4.2 Seismic Reflection Method Limitations:

3.4.2.1 The major disadvantage to using reflection data is that a precise depth
determination cannot be made. Velocities obtained from most reflection data are at least 10% and
can be 20% of the true velocities. The interpretation of reflection data requires a qualitative
approach. In addition to being more labor intensive, the acquisition of reflection data is more
complex than refraction data.

3.4.2.2 The reflection method places higher requirements on the capabilities of the seismic
equipment. Reflection data is commonly used in the petroleum exploration industry and requires
a large amount of data processing time and lengthy data collection procedures. Although
mainframe computers are often used in the reduction and analysis of large amounts of reflection
data, recent advances have allowed for the use of personal computers on small reflection surveys
for engineering purposes. In most cases, the data must be recorded digitally or converted to a digital
format, to employ various numerical processing operations. The use of high resolution reflection
seismic methods places a large burden on the resources of the geophysicist, in terms of computer
capacity, data reduction and processing programs, resolution capabilities of the seismograph and
geophones, and the ingenuity of the interpreter. These factors should be carefully considered before
a reflection survey is recommended.

3.5 Ground Penetrating Radar Limitations

3.5.1 One of the major limitations of GPR is the site specific nature of the technique. Another
limitation is the cost of site preparation necessary prior to performing the survey. Most GPR units are towed
across the ground surface. Ideally, the ground surface should be flat,dry, and clear of any brush or debris.
The quality of the data can be degraded by a variety of factors such as an uneven ground surface or various
cultural noise sources. For these reasons, it is mandatory that the site be visited by the project geophysicist
before a GPR investigation is proposed. The geophysicist should also evaluate all stratigraphic information
available, such as bore hold data and information on the depth to water table in the survey area.

4.0 APPARATUS AND MATERIALS
4.1 Magnetics

4.1.1 GEM GSM-19G magnetometer/gradiometer, EDA OMNI IV magnetometer/gradiometer,
Geonics 856AGX (with built-in data logger) or equivalent

4.1.2 Magnetometer base station

FMC-C-020-6

-------
4.1.3	300-ft. tape measure

4.1.4	Non-ferrous survey stakes (wooden or plastic)

4.2	Electromagnetics

4.2.1	Geonics EM-31, EM-34 or equivalent

4.2.2	Polycorder data logger

4.2.3	Dat 31Q software (data dump software)

4.2.4	300-ft. tape measure

4.2.5	Survey stakes

4.3	Electrical Resistivity

4.3.1	DC resistivity unit (non-specific)

4.3.2	Four (4) electrodes and appropriate cables (length dependent on depth of survey)

4.3.3	1 or 2 - 12 volt car batteries

4.3.4	300-ft. tape measure

4.4	Seismic

4.4.1	12 or 24 channel peesmograph (Geometries 2401 or equivalent)

4.4.2	Thirty (30) 10Hz-14Hz (for refraction)

4.4.3	Thirty (30) 50Hz or greater (for reflection)

4.4.4	300-ft. tape measure

4.4.5	Survey stakes

4.4.6	Sledge hammer and metal plate or explosives

4.5	Ground Penetrating Radar

4.5.1	GSSI SIR-8 or equivalent

4.5.2	80 MHz, 10 MHz or 300 MHz antenna/receiver pit

4.5.3	200-ft. cable

4.5.4	300-ft. tape measure

5.0 REAGENTS

This section is not applicable to this SOP.

FMC-C-020-7

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

This section is not applicable to this SOP.

7.0 PROCEDURES

7.1 Refer to the manufacturer's operating manual for specific procedures relating to operation.

7.2 Calculations

7.2.1 Calculations vary based on the geophysical method employed. Refer to the
instrument-specific usersmanual for specific formulas.

7.3 Health and Safety

7.3.1 When working with potentially hazardous materials, follow USEPA, OSHA and corporate
health and safety practices.

8.0 QUALITY CONTROL

8.1 The following general quality assurance activities apply to the implementation of these procedures.

8.1.1 All data must be documented on field data sheets or within site logbooks.

8.1.2 All instrumentation must be operated in accordance with operating instructions as supplied
by the manufacturer, unless otherwise specified in the work plan. Equipment check out and calibration
activities must occur prior to sampling/operation, and they must be documented.

8.2 Method specific quality assurance procedures may be found in the user's manual.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Breiner, S., 1973, Applications Manual for Portable Magnetometers: EG&G GeoMetrics,
Sunny vale,California.

2. Fowler, J. and Pasicznyk, D., 1985, Magnetic Survey Methods used in the Initial Assessment of a Waste
Disposal Site: National Water Well Association Conference on Surface and Borehole Geophysics, February 1985.

3. Lilley, F., 1968, Optimum direction of survey lines: Geophysics, vol. 33, no. 2, p. 329-336.

4. Nettleton, L.L., 1976, Elementary Gravity and Magnetics for Geologists and Seismologists: Society of
Exploration Geophysicists, Monograph Series Number 1.

4. Redford, M.S., 1964, Magnetic anomalies over thin sheets: Geophysics, vol. 29, no. 4, p. 532-536.

5. Redford, M.S., 1964, Airborne magnetometer surveys for petroleum exploration: Aero Service Corporation,
Houston, Texas.

FMC-C-020-8

-------
6.	Vacquier, V., and others, 1951, Interpretation of aero magnetic maps: Geological Society of America,Memoir
Number 47.

7.	Duran, P.B., 1982, The use of electromagnetic conductivity techniques in the delineation of groundwater
pollution plumes: Unpublished master's thesis, Boston University.

8.	Grant, F.S., and West, G.F., 1965, Interpretation theory in applied geophysics: McGraw-Hill Book
Company, New York.

9.	Greenhouse, J.P., and Slaine, D.D., 1983, The use of reconnaissance electromagnetic methods to map
contaminant migration: Ground Water Monitoring Review, vol. 3, no. 2.

10.	Keller, G.V., and Frischknecht, F.C., 1966, Electrical methods in geophysical prospecting: Pergamon Press,
Inc., Long Island City, New York.

11.	McNeill, J.D., 1980, Electromagnetic terrain conductivity measurements at low induction numbers:Technical
Note TN-6, Geonics Limited, Mississauga, Ontario, Canada.

12.	McNeill, J.D., 1980, EM34-3 survey interpretation techniques: Technical Note TN-8, Geonics Limited,
Mississauga, Ontario, Canada.

13.	McNeill, J.D., 1980, Electrical conductivity of soils and rocks: Technical Note TN-5, Geonics Limited,
Mississauga, Ontario, Canada.

14.	McNeill, J.D., and Bosnar, M., 1986, Surface and borehole electro-magnetic groundwater contamination
surveys, Pittman lateral transect, Nevada: Technical Note TN-22, Geonics Limited, Mississauga, Ontario, Canada.

15.	Stewart, M.T., 1982, Evaluation of electromagnetic methods for rapid mapping of salt-water interfaces in
coastal aquifers: Ground Water, vol. 20.

16.	Telford, W.M., Geldart, L.P., Sheriff, R.E., and Keys, D.A., 1977, Applied geophysics: Cambridge
University Press, New York.

17.	Bisdorf, R.J., 1985, Electrical techniques for engineering applications: Bulletin of the Assoc. of Engineering
Geologist, vol. 22, no. 4.

18.	Grant, F.S., and West, G.F., 1965, Interpretation theory in applied geophysics: McGraw-Hill Book
Company, New York, New York.

19.	Keller, G.V., and Frischnecht, F.C., 1966, Electrical methods in geophysical prospecting: Pergamon Press,
Inc., Long Island City, New York.

20.	Kelly, W.E., and Frohlich, R.K., 1985, Relations between aquifer electrical and hydraulic properties:Ground
Water, vol. 23, no. 2.

21.	Stollar, R., and Roux, P., 1975, Earth resistivity surveys - a method for defining groundwater contamination:
Ground Water, vol. 13.

22.	Sumner, J.S., 1976, Principles of induced polarization for geophysical exploration: Elsevier Scientific
Publishing Co., New York, New York.

23.	Telford, W.M., Geldart, L.P., Sheriff, R.E., and Keys, D.A., 1977, Applied geophysics:
CambridgeUniversity Press, New York, New York.

FMC-C-020-9

-------
24.	Urish, D.W., 1983, The practical application of surface electrical resistivity to detection of groundwater
pollution: Ground Water, vol. 21.

25.	Van Nostrand, R.E., and Cook, K.L., 1966, Interpretation of resistivity data: U.S. Geological Survey
Professional Paper 499, Washington, D.C.

26.	Zohdy, A.A.R., 1975, Automatic interpretation of Schlumberger sounding curves using modified DarZarrouk
functions: U.S. Geological Survey Bulletin 1313-E, Denver, Colorado.

27.	Coffeen, J.A., 1978, Seismic exploration fundamentals; Tulsa, Oklahoma: PennWell Publishing Co.

28.	Dobrin, M.B., 1976, Introduction to geophysical prospecting; 3rd ed., New York, New York: McGraw-Hill.

29.	Griffiths, D.H. and King, R.E., 1981, Applied geophysics for geologists and engineers; 2nd ed.,Oxford,
England: Pergamon Press.

30.	Miller, R.D., Pullan, S.E., Waldner, J.S., and Haeni, F.P., 1986, Field comparison of shallow seismic
sources; Geophysics, vol. 51, no. 11, p. 2067-2092.

31.	Musgrave, A.W., 1967, Seismic refraction prospecting; Tulsa, Oklahoma: The Society of Exploration
Geophysicists.

32.	Telford, W.M., Geldant, L.P., Sheriff, R.E., and Keys, D.A., 1985, Applied Geophysics; Cambridge,England:
Cambridge University Press.

33.	Benson, R.C., Glaccum, R.A., and Noel, M.R., 1982, Geophysical techniques for sensing buried wastes and
waste migrations: Miami, FL, Technos Inc., 236 p.

34.	Olehoft, G.R., 1984, Applications and limitations of ground penetrating radar: Expanded Abstracts,Soc.
expl. Geoph. 54th Annual Meeting., Dec. 2-6 1984, Atlanta, GA, p. 147-148.

FMC-C-020-10

-------
ERT Method

7-DAY STANDARD REFERENCE TOXICITY TEST USING LARVAL PIMEPHALES PROMELAS

1.0 SCOPE AND APPLICATION

1.1 The procedure for conducting a standard reference toxicity test using sodium pentachlorophenate
(NaPCP) as the toxicant and larval Pimephales promelas (fathead minnows) as the test organism is described
below. This test estimates the fitness, condition, and sensitivity of the organisms used in a definitive toxicity test.
It allows for inter, and intralaboratory comparisons of toxicity information and provides an experimental control
(Lee, 1980). Response of the organisms should be within two (2) standard deviations from the accepted mortality
values for the definitive test data to be considered valid (Standard Methods, 1971). Other standard reference
toxicants may be used if justified and the appropriate reference cited. Reference toxicants are available from the
US EPA Environmental Monitoring and Support Laboratory, Cincinnati, OH.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Fathead minnow larvae are exposed to several concentrations of the standard reference toxicant. This
test is conducted following the same procedures used for the definitive test. The range of concentration used in
the standard reference toxicant test are selected to encompass the EC50 of the standard reference toxicant used.
The lethal threshold of NaPCP is 0.1 - 0.2 mg/L at about 24 hours (Adelman et al., 1980). The U.S. EPA LC50 of
NaPCP is 0.08 -0.19 mg/L.

3.0 INTERFERENCES

3.1 When conducting a toxicity test with sodium pentachlorophenate, the pH needs to be kept above 7.4.
The toxicity of NaPCP increases as the pH drops, which could give erroneous results (Lee, 1980).

3.2 Non-target chemicals (i.e. residual chlorine) cause adverse effects to the organisms, giving false
results.

3.3 Dissolved oxygen depletion due to biological oxygen demand, chemical oxygen demand and
metabolic wastes is also a potential problem.

3.4 Loss of a toxicant through volatilization and adsorption to exposure chambers may occur.
4.0 APPARATUS AND MATERIALS

4.1 Apparatus

4.1.1 12 small cups: Glass or plastic.

4.1.2 12 exposure chambers: Glass or plastic, 2L.

FMC-C-021-1

-------
4.1.3

3 graduated cylinders: 1L.

4.1.4 6 beakers: 250 mL or larger volumetric flask - 2L.

4.1.5 2 mixing buckets or beakers.

4.1.6 Pipettes: 10 mL or smaller.

4.1.7 Tubing: Plastic, 3/8" outside diameter.

4.1.8 Screening: Plastic, a mesh smaller than the fish.

4.1.9 Dilution water: 11 L/day standard reference toxicant - sodium pentachlorophenate.

4.1.10 Bore pipettes: Wide, 1.5 times the length of the fish.

4.2 Test Organisms

4.2.1 Test organisms may be reared in house or received from an outside source. All fathead minnow
larvae must be less than 24 hours old. To insure larvae less than 24-hours old, use eggs that were laid
approximately 3-4 days prior to the beginning of the test. Place the substrate containing the eggs into a
bucket containing dilution water. This allows the test organisms to become acclimated to the dilution
water, reducing stress. Aerate the eggs vigorously to avoid fungal growth and use populations of fish that
have less than 5% mortality (Standard Methods, 1971). Peltier and Weber (1985) and Denny (1987)
provide more detail and information including culturing, care, handling, and disease prevention of fathead
minnows.

4.3 Equipment for Chemical Analysis

4.3.1 Meters are needed to measure dissolved oxygen, temperature, pH and conductivity. Calibrate the
meters according to the manufacturers instructions. Measure and record alkalinity and hardness according
to a standard method (Standard Methods, 1971).

5.0 REAGENTS

5.1 Dilution Water: Dilution water is moderately hard, reconstituted deionized water unless otherwise
specified. See Horning and Weber (1985) for the preparation of synthetic fresh water.

5.2 Test Media: As a quality control measure, the accuracy of the dilutions should be measured on test
concentrations to provide an estimate of the accuracy of the dilutions so that results from one test are comparable
to other tests. If the reference toxicant is from the U.S. EPA, instructions are included on how to prepare a stock
solution. If not, a stock solution should be prepared in advance to facilitate the preparation of test concentrations.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Once collected, the samples will be placed in containers constructed from materials suitable for the
suspected contaminants. Because surrogate test species will be exposed to varying concentrations of the sample
material, no chemical preservatives are to be used. The preservation and storage protocol is therefore limited to
holding the samples on ice at 4°C for the holding time specified by the analytical method. Prior to shipping, the

FMC-C-021-2

-------
laboratory performing the toxicity tests will be notified of any potential hazards that may be associated with the
samples.

7.0 PROCEDURES

7.1 Choose a range of concentrations that span those causing zero mortality to those causing complete
mortality. Two replicates per concentration and two control replicates following a geometric or logarithmic
concentration should be used. The example below provides an example of standard reference concentrations that
may be used.

7.2 Label clean exposure chambers, rinse in dilution water, and then place chambers on a table that will
meet test requirements in Table 1 (Appendix A). Dilution water must be 25 + 2°C.

7.3 Pour 1L of dilution water into each control exposure chamber. Then prepare the NaPCP stock
solution by diluting 10 mL of NaPCP up to 100 mL. This will provide a 321 mg/L stock solution.

7.4 To prepare the first exposure chamber, measure 0.2 mL of the stock solution into a flask and dilute to
2L with the dilution water. Pour 1L each into the replicate exposure chambers that are labelled 0.03 mg/L.

7.5 Working in order of increasing concentration, prepare the exposure solutions following the example
below.

Example 1. Test Dilutions

Test Dilutions

Standard Reference Concentration (Volume mL)
(mg/L NaPCP) Diluent NaPCP

0 2000.0 0

0.03 1999.8 0.2

0.06 1999.6 0.4

0.08 1999.5 0.5

0.16 1999.0 1.0

0.30 1998.0 2.0

7.6 After all exposure chambers are filled, the fish may be added to the chambers. Using a wide bore
pipette, select one fish at a time from the test population and place into a small cup. Prepare 12 cups containing
10 fish each.

7.7 After the 12 cups have been prepared, randomly select a cup and gently submerse the cup below the
surface of the water and gently pour the fish into the chamber.

7.8 The addition of the fish signifies the beginning of the test. The start time should be recorded on a data

sheet.

7.9 Mortality should be noted 2 hours after initiation of the test, and thereafter, on a daily basis.

FMC-C-021-3

-------
7.10 Measure temperature, pH, conductivity, and dissolved oxygen directly from the exposure chamber and
measure hardness and alkalinity from an aliquot removed from a chamber. Measurement should be conducted
after the fish have been added to the chambers.

7.11 Feed larval fish three times daily at 4 hour intervals (i.e., 0800, 1200, and 1600). Use a commercially
prepared food suitable to larval fish or a freshwater rinsed concentrated suspension of newly hatched brine
shrimp.

7.12 If brine shrimp are used for food, add approximately 700-1000 nauplii (0.1 mL) to each chamber.

7.13 New exposure solutions must be prepared daily. Carefully draw out the old exposure solution, waste
debris and food as possible (leave sufficient volume to cover the test fish).

7.14 Replace the old solution with new solution by carefully pouring the new solution down the sides of
the test chamber.

7.15 Steps 9-13 must be conducted every day of the test.

7.16 On the last day of the test, renewal of the test solution is not conducted. Live test fish are removed,
preserved in 4% buffered formalin and weighed and measured as required.

7.17 Calculations

7.17.1 The methods used to determine the EC50 differ depending on the results of the test. If there is
no partial effects in any replicate (i.e. all alive and healthy or all dead), then the Moving-Average Method
may be used to determine the EC50. If there are partial effects within a replicate, then the Probit Method
should be used to calculate the EC50. Also the Lowest Observable Effect Concentration (LOEC), the No
Observable Effects Concentration (NOEC) and the chronic value (CHV) are recorded (Peltier and Weber,
1985). Measure growth in larvae to determine the effect of the standard reference toxicant on the life cycle.
Compare the dry weight of the fish in the various concentrations to the dry weight of a control group of fish
raised under the same conditions.

7.18 Health and Safety

7.18.1 When working with potentially hazardous materials, follow US EPA, OSHA and corporate
health and safety procedures.

8.0 QUALITY CONTROL

8.1 Quality control should encompass the following parameters to ensure a valid test. The guidelines in
this text and in Table 1, (Appendix A) should be followed to insure adequate QA/QC. This includes:

8.1.1 Test organisms.

8.1.2 Facilities/equipment.

8.1.3 Standard reference toxicant quality and preparation.

8.1.4 Dilution water.

8.1.5 Test conditions.

9.0 METHOD PERFORMANCE

FMC-C-021-4

-------
Information not available.

10.0 REFERENCES

1. Adelman, I.R., Smith, L.L. and Siesennop, G.D. 1967. JFRBC 33(2):203-208.

2. Denny, J.S. 1987. Guidelines for the Culturing of Fathead Minnows for use in Toxicity Tests.
EPA/600/3-87/001. Environmental Research Laboratory, Duluth, MN. 49 pp.

4. Huston, Mark, March 1988. SOP-A. 7-Day Standard Reference Toxicity Test Using Larval Pimephales
Promelas. U.S. EPA Environmental Response Team - Technical Assistance Team, TDD: 11871206.

5. Lee, D.R. 1980. Reference Toxicants in Quality Control of Aquatic Bioassays. In Aquatic Invertebrate
Bioassays. ASTM STP 715. A.L. Buikema and J. Cains (eds.). American Society for Testing and materials, pp.
188-199.

7. Sprague, J.B. 1973. The ABC's of Pollutant Bioassay using Fish in Biological Methods for the Assessment
of Water Quality. ASTM STP 528. American Society for Testing and Materials, pp. 6-30.

8. Standard Methods for the Examination of Water and Wastewater. 1971. American Public Health
Association, 13th ed. 379 pp.

FMC-C-021-5

-------
ERT Method

24-HOUR RANGE FINDING TEST USING DAPHNIA MAGNA AND DAPHNIA PULEX

1.0 SCOPE AND APPLICATION

1.1 The procedure for conducting a 24-hour rangefinding toxicity test using Daphnia magna or D. pulex is
described below. This test is applicable to leachates, effluents, and liquid phases of sediments. The selection of
concentrations to use in a definitive toxicity test are based on the results of the rangefinder.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Larval daphnids are placed in individual containers and exposed to a wide range of test media
concentrations. No replicates are needed and only a few concentrations (i.e. 0, 1, 10 and 100%) are used.

3.0 INTERFERENCES

3.1 The results of a static toxicity test do not reflect temporal fluctuation in effluent toxicity (Peltier and
Weber, 1985). This is a preliminary test which provides an estimate of toxicity and the results are viewed as
such.

3.2 Non-target chemicals (i.e. residual chlorine) cause adverse effects to the organisms giving false
results.

3.3 Dissolved oxygen depletion due to biological oxygen demand, chemical oxygen demand or metabolic
wastes is a potential problem.

3.4 Loss of a toxicant through volatilization and adsorption to exposure chambers also may occur (Peltier
and Weber, 1985).

4.0 APPARATUS AND MATERIAL
4.1 Apparatus

4.1.1 25 larval daphnids: Acclimated 24 hours to dilution water.

4.1.2 4 exposure chambers: 100 mL/chamber rinsed in dilution water.

4.1.3 Trav: To hold exposure chambers and glass covers.

4.1.4 Bore pipettes: Wide, 1.5 times the size of the daphnid.

4.1.5 Graduated cylinders: 250 mL.

FMC-C-022-1

-------
4.1.6 Beakers for chemical measurements.

4.1.7 Suitable food.

4.1.8 Test media: 150 mL.

4.1.9 Diluent: 300 mL.

4.1.10 Pipette: 1 mL.

4.2 Test Organisms

4.2.1 Test organisms may be reared inhouse or obtained from an outside source. Positive identification
of the species is required before beginning testing. Daphnids to be used must be less than 24 hours old and
from the second to the sixth brood of a healthy adult. Populations of healthy daphnids have large
individuals, an absence of floaters, an absence of ephippia, no parasites, and individuals are dark colored
and produce large numbers of young (Biesinger, et al. 1987).

4.3 Equipment for Chemical Analysis

5.0 REAGENTS

5.1 Dilution Water: Dilution water is moderately hard, reconstituted deionized water unless otherwise
specified. See Horning and Weber (1985) for the preparation of synthetic fresh water. The dilution
water for a test is the same as the water used to culture daphnids and the water used to acclimate
daphnids before the beginning of the test.

5.2 Test Media: If the test medium is a liquid, dilutions may be made directly for the required
concentrations. If the test medium is a sediment, preliminary filtration and dilutions are required to
produce a liquid phase.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 The selected environmental matrix will be sampled utilizing the methodology detailed in ERT
Standard Operating Procedures (SOPs) #2012, Soil Sampling; #2013, Surface Water Sampling; #2016, Sediment
Sampling; and any other procedure applicable for the media sampled.

6.2 Once collected, the samples will be placed in containers constructed from materials suitable for the
suspected contaminants. Because surrogate test species will be exposed to varying concentrations of the sample
material, no chemical preservatives are to be used. The preservation and storage protocol is therefore limited to
holding the samples on ice at 4°C for the holding time specified by the analytical method. Prior to shipping, the
laboratory performing the toxicity tests will be notified of any potential hazards that may be associated with the
samples.

FMC-C-022-2

-------
7.0 PROCEDURES

7.1 Choose a wide range of concentrations to estimate the toxicity of the test media. The concentrations
cited below are used as an example and may be adjusted to meet the criteria of the specific situation. A
geometric or logarithmic range of concentrations may be used (Sprague, 1973).

7.2 The example below provides enough test media for three test chambers containing 80 mL each. In
addition, 100 mL each of dilution water and test media are required for chemical analyses. Temperature, pH,
conductivity, dissolved oxygen, alkalinity and hardness should be measured prior to the start of the test.

Example 1. Test Dilution

Test Media Concentrations
test medial

Diluent

Volume (mL)

Test Media

10
100

100
99
90
0

10
100

7.3 Label clean exposure chambers and rinse in dilution water, except for the chamber containing 100%
test media.

7.4 To prepare test solutions, measure 1.0 mL of the test media into a beaker and dilute to 100 mL with
dilution water.

7.5 Using a graduated cylinder, pour 80 mL into the exposure chamber. Continue these steps for all
concentrations. Always work from the lowest concentrations to the highest.

7.6 Using a wide bore pipette, randomly select a daphnid, place the pipette below the surface of the test
solution and gently expel each daphnid individually into the exposure chamber.

7.7 The test begins when half of the organisms have been placed into exposure chambers. Mortality
should be determined an 1 hour and again at 24 hours.

7.8 Calculations

7.8.1 The methods used to determine the LC50 differ depending on the results of the test. The
Moving-Average Method is used to determine the LC50 when there is no partial mortality in any replicate
(i.e. all alive or all dead). If there is partial mortality, the Probit Method is used to calculate the LC50. The
Lowest Observable Effect Concentration (LOEC) is recorded and the No Observable Effect Concentration
(NOEC) is recorded (Peltier and Weber, 1985). Since this is a simple acute test, only mortality is recorded.
Other methods of estimating the LC50 may be used if justified and an accepted reference is cited (Biesinger,
et al. 1987).

FMC-C-022-3

-------
7.9 Health and Safety

7.9.1 When working with potentially hazardous materials, follow US EPA, OSHA and corporate health
and safety procedures.

8.0 QUALITY CONTROL

8.1 Follow the guidelines below and in Table 1 (Appendix A) to ensure a valid test and to meet quality
assurance/quality control standards.

8.1.1 Effluent sampling.

8.1.2 Test organisms.

8.1.3 Facilities equipment.

8.1.4 Effluent/leachate preparation.

8.1.5 Dilution water.

8.1.6 Test conditions.

8.1.7 Standard reference toxicant.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Biesinger, K.E., L.R. Williams, and W.H. van der Schalie. 1987. Procedures for Conducting Daphnia
magna Toxicity Bioassays. EPA/600/8 - 87/011. Environmental Monitoring and Support Laboratory.
Cincinnati, OH. 57 pp.

2. Horning, W.B. and C. Weber. 1985. Short-term Methods for Estimating the Chronic Toxicity of Effluents
and Receiving Waters to Freshwater Organisms. EPA/600/4-85/014. Environmental Monitoring and Support
Laboratory, Cincinnati, OH. 162 pp.

3. Huston, Mark. May, 1988. SOP B 24 hour Rangefinding test using Daphnia magna and Daphnia pulex.
US EPA Environmental Response Team - Technical Assistance Team. TDD: 11871206.

4. Peltier, William H. and Cornelius Weber. 1985. Methods for Measuring the Acute Toxicity of Effluents to
Freshwater and Marine Organisms. EPA/600/4-85/013. Environmental Monitoring and Support Laboratory,
Cincinnati, OH. 216 pp.

5. Standard Methods for the Examination of Water and Wastewater. 1985. American Public Health
Association, 16th ed. 379 pp.

FMC-C-022-4

-------
ERT Method

96-HOUR ACUTE TOXICITY TEST USING
LARVAL FATHEAD MINNOWS (TTMEPHALES PROMELAS1

1.0 SCOPE AND APPLICATION

1.1 The procedure for conducting a 96-hour acute toxicity test using larval fathead minnows (Pimephales
promelas') is described below. This test is applicable to effluents, leachates, and liquid phases of sediment which
require an acute toxicity estimate.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Larval fathead minnows are exposed to different concentrations of a test media over a 96-hour period.
Survival results are used to determine the LC50 of the test media. Test concentrations are renewed daily and
mortality is the endpoint of the test.

3.0 INTERFERENCES

3.1 The results of a static toxicity test do not reflect temporal changes in effluent toxicity. This method is
less sensitive than a flow-through toxicity test and the sensitivity is dependent on the accuracy of the dilutions
(Peltier and Weber, 1985).

3.2 Non-target chemicals (i.e. residual chlorine) cause adverse effects to the organisms giving false
results.

3.3 Dissolved oxygen depletion due to biological oxygen demand, chemical oxygen demand and
metabolic wastes also is a potential problem.

3.4 Loss of a toxicant through volatilization and adsorption to exposure chambers may occur (Peltier and
Weber, 1985).

4.0 APPARATUS AND MATERIALS
4.1 Apparatus

120 Larval fathead minnows: Less than 30

days old.

12 exposure chambers: 1L elass or plastic.

labeled.

12 small cups: 50 mL.

Graduated cylinders: 1L and 10 mL.

FMC-C-023-1

-------
4.1.5 Mixing bucket: 2L or larger.

4.1.6 Tubing: Plastic, 3/8" outside diameter.

4.1.7 Plastic screening dilution.

4.1.8 Water: 4 L/day.

4.1.9 Test media: 2 L/day.

4.1.10 Bore pipettes: Wide, 1.5 times the length of the organism.

4.1.11 Waste containers.

4.1.12 Brine shrimp nauplii.

4.2 Test Organisms

4.2.1 Larval fathead minnows may be cultured in-house or obtained from an outside source. Positive
identification of the species must be made prior to beginning the test. Fish to be used for acclimation and
toxicity tests must be healthy and have less than five percent mortality. If test media and dilution water are
limited, use smaller test organisms. This will also ensure that the exposure chambers are not over loaded.
Fish selected for acclimation need to be similar in size, not more than 1.5 times the length of each other.
Larval fathead minnows must be fed during the acclimation period as well as during the test. Brine shrimp
nauplii or other suitable larval fish food may be used. Acclimate fish to the dilution water for at least 24
hours prior to beginning of the test. Use a small pump and drip the dilution water into the acclimation
chamber so that the entire volume of water is replaced over a 24-hour period. Leave the fish in this tank for
another 24 hours to complete the acclimation. During this time, adjust the temperature to 25°C. Peltier and
Weber (1985) and Denny (1987) provide more detail and information including culturing, care, handling,
and disease prevention of fathead minnows.

4.3 Equipment for Chemical Analysis

4.3.1 Meters are needed to measure dissolved oxygen, temperature, pH, and conductivity. Calibrate the
meters according to the manufacturers instructions. Measure and record alkalinity and hardness using a
standard method (Standard Methods, 1985).

5.0 REAGENTS

5.1 Dilution Water: Dilution water is moderately hard, reconstituted deionized water unless otherwise
specified. See Horning and Weber (1985) for the preparation of synthetic fresh water.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

FMC-C-023-2

-------
material, no chemical preservative are to be used. The preservation and storage protocol is therefore limited to
holding the samples on ice at 4°C for the holding time specified by the analytical method. Prior to shipping, the
laboratory performing the toxicity tests will be notified of any potential hazards that may be associated with the
samples.

7.0 PROCEDURES

7.1 Choose a range of concentrations that span those causing zero mortality to those causing complete
mortality. The concentrations cited below are used as an example and may be adjusted to meet the criteria of the
specific situation. A geometric or logarithmic range of concentrations also may be used (Sprague, 1973).

7.1.2 The example below provides six (6) concentrations with two 500 ml replicates.

Example 1. Test Dilution

Test Concentrations Volume (mL)

test medial Diluent Test Media

100

7.3 Label the outside of the chamber and rinse all exposure chambers, except the chamber containing
100% test media, in dilution water.

7.4 Prepare test concentrations, working from the lowest concentration to the highest. Measure 500 mL
of dilution water and pour into each control exposure chamber replicate.

7.5 Measure 10 mL of the test media into a beaker and dilute to 1000 ml with dilution water. Using a
graduated cylinder, pour 500 mL into each exposure chamber.

7.6 Continue these steps for all concentrations.

7.7 Using a pipette, randomly place one fish at a time into a small cup until there are ten (10) fish in each
cup. Randomly select the cups and carefully pour the fish into the exposure chambers. Submerse the cup below
the test media surface, gently tilt the cup and pour the fish into the exposure chamber.

7.8 Record survival at one hour and then daily thereafter. Measure and record temperature, dissolved
oxygen, pH, conductivity, alkalinity and hardness on all test solutions after addition of the fish.

7.9 Feed fish during the acclimation period and during the toxicity test. Feed larval fish three times daily
at four-hour intervals (i.e. 0800, 1200, and 1600). Use a freshwater rinsed concentrated suspension of

newly-hatched brine shrimp. Add approximately 700-1000 nauplii (0.1 ml) to each container (Horning and
Weber, 1985). Other food may be used if it is suitable larval fish food.

FMC-C-023-3

-------
7.10 Test solutions must be replaced daily. Mix concentrations as done the day before and slowly pour the
new concentrations into the exposure chambers. The temperatures of the new test concentrations must be equal
to that of what is in the exposure chamber so that the fish are not stressed. Using a length a plastic tubing
covered with netting, siphon out the concentrations from the exposure chambers. Leave a small amount of test
solution in the bottom of the chamber. While siphoning, remove as much dead brine shrimp and waste debris as
possible.

7.11 The test is complete after 96 hours final mortality and chemical measurements are recorded; test
solution disposed of in a manner consistent with good lab practices.

7.12 Calculations

7.12.1 The methods used to determine the LC50 differ depending on the results of the test. If there is
no partial mortality in any replicate (i.e. all alive or all dead), then the Moving-Average Method may be
used to determine the LC50. If there is partial mortality within a replicate, then the Probit Method should be
used to calculate the LC50. Also the Lowest Observable Effect Concentration (LOEC) is recorded and the
No Observable Effects Concentration (NOEC) is recorded (Peltier and Weber, 1985). Other methods may
be used if justified and the appropriate reference cited. See Sprague (1973) or Peltier and Weber (1985) for
more detail on the calculations.

7.13 Health and Safety

7.13.1 When working with potentially hazardous materials, follow USEPA, OSHA, and corporate
health and safety procedures.

8.0 QUALITY CONTROL

8.1 Quality control should encompass the following parameters to ensure a valid test. The guidelines in
this text and in Table 1 (Appendix A) should be followed to insure adequate QA/QC.

8.1.1 Effluent sampling.

8.1.2 Test organisms.

8.1.3 Facilities equipment.

8.1.4 Test media preparation.

8.1.5 Dilution water preparation.

8.1.6 Test conditions.

8.1.7 Standard reference toxicant.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Denny, J.S. 1987. Guidelines for the Culturing of Fathead Minnows for use in Toxicity Tests.
EPA/600/3-87/001. Environmental Research Laboratory, Duluth, MN. 49 pp.

FMC-C-023-4

-------
2.	Horning, W.B. and C. Weber. 1985. Short-term Methods for Estimating the Chronic Toxicity of Effluents
and Receiving Waters to Freshwater Organisms. EPA/600/4-85/014. Environmental Monitoring and Support
Laboratory, Cincinnati, OH. 162 pp.

3.	Huston, Mark. May, 1988. SOP C. 48 Hour Acute Toxicity Test Using Larval Fathead Minnows
(Pimephales Promelas'). USEPA Environmental Response Team - Technical Assistance Team. TDD: 11871206.

4.	Peltier, William H. and Cornelius Weber. 1985. Methods for Measuring the Acute Toxicity of Effluents to
Freshwater and Marine Organisms. EPA/600/ 4-85/013. Environmental Monitoring and Support Laboratory,
Cincinnati, OH. 216 pp.

5.	Sprague, J.B. 1973. The ABC's of Pollutant Bioassay using fish in Biological Methods for the Assessment
of Water Quality. ASTM STP 528. American Society for Testing and Materials, pp. 6-30.

6.	Standard Methods for the Examination of Water and Wastewater. 1985. American Public Health
Association, 16th ed.

FMC-C-023-5

-------
ERT Method

24-HOUR RANGEFINDING TEST USING LARVAL PIMEPHALES PROMELAS

1.0 SCOPE AND APPLICATION

1.1 The procedure for conducting a 24 hour rangefinding test using larval Pimephales promelas (fathead
minnow) is described below. This test is used as a preliminary guide when testing an effluent, leachate, or liquid
phase of a sediment with an unknown toxicity. The results of this test are used to determine the concentration
range of a definitive toxicity test.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Larval fathead minnows are exposed to various concentrations of a test media over a 24-hour period.
Survival and mortality data are used to determine the definitive concentration range to be used in a static or
flow-through toxicity test.

3.0 INTERFERENCES

3.1 The results of a static toxicity test do not reflect temporal changes in effluent toxicity (Peltier and
Weber, 1985). This method is less sensitive than a flow-through toxicity test and the sensitivity is dependent on
the accuracy of the dilutions.

3.2 Non-target chemicals (i.e. residual chlorine) may cause adverse effects to the organisms giving false
results.

3.3 Dissolved oxygen depletion due to biological oxygen demand, chemical oxygen demand or metabolic
wastes also is a potential problem.

3.4 Loss of a toxicant through volatilization and adsorption to exposure chambers may occur.
4.0 APPARATUS AND MATERIALS

4.1 Apparatus

4.1.1 40 fathead minnows: Less than 30 days old.

4.1.2 4 small cups: 50 mL.

4.1.3 4 exposure chambers: 1 L glass or plastic, labeled graduated cylinders - 1 L and 10 mL.

4.1.4 Mixing bucket: 1 L or larger.

4.1.5 Tubing: Plastic, 3/8" outside diameter.

FMC-C-024-1

-------
4.1.6 Plastic screening.

4.1.7 Dilution water: 3 L.

4.1.8 Test media: 1.5L.

4.1.9 Pipettes: Wide bore, 1.5 times the length of the organism

4.1.10 Waste containers.

4.1.11 Brine shrimp or other suitable food.

4.2 Test Organisms

4.2.1 Test organisms may be reared in-house or received from an outside source. Positive identification
of the test organisms must be made prior to starting the test. The fish to be used for a rangefinding test
must be the same age (less than 30 days old), in the same condition, and come from the same culture as
those to be used for the definitive test. Place fish into a holding tank and slowly drip the dilution water into
the tank over a 24 hour period. Then leave the fish in this water for another 24 hours so that the fish
become acclimated to the dilution water. Use populations of fish that have less than 5% mortality and that
are healthy. For more detail and information including culturing, care, and handling, and disease prevention
of Pimephales promelas see Peltier and Weber (1985) and Denny (1987).

4.3 Equipment for Chemical Analysis

4.3.1 Meters are needed to measure dissolved oxygen, temperature, pH and conductivity. Calibrate the
meters according to the manufacturers instructions. Use a standard method to measure alkalinity and
hardness (Standard Methods, 1985). Record all measurements on data sheets.

5.0 REAGENTS

5.1 Dilution Water: Dilution water is moderately hard, reconstituted deionized water unless otherwise
specified. See Horning and Weber (1985) for the preparation of synthetic fresh water. The dilution water
for a test is the same as the water used to acclimate the fish before the beginning of the test.

5.2 Test Medium: If the test medium is a liquid, dilutions may be made directly for the required
concentrations. If the test media is a liquid phase of a soil, preliminary filtration and dilutions are required.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

7.0 PROCEDURES

FMC-C-024-2

-------
7.1 In order to determine the range of concentrations to be used for a definitive toxicity test, a preliminary
rangefinding test is conducted. Ten fish are placed into exposure chambers with a broad range of concentrations
(0, 1, 10, and 100% test media).

7.2 Survival and mortality are recorded after one (1) and 24 hours and the results are used to determine
definitive test concentrations.

7.3 Replicates are not necessary for this test.

7.4 The concentrations cited below are used as an example and may be adjusted to meet the criteria of the
specific situation. A geometric or logarithmic range of concentrations also may be used (Sprague, 1973). Other
ranges may be used according to the needs of the specific situation.

Example 1. Test Dilution

Test Concentrations
test medial

Diluent

Volume (mL)

Test Media

10
100

750.0
742.5
675.0
0

7.5
75.0
750.0

7.5 Rinse all exposure chambers, except the chamber containing 100% test media, in dilution water.

7.6 Measure 750 mL of dilution water and pour into the control exposure chamber.

7.7 Measure 7.5 mL of test media and dilute to 750 ml with dilution water. Pour this mixture into the
exposure chamber. Continue this procedure until all the concentrations are prepared. Always go from the lowest
concentration to the highest in order to minimize the risk of cross contamination.

7.8 Using a wide bore pipette, randomly select one fish at a time into a small cup, placing ten (10) fish
into each cup. After all the fish have been selected, pour into the exposure chambers. Gently submerse the cup
below the water surface and pour the fish out.

7.9 Measure and record temperature, dissolved oxygen, pH, conductivity, alkalinity and hardness at the
beginning of the test after the fish have been added to the exposure chamber.

7.10 Calculations

7.10.1 The methods used to determine the LC50 differ depending on the results of the test. If there is
no partial mortality in any replicate (i.e. all alive or all dead), then the Moving-Average Method may be
used to determine the LC50. If there is partial mortality within a replicate, then the Probit Method should be
used to calculate the LC50 (Peltier and Weber, 1985). Since the results of this test are only preliminary,
exact calculations need not be made. An estimate of the LC50 is needed to determine the range of
concentrations to be used for the definitive test. Other methods to determine the LC50 of the test media may
be used if justified and the appropriate reference cited.

7.11 Health and Safety

FMC-C-024-3

-------
7.11.1 When working with potentially hazardous materials, follow US EPA, OSHA, and corporate
health and safety procedures.

8.0 QUALITY CONTROL

8.1. Quality control should encompass the following parameters to ensure a valid test. The guidelines in
this text and in Table 1 (Appendix A) should be followed to insure adequate QA/QC.

8.1.1 Test media sampling.

8.1.2 Test organisms.

8.1.3 Facilities equipment.

8.1.4 Test media preparation.

8.1.5 Dilution water.

8.1.6 Test conditions.

8.1.7 Standard reference toxicant.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Denny, J.S. 1987. Guidelines for the Culturing of Fathead Minnows for use in Toxicity Tests.
EPA/600/3-87/001. Environmental Research Laboratory, Duluth, MN.49 pp.

3. Huston, Mark, March 1988. SOP-A. 7-Day Standard Reference Toxicity Test Using Larval Pimephales
Promelas. U.S. EPA Environmental Response Team - Technical Assistance Team, TDD: 11871206.

5. Sprague, J.B. 1973. The ABC's of Pollutant Bioassay using Fish in Biological Methods for the Assessment
of Water Quality. ASTM STP 528. American Society for Testing and Materials, pp. 6-30.

6. Standard Methods for the Examination of Water and Wastewater. 1985. American Public Health
Association, 16th ed.

FMC-C-024-4

-------
ERT Method

48-HOUR ACUTE TOXICITY TEST USING DAPHNIA MAGNA AND DAPHNIA PULEX

1.0 SCOPE AND APPLICATION

1.1 The procedure for conducting a 48-hour (hr) acute toxicity test using Daphnia magna or Daphnia
pulex is described below. This test is applicable to leachates, effluents, and liquid phases of sediments.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Larval daphnids are placed in individual containers and exposed to various concentrations of a test
media over a 48-hr period. Mortality is the endpoint of the test.

3.0 INTERFERENCES

3.1 Non-target chemicals (i.e. residual chlorine) cause adverse effects to the organisms giving false
results.

3.2 Dissolved oxygen depletion due to biological oxygen demand, chemical oxygen demand and
metabolic wastes also is a potential problem.

3.3 Loss of a toxicant through volatilization and adsorption to exposure chambers may occur (Peltier and
Weber, 1985).

3.4 The results of a static toxicity test do not reflect temporal fluctuation in test media toxicity (Peltier
and Weber, 1985).

4.0 APPARATUS AND MATERIALS
4.1 Apparatus

4.1.1 60 larval daphnids: Acclimated at least 24-hr to dilution water.

4.1.2 60 exposure chambers: 100 mL volume, labeled.

4.1.3 Trav: To hold exposure chambers and glass covers.

4.1.4 Pipettes: Wide bore, inside diameter 1.5 times the length of the daphnid.

4.1.5 Graduated cylinders: 250 mL and 1 L.

4.1.6 Pipette: 1 mL.

FMC-C-025-1

-------
4.1.7 Beakers: For chemical measurements, 250 mL.

4.1.8 Test medium: 1 L.

4.1.9 Diluent: 3 L.

4.1.10 Waste containers.

4.1.11 Light table: To aid in counting the organisms.

4.1.12 Suitable food.

4.2 Test Organisms

4.2.1 Test organisms may be reared in-house or obtained from an outside source. Positive identification
of the species is required before beginning testing. Daphnids to be used must be less than 24-hr old and
from the second to the sixth brood of healthy adults. Populations of healthy daphnids have large
individuals, have an absence of floaters, have an absence of ephippia, no parasites, individuals are dark
colored and produce large numbers of young (Biesinger, et al. 1987). Place the parent generation into
individual cups containing dilution water for a 24-hr prior to the beginning of the test to ensure that less
than 24-hr old daphnids are available.

4.3 Equipment for Chemical Analysis

4.3.1 Meters are needed to measure dissolved oxygen, temperature, pH and conductivity. Calibrate the
meters according to the manufacturers instructions. Measure alkalinity and hardness according to a
standard method (Standard Methods, 1985).

5.0 REAGENTS

5.1 Dilution Water: Dilution water is reconstituted, deionized water. The water type should be
moderately hard unless otherwise specified. See Horning and Weber (1985) for the preparation of synthetic fresh
water. The dilution water for a test is the same as the water used to culture daphnids and the water used to
acclimate daphnids before the beginning of the test.

5.2 Test Medium: If the test medium is a liquid, dilutions may be made directly for the required
concentrations. If the test medium is a sediment, preliminary filtration and dilutions are required to produce a
liquid phase. The optimum pH range for daphnids is 6.8 - 8.5; therefore, the pH of the dilution water or the
concentrations may have to be adjusted prior to the start of the test (Briesinger et al. 1987).

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Once collected, the samples will be placed in containers constructed from materials suitable for the
suspected contaminants. Because surrogate test species will be exposed to varying concentrations of the sample
material, no chemical preservatives are to be used. The preservation and storage protocol is therefore limited to
holding the samples on ice at 4°C for the holding time specified by the analytical method. Prior to shipping, the
laboratory performing the toxicity tests will be notified of any potential hazards that may be associated with the
samples.

FMC-C-025-2

-------
7.0 PROCEDURES

7.1 Select a range of concentrations that span those causing zero mortality to those causing complete
mortality. The concentrations cited below are used as an example and may be adjusted to meet the criteria of the
specific situation. A geometric or logarithmic range of concentrations also may be used (Sprague, 1973). The
example below provides enough test media for five replicates containing 50 mL each and extra for chemical
analysis.

Example 1. Test Dilution

Test Concentrations Volume (mL)

test medial Diluent Test Media

0.0

500.0

0.0

0.1

499.5

0.5

1.0

495.0

5.0

10.0

450.0

50.0

250.0

100.0

0.0

500.0

7.2 Rinse all exposure chambers, except the chamber containing 100% test media, in dilution water.

7.3 Mix concentrations and pour into each exposure chamber.

7.4 Measure 0.5 mL of the test media into a beaker and dilute to 500 ml.

7.5 Using a graduated cylinder, pour out 50 mL into each exposure chamber and pour the rest into a
beaker for chemical measurements.

7.6 Continue these steps for all concentrations. Always work form the lowest concentration to the highest
in order to minimize the risk of cross contamination.

7.7 Using a wide-bore pipette, randomly select and carefully place ten daphnids into each exposure
chamber. Place the pipette tip below the surface and gently expel each daphnid individually into the chamber.

7.8 The test begins when half of the organisms are in the exposure chambers.

7.9 Measure and record mortality and survival at one (1) hour and then at 24 and 48 hr.

7.10 Measure and record temperature, dissolved oxygen, pH, conductivity, alkalinity, and hardness after
the test begins and at the completion of the test.

7.11 The test is complete at the end of 48 hours.

7.12 Calculations

7.12.1 The methods used to determine the LC50 differ depending on the results of the test. If there is

no partial mortality in any replicate (i.e. all alive or all dead), then the Moving-Average Method may be

used to determine the LC50. If there is partial mortality within a replicate, then the Probit Method should be

FMC-C-025-3

-------
used to calculate the LC50. Also the Lowest Observable Effect Concentration (LOEC) is recorded and the
No Observable Effects Concentration (NOEC) is recorded (Peltier and Weber,1985). Since this is a simple
acute test, only mortality is recorded. Other methods of estimating the LC50 may be used if justified and an
accepted reference is cited (Biesinger, et al. 1987).

7.13 Health and Safety

7.13.1 When working with potentially hazardous materials, refer to US EPA, OSHA, and corporate
health and safety procedures.

8.0 QUALITY CONTROL

8.1 Quality control should encompass the following parameters to ensure a valid test. The guidelines in
this text and in Table 1 (Appendix A) should be followed to insure adequate QA/QC.

8.1.1 Test media sampling

8.1.2 Test organisms

8.1.3 Facilities equipment

8.1.4 Test media/leachate preparation

8.1.5 Dilution water

8.1.6 Test conditions

8.1.7 Standard reference toxicant
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Biesinger, K.E., L.R. Williams, and W.H. van der Schalie. 1987. Procedures for Conducting Daphnia
magna Toxicity Bioassays. EPA/600/8 - 87/011. Environmental Monitoring and Support Laboratory.

Cincinnati, OH. 57 pp.

3. Huston, Mark, March 1988. SOP-E. 7-Day Standard Reference Toxicity Test Using Larval Pimephales
Promelas, U.S. EPA Environmental Response Team - Technical Assistance Team, TDD: 11871206.

5. Spraque, J.B. 1973. The ABC's of Pollutant Bioassay using Fish. pp. 6 - 13 in Biological Methods for the
Assessment of Water Quality. J. Cairns and K. Dickson (eds.). STP 528. American Society for Testing and
Materials, Phila., PA 256 pp.

FMC-C-025-4

-------
6. Standard Methods for the Examination of Water and Wastewater. 1985. American Public Health
Association, 16th ed.

FMC-C-025-5

-------
ERT Method

7-DAY STATIC RENEWAL TOXICITY TEST USING CERIODAPHNIA DUBIA

1.0 SCOPE AND APPLICATION

1.1 The procedure for conducting a 7-day toxicity test using Ceriodaphnia dubia is described below. This
test is applicable to effluents, leachates, and liquid phases of sediments which require a chronic toxicity estimate.
This method uses reproductive success as well as mortality as end points for the test.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Ceriodaphnia dubia are placed in individual exposure chambers containing 15 ml of the test media
concentration. Mortality and survival are recorded over a 7-day period as well as the number of broods, the brood
size, and live or dead young. These data are used to determine the Lowest Observable Effect Concentration
(LOEC), the No Observable Effect Concentration (NOEC), the EC50 and the chronic value of the test media.

3.0 INTERFERENCES

3.2 Non-target chemicals (i.e., residual chlorine) cause adverse effects to the organisms giving false
results.

3.3 Dissolved oxygen depletion due to biological oxygen demand, chemical oxygen demand and
metabolic wastes also is a potential problem.

3.4 Loss of a toxicant through volatilization and adsorption to exposure chambers may occur (Peltier and
Weber, 1985).

4.0 APPARATUS AND MATERIALS
4.1 Apparatus

4.1.1 75 Ceriodaphnia dubia: Less than 24 hours old and released during the same 4 hour period.

4.1.2 60 exposure chambers/dav: 30 mL or larger, labeled.

4.1.3 Travs and glass covers: For the chambers.

4.1.4 Pipettes: Wide-bore, inside diameter 1.5 times the length of the organisms.

FMC-C-026-1

-------
4.1.5 Dilution water: 1.5L/day.

4.1.6 Test media: 500 mL/day.

4.1.7 Graduated cylinder: 500 mL and 10 mL.

4.1.8 Mixing bucket: 500 mL or larger.

4.1.9 Pipettes: 1 mL.

4.1.10 Beakers: 250 mL.

4.1.11 Light table: To aid in counting the organisms.

4.1.12 Suitable food.

4.1.13 Waste containers.

4.2 Test Organisms

4.2.1 Test organisms may be reared in house or obtained from an outside source. Positive identification
of Ceriodaphnia dubia is required before beginning the test (Berner, 1986). Ceriodaphnia dubia to be used
must be less than 24-hours old and from the second to the sixth brood of an healthy adult. Adults to be used
should be placed into individual cups containing dilution water 24 hours prior to the start of the test in order
to ensure less than 24-hour old organisms.

4.3 Equipment for Chemical Analysis

4.3.1 Meters are needed to measure dissolved oxygen, temperature, pH and conductivity. Calibrate the
meters according to the manufacturers instructions. Use a standard method to measure and record alkalinity
and hardness (Standard Methods, 1985). Record all measurements on data sheets.

5.0 REAGENTS

5.1 Dilution Water: Dilution water is moderately hard,reconstituted deionized water unless otherwise
specified. See Horning and Weber (1985) for the preparation of synthetic fresh water. The dilution water used in
a test should be the same as the water used to culture and acclimate the test species.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Once collected, the samples will be placed in containers constructed from materials suitable for the
suspected contaminants. Because surrogate test species will be exposed to varying concentrations of the sample
material, no chemical preservatives are to be used. The preservation and storage protocol is therefore limited to
holding the samples on ice at 4°C for the holding time specified by the analytical method. Prior to shipping, the

FMC-C-026-2

-------
laboratory performing the toxicity tests will be notified of any potential hazards that may be associated with the
samples.

7.0 PROCEDURES

7.1 Select a range of concentrations that span those causing zero mortality to those causing complete
mortality. The concentrations cited below are used as an example and may be adjusted to meet the criteria of the
specific situation. A geometric or logarithmic range of concentrations also may be used (Sprague, 1973). The
example below provides enough effluent for ten (10) exposure chambers per concentration, each containing 15
mL and extra for chemical analysis. Other ranges may be used according to needs of the analyses.

Example 1. Test Dilution

Test Concentrations Volume (mL)

test medial Diluent Test Media

0.0

300.0

0.0

0.1

299.6

0.3

1.0

297.0

3.0

10.0

270.0

30.0

50.0

150.0

100.0

0.0

300.0

7.2 Rinse all exposure chambers, except the chamber containing 100% test media, in dilution water.

7.3 To prepare test solutions, measure 0.30 mL of the test media into a beaker and dilute to 300 mL using
dilution water.

7.4 Using a graduated cylinder, pour 15 mL into each exposure chamber and pour the rest into a beaker
for chemical analyses.

7.5 Continue these steps for all concentrations. Always work from lowest concentration to the highest in
order to minimize the risk of cross contamination.

7.6 Using a wide bore pipette, randomly select one less than 24 hour old, acclimated Ceriodaphnia dubia
into each cup, placing the organism under the surface of the test media and gently expelling the animal into the
test chamber.

7.7 Measure and record survival at one (1) hour.

7.8 Measure and record temperature, dissolved oxygen, pH, conductivity, alkalinity and hardness daily on
all new test solutions.

7.9 Dissolved oxygen is measured and recorded daily from both old and new test solutions and the
control. This is done prior to pouring the test concentrations into the individual exposure chambers.

7.10 On the 2nd day, prepare new test media concentrations and a new set of exposure chambers.

FMC-C-026-3

-------
7.11 Pour new concentrations into new chambers as done previously and use the excess for chemical
analyses.

7.12 Count the number of broods, the brood size, and the number of live or dead organisms. Ceriodaphnia
dubia usually start to produce offspring after the third day of the test and they should have three broods by the
completion of the test. The endpoint of the test is when 60% of the control organisms have at least three broods
and at least 90 young (an average of nine per organism).

7.13 Transfer adult Ceriodaphnia dubia by carefully removing with a wide bore pipette and transferring
into the new exposure chamber.

7.14 Add 0.1 mL (1 drop) of a suitable food to each exposure chamber as food. On the first day, do this
after Ceriodaphnia dubia are placed in the exposure chamber.

7.15 Thereafter, place a drop of food into the exposure chamber after the concentrations have been renewed
but before the test organisms are transferred in to the chamber. This provides for more consistent water quality
between changes.

7.16 Place a cover loosely over the exposure chambers to prevent evaporation.

7.17 Calculations

7.17.1 The methods used to determine the EC50 differ depending on the results of the test. If there
are no partial effects in any replicate (i.e. all alive and healthy or all dead), then the Moving-Average
Method may be used to determine the EC50. If there is partial effects within a replicate, then the Probit
Method should be used to calculate the EC50. Also the Lowest Observable Effect Concentration (LOEC),
the No Observable Effects Concentration (NOEC) and the chronic value are recorded (Peltier and Weber,
1985). Other methods of determining the EC50 may be used if justified and the appropriate reference is
cited.

7.18 Health and Safety

7.18.1 When working with potentially hazardous materials, follow US EPA, OSHA and corporate
health and safety procedures.

8.0 QUALITY CONTROL

8.1 Quality control should encompass the guidelines in this text and in Table 1 (Appendix A), as well as
the information below to ensure a valid test.

8.1.1 Effluent sampling.

8.1.2 Test organisms.

8.1.3 Facilities equipment.

8.1.4 Test media preparation.

8.1.5 Dilution water.

8.1.6 Test conditions.

8.1.7 Standard reference toxicant.

FMC-C-026-4

-------
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1.	Berner, D.B. 1986. Taxonomy of Ceriodaphnia fCrustacea:Cladocera') in U.S. Environmental Protection
Agency Cultures. EPA/600/4-86/032. Environmental Monitoring and Support Laboratory, Cincinnati, OH 34 pp.

2.	Horning, W.B. and C. Weber. 1985. Short-term Methods for Estimating the Chronic Toxicity of Effluents
and Receiving Waters to Freshwater Organisms. EPA/600/4-85/014. Environmental Monitoring and Support
Laboratory, Cincinnati, OH 162 pp.

3.	Huston, Mark, March 1988. SOP-A. 7-Day Standard Reference Toxicity Test Using Larval Pimephales
Promelas, U.S. EPA Environmental Response Team - Technical Assistance Team, TDD: 11871206.

4.	Peltier, William H. and Cornelius Weber. 1985. Methods for Measuring the Acute Toxicity of Effluents to
Freshwater and Marine Organisms. EPA/600/4-85/013. Environmental Monitoring and Support Laboratory,
Cincinnati, OH 216 pp.

5.	Spraque, J.B. 1973. The ABC's of Pollutant Bioassay Using Fish. pp. 6 - 13 in Biological Methods for the
Assessment of Water Quality. J. Cairns and K. Dickson (eds.). STP 528. American Society for Testing and
Materials, Phila., PA 256 pp.

6.	Standard Methods for the Examination of Water and Wastewater. 1985. American Public Health
Association, 16th ed.

FMC-C-026-5

-------
ERT Method

7-DAY STATIC TOXICITY TEST USING LARVAL PIMEPHALES PROMELAS

1.0 SCOPE AND APPLICATION

1.1 The procedure for conducting a 7-day static renewal toxicity test using larval fathead minnows
(Pimephales promelas') is described below. This test is applicable to effluents, leachates, and sediments which
require a chronic toxicity estimate.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Larval fathead minnows are exposed to different concentrations of a test media over a 7-day period.
Survival and growth results are used to determine the No Observable Effect Concentration (NOEC), the Lowest
Observable Effect Concentration (LOEC), the EC50, and the chronic value (CHV) of the test media. Test
concentrations are renewed daily.

3.0 INTERFERENCES

3.1 The results of a static toxicity test do not reflect temporal changes in effluent toxicity. This method is
less sensitive than a flow-through toxicity test and the sensitivity is dependent upon the accuracy of the solutions
(Peltier and Weber, 1985).

3.2 Non-target chemicals (i.e. residual chlorine) cause adverse effects to the organisms, giving false
results.

3.3 Dissolved oxygen depletion due to biological oxygen demand, chemical oxygen demand, and
metabolic wastes also is a potential problem.

3.4 Loss of a toxicant through volatilization and adsorption to exposure chambers may occur (Peltier and
Weber, 1975).

4.0 APPARATUS AND MATERIALS
4.1 Apparatus

120 larval fathead minnows: Less than 24 hours old.

12 exposure chambers: 1 L. labeled.

12 small cups: 50 mL.

Test media: 2 L/dav.

FMC-C-027-1

-------
4.1.5 Diluent: 4.25 L/day.

4.1.6 Graduated cylinders: Three 1 L.

4.1.7 Beakers: 250 mL.

4.1.8 Mixing buckets: 2L.

4.1.9 Tubing: Plastic, "3/8" outside diameter.

4.1.10 Plastic screening: Mesh smaller than that of the fish.

4.1.11 Pipettes: Wide-bore, 1.5 times the size of the fish.

4.1.12 Waste containers.

4.1.13 Brine shrimp or other suitable food.

4.2 Test Organisms

4.2.1 Larval fathead minnows may be cultured in-house or obtained from an outside source. Positive
identification of the species must be made prior to beginning the test. F athead minnows to be used for the
test must be healthy. Place the substrate holding the eggs into the dilution water 24-hours prior to the
beginning of the test to ensure that the fish to be used are less than 24-hours old. Larval fathead minnows
must be fed during the acclimation period as well as during the test. Brine shrimp nauplii or other suitable
larval fish food may be used. Peltier and Weber (1985) and Denny (1987) provide more detail and
information including culturing, care, handling, and disease prevention of fathead minnows.

4.2.2 Place the substrate containing the eggs into a bucket containing dilution water 24 hours prior to the
beginning of the test. This allows the test organisms to become acclimated to the test media and provides
the proper aged fish. Aerate the eggs vigorously to avoid fungal growth and use populations of fish that
have less than 5% mortality (Standard Methods, 1985). During this time, adjust the temperature to 25°C.
Feed fish during the acclimation period and during the toxicity test.

4.3 Equipment for Chemical Analysis

5.0 REAGENTS

5.1 Dilution Water: Dilution water is moderately hard, reconstituted deionized water unless otherwise
specified. See Horning and Weber (1985) for the preparation of synthetic fresh water. Set up a laboratory or
standard dilution water control when receiving waters are used as the dilution water.

5.2 Test Medium: If the test medium is a liquid, dilutions may be made directly for the required
concentrations. If the test medium is to be a liquid phase of a soil, preliminary filtration and dilutions are
required.

6.0 SAMPLING COLLECTION, PRESERVATION, AND HANDLING

FMC-C-027-2

-------
6.1 The selected environmental matrix will be sampled utilizing the methodology detailed in ERT
Standard Operating Procedures (SOPs) #2012, Soil Sampling; #2013, Surface Water Sampling; #2016, Sediment
Sampling, and any other procedure applicable for the media sampled.

6.2 Once collected, the samples will be placed in containers constructed from materials suitable for the
suspected contaminants. Because surrogate test species will be exposed to varying concentrations of the sample
material, no chemical preservatives are to be used. The preservation and storage protocol is therefore limited to
holding the samples on ice at 4°C for the holding time specified by the analytical method. Prior to shipping, the
laboratory performing the toxicity tests will be notified of any potential hazards that may be associated with the
samples.

7.0 PROCEDURES

7.1 Choose a range of concentrations that span those causing no effect to those causing complete
mortality. The concentrations cited below are used as an example and may be adjusted to meet the criteria of the
specific situation. A geometric or logarithmic range of concentrations also may be used (Sprague, 1973). The
example below provides enough test media for two replicates containing 500 mL each.

Example 1. Test Dilution

Test Concentrations Volume (mL)

test medial Diluent Test Media

1000

990

900

100

750

250

500

100

1000

7.2 Rinse all exposure chambers, except the chamber containing 100% test media, in dilution water.

7.3 Prepare the test dilutions by pouring 500 mL of dilution water into each control chamber. Then
measure out 10 mL of the test media into a bucket and pour 990 mL of dilution water into the bucket and mix.
Using a graduated cylinder, pour 500 mL into each 1% exposure chamber.

7.4 Continue these steps for all concentrations. Always work from the lowest concentration to the highest
in order to minimize the risk of cross contamination.

7.5 Using a pipette, randomly place one fish at a time into a small cup until there are ten (10) fish in each

cup.

7.6 Randomly select the cups and carefully pour the fish into the exposure chambers. Submerse the cup
below the test media surface, gently tilt the cup and pour the fish into the exposure chamber.

7.7 Record survival at one (1) hour and then daily thereafter.

7.8 Measure and record dissolved oxygen, temperature, pH, and conductivity alkalinity and hardness on
all test solutions after the fish have been placed into the chambers and then daily thereafter.

FMC-C-027-3

-------
7.9 Feed larval fish three times daily at four (4) hour intervals (i.e. 0800, 1200, and 1600). Use a
commercially prepared food suitable to larval fish or a freshwater rinsed concentrated suspension of newly
hatched brine shrimp.

7.10 Add approximately 700-1000 nauplii (0.1 mL) to each container.

7.11 Prepare new dilutions as done the day before.

7.12 Place plastic screening over a length of tubing and create a siphon using the dilution water. Carefully
draw out as much of the old solutions, dead brine shrimp and waste debris as possible from the exposure chamber
without disturbing the fish. Again, work from the lowest concentration to the highest in order to minimize the
risk of cross contamination.

7.13 Discard tubing and the waste concentrations in a manner consistent with standard laboratory
procedures.

7.14 Use care when pouring the new test solutions into the exposure chambers. These procedures are
repeated throughout the duration of the test except for the last day of the test.

7.15 Calculations

7.15.1 The methods used to determine the EC50 differ depending on the results of the test. If there is
no partial effects in any replicate (i.e. all alive and healthy or all dead), then the Moving-Average Method
may be used to determine the EC50. If there is partial effects within a replicate, then the Probit Method
should be used to calculate the EC50. Also the Lowest Observable Effect Concentration (LOEC), the No
Observable Effect Concentration (NOEC) and the chronic value (CHV) are recorded (Peltier and Weber,
1985). Growth is also measured in the larvae to determine the effect of the test media on the life cycle.

This is done by comparing the dry weight of the fish in the various concentrations to the dry weight of a
control group of fish raised under the same conditions.

7.16 Health and Safety

7.16.1 When working with potentially hazardous materials, follow US EPA, OSHA and corporate
health and safety procedures.

8.0 QUALITY CONTROL

8.1 Quality control should encompass the following parameters and the guidelines in this text and in
Table 1 (Appendix A) to ensure a valid test and adequate QA/QC.

Test media sampling.

Test organisms.

F acilities equipment.

Test media preparation.

Dilution water preparation.

Test conditions.

Standard reference toxicant

FMC-C-027-4

-------
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1.	Denny, J.S. 1987. Guidelines for the Culturing of Fathead Minnows for use in Toxicity Tests.
EPA/600/3-87/001. Environmental Research Laboratory, Duluth, MN. 49 pp.

2.	Horning, W.B. and C. Weber. 1985. Short-term Methods for Estimating the Chronic Toxicity of Effluents
and Receiving Waters to Freshwater Organisms. EPA/600/4-85/014. Environmental Monitoring and Support
Laboratory, Cincinnati, OH. 162 pp.

3.	Huston, Mark, March 1988. SOP-A. 7-Day Standard Reference Toxicity Test Using Larval Pimephales
promelas. U.S. EPA Environmental Response Team - Technical Assistance Team, TDD: 11871206.

4.	Peltier, William H. and Cornelius Weber. 1985. Methods for Measuring the Acute Toxicity of Effluents to
Freshwater and Marine Organisms. EPA/600/4-85/013. Environmental Monitoring and Support Laboratory,
Cincinnati, OH. 216 pp.

5.	Sprague, J.B. 1973. The ABC's of Pollutant Bioassay Using Fish in Biological Methods for the
Assessment of Water Quality. ASTM STP 528. American Society for Testing and Materials, pp. 6-30.

6.	Standard Methods for the Examination of Water and Wastewater. 1985. American Public Health
Association, 16th ed.

FMC-C-027-5

-------
ERT Method

96-HOUR STATIC TOXICITY TEST
USING SELENASTRUM CAPRICORNUTUM

1.0 SCOPE AND APPLICATION

1.1	The procedure for conducting a 96-hour static toxicity test using Selenastrum capricornutum is
described below. The endpoint of this test is growth, measured by increase in cell count, chlorophyll content,
biomass, or absorbance (turbidity). This test may be conducted on effluents, leachates or liquid phase of
sediments. This test will also identify a test media that is biostimulatory (Horning and Weber, 1985).

1.2	These are standard (i.e., typically applicable) operating procedures which may be varied or changed as
required, dependent on site conditions, equipment limitations or limitations imposed by the procedure or other
procedure limitations. In all instances, the ultimate procedures employed should be documented and associated
with the final report.

1.3	Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Selenastrum capricornutum is exposed to various concentrations of a test media over a 96-hour period
and growth is measured at the end of the test.

3.0 INTERFERENCES

3.1	The results of a static toxicity test do not reflect temporal changes in effluent toxicity.

3.2	The detection limits of the toxicity of a test media are organism dependent (Horning and Weber,

1985).

3.3	Non-target chemicals (i.e. residual chlorine) cause adverse effects to the organisms giving false
results.

3.4	Loss of a toxicant through volatilization and adsorption to exposure chambers may occur (Peltier and
Weber, 1985).

3.5	The concentrations of natural nutrients in the test media may affect the results (Horning and Weber,
1985).

4.0 APPARATUS AND MATERIALS
4.1 Apparatus

4.1

.1

Selenastrum capricornutum culture.

4.1

.2

18 Erlenmever flasks: 250 mL.

4.1

.3

Dilution water: 1.5 L.

4.1

.4

Test media: 1 L.

FMC-C-028-1

-------
4.1.5 Stock nutrient solutions.

4.1.6 Centrifuge: 15 - 100 mL capacity.

4.1.7 Graduated cylinders: 10 mL and 100 mL.

4.1.8 Erlenmever flask: 500 mL.

4.1.9 Microscope.

4.2 Washing Procedure

4.2.1 Wash with warm tap water and non-phosphate detergent.

4.2.2 Rinse with tap water.

4.2.3 Rinse with 10% HC1.

4.2.4 Rinse with deionized water.

4.2.5 Rinse with acetone.

4.2.6 Rinse with deionized water.

4.2.7 Final rinse with dilution water.

4.3 Test Organisms

4.3.1 Selenastrum capricornutum may be raised in house or received from an outside source. Positive
identification of the species is required before beginning the test. A stock culture that is 4-7 days old is
required for this test. Horning and Weber (1985) provide detailed information on the preparation of culture
media and stock culture.

4.4 Equipment for Chemical Analysis

4.4.1 Meters are needed to measure dissolved oxygen, temperature, pH, and conductivity. Calibrate the
meters according to the manufacturers specifications. Measure and record alkalinity and hardness
according to a standard method (APHA, 1985).

5.0 REAGENTS

5.1 Dilution Water: Dilution water is moderately hard, reconstituted deionized water unless otherwise
specified. The dilution water for the test is the same water used to culture Selenastrum capricornutum. See
Horning and Weber (1985) for the preparation of synthetic fresh water.

5.2 Test Media: If the test media is a liquid, dilutions may be made directly for the required
concentrations. If the test media is a liquid phase of a sediment, preliminary filtration and dilutions are required.
To eliminate false negative results due to low nutrient concentrations, add 1 mL of stock culture solution (except
EDTA) per liter of test media prior to preparing test concentrations.

5.3 Stock Culture Solution: The methods needed to prepare the stock culture solution and the amount of
chemicals needed to prepare the solution are found in Horning and Weber, 1985. One liter of test media will

FMC-C-028-2

-------
provide three (3) replicates of 100 mL each for six (6) concentrations and 400 mL for chemical analysis (Horning
and Weber, 1985).

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.2 Once collected, samples will be placed in containers constructed from materials suitable for the
suspected contaminants. Because surrogate test species will be exposed to varying concentrations of the sample
material, no chemical preservative are to be used. The preservation and storage protocol is therefore limited to
holding the samples on ice at 4°C for the holding time specified by the analytical method. Prior to shipping, the
laboratory performing the toxicity tests will be notified of any potential hazards that may be associated with the
samples.

7.0 PROCEDURES

7.1. Maintain a stock culture of algae at 24 ± 2°C under continuous lighting.

7.2 Transfer 1-2 mL aseptically to new test media once a week in order to maintain an uncontaminated
and healthy culture.

7.3 To prepare the inoculum, follow the steps below (Horning and Weber, 1985).

7.4 An inoculum is prepared from the stock solution 2-3 hours prior to the beginning of the test. Each
milliliter of inoculum must contain enough cells to provide an initial cell density of 10,000 cells/mL in the
exposure chamber. Therefore, each milliliter of inoculum must contain 1 million cells if using 100 mL test
volume. Use the formula below to determine the amount of stock solution required for the test.

7.5 Volume of stock solution required (mL) = (# of flasks) (vol. of test soln./flask) x 10,000 cells/mL cell
density in stock culture.

7.5.1 Determine the density of cells in the stock solution.

7.5.2 Calculate the required volume of stock solution (from the equation above).

7.5.3 Centrifuge 50% more than the calculated value of stock solution at 1000 x g for 5 minutes.

7.5.4 Decant the supernatant and resuspend in 15 mL of deionized water.

7.5.5 Repeat steps 7.5.3 and 7.5.4.

7.5.6 Mix and determine the cell count and dilute as necessary to obtain a cell density of 106 cells/mL.

7.6 If possible, choose a range of concentrations that will span those with no effect to that which will
cause complete mortality. The table below is used as an example and the concentrations may be adjusted to meet
the specific needs of the test.

Example 1. Test Dilution

FMC-C-028-3

-------
Test media (%~\

Dilution water rmT,^

Test Media rmT,^

300.0

0.0

297.0

3.0

291.0

9.0

270.0

30.0

210.0

90.0

100

0.0

300.0

7.7 Measure 100 mL of dilution water into each of the three (3) control flasks.

7.8 Mix 3 mL of test media with 297 mL of dilution water into a mixing bucket.

7.9 Pour 100 mL into each one (1) percent test media flasks.

7.10 Continue with these dilutions until all concentrations are mixed.

7.11 Add 1 mL of test inoculum to each flask and begin the test.

7.12 At 1-2 hours, check the cell density of the controls to ensure sufficient test organisms. There are no
renewals of test solutions for the duration of the test and the test is complete at 96 hours.

7.13 Measure and record temperature, dissolved oxygen, pH, conductivity, alkalinity, and hardness on all
test solutions.

7.14 Growth is measured at the end of the test by cell counts, chlorophyll content or turbidity (light
absorbance), or biomass. Cell counts may be determined by using a automatic particle counter or manually under
a microscope. Chlorophyll content may be measured using in-vivo or in-vitro fluorescence or in-vitro
spectrophotometry. Turbidity may be measured by spectrophotometry at 750 nm. Biomass is measured by
multiplying the cell count by the mean cell volume or by direct gravimetric dry weight analysis. Horning and
Weber (1985) provide details of the methodologies for these measurements.

7.15 At the completion of the test, samples should be checked under a microscope to detect any abnormal
cell growth or other deviations.

7.16 It also may be necessary to check algal growth on a daily basis depending on the test media.

7.17 Calculations

7.17.1 The No Observable Effect Concentration (NOEC), the Lowest Observable Effect
Concentration (LOEC), and the chronic value (CHV) are measured and recorded at the end of 96 hours.
Dunnetts procedure or the Probit Method may be used to calculate the NOEC and LOEC. When the
assumptions for normality and homogeneity of variance are not met, Steel's Many - One Rank Test may be
used. Other methods may be used if justified and the appropriate method is cited. Calculate the percent
stimulation (%S) if growth in the concentrations exceeds the growth in the controls.

7.18 Health and Safety

7.18.1 When working with potentially hazardous materials, follow US EPA, OSHA and corporate
health and safety guidelines.

FMC-C-028-4

-------
8.0 QUALITY CONTROL

8.1 Quality control should encompass the following parameters to ensure a valid test. The guidelines in
this text and in Table 1 (Appendix A) should be followed to insure adequate QA/QC.

8.1.1	Test organisms.

8.1.2	Facilities/equipment.

8.1.3	Test media preparation.

8.1.4	Dilution water.

8.1.5	Test conditions.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1.	APHA. 1985. Standard Methods for the Examination of Water and Wastewater. 16th Ed. American Public
Health Association, Washington, D.C.

2.	Horning, W.B. and C. Weber. 1985. Short-term Methods for Estimating the Chronic Toxicity of Effluents
and Receiving Waters to Freshwater Organisms. EPA/600/4-85/014. Environmental Monitoring and Support
Laboratory, Cincinnati, OH. 162 pp.

3.	Houston, Mark, SOP H. 96-Hour Static Toxicity Test Using Selenastrum Capricornutum. U.S. EPA
Environmental Response Team - Technical Assistance Team TDD: 11871206.

4.	Peltier, William H. and Cornelius Weber. 1985. Methods for Measuring the Acute Toxicity of Effluents to
Freshwater and Marine Organisms. EPA/600/4-85/013. Environmental Monitoring and Support Laboratory,
Cincinnati, OH. 216 pp.

FMC-C-028-5

-------
Region IV TAT

HAZARD CATEGORIZATION FIELD METHODOLOGY

1.0 SCOPE AND APLLICATION

1.1 Chemical compounds have inherent properties which determine the hazard type they present. These
properties can be useful in evaluating risks to personnel and the environment and in determining such things as
mitigation, treatment, and, in general, what course of action should be pursued. Hazard categorization in the field,
then, would give enough information to an OSC about the potential threat of an unknown material such that a more
educated decision as to the course of action could be made.

1.1 After obtaining samples of unknowns, using EPA and TAT Standard Operating Procedures, this
methodology can be used to classify the unknown using physical and chemical characteristics of the material. A
TAT, in the field, following this methodology, could give an educated answer to the OSC as to the characteristics
of an unknown.

1.3 This methodology is simple in content and usage. Everything required is contained within the FIELD
CATEGORIZATION KIT. A list of components is included in this documentation. Recording of test results is
done through the use of the attached FIELD CATEGORIZATION RECORD SHEET. This record sheet presents,
in concise form, the results obtained from tests performed on a particular unknown.

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

See specific test.

5.0 REAGENTS

See specific test.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not available.

FMC-K-001-1

-------
7.0 PROCEDURE
7.1 Logic Path

NOTES: 1) "Go to *" refers to section of outline to which to proceed.

2)	"+" denotes positive test outcome.

3)	denotes negative test outcome.

I. Observations

A.	Fuming material

+ {Fumes are probably corrosive} Go to I G. (Reported sulfur smell)

-	Go to I B. (Reported strong odor)

B.	Reported strong odor

+ Go to I G. (Reported sulfur smell)

-	Go to I C. (Evaporates quickly)

C.	Evaporates quickly

+ Go to I G. (Reported sulfur smell)

-	Go to I D. (Crystals formed on container)

D.	Crystals formed on container
CAUTION: MAY BE EXPLOSIVE!

+ Go to IV (Peroxide Test)

-	Go to I E. (Colored granular material)

E.	Colored granular material

+ {Probably pesticide} Go to III (Water Solubility Test)

-	Go to IF. (Fibrous, easily crumbled material)

F.	Fibrous, easily crumbled material

+ {Probably asbestos. This material is carcinogenic. Do not proceed with testing.}

-	Go to I H. (No apparent risk)

G.	Reported sulfur smell

+ {Possibly pesticide} Go to III (Water Solubility Test)

-	Go to II (Oxidizer Test)

H.	No apparent risk

+ Go to II (Oxidizer Test)

-	Go to I A. (Fuming material)

FMC-K-001-2

-------
II.	Oxidizer Test [Refer to TEST DESCRIPTIONS; Page 12]

A. Oxidizer (Strong, moderate, or weak)

+ Go to V (pH Test)

-	Go to VI (Acid Test)

III.	Water Solubility Test [Refer to TEST DESCRIPTIONS; Page 15]

A.	Emulsion (i.e., stable mixture immiscible liquids held in suspension) is formed

+ {Most likely a pesticide} Go to V (pH Test)

-	Go to III B. (Becomes stringy white and curdles)

B.	Becomes stringy white and curdles

+ {Most likely a plastic resin substance such as polysulfide, polyureathane, or styrene} [May be acid
carrier] Go to V (pH Test)

-	Go to III C. (Soluble)

C.	Soluble

+ {Inorganic or polar organic} Go to VII (Hexane Solubility Test)

-	Go to III D. (Floats)

D.	Floats

+ {Non-halogenated non-polar organic} Go to VII (Hexane Solubility Test)

-	Go to III E. (Sinks)

E.	Sinks

+ {Halogenated non-polar organic} Go to VII (Hexane Solubility Test)

-	Go to III F. (Forms globules)

F.	Forms globules

+ {Most likely a silica type substance} [May be acid carrier} Go to V (pH Test)

-	Go to III G. (Reacts violently)

G.	Reacts violently

+ Go to V (pH Test)

-	Go to III A. (Emulsifies)

IV.	Peroxide Test [Refer to TEST DESCRIPTIONS; page 13]

A. When touched to crystals

FMC-K-001-3

-------
+ (CAUTION: PROBABLY EXPLOSIVE!!! Do not proceed with testing.}

-	{Probably a solid dissolved in a liquid} Go to II (Oxidizer Test)

B. When placed in liquid

+ Go to VIII (Combustibility Test)

-	{Possibly disinfectant, bleach, ammonia, etc., type cleaning
solution} Go to IX (Halogenation Test)

V pH Test [Refer to TEST DESCRIPTIONS; page 14]

A.	pH of 2.0 or less

+ {Corrosive acid}

-	Go to V B. (pH 4.0 or less)

B.	pH of 4.0 or less

+ {Acid} Go to IV (Peroxide Test)

-	Go to V C. (pH 5.0 - 8.0)

C.	pH 5.0 - 9.0

+ {Neutral} Go to IV (Peroxide Test)

-	Go to V D. (pH of 9.0 or greater)

D.	pH of 9.0 or greater

+ {Basic} Go to IV (Peroxides Test)

-	Go to V E. (pH of 11.0 or greater)

E.	pH of 11.0 or greater

+ {Corrosive base} Go to IV (Peroxide Test)

-	Go to V A. (pH of 2.0 or less)

VI. Acid Test [Refer to TEST DESCRIPTIONS; page 8]

A.	Yellow 

+ {Probably sulfide substance)

-	Go to VI B. (Bubbling/effervescing)

B.	Bubbling/effervescing

+ (CAUTION: May contain cyanide!} Go to III (Water
Solubility Test)

-	Go to VI C. (Green)

C.	Green

FMC-K-001-4

-------
+ (CAUTION: May contain arsenic!! Go to III (Water
Solubility Test)

-	Go to VI D. (None of the above)

D. None of the above

+ Go to III (Water Solubility Test)

-	Go to VI A. (Yellow)

VII. Hexane Solubility Test [Refer to TEST DESCRIPTIONS; page 11]
A. Soluble

+ {Polar or non-polar organic} Go to VIII (Combustibility
Test)

- {Inorganic} Go to V (pH Test)

VIII.	Combustibility Test [Refer to TEST DESCRIPTIONS; page 9]
A. Sample catches fire

+ {Could be flammable or combustible [see test description
for determination] Go to IX (Halogenation Test)

-	{Non-flammable} Go to IX (Halogenation Test)

IX.	Halogenation Test [Refer to TEST DESCRIPTIONS; page 10]
A. Green flame

+ {Halogenated - most common is chlorine}

-	{Non-halogenated} [If testing oil, try Chlor-in-oil 50
(tm) test as 500 ppm or greater chlorine is needed to
show "+" on Halogenation Test]

FMC-K-001-5

-------
7.2 Test Descriptions

NOTES: 1) Remember: Only small quantities of unknown are used.

2)	Always utilize pipets when handling liquids.

3)	Always utilize scoops/spoons when handling solids/sludges.

4)	If a sample taken from its source consists of layers or
phases, the categorization tests should be performed on
each layer or phase separately.

5)	Never point a test tube at anyone.

6)	Always add unknown to water (slowly); Never add water to
unknown.

7)	All field characterizations should be carried out in a

level or respiratory protection suitable to the circumstances.

8)	The water used in the tests should be deionized/distilled.

9)	Do not use the same test tube for more than one test, to
insure no contamination from test to test. A pH test may
be done on the water solubility test just performed.

10)	Always utilize test tube clamps when handling tubes containing
or unknowns.

11)	Never return reagents to their container, to avoid contamination.

12)	Never cork a test tube containing reacting materials.

13)	Always keep test strips and reagents closed to avoid
possible contamination and erroneous results.

14)	Normal decon procedures shall apply to reusable items
such as scoops and test tube clamps.

reagents

FMC-K-001-6

-------
***** Acid Test *****

Equipment:

Test tube

Hydrochloric acid (IN)
Pipet and/or scoop
Test tube clamp

Procedure:

1)	Place a small amount of sample in test tube.

2)	Slowly add IN Hydrochloric acid, a drop at a time (no more than 5-6 drops).

3)	Observe and record results.

Possible Results:

1)	Yellow color ; indication of the probable presence of sulfides.

2)	Bubbling or effervescing; CAUTION: May indicate cyanide!

3)	A green color; CAUTION: May indicate arsenic!

FMC-K-001-7

-------
***** Combustibility Test *****

Equipment:

Propane torch
Cotton swab
Test tube

Pipet and/or scoop

Procedure:

1)	Dip cotton swab into sample contained in test tube.

2)	Hold coated swab slightly above flame source.

3)	If flame does not jump to swab, then lower swab into flame.

4)	Remove swab from flame.

5)	Observe and record results.

Possible Results:

NOTE: Assure that the sample, and not the swab alone is burning.

1)	Flame jumps from source to sample; indication of an extremely flammable substance.

2)	Sample catches fire as soon as flame touches it, and continues to burn when flame is removed; an indication
of flammable substance.

3)	Sample catches fire after application of 3 to 4 seconds of flames, and continues to burn when flame is removed;
indication of combustible substance.

4)	Sample will not catch fire; indication of a non-flammable substance.

FMC-K-001-8

-------
***** Halogenation Test *****

Definition: Halogenation - Incorporation of one of the halogen elements, usually chlorine or bromine, into a chemical
compound.

Equipment:

Test tube
Propane torch
Wire wand
Pipet and/or scoop

Ensure wire wand is cleared of all previous substances prior to use on new sample. To accomplish this, heat in flame
source until all green flame has dissipated. A container of clean water may be useful for faster cleaning and cooling
of the wire wand. When green flame can no longer be dissipated, dispose of wand and use another (See below).

Procedure:

1)	Dip hot wire (cold wire, if material is flammable) in test tube containing	a small amount of sample.

2)	Place coated wire in flame source.

3)	Observe and record results.

Possible Results:

1) A green flame; indication of a halogenated substance.

Procedure for making a wire wand:

Insert one end of a 6 - 8 inch length of coat hanger wire into a cork. Wrap duct tape around the cork. Wrap the free
end of the coat hanger wire with thin (24 -30 gauge) copper wire.

FMC-K-001-9

-------
***** Hexane Solubility Test *****

Definition: Organic - Compounds of carbon.

Equipment:

Test tube
Hexane

Pipet and/or scoop
Test tube clamp

Procedure:

1)	Place 1 mL of hexane in a test tube.

2)	Add a small amount of sample to the tube.

3)	Mix thoroughly by swirling.

4)	Observe and record results.

Possible Results:

1)	Sample dissolves; indicates a polar or non-polar organic substance.

2)	Sample is insoluble; indicates an inorganic substance.

FMC-K-001-10

-------
***** Oxidizer Test *****

Definition: Oxidizer - A material that initiates or promotes combustion in other materials.

Equipment:

Test tube
Test tube clamp
Potassium iodide starch paper
Hydrochloric acid (IN)

Pipet and/or scoop

Procedure:

1)	Add a small amount of sample to the tube.

2)	Add 2 drops of hydrochloric acid to a potassium iodide starch test strip.

3)	Place the test strip in the test tube with the sample.

4)	Observe and record the results.

Possible Results:

1)	Blue or black color formation; indication of an oxidizer.

2)	No color change; indication of a non-oxidizer.

FMC-K-001-11

-------
***** Peroxide Test *****

Equipment:

Test tube

Test tube clamp

Water

Pipet and/or scoop
Peroxide paper

Procedure:

1)	Wet peroxide test paper with a few drops of deionized water.

2)	Touch paper to crystals;

- or -

Dip paper into test tube containing 1 mL of sample.

3)	Observe and record results.

Possible results:

1)	Test paper turns blue; indicates a positive test.

a)	A positive when in contact with crystals indicates probable explosive hazard. CAUTION: EXPLOSIVE
!!!

b)	A positive when in contact with a liquid sample indicates a peroxide forming material.

2)	No color change; indicates a negative test.

a)	A negative when in contact with crystals indicates that there are probably solids dissolved in a liquid.

b)	A negative when in contact with a liquid sample indicates a non-peroxide.

FMC-K-001-12

-------
***** pjj Test *****

Definition: pH - Value taken to represent the acidity or alkalinity of an aqueous solution.

Equipment:

Test tube
Test tube clamp
Pipet and/or scoop
Water
pH paper

Procedure:

1)	Dip pH test paper in sample of liquid unknown contained in a test tube.
- or -

Wet pH paper and touch to sample of solid unknown.

2)	Compare color of test paper to color chart accompanying the test paper.

3)	Observe and record results.

Possible Results:

Comparison of test paper with coded color chart will reveal pH to be between 0 and 13. A particular color will
correspond to a particular pH measurement. The following applies:

1)	<2; indicates a corrosive acid

2)	<4; indicates an acid

3)	5-8; indicates a neutral

4)	9>; indicates a base

5)	11>; indicates a corrosive base

FMC-K-001-13

-------
***** Water Solubility Test *****

Equipment:

Test tube

Test tube clamp

Water

Pipet and/or scoop

Procedure:

1)	Place 1 mL of deionized water in a test tube.

2)	Add a small amount of sample to the tube.

3)	Mix thoroughly by swirling.

4)	Observe and record results.

Possible Results:

1)	Sample is soluble in water; indication of inorganic or polar organic substance.

2)	Emulsion is formed; indication of a slightly polar organic (most likely a pesticide).

3)	Sample floats; indication of a non-halogenated non-polar organic.

4)	Sample sinks; indication of halogenated non-polar organic.

5)	Sample becomes stringy white and curdles; typically a liquid plastic resin.

6)	Globules are formed; indication of a silica substance.

7)	Violent reaction; most likely an acid or base. Reactions that could occur include the generation of heat, the test
tube becoming cold, generation of fumes, and boiling.

FMC-K-001-14

-------
FIELD CATEGORIZATION RECORD SHEET

NOTE: If more than one layer or phase exists per sample, use one record sheet per layer/phase.
Description of sample:

Results Record:

(Record visual results in blanks)

Oxidizer Test	+

Water Solubility Test 	

Peroxide Test	+

pH Test		

Acid Test		

Hexane Solubility Test +

Combustibility Test XF1 F1 Cmb NonFl
Halogenation Test +

Remarks/Comments:

FMC-K-001-15

-------
8.0 QUALITY CONTROL

Information not available.
9.0 METHOD PERFORMANCE

Information not available.
10.0 REFERENCES

Information not available.

FMC-K-001-16

-------
Region V TAT
COMPATIBILITY TESTING

1.0 SCOPE AND APPLICATION

1.1 The purpose of the following testing scheme is:

1.1.1	To separate and classify various unknown containerized waste materials into compatible groups based
on their physical and chemical characteristics.

1.1.2	To identify incompatible waste materials and some hazardous components.

1.1.3	To simulate field bulking operations in the laboratory assuring that no reactions occur during these
operations.

2.0 SUMMARY OF METHOD
Information not available.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS
See specific test.

5.0 REAGENTS

See specific test.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not available.

FMC-K-002-1

-------
7.0 PROCEDURE

7.1 Compatibility Procedural Outline

(1)	Description of physical nature:

color

viscosity

opacity

homogeneity

turbidity

phase ratio

(2)	HNU, CGI readings

(3)	Air reactivity:

-	place small amount of sample on watch glass

-	watch for fuming, ignition, heat generation

(4)	H20 solubility

-	slowly add 10 mL of sample to 10 mL H20

-	note if it goes into solution:

soluble - mixes completely
slightly soluble - goes into solution in a 1:5 ratio
suspension - mixture forms rather than solution
insoluble - more than one phase or layer

-	may pursue solubility further in (16)

(5)	H20 reactivity:

-	place 10 mL H20 in test tube

-	note temperature

-	add 10 mL sample

-	note any temperature change (>10), fuming, ignition

(6)	Specific gravity:

-	relative to H20, eg. floats vs. sinks

-	can use hydrometers for more specific results

(7) pH determination:

FMC-K-002-2

-------
-	pH meter for clean solutions

-	pH paper for all others; if too viscous, mix with DI H20 in no more than 5:1 ratio

-	pH>9 - check for N C and S (10) and (11)

-	pH<7 - check for oxidizers (9) and nitric acid (13)

(8) Chlorinated (Beilstein)

-	run if sample: - H20 insoluble

-	slightly soluble

-	specific gravity >1

-	HNU reading >200 ppm

-	positive reading on CGI

-	heat copper wire until yellow flame (no green)

-	cool in air by waving

-	dip wire in sample solution

-	insert sample wire into flame

-	green flame is positive test

-	chlorine titraters where concentration desired

(9)	Oxidizers:

-	wet KI strip with 5% HCL

-	insert into sample

-	light brown/purple/black is a positive test

(10)	Cyanides

-	place 5 mL sample in test tube

-	raise pH to 11 or greater with 50% NaOH

-	add 3-5 drops of p-dimethylaminobenzal rhodamine solution and swirl gently

-	add 1 drop .0192 AgN03

-	no change is a positive test

-	ppt formation and color change to dirty brown/green is a negative test

Alternate procedure:

-	place three drops of sample on watch glass

-	neutralize with 10% HC1

-	add one drop Chloramine T solution

-	add one drop pyridine-barbituric acid solution

-	wait one minute:

pink - 0.5 ppm or greater
yellow - negative test

May also screen for by acidifying and utilizing Monitox unit

(11)	Sulfides

-	place 5 mL sample in test tube

FMC-K-002-3

-------
-	adjust pH to <4 with HC1

-	wet Pb Acetate paper with DI H20

-	hold paper in head space 30-60 seconds

-	darkened paper is positive test

-	can also screen any acidifying and utilizing Monitox unit

(12)	Organic peroxides:

-	immerse EM Quant peroxide strip in sample for 5 seconds

-	blue color is positive test

(13)	Perchloric acid/Nitric acid

-	place 2 mL sample into test tube

-	add .5 mL diphenylamine and .5 mL sulfuric acid

-	deep purple indicates presence of nitrate, chlorate ions

(14)	Flammability

Flammable:

-	SETA FP <100 or unknown AND

-	CGI >1% OR IF

-	HNU (10.2eV/9.8) >200 and BIC test is (+), (+/-) OR IF

-	CGI <1%, HNU <200, BIC is (+)

Combustible:

-CGI is 0-1% AND

-	HNU is 50-200 ppm AND

-	BIC is (+/-)

Nonflammable/Noncombustible:

-CGI is 0% AND

-	HNU <50 ppm

-	BIC is (-)

BIC TEST

(+) Flammable - ignites readily/voraciously on exposure to flame;	FP <100

(+/-) Combustible - eventually ignites and sustains

(-) Nonflammable/noncom - does not ignite or sustain; FP >200

(15)	Poly chlorinated biphenyls

-	see screen for chlorine

-	use kit if available

(16)	Solubility evaluation:

(a) Soluble in H20:

FMC-K-002-4

-------
-	inorganic or low MW polar organic (ROH, RN, RC02H)

-	distinguish with ignitability:

organic - melts, burns, ignites, sooty smoke, little residue

inorganic - none of above; heavy ash residue; decomposes with heat

mixture - burns with heavy residue (resins pigmented with	inorganics)

(b)	Insoluble in H20:

-	organic or inorganic

-	distinguish as in (a)

(c)	Organic, H20 insoluble, SG<1 - Hydrocarbon with minimal 0, X

(d)	Organic, H20 insoluble, SG>1 - Heavily oxygenated or halogenated

- Potential Pesticide, PCB

(e)	H20 insoluble, 5%HC1 insoluble, 5% NaOH soluble - organic acid

(f)	As above, plus 5%NHC03 soluble - Strong organic acid

(g)	Methylene chloride soluble - Organic
8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

Information not available.

FMC-K-002-5

-------
CSL Method

QUALITY CONTROL FOR SAMPLE PREPARATION. COUNTING. AND DATA HANDLING

1.0 SCOPE AND APPLICATION

1.1 This procedure addresses counting techniques and data handling methods used by CH2M HILL CSL
for screening samples.

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

Information not available.

5.0 REAGENTS

Information not available.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not avialable.

7.0 PROCEDURE

7.1 Gross Alpha/Beta in Soil

The laboratory has provided the CSL with a blank (background) soil sample and a process standard
(NBS 144 Uranium Solution) for use in preparing CSL blanks and standards. These standards and blanks
will be used for calibration and QC checks of the CSL laboratory counter (Tennelec LB5100 Gas
Proportional Counter).

7.1.1 Background Soil Sample:

7.1.1.1 Transfer a 100 milligram (mg) aliquot of soil to a tared standard counting planchet (2-in.
polished stainless steel planchet). Spread the sample evenly onto the planchet.

7.1.1.2 A 1 -mL aliquot of 50 percent 2-Propanol is added to the sample and carefully mixed using the
disposal pipet tip (to aid drying and fixin the soil to the planchet). The sample is then dried slowly under
an infrared heat lamp.

7.1.2 Process Soil Standard fNBS No. 114 Uranium'):

7.1.2.1 The soil standard is prepared in the same manner as described in (7.1.1). Add 1 mL of a
uranium standard (375 dpm/mL alpha and beta).

FMC-R-001-1

-------
7.1.2.2 The uranium standard (NBS No. 114) is pipetted dropwise onto the soil surface and dried
under an infrared heat lamp.

7.2 Gross Alpha/Beta in Water

7.2.1 D.I. Water Blank:

7.2.1.1 A 100-mL aliquot of D.I. water is transferred to a 250-mL glass beaker and placed in the fume
hood. Slowly add a 50-mL aliquot of 8N HN03 and stir thoroughly.

7.2.1.2 Oxidize any organic matter by treating sample with 8N HN03, and H202 30 percent, if
required. Dissolve the residue with 0.5N HN03 and transfer to a tared counting planchet. Complete
transfer using 3 washings and a rubber policemen. Dry the sample under an infrared heat lamp.

7.2.2 Process Water Standard:

7.2.2.1 The processed water standard shall be prepared in the same manner as described in (7.2. 1),
except a 1 -mL U-238 Standard (NBS No. 114) will be added to the sample before the stirring is begun.

7.2.3 Site Investigation Samples:

7.2.3.1 The site investigation water samples should be centrifuged after adding 8N HN03.

7.2.3.2 Transfer a well-mixed aliquot from the sample container to a 100-mL graduated cylinder.

NOTE: To centrifuge: select 4 glass centrifuge (35-mL) bottles with caps. Place bottles in metal tube
holders. (Ensure holders have rubber cushions.) The sample is transferred in equal aliquots to three
of the centrifuge bottles. To balance the centrifuge load, fill the fourth bottle with 35 ml of D.I.

Water.

7.2.3.3 Place centrifuge bottles containing sample into centrifuge tube holders and centrifuge for 10
min at 2,500 rpm.

7.2.3.4 The solid portion of the sample is dried and counted as the suspended fraction.

7.2.3.5 The filtrate is treated as described in 7.2 and the activity counted is additive for both the solid
and filtrate.

7.3 The process blanks/standards from Methods 7.1 and 7.2 will be counted in the same counting
geometries as the plated standards and used to determine the background and counter efficiencies for samples
prepared by the CSL and counted in the LB5100 counter.

7.4 Gas Flow Proportional Counter (Tennelec LB5100')

7.4.1 The counter should meet the tennelec acceptance test procedure and verify with monthly test
sources; thorium-230 for alpha and technetium-99 for beta.

7.4.2 These sources are counted monthly, with a blank planchet counted daily. Control charts are
maintained for all STD and BKGD sources. Each control chart has an upper and lower acceptance range to
be able to have an indicator for maintaining acceptable counter (high voltage) operating range.

7.4.3 The counter calibration is determined using these standards and sample efficiencies are calculated
using the background and tertiary standards as prepared in Steps 7.1 and 7.2. Complete plateau (high

FMC-R-001-2

-------
voltage settings) checks are not made routinely for the LB5100. Experience has shown that it is best to
leave these voltage s*attings stable when the semi-daily operational checks indicate the counter operation is
within established criteria.

7.5 Counter Efficiency Techniques fRad Screening Samples')

7.5.1 Soils-Alpha Beta:

7.5.1.1 An efficiency for counting "soils" in a 2-in.-diameter planchet geometry has been determined
for the Tennelec LB5100 counter. This efficiency is referenced to NIST Standard No. 114. The net
sample counts per minute (cpm) is divided by the known disintegration per minute of the standard
solution (dpm). This result is expressed in units of cpm/dpm (cpm/dpm x 100 = percent efficiency).

7.5.2 Water

Water > 10 to 100 mg solid per 2-in. planchet: The efficiency for the counting of water samples is
determined as follows:

7.5.2.1 Alpha:

7.5.2.1.1 A 1-mL solution of U-238 in D.I. water (100-mL) is processed (using the standard water
procedure). The net cpm is divided by the known dpm of the standard solution. This result is
cpm/dpm or percent efficiency.

7.5.2.1.2 The recovery is accounted for in the efficiency, and the selfabsorption factor was
determined by a method identified in EPA-LV-0539-17. The self-absorption factor is based on the
weight of solids on the planchet. The total activity per unit is corrected by the self-absorption
correction factor.

7.5.2.2 Beta:

7.5.2.2.1 A 1-mL solution of Tc-99 is evaporated dropwise onto the surface of a 2-in. counting
planchet and counted. The net cpm is divided by the known dpm of the standard solution. This result
is cpm/dpm or percent efficiency.

7.5.2.2.2 The recovery is included in the efficiency and is estimated at 70 percent (based on a
series of Tc-99 in D.I. water samples); the self-absorption is 1 (unity) when the mass on the planchet
is < 10 mg. The self-absorption factor was determined by a method identified in EPA-LV-0539-17.

7.6 Counter Techniques fRad Screening Samples')

7.6.1 All samples are be counted in the same configuration as the processed background, soil, and water
stanards.

7.6.2 Each sample group (rad screening samples) should be loaded as shown below:

• blank counting planchet;

• process background sample: (soil or water);

• process standard sample; and

• processed samples (site investigation samples plus laboratory blanks/ duplicates).

FMC-R-001-3

-------
7.6.3 Each sample is placed in a labeled planchet. Counter sample carriers are coded with the carrier
number, which is recorded in the sample logbook.

7.6.4	The LB5100 counter is a microprocessor instrument capable of having the various counting
parameters entered and the output listed to a terminal (printer). All data (raw and collected) are transmitted
to a storage device (5-1/4-in. floppy disk) for data retrieval and QC/quality assurance (QA) review.

7.6.5	Each sample set is accompanied by a radiochemical analysis sheet that carries the CH2M HILL
sample number and counting results.

7.6.6	Sample activities and minimum detection concentration (MDC) are calculated using methods (1)
described in EPA-600/4-80-032, "Prescribed Procedures for Measurement of Radioactivity in Drinking
Water," August 1980, and (2) referenced to HASL-300, A-06-04, and NRC Regulatory Guide 4.14
(Appendix B-8.30-15/16).

7.6.7	The samples processed and counted by the CSL in support of the site investigation will meet the
Department of Transportation's (DOT's) shipping limits (10 CFR 49) at a minimum prior to shipment
offsite.

7.7 Data Handling

The counting system (LB5100) is a microprocessing system capable of output in an activity per unit value.
The output value is calculated by dividing the net cpm by a correction factor [a multiplicative factor derived by
multiplying 2.22 pCi/dpm x volume/weight x (efficiency including recovery) x self-absorption]. The value
calculated is rounded to one significant figure past the decimal, using standard rounding techniques.

Examples:

1.	4.135 = 4.1
4.153 = 4.2

2.	0.146 = 0.1
0.151 =0.2

3.	1.943 = 1.9
1.963 = 2.0

All negative numbers are handled the same as positive values, with the minus sign included.

7.7.1 CSL Sample Logbook:

The samples received for analysis are accompanied by a CH2M HILL chain of custody tracking form.
The sample numbers and other sample parameters are checked for accuracy. If samples and information
on the sample custody form match, sample custody is accepted. Each sample is logged into the CSL
sample logbook (using the CH2M HILL sample number). The following information is recorded at the
time of receipt:

•	CH2M HILL sample number;

•	Type of sample;

•	Sample weight (wet)/volume;

FMC-R-001-4

-------
•	Pretreatment;

•	Aliquot taken: (entered when sample processed); and

•	Date received and initials of person logging in the sample(s).

7.7.2	The following information is recorded at the time sample(s) are placed on the counter:

•	Date counted; and

•	LB5100 (counter) carrier number.

7.7.3	The following information is recorded after the samples have been counted:

•	Gross counts—alpha;

•	Gross counts—beta;

•	Net cpm: (background subtracted)

Net alpha

Net beta;

•	Activity/unit (pCi/unit);

•	Initials of reporting (chemist/technician); and

•	Comments.

7.7.4	Data Correction

All corrections (to initial data entries) are made as follows:

•	A single line is made through the entry;

•	The correction is made over the erratum;

•	Chemist/technician making corrections initials and dates the corrections; and

•	All corrections are made in ink (black).

7.7.5	Data Reporting

When all entries for a sample(s) group are entered into the CSL logbook, a report form can be fill out.
The following information is included:

•	Sample originator (CH2M HILL);

•	Initials of chemist/technicism reporting data;

•	Sample type (soil/water/seiiment/vegetation/other);

•	Date (date the sample results reported);

FMC-R-001-5

-------
•	CH2M HILL sample number;

•	Weight/volume of aliquot analyzed;

•	Sample activity (pCi/g/1);

•	Sample activity results (from CSL logbook);

•	Signature of chemist/technician reporting data (optional); and

•	Signature/initials of radiochemist reviewing report.
8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-R-001-6

-------
CSL Method

DETERMINATION OF GROSS ALPHA/BETA IN SOIL SAMPLES fSIMPLIFIED METHOD')

1.0 SCOPE AND APPLICATION

1.1	This method is applicable to soil, bottom sediments, sludges, and slit core samples collected as part of
the Site Investigation which, when processed and transfered onto a counting planchet should leave a solid residue
< 5 mg/cm2.

1.2	The limits for reported activity are 15 pCi/gm-wet gross alpha and 50 pCi/gm-wet gross beta for
shipments to CH2M HILL" laboratories. The limits set for shipment to vendor laboratories have been established
as the limits listed in 10CFR part 49 (2000 pCi/gm gross activity).

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

3.1	Self-shielding caused by buildup of residues on the counting planchet will reduce counting efficiency.

3.2	The CSL assumes that the sample received for rad screening, is a true field composite and that the 100
mg aliquot is representative of the sample to be shipped. Therefore variabilities between aliquots of the same
sample should be within normal statistical variations.

4.0 APPARATUS AND MATERIALS

4.1	Tweezers.

4.2	Micro Spatula.

4.3	2-inch Counting Planchet.

4.4	Sample Mill Bottles.

4.5	Fume Hood.

4.6	Heat Lamp.

4.7	Analytical Balance.

4.8	Automatic Pipet.

4.9	Transfer Pipet: Disposable (1-mL).

4.10	Cvlotec Sample Mill.

5.0 REAGENTS

FMC-R-002-1

-------
5.1 2-Propanol: 50 percent.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Obtain a blank planchet and place the sample number, from the milled sample bottle, on the bottom of
the planchet.

7.2 Place the numbered sample bottle, planchet and micro-spatula in a sample tray and proceed to
analytical balance table.

7.3 Turn on the analytical balance; insure that the balance sets to zero.

7.4 Open the balance side door and using tweezers place the planchet on the balance pan; press
(momentarily the re-zero) and the scale should go to a zero setting.

7.5 Carefully transfer (using the micro-spatula), small quantities of the soil, from the sample milling bottle.
Continue this transfer until a 100 mg of the sample has been spread (everly) onto the planchet. Close the balance
door to obtain the final weight. Record weight in sample logbook.

7.6 Remove the planchet from the analytical balance and take care to ensure there is no loss of the sample.

NOTE: Don't use balance when the heater fan is on.

7.7 Use the sample tray to move the sample planchet to the fume hood (Insure that the fume hood fan is
OFF or considerable sample could be lost).

7.8 Place the planchet, on the lamp base, under the heat lamp; using a automatic pipet, pipet 1 mL of
2-Propanol (50 percent) dropwise onto the planchet.

7.9 Use the tip of the pipet (disposale) to gently mix the sample, for even distribution, over the surface of
the planchet. (Take care to keep the sample off the sidewalls of the planchet).

7.10 Turn on the fume hood and the heat lamp and allow the sample to dry.

NOTE: Place the milled sample bottle in the samples counting tray until the data are calculated.

7.11 Remove the dried sample planchet and allow to cool.

7.12 Place sample (planchet) in a sample tray and transfer to the count room for counting.

7.13 Calculation

7.13.1 Sample activity is reported as pCi/gm with the appropraite mathematical conversion factor

applied.

= SR -BR

2. 22 xExVxAxY

Where: C = Sample concentration in pCi/gm.

FMC-R-002-2

-------
SR	= Sample gross count rate (CPM).

BR	= Background count rate (CPM).

E =	Counting efficiency (CPM/DPM).

V	=	Sample mass (grams).
A =	Self-absorption factor.
2.22	= dpmperpCi.

Y	=	Chemical yield.

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-R-002-3

-------
CSL Method

SOIL SAMPLE PREPARATION

1.0 SCOPE AND APPLICATION

1.1 This procedure describes the handling and preparation of soil samples for radiological analysis by the

CSL.

1.2 These instruction apply to soil, sediment, sludges, and gravel samples submitted in support of the Site
Investigation activities

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

Information not available.

5.0 REAGENTS

Information not available.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Obtain a sample wet weight and record weight in the CSL Sample Logbook.

7.2 When the sample contains a field screened aliquot (foreign matter and rocks removed) or sufficient soil
volume exists, the sample can be transferred directly to the drying pan. Proceed to step 7.3.1 if sufficient gravel,
rocks or other foreign matter exists to impede obtaining a proper weight of the sample for drying and processing.

7.2.1 Using D.I. water wash the sample to remove the soil, sand and fines. Use sufficient water to
remove the material of interest.

7.2.2 After the wash; reweigh the container and record the difference between the original weight and
the new weight on the sample container.

7.2.3 Obtain an aluminum drying pan (small loaf pan or weighing tin) and place the; CH2M HILL
sample number on the (inside) bottom and front of the pan; use a broad tip marking pen.

7.2.4 Turn the Top Loading Scale On; place the drying pan on the scale and press Tare.

FMC-R-003-1

-------
7.2.5 Use a wooden tonque depressor; transfer an aliquot of the sample from the sample jar (about 15 to
20 grams) to the drying pan.

7.3 Place the (numbered) drying pan in the drying oven (preset to 100°C) and dry for a minimum of 8

hours.

7.3.1 If the sample has high organic content, transfer an aliquot of the milled sample to a tin. Place the
tin in the oven at 100°F with a vacuum filter, as required, to volatilize organic matter.

7.4 Remove dried sample from the drying oven and allow to cool. (Cover sample with food wrap).

7.5 Transfer a small amount of the sample to a mortar and pestle set. If the sample was received without a
green or red sticker, proceed to 7.7.

7.6 If the sample was labeled with a red sticker, it will only be crushed with the mortar and pestle prior to
analysis. The sample may be crushed in the sample milling unit only if analytical results show that the activity
concentration is at or below DOT shipping limits (2000 pCi/g).

7.7 Using the pestle; crush the sample aliquot sufficiently to feed into the CSL Sample Milling unit. Cover
the remaing sample and retain until the results are reported.

7.8 Obtain a milling sample jar and the CH2M HILL Sample Number on it; place the jar under the outlet
sample milling unit and lock into place.

7.9 Transfer the sample from the drying pan to the sample reservoir of the milling unit. Energize the
milling unit and slowly feed the sample into the milling hopper. Continue to feed the sample into the hopper until
all the sample has been milled.

7.10 Remove the sample jar from the milling unit and cap the jar.

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-R-003-2

-------
CSL Method

DETERMINATION OF GROSS ALPHA AND GROSS BETA IN WATER SAMPLES

1.0 SCOPE AND APPLICATION

1.1 This method is applicable to water samples collected as part of the Site Investigation which, when
processed and evaporated onto a counting planchet should leave a soild residue on the palnchet of about 5 mg/cm2
thick.

1.2 The limit on gross alpha/beta activity have been established for shipment to CH2M HILL laboratory.
The limit for gross alpha is 30 pCi/L, and for gross beta is 500 pCi/L.

1.3 The limits set for shipment to vendor laboratories are limits listed in , 10CFR part 49, Department of
Transportation (DOT) Regulations.

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

3.1 Self-shielding caused by buildup of residues on the counting planchet will reduce counting efficiency.

3.2 Alpha/beta "crosstalk" between the seprate counting channels is significant if the levels of either type
of radiation is excessively high compared to a low level of the companion radiation.

4.0 APPARATUS AND MATERIALS

4.1 Drying Oven: Oven with temperature control.

4.2 Milling/Homogenizer.

4.3 Stainless Steel Planchet.

4.4 Low Background Gas Flow Proportional Counter: Capable of determining alpha and beta activity
simultaneously.

4.5 Centrifuge.

4.6 Laboratory Volumetric Glassware. Hot Plates. Magnetic Stirring. Heat Lamps, and Fume Hoods.
5.0 REAGENTS

5.1 Nitric Acid. HNO:

5.2 Hydrogen Peroxide GO percent). H2Q2.

5.3 Certified Uranium-238 and Technetium-99 Process Solution.

5.4

Alpha and Beta Process Solution: used for counter efficiency determination.

FMC-R-004-1

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Incomming samples shall be logged into the CSL sample log book using the CH2M HILL sample
numbering system and description.

6.2 All samples residues, from the analysis, shall be placed into a plastic bag, sealed and returned to CH2M
HILL for storage and disposal.

7.0 PROCEDURE

7.1 Sample Preaparation

All water samples will require a gross alpha and gross beta analysis with certain samples requiring a
determination of the dissolved and suspended phases of the sample. The results of the dissolved and
suspended phases being additive to give a total gross activity for the sample.

7.1.1 Ensure the sample is logged in the CSL sample log book.

7.1.2 Shake the sample container vigorously prior to removal of an aliquot for analysis.

7.2 Sample Analysis

7.2.1 Transfer a 100 mL aliquot of the well mixed sample to a graduated cylinder.

7.2.2 Transfer the sample to a clean 250-mL glass beaker. The sample number should be recorded on
the beaker.

7.2.3 Inspect the sample for turbidity. If the sample is clear, proceed to 7.2.4. If sample appears cloudy,
go to the following steps for separation by centrifuging and supernate/solid preparation.

7.2.3.1 Transfer the sample to the centrifuge bottles with screw-type caps into centrifuge tube holders
and centrifuge for 10 minutes at 2500 RPM.

7.2.3.2 Transfer the residue with 0.5N HN03 to a tared stainless steel planchet and allow to dry under
heat lamp. If solid content is > 100 mg, treat as a soil sample. Obtain activity concentration pCi/g by
using the density for water and convert to pCi/L. Sum the activity concentration from the supernate and
residue to yield total activity concentration.

7.2.3.3 If solid content is < 100 mg, treat as part of water sample and use appropriate self-absorption
factor.

7.2.3.4 The supernate is treated as a typical water sample (proceed to 7.2.4).

7.2.4 Place beaker with sample in fume hood, add 10-15 mL 8N HN03.

7.2.5 Place beaker on hot plate and evaporate to wet dryness in fume hood. Use heat setting "3" on the
hot plate. (NOTE: Do not allow beakers to remain on hot plate after supernate has evaporated, or residue
will bake onto glass and low recoveries may result.)

7.2.6 Remove the beaker from hot plate and allow to cool; wet ash using about 10 mL of 8N HN03, and
about 20 mL of30 percent H202 if necessary, until residue appears colorless.

FMC-R-004-2

-------
7.2.7	Place a tared and numbered planchet under a heat lamp using small aliquots of 0.5N HN03 (3
washings) and a rubber policemen transfer the clear residue to the planchet. (NOTE: Transfer only one
washing at a time and allow to dry to avoid salt buildup on the sides of the planchet.)

7.2.8	Remove sample from heat lamp and allow to cool; reweigh planchet and record weight of residue.

7.2.9	Place all samples and paperwork in the counting bin.

7.3	Sample Counting

7.3.1	Processed sample planchets are loaded into LB5100 gas proportional counter with D.I. water
blanks, and alpha/beta standard (technetium-99 NBS No.211-45 and uranium-238 NBS No.l 14).

7.3.2	All planchets should be counted for a minimum of 50 minutes and the count group set for 1 count
per sample. Additional group settings can be used on the LB5100 for longer count times, if required.

7.4	Calculation

7.4.1 Sample activity is reported as pCi/L with the appropraite mathematical conversion factor applied.

= 	SR -BR	

2. 22 xExVxAxY

Where: C = Sample concentration in pCi/L.
SR = Sample gross count rate (CPM).
BR = Background count rate (CPM).

E = Counting efficiency (CPM/DPM).

V	= Sample (liter).

A = Self-absorption factor.

2.22 = dpmperpCi.

Y	= Chemical yield = 1 (accounted for in the efficiency).
8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-R-004-3

-------
CSL Method

DETERMINATION OF GROSS ALPHA AND GROSS BETA IN WATER SAMPLES (DOT LEVEL!

1.0 SCOPE AND APPLICATION

1.1 This method is applicable only for the water samples that come from known contaminated wells.

1.2 This method is applicable to water samples collected as part of the Site Investigation which, when
processed and evaporated onto a counting planchet should leave a soild residue on the palnchet of about 5 mg/cm2
thick.

1.3 The limits set for shipment to vendor laboratories have been established to coicide with the DOT
regulations, 10CFR part 49, definition of radioactive material ^ 2,000 pCi/g gross activity.

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

3.1 Self-shielding caused by buildup of residues on the counting planchet will reduce counting efficiency.

3.2 Alpha/beta "crosstalk" between the seprate counting channels is significant if the levels of either type
of radiation is excessively high compared to a low level of the companion radiation.

4.0 APPARATUS AND MATERIALS

4.1 Drying Oven: Oven with temperature control.

4.2 Milling/Homogenizer.

4.3 Stainless Steel Planchet.

4.4 Low Background Gas Flow Proportional Counter: Capable of determining alpha and beta activity
simultaneously.

4.5 Centrifuge.

4.6 Laboratory Volumetric Glassware. Hot Plates. Magnetic Stirring. Heat Lamps, and Fume Hoods.
5.0 REAGENTS

5.1 Nitric Acid. HNO:

5.2 Hydrogen Peroxide GO percent). H2Q2.

5.3 Certified Uranium-238 and Technetium-99 Process Solution.

5.4 Alpha and Beta Process Solution: Used for counter efficiency determination.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

FMC-R-005-1

-------
6.1 Incomming samples shall be logged into the CSL sample log book using the CH2M HILL sample
numbering system and description.

6.2 All samples residues, from the analysis, shall be placed into a plastic bag, sealed and returned to CH2M
HILL for storage and disposal.

7.0 PROCEDURE

7.1 Sample Preaparation

7.1.1 Ensure the sample is logged in the CSL sample log book.

7.1.2 Shake the sample container vigorously prior to removal of an aliquot for analysis.

7.2 Sample Analysis

7.2.1 Transfer a 20 mL aliquot of the well mixed sample to a graduated cylinder.

7.2.2 Transfer the sample to a clean 250-mL glass beaker. The sample number should be recorded on
the beaker.

7.2.3 Place beaker with sample in fume hood, add 10-15 mL 8N HN03.

7.2.4 Place beaker on hot plate and evaporate to wet dryness in fume hood. Use heat setting "3" on the
hot plate. [Do not allow beakers to remain on hot plate after supernate has evaporated, or residue
will bake onto glass and low recoveries may result.]

7.2.5 Remove the beaker from hot plate and allow to cool; wet ash using about 10 mL of 8N HN03, and
about 20 mL of30 percent H202 if necessary, until residue appears colorless.

7.2.6 Place a tared and numbered planchet under a heat lamp using small aliquots of 0.5N HN03 (3
washings) and a rubber policemen transfer the clear residue to the planchet. (NOTE: Transfer only one
washing at a time and allow to dry to avoid salt buildup on the sides of the planchet.)

7.2.7 Remove sample from heat lamp and allow to cool; reweigh planchet and record weight of residue.

7.2.8 Place all samples and paperwork in the counting bin.

7.3 Sample Counting

7.3.1 Processed sample planchets are loaded into LB5100 gas proportional counter with D.I. water
blanks, and alpha/beta standard (technetium-99 NBS No.211-45 and uranium-238 NBS No.l 14).

7.3.2 All planchets should be counted for a minimum of 20 minutes and the count group set for 1 count
per sample. Additional group settings can be used on the LB5100 for longer count times, if required.

7.4 Calculation

7.4.1 Sample activity is reported as pCi/L with the appropraite mathematical conversion factor applied.

FMC-R-005-2

-------
= 	SR -BR	

2. 22 xExVxAxY

Where: C = Sample concentration in pCi/L.
SR = Sample gross count rate (CPM).
BR = Background count rate (CPM).

E = Counting efficiency (CPM/DPM).

V	= Sample volume (liter).

A = Self-absorption factor.

2.22 = dpmperpCi.

Y	= Chemical yield = 1 (accounted for in the efficiency).
8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-R-005-3

-------
CSL Method

DETERMINATION OF GROSS ALPHA AND GROSS BETA IN
CORE SAMPLES. SOILS. BOTTOM SEDIMENTS. SLUDGES. AND SILTS SAMPLES

1.0 SCOPE AND APPLICATION

1.1 This method is applicable to "soil type" samples collected as part of the Site Investigation which, when
processed and deposited onto a counting planchet should leave a sample residue < 5 mg/cm2.

1.2 The limits for reported activity are 15 pCi/gm-wet gross alpha and 50 pCi/gm-wet gross beta for
shipments to CH2M HILL" laboratories. The limits set for shipment to vendor laboratories have been established
as the limits listed in 10CFR49 part 173 Department of Transportation (DOT) Regulations.

1.3 This method is applicable to "soil type" samples having considerable organic content; whereby a
leaching technique is most practical means of acessing the gross alpha and gross beta activity of the sample.

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

3.1 Self-shielding caused by buildup of residues on the counting planchet will reduce counting efficiency.

3.2 Alpha/beta "crosstalk" between the seprate counting channels is significant if the levels of either type
of radiation is excessively high compared to a low level of the companion radiation.

4.0 APPARATUS AND MATERIALS

4.1 Drying Oven.

4.2 Milling/Homogenizer.

4.3 Stainless Steel Planchet.

4.4 Low Background Gas Flow Proportional Counter: Capable of determining alpha and beta activity
simultaneously.

4.5 Centrifuge: With timer and glass centrifuge bottles with screw type caps.

4.6 Laboratory Volumetric Glassware. Hot Plates. Heat Lamps, and Fume Hoods.

5.0 REAGENTS

5.1 Nitric Acid. HNO:

5.2 Hydrochloric Acid. HCL.

5.3 Hydrogen Peroxide GO percent). H2Q2.

5.4 Certified Uranium and Technetium-99 Process Solution.

FMC-R-006-1

-------
5.5 Alpha and Beta Process Solution: Used for counter efficiency determination.

5.6 Distilled Water.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Incomming samples shall be logged into the CSL sample log book using the CH2M HILL sample
numbering system and description.

6.2 All samples residues, from the analysis, shall be placed into a plastic bag, sealed and returned to CH2M
HILL for storage and disposal.

7.0 PROCEDURE

7.1 Sample Preaparation

All "solid" samples will require a gross alpha and gross beta analysis with a determination of the
dissolved liquid phases of the leachate.

7.1.1 Ensure the sample is logged in the CSL sample log book.

7.1.2 Place a tared drying pan or weighing tin on the lab bench, record the sample number on container
and transfer sufficient sample for analysis. Reweigh and record the sample wet weight on the analysis
sheet.

7.1.3 Place the sample in the drying oven (preset to 100°C) and dry for sufficient time to remove all
moisture from the sample.

7.1.4 Remove the dried sample and allow to cool.

7.1.5 Dried samples will be crushed using a mortar and pestle and then passed through the
milling/homogenizigg unit.

7.1.6 If the sample was received without a red sticker, the sample is then passed through the
milling/homogenizing unit.

7.1.7 If the sample is labelled with a red sticker, it can only be crushed with the mortar and peste prior
to analysis. The sample may be crushed in the sample milling unit only if analytical results show that the
sample activated concentration is at or below DOT shipping limits (2,000 pCi/gm).

7.1.8 If the sample has high organic content, an aliquot of the milled sample is transferred to a tin placed
in an oven at 100°C with a vacuum filter, as required, to volatilize any organics.

7.1.9 Place a cap on the milled sample bottle with sample number and place in "Sample Analysis Bin."

7.2 Sample Analysis

7.2.1 Transfer 100 mg of the sample to a tared 250 mL glass beaker. The sample number should be
recorded on the beaker.

7.2.2 Place beaker with sample in fume hood and add 100 mL HC1.

FMC-R-006-2

-------
7.2.3 Using a glass pipet transfer 10 mL of the liquid to a 250 mL beaker (marked with the sample
number).

7.2.4 Add 90 mL of 8N HN03.

7.2.5 Place four 35 mL glass centrifuge bottles (with caps) in centrifuge tube holders. Place the holders
in a tube tack and set in the fume hood.

7.2.6 Carefully decant the sample into a 100 mL graduated cylinder.

7.2.7 Carefully decant equal volumes of the sample into three of the centrifuge bottles.

7.2.8 Using an automatic pipeter with disposable tips add 10 drops of 8N HN03 to each sample; cap
each sample and shake.

7.2.9 Fill the fourth centrifuge bottle with D.I. water and cap.

7.2.10 Transfer the centrifuge tube rack with sample to the centrifuge table; place the holders in a
balanced order into the centrifuge; close and lock the centrifuge cover.

7.2.11 Turn centrifuge power "ON" and set timer for 10 minutes. Then slowly increase the RPM switch
from OFF to 3/4 or until meter reads 2500 RPM.

NOTE: Allow the centrifuge to come to a complete stop before opening the cover.

7.2.12 Transfer the supenate to a clean 250 mL breaker and evaporate to wet dryness on a hot plate,
inside the fume hood. Use medium heat and a watch glass to avoid spattering. (NOTE: Do not allow
beakers to remain on the hot plate affer the supernate has evaporated to near dryness or residue will bake
onto glass and low recoveries can result).

7.2.13 Remove the beaker from hot plate and allow to cool. Wet ash with 8N HN03 and 30 percent
H202., if required, until residue appears colorless. Repeat wet ashing process if necessary.

7.2.14 Place a tared and numbered counting planchet under a heat lamp. Using a 2 mL aliquot of 0.5N
HN03 (3 washings) and a rubber policeman transfer the residue to the planchet. (NOTE: Transfer only one
washing at a time and allow to dry to avoid salt buildup on the sides of the planchet).

7.2.15 Remove sample from under the heat lamp and allow to cool. Reweigh planchet and record
weight of residue.

7.3 Sample Counting

7.3.1 Processed sample planchets are loaded into LB5100 gas proportional counter with D.I. water
blanks, sample blanks spikes and screening samples.

7.3.2 All planchets should be counted for a minimum of 50 minutes and the count group set for 1 count
per sample. Additional group settings can be used on the LB5100 for longer count times, if required.

7.4 Calculation

7.4.1 Sample activity is reported as pCi/g with the appropraite mathematical conversion factor applied.

FMC-R-006-3

-------
SR -BR
2.22 xExVxAxY

Where: C = Sample concentration in pCi/g.
SR = Sample gross count rate (CPM).
BR = Background count rate (CPM).

E = Counting efficiency (CPM/DPM).

V	= Sample weight ratio (liquid/solid[grams]).

A = Self-absorption factor = 1 (acounted for in the efficiency).
2.22 = dpmperpCi.

Y	= Chemical yield = 1 (accounted for in the efficiency).
8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-R-006-4

-------
CSL Method

DETERMINATION OF GROSS ALPHA/BETA IN BIOTA

fVEGETATION/FOODSTUFFVSIMPLIFIED METHOD

1.0 SCOPE AND APPLICATION

1.1	This method is applicable to "biota type" samples collected as part of the Site Investigation which,
when processed and deposited onto a counting planchet should leave a sample residue < 5 mg/cm2.

1.2	The limits for reported activity are 15 pCi/gm-wet gross alpha and 50 pCi/gm-wet gross beta for
shipments to CH2M HILL" laboratories. The limits set for shipment to vendor laboratories have been established
as the limits listed in 10CFR49 part 173 Department of Transportation (DOT) Regulations.

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

3.1	Self-shielding caused by buildup of residues on the counting planchet will reduce counting efficiency.

3.2	Biota sample normally contain the natural isotope K-40 (Potassium 40), a beta emitter, at activity levels
between 12 to 20 pCi/gram wet. These type samples could contain other beta emitters as residuals of world wide
fallout.

4.0 APPARATUS AND MATERIALS

4.1	Fume Hood.

4.2	Drying Oven (Temperature Control').

4.3	Milling/Homogenizer.

4.4	Blender.

4.5	Heat Lamps.

4.6	Aluminum Drying Pans.

4.7	Mortar/Pestle Set.

4.8	Analytical Balance.

4.9	Stainless Steel Planchet.

5.0 REAGENTS

5.1	Nitric Acid (8N). HNO:

5.2	Nitric Acid (12N). HNO:

FMC-R-007-1

-------
5.3 Nitric Acid (16N). HNO:

5.4 Nitric Acid (0.5N). HNO:

5.5 Hydrogen Peroxide GO percent). H2Q2.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Sample Preaparation

7.1.1 To facilitate sample analysis data turn around time, modifications to standard radioanalytical
methods are required.

7.1.2 Sample preparation volumes should consist of sufficient sample, as deemed by the CSL
Radiochemist, to provide statistically accurate screening data.

7.1.3 Biota sample (do not wash) is transferred to a tared aluminum drying pan; weigh sample and
record the wet weight in the FSL Sample Logbook. Place sample and pan in the drying oven (set to
125°C); dry sample for 24 hours.

7.1.4 Remove sample from oven and allow to cool. Reweigh the sample and record the dry weight on
the Biota Radiochemistry Worksheet.

7.1.5 Assemble the blender unit, in the fume hood, transfer dried sample to the unit. Place top on
blender and grind sample.

7.1.6 Remove blender jar and proceed to the milling unit; place a milling jar, with the sample number,
under tie milling unit outlet and lock in-place.

7.1.7 Slowly transfer the sample into tie milling hopper and allow the sample to pass through the milling
rotor. Remove sample jar properly and cap; proceed to clean the mining unit.

7.1.8 Place the mill jar in a sample tray; procedd to the analytical balance.

7.1.9 Place the analytical balance "ON"; place a weighing tin on the balance pan; rezero the balance.
Carefully transfer 0.5 gram of the sample to the weighinh tin; record the final weight on the radiochemical
worksheet.

7.1.10 Remove the weighing tin, with sample, and power "OFF" the analytical balance; proceed to the
fume hood.

7.2 Sample Analysis

7.2.1 Obtain a 250 milliliter glass beaker and mark with the sample number.

7.2.2 Transfer 0.5 gram sample, in the weighing tin, to a 250 milliliter glass beaker.

7.2.3 Add a 100 mL aliquot of 8N HN03 to the beaker and a stirring bar. Place the beaker on a
magnetic stirrer and stir for 1 hour. Remove beaker.

FMC-R-007-2

-------
7.2.4	Wet ash sample using HN03. Begin with small aliquot of 12N HN03 to avoid too rapid ashing.
Carefully increase the concentration of HN03 to 16N. A mixture of 2 mL H202 and 1 mL HN03 will aid
wet ashing near end of procedure; continue until reddish brown fumes no longer evolve for the sample.

7.2.5	Obtain a numbered and tared stainless steel planchet; place the planchet on the lamp base under
the heat lamps. Using a rubber-policeman and 0.5N HN03 transfer the residue remaining in the beaker
following wet ashing to the planchet. Use three separate washings and allow each transfer to dry (to avoid
salt buildup on the side of the planchet) before adding the next aliquot.

7.2.6	Allow the sample to dry; remove sample and allow to cool.

7.2.7	Place the sample on a sample tray and proceed to the analytical balance; weigh sample and record
the sample weight on the radiochemistry worksheet.

7.2.8	Count the sample and report the data results as pCi/gram-wet activity.

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-R-007-3

-------
CSL Method

DETERMINATION OF GROSS ALPHA/BETA IN BIOTA

fVEGETATION/FOODSTUFFl/EXTENDED METHOD

1.0 SCOPE AND APPLICATION

1.1	This method is applicable to "biota type" samples collected as part of the Site Investigation which,
when processed and deposited onto a counting planchet should leave a sample residue < 5 mg/cm2.

1.2	The limits for reported activity are 15 pCi/gm-wet gross alpha and 50 pCi/gm-wet gross beta for
shipments to CH2M HILL" laboratories. The limits set for shipment to vendor laboratories have been established
as the limits listed in 10CFR49 part 173 Department of Transportation (DOT) Regulations.

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

3.1	Self-shielding caused by buildup of residues on the counting planchet will reduce counting efficiency.

3.2	Biota sample normally contain the natural isotope K-40 (Potassium 40), a beta emitter, at activity levels
between 12 to 20 pCi/gram wet. These type samples could contain other beta emitters as residuals of world wide
fallout.

4.0 APPARATUS AND MATERIALS

4.1	Fume Hood.

4.2	Drying Oven (Temperature Control').

4.3	Muffle Furnace.

4.4	Milling/Homogenizer.

4.5	Blender.

4.6	Heat Lamps.

4.7	Aluminum Drying Pans.

4.8	Mortar/Pestle Set.

4.9	Analytical Balance.

4.10	Ceramic Ashing Crucibles.

4.11	Stainless Steel Planchet.

5.0 REAGENTS

FMC-R-008-1

-------
5.1 Nitric Acid (8N). HNO:

5.2 Nitric Acid (12N). HNO:

5.3 Nitric Acid (16N). HNO:

5.4 Nitric Acid (0.5N). HNO:

5.5 Hydrogen Peroxide GO percent). H2Q2.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1 Sample Preaparation

7.1.1 To facilitate sample analysis data turn around time, modifications to standard radioanalytical
methods are required.

7.1.2 Sample preparation volumes should consist of sufficient sample, as deemed by the CSL
Radiochemist, to provide statistically accurate screening data.

7.1.4 Remove sample from oven and allow to cool. Reweigh the sample and record the dry weight on
the Biota Radiochemistry Worksheet.

7.1.5 Assemble the blender unit, in the fume hood, transfer dried sample to the unit. Place top on
blender and grind sample.

7.1.6 Remove blender jar and proceed to the milling unit; place a milling jar, with the sample number,
under tie milling unit outlet and lock in-place.

7.1.7 Slowly transfer the sample into tie milling hopper and allow the sample to pass through the milling
rotor. Remove sample jar properly and cap; proceed to clean the mining unit.

7.1.8 Transfer 10 grams of the sample to a tared ashing crucible and place in the muffle furnace. Set the
Per Cent Time on switch to Lo. (Setting will allow the temperature to increase slow to 300°C).

7.1.8.1 Allow the ashing furnace to remain at this setting for 4 hours. Then set the Per Cent Time On
to 1.9; this setting will allow the temperature of the furnace to slowly increase to 48°C. Allow the
furnace to remain at this temperature of a period of 8 hours.

7.1.9 Power "OFF" the ashing furnace remove the sample(s); allow to cool proceed to analysis
procedure.

7.2 Sample Analysis

7.2.1 Obtain a 250 milliliter glass beaker and mark with the sample number.

FMC-R-008-2

-------
7.2.2	Transfer 1 gram of the ashen sample to a 250 milliliter glass beaker.

7.2.3	Add a 100 mL aliquot of 8N HN03 to the beaker and a stirring bar. Place the beaker on a
magnetic stirrer and stir for 1 hour. Remove beaker.

7.2.4	Wet ash sample using HN03; begin with small aliquot of 12N HN03 to avoid too rapid ashing.
Carefully increase the concentration of HN03 to 16N. A mixture of 2 mL H202 and 1 mL HN03 will aid
wet ashing near end of procedure; continue until reddish brown fumes no longer evolve for the sample.

7.2.5	Obtain a numbered and tared stainless steel planchet; place the planchet on the lamp base under
the heat lamps. Using a rubber-policeman and 0.5N HN03 transfer the residue remaining in the beaker
following wet ashing to the planchet. Use three separate washings and allow each transfer to dry (to avoid
salt buildup on the side of the planchet) before adding the next aliquot.

7.2.6	Allow the sample to dry; remove sample and allow to cool.

7.2.7	Place the sample on a sample tray and proceed to the analytical balance; weigh sample and record
the sample weight on the radiochemistry worksheet.

7.2.8	Count the sample and report the data results as pCi/gram-wet activity.

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

FMC-R-008-3

-------
ERT Method

X-MET 880 FIELD PORTABLE X-RAY FLUORESCENCE OPERATING PROCEDURE

1.0 SCOPE AND APPLICATION

1.1 The purpose of this standard operating procedure (SOP) is to serve as a guide to the start-up, check-out,
operation, calibration, and routine use of the X-Met 880 instrument, for field use in screening of hazardous or
potentially hazardous inorganics. It is not intended to replace or diminish the use of the X-MET 880 Operating
Instructions. The Operating Instructions contain additional helpful information to assist in the optimum
instrument utilization and which form the basis on which new and varying applications can later be based.

1.2 The procedures contained herein are general operating procedures which may be changed as required,
dependent on site conditions, equipment limitations, limitations imposed by the QA\QC procedure or other
protocol limitations. In all instances, the ultimate procedures employed should be documented and associated
with the final report.

1.3 Principles of Operation

1.3.1 X-Ray Fluorescence Spectroscopy (XRF) is a nondestructive qualitative and quantitative
analytical technique used to determine the chemical composition of samples. In a source excited XRF
analysis, primary X-rays emitted from a sealed radioisotope source are utilized to irradiate samples. During
interaction of the source X-rays with samples, they may either undergo scattering (dominating process) or
absorption by sample atoms in a process known as the photoelectric effect (absorption coefficient). This
most useful analytical phenomenon originates when incident radiation knocks out an electron from the
innermost shell of an atom. The atom is excited and releases its surplus energy almost instantly by filling
the vacancy created with an electron from one of the higher energy shells. This rearrangement of electrons
is associated with emission of X-rays characteristic (in terms of energy) of the given atom. This process is
referred to as emission of fluorescent X-rays (fluorescent yield). The overall efficiency of the process
described is referred to as excitation efficiency and is proportional to the product of absorption coefficient
and fluorescent yield.

1.3.2 Generally, the X-MET 880 utilizes characteristic X-ray lines originating from the innermost shells
of the atoms, K, L, and occasionally M. The characteristic X-ray lines of the K series are the most energetic
lines for any element and, therefore, are the preferred analytical lines. The K lines are always accompanied
by the L and M lines of the same element. However, being of much lower energy than the K lines, they can
usually be neglected for those elements for which the K lines are analytically useful. For heavy elements
(such as Ce, atomic number (Z)=58, to U, Z=92), the L lines are the preferred lines for X-MET 880
analysis. The Laand Lplines have almost equal intensities and the choice of one or the other depends on
what interfering lines might be present. A source just energetic enough to excite the L lines will not excite
the K lines of the same element. The M lines will appear together with the L lines. The X-MET 880
Operating Instructions contain tables that show the energies and relative intensities of the primary
characteristic X-ray lines for all the applicable elements.

1.3.3 An X-ray source can excite characteristic X-rays from an element only if the source energy is
greater than the absorption edge energy for the particular line group (i.e., K absorption edge, L absorption
edge, M absorption edge) of the element. The absorption edge energy is somewhat greater than the cor-
responding line energy. Actually, the K absorption edge energy is approximately the sum of the K, L and
M line energies, and the L absorption edge energy is approximately the sum of the L and M line energies of
the particular element.

-------
1.3.4 Energies of the characteristic, fluorescent X-rays are converted (within the detector) into a train of
electric pulses, the amplitudes of which are linearly proportional to the energy. An electronic multichannel
analyzer (electronic unit) measures the pulse amplitudes which, since they are proportional to original
energies of emitted characteristic X-rays, are the basis of a qualitative X-ray analysis. The number of
equivalent counts at a given energy is representative of element concentration in a sample basis for
quantitative analysis.

1.3.5 Scattered X-rays: The source radiation is scattered from the sample by two physical reactions:
coherent or elastic scattering (no energy loss) and Compton or inelastic scattering (small energy loss).

Thus, the backscatter (background signal) actually consists of two components with X-ray lines close
together, the higher energy line being equal to the source energy. Since the whole sample takes part in
scattering, the scattered X-rays usually yield the most intense lines in the spectrum. It is also obvious from
the aforementioned that the scattered X-rays have the highest energies in the spectrum and contribute the
most part of the total measured intensity signal.

1.4 Sample Types

1.4.1 Solid and liquid samples can be analyzed for elements A1 (aluminum) through U (uranium) with
proper X-ray source selection. Typical environmental applications are:

• Heavy metals in soil (in-situ or samples collected from the surface or from bore hole drillings, etc.),
sludges, and liquids (i.e., Pb in gasoline);

• Light elements in liquids (i.e., P, S and CI in organic solutions);

• Heavy metals in industrial waste stream effluents;

• PCB in transformer oil by CI analysis; and

• Heavy metal air particulates collected on membrane filters, either from personnel samplers or from
high volume samplers.

2.0 SUMMARY OF METHOD

2.1 The X-MET 880 Portable XRF Analyzer employs radioactive isotopes, such as Fe-55, Cm-244, Cd-109
and Am-241 for the production of primary X-rays. Each source emits a specific energy range of primary X-rays
that cause a corresponding range of elements in a sample to produce fluorescent X-rays. When more than one
source can excite the elements of interest, the appropriate source(s) is selected according to its excitation
efficiency for the elements of interest. See X-MET 880 Operating Instructions for a chart of source type versus
element range, Section 1.17.

2.2 For measurement, the sample is positioned in front of the source-detector window and exposed to the
primary (source) X-rays by pulling a trigger on the probe (or pushing the top of the probe unit back on the sample
type probe) which exposes the sample to radiation from the source. The sample fluorescent and backscattered X-
rays enter through the beryllium (Be) detector window and are detected in the active volume of a high-resolution,
gas-filled proportional counter.

2.3 Elemental count rates (number of net element pulses per second) are used in correlation with actual
sample compositions to generate calibration models for qualitative and quantitative measurements.

2.4 Analysis time is user selectable from 1 to 32767 seconds. The shorter measurement times (30 - 100s)
are generally used for initial screening and hot spot delineation, while longer measurement times (100 - 500s) are
typically used for higher precision and accuracy requirements.

-------
3.0 INTERFERENCES

3.1 The total error of XRF analysis is defined as the square root of the sum of squares of both instrument
precision and user or application related error. Generally, the instrument precision is the least significant source
of error in XRF analysis. User or application related error is generally the more significant source of error and
will vary with each site and method used. The components of the user or application related error are the
following:

3.2 Sample Placement This is a potential source of error since the X-ray signal decreases as you increase
the distance from the radioactive source. However, this error is minimized by maintaining the same sample
distance from the source.

3.3 Sample Representivitv: This can be a major source of error if the sample and/or the site-specific or
site-typical calibration samples (see Section 4.0) are not representative of the site. Representivity is affected by
the soil macro- and micro-heterogencity. For example, a site contaminated with pieces of slag dumped about by a
smelting operation will be less homogeneous than a site contaminated by liquid plating waste. This error can be
minimized by either homogenizing a large volume of sample prior to analyzing an aliquot, or by analyzing several
samples (in-situ) at each sampling point and averaging the results.

3.4 Reference Analysis: Soil chemical and physical matrix effects may be corrected by using Inductively-
Coupled Plasma (ICP) or Atomic Absorption (AA) spectrometer analyzed site-specific soil samples as calibration
samples. A major source of error can result if the samples analyzed are not representative of the site and/or the
analytical error is large. With XRF calibrations based on reference analyses results, the XRF analytical results
can be reported in the same units as the calibration samples reference analyses. Results, for example, will be in
Contract Laboratory Protocol (CLP) extractable metals if the CLP specified HN03/H202 digestion is used.

Results will be in total metals if total (HF) digestion or KOH fusion is used.

3.5 Chemical Matrix Effects (Effects due to the chemical composition of the sample): Chemical matrix
effects result from differences in concentrations of interfering elements. These effects appear as either spectral
interferences (peak overlaps) or as X-ray absorption/enhancement phenomena. Both effects are common in soils
contaminated with heavy metals. For example, Fe (iron) tends to absorb Cu (copper) K shell X-rays, reducing the
intensity of Cu measured by the detector. This effect can be corrected if the relationship between Fe absorption
and the Cu X-ray intensities can be modeled mathematically. Obviously, establishing all chemical matrix
relationships during the time of instrument calibration is critical. These relationships are modeled
mathematically, with X-MET 880 internal software, using ICP or AA analyzed site-specific soil samples as the
XRF calibration standards. Additionally, increasing the number of standards and the range of the standard
concentrations used may decrease the error in the calibration mathematical modeling. Generally, as rule-of-
thumb, a minimum of five calibration samples per element to be analyzed are used to generate reliable X-MET
880 calibration models.

3.6 Physical Matrix Effects (Effects due to sample morphology'): Physical matrix effects are the result of
variations in the physical character of the sample. They may include such parameters as particle size, uniformity,
homogeneity and surface condition. For example, consider a sample in which the analyte exists in the form of
very fine particles within a matrix composed of much courser material. If two separate aliquots of the sample are
ground in such a way that the matrix particles in one are much larger than in the other, then the relative volume of
analyte occupied by the analyte-containing particles will be different in each. When measured, a larger amount of
the analyte will be exposed to the source X-rays in the sample containing finer matrix particles; this results in a
higher intensity reading for that sample and, consequently, in apparently higher measured concentration of that
element.

3.7 Modeling Error: The error in the calibration mathematical modeling is insignificant (relative to the
other sources of error) IF the instrument's modeling operating instructions are followed correctly (see Section
14.0).

-------
3.8 Moisture Content: If measurement of soils or sludges is intended, the sample moisture content will
affect the accuracy of the analysis. The overall error from moisture may be a secondary source of error when the
moisture range is small (5-20%), or may be a major source of error when measuring on the surface of soils that
are saturated with water.

3.9 Cases of Severe X-rav Spectrum Overlaps

3.9.1 Certain X-ray lines from different elements, when present in the sample, can be very close in
energy and, therefore, interfere by producing a severely overlapped spectrum.

3.9.2 The typical spectral overlaps are caused by the Kpline of element Z-l (or as with heavier elements,
Z-2 or Z-3) overlapping with the Kaline of element Z line. This is the so-called Ka/Kpinterference. Since
the Ka:Kpintensity ratio for the given element usually varies from 5:1 to 7:1, the interfering element, (Z-1),
must be present in large concentrations in order to disturb the measurement of analyte Z. The presence of
large concentrations of titanium (Ti) could disturb the measurement of chromium (Cr). The TiKa and Kp
energies are 4.51 and 4.93 Kev, respectively. The CrKa energy is 5.41 Kev. The resolution of the detector
is approximately 850 eV. Therefore, large amounts of Ti in a sample will result in spectral overlap of the
TiKp with the CrKa peak.

3.9.3 Other interferences are K/L, K/M and L/M. While these are less common, the following are
examples of a severe overlap:

AsKa/PbLa, SK^bM.

In the arsenic/lead case, lead can be measured from the PbLpline, and arsenic from either the AsKa or the
AsKp line; this way the unwanted interference can be corrected. However, due to the severeness of the
overlap (energy of AsKa is almost identical to that of PbLJ, measurement sensitivity is reduced.

3.10 Inappropriate Pure Element Calibration: It is of paramount importance that the pure element
calibration, also called "instrument calibration" (see Section 10), include all elements that can be present at the
site, (i.e., in the samples to be analyzed). This means that even if the element is not a target element, as long as it
is present in detectable amounts with the source in use, it must be included in the pure element calibration in
order for the X-MET 880 to correct for its potential spectral interference effect on the target element.

4.0 APPARATUS AND MATERIALS

4.1 Description of the X-Met 880 System

4.1.1 The X-MET 880 analyzer includes a compact, sealed radiation source contained that is in a
measuring probe. This probe is connected by cable to an environmentally sealed electronic module.

4.1.2 The analyzer utilizes the method of Energy Dispersive X-Ray Fluorescence (EDXRF)
spectrometry to determine the elemental composition of soils, sludges, aqueous solutions, oils, and other
waste materials.

4.1.3 Each probe is equipped with a high resolution gas-filled proportional detector, or a high resolution
solid state lithium drifted silicon (Si/Li) detector.

4.1.4 The complete X-MET 880 system consists of five alternate configurations.

4.1.4.1 The X-MET 880ES Extended Range X-MET 880 Silicon Detector System includes the
Silicon Detector Surface Probe System (SDPS) with a 60 millicurie (mCi) Curium-244* (Cm-244)
excitation source and a 30 mCi Americium-241** (Am-241) excitation source.

-------
4.1.4.2	The X-MET 880SH, Standard X-MET 880 System comes with a SAPS probe containing a 60
mCi Cm-244* excitation source.

4.1.4.3	The X-MET 880ER Extended Range X-MET 880 System comes with a DOPS probe that
contains a 60 mCi Cm-244* excitation source and a 30 mCi Am-241** excitation source.

4.1.4.4	The X-MET 880AS Alternate Standard Range X-MET 880 System comes with a SAPS probe
containing 10 mCi Cd-109*** (in place of the 60 mCi Cm-244).

4.1.4.5	The X-MET 880AE Alternate Extended Range X-MET 880 System includes the DOPS with
10 mCi Cd-109*** plus 30 mCi Am-241**.

* Cm-244 in SDPS probe (or Surface Analysis Probe Set (SAPS) and Double Source Surface Probe
Set (DOPS) probes) will allow analysis of all elements from atomic number 19 (potassium) to 35
(bromine) and from atomic number 56 (barium) to atomic number 83 (bismuth).

** The Am-241 excitation source extends the elemental range of the system to include such important
priority pollutants as Cd, Ag, and Ba. Am-241 in SDPS, SAPS or DOPS will allow analysis of all
elements from atomic number 30 (zinc) to 60 (neodymium), and atomic number 73 (tantalum) to
92 (uranium).

*** Replacing the Cm-244 with Cd-109 provides somewhat improved precision and accuracy for
Pb when As is present. Cd-109 in SAPS or DOPS will allow analysis of elements from
atomic number 24 (chromium) to 42 (molybdenum) and from 65 (terbium) to 92 (uranium).

4.1.5	Optional sample type probes (for laboratory or mobile lab use only) are available for use when all
samples will be contained in X-ray cups. These probes can contain any of the excitation sources described
above.

4.1.6	The use of the special optional sample probes, Light Element sample Probe System (LEPS), or the
Surface Light element Probe System (SLPS), with the Fe-55 ring source, enables analysis of light elements
ranging from atomic number 13, (aluminum) to atomic number 24 (chromium) and heavy elements from 37
(rubidium) to 56 (barium).

4.1.7	The electronic module includes a 256 channel multi-channel analyzer and a high speed, 16/32 bit,
Motorola 68000 microprocessor. Up to 32 multi-element analysis programs, called models, can be stored in
its memory.

4.1.8	The unit comes factory pre-calibrated based on the Outokumpu Electronics synthetic soil
calibration suite, or based on customer supplied standards (see supplemental documentation on factory
calibration for calibration data specific to each X-MET 880).

4.1.9	Optional calibrations can be installed at the factory for other soil or waste material types on
request.

4.1.10	Additional models tailored to specific needs may be added by the user after attending the X-MET
880 Calibration and Operators Training Course which is conducted by Ouotkumpu Electronics at regular
intervals. (Request course description and schedule from Outokumpu Electronics, Langhorne, PA.)

4.1.11	The X-MET 880 can be operated from a 115-volt (or 220-volt) wall outlet or its 12-volt, 10-hour
capacity battery, or a standard 12-volt car or truck battery.

-------
4.1.12	The X-MET 880 can be operated in a temperature range from 32 to 140° Fahrenheit (F), or may
be operated down to -13° F with the low temperature option. The freezing point of a discharged battery is
14° F.

4.1.13	The probe and electronic unit may be exposed to a light rain. However, additional protection is
provided if the system (electronic unit and probe) is contained in the optional water repellant carrying case.

4.1.14	The instrument can be calibrated for up to 10 elements per model, six (6 target elements) of
which can provide a readout in the Assay Mode.

4.1.15	In the Assay Mode, up to 30 reference samples per assay model can be used to generate the
sample calibration curve in the X-MET 880.

4.2 Equipment and Apparatus List

4.2.1 X-MET 880 Analyzer System: The complete X-MET 880 Analyzer System includes:

4.2.1.1	880 Electronics Module

4.2.1.2	Single source SAPS or DOPS or SDPS with optional LEPS or optional Heavy Element
Sample Probe Set (HEPS) in place of, or in addition to, the SAPS and/or DOPS, each containing
appropriate excitation source(s)

4.2.1

.3

Pure element standards

4.2.1

.4

Battery charger

4.2.1

.5

Battery pack

4.2.1

.6

X-MET 880 Operating Instructions, X-MET 880 Operator's Manual and any applicable X-

MET 880 factory calibration documentation.

4.2.2	Optional Items

4.2.2.1	31 millimeter (mm) diameter sample cups

4.2.2.2	XRF polypropylene film, 0.2mm thickness

4.2.2.3	Nylon reinforced, water-repellant backpack

4.2.2.4	Metal reinforced shipping case with die-cut foam inserts for X-MET 880 and accessories

4.2.2.5	Peripheral devices such as the Terminal/Printer data logger, the DMS-1 Data Management
System, the ESP extended software package for use with IBM compatible Personal Computer (PC).

4.2.2.6	Surface probe shield assembly. Shield assembly must be used when the SAPS or DOPS
probes are inverted for measuring sample in XRF cups.

4.2.3	Limits and Precautions: The probes should be handled in accordance with the following
radiological control practices:

4.2.3.1 The probe should always be in contact with the surface of the material being analyzed and the
analyzed material should completely cover the probe opening (aperture), when the probe shutter is open.

-------
The indicator flag on the side of the DOPS and SAPS probes is green when the shutter is closed and red
when it is open.

4.2.3.2 Under no circumstances should the probe be pointed at the operator or surrounding personnel
with the shutter open.

4.2.3.3 Do not place any part of the operator's or co-worker's body in line of exposure when the
shutter is opened and not fully covered.

4.2.3.4 The SAPS or DOPS probe trigger must be key-locked when not in use.

4.2.3.5 Notify Outokumpu Electronics immediately of any condition or concern relative to the probe
structural integrity, source shielding, shutter condition or operability.

4.2.3.6 Notify the appropriate state agency or Nuclear Regulatory Commission (NRC) office (see
factory supplied data on radiological safety) immediately of any damage to the radioactive source, or any
loss or theft of the device.

4.2.3.7 Labels or instructions on the probe(s) must not be altered or removed.

4.2.3.8 The user must not remove the probe covers or attempt to open the probe.

4.2.3.9 The source(s) in the probe must be leak tested every six (6) months as described in the X-
MET 880 Operating Instructions. The Leak Test Certificates must be kept on file and a copy must
accompany the instrument at all times.

4.2.3.10 The probe shield assembly must be used when the SAPS or DOPS probe is inverted for
measuring samples contained in cups.

4.2.3.11 During operation, keep the probe at least 10 feet from computer monitors and any other
source of radio frequency (RF). Some monitors have very poor RF shielding and will affect
measurement results.

4.2.3.12 The X-MET 880 should not be dropped or exposed to conditions of excessive shock or
vibration.

4.2.3.13 Keep the force on the probe, with the trigger pulled, to less than four (4) pounds to avoid
shutter binding.

4.2.3.14 Do not pull on the probe wire to unplug the probe. Grasp the probe plug at the ribbed rubber
connector cover and squeeze, then press firmly while plugging, and pull while unplugging the connector.

4.2.3.15 Do not attempt to rotate the handle on the electronic unit unless the release buttons on each
side of the handle are depressed.

4.2.3.16 The X-MET 880 should not be operated or stored at an ambient temperature below 32°F (-
13°F with low temperature version) or above 140° F.

4.2.3.17 The battery charging unit should only be used indoors at dry conditions.

4.3 Peripheral Devices

IFMCJA-4MR-77

-------
4.3.1 The X-MET 880 may be used with a wide range of peripheral devices for electronic data capture
or printed readout as long as they are equipped with input compatible with the RS-232 serial protocol. Such
devices include terminals, printers, electronic data loggers, personal computers, etc. Any time a peripheral
device is connected to the X-MET 880, all text and commands shown on the X-MET 880 display will be
automatically output to and copied by the peripheral.

4.3.2 Communication Cable Connection:

4.3.2.1 Plug the round connector of the RS-232 cable, into the X-MET 880 "IN/OUT" port (the
connection just above the probe connection on the electronic unit), and the rectangular (25 pin) connector
of the cable to the RS-232 port of the receiving device (serial port).

4.3.2.2 If the receiving device, serial port, does not have a 25 pin, male, RS-232 C standard
connector, THEN it will be necessary to obtain a "gender mender plug" (male-to-female converter), OR.
in the case of 9 pin device connectors, a 25 to 9 pin adapter (with or without gender changer, depending
on the gender of the connector at the receiving device). All Outokumpu supplied peripherals are
delivered with appropriate connections.

4.3.3 Communication Speed:

4.3.3.1 To communicate with the external device, the X-MET 880 MUST be set at the same Baud
Rate as the receiving device. The X-MET 880 command for setting or resetting the Baud Rate is CSI
(Configure Serial Interface). The CSI command is a sub-command under the EMP (Enter Maintenance
Parameters) command, which must therefore precede it. Enter EMP followed by "CONT/YES", THEN
enter CSI on the keypad FOLLOWED by "CONT/YES". The X-MET 880 will display

BAUD RATE: XXXX NEW?

4.3.3.2 Press "CONT/YES" until the desired baud rate (data transfer speed) is in the display, then
press "END/NO" to accept the displayed reading. The baud rate can have values 50, 75, 110, 134.5, 150,
200, 300, 600, 1200, 1800, 2400, 4800, 9600 and 19200 baud. Select the baud rate of the peripheral
device with which you are communicating.

4.3.4 Character Set: The RS-232 C interface supports all the standard ASCII characters. Upper and
lower case letters are equivalent in data transmission. This means that the X-MET 880 will execute any
legal command typed in lower case on the peripheral keyboard. (See Section 4.3.5 for some special keys.)
The serial data format is:

* 1 start bit (SPACE)

* 8 data bits (ASCII from LSB to MSB)

* 1 stop bit (MARK)

4.3.5 Parity: Parity MUST be set to NO PARITY.

4.3.6 Terminal Emulation: Although most keys on the standard typewriter style keypad (as used on
most terminals and computers) are the same as the X-MET 880 keypad, there are, however, some specific
keys on the X-MET 880 that require the operator to use an "equivalent" key on the terminal. The following
lists correlates the unique X-MET 880 keys and their terminal equivalents:

X-MET 880 KEY TERMINAL KEY for key combination)

CONT/YES ENTER (or RETURN on some devices)

END/NO ESC

MODEL CTRL D

-------
MTIME
RECALC

CTRL T
CTRL R

<
A

SHIFT <
SHIFT A

START

CTRL A

4.3.7 User Software: Refer to your PC software manual for details on additional settings that may be
required for proper interfacing between X-MET 880 and your particular software.

4.4 Instrument Maintenance

4.4.1 Probe Window:

4.4.1.1 Should the probe window become damaged or punctured, it should be replaced as soon as
possible to prevent dust and moisture from entering the probe. Replacement window assemblies can be
ordered from Outokumpu Electronics. Simply pry out the old window aperture using a small, flat-blade
screwdriver, or similar. PRIOR to reinstalling the new aperture, rub a very thin film of silicon grease (or
liquid soap, IF silicon grease is not available) around the rubber "O" ring, inside the probe aperture
opening, to facilitate re-installation.

4.4.1.2 The removal of any loose dirt on the probe window should be done with a soft brush or cloth
and then blown with air. To remove adhering dirt, a solvent such as methanol or ethanol may be used.

4.4.2 Further Information and Troubleshooting: Refer to the X-MET 880 Operating Instructions (or
optional Maintenance Manual) for additional detailed operational and/or maintenance and troubleshooting
instructions. IF no solution is not found in either manual, THEN contact Outokumpu Electronics for
assistance.lt is recommended that an Instrument Log be maintained for documenting specific corrective
actions taken to alleviate any instrumental problems, or to record any service that has been performed.

5.0 REAGENTS

5.1 Site-Specific Calibration Standards fSSCS)

5.1.1 The SSCS must be representative of the matrix to be analyzed by the XRF. They are employed in
the "sample calibration" stage of programming the instrument (see Section 7.5.6). They are also employed
in the subsequent calibration checks (see Section 7.2 and 9.0) and any re-calibrations that may be
performed.

5.1.2 The concentration of the target elements in the SSCS should be determined by independent AA or
ICP analysis that meets an acceptable quality for referee data.

5.1.3 Additionally, the concentration in the SSCS of elements adjacent {+1-2 atomic numbers Z) to the Z
of the target element should be determined by independent AA or ICP analysis if: 1) they are excited by the
source used, and/or 2) their concentrations are unknown or suspected to be greater than ten percent of the
target element concentration and/or 3) it is unknown or suspected that their concentration variance is
greater than twenty percent in the site matrix, or if this variance (if greater than twenty percent) has a non-
linear relationship to the variance of the target element concentration.

5.1.4 For example, the requested target elements are Cd and Sb for a site. Review of the site history
indicates that Sn and Ag may be present. The SSCS should be analyzed for Sn and Ag in addition to Cd
and Sb, to determine their concentrations and the relationship (linear or non-linear) to the Cd and Sb
concentrations in the SSCS samples.

-------
5.1.5 SSCS Sampling:

5.1.5.1 Review Section 4.2 on sample representivity. The SSCS samples must be representative of
the matrix to be analyzed by XRF. It does not make sense to collect the SSCS samples in the site
containment area if you are interested in investigating off-site contaminant migration. The matrices may
be different and could affect the accuracy of the XRF results. If there are two different matrices on-site,
collect two sets of SSCS samples.

5.1.5.2 A full range of target element concentrations is needed to provide a representative calibration
curve. Mixing high and low concentration soils to provide a full range of target element concentrations
is not recommended due to homogenization problems. The highest and lowest SSCS samples will
determine the linear calibration range. Unlike liquid samples, solid samples cannot be diluted and re-
analyzed.

5.1.5.3 The number of SSCS samples needed for calibrating an assay model depends on:

• The number of target elements (analyte). For each additional target element, increase the number
of SSCS samples by five (up to a maximum of 30); and

• The number of elements adjacent to the target elements. For each additional adjacent element
known or found to be present in the samples, you should increase the number of SSCS samples by
five (up to a maximum of 30) to insure that the calibration model properly corrects for X-ray
interferences and spectral overlaps.

5.1.5.4 Additionally, collect several SSCS samples in the concentration range of interest. If the
action level of the site is 500 mg/kg, providing several SSCS samples in this concentration range will
tend to improve the XRF analytical accuracy in this concentration range.

5.1.5.5 Generally, a minimum of 10 and a maximum of 30 appropriate SSCS samples should be
taken. A minimum of a 4 oz. sample is required. A larger size sample should be provided to
compensate for samples with a greater content of non-representative material such as rocks and/or
organic debris. Standard glass sampling jars should be used.

5.1.6 SSCS Preparation:

5.1.5.1 The SSCS samples should be dried either by air drying overnight, or oven drying at less than
105° C. Aluminum drying pans or large plastic weighing boats for air drying may be used. After drying,
remove all large organic debris and non-representative material (twigs, leaves, roots, insects, asphalt,
rocks, etc.).

5.1.5.2 The sample should be sieved through a 20-mesh stainless steel sieve. Clumps of soil and
sludge should be broken up against the sieve using a stainless steel spoon. Pebbles and organic matter
remaining in the sieve should be discarded. The under-sieve fraction of the material constitutes a
sample.

5.1.5.3 Although a maximum final particle size of 20-mesh is normally recommended, a smaller
particle size may be desired (see Section 4.5). The sample should be homogenized by dividing the
sieved soil into quarters and physically mixing opposite quarters with a clean stainless steel spoon. Re-
composite and then repeat the quartering and mixing procedure three times. Place the sieved sample in a
clean glass sample jar and label it using both the site name and sample identification information.

5.1.5.4 The stainless steel sieves should be decontaminated using soap and water and dried between
samples.

sac-jMH-n®

-------
5.1.5.5 One or more plastic XRF sample cups should be filled with the sieved soil for each SSCS
sample. A piece of ,2mm polypropylene film is cut and tensioned, wrinkle-free, over the top of the x-ray
sample cup and then sealed using the plastic film securing ring. The cup should be labeled using both
the site name and specimen identification information.

5.1.5.6 Either the XRF sample cup or the balance of the prepared sample is submitted to the approved
laboratory for analysis of the requested element(s) by AA or ICP.

5.2 Site-Tvpical Calibration Standards fSTCS)

5.2.1 When the goal of the analysis with X-MET 880 is semi-quantitative measurements, such as hot
spot delineation or determination of sampling points for a SSCS, then use of a STCS may be the most
appropriate method. STCS are SSCS from a different site that have the identical target elements in a
similar range and matrix as the site that is to be analyzed. It should be noted that the STCS are not from the
site to be analyzed and may generate false positive and negative results.

5.2.2 For example, samples are going to be taken at lead battery manufacturing site for a SSCS. There
is no information in the site history on the location or concentration of the Pb contamination. A model
calibrated for Pb with a SSCS from another battery breakage site could be used as a STCS to screen this site
and locate low, mid and high Pb contamination points for the SSCS sampling.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 This SOP specifically describes equipment operating procedures for the X-MET 880; hence, this
section is not applicable to this SOP.

7.0 PROCEDURE

7.1 Prerequisites

If the X-MET 880 will be used in a location where AC power outlets are conveniently accessible,
connect the battery charger to the battery and plug the charger cord into the outlet. The cable probe must be
connected before the power is switched on. Plugging and unplugging this cable with the power on can
damage the detector.

Verify that the probe shutter is closed by checking the mechanical flag color on the side of the SAPS or
DOPS. When the flag is green the shutter is closed and open when it is red.

Connect the probe cable to the connector labeled "PROBE" on the electronic module. Make certain the
plug has been firmly pushed in all the way (you will feel and hear a slight "click" as the probe connector
locks into position).

Apply power to the X-MET 880 by pressing the "ON" button.

Verify that the display briefly reads:

X-MET 880 VX.X.X (software version) and DATE

SELF TEST COMPLETED, followed by (if the X-MET 880 has been off, more than a few minutes)
the message:

GAIN CONTROL: COUNT RATE TOO LOW

EMC-m-«H-im

-------
will flash intermittently (along with a "beep") on the display. This is normal and will stop approximately 30
seconds after power is on.

Verify that a prompt sign (>) appears in the lower left corner of the display after the gain control message
has stopped flashing.

Verify that the upper right corner of the display reads the number of seconds (0 - 32,000s) on the top line
and the model number (1 - 32) on the bottom line.

If a "battery low" message appears recharge the battery before proceeding or operate using line voltage.
Allow the X-MET 880 to warm up for approximately 60 minutes.

If the X-MET 880 is being used in a location where the temperature of the environment has changed by
more than 5° F, then allow the X-MET 880 to stabilize at the new ambient temperature. Approximately 1
minute stabilization time for each 1° F change in ambient temperature should be allowed.

7.1.1 Gain Control:

Allow 5 minutes after temperature stabilization for the X-MET 880 to perform a complete cycle of
automatic electronic gain control. The trigger must be released on the probe to activate the gain control
operation. Additionally, the prompt sign (>) must be in the display.

The X-ray spectrum contains a number of incident X-ray quantum energies of which there are
corresponding channels in the multichannel analyzer. These channels are limited by certain changes in
conditions such as the resolution of the detector and temperature coefficients. This means that a
proportionally large error from measurement would be obtained, if no compensation was made for these
variations.

The elimination of such errors is made possible by monitoring the state of the probe spectrum and
compensating for any spectral drift as described in Section 7.1.2.

The state of the detection region is maintained by a feedback gain control system, which operates all the
time the probe is in a non-operative position (gain control position, DOPS, SAPS, SLPS placed on their
sides, HEPS, LEPS with the lid in the forward position) and the instrument is not under any command
(i.e., prompt displayed (>_)).

The gain control routine is accomplished by allowing the X-MET 880 to measure a reference material
(usually copper) mounted on the shutter and then maintaining a track on the peak spectral position.

The initial peak position is set up during the initialization of the probe (INI) and from this point the
instrument will adjust accordingly, during gain control.

7.1.2 Gain Control Monitoring:

During initialization, the initial peak channel is established for the gain control. During gain control,
adjustments are made to return the maximum peak (usually copper), after the backscatter peak, to this
initial peak channel location. The peak channel is monitored and recorded to verify if the gain control
mechanism is working and returning the peak to the correct channel. Failure of the gain control
mechanism will result in spectral drift and calculation of incorrect intensities in the element windows or
incorrect pure element window calibration. The gain control peak channel should be measured and
recorded a the beginning, end, and every 25 to 40 minutes during the following operations:

EMC-m-«H-112

-------
1. Pure element calibration

2. SSCS Measurements

3. All sample analysis

4. All preoperational check sample measurements.

The gain control peak channel measurement is performed with the probe in the same position as it was
during gain control (shutter is closed for the DOPS or SAPS probes and the sample chamber is pulled
forward for the HEPS probe). The instrument should be set for a minimum measuring time of 60
seconds. The enter maintenance program command (EMP) is entered followed by "CONT/YES"
command. Then the test measurement (TSM) command is entered followed by the "CONT/YES". The
peak channel (PKCH), the full width half-maximum (FWHM) of the peak and the counts will be
displayed. Record the PKCH and the FWHM in a log book.

The peak channel (N) should not vary more than N+l during all of the operations listed above.

If the PKCH varies more than one channel, allow the instrument to gain control for another 5.0 minutes.
If the peak channel continues to drift after allowing it to gain control several times, contact an
Outokumpu representative. DO NOT continue to perform any analysis until the problem has been
corrected.

7.2 Preoperational Checks

7.2.1 Select a minimum of one low, mid and high SSCS (used in the model to be checked, not detected)
for all target elements for every model to be checked. Select a low SSCS above the typical detection limit
for each target element (i.e., typical detection limits for lead are 100-200 mg/kg. Selection of a 300 or 400
mg/kg SSCS would be appropriate). Select a mid SSCS at or near the action level for each target element
or an SSCS about 5 or 10 times the low SSCS concentration (i.e., typical action levels for lead are 500-2000
mg/kg. Selection of a 1000 mg/kg SSCS would be appropriate). Select a high SSCS at or near the end of
the linear calibration range of each target element.

7.2.2 These SSCS should be measured using the same measuring that will be applied to the sample
analysis. However, a minimum of 60 seconds should be used for Model verification and preoperational
checks if the instrument is going to be using 15 to 30 second screening analysis.

7.2.3 The low SSCS should be measured ten times, using the anticipated site measuring time, after the
model calibration has been completed. These results will be used to calculate a preliminary detection limit
(DL) and quantitation limit (QL) as described in Section 15.0. A control range may be calculated using the
average of the results plus or minus the detection limit (i.e., a low SSCS has a mean of 200 mg/kg and a DL
of 120 mg/kg; the control range would be 80 to 320 mg/kg). The low SSCS will have the largest relative
percent variance due to its proximity to the DL.

7.2.4 The mid and high SSCS can be measured as described above and a range calculated using the
average plus or minus three times the standard deviation of the results. Generally, three measurements of
the standards is sufficient. A control range may be calculated using the average of the three measurements
plus or minus twenty-five percent of the average.

7.2.5 These SSCS should be measured at least once whenever the instrument is transported.
Additionally, they should be analyzed at the beginning of each analysis day and at the end of the analytical
period. All results should be logged in the operator's log book or saved on a computer disk in a report
format.

7.2.6 These SSCS may be used for verifying the model as described in Section 7.5.10 and for Quality
Assurance and Control as described in Section 9.0.

sac-iMffl-e

-------
7.2.7 Results outside the described range indicate that there is an instrument problem.

7.3 Normalization and Standardization

7.3.1 Normalization and standardization should never be performed. These procedures have never been
needed at ERT/REAC and have never been performed. It is recommended that the operator recalibrate the
model if the calibration is older than four months for a Cd-109 source; six months for an Fe-SS source; and
three years for a Cm-244 source. Recalibration is never required for the Am-241 source.

7.4 General Kevs and Commands

7.4.1 The "Shift" Key:

Prior to any operations using the keypad, determine which keypad function is to be used:

ALPHA = SH showing in display
NUMERIC = SH not showing in display

Then press the "SHIFT" key to change keypad functions. For selecting the model as outlined in Section

7.4.2 below, the SH must not be showing in the display.

7.4.2 The "Model" (Selection) Key:

If it is desired to change models, then depress the "MODEL" key. The analyzer will show the current
model in the lower right corner of the display. The analyzer active display will read:

MODEL Y?

Where Y is the currently selected model number.

Enter the desired model number using the number keys and press the "CONT/YES" key. The analyzer
will display the model type, UNCALIBRATED (no calibration - spectral data only), INTENSITY (pure
element intensities only - if the pure element routine has been completed), LIBRARY (identification
calibration completed), or ASSAY (chemistry or composition calibration completed), along with the
model's name (if assigned a name). Note that the change in model number (and the associated pre-
programmed measuring time) has been registered in the lower right corner of the display.

If no new model number is entered and only the "CONT/YES" or "END/NO" key is pressed, the model
number remains unchanged.

Example of model selection:

>MODEL
MODEL 1?

UNCALIBRATED MODEL

CONT/YES 15s

>MODEL
MODEL 1?

CONT/YES 10s

OLD LIBRARY MODEL PB LEVEL

-------
or

>MODEL
MODEL 1?

OLD ASSAY MODEL SITE X

32 CONT/YES 100s
32

The factory pre-programmed measurement time for each model can be changed using the MTM,
Measurement Time by Model, command. The change will not be executed until the model is exited and
re-selected.

7.4.3 The "MTIME" (Measurement Time Selection) Key:

If the measurement time needs to be changed, depress the "MTIME" key. The analyzer will show the
measuring time in seconds followed by a lower case "s" in the upper right corner of the display. The
active display (bottom line) will read:

MEASURING TIME XXX?

Depress the number keys to enter the desired measurement time (15 to 240 seconds are typical
measuring time for hazardous waste application - 1 to 32767 is the total range) and depress the
"CONT/YES" key. Note the corresponding change in measuring time in the upper right corner of the
display.

The measurement time remains unchanged if the "CONT/YES" or "END/NO" keys alone are pressed.
The new measurement time replaces the old value in the upper right hand corner of the display.

All uncalibrated models are defaulted to a measuring time of 15 seconds. All calibrated models are
defaulted to the pre-programmed (under the MTM command) measurement time.

Example of selection of measurement time:

The MTIME command provides a temporary change in the measurement time. The measurement time
will return to the model pre-programmed (MTM command) measurement time when a new model is
selected.

7.4.4 AMS Command: Data Averaging Mode:

Use the AMS command (Average Measurement Service) if an average of several measurements is
desired. First, select the desired model (see Section 7.4.2). Then enter the command AMS and depress
"CONT/YES". The analyzer will display:

Measure the sample(s). Depress the "END/NO" key to terminate the AMS command and display the
average of the measurements.

7.4.5 The "RECALC" Key:

Mil MI

MEASURING TIME 15 ?

CONT/YES

MEASURE

EMC-m-«H-115

-------
Results (spectrum) from the last measurement can be recalculated using another model. This is done
by switching to a new model, and pressing the "RECALC" key. If the new model is for two sources,
only the result for the Last Source Measurement can be calculated; if this is not sufficient, a new
measurement has to be carried out.

7.4.6 The Function Keys "F1 - F5":

The five function keys can be programmed to contain any of the three letter command acronyms. Up
to five (5) pre-programmed expressions can be stored in the analyzer's memory and are retained as long
as a charged battery is connected. The programming is initiated with the FNC command.

If the keyboard is locked (LOC command), only the "ON, OFF, CONT/YES, END/NO, RECALC,
START, and F1 - F5" keys can be used.

7.4.7 STD Command: Standard Deviations

The STD command computes the statistical standard deviations, the error due to counting statistics,
from the last measured sample spectrum for the analyzed (target) elements.

The display format is similar to the concentration output:

STDEVS: FE 1.04 CR .361 CU.142 PB .006

This does not reflect the total error of the measurement (accuracy), but only the part due to counting
statistics (precision). Generally, it is a good estimate of the instrument's precision. The statistical error
is reduced fifty percent for each quadrupling (multiplying by four) of the measurement time.

7.4.8 Other Commands:

Many other commands are available on the X-MET 880 and are confirmed and executed with the
"CONT/YES key. Refer to the X-MET 880 Operating Instructions for further information.

7.5 Instrument Calibration

7.5.1 DEL Command: Deleting a Model

If all 32 models have (an) old library(s) or assay model(s) in them, then a model must be deleted
before proceeding with a new calibration. Enter DEL followed by the model number (1-32) and confirm
the action by pressing the "CONT/YES" key. The X-MET 880 will display the selected model number
and it's name and ask if this model is to be deleted. Another "CONT/YES" key response deletes the old
model clearing the space for a new model. Therefore, deleting a model with the DEL command means
that a new pure element and sample calibration will be required.

Example:

To delete model 6:

>DEL CONT/YES

WHICH MODEL TO DELETE (1-32)? 6 CONT/YES
DELETE MODEL 6 CRFECU CHEM ? CONT/YES
DELETED
>

sac-wn-ii

-------
An "END/NO" key response to the above will result in the following display:

NOTHING CHANGED
and the model will not be deleted.

7.5.2 Changing a Model's "Maximum Count Rate" and Default Measuring Time:

All uncalibrated models have a default maximum count rate limit of 6 Khz (6000 counts per second)
and a default measuring time of 15 seconds. Prior to pure element calibration, the maximum count-rate
limit should be increased to 15 Khz. Simultaneously, the model default measuring time can be changed
to the anticipated calibration time (and after calibration, to the anticipated field or sample analysis time).
These changes are performed with the following procedure.

Unlock the maintenance program by typing in the EMP command, followed by the "CONT/YES" key.
This enables the maintenance program. Enter the model parameters section of the maintenance program
by typing in the PRM command, (Parameters command) followed by the "CONT/YES" key. Enter the
number of the model to be accessed (1-32), or accept the number offered by pressing the "CONT/YES"
key. The words "UNCALIBRATED MODEL" will be displayed. Press the "CONT/YES" key. The
words "GENERAL PARAMETERS" (the general parameters sub-section of the overall model
parameters) will be displayed. This sub-section is accepted by pressing the "CONT/YES" key. If the
model has already been assigned a name, the name of the model number entered will appear next and the
model can be re-named if desired, if not, press the "CONT/YES" key. The model type will appear at the
prompt. Enter "CONT/YES".

Entering "END/NO" at this query will change the type of model to one of the three choices:

Identification (IDENT), Assay (ASSAY), or Undefined (UNDEF). The wrong computational algorithm
will be applied if the incorrect type of model is entered. Answer "END/NO" to the incorrect model type
and "CONT/YES" to the correct model type.

The measuring time will be displayed next. Key in the new default measuring time (performs the same
function as using the MTM command) or accept the offered time by pressing the "CONT/YES" key.
The display will show "Number of channels: XX". Continue past this with the "CONT/YES" key. The
title "Flow Check Channel" will appear at the prompt. Press the "CONT/YES" key. The title "Check
Count Rate" will appear at the prompt. Press the "CONT/YES" key. The title "Max Count Rate" will
appear at the prompt followed by "6 Khz ?". Press the "END/NO" key. This will scroll the display to
the next count rate default of 10 Khz. Press the "END/NO" key and the display will show "15 Khz?".
To accept the 15 Khz maximum count rate limit press "CONT/YES". The display will show "Safety
Limit". Continue past this with the "CONT/YES" key. The title "CHANNEL PARAMETERS?", which
is the next sub-section of the PRM command, will appear at the prompt. Enter the "END/NO" key. The
title "G-MATRIX?", the next sub-section of the PRM command, will appear at the prompt. Enter the
"END/NO" key. The title "ASSAY/IDENT PARAMETERS?", which is the last sub-section of the PRM
command, will appear at the prompt. Enter the "END/NO" key. You have exited the PRM file, which
is evidenced by the reappearance of the prompt sign ">" on the display.

To re-lock the parameters file type in the XMP command, followed by the "CONT/YES" key. This
inhibits access to the maintenance program.

Example of changing a model's Maximum Count Rate limit and Default Measuring Time:

>EMP CONT/YES

>PRM CONT/YES

MODEL 5 ? CONT/YES

EMC-m-«H-lD7

-------
UNCALIBRATED MODEL
GENERAL PARAMETERS ?

CONT/YES
CONT/YES

Name: ?

Type: UNDEF ?
Meas. Time: 15?
No. of channels: 0 ?

200

CONT/YES

CONT/YES
CONT/YES

CONT/YES

Flow check channel: 0 ?
Check count rate: 0.00 ?
Max count rate: 6 Khz ?
Max count rate: 10 Khz ?
Max count rate: 15 Khz ?

CONT/YES
CONT/YES
END/NO

END/NO

CONT/YES
CONT/YES

Safety limit %: 0.00 ?

CHANNEL PARAMETERS ?
G MATRIX ?

ASSAY/IDENT PARAMETERS ?

END/NO
END/NO

END/NO

7.5.3 PUR Command: Pure Element Calibration:

7.5.3.1 Introduction

During pure element calibration, the analyzer determines the locations of the channels which will
bracket the energy of the element(s) to be measured, including the backscatter peak. The analyzer
also simultaneously calculates the element spectral overlap factors, or the values to be used in the "G-
Matrix" table to correct each channel for the influence of adjacent element peaks (in the form of
spectral overlap).

The pure element samples for the up to 10 elements chosen for calibration (1 to 9 elements plus
backscatter) may be measured in any order, however, it is recommended that the elements be
measured in order of their respective X-ray energies to facilitate operator review of the channel limit
(LIM command) settings (LIM review follows the PUR command).

The elements selected for an assay model should include all elements to be analyzed plus any
elements that might interfere, either by spectral overlap or by matrix interference.

The analyzer stores the spectra measured in a main spectra table and computes the correct channel
limits for each element, that are assigned to the specific model. Pulses falling between these limits
are included in the channel or "window" of the respective element. The analyzer calculates spectral
overlap factors and stores them in the G-MATRIX. This is the information from the spectra that will
be required for the deconvolution calculations. Each spectrum and the respective channel limits are
automatically labeled with the element, probe number and source used.

The instrument must be stabilized (powered-up for electrical stabilization and kept in a constant
temperature environment for thermal stabilization) for 60 minutes, and allowed to gain control for 5.0
minutes prior to the pure element calibration. The instrument must be allowed to gain control for 5.0
minutes every 25 minutes during pure element calibration. The area in which the instrument is being
calibrated in must be thermally stable to within +/- 3°F. A minimum measurement time of 240
seconds is normally used for pure element calibration.

sac-wii-

-------
Pure element spectra are stored in a main spectra storage table to facilitate copying to another model.
This gives the operator the option of performing pure element calibration in several models without
measuring the pure elements each time. Pure element spectra stored in the main spectrum table
should not be used unless they have been acquired and stored within the previous eight hours by the
same operator that performed the initial pure element calibration.

The model channel limits can be reviewed and re-set manually after pure element calibration using the
LIM command. They can be output to a peripheral device by using P command (print) followed by
the "CONT/YES" key while in the LIM Table.

7.5.3.2 Operation

Gain control monitoring must be performed as described in Section 7.1.2. Pure element calibration
is started by entering the PUR command followed by the "CONT/YES" key. The instrument asks if
you wish to "Delete the old spectra?". This is answered by the "CONT/YES" or "END/NO" key.
Answering with the "CONT/YES" key erases all spectra in the library, making copying impossible
until new spectra have been generated from pure element measurements.

The X-MET 880 asks for a new model name if the model has not been previously calibrated. It is
recommended that the operator include a statement in the model name's title concerning the
concentration of the XRF readings (e.g., if the assay model is going to measure 0 -20,000 ppm Pb
(mg/kg), the assay values will have to be entered as parts per million by weight (ppmw) or mg/kg/10
since the instrument only has 4 places before and after the decimal point for data entry). To ensure all
operators are aware of this, it is recommended that in addition to noting this fact in the XRF logbook
(see Section 19.0), the model name reflects this also (i.e., title: BBATY PPM = XRFX10).

Next, the instrument prompts for the first element and asks for it to be measured. The elements can
be named either by their one or two letter element symbol or by their atomic number. The scattering
sample has to be named by the symbol BS (or atomic number 0).

For POPS Probe only

If the DOPS probe is being used, the instrument prompts for the source to be used (either source A or
B). The operator should determine the appropriate source for the most efficient excitation of the
desired target element(s) (see source selection chart in X-MET 880 Operating Instructions) and select
the appropriate source(s) for the target element(s). Source A is the Am-241 source and source B is the
Cm-244 source (or the Cd-109 source in the 880EA system). Both sources can be used in a model to
analyze different target elements. If a dual source method is used, a total maximum of 10 pure
element calibrations may be used in the model for both sources (i.e., an even division of pure elements
between two sources could result in 4 elements and a backscatter for Source A and 4 elements and a
backscatter for Source B for a total of 10 pure elements in the model). Remember to include all
elements that might interfere, either by spectral overlap or by matrix effect in each source pure
element calibration.

For example, a site requires the soil analysis of cadmium (Cd) and nickel (Ni). Ni analysis requires
the use of the Cm-244 source (B). Cd analysis requires the use of the Am-241 source (A). The
operator notes that there is also tin (Sn) present in the soil and this may cause spectral overlap in the
Cd window due to the fact that Sn is an adjacent element to Cd. The minimum PUR command
calibration elements for source A would includeCd, Sn, Fe, and BS (backscatter peak). Fe is always
included in the PUR calibration of all sources because it is always present in soil. The minimum PUR
calibration for source B would include Fe, Ni, and Bs. Note that the Fe and BS must be measured
twice, once for each source used. The channel limits for an element cannot be interchanged between
sources.

sac-wn-if

-------
For POPS or SAPS Probes

Place the pure element sample in position and start the measurement by pressing the "START" key
(sample type probe) or by pulling the trigger on the surface probe and holding it open until the
measurement is completed. On DOPS probe, make sure the appropriate source is selected by
observing the source window display on the side of the DOPS probe and the display panel on the X-
MET 880 electronic unit.

Interrupt any measurements that start with an incorrect source by releasing the trigger and pressing the
"END/NO" key. Then re-enter the program with the PUR command and respond to the X-MET 880
prompts until you return to the desired channel number. Type in the desired element symbol and re-
start the measurement.

It is recommended that the operator examine each pure element sample prior to use to ensure that the
pure element plastic or metallic disc is still fixed in place and has not fallen out.

It is recommended that the elements be measured in order of their respective X-ray energies to
facilitate operator review of the channel limit (LIM command) settings (LIM review follows the PUR
command).

All of the calibration samples will have to be re-measured, if any pure elements are added, deleted, or
re-measured with the PUR command after the calibration samples have been measured using the CAL
command.

While the measurement is in progress, the remaining measurement time is continuously displayed.
When the measurement is completed, the peak channel and the Full-Width at Half-Maximum
(FWHM) of the pure element spectrum is displayed and the instrument requests the next pure element.
The PUR calibration can be terminated with the "END/NO" key.

Example of pure element calibration of a new model using a DOPS probe (6), with an Am-241 source
(A) and a Cm-244 source (B):

>PUR CONT/YES

DELETE OLD SPECTRA ? END/NO or CONT/YES*

* (CONT/YES deletes all existing spectra in main spectral library; maximum = 20)
CALIBRATING A NEW MODEL

NAME? PLATE PPM=XRFX10 CONT/YES

1. PURE SAMPLE: CR CONT/YES
SOURCE A ? END/NO
SOURCE B ? CONT/YES
MEASURE CR6B PULL TRIGGER

MEASURING: PROBE 6 TYPE DOPS (B) 200 SECONDS - measurement, time is counted

down; at conclusion display reads:
PEAK CHANNEL: 69 FWHM: 12 (peak channel & channel width)

2. PURE SAMPLE: MN CONT/YES
SOURCE A ? END/NO
SOURCE B ? CONT/YES

MEASURE MN6B PULL TRIGGER

MEASURING: PROBE 6 TYPE DOPS (B) 200 SECONDS

SlC-lMll-M

-------
PEAK CHANNEL: 75 FWHM: 12
3. PURE SAMPLE: FE
SOURCE A ?

SOURCE B ?

MEASURE FE6B

CONT/YES

END/NO
CONT/YES
PULL TRIGGER

MEASURING: PROBE 6 TYPE DOPS (B) 200 SECONDS
PEAK CHANNEL: 81 FWHM: 12

4. PURE SAMPLE: BS

CONT/YES

(scattering sample)

SOURCE A ?
SOURCE B ?
MEASURE BS6B

END/NO
CONT/YES
PULL TRIGGER

MEASURING: PROBE 6 TYPE DOPS (B) 200 SECONDS
PEAK CHANNEL: 255 FWHM: 1
5. PURE SAMPLE:

CALIBRATION FINISHED

END/NO

7.5.3.3 Multiple Models

Pure element calibration can be performed using the pure element spectra stored in the buffer
memory called the spectrum table, which holds 20 complete pure element spectra. The pure element
spectra stored in the spectrum table can be copied into any model(s) using the PUR command. Each
model can accept up to 10 such spectra. These pure element spectra are accessed during PUR
calibration for transfer of the appropriate channel limits data as well as for calculating the appropriate
G-Matrix overlap factor corrections. Thereafter, the model no longer needs to refer to the spectrum
table. Therefore, the 20 element limitation of the spectrum table does not limit the X-MET 880 to the
measurement of only 20 elements. If more than 20 spectra are added, the 21st one will overwrite the
first one in the spectra table, and so on, but previously calibrated models will not be affected. If
calibrating several models with more than 20 total elements using PUR, it is advisable to begin with
those elements that occur only in the first model(s) to be calibrated as they will be overwritten in the
spectrum table, but not in the calibrated model(s). Pure element spectra stored in the main spectrum
table should not be used unless they have been acquired and stored within the previous eight hours by
the same operator that performed the initial pure element calibration in the spectrum table.

7.5.3.4 LIM Command: Examining and Verifying the Channel Limits

The channel limits are printed out and examined using the LIM command once the pure element
calibration has been completed. The LIM command first displays the number of channels and asks if
the operator wants to examine the individual channel information. The bottom line (active line) of the
X-MET 880 display reads: "EXAMINE ?". Pressing the "END/NO" key exits the LIM command.
The operator may use "CONT/YES" key to review the data for the first channel; element symbol,
probe and source identification, pure element gross count rate and the normalization coefficient. On
the second line, the X-MET 880 displays the channel limits. Element channels are advanced in the
forward direction with the "CONT/YES" key and backwards with the "A" (up arrow) key. The P
command followed by the "CONT/YES" key gives an output in table form to a printer or a terminal
(see Section 5.3).

During scanning, new channel limits can be manually entered in place of the old ones. The count-rate
for the new channel limits will then change accordingly. Manual channel limit setting is required in
certain situations, such as when setting a channel at an L-beta line, (i.e., when the L-alpha line has an
overlap with another element channel (such as the case of As (arsenic) K-alpha overlapped with Pb

EMC-m-«H-211

-------
(lead) L-alpha). The pure element spectra must be in the spectrum table in order to manually change
the channel limits.

Before proceeding to the next step, the pure element channel limits must be examined and verified for
each source. None of the pure element channel limits should overlap or coincide. If any do, the
overlapping pure element spectra should be deleted and remeasured. Additionally, the order of the
channel limits must be identical to the corresponding X-ray energy order of the elements measured
(low to high measurement order facilitates this review). Note in the example below, that the order of
the Cr (chromium), Mn (manganese) and Fe (Iron) channel limits corresponds to the atomic number
order and the X-ray energy order of the elements. If the channel limits do not follow this pattern, the
anomalous pure element spectra should be deleted and remeasured.

Stepping through channel limits is discontinued with the "END/NO" key. After termination of the
command, the instrument pure element calibration data (spectral overlap factors called G-Matrix) is
re-calculated on the basis of the new channel limits.

Example of examining the channel limits:

> LIM CONT/YES

4 channels

EXAMINE ? CONT/YES

CR6B 820.17 1.000 63 71 NEW ? P CONT/YES

P command initiates formatted printout, if printer is connected):
(MODEL 5: PLATE PPM=XRFX10)

ELEM PROBE COUNT RATE NORM.FACTOR LIMITS

CR 6B 820.17 1.000 63 71

MN 6B 1194.64 1.000 72 77

FE 6B 450.06 1.000 78 86

BS 6B 185.18 1.000 255 255

7.5.4 SPE Command: Examining Spectra

The pure element and sample spectra can be output by the SPE command. The last sample spectrum
is output by answering "CONT/YES" to the query "LATEST?" (latest measurement). Pure element
spectrum are output by answering "END/NO" to the query "LATEST?". If "END/NO" is selected, the
pure element spectrum can be specified the following three ways:

1. The position number in the spectrum table (1-20).

2. The pure element symbol.

3. The atomic number of the pure element (but only if it is larger than 20; otherwise it is interpreted
by the instrument as the position number in table).

If the same pure element has been measured with more than one probe, the program will also prompt for
the probe number (and for source A or B if DOPS probe is being used) after entry of the symbol or
element number. When the pure element has been specified with its position number or symbol, then the
probe number and measurement time will be displayed. Display of the channel numbers and counts of
two channels at a time can be obtained by scanning backwards or forwards. Forward scanning is done
with the "CONT/YES" key and backward scanning with the "A" (up arrow) key. Keying in the micro-
channel number n (0 to 255) displays the counts of micro-channel n. Scanning is discontinued with the

-------
"END/NO" key and the instrument will then ask for a new pure element spectrum. Another "END/NO"
at this point will terminate the SPE function.

7.5.5 SPL Command: Spectrum Plot Using a Peripheral Device

A spectrum can be plotted with a printer or on a computer terminal by using the command SPL. The
spectrum is chosen as in the SPE command. Thereafter, X-MET 880 will prompt for the first and last
channels, the output window settings and the lower and upper limits for the scaling of the counts axis.
The output "window" means the number of micro-channels which are integrated and printed as one
channel of the plot. If the automatic lower and upper limits are not changed, the plot will be scaled
according to the highest peak of the spectrum.

7.5.6 CAL Command: Assay Model Sample Calibration

7.5.6.1 Introduction

When the pure element calibration (PUR command) of the analyzer has been carried out, the X-
MET 880 is capable of computing the net counts (intensities) in the element channels. In order to
proceed from net intensities to concentrations (assay), sample calibration is required. This entails
measuring known samples using the CAL calibrate command (assay readout).

Assay models are used for hazardous waste application models since they provide results in a
concentration which can be QA/QC'd. Identification models produce identification names of the
sample types by the quality of spectral matchings (i.e., LOW PB LEVEL or HIGH PB LEVEL).
Identification models are never used for hazardous waste applications because matching low
resolution spectra can result in false qualitative and quantitative results. Additionally, identification
models will not be addressed in this operating procedure.

For calibration of an assay model, the samples are measured using the CAL command, and the assay
model is calculated using X-MET 880 internal software by multi-variable regression analysis. The
calculation can be performed either internally, using the analyzer software (with a maximum of 30
calibration samples), or, externally in which case there is no restriction on the number of samples
used. This operating procedure will only address internal calculations since ERT/REAC does not
have external software.

7.5.6.2 Measurement of Calibration Samples

The instrument must be stabilized (turned-on and warmed- up for 60 minutes) and allowed to gain
control for 5.0 minutes prior to the measurement of calibration samples. The area in which the
instrument is being calibrated should be thermally stable (maintain +/- 3°F). A measurement time of
200 seconds or more should be used for measurement of calibration samples. The instrument must be
allowed to gain control for 5.0 minutes after measuring every 6th calibration sample, or every 25
minutes, during the CAL sample measurements. Gain control monitoring must be performed as
described in Section 7.1.2.

In the sample calibration of an assay model, the X-MET 880 stores the intensities of the calibration
samples in a calibration intensities table, from which they can be output using the CIN command, or
used directly for the generation of a regression model by the internal regression program of the X-
MET 880 (MOD calibration modeling command). The calibration intensities table is an electronic
scratch-pad that is erased after each model is completed and then moved to the next model to be
calibrated. This table can be used for the calculation of only one model at a time. The maximum size
of the calibration intensities table is 30 samples, hence, if a greater number of samples is required, the
intensities must be output for external calculation of the regression model. The calibration samples

-------
can be measured in an arbitrary order, AS LONG AS THE ORDER IS DOCUMENTED. Therefore,
be sure to make a note of the order used and document it in the operator's log book. The calibration
intensities table stores the samples by cardinal number (1-30) only, in the order they were measured.
The function is started with the CAL command. The X-MET 880 begins by displaying the status of
the calibration table:

- NO OLD DATA

- OLD DATA: 30 SAMPLES (TABLE FULL) or

- OLD DATA: n SAMPLES, MODEL XX OVERWRITE?

If the OVERWRITE? question appears, it is reminding the operator to finish the modeling
calculations using the calibration intensities table measured in an earlier model. If the earlier model is
already completed (modeling is finished using the MOD command) and the calibration coefficients
are already calculated, then the "CONT/YES" key should be pressed, to erase the old model
scratchpad and move it to the current model. If the earlier model is not completed, then the
"END/NO" key should be pressed and calibration calculations finished in the earlier model. NOTE: if
"CONT/YES" is pressed only new samples can be measured and the old calibration intensities table is
erased.

The X-MET 880 asks for one sample at a time:

MEASURE SAMPLE n

This can be answered in any of the following ways:

Measure the sample PULL TRIGGER

Proceed to Sample m Enter sample number m,

followed by: CONT/YES
Exit from Sample query END/NO

Repeat measurement of a particular sample can be accomplished by means of the sample number.
After pressing "END/NO", the last sample to be stored is verified.

LAST SAMPLE n ?

This can be answered with a smaller number if it is desired to omit some of the samples. If the table
becomes full, the message TABLE FULL is displayed and the command is terminated.

7.5.6.3 Sample Calibration of a Model Using Both Sources in a DOPS Probe

A given analysis may require the use of both sources in a DOPS probe to cover all the elements to
be measured. A single model employing both sources in the DOPS probe can be calibrated as
follows:

Every element to be measured by each source must undergo independent pure element calibration for
each source.

If BS is going to be used in the calibration of both sources A & B, then the BS sample must be
measured by both sources A & B during the pure element calibration (PUR) .

If the model's pure element calibration channel limits contain limits for both sources, then during
sample calibration the DOPS probe will automatically switch between sources, as required, to
measure the spectra for both sources, and store the intensities in the respective source's element

EMC-m-«H-24

-------
channels. Be sure to continue to hold the trigger open after the 1st source measurement. The X-MET
880 will indicate the completion of the first of the two measurements with a "beep-beep-beep". This
is immediately followed by a clicking noise that is the sound of the source changer switching sources.
Do not release the trigger until the 2nd source has completed its measurement.

During measurements, always verify that the appropriate source is selected by observing the display
on the side of the DOPS probe. Interrupt and end ("END/NO") any measurements started with an
incorrect source.

7.5.6.4 Deletion of the Calibration Intensities Table

The calibration intensities table can only be deleted by going to a different model to obtain the
"OVERWRITE" message. The operator can then either go back to the previous model or stay with
the new model to start a new calibration intensities table.

Example:

>MODEL CONT/YES

MODEL 4 ? CONT/YES

>CAL CONT/YES

OLD DATA: 11 SAMPLES, MODEL 2 (means previous calibration is in Model 2)

OVERWRITE? CONT/YES

MEASURE SAMPLE 1 PULL TRIGGER

MEASURING: PROBE 6 TYPE DOPS (B)

200 SECONDS

MEASURE SAMPLE 9 END/NO

LAST SAMPLE 8? CONT/YES

8 SAMPLES

If it is discovered that after measuring eight samples, sample # 4 was incorrect, then measuring the
correct sample will automatically overwrite the previous # 4 sample data in the table.

>CAL CONT/YES

OLD DATA: 8 SAMPLES

MEASURE SAMPLE 9 4 CONT/YES

MEASURE SAMPLE 4 PULL TRIGGER
MEASURING: PROBE 6 TYPE DOPS (B)

200 SECONDS

MEASURE SAMPLE 5 END/NO

LAST SAMPLE 8 ? CONT/YES

8 SAMPLES

7.5.7 ASY Command: Input of Calibration Sample Assay Values

The chemical metal analysis (assay) results of the SSCS are entered using the ASY command. The
X-MET 880 starts by prompting for the target elements for which concentrations are required (these are
known as the DEPENDENTS). This is answered by entering the element symbols (XX) of all the
desired elements for readout (up to six) using the "SPACE" key in between the symbols, but not
following the last entry. To enter the element symbols typed onto the display press "CONT/YES". The
instrument will then start asking for each sample assay value to be entered. Type in each assay value for

sac-iMffl-s

-------
each sample followed by "CONT/YES", until all the calibration samples assay values have been entered.
The concentrations can be changed afterwards if required by stepping backward with the "A" (up-arrow).
If concentration values for newly measured samples, or additional elements, are desired to be added
later, then re-enter the ASY command and press "CONT/YES" until the first assay value is on the lower
line of the display. Next, type a (/) followed by the sample number you desire to jump to. The use of a
(/) mark in front of the sample number advances the assay table directly to the sample number entered.
From any location in the assay table, P followed bv "CONT/YES" gives output in tabular form to a
printer or a terminal.

CAUTION: Do not enter a 1' "CONT/YES" command while in the first section of the ASY

command, the entry of DEPENDENTS, as in this section a P will be interpreted as
the element phosphorus. Should this be done aecidentlv. the instrument will ask for
re-verification that the element 1' (phosphorus) is desired in place of the previously
selected elemenl(s). At this point the operator would simply re-enter the correct
element symbols prior to pressing "CONT/YES" which accepts the offered element
(P). Hi the symbol P is inadvertently accepted as the element, by acknowledging it
with "CONT/YES" twice, it will then be necessary to re-enter ASY and the correct
elements svmbols and re-install all the assav values.

-------
NOT]i: Only assay values with less than four significant figures in
front of the deeinial point ean be entered into this table.
Therefore, if any samples contain assay values with greater
than 4 significant figures in front of the decimal point Al.l.
assay values for all elements in the suite should be divided by
some power of 10 (such as 10. 100, 1000, or 10.000) prior to
entry into the assay table, for example, one sample in the suite
is assayed at 33.999 mg/kg. The decimal fraction resulting
from the division of 10 would convert this value to 3.399.9.
Therefore, the value 3.399.9 would be entered into the assay
table and all other element assays in the calibration suite would
likewise be divided by 10 prior to entry into the assay table.

Example 1: Entering Cr and Cu assays, for eight calibration samples that have been measured using the CAL
command.

> ASY

OLD DEPENDENTS: NO OLD DEPENDENTS
NEW: CR CU

NEW DEPENDENTS?: CR CU
1. SAMPLE CR: 0.0000 ? 10.97
1. SAMPLE CR: 10.9700

CONT/YES

CONT/YES
CONT/YES
CONT/YES
CONT/YES

1. SAMPLE CU: 0.0000 ? 34.23
1. SAMPLE CU: 34.2300

CONT/YES

2. SAMPLE CR
2. SAMPLE CR
2. SAMPLE CU

0.0000 ? 8.56
8.5600

0.0000 ? 42.29

CONT/YES
CONT/YES

8. SAMPLE CR: 0.0000 22.39
8. SAMPLE CR: 22.3900

8. SAMPLE CU: 0.0000 ? 15.00
(Terminates assay command automatically)

8*2 ASSAYS
>

Example 2: Changing dependents from the old ones Cr, Cu, to new: Cr, Cu and Fe. NOTE: This will not erase
the previous assay table data, but will open up space to add Fe data.

>ASY CONT/YES

OLD DEPENDENTS: CR CU

NEW ? CR CU FE CONT/YES

CONT/YES
CONT/YES

EME4EM5M-257

-------
1. SAMPLE CR: 10.9700 ?
1. SAMPLE CR: 10.9700

CONT/YES

1. SAMPLE CU:
1. SAMPLE CU:

34.2300?
34.2300

CONT/YES

1. SAMPLE FE:
1. SAMPLE FE:

0.0000 ?
40.2000

40.2

CONT/YES

2. SAMPLE CR:
2. SAMPLE CR:

34.2300?
34.2300

CONT/YES

8. SAMPLE CR:
8. SAMPLE CU:
8. SAMPLE FE:

22.3900
15.0000 ?
0.0000 ?

51.00

(Terminates assay command automatically)

8*3 ASSAYS
>

CONT/YES
CONT/YES
CONT/YES

7.5.8 MOD Command: Generating the Regression Model

The MOD command of the X-MET 880 initiates the program for calculation of multi-variable
regression model coefficients. The program offers regression calculations for the DEPENDENTS (assay
values) given in the ASY command (i.e., those elements whose symbols were entered as
DEPENDENTS).

7.5.8.1 Setting the Dependents

>MOD	CONT/YES

REGRESSION FOR CR ?	END/NO

REGRESSION FOR FE ?	CONT/YES

Upon an affirmative answer ("CONT/YES"), the INDEPENDENTS (elements'
intensities) for the element(s) in question are requested: i.e., those elements
that may affect the slope of the dependent element are entered with the
element symbol, to be included in the regression calculation.

7.5.8.2 Setting the Independents

DEFINE INDEPENDENTS:

Stop indep input by END-key

1.	indep: ? FE	CONT/YES

2.	indep: ? CR	CONT/YES

3.	indep: ?	END/NO

At this stage it is possible to scan forward with the "CONT/YES" command and
backwards with the "A" (up arrow) command: deletes an independent. "END/NO"
terminates input, computes the regression model and displays the quality-of-fit of the
regression line.

-------
The simplest independent expressions are recommended at first. The element can be
specified either by its symbol or its element number. The other permissible forms of
expression are as follows using iron, chromium and backscatter as examples:

FE

FE/ or FE/BS BS = scatter intensity
FE*CR

FE*CR/	means FE*CR/(BS*BS)

BS/	means 1/BS

FE*BS/	means FE/(BS*BS)

BS*BS	means 1/(BS*BS)

If independents have been entered incorrectly, i.e., using elements that are not included
in the instrument calibration, the X-MET 880 responds by beeping and then listing the
possible elements for inclusion as independents (only those that were included in the
pure element calibration) and then displays a repetition of the query:

"beep"

USE CR FE CU
1. indep:

7.5.8.3 Reviewing the Regression Fit Parameters

After defining the independents, "END/NO" terminates the independent input
and calculates the internal regression fit. The figure-of-merit parameters are then
displayed:

R	= correlation coefficient

S	= standard deviation around regression line

F (M,N)	= F-test value of regression with degrees of freedom M,N

M	= number of independents

N	= number of samples M-l

Example:

R=0.975 S=1.55 F=(2.5)=4.25
RESIDUALS ?

7.5.8.4 Examining the Residuals Table

The X-MET 880 then asks if it is desired to examine the residuals (i.e., the
comparison of concentrations calculated by the model with the assay values entered).
If these are not required, reply "END/NO"; otherwise "CONT/YES" leads to scanning
of the residuals. The notation is as follows:

ASSAY = concentration entered (from the AA, ICP or referee analysis)

ESTIM. = concentration calculated with the model

RE SID. = ASSAY - ESTIM

ST.RES = RESID/standard deviation S

Example:

SlC-lMll-B

-------
NO ASSAY
1	30.300

ESTIM
29.875

RESID
0.425

ST.RES
0.274

Forward scanning is done with the "CONT/YES" command, backward scanning with
the "A" (up-arrow) command; entering the number of a calibration sample followed by
"CONT/YES" leads directly to that sample in a table. P "CONT/YES" sends the
output, in table form, to the printer or other peripheral device, D "CONT/YES" sends a
calibration Data plot diagram to the printer or other peripheral device.

"END/NO" terminates the scanning.

7.5.8.5 Deleting Points

The scanning of residuals is followed by the question:

DELETE POINTS:

If it is required to delete samples from the regression model calculation, enter the
numbers of such samples, i.e., 3 SPACE 5 and press "CONT/YES". This will calculate
a new regression model and display the new figure-of- merit data for this new
regression model. This display will be followed by the RESIDUALS ? query. A
"CONT/YES" response leads to scanning the new residual table (using the new
regression model calculated without the deleted points). This table may be scanned
also. "END/NO" terminates the scanning and returns to the DELETE POINTS:
prompt. Additional points may be deleted at this time.

NOT] i: If the new residual table is scanned I'orw ard using the "C( )NT/Y1 iS"

command and backward using the "A" (up arrow ) command, the deleted
point(s) will simply be missing in the residual table.

If the new residual table is output in tabular form using the P "CONT/YES" command,
then the calibration table knows the samples by cardinal number (1-30) only. The
residual table's sample numbers will change for points with cardinal numbers larger
than those which are deleted. For example: Using a calibration table with 20 samples,
an operator deletes point number 5 and returns to the residual table. The new residual
table will contain points 1-19. Points 1-4 in the "output" new residual table will
correspond to the cardinal numbers 1-4 in the calibration table. Points 5-19 correspond
to the original calibration cardinal numbers 6-20. Therefore, if the operator wants to
delete sample number 9 in the "output" residual table, sample (calibration cardinal)
number 10 must be entered to the DELETE POINTS: prompt after terminating the
residual scanning.

The next new residual table will contain residuals for points 1-18 now. Points 1-4 in
this new residual table correspond to the calibration cardinal numbers 1-4. Points 5-8
in the new residual table correspond to calibration cardinal numbers 6-9. Points 10-18
in the new residual table correspond to calibration cardinal numbers 11-20.

sac-wii-

-3®

-------
This loop will continue until the reply to the DELETE POINTS: prompt is
"CONT/YES" or "END/NO". The X-MET 880 response to an incorrect input is "GIVE
POINT NUMBERS".

If the residuals are not examined, or the response to the "DELETE POINTS" prompt is
"CONT/YES" or "END/NO", the next question is COEFFICIENTS AND T
VALUES?.

7.5.8.6	Examining Coefficients and T Values
To the question:

COEFFICIENTS AND T-VALUES ?

a response of "CONT/YES" will allow you to scan the coefficients and T-Values for
each independent used in the regression model. Forward scanning is done with the
"CONT/YES" command, backward scanning with the "A" (up-arrow) command.

INTERCEPT = 1.23 E-4

SLOPE 1 = 3.827E-2 T = 15.60	CONT/YES

SLOPE 2 =-1.00837 T =-9.86

The slope and t-value for slope 1 correspond to the first independent (element). The
slope and t-value for slope 2 correspond to the second independent, etc.

"END/NO" terminates the scanning. P "CONT/YES" gives output in table
form:

COEFFICIENTS AND T-VALUES ?

CONT/YES

INTERCEPT = -1.1433235E+1

SLOPE 1 = 7.6707910E+2 T = 83.40 P CONT/YES

COEFFICIENTS AND T-VALUES FOR *NI*

ITC	NI/	NI*FE

SL	-11.433235	767.079104 -0.000234

T VALUE	83.401736 -7.457542

7.5.8.7	Reiterating the Model or Exiting

After terminating the scanning with the "END/NO" command, the query
CHANGE INDEPENDENTS? is displayed. If the model created for the element does
not require changing, reply "END/NO". This will terminate the regression for the
dependent (element) you have been working on. You will be asked if you want to enter
the next dependent regression ("CONT/YES" if yes) or you will pass it and go to the
next element (END/NO).

If the reply "CONT/YES" is entered, all points deleted at previous stages will be
reinstated, and the dependent regression returns to the independents query:

Example: l.indep:FE?

SlC-lMffl-M

-------
In this way, it is possible to stay in a loop (in a dependent regression), reiterating the
model with new independents, computing a new regression, possibly deleting points
and computing a new regression again, until the best possible regression model is found
(see Section 14.2).

When all elements in the model are finished, exit the MOD program with "END/NO"
which returns the display to the prompt (>_).

7.5.9 Model Optimization Methodology
7.5.9.1 Basic Theory

The X-MET 880 uses the so-called empirical calibration approach, that is, the
calibration equations are developed based on intensities measured on known calibration
samples. The general calibration formula is patterned after the intensity correction
model of Lucas-Tooth and Price. The generalized calibration equation for the analyte i
in a sample can be written as follows:

C, = I *(Ki + SlJM(Kii*Ii)) + Bj + SlJM(l3ii*Ii)

j-i

Terms: 12 3 4

The model assumes that the analyte concentration is a function of the intensities from
elements in the sample. While this model is limited to relatively narrow concentration
ranges, it has an important advantage that only the analyte need be chemically assayed
in order to develop it.

If no matrix effects are present in the sample, the calibration equation would have only
part 1 and 3, and would be a simple straight line equation.

The second term modifies the slope of the calibration line, according to the amounts of
other elements present in the sample, as determined bv their intensities. This
correction is needed when the matrix element is close in energy to the analyte, so that it
strongly absorbs or excites its radiation (matrix interference). This slope modification
is also useful when the matrix element varies over such a large concentration range that
it significantly changes the effective matrix absorption of the incident or emitted x-
rays. The square term, 1;*^, would be the correction for self-absorption.

The fourth term reflects the change in background intensity under the analyte peak.

This term is significant if matrix element(s) vary enough to alter the matrix scattering
and its power to change the general shape of the background, or more commonly, if the
matrix element has a spectral peak that overlaps the analyte peak. The overlapping
peak may also be an escape peak. This situation often arises in alloy analysis where
strong peaks of iron, chromium or nickel can produce escape peaks (2.9 keV), which
are to the low energy side of their fluorescent peaks (caused by argon filling).

7.5.9.2 Parameters Used in Regression Modeling

-------
R - COEFFICIENT OF CORRELATION. This calculation tells how well the
given calibration equation explains the variation of data. Its value varies between 0 and
1. The closer its value is to 1.000 (i.e., a one-to- one correlation between the calculated
element assay values and the corresponding element intensity values), the better the
calibration model is. It should have a value greater than .65 to be meaningful. The R
value is a function of the number of independents, the number of data points, and
usually increases as those numbers increase.

NOT]i: The R coefficient alone, however good, cannot be the only basis of

determining the quality or goodness of the model. ()ften in the case of
too lew data points and/or over-complicating the calibration equation
(too many independents), one can get a "perfect" R = 1.000. which may
be meaningless.

S - STANDARD ERROR OF THE FIT. Also known under the term "Sum of Squares
for Error" (SSE), or "Root Mean Square Error" (RMS). This is one standard deviation
of the spread of data points around the fitted calibration line. The greater its value
(error), the more scattered the data points. If two lines are drawn parallel to the
calibration line at plus S and minus S distance from it, the band created around the
calibration line will contain about 68% of all the data. The value of S is expressed in
the units of the dependent variable being fit (generally concentration units as in the case
- mg/kg of soil). During the modeling one should try to minimize this parameter. It
should be noted that if the dependent mg/kg assay values are divided by 10 or 100
before being entered into the assay (ASY) table, the S value displayed must be
multiplied by the same factor to get mg/kg values.

F - TEST VALUE. This is a statistic which is expressed as the ratio of the sum of
squares explained by the given regression model, to the sum of squares not explained
by the model (our familiar parameter S). If its value is low, say 5 to 10, then the model
is not reliable, and may not be stable if a different data set is used for its calibration.
Alternatively, we might say that a low F value indicates the inability of a proposed
regression model to predict the correlation between concentrations and intensities of
the element being fit. Assuming that an average calibration set has 10 samples, the
value of the F statistics should not be smaller than 10 for us to say with 95%
confidence that the given model is a valid one. F is a function of the number of data
points, the number of independents and S. It usually decreases if the number of
variables increases. It is a dimensionless number.

T - TEST VALUE. This statistic is a test of significance for the calculated slope. It is
expressed as the ratio of the slope value to the estimate of error of that slope. For
example, a T-value equal to 10, means that the error on the estimate of the slope is one
tenth (or 10%) of the slope itself, which is significant. For an average case of ten
calibration samples the absolute value of T should not be smaller than 2.5 for us to say
with 95% confidence that the given slope is statistically valid. Therefore, the rule of
thumb would be to eliminate from the model all independents featuring a T value less
than |2.5| (+/- 2.5). The T test is a dimensionless number and has the same sign as its
slope.

-------
STDEV - STANDARD DEVIATION DUE TO COUNTING STATISTICS. This is
the error caused by the random nature of radioactive decay and counting statistics. It
is, by definition, equal to the square root of the total number of counts accumulated
within a given period of time. Alternatively, standard deviation of intensity I is equal
to the square root of intensity I, divided by the square root of the time the intensity was
measured for. It is seen that by extending the measurement time by a factor of 4, one
can reduce the standard deviation of counting (error) by a factor of 2. This error is the
only one easily controlled. It should be noted that if the dependent mg/kg assay values
are divided by 10 or 100 prior to entry into the assay (ASY) table, the STDEV value
displayed must be multiplied by the same factor to get mg/kg values.

7.5.9.3 Iterative Process of Building the Model

STEP 1

Always start with the intensity of the element of interest as the first
independent variable. Next, depending on the nature of the sample matrix, try the
intensity of the analyte ratioed to the intensity of the backscattered (BS) radiation
(XX/BS). This usually works for sulfur in oil, chlorine in oil, metals in soil, or any
element in a light (or highly scattering) matrix. If the analyte range is relatively wide
(such as several percent), try the square term of the analyte intensity (XX*XX)-
(example: Pb in soil in the range of 0 to 10%). For each regression note the values of
R, S, and F. The focus should be to MINIMIZE S as this parameter is closely related
to the accuracy of the method. It can be shown mathematically that R and F are
functions of S.

Therefore, by concentrating on S we usually drive R and F in the desired direction, that
is high. Save the regression which yields the smaller S. However, keep in mind that
two values of S, for example one of . 12 and another of . 11, ARE F OR ALL
PRACTICAL PURPOSES THE SAME. The difference between the S's should be at
least about 20% to be a criterion for selection. IF the S's are similar then select the
model with the higher F and/or the higher R.

Examine the table of residuals. Make note of the points which are clearly off. The last
column of the table tells how many S's below or above (+/-) the curve the given point
is. About 68% of the data points should have a STRES (last column) value smaller
than the absolute 1, 95% smaller than the absolute 2, and 99.9% (for practical reasons
all points) smaller than the absolute 3.

Here is a worked example:

Total number of data points is 17 (17 samples). Therefore, about 12 points (.68*17 =
11.56 or 12 points) should have a STRES (the last column) value between -1.0 and
+1.0.

About 16 points (.95*17 = 16.15 or 16 points) should have a STRES value between -
2.0 and +2.0. This also means that four points may fall between -2.0 and -1.0 and
between +1.0 and +2.0.

At the most, only one data point should have an absolute value between 2.0 and 3.0.

The number of points in each band may vary at least by one from the predicted number
due to randomness.

SlC-lMll-M

-------
If any point is distant by more than +/-(3S) from the line, it becomes a candidate for
deletion. However, the reason for deviation should be established first. Often it is the
incorrect entry of the referee assay (ASY command) for this point. Sometimes it just
may be a bad measurement which can be easily corrected by remeasuring the
sample(s). It may also be a case of the (outlying) sample being incompatible (i.e.,
different matrix) with the rest of the set. If all available information indicates that none
of the above applies, then it is probably best to delete the point from the regression. If
deleting the "outlier" results in significant improvement of the model, then usually it is
justified.

Often all data points will be within the +/-(3S) band, but more of them than expected
will exhibit large deviations from the line. In most cases this is caused by
incompleteness of the model. Examining the composition of those samples which
deviate too much may reveal that those particular samples contain significant amounts
of some other element(s) which was not yet accounted for in the model. This situation
provides a hint as to which independent to include in the next round of the modeling
process. Examine the table of residuals and the plot of the data. Is any point, or group
of points, indicating curvature of the calibration line which could be corrected by
including in the model a square term (XX»XX)?

STEP 2

Now is the time to add to our first independent term the next one. It may
already be obvious what to do from the examination of the table of residuals as
mentioned above in STEP 1. However, there are some guidelines to keep in mind. The
matrix element with the highest concentration should be examined, by including its
intensity in the model as the next variable. If that element happens to be close in
energy to the analyte peak, then the non-linear term in the form of the product of the
analyte and interfering element intensities (XX*YY) may prove to be helpful. Check
the S, R, and F values again. If the S does not improve, the independent should be
rejected and another one tried. To assess progress in reducing the S parameter, it is
convenient to use the ratios of S's and F's from the two models. If one model is better
than the other one then:

^bettei^'worse ^ C^worse^^better) '

where "better" refers to the smaller S value.

Examine the table of residuals and the plot of the data. Examine the t test values of the
slopes. Reject independent(s) which show T smaller than +/-2.5.

Exit the modeling and enter the STD command. The X-MET 880 should still have in
its buffer memory the spectrum of the last measured calibration sample. Therefore, it
should output on the display the values of the standard deviations due to the counting
statistics for all of the already modeled elements. Check and make a note of those
STD's. THEY CANNOT BE LARGER THAN THE S ERROR(S) OBTAINED
DURING MODELING. If they are larger, then the model is over-corrected and should
be changed by rejecting the variable (independent) with the lowest t value. The S error,
by definition, includes the standard deviation, and cannot (be smaller than any of its
components.

Continue the iterative process of modeling by repeating STEP 2 until no further
improvement seems feasible.

-------
7.5.9.4 Concluding Remarks

Examination of the table of residuals during the iterative process is very
important. During the examination of the table of residuals, keep the following in
mind:

1.	The results displayed in the table are in the same concentration as the values
entered into the assay (ASY) table (i.e., values entered in the assay table were
mg/kg/10. Therefore, the values in the table of residuals must be multiplied by
10 to get mg/kg.

2.	A calibration based on several low concentration SSCS and one or two high
concentration SSCS will report a very low S value. This low S value may be
meaningless with respect to the analytical accuracy of samples with
concentrations between the low and high SSCS. The possibility of large
analytical errors for samples in this concentration range should be brought to
the attention of the task leader or project manager prior to mobilization if
SSCS cannot be obtained for this concentration range.

3.	Development of a model with SSCS concentrations greater than one or two
percent will generally result in increased analytical error in the region of the
detection limit and the site action level (500 to 2000 mg/kg). Development of
a low (DL to 1 or 2 percent concentration) and a high (one to ten percent
concentration) concentration models usually solves this problem. The
recalculation function (see "RECALC" Key Section) can be used to recalculate
concentrations from spectra generated in the other model.

4.	Pay particular attention to the SSCS with assay values in the critical analytical
region. The critical analytical region is located between the DL and four or
five times the site action level. The goal of the operator should be to bring the
estimated values off the SSCS in the region as close to their assay values as
possible. Ideally, half of these SSCS should have estimated values higher then
their assay values and half should have estimated values lower then their assay
values. Select the model with the majority of the SSCS estimated values
above their assay values if an even distribution is impossible. The goal is to
provide the most accurate analysis in the critical analytical region because this
is where managers are going to make removal/remedial/health and
safety/sampling decisions. Additionally, high-biased or false positive data is
typically preferred over low-biased or false negative data.

A higher S value and an independent with a|T| value <2.5 can be tolerated if
the model provides improved accuracy in the critical analytical region.
Additionally, SSCS in the critical analytical region should be deleted only if
there is a large number of SSCS in the region and the dilution of the point
provides significant improvement (greater than 20 percent) in the estimated
values of the SSCS in the region.

Select as the final model the one with the best (smallest) S and the best (most
accurate) estimated values for SSCS in the critical analytical region. If two
models have a very similar S, select the one with greater value of F. If by
including in the model one more independent(s), only a small improvement of
S is obtained, consider keeping the model with the larger S but with smaller

-------
STD value. In most cases, the smaller the number of independents in the
model, the better (smaller error) the STD value.

Use common sense. Remember that simpler is better. It is always easier to
correct or knowingly change the model which has the smaller number of
parameters. Do not over-correct. If the number of calibration samples is too
small, it is just not possible to develop a good model. The rule of thumb is
that if you fit the equation with k independents, the number of samples in the
model should be at least twice as much, that is N>=2»K. If the calibration set
has only 6 samples and you fit the calibration equation with 5 terms
(independents), then you will get a "perfect fit" with R= 1.000, S=0.000 and
F=****. However, this "forced fit" will yield a calibration equation which
will not work in practice, as it is not mathematically representing the real-life
scenario. This is a case of over-defining the model on the grounds of
statistical analysis.

As a rule, do not bother to include as independents those intensities whose
element concentrations in samples are very small compared to the
concentration range of the analyte.

There are some exceptions from the rules we tried to spell out above. One of
the most significant exceptions is the calibration for an element which is very
strongly affected by the presence of all matrix elements. A classical example
is the analysis of phosphorus in phosphate rock. Phosphorus x-rays are
absorbed by calcium, silica, potassium, sulfur, all of which may be present in
the sample in quantities that call for each to be included in the calibration.
Usually, for that calibration the t values of all of the slopes are quite marginal.
However, none of the variables can be rejected without significant degradation
of the model parameters.

When testing the final model for accuracy, keep in mind when comparing the
measured values to the given ones (X-MET 880 computed), that if the
difference seems too large, perhaps the measured sample was also off during
the calibration and modeling. THEREFORE, COMPARE THE MEASURED
RESULT WITH THE VALUE OBTAINED DURING MODELING (in the
table of residuals) RATHER THAN WITH THE GIVEN ONE. If the
difference between the S value and the STD value (for the same measurement
time) is significant, then the S error should be used as the criterion for judging
any discrepancies between the measured and the given values. This applies if
S is about twice the corresponding STD.

7.5.10 Verifying the Accuracy of the Regression Model

The Regression Model should be verified whenever possible, prior to sample analysis,
to ensure that everything was done properly. Ideally, all SSCS used (not deleted) in the model
should be measured by the model to verify its accuracy. As a minimum, one low, mid and high
SSCS should be used to verify the model as described in Section 7.2. Read Section 9.0 on
recommended Quality Assurance and Control methods.

7.5.11 Documenting the Regression Model

-------
After the regression model has been completed for all the dependents the results should
be captured to a peripheral device such as a printer or a PC floppy disk using ProComm+, or
other communication software (see Section 5.3).

7.6 Calculations

7.6.1 The X-MET 880 is a direct readout instrument. The element concentrations displayed in
the readout are identical to the assay value concentration entered during instrument calibration (see
Section 7.5.7).

7.7 Health and Safety

7.7.1 When working with potentially hazardous materials, follow USEPA, OSHA, corporate
and/or any other applicable health and safety practices.

9.0 QUALITY ASSURANCE/QUALITY CONTROL

9.1 Precision

The precision of the method is monitored by reading the low SSCS selected as described in
Section 7.2 at the start and end of sample analysis and after approximately every tenth sample. The low
concentration sample is analyzed by the instrument for the normal field analysis time, and the results are
recorded in a log book. The standard deviation for each dependent element is calculated (using the N-l
formula).

9.1.1 Preliminary Detection Limit (DL) and Quantitation Limit (QL)

A preliminary DL and QL is needed to give the operator an indication of the
instruments capability out in the field. A low SSCS sample is selected as described in Section
7.2. Models with multiple dependent elements may require the use of more than one standard to
obtain low concentration values for each element.

The sample is measured ten times without moving it, using the anticipated field analysis
measuring time. The standard deviation of the mean for each dependent element is calculated
(using the N-l formula).

If the standard deviation has a fractional component, round up to the next whole number prior to
calculating the DL and QL.

The definition of the DL is three times the calculated standard deviation value.

The definition of the QL is 10 times the calculated standard deviation value.

9.1.2 The Field Detection Limit (FDL) and Field Limit of Quantitation (FLOQ)

The precision of the method is monitored in the field by reading the low SSCS selected
as described in Section 7.2 at the start and end of sample analysis and after approximately every
tenth sample. The low concentration sample is analyzed by the instrument for the normal field
analysis time, and the results are recorded in a log book. The standard deviation for each
dependent element is calculated (using the N-l formula) using the measurements from the entire
sampling period.

-------
If the standard deviation has fractional component, round up to the next whole number prior to
calculating the FDL and FLOQ.

The definition of the FDL is three times the calculated standard deviation value.

The definition of the FLOQ is 10 times the calculated standard deviation value.

9.2 Reporting Results

All raw XRF data should be reported including the individual results of multiple analyses of
samples and sampling points. The average and standard deviation (using the N-l formula) of each
multiple analysis should also be reported.

A "reported" value for each analysis or average of multiple analyses should be messaged in the following
manner.

1. First round the value to the same degree of significance contained in the SSCS sample assay
values (usually 2).

2. All values less than or equal to the FDL are reported not detected (ND).

3. All values greater than the FDL and less than or equal to the FLOQ are flagged (usually with a
"J" next to the reported value) and noted as such.

4. All values above the FLOQ and within the linear calibration range are reported as is.

5. All values above the linear calibration range (greater than the highest SSCS used in the model)
are flagged (usually with a next to the reported value) and noted as such.

9.3 Accuracy

The accuracy of the method is monitored and verified by sending an XRF analyzed sample or
sample cup out for AA or ICP analysis at an independent laboratory.

Although AA and ICP are generally recognized as having good accuracy and precision over the
concentration range typical of metals contamination in soil, it is most important to recognize the
possibility of real differences in the composition of samples sent in for comparative analysis, due to
heterogeneity of the soil. It is recommended that the prepared sample cups be sent in for analysis if the
samples were prepared in this manner.

Another very important source of potential difference between XRF and AA or ICP results is incomplete
digestion of the leaching technique. Since XRF is a total elemental technique, any comparison with
referee results must account for the possibility of variable extraction depending upon the extraction
method used and its ability to dissolve the mineral form in question.

9.3.1 Additional QA/QC

Additional QA/QC plans may call for monitoring for potential instrumental drift by
measuring a mid-range calibration sample at regular intervals (such as every 20th sample) in
order to validate the previous measurements. The use of such measures insures that the
instrument is continuing to provide the same level of accuracy throughout the entire series of
samples at a given site. Should, for example a cold front blow through during a series of
measurements, it is required that the X-MET 880 be allowed a gain control period of five

sac-iMii-®

-------
minutes to compensate for temperature effects on the detector gain. The need for such a gain
control cycle would become apparent based on any inaccuracies noted during the QA/QC
sample tests.

9.3.2 Matrix Considerations

Other types of QA/QC verification should include verification that the instrument
calibration is appropriate for the specific site to be assessed. This should include verification of
the potentially multiple soil matrix types that may exist at a site. Matrix variations that affect
the XRF include large variations in calcium content, such as may be encountered when going
from siliceous to calcareous soils, as well as variations in iron content.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Outokumpu X-MET 880 Portable XRF Analyzer Operating Instructions, Revision A, October, 1989.

2. Outokumpu Notes and General Information on the Regulatory Requirements for owners of the
Outokumpu X-MET 880.

3. 'Outokumpu Supplemental Documentation on the factory calibration of X-MET 880 (if calibrated at
Outokumpu prior to delivery), including Table of Check samples and Normalizing Samples for Assay Models.

4. "X-ray Fluorescence Analysis of Environmental Samples", Dzubay, T., Ed, Ann Arbor Science, 1977, p.
310.

5. "Advancements in Portable XRF Technologies for On-Site Hazardous Waste Screening", Pasmore, J.,
Piorek S., and McLaughlin, J.

6. "Portable X-ray Fluorescence as a Screening Tool for Analysis of Heavy Metals in Soils and Mine
Wastes", Chappell, R., Davis, A., Olsen, R. Proceedings Conference Management of Uncontrolled Hazardous
Waste Sites, Washington, D.C., 1986, p 115.

7. "A New Calibration Technique for X-ray Analyzers Used in Hazardous Waste Screening, Piorek, S.,
Rhodes, J., Proceedings 5th National RCRA/Superfund Conference, April 1988, Las Vegas, NV.

8. "Data Quality Objectives for Remedial Response Activities", EPA\540\G-87\004, March 1987.

9. "Portable X-ray Survey Meters for In-Situ Trace Element Monitoring of Air Particulates", Rhodes, J.,
Stout, J., Schlinder, J., and Piorek, S., American Society for Testing and Materials, Special Technical Publication
786, 1982, pp. 70 - 82.

10. "In-Situ Analysis of Waste Water Using Portable Pre-concentration Techniques and a Portable XRF
Analyzer", Piorek, S., Rhodes, J., Presented at the Electron Microscopy and X-ray Applications to Environmental
and Occupational Health Analysis Symposium, Penn. State Univ., Oct. 14 - 17, 1980.

11. "Hazardous Waste Screening Using a Portable X-ray Analyzer", Piorek, S., Rhodes, J., Presented at the
Symposium on Waste Minimization and Environmental Programs within D.O.D., American Defense
Preparedness Assoc., Long Beach, CA., April 1987.

-------
12. "Field-Portable X-Ray Fluorescence", U.S. EPA/ERT Quality Assurance Technical Information Bulletin,
Vol. 1, No. 4, May 1991.

-------

-------

-------
ERT Method

SENTEX SCENTOGRAPH GAS CHROMATOGRAPH FIELD USE

1.0 SCOPE AND APPLICATION

1.1 This standard operating procedure (SOP) deals primarily with the assessment of gaseous matrix
samples. The Sentex Scentograph Gas Chromatograph (GC) can work in two detector configurations: the
Electron Capture Detector (ECD) or the Argon Ionization Detector (AID). When the ECD is employed, volatile
chlorinated compounds will be analyzed, as the ECD is very sensitive to electrophilic compounds such as
chlorinated organics. The AID is a more universal detector, responding to most compounds with ionization
potentials at or below 11.7eV. As such, it will respond to most aromatic compounds and many chlorinated
compounds of environmental interest.

1.2 At present, only vapor phase samples (i.e., soil gas samples, Tedlar gas sampling bags, and ambient
air samples) are being analyzed through the activation of the instrument's internal sampling pump. The Sentex
GC unit does have a syringe injection port, but this is not being employed for any ERT applications at present.
An optional purge and trap unit is available to determine purgeable organics in soil or water matrices. However,
this SOP does not cover that capability.

1.3 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as
required dependent on site conditions, equipment limitations or limitations imposed by the procedure or other
procedure limitations. In all instances, the ultimate procedures employed should be documented and associated
with the final report.

1.4 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 The initial step in Sentex Scentograph Gas Chromatograph sampling is to boot up the Toshiba T1100
computer. The computer runs the data acquisition program and stores all parameters and data. Begin by inserting
the program "A" and data "B" disks into the appropriate upper and lower disk drives of the computer. Next, turn
on the Sentex GC, and following the menu prompts, enter the GC parameters into the computer. Calibration
analysis is then performed and stored. Calibration standards can be run either in the field, or in the laboratory
prior to field sampling. In the latter case, a field calibration run must still be conducted to ensure that the lab
calibrations are valid. A Tedlar bag containing a standards mixture can be attached to the Sentex GC upper inlet
port at this point, or the internal calibration gas cylinder can be used.

2.2 Once calibration analysis is validated and stored, a Tedlar bag containing an unknown sample is
attached to the Sentex GC's lower sampling inlet port, and the bag valve is opened. By selecting Function #3, a
manual analysis can be run.

2.3 Once the sampling pump stops, the sample bag's valve is closed, and the entire bag is removed from
the inlet port and stored for future laboratory analysis.

2.4 While this procedure is standard for all Sentex GC sampling, actual operating conditions (i.e., detector
used, column packing material, oven temperature) will vary as required by the sample matrix encountered, and by
the physical and chemical nature of the samples analyzed. Appendix A lists the operational parameters menus for
entering and storing different GC conditions in the Sentex. New operating parameters are determined as new
target compounds are selected for analysis.

-------
3.0 INTERFERENCES

3.1 Since the Sentex units employ gas chromatography, target compounds are identified by retention time
indices (RTI). If the RTI of the sample peak(s) match the RTI of the standard peak(s), they are assumed to be
identical. If any non-target compounds has the same RTI, it can be misidentified as a target compound. This
problem occurs more frequently with the AID, since it will respond to any compound at or below 11.7eV. Often
soil gas samples will have very high (ppm) levels of C[ to C6 hydrocarbons as well as low (ppb) levels of target
compounds. The AID will respond to these hydrocarbons, whose signal often can "swamp" or obscure the signal
of the lower level target compounds. In this case, it is better to use the ECD. If this is not possible, a different
GC column (one able to separate the target compounds from the interference of the sample matrix) must be
utilized. Moisture within the Tedlar bags will yield interference peaks that can obscure the resolution of the
target compounds. It has not been determined whether it is the moisture itself, or contaminants in the moisture,
that yield these contamination peaks, but the effect is seen on both the AID and the ECD. Typically, when water
is found in the Tedlar bags the results of that bag's analysis is considered questionable. Typical ambient air
relative humidity seems to have no appreciable effect on the signal response.

4.0 APPARATUS AND MATERIALS

4.1 A Sentex model Scentograph GC can be configured for AID or ECD. Interfaced with the unit is a
Toshiba model T1100 lap top computer which runs the data acquisition program and stores all parameters and
data. The Sentex unit has an internal battery pack which is charged from a Power Sonic Corp. model PSC-12400,
(115 VAC to 12 VDC) charger. Attached to the T 1100 is a Hewlett-Packard Model 2225P Think Jet printer.

This produces hard copies of chromatograms and peak data information. No other equipment is required to
operate the Sentex Scentograph unit.

5.0 REAGENTS

5.1 The Sentex AID requires ultra high purity (99.99% or above) Argon as carrier gas. The ECD can use
either ultra high purity Argon or Helium (these can be ordered from Scott Gas, Matheson or any other reliable
vendor). Gas standards are purchased as certified mixtures from Scott Gas or Matheson, at fairly high
concentrations (i.e., 1-50 ppm). These concentrations are for subsequent dilution to various concentrations that
enable construction of a standard calibration curve. If the internal calibration cylinder is to be used a low level
standard, 0.5-1.0 ppm v should be used.

5.2 If liquid phase reagents are required to make vapor phase standards, they must also be of the highest
purity, such as Aldrich Gold Label or Supelco Environmental standards kits. If air is to be used for
sample/standards dilutions, it must also be ultra high purity gas.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 The vast majority of Sentex applications are for soil gas analysis. These soil gas samples are
collected and stored as outlined in ERT SOP #2149, Soil Gas Sampling.

7.0 PROCEDURE

7.1 All operational parameters are entered via the T1100 computer. This is accessed from the operations
Menu, Function #1, which appears once the Sentex unit is turned on (Appendix A). Once the parameters are
entered, a calibration run, Function #4, must be run. This is not a true calibration, since the Sentex calculates a
pseudo-concentration against only one concentration. The calibration function is used only when operating
parameters under Function #1 are changed. In all other cases, it is ignored. The run is typically aborted after the
first "junk" or noise peak is identified in the calibration run. Occasionally, a Tedlar bag or the internal calibration
gas cylinder can be sampled in the calibration mode but this would be for peak identification only and semi-
quantification purposes, since it is only a single point calibration.

-------
7.2 Calibration

7.2.1 The generation of calibration standard to be run in the field can be performed either in the field or
in the laboratory prior to entering the field. If the latter is done, field standards must still be run to ensure
calibration runs stored on the data disks are valid and close to standards run in the lab. Dilutions are
typically made from the certified gas standards cylinders using Hamilton 500, 1000 and 1500cc model
"Super syringes" and Tedlar sampling bags. Simple volumetric dilutions are made and the set of standards
are analyzed as if they were typical samples.

7.2.2 At least three (3) concentrations of each standard must be run. It is preferable that more standards
be run to establish the minimum ranges for the linear response of the Sentex detectors for each individual
target compound. In the laboratory, a Multi-Channel Mass Flow Control can be used to meter selected flow
rates from 2-4 separate compressed gas cylinders. A continuous flow of selected concentration of mixtures
can be established to either fill Tedlar bags for analysis or to create a flow-through-cell from which the
Sentex GC can sample. This has been used extensively to establish minimum and maximum detection
levels in an efficient and timely manner.

7.2.3 The Sentex GC software does perform a single point calibration on up to 16 compounds contained
in the internal calibration cylinder. This is adequate for most field screening needs. A linear calibration
curve will be developed on a daily basis while analyzing in the field. Consequently, three (3)
concentrations of each standard, per target compound will be analyzed by the Sentex GC as if they were
samples, and their GC response will be used to construct a linear regression curve.

7.3 Sample Analysis

7.3.1 The following are stepwise procedures for analyzing vapor phase samples via the Scentograph
Sentex GC:

7.3.1.1 Insert Disks "A" and "B" into upper and lower T1100 disk drives, respectively, and turn on
Sentex GC.

7.3.1.2 Follow menu prompts and input GC parameters as per Appendix A (Sentograph Operating
Parameter Menu).

7.3.1.3 Select Function #4 to run and store calibration analysis. A Tedlar bag of a standards mixture
may be attached to lower inlet.

7.3.1.4 Attach Tedlar bag with unknown sample to the lower sample inlet port and slide the bag valve
down to open.

7.3.1.5 Select Function #3 to run a manual analysis, at prompt enter sample name, press "ENTER" a
second time to inject.

7.3.1.6 Immediately after sampling pump stops, pull bag valve out to close, remove bag from inlet
port.

7.3.1.7 Sample and calibration analysis can be aborted by holding down the reset key on the GC
panel until "RETURN" prompt appears.

7.3.1.8 Any changes in operating parameters entered in Function #1 must be followed by a
calibration run prior to an analysis run.

7.4 Calculations

EMC-m-MDll-S

-------
7.4.1 A calibration curve of at least three (3) concentrations must be constructed for each target
compound. A straight line equation in the form of y = (m)(x) + b; (where: x = concentration, y = area
counts, m = slope and b = the intercept) is fit to the standards raw data. The (y), or the unknown
concentration for the sample, is determined from the above straight line equation. Non-linear data is
indicative of erroneous detector response, alternatively sample concentration can be calculated as below:

^ (standard conc.) x (sample area)

Sample Conc. = — ¦ : — —

(standard area)

7.4.2 The Sentex does perform a one point calibration for compounds present in the internal calibration
cylinder that were entered in the library. If the samples and library standard are in the linear range, this one
point calibration is considered valid for field screening purposes.

7.5 Health and Safety

7.5.1 When working with potentially hazardous materials follow USEPA, OSHA and corporate health
and safety guidelines. More specifically, analysis should be performed in a well ventilated room. When
liquid reagents are used to prepare standards etc., disposable protective gloves should be worn, and work
should be performed under a vented hood.

8.0 QUALITY CONTROL

8.1 The following QA/QC protocols are applicable:

8.1.1 A complete calibration curve must be run daily.

8.1.2 Replicates of a gas standard, in the mid-range of the calibration curve and preferably close to
sample results, should be run every ten (10) samples to ensure detector response is constant.

8.1.3 Two or three replicates for each sample and standard should be run. In terms of area count and
retention time values, these replicate responses should be within 10-20% of each other.

8.1.4 Matrix spikes, or spiking samples with known levels of standards, are not typically required as the
same Tedlar bag may be analyzed by other field instrumentation (i.e., Photovac, organic vapor analyzer
[OVA], etc.) and/or collected onto traps for GC/MS confirmation. If Tedlar bags are used to prepare
standards, the time of preparation should be noted.

8.1.5 During sample analysis, one of the standards should be periodically re-analyzed to ascertain if any
sample loss occurs in the bag over time since many compounds will degrade or permeate Tedlar sample
bags.

8.1.6 A performance evaluation sample (PE) is typically sent along with the sampling efforts to
determine if any loss or contamination occurs from transit or handling during sampling.

8.1.7 A trip blank, consisting of a Tedlar bag filled with zero air, is also sent along and is analyzed at the
end of the sampling run to determine if any contamination of the Tedlar bags occurred during transit.

9.0 METHOD PERFORMANCE
Information not available.

-------
10.0 REFERENCES

This section is not applicable to this SOP.

EME-m-MDll-5

-------
ERT Method

GC/MS ANALYSIS OF TEN AX/CMS CARTRIDGES AND SUMMA CANISTERS

1.0 SCOPE AND APPLICATION

1.1 The purpose of this Standard Operating Procedure (SOP) is to describe the analysis of air samples
collected on either Tenax/Carbonized Molecular Sieve (CMS) cartridges or in Summa canisters by Gas
Cromatography/Mass Spectrometry (GC/MS). These methods are applicable to Volatile Organic Compounds
(VOCs) that can be sampled by one or both of these media. The VOCs that can be routinely analyzed at the parts
per billion (ppb) level for both sample collection methods are listed in Table 1 (Appendix A).

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as
required, dependent on site conditions, equipment limitaitons or limitations imposed by the procedure or other
procedure limitations. In all instances, the ultimate procedures employed should be documented and associated
with the final report.

1.3 Mention of trade names or commercial products does not constitue U.S. EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 These methods involve thermal desorption of cartridges or canisters into a cryogenic trap which
cryofocuses the sample onto the head of the analytical column, followed by flash heating and separation by gas
chromatography. Following separation, compounds are analyzed by a positive ion electron impact mass
spectrometer.

2.2 Tenax/CMS Cartridges: Analysis of Tenax/CMS cartridges combines methods T01(1) and T02(1) for
the analysis of toxic organics in ambient air by placing two different sorbent media in the same sample cartridge.
The gas sample is drawn through a glass tube containing Tenax (a porous polymer of 2,6-diphenyl phenylene
oxide, the sorbent media for TOl) and Carbonized Molecular Sieve (CMS, the sorbent media for T02). Further
information on Tenax/CMS tube sampling may be found in ERT/REAC SOP #2052, Tenax Tube Sampling.

2.2 Summa Canisters: Alternatively, air samples can be collected in passivated, 6-liter, stainless steel
Summa canisters and analyzed in a procedure similar to the Tenax/CMS cartridges, according to method T014(1).
Information on Summa canister sampling may be found in ERT/REAC SOP #1704, Summa Canister Sampling.

3.0 INTERFERENCES AND POTENTIAL PROBLEMS

3.1 Structural isomers having coeluting retention times and identical mass spectra will interfere with this
method. The most common interference seen in these methods is between meta-xylene and para-xylene.

3.2 Excessive moisture in Tenax/CMS samples will cause the cryotrap to freeze, restricting sample flow
from the desorber oven and resulting in poor recoveries. In general, trapping efficiencies for components with
boiling points greater than water are more adversely affected than those with lower boiling points. If excessive
moisture is suspected, the CMS section of the cartridge should be removed prior to sample desorption. If this
step is taken, the lower boiling point compounds trapped by the CMS, such as chloromethane and vinyl chloride,
will not be seen in the analysis.

3.3 Canister samples suspected of having high concentrations of carbon dioxide, such as those collected
from landfills or fire plumes, cannot be directly analyzed because the carbon dioxide will collect and freeze the

SMCmiDE-ll

-------
cryotrap. This can be avoided by adsorbing the sample on a Tenax/CMS cartridge, which does not adsorb carbon
dioxide, but retains the organic contaminants.

4.0 APPARATUS AND MATERIALS

4.1	GC/MS: Gas chromatograph capable of sub-ambient temperature programming interfaced with a mass
spectrometric detector (Hewlett Packard 5996 GC/MS equipped with Series 1000E computer and RTE-6
software, or equivalent).

4.2	Thermal Desorber: Capable of a -170°C to 250°C temperature range, equipped with GC interface
(Tekmar 5010 GT automatic thermal desorption/cryofocusing unit, or equivalent).

4.3	Chromatographic Column: Capillary column, 30 m x 0.32 mm, 0.25 um film thickness, (J & W
Scientific, Inc. DB-624, or Restek, Inc. RTx-5, or equivalent).

4.4	Pre-column: Capillary fused silica column, 0.5 m x 0.32 mm, with column connector (Restek, Inc., or
equivalent).

4.5	Tenax/CMS Cartridges: 150 mg Tenax 35/50 mesh and 150 mg CMS packed into 6 x 120 mm
borosilicate glass tubing with Pyrex glass wool on each end and between each phase, provided in sealed glass
ampoules1-2-1 (Supelco, Inc., or equivalent).

4.6	Canisters: Passivated 6-liter Summa canisters (Andersen Samplers, Inc., or equivalent).

4.7	Mass Flow Controller: 0-100 ml/min, to maintain constant flow for measuring canister sample
volumes (Unit Instruments, Inc., UFC-1100 with URS 100 Readout Power Supply, or equivalent).

4.8	Stainless Steel Vacuum/Pressure Gauge: Capable of measuring 0 to 50 psi (Pennwalt Corp., Wallace
and Tiernan Division, Model series 1500 dial instrument, or equivalent).

4.9	Chromatographic Grade Stainless Steel Tubing and Stainless Steel Plumbing Fittings.

4.10	Stainless steel Cylinder Regulators (5): Two-stage pressure regulators for helium, zero grade air,
calibration standards, and surrogate standards cylinders.

4.11	Syringes: 2.5-10 ml, for injecting calibration and surrogate standards (Dynatech - Precision Sampling,
Inc., or equivalent).

4.12	9.5 mm septa (Supelco. Inc. Microsep F-174. or equivalentY

4.13	Culture tubes. Pvrex and Teflon tape: For preserving Tenax/CMS samples.

4.14	Rotameter: 0-100 ml/min (Matheson Gas Products, Inc., or equivalent).

4.15	Cotton Cloths: 9" by 9", for Tenax/CMS cartridge handling (Texwipe, Co., or equivalent).

4.16	Tweezers: For inserting and removing cartridge samples from thermal desorber.

4.17	O-rings: Viton, 6 mm i.d., for retaining Tenax/CMS cartridges in thermal desorber (Hewlett-Packard
part no. 5061-5867, or equivalent).

5.0 REAGENTS

EMC-m-MDE-2

-------
5.1 Calibration Standards: At approximately 1 ppmv with the balance as nitrogen (Matheson Gas Products,
Inc., or equivalent).

5.2 Bromochloromethane fBCA/D and p-Bromofluorobenzene fEFB): At approximately 1 ppmv in nitrogen
in a separate cylinder; both compounds used as surrogate standards, BFB also used for tuning GC/MS (Scott
Specialty Gases, Inc. or equivalent).

5.3 Perfluorotributvlamine fPFTBA): For tuning the mass spectrometer (Hewlett Packard, Inc., or
equivalent).

5.4 Liquid Nitrogen: For cryogenic cooling (SOS Gases, Inc., or equivalent).

5.5 Helium: Ultra high purity, used as carrier gas and as purge gas in the thermal desorber (Matheson Gas
Products, Inc., or equivalent).

5.6 Carbon Dioxide: Bone dry high pressure liquid, for chromatograph oven cooling (Matheson Gas
Products, Inc., or equivalent).

5.7 Compressed Air: Ultra-zero grade, for chromatograph oven door control (Matheson Gas Products, Inc.,
or equivalent).

5.8 Nitrogen: Ultra high purity, for pressurizing canister samples and purging canister analysis train lines
(Matheson Gas Products, Inc., or equivalent).

6.0 SAMPLE PRESERVATION, CONTAINERS, HANDLING, AND STORAGE

6.1 Tenax/CMS Cartridges

6.1.1 Samples collected on Tenax/CMS cartridges are placed in clean culture tubes and forwarded as
soon as possible to the laboratory. The culture tubes should be labeled and sealed with Teflon tape around
the cap. Samples must be accompanied by a chain of custody (COC) indicating sampling locations, sample
numbers, date collected, sample matrix, and sample volumes. The COC should agree with the information
on the culture tube labels, and discrepancies must be noted on the COC at the time of receipt by the
laboratory. In addition, any looseness of culture tube caps or any obvious physical damage or
contamination (e.g., broken cartridges, condensate in the culture tubes, or discoloration of the Tenax bed),
must also be recorded on the COC.

6.1.2 Once samples have arrived at the laboratory, they should be refrigerated until they are analyzed.
Analysis of Tenax/CMS samples must be completed within the fourteen (14) day holding time specified by
TOl and T02. The holding time begins when the sample is first drawn onto the tube, not when the sample
is received by the laboratory.

6.2 Summa Canisters

6.2.1 Samples collected in canisters should arrive at the laboratory with the canister valve closed and the
sampling port capped. An identification tag should be attached, and should agree with the information on
the COC.

6.2.2 One of the advantages of canister samples is that they do not need any refrigeration or special
handling until they are analyzed. Method TOM does not specify a holding time for canister samples.

7.0 PROCEDURES

EMC-m-MDE-S

-------
7.1 Daily GC/MS Tuning

7.1.1 At the beginning of each day, the GC/MS system must be tuned to verify that acceptable
performance criteria can be achieved. The mass spectrometer should first be automatically or manually
tuned on perfluorotributylamine (PFTBA). PFTBA tuning is done to demonstrate that the instrument is
operating properly and, upon analysis of p-bromofluorobenzene (BFB), will give a spectrum that meets the
abundance criteria listed in EPA Method 624 (Table 2, Appendix A).

7.1.2 After PFTBA tuning, BFB is analyzed to check GC column performance and is used as the
GC/MS performance standard. This performance test must be passed before any samples, standards, or
blanks are analyzed, and must be repeated every twelve hours of continuous operation. A background
correction mass spectrum from the performance test must satisfy the criteria set forth in U.S. EPA Method
624. If the criteria are not met, the analyst must re-tune the mass spectrometer and repeat the test until all
criteria are met.

7.2 GC/MS Calibration

7.2.1 Initial Calibration: Before any analysis, the GC/MS is initially calibrated using standards
contained in pressurized cylinders at approximately 1 ppmv in nitrogen. A list of the target compounds in
the calibration standards is given in Table 3 (Appendix A), along with the ions used for quantitation. A
multipoint calibration is created by injecting three to five different volumes into the thermal desorber and
analyzing them in the GC/MS. Typical volumes range from 1-10 ml, corresponding to concentrations of
100 ppb to 1 ppm. Following analysis of all calibration points, a calibration report is prepared listing the
average response factors and their Relative Standard Deviation (RSD), which must be <25% for each
compound. For each compound in the calibration, the retention times and relative abundances of selected
ions are stored on the hard disk of the GC/MS computer to be used for compound identification.

7.2.2 Continuing Calibration: For each day of analysis, the GC/MS calibration is checked before sample
analysis with a daily standard, usually at the 1 ppmv concentration. The continuing calibration is only
acceptable when all compound abundances in the daily standard are + 25% of the average response factor of
the calibration curve.

7.3 Analysis Conditions
7.3.1 Sample Desorption:

7.3.1.1 All samples are prepared for GC/MS analysis by using a thermal desorption/cryogenic
trapping unit. The unit is equipped with a 0.25" by 7" oven chamber for desorbing samples, an internal
cryogenic trap (C-l) consisting of a 0.125" stainless tube filled with Pyrex glass beads, an eight port
switching valve, and an external cryogenic trap (C-2) located just above the head of the pre-column
(Figure 3, Appendix B). A 60" silcosteel transfer line connects the two cryotraps. The pre-column
connects C-2 with the analytical column, and is installed to prevent the column from being exposed to
the wide temperature swings that occur at the trap. After surrogates have been introduced on a sample
cartridge, the sample is then thermally desorbed by heating the oven while purging with helium.

7.3.1.2 The helium transfers the VOCs from the cartridge to the C-l trap. The sample is then passed
through a heated transfer line and cryofocused at C-2, at the front of the pre-column, where it is injected
by flash heating. Following is a summary of typical desorber conditions:

Desorb Temp :240° C

Desorb Time :10.0 minutes (Tenax/CMS only)

Cryotrap-1 (C-l) Temperature :-160°C

EMC-m-MDE-41

-------
Cryotrap-1 Desorb Temperature	:250°C

Transfer (C-l to C-2)	:3.5 minutes

Cryotrap-2 (C-2) Temperature :-160°C
Cryotrap-2 Desorb Temperature	: 250°C

Cryotrap-2 Desorb Time	:2.0 minutes

7.3.2 Chromatographic Conditions

7.3.2.1 The chromatographic conditions used are those listed below, as modified from U.S. EPA
Method 524.2(3):

Initial Temperature	5.0°C

Initial Time	3.0 minutes

Ramp Rate	8.0°C/min
Final Temperature 185.0°C

Run Time	25.5 minutes

An example of this is found in Figure 1 (Appendix B), which includes target and surrogate compounds
in elution order, and Figure 2 (Appendix B), which is the corresponding chromatogram.

7.4 Tenax/CMS Cartridge Analysis: All Tenax/CMS samples should be handled only with cotton cloth or
gloves and tweezers to avoid contamination. Analysis of a cartridge sample follows either one of the procedures
specified in sections 7.4.1 or 7.4.2:

7.4.1 Cartridge spike outside Tekmar:

7.4.1.1	An o-ring is put on the Tenax side of the cartridge and the cartridge is secured tightly in one
end of a "T" with a Swagelok fitting. The other end of the "T" is connected to a source of ultra zero air
at a flow rate of 20 ml/min. The side port of the "T" consists of a septum cap.

7.4.1.2	While the cartridge is being purged, a 1 ppm mixture of the surrogate standards,
bromochloromethane (BCM) and p-bromofluorobenzene (BFB), are spiked onto the sample by injecting
10 ml onto the Tenax side of each cartridge.

7.4.1.3	After the surrogates have been introduced on the tube, the first cryogenic trap (C-l) on the
Tekmar is cooled with liquid nitrogen to -160°C. At this time the cartridge is removed from the "T", the
0-ring is moved to the CMS side, and the cartridge is inserted into the desorb oven with the Tenax side in
first.

7.4.1.4	The thermal desorber is stepped to the desorb cycle, allowing the surrogates to desorb from
the Tenax and CMS with the sample and flow directly to C-l.

7.4.1.5	At the end of desorb, the desorber is stepped again, cooling the C-2 cryotrap. When C-2 is
cooled, the desorber will automatically step to the transfer step, and the sample is cryofocused at C-2.

7.4.1.6	When transfer is complete, the sample will be injected by automatic flash heating of C-2. The
analysis then follows the chromatographic conditions in Section 7.3.2.

7.4.2 Cartridge spike inside Tekmar:

7.4.2.1 Place the cartridge in the desorb oven with the CMS side in first. Start the thermal desorber,
going into the purge step. Set the flow at 20 ml/min.

EMC-m-MDE-5

-------
7.4.2.2 During the purge step a 1 ppm mixture of the surrogate standards bromochloromethane
(BCM) and p-bromofluorobenzene (BFB) are spiked onto samples by injecting 10 ml onto the Tenax side
of each cartridge. During spiking, the purge flow should be lowered to 5 ml/min so that the combined
pressure of the flow and the injection does not exceed 20 ml/min.

7.4.2.3 After the surrogates have been introduced on the tube and the purge cycle has been
completed, the first cryogenic trap (C-l) is cooled with liquid nitrogen to -160°C. At this time the
cartridge is removed, turned around, and reinserted into the desorb oven.

7.4.2.4 Once the tube has been inverted and C-l has been cooled, the thermal desorber is stepped to
the desorb cycle, allowing the surrogates to desorb from the Tenax and CMS with the sample.

7.4.2.5 At the end of desorb, the desorber is stepped again, cooling the C-2 cryotrap. When C-2 is
cooled, the desorber will automatically step to the transfer step, and the sample is cryofocused at C-2.

7.4.2.6 When transfer is complete, the sample will be injected by automatic flash heating of C-2. The
analysis then follows the chromatographic conditions in Section 7.3.2.

7.5 Canister Sample Analysis: Canister samples are usually collected at or near atmospheric pressure. To
allow the sample to flow from the canister, the canister pressure must be raised above one atmosphere with ultra
high purity nitrogen. Normally, sample pressure is doubled for ease of calculation.

7.5.1 Before attaching the canister sample, purge the pressurizing line of the apparatus with nitrogen as
indicated in Figure 4 (Appendix B). Attach the canister sample to the pressurizing apparatus and close the
regulator to nitrogen cylinder. Open the canister valve, allow the pressure to equilibrate, and record the
initial pressure (P;) in the analysis log.

7.5.2 Open the cylinder regulator slowly so the pressure gradually increases. When the canister pressure
reaches twice the P;, close the regulator, then close the canister valve, and record the final pressure (Pf) in
the analysis log.

7.5.3 Attach the canister to the analysis train at the desorb oven as shown in Figure 5 (Appenidx B).

With the mass flow controller valve closed, open the canister valve to allow the sample to come to
equilibrilium in the sample train.

7.5.4 Start the thermal desorber, and step through the purge step to the step that cools C-l. When the
desorber steps to desorb, lower the flow to zero. Open the mass flow controller valve and begin timing
sample flow. The controller flow rate and the desorb time needed for the sample to flow are calculated
based on the sample volume required and the equations in Section 8.0.

7.5.5 Close the canister valve after the precise amount of desorb time has elapsed. Close the mass flow
controller valve after the analysis train pressure reaches zero.

7.5.6 Replace the desorb oven cover attached to the canister analysis train with the desorb oven cover
used for Tenax/CMS samples. Raise the helium flow up to 5 ml/min, and inject 10 ml of the surrogate
standards while still in desorb. At the end of desorb, follow the analysis procedure in Section 7.4, steps 5
and 6.

7.6 Analysis of Canister Samples Adsorbed on Cartridges: Canister samples are adsorbed on Tenax/CMS
cartridges when the samples are suspected of containing high levels of carbon dioxide or other permanent gases
that would freeze the cryotraps.

7.6.1 Follow the procedure in Section 7.5, steps 1 and 2, for the pressurization of the canister sample.

-------
7.6.2 Place a Tenax/CMS cartridge in the desorb oven with the CMS side in first. Attach the canister to
the analysis train as shown in Figure 6 (Appendix B).

7.6.3 With the mass flow controller valve closed, open the canister valve to allow the sample to come to
equilibrilium in the sample train.

7.6.4 Start the thermal desorber into the purge step. Lower the purge flow to zero. Open the mass flow
controller valve and let the desired sample volume adsorb onto the cartridge.

7.6.5 After the sample has been adsorbed, close the canister and mass flow controller valves, replace the
desorb oven cover, and inject 10 ml of the surrogate standards while still in the purge step.

7.6.6 After surrogates have been spiked on the cartridge, step the desorber to cool C-l, and follow the
Tenax/CMS analysis procedure in Section 7.4, steps 3 through 6.

7.7 Calculations

7.7.1 Concentrations of target compounds are calculated by the GC/MS computer software. To
establish concentration limits that have been demonstrated to be measured, limits of quantitation (LOQ) are
calculated for each sample. LOQs are calculated by the following:

_ Lowest Calibration Volume x Standard Concentration

Sample Volume

where the sample volume is in milliliters. LOQ varies inversely with the sample volume, and can range
from 500 ppb for a minimal sample volume of 5 ml, to as low as 0.1 ppb for a 25 L sample.

7.7.2 When the canister pressure is increased, the dilution factor (DF) is calculated by the following:

DF=—-

where: Pf = Canister pressure (psi) after pressurization, and
P; = Canister pressure (psi) before pressurization

7.7.3 The following equation calculates the desorb time (minutes) necessary for a given sample volume
and flow rate (in ml/minute):

„ , m. Sample Volume x DF

Desorb Time = —

Flow Ra te

where the sample volume is in milliliters, the Dilution Factor (DF) is usually 2, and the flow rate is in
ml/min. For example, with a DF of 2 and a flow rate of 40 ml/min, it would take 5 minutes to desorb 100
ml of unpressurized sample (equivalent to 200 ml of prssurized sample). For larger sample volumes, it may
be necessary to set the thermal desorber for desorb times longer than 10 minutes to desorb the sample and
allow time for surrogate spiking.

EMC-m-MDE-17

-------
7.8 Health and Safety

7.8.1 When working with potentially hazardous materials, follow U.S. EPA, OSHA, and laboratory
health and safety practices.

8.0 QUALITY CONTROL

8.1 Two criteria must be satisfied to verify the identification of a target compound:

8.1.1 Retention Time - A sample component's retention time (RT) must be within + 0.50 minutes of the
RT of the standard component. For reference, the standard must be run on the same day as the sample.

8.1.2 Spectra - (1) All ions present in the standard mass spectra at a relative intensity greater than 10%
(where the most abundant ion in the spectrum equals 100%) must be present in the sample spectrum. (2)
The relative intensities of the ions specified above must agree within + 20% between the sample and the
reference spectra.

8.2 The GC/MS is tuned daily for PFTBA to meet the abundance criteria for BFB as listed in U.S. EPA
Method 624(4). The tune is adjusted when necessary.

8.3 An acceptable three-to-five point calibration of the standards must be run before the analysis. A
calibration is acceptable if the Relative Standard Deviation is <25% of the average response factors for each
compound. Samples are quantitated on the average response factors of the calibration range.

8.4 A continuing calibration standard must be run for each day of analysis. Standards are checked against
the average response factors of the calibration range; if any standard component varies by >25% of the average
response factor, re-run the continuing calibration. If the second continuing calibration has components varying by
>25% of the average response factor, run a new initial calibration.

8.5 A surrogate standard of BFB and BCM is added to all standards and samples. Percent recoveries for
samples are calculated against daily standards. Recoveries should be within 70% to 130% for BFB and BCM.

8.6 Method blanks are analyzed after a standard analysis to check for carryover, and are also necessary
after analyzing samples with high levels of contamination. For Tenax/CMS samples, a method blank is an
analysis of a new cartridge spiked with surrogates. For canister samples, a method blank is flowing the same
volume of nitrogen as in the samples into the desorber, followed by surrogate spiking. For canister samples
adsorbed onto cartridges, a method blank is a volume of nitrogen equal to the sample volumes adsorbed on a
cartridge, followed by surrogate spiking and analysis.

8.7 Ten percent (10%) of all samples received are to be analyzed in replicate.

8.8 Performance Evaluation (PE) canisters containing known concentrations of VOCs should be analyzed
at least once per analysis for canister samples. The analytical procedure is the same for canister samples.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. "Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air", U.S. EPA
600/4-84-041, Methods TOl and T02.

-------
2.	"Standard Operating Procedure for Preparation of Clean Tenax Cartridges" EMSL/RTP-SOP-EMD-013
(USEPA).

3.	"Methods for the Determination of Organic Compounds in Drinking Water", EPA 600/4-88/039, Method
524.2.

4	40CFR136, Appendix A, Methods for Organic Chemical Analysis of Municipal and Industrial

Wastewater, Method 624 - Purgeables.

-------
APPENDIX A
TABLES
SOP # 1705
AUGUST, 1991

IFMEMDSMfflEE-lKD

-------
Table 1. Compounds Analyzed in Tenax/CMS Cartridges
or Summa Canisters

acetone

C2-C8 alcohols
C4-C12 alkanes
C4-C12 alkenes
C3-C6 alkylbenzenes
benzene

bromochloromethane
bromodichloromethane
p-bromofluorbenzene
2-butanone (MEK)
carbon tetrachloride
chlorobenzene
chloroethane
chloromethane
chlorotoluene
C5-C12 cycloalkanes
dibromomethane
1,1 -dichloroethane
1,2-dichloroethane

1,1 -dichloroethane
C4-C12 dienes
ethylbenzene

4-methyl-2-pentanone (MIBK)

methylene chloride

napthalene

styrene

CIO terpenes

1,1,2,2-tetrachloroethane

tetrachloroethene (PCE)

toluene

trans-1,2-dichloroethene
1,1,1 -trichloroethane
1,1,2-trichloroethane
trichloroethene (TCE)
trichlorofluoromethane
trichloromethane
vinyl chloride
xylenes

ffMKT-m-«Bi2-nn

-------
Table 2. GC/MS Performance Criteria for p-Bromofluorobenzene
(EPA Method 624)

m/z	Ion Abundance Criteria

50	15-40% of mass 95

75	30-60% of mass 95

95	Base Peak, 100% relative abundance

96	5-9% of mass 95

173	Less than 2% of mass 174

174	Greater than 50% of mass 95

175	5-9% of mass 174

176	95-101% of mass 174

177	5-9% of mass 176

BMEMDSMfflEE-llZ

-------
Table 3. Target Compounds Analyzed for Calibration

Compound	Quantitation Ions

benzene

bromodichloromethane
carbon tetrachloride
chloroethane
chloromethane

dibromomethane	174

1,1 -dichloroethane
1,2-dichloroethane
1,1 -dichloroethene

trans-1,2-dichloroethene	61

ethylbenzene

m-ethyltoluene

methylene chloride

styrene

1,1,2,2-tetrachloroethane	83

tetrachloroethene

1,1,1 -trichloroethane

1,1,2-trichloroethane

trichloroethene

trichlorofluoromethane

trichloromethane

toluene

vinyl chloride

m-xylene

o-xylene

78

83

117

64

50

63

62

61

91

120

84

104

166

97

97

130

101

83

92

62

91

91

BMEMDSMfflEE-lIB

-------
APPENDIX B
FIGURES
SOP# 1705
AUGUST, 1991

BMEMDSMfflEE-M

-------
Figure 1. Quant Report

Operator ID: BOB
Output File: A83874::D4
Data File: >83874::D4
Name: DAILY STANDARD
Misc: + 10 ml Surrogates

ID File: ID_SCT::D3

Title: GC/MS ANALYSIS OF TENAX/CMS CARTRIDGES (TO-1 & TO-2)
Last Calibration: 910411 14:17

Compound

q



R.T.



Scan#



Area



Cone.



Units

1)	#CHL OROMETHANE

74

2)	#VINYL CHLORIDE

1

.16



6



13555



664.87



PPR

1.25



16



13287



945.36



PPR

88

3) #CHLOROETHANE

1.55



47



6583



881.16



PPR

93

4) #TRICHL OROFLUOROMETHANE

1.85



79



30141



814.42



PPR

95

5) #1,1 -DICHL OROETHENE

QQ



2.27



123



24379



825.44



PPR

OO

6) #METHYLENE CHLRODE

2.56



154



21909



803.94



PPR

93

7) #TRANS-l,2-DICHLOROETHENE

3.15



216



25986



935.12



PPR

88

8)	#1,1-DICHL OROETHANE

95

9)	#BROMOCHLOROMETHANE

99

10)	#TRICHLOROMETHANE



3.50



253



29558



826.53



PPR



4.49



358



60788



1767.00



PPR

4.55



364



35369



880.60



PPR

92

11)	# 1,1,1 -TRICHLOROETHANE

90

12)	#1,2-DICHL OROETHANE



5.24



432



32525



887.10



PPR

5.39



453



28951



914.97



PPR

99

13)	CARBON TETRACHLORIDE

94

14)	#BENZENE



5.67



482



25779



881.95



PPR

5.67



482



38009



775.10



PPR

93

15) #TRICHLOROETHYLENE

6.77



598



23850



873.51



PPR

94

16)	#DIBROMOMETHANE

65

17)	#BROMODICHLOROMETHANE

QQ



6.79



601



29591



923.39



PPR



6.98



620



35690



928.61



PPR

o y

18) #TOLUENE

8.63



795



52178



888.48



PPR

87

19) #l,l,2-TRICHLOROETHANE

QQ



8.80



813



21806



892.69



PPR

o y

20)	#TETRACHLOROETHYLENE

95

21)	#ETHYLBENZENE



9.76



914



34262



861.90



PPR

11.14



1060



72692



925.43



PPR

82

22)	#META-XYLENE

92

23)	#STYRENE



11.34



1081



59722



939.36



PPR

11.88



1138



39679



1004.09



PPR

89

24) #ORTHO-XYLENE

11.93



1143



64382



1008.13



PPR

79

BMEMDSMfflEE-llS

Quant Rev: 6	Quant Tme: 910416 14:30

Injected at: 910416 14:09
Dilution Factor: 1.00000

-------
25)	#1,1,2,2-TETRACHLOROETHANE

26)	#p-BROMOFLUOROBENZENE

98

27)	#META-ETHYLTOLUENE
# Compound uses FSTD

12.41	1194	53557	795.33	PPR 92

12.69	1223	37795	1142.98	PPR

13.61	1320	21354	979.34	PPR 93

ffMKT-m-«B12-n®

-------
Figure 2. Total Ion Chromatogram

-------
Figure 3. Tekmar Model 5010

BMEMDSMfflEE-llffi

-------
Figure 4. Summa Canister Sample Dilution Line

ffMKT-m-^BE-ll®

-------
Figure 5. Summa Canister Analysis Train

-------
Figure 6. Canister Sample Absorbed onto Tenax

-------
ERT Method

PHOTOIONIZATION DETECTOR fPIDI HNU

1.0 SCOPE AND APPLICATION

1.1 The purpose of this Standard Operating Procedure (SOP) is to describe the procedure for using a photoionization
detector (PID). The PID is a portable, nonspecific, vapor/gas detector employing the principle of photoionization to detect a
variety of chemical compounds, both organic and inorganic, in air. This procedure is applicable to the HNU PI-101, HNU ISPI-
101, and HW-101 used for air monitoring.

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required,
dependent on site conditions, equipment limitations or limitations imposed by the procedure. In all instances, the ultimate
procedures employed should be documented and associated with the final report.

1.3 Mention of trade names or commercial products does not constitute U.S. EPA endorsement or recommendation for use.
2.0 SUMMARY OF METHOD

2.1 The PID is a useful general survey instrument at hazardous waste sites. A PID is capable of detecting and measuring
real-time concentrations of many organic and inorganic vapors in air. A PID is similar to a flame ionization detector (FID) in
application; however, the PID has somewhat broader capabilities in that it can detect certain inorganic vapors. Conversely, the PID
is unable to respond to certain low molecular weight hydrocarbons, such as methane and ethane, that are readily detected by FID
instruments.

2.2 The PID employs the principle of photoionization. The analyzer will respond to most vapors that have an ionization
potential less than or equal to that supplied by the ionization source, which is an ultraviolet (UV) lamp. Photoionization occurs
when an atom or molecule absorbs a photon of sufficient energy to release an electron and form a positive ion. This will occur
when the ionization potential of the molecule in electron volts (eV) is less than the energy of the photon. The sensor is housed in a
probe and consists of a sealed ultraviolet light source that emits photons with an energy level high enough to ionize many trace
organics, but not enough to ionize the major components of air (e.g., nitrogen, oxygen, carbon dioxide). The ionization chamber
exposed to the light source contains a pair of electrodes, one a bias electrode, and the second the collector electrode. When a
positive potential is applied to the bias electrode, an electro-magnetic field is created in the chamber. Ions formed by the
adsorption of photons are driven to the collector electrode. The current produced is then measured and the corresponding
concentration displayed on a meter, directly, in units above background. Several probes are available for the PID, each having a
different eV lamp and a different ionization potential. The selection of the appropriate probe is essential in obtaining useful field
results. Though it can be calibrated to a particular compound, the instrument cannot distinguish between detectable compounds in
a mixture of gases and, therefore, indicates an integrated response to the mixture.

2.3 Three probes, each containing a different UV light source, are available for use with the HNU. Energies are 9.5, 10.2,
and 11.7 eV. All three detect many aromatic and large molecular hydrocarbons. The 10.2 eV and 11.7 eV probes, in addition,
detect some smaller organic molecules and some halogenated hydrocarbons. The 10.2 eV probe is the most useful for
environmental response work, as it is more durable than the 11.7 eV probe and detects more compounds than the 9.5 eV probe.

2.4 Gases with ionization potentials near to or less than that of the lamp will be ionized. These gases will thus be detected
and measured by the analyzer. Gases with ionization potentials higher than that of the lamp will not be detected. Ionization
potentials for various atoms, molecules, and compounds are given in Table 1 (Appendix A). The ionization potential of the major
components of air, oxygen, nitrogen, and carbon dioxide, range from about 12.0 eV to about 15.6 eV and are not ionized by any of
the three lamps.

2.5 Table 2 (Appendix A) illustrates ionization sensitivities for a large number of individual species when exposed to
photons from a 10.2 eV lamp. Applications of each probe are included in Table 3 (Appendix A).

IMCmiDB-ll

-------
2.6 While the primary use of the HNU is as a quantitative instrument, it can also be used to detect certain contaminants, or
at least to narrow the range of possibilities. Noting instrument response to a contaminant source with different probes can
eliminate some contaminants from consideration. For instance, a compound's ionization potential may be such that the 9.5 eV
probe produces no response, but the 10.2 eV and 11.7 eV probes do elicit a response.

3.0 INTERFERENCES

3.1 PIP Instrument Limitations

3.1.1 The PID is a nonspecific total vapor detector. It cannot be used to identify unknown substances; it can only roughly
quantify them.

3.1.2 The PID must be calibrated to a specific compound.

3.1.3 The PID does not respond to certain low molecular weight hydrocarbons, such as methane and ethane. In addition,
the HNU does not detect a compound if the probe has a lower energy than the compound's ionization potential.

3.1.4 Certain toxic gases and vapors, such as carbon tetrachloride and hydrogen cyanide, have high ionization potentials
and cannot be detected with a PID.

3.1.5 Certain models of PID instruments are not intrinsically safe. The HNU PI-101 and HW-101 are not designed for
use in potentially flammable or combustible atmospheres. Therefore, these models should be used in conjunction with a
Combustible Gas Indicator. The ISPI-101 is intrinsically safe, however.

3.1.6 Electrical power lines or power transformers may cause interference with the instrument and thus cause
measurement errors. Static voltage sources such as power lines, radio transmissions, or transformers may also interfere with
measurements.

3.1.7 High winds and high humidity will affect measurement readings. The HNU may become unusable under foggy or
humid conditions. An indication of this is the needle dropping below 0, or a slow constant climb on the read-out dial.

3.1.8 The lamp window must be periodically cleaned to ensure ionization of the new compounds by the probe (i.e., new
air contaminants).

3.1.9 The HNU measures concentrations from about 1-2000 ppm, although the response is not linear over this entire
range. For example, if calibrated to benzene, the response is linear from about 0-600 units above background. This means
the HNU reads a true concentration of benzene only between 0 and 600. Greater concentrations are detected at a lower level
than the true value.

3.1.10 This instrument is not to be exposed to precipitation (rain). The units are not designed for this service.

3.1.11 Do not use this instrument for head space analysis where liquids can inadvertently be drawn into the probe.

3.2 Regulatory Limitations

3.2.1 Transport of calibration gas cylinders by passenger and cargo aircraft must comply with International Air Transport
Association (IATA) Dangerous Goods Regulations or the U.S. Code of Federal Regulations, 49 CFR Parts 100-177. A
typical calibration gas included with a PID is isobutylene. It is classified as a non-flammable gas, UN #1556 and the proper
shipping name is Compressed Gas. It must be shipped by cargo aircraft only.

4.0 APPARATUS AND MATERIALS

4.1 The following equipment is required for PID operation:

EMC-m-MDB-2

-------
4.1.1	PID(HNU).

4.1.2	Operating manual.

4.1.3	Probes: 9.5 eV, 10.2 eV, or 11.7 eV.

4.1.4	Battery charger for PID.

4.1.5	Spare batteries.

4.1.6	Jeweler's scrwdriver for adjustments.

4.1.7	Tygon tubing.

4.1.8	NBS traceable calibration gas.

4.1.9	"T" valve for calibration.

4.1.10	Field Data Sheets/Site Logbook.

4.1.11	Intake assembly extension.

4.1.12	Strap for carrying PID.

4.1.13	Teflon tubing for downhole measurements.

4.1.14	Plastic bags for protecting the PID from moisture and dirt.

Note: Battery charge status - This instrument may be kept on continuous charge without battery damage.
5.0 REAGENTS

5.1	Isobutvlene Standards: For calibration.

5.2	Benzene Reference Standard.

5.3	Methanol: For cleaning ionization chamber (GC grade).

5.4	Mild Soap: Solution for cleaning unit surfaces.

5.5	Specific Gas Standards: When calibrating to a specific compound.

5.6	Light Source Cleaning Compound: Cat No. PA101534-A1 (For use only with 9.5 and 10.2 lamps).

5.7	The HNU is calibrated in accordance with the operations manual using isobutylene as the calibration standard. The
operations manual may also be referred to for alternate calibration to a specific compound.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

This section is not applicable to this SOP.

7.0 PROCEDURES

EMC-m-MDB-3

-------
7.1 Preparation

7.1.1 Check out and ensure the proper operation of the PID, as appropriate, using the equipment checklist provided in
Sections 5.0 and 6.0 and the steps listed below.

7.2 Start-up Procedures

7.2.1 Allow the temperature of the unit to equilibrate to its surrounding. This should take about five (5) minutes.

7.2.2 Attach the probe to the read-out unit. Match the alignment key, then twist the connector clockwise until a distinct
locking is felt. Make sure the microswitch (red button) is depressed by the locking ring.

7.2.3 Turn the FUNCTION switch to the battery check position. Check to ensure that the indicator reads within or
beyond the green battery arc on the scale plate. If the indicator is below the green arc, or if the red LED comes on, the
battery must be charged prior to using.

7.2.4 To zero the instrument, turn the FUNCTION switch to the STANDBY position and rotate the ZERO
POTENTIOMETER until the meter reads zero. Wait 15-20 seconds to ensure that the zero adjustment is stable; if not, then
readjust.

7.2.5 Check to see that the SPAN POTENTIOMETER is set at the appropriate setting for the probe being used (i.e., 9.8
for the 10.2 eV probe, 5.0 for the 11.7 eV probe, 1 for the 9.5 eV probe. Note: The setting may vary based on the intensity
of the light source).

7.2.6 Set the FUNCTION switch to the desired range (i.e., 0-20, 0-200, 0-2000).

7.2.7 Listen for the fan operation to verify fan function.

7.2.8 Look for ultraviolet light source in the probe to verify function. Do not look at light source from closer than six (6)
inches with unprotected eyes, observe only briefly.

7.2.9 Check instrument with an organic point source, such as a magic marker, prior to survey to verify instrument
function.

7.2.10 Routinely during the day, verify the useful battery life by turning the function switch to BATT and schedule the
instrument's use accordingly.

7.3 Field Operation
7.3.1 Field Calibration

7.3.1.1 F ollow the start-up procedure in Section 7.2.

7.3.1.2 Set the FUNCTION switch to the range setting which includes the concentration of the calibration gas.

7.3.1.3 Attach a regulator to a disposable cylinder of calibration gas. Connect the regulator to the probe of the HNU
with a piece of clean tygon tubing. Open the valve on the regulator.

7.3.1.4 After 15 seconds, the meter reading should equal the response value as indicated on the calibration gas cylinder
used. If the reading is within +15% of the response value, then the instrument can be field calibrated to the response value
using the external SPAN ADJUSTMENT control. The SPAN ADJUSTMENT control should be adjusted to a lower
setting until the correct reading has been obtained. The lower the number on the SPAN ADJUSTMENT conrol, the

-------
greater the instrument sensitivity. If the SPAN ADJUSTMENT control has to be adjusted below a setting of 4.00, the unit
should be red-tagged and returned for repairs.

7.3.1.5 If the meter reading is greater than ±15% of the response value of the calibration gas used, then the instrument
should be red-tagged and returned for re-calibration.

7.3.1.6 Record the following information in the site logbook: the instrument ID number (U.S. EPA decal or serial
number if the instrument is a rental), the initial and final span settings, the date and time, concentration and type of
calibration gas used, and the name of the person who field calibrated the instrument.

7.3.1.7 If the PID does not start up, check out, or calibrate properly, the instrument should not be used. Under no
circumstances is work requiring air monitoring with a PID to be done without a proper functioning instrument.

7.3.1.8 In some field applications, with the exception of the probe's inlet and exhaust, the PID should be wrapped in
clear plastic to prevent it from becoming contaminated and to prevent water from getting inside in the event of
precipitation.

7.3.2 Operation

7.3.2.1 All readings are to be recorded in the site logbook. Readings should be recorded, following background
readings, as "units above background," not ppm.

7.3.2.2 As with any field instrument, accurate results depend on the operator being completely familiar with the
operator's manual. The instructions in the operating manual should be followed explicitly in order to obtain accurate
results.

7.3.2.3 Position the probe assembly close to the area to be monitored because the low sampling rate allows for only
very localized readings. Under no circumstances should the probe tip assembly be immersed in fluid.

7.3.2.4 While taking care to prevent the PID from being exposed to excessive moisture, dirt, or contamination, monitor
the work activity as specified in the site Health and Safety Plan. The PID survey should be conducted at a slow to
moderate rate of speed and the intake assembly (the probe) slowly swept from side to side. There is a three to five second
delay in read-out depending upon the instruments sensitivity to the contaminant.

7.3.2.5 During drilling activities, PID monitoring is performed at regular intervals downhole, at the headspace, and in
the breathing zone. In addition, where elevated organic vapor levels are encountered, monitoring may be performed in the
breathing zone during actual drilling. When the activity being monitored is other than drilling, readings should emphasize
breathing zone conditions.

7.3.2.6 When the activity is completed or at the end of the day, carefully clean the outside of the PID with a damp
disposable towel to remove any visible dirt.

7.4 Post Operation

7.4.1 Turn FUNCTION Switch to OFF.

7.4.2 Return the PID to a secure area and check the calibration (Section 7.3.1.) before charging. Connect the instrument
to charger and plug in the charger. The probe must be connected to the readout unit to charge the HNU.

7.4.3 Complete logbook entries, verifying the accuracy of entries and signing/initialing all pages. Following completion
of a series of "0" readings, verify the instrument is working as in Section 7.3.1.

7.4.4 Check the equipment, repair or replace damaged equipment, and charge the batteries.

EMC-m-MDB-5

-------
7.5 Equipment Calibration

7.5.1 Follow the start-up procedure in Section 7.2.

7.5.2 Set the FUNCTION switch to the range setting which includes the concentration of the calibration gas.

7.5.3 Attach a regulator to a cylinder of calibration gas. Connect the regulator to the probe of the NHU with a piece of
clean tygon tubing. Open the valve on the regulator.

7.5.4 After 15 seconds, the meter reading should equal the response value as indicated on the calibration gas cylinder
used. If the reading is greater than +15% of the actual concentration, an internal calibration is necessary. Unlock the SPAN
POTENTIOMETER dial before adjusting it. Adjust the SPAN POTENTIOMETER to the span setting recommended for the
probe being used (i.e., 9.8 for the 10.2 eV probe, 5.0 for the 11.7 eV probe, 1 for the 9.5 eV probe). To calibrate the
instrument, unscrew the bottom support screw and lift the instrument out of the case. Locate and adjust the trimpot "R-32"
(near the top of the printed circuit board) by inserting a small screwdriver and gently turning. When the instrument gives the
correct reading for the calibration gas being used, reassemble it.

7.5.5 Record the following information in the calibration logbook: the instrument identification number (U.S. EPA
barcode number or serial number if the instrument is a rental), the initial and final span settings, the date and time,
concentration and type of calibration gas used, and the name of the person who calibrated the instrument. Affix a sticker to
the instrument indicating the person who performed the calibration, the date of calibration, and the due date of the next
calibration.

7.5.6 Turn the FUNCTION switch to OFF and connect the instrument to the charger. The probe must be connected to the
readout unit to ensure that the unit accepts a charge.

7.6 Calculations

7.6.1 The HNU is a direct reading instrument. Readings are interpreted as units above background rather than ppm.

7.7 Health and Safety

7.7.1 When working with potentially hazardous materials, follow U.S. EPA, OSHA, or corporate health and safety
practices.

7.7.2 The HNU is certified by OSHA standards for use in Class 1, Division 2, Groups A, B, C, and D locations.
8.0 QUALITY CONTROL

8.1 There are no specific quality assurance activities which apply to the implementation of these procedures. However, the
following general QA procedures apply:

8.1.1 All data must be documented on field data sheets or within site logbooks.

8.1.2 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer,
unless otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to
sampling/operation, and they must be documented.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

-------
1.	HNU Systems, Inc. 1975. "Instruction Manual for Model PI-101 Photoionization Analyzer."

2.	U.S. Code of Federal Regulations, 49 CFR Parts 100 to 177, Transportation, revised November 1, 1985.

3.	U.S. Environmental Protection Agency. 1984. "Characterization of Hazardous Waste Sites - A Methods Manual: Volume
II, Available Sampling Methods, Second Edition", EPA-600/4-84-076, Environmental Monitoring Systems Laboratory, Office of
Research and Development, Las Vegas, Nevada.

4.	International Air Transport Association Dangerous Goods Regulations

EMC^A-MDB-17

-------
ERT Method

PHOTO VAC 10A10 PORTABLE GAS CHROMATOGRAPH OPERATION

1.0 SCOPE AND APPLICATION

1.1 This standard operating procedure (SOP) pertains to the use, calibration and maintenance of the Photovac 10A10
portable Gas Chromatograph. The Photovac 10A10 Gas Chromatograph is used for field and laboratory screening of air, soil gas,
water, and soil headspace samples for chlorinated and nonchlorinated alkenes and aromatic hydrocarbons down to the 1 to 20 part
per billion (ppb) range.

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required,
dependent on site conditions, equipment limitations or limitations imposed by the procedure or other procedure limitations. In all
instances, the ultimate procedures employed should be documented and associated with the final report.

1.3 Mention of trade names or commercial products does not constitute US EPA endorsement or recommendation for use.
2.0 SUMMARY OF METHOD

2.1 The Photovac 10A10 is a battery/AC operated photoionization detector (PID) portable Gas Chromatograph. It is a field
instrument capable of monitoring for many organic vapors using an ultraviolet light source and a photoionization detector.

Gaseous contaminants are ionized as they emerge from the column. The ions are then attracted to an oppositely charged electrode
which causes a current and electronic signal to a strip chart recorder.

2.2 The samples will be introduced into the 10A10 via gas tight syringes. As the compounds are detected by the PID, the
resulting response will be recorded by an attached strip chart recorder or alternately, an integrator/plotter system.

3.0 INTERFERENCES

3.1 This instrument is not to be exposed to precipitation or high humidity. Liquids are not to be injected into this
instrument. The instrument is best utilized in a stable, temperature controlled environment. It is advisable to avoid combustion
fumes while using the instrument in the field because they can contaminate the columns. Readings can only be reported relative to
the calibration standard used. High alkane concentrations may interfere with the resolution and detector response of early-eluting
chlorinated alkenes, and aromatic compounds.

3.2 Since the Photovac is a GC, the target compounds are identified by their retention times (RT). If the RT of the sample
peak(s) match the RT of the standard peak(s) they are assumed to be identical. If any non-target compounds has the same RT, it
can be misidentified as a target compound.

4.0 APPARATUS AND MATERIALS

4.1 The following equipment is required for Photovac operation:

4.1.1 Photovac 10A10 Gas Chromatograph: With manual and power cord.

4.1.2 Extra source lamp.

4.1.3 Photovac lamp tuning screwdriver.

4.1.4 Extra columns/fittings.

4.1.5 Ultra Zero Air carrier gas.

EMC-m-«-ll

-------
4.1.6 Two stage regulator: With quick-connect fitting.

4.1.7 One flowmeter per Photovac: Either bubble-meter, rotameter, or Gilibrator.

4.1.8 Septa: 6 mm diameter.

4.1.9 Syringes: Gas-tight, 10 uL to 1 mL.

4.1.10 VOA vials filled with activated charcoal: For syringe cleaning.

4.1.11 Integrator or strip-chart recorder: With appropriate connections.

4.1.12 Labels.

4.1.13 Tools: Large adjustable wrench, wrenches (5/16" to 9/16"), screwdrivers (Flat head and Phillips head),
nosepliers, jeweler's screwdrivers, Allen wrenches

4.1.

Duct tape.

4.1.

Teflon tape.

4.1.

Power strip.

4.1.

Snoop.

4.1.

Kimwipes.

5.0 REAGENTS

5.1 Carrier Gas Cylinder: (Compressed ultra zero air, 0.1 ppm total hydrocarbons).

5.2 Headspace Calibration Standards: Supelco A and B or equivalent.

5.3 Certified Gas Calibration Standards: With a+/-2% level of accuracy. These can be obtained from Scott Speciality
Gas, Matheson Gas, or other reliable sources.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

This section is not applicable to this SOP.

7.0 PROCEDURES

7.1 Laboratory Operation

7.1.1 The carrier gas (air) cylinder is attached to the 1 OA 10 and a maximum of 40 psi is delivered via the second stage of
the dual stage regulator.

7.1.2 The flow rate will vary according to the target compounds in question and the column used. The carrier gas flow is
adjusted using the curled knob to the left of the 10A10, labeled Column 1 or Column 2. The flow is measured by attaching a
flow meter to the vent port at the top left of the unit (see Figure 1, Appendix C). Once the flow is set, the PID will stabilize
after approximately 1/2 hour warm-up time. The output is then set at 10 mV using the offset knob in the center of the unit.

-------
7.1.3 An interface cable is attached from the output lead on the 1 OA 10 to a strip chart recorder or more preferably a
plotter-integrator such as the Hewlett Packard 3396A. The voltage input and/or attenuation is selected on the chart or
integrator to keep peaks on scale. Check that the electrical controls are set as follows:

7.1.3.1 Power Switch to " Off".

7.1.3.2 Charge Switch to "Off".

7.1.3.3 Attenuation Switch to "100" (lowest sensitivity).

7.1.3.4 Offset dial to "zero".

7.1.3.5 Connect chart recorder to the coaxial Output connector.

7.1.3.6 Set the chart recorder to 100 mV full scale and chart speed to 1 cm/min.

7.1.3.7 Plug the Power Cord into the panel socket and the red AC indicator light will come on.

7.1.3.8 The instrument is now in its Power Down condition and is ready for starting.

7.1.4 With the chart recorder off, switch on the Power switch. The red source Off indicator will light and stay on for up
to five (5) minutes. During this time, the lamp-start sequence is being automatically initiated.

7.1.5 As soon as the Source Off light is extinguished, the meter should show a high reading which should fall as
conditions in the photoionizing chamber stabilize.

7.1.6 Establish an acceptable base line on the chart recorder. The instrument is now ready for calibration.

7.2 Calibration Procedure (Refer to Appendix A for Calibration and Maintenance Schedule)

7.2.1 Photovac Incorporated conducts an instrument calibration and includes the chromatogram as a component of that
instrument's instruction manual. A check of the instrument's performance can be accomplished by duplicating the factory
calibration check and comparing the results. The procedure is as follows:

7.2.1.1 Take a clean 1-liter sample bottle, or a clean 1-liter Tedlar bag fitted with a septum cap, and completely flush
with good quality bottled air.

7.2.1.2 Go to the factory calibration data sheet and calculate the required amounts of each calibration compound
required to generate an air standard (1-liter total volume) which is identical to that run by Photovac in the factory
calibration.

7.2.1.3 Using an appropriate volume gas-tight syringe, aspirate the required amounts of each compound from the
headspace of the storage bottles at room temperature, and inject it into the purged 1-L sample bottle. Be careful to fully
flush the syringe with clean air between each compound.

7.2.1.4 Allow 10 minutes for the standard to equilibrate.

7.2.1.5 Using a clean 100-uL gas-tight syringe, aspirate the required injection volume from the 1-liter standard. With a
crisp and snappy action, inject the standard into the proper "injection port" of the Photovac 10A10.

7.2.1.6 Start and mark the strip chart recorder. The resulting chromatogram should be similar to the factory calibration
chromatogram, under similar conditions.

EMC-m-MDM-S

-------
7.2.1.7 A simple calibration curve can be constructed by injecting the same volume of several standards with varying
concentration levels of the target compounds. Alternatively, a calibration curve can also be constructed by injecting
various volumes (10-1000 uL) of the same standard. In this case the response of the standards and samples should be
normalized to one injection volume. Both standards and samples present in Tedlar bags can be diluted in the field.

7.3 Field Operation

7.3.1 Prior to any field analyses, check to ensure that the instrument is operational and clean. Remove closure fittings on
the "Detector Out" port. Closure fittings may have been engaged to prevent static contamination.

7.3.2 Check that the lecture bottle gas supply is adequate (charge supply is 1800 PSI and should last approximately 3 days
or less depending on carrier flow rates).

7.3.3 Set the pressure regulator to zero (fully counterclockwise) and turn on the main valve of the lecture bottle.

7.3.4 Slowly turn the regulator control clockwise until air begins to escape from the quick-disconnect connection. Allow
the line to purge for 10 seconds.

7.3.5 Plug the quick-disconnect fitting into the free "carrier in" port. Shut off and disconnect the laboratory air supply.
Adjust the lecture bottle regulator to 40 psig. Set the required flow rate as described previously using a bubble meter,
calibrated rotameter, or Gilibrator.

7.3.6 With the instrument in the power down mode, disconnect the AC power supply. This automatically switches the
instrument to battery power. The instrument is now completely self-contained, and together with a battery powered recorder,
may be taken into the field. Check the battery charge on the Photovac.

7.3.7 The instrument is now ready to be run through the start up procedures described under Laboratory Operation, Parts
4-8 of the Manual.

7.3.8 If there are significant changes in ambient temperature when moving the instrument from place to place, the column
will require time to stabilize thermally. At higher sensitivities, a non-thermally stabilized column will manifest itself as
baseline drift.

7.3.9 For trouble shooting information, refer to Appendix B.

7.4 Shut Down

7.4.1 Turn the Power Switch to "Off".

7.4.2 Reduce the carrier gas flow to 2-5 cc/min.

7.4.3 Place instrument on low charge while on the bench, and maintain as described in Maintenance and Calibration
Schedule Section.

7.4.4 Unplug the unit except when charging batteries.

7.5 Calculations

7.5.1 C alibration Curve

7.5.1.1 A calibration curve of at least three (3) concentrations must be constructed for each target compound. A
straight line equation in the form of y = (m)(x) + b (where: x = concentration, y = area counts, m = slope, and b = the

-------
intercept) is fit to the standards raw data. The (y), or the unknown concentration for the sample, is determined from the
above straight line equation. Non-linear data is indicative of detector response range limitations.

7.5.1.2 Alternatively, sample concentration can be calculated as below:

A V

[Sample] = [Std] — x —

A2 v1

Where: A[ = Peak area of sample;

A2 = Peak area of standard;

V[ = Injection volume of sample; and

V2 = Injection volume of standard.

7.5.2 Standard Response Generation/Duplication of Factory Calibration Date

7.5.2.1 If appropriate gas standard mixtures are not available, gas standards can be made using the headspace from 40
mL VOA bottles, with Teflon-lined septa screw caps, partically filled with the desired neat volatile liquid. Factory
instrument response is generally determined using the following 3 compounds:	

Compound

Pvap 20 °C

methylene chloride
n-hexane
benzene

347 mm Hg
126 mm Hg
74 mm Hg

7.5.2.2	These compounds are toxic and should be stored and worked with under a hood. The general formula for
preparing a standard from the headspace above a volatile liquid is:

= ^(o m

vap

Where: VHS = Volume of Headspace (uL);

Pvap = Vapor Pressure of Liquid (mm Hg) (Use appropriate tables to determine compound vapor pressure if

working environment temperature is not 20°C.);

C = Desired Concentration (ppm); and
V = Volume of Standard Vessel (liters).

7.5.2.3	A determined volume of neat liquid headspace may be introduced to the standard vessel through the
septa if using a Tedlar bag with the appropriate fitting. Bags or vessels used should be labelled with content
concentrations, date, and time of preparation.

7.6 Health and Safety

7.6.1 When working with potentially hazardous materials, follow USEPA, OSHA, and corporate health and safety
practices.

-------
8.0 QUALITY CONTROL

8.1 There are no specific quality assurance activities which apply to the operation of the Photovac. However, the following
general QA procedure applies:

8.1.1 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer,
unless otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to
sampling/operation and they must be documented.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Photovac 10A10 Operations Manual, Photovac International, Thornhill, Ontario, Canada L3T 2L3.

-------
ERT Method

PHOTOVAC 10S50. 10S55. AND 10S70 GAS CHROMATOGRAPH OPERATION

1.0 SCOPE AND APPLICATION

1.1 This standard operating procedure (SOP) pertains to the use, calibration, and maintenance of the Photovac 10S Series
Portable Gas Chromatographs. The 10S Series Gas Chromatographs are used for expedient field and laboratory screening of air,
soil gas, and water and soil headspace for chlorinated and non-chlorinated alkene and aromatic compounds with detection limits of
1-5 ppb (parts per billion) for headspace analysis to 10-50 ppb for soil gas analysis.

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required,
dependent on site conditions, equipment limitations or limitations imposed by the procedure or other procedure limitations. In all
instances, the ultimate procedures employed should be documented and associated with the final report.

1.3 Mention of trade names or commercial products does not constitute EPA endorsement or recommendation for use.
2.0 SUMMARY OF METHOD

2.1 The Photovac 10S Series are battery/AC operated portable, Gas Chromatographs with photoionization detectors. They
are field/laboratory instruments capable of screening for many organic vapors using an ultraviolet light source and photoionization
detector. Gaseous contaminants are ionized as they emerge from the column. The ions are then attracted to an oppositely charged
electrode which causes a current and sends an electronic signal to the Photovac internal microprocessor or optional integration
device.

4.0 INTERFERENCES AND POTENTIAL PROBLEMS

These instruments are not to be exposed to precipitation. The instruments are best utilized in stable, temperature-controlled
environments (even when using the internal temperature-controlled oven assembly which may only reduce the effect of external
atmospheric temperature variances). When using directly in the field, it is best to maintain constant temperatures to avoid the
fluctuating retention times which may occur with changing temperatures. Readings can only be reported relative to retention times
of the calibration standard used. It is advisable to avoid combustion fumes while using the instrument as they can contaminate the
column. High sample alkane concentration, C^Cg, as in many landfill samples, may interfere with the resolution and detector
response of early eluting aromatics and chlorinated alkenes.

4.0 APPARATUS AND MATERIALS

4.1 The following equipment is required for Photovac operation:

4.1.1 Photovac IPS Series Gas Chromatograph: With manual and power cord.

4.1.2 Extra source lamp.

4.1.3 Photovac lamp tuning screwdriver.

4.1.4 Extra columns/fittings.

4.1.5 Ultra Zero Air carrier gas.

4.1.6 Two stage regulator: With quick-connect fitting.

4.1.7 One flowmeter per Photovac: Either bubble-meter, rotameter, or Gilibrator.

SMCmiDB-ll

-------
4.1.8	Septa: 6-mm diameter.

4.1.9	Syringes: Gas-tight, 10-uL to 1-mL.

4.1.10	VOA vials: Filled with activated charcoal, for syringe cleaning.

4.1.11	Extra Photovac integrator pens.

4.1.12	Extra Photovac integrator paper.

4.1.13	Labels.

4.1.14	Tools: large adjustable wrench, wrenches (5/16" to 9/16"), screwdrivers (Flat head and Phillips head),
nosepliers, jeweler's screwdrivers, Allen wrenches.

4.1.

15

Duct tape.

4.1.

16

Teflon tape.

4.1.

17

Power strip.

4.1.

18

Scoop.

4.1.

19

Kimwipes.

4.1.20

Pelican cases.

4.2 Maintenance and calibration schedule and information can be found in Appendix A.

5.0 REAGENTS

5.1	Carrier Gas: Ultra zero air (<0.1 ppm total hydrocarbons).

5.2	Appropriate Calibration Standards: Gas or liquid.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

This section is not applicable to this SOP.

7.0 PROCEDURES

7.1	Shipping

7.1.1 The Photovac is initially shipped to the user in a cardboard box provided by Photovac International. Repeatedly
shipping Photovacs in these boxes to field locations has resulted in occasional electrical and mechanical problems. It is
recommended that the Photovacs be shipped in a more rugged container, such as the Pelican King Size Case (Orr Safety
Equipment Co.), or equivalent. In addition to shipping, the Photovac can be left in the case while running to prevent static
electricity and provide thermal stability.

7.2	Pre-Operational Checkout

HfflC-M-lDM

-------
7.2.1 Check the instrument for any obvious damage. Plug the power cord into an AC power source if available. Remove
any closure fittings which may have been affixed to the DETECTOR OUT, AUX OUT, and CAL OUT ports in order to
minimize contamination.

7.2.2 Raise the "Computer Module". Check that all compression fittings associated with the columns (pre-and analytical)
and valving, subject to carrier gas flow, are FINGER tight. DO NOT OVER TIGHTEN. Fittings may loosen in transit.
Check which injection port is connected to the columns (only one may be used at a time). Normally, the Photovac is supplied
with an SE-30 5% packed 6-inch pre-column and 4-feet of analytical column unless otherwise specified (Figure 1, Appendix
B). If a capillary column (usually CP Sil-5, blue, equivalent to the properties of the SE-30) with oven temperature control
module is being used, make sure the oven ribbon connection is tight. Attach the external 12V battery with adapter to the
BNC "EXT DC" connector on the left side of the Photovac top panel. Adjust the oven module temperature to at least 5°C
greater (usually > 40°C) than internal operating temperature. Close the computer module. Allow at least 40 minutes for
oven temperature stabilization.

7.2.3 Check that the septum is new. Make sure the septum retainer is tight. DO NOT OVER TIGHTEN.

7.2.4 Engage carrier gas flow (Ultra Zero Air). Carrier gas can be introduced either by connecting an external low
pressure source (attached by a Quick-Connect to the EXTERNAL CARRIER IN receptacle) or by recharging the Photovac
internal high pressure refill attachment (Appendix C, Carrier Gas Supply System Options). If operating from an external
cylinder, a clean, GC grade, two-stage regulator should be used. Set delivery pressure to a maximum of 40 psi. One-eighth
inch Teflon lines, brass or stainless steel swagelock fittings and a quick-connect are used to attach the external carrier gas to
the Photovac GC. Lines are purged 5-10 seconds with Ultra Zero Air carrier gas before connection to the Photovac
EXTERNAL CARRIER gas inlet.

7.3 Carrier Gas Flow Rate Adjustment

7.3.1 Set carrier gas flow rates by attaching appropriate flow rate indicators (calibrated rotameters, Gilibrators, bubble
meters, etc.) to the DETECTOR OUT port (red dial) and adjusting the appropriate needle valves to give a flow of 40-50
cc/min for a packed column and 10-15 cc/min for a capillary column.

7.3.2 After flow through the detector is determined it is advisable to turn on the instrument and warm up the electronics
while fine tuning the desired flow rates. The instrument (column/valving/detectors) should be purged of residual
contamination encountered in transit by carrier gas flow for at least one hour prior to use.

7.4 Photovac Settings

7.4.1 Turn the instrument on, press ON. "LAMP NOT READY" appears on the LCD. It takes approximately 1-2
minutes for the lamp to light. DO NOT allow more than 3 minutes for the lamp to light, or electronic problems can occur.

7.4.2 Date/Time Entry

7.4.2.1 In the "library" section on the top control panel press USE (there are 4 libraries which may be used) then
ENTER. The LCD will prompt for entry of the "date" and "time".

7.4.3 Library Listing

7.4.3.1 Obtain a listing of compounds contained in the library selected for use by pressing LIST, then ENTER. If they
are not desired they may be deleted by pressing EDIT. You will be prompted by the LCD to enter the ID of the compound
in the library you wish to edit, the ID# as stated on the printout, then press CLEAR, then ENTER. That compound is then
removed from the library. Repeat the EDIT sequence until all undesired compounds have been removed from the library
selected for use.

7.4.4 Gam

-------
7.4.4.1 Whenever the Photovac is turned off and then on, it reverts to the default GAIN setting of 2. A GAIN of at
least 50 is necessary for detection of most common pollutants (i.e., aromatics and chlorinated alkenes) down to a 5-20 ppb
range using a 100-250 ul sample injection volume. Since this is a non-destructive detector, small sample injection
volumes are desirable to minimize analyst exposure. Beside safety factors, injection volumes >1 ml are not recommended
due to column and detection volume capacity. Peak resolution and quantitation may be distorted by large injection
volumes. To adjust the gain setting press GAIN in the "SET UP" section of the Photovac top panel. Increase the gain to
50 by depressing the up arrow key.

7.4.4.2 When 50 appears on the LCD press ENTER. Return to Section 7.2 to fine tune carrier flow, if necessary.
Otherwise proceed with instrument settings.

7.4.5 Chart Recorder

7.4.5 Press CHART. Using arrow keys, obtain LCD readout "Chart Recorder on with Baseline". Press ENTER.
The Baseline mode is recommended because it allows the operator to observe integration parameters and make
adjustments when necessary. SPEED? CM/MIN appears on the LCD. Use arrow keys to obtain 0.5 cm/min on the LCD,
press ENTER.

7.4.6 Peak Integration Parameters

7.4.6.1 Press SENS. When prompted by the LCD, using the arrow keys and ENTER adjust settings to:

UPSLOPE : 18

DOWNSLOPE : 14
PW @ 4 : 6

7.4.6.2 "Upslope" and "Downslope" refer to the change in baseline slope necessary for the integrator to recognize a
beginning and end of a peak. The Downslope is kept lower than the Upslope so the tails of peaks are fully integrated.
"PW@4" refers to the peak width in seconds at 4 min - this value is proportionally adjusted by the integrator for retention
times other than 4 min.

7.4.7 Peak Window

7.4.7.1 The window settings are pertinent only if using the internal Photovac microprocessor's library. Peak
identification in gas chromatography is based on retention time (RT) matches with the standards used. When operating at
"ambient" temperature, fluctuations in external temperature will affect compound retention times, making peak
identification difficult and questionable. It is for this reason that the Photovac should be operated in a stable temperature
environment. Press WINDO, using the arrow keys and ENTER to adjust the following settings:

0 Packed Column Capillary Column

WINDO: 10 sec. 5 sec.

7.4.7.2 The internal microprocessor applies an equation allowing for more extensive fluctuations in RTs of later eluting
compounds relative to early eluting compounds using the WINDO setting selected.

7.4.8 Area of Rejection

7.4.8.1 This setting is used to eliminate the reporting of "noise" peaks on the report printed at the end of each run. It
designates the minimum peak area (volt - seconds) recognized by the integration system. A setting of 100 mVs is usually
sufficient for detection of aromatics and chlorinated alkenes at the 5-20 ppb level at a gain of 50.

7.4.8.2 Press AREA. Press the arrow keys until 100 mVs appear on the LCD. Press ENTER.

HfflC-M-lDM

-------
7.4.9 Events (Manual Injection)

7.4.9.1 Manual injection operation of the Photovac 10S series with serial flow involves the use of only EVENT (valve
actuators) 1 (a pump, with audible sound used only for injection timing). EVENT 1, the pump timer, is set for a
recommended maximum of 2 seconds.

7.4.9.2 Press EVENT. When prompted by the LCD readout, make the following entries:

OFF

EVENT #

(Sec)

7.4.9.3 Pressing STATUS/TEST, ENTER will produce a hard copy of the EVENTs just entered, to check for accuracy
of entries and for the record of analytical procedures.

7.4.10 Analysis Time

7.4.10.1 The Photovac GC run time (length of time peaks are recognized for integration by the internal

microprocessor) is set using the CYCLE key. Press CYCLE, the LCD will prompt you for "Timer Delay (sec)". The
number of seconds entered (by the numeric keys) will be the length of time, after pressing the start key to begin the run,
before the chart record will began (i.e., the ZERO reference point for all peak retention times). This value should
normally coincide with the point at which the sample is injection (i.e., EVENT 1 "OFF" time). Press 7, ENTER.

"Analysis Time" will appear on the LCD readout. Using the numeric key pad, press 3000, ENTER. This can be shortened
later. The longest analysis time possible with the Photovac is 3267 seconds (54 minutes). "Cycle Time" appears on the
LCD. Press 0, ENTER.

7.4.11 Baseline Check for Photovac Operational Readiness

7.4.11.1 For operational readiness, runs need only be 600-700 seconds. Run time progression may be determined
by pressing the up arrow key. An initial negative baseline indicates the detector is still "warming up". An elevated or
irregular baseline, after proper flow adjustments, indicates possible contamination. Additional purging time may be
required. After a suitable baseline has been obtained, the instrument is ready for calibration.

7.5 Calibration Procedure

7.5.1 Photovac Incorporated conducts an instrument calibration and includes the chromatogram as a component of that
instrument's instruction manual. A check of the instrument's performance can be accomplished by duplicating the factory
calibration check and comparing the results. The procedure is as follows:

7.5.1.1 Take a clean 1-liter sample bottle or a clean 1-liter Tedlarbag fitted with a septum cap, and completely flush
with a good quality bottled air.

-------
7.5.1.2 Go to the factory calibration data sheet and calculate the required amounts of each calibration compound
required to generate an air standard (1-liter total volume) which is identical to that run by Photovac in the factory
calibration. Refer to 7.0, Calculations, in Photovac Manual if a suitable gas standard mixture is not available.

7.5.1.3 Using an appropriate volume gas tight syringe, aspirate the required amounts of each compound from the
headspace of the storage bottles at room temperature, and inject it into the purged 1-liter sample bottle. Be careful to fully
flush the syringe with clean air between each compound.

7.5.1.4 Fill Tedlar bag with factory calibration standard.

7.5.1.5 Allow 10 minutes for the standard to equilibrate.

7.5.1.6 Using a clean 100-uL gas-tight syringe, aspirate the required injection volume from the 1-liter standard. With a
crisp and snappy action, inject the standard into the proper "injection port" of the Photovac.

7.5.1.7 Compare the chromatograph generated with the factory supplied "specification chromatogram".

7.5.1.8 NOTE: If the difference is significant, review the procedures and technique used in the analysis and repeat. If
results are still unsatisfactory, call Photovac technical service.

7.6 Alternate Procedure

7.6.1 Following the start-up procedure in the instruction manual, get the Photovac on-line ready to accept a sample.

7.6.2 Obtain a gas standard mixture certified to +2% accuracy, commercially available from Matheson Gas Products or
equivalent.

7.6.3 Perform the final two steps of the above procedure and compare the newly generated chromatogram with a known
chromatogram. If results are not satisfactory, refer to step 7 listed above.

7.7 Shut Down

7.7.1 Press OFF, ENTER.

7.7.2 Reset the carrier gas flow to 2-5 cc/min.

7.7.3 Place instrument on charge while on the bench and maintain as described in Maintenance and Calibration Schedule
Section (Appendix A).

7.7.4 Unplug the unit except when charging batteries.

7.8 Troubleshooting information and corrective action procedures can be found in Appendix D.

7.9 Calculations

7.9.1 C alibration Curve

7.9.1.1 A calibration curve of at least three (3) concentrations must be constructed for each target compound. A
straight line equation in the form of y = (m)(x) + b; (where: x = concentration, y = area counts, m = slope and b = the
intercept) is fit to the standards raw data. The (y), or the unknown concentration for the sample, is determined from the
above straight line equation. Non-linear data is indicative of detector response range limitations.

7.9.1.2 Alternatively, sample concentration can be calculated as below:

-------
A V

[Sample] = [Std] — x —

A2	V1

Where: Al = Peak area of sample;

A2 = Peak area of standard;

V[ = Injection volume of sample; and

V2 = Injection volume of standard.

7.9.2 Standard Response Generation/Duplication of Factory Calibration Date.

7.9.2.1 If appropriate gas standard mixtures are not available, gas standards can be made using the headspace from 40-
ml VOA bottles, with Teflon-lined septa screw caps, partially filled with the desired neat volatile liquid. Factory
instrument response is generally determined using the following three (3) compounds:

Compound

Pvap 20 °C

methylene chloride
n-hexane
benzene

347 mm Hg
126 mm Hg
74 mm Hg

7.9.2.2	These compounds are toxic and should be stored and worked with under a hood. The general formula for
preparing a standard from the headspace above a volatile liquid is:

= ^(o m

vap

Where: VHS = Volume of Headspace (uL);

Pvap = Vapor Pressure of Liquid (mm Hg) (Use appropriate tables to determine compound vapor pressure if

working environment temperature is not 20°C.);

C	= Desired Concentration (ppm); and

V	= Volume of Standard Vessel (liters).

7.9.2.3	A determined volume of neat liquid headspace may be introduced to the standard vessel through the
septa if using a Tedlar bag with the appropriate fitting. Bags or vessels used should be labelled with content
concentrations, date, and time of preparation.

7.10 Health and Safety

7.10.1 When working with potentially hazardous materials, follow USEPA, OSHA, or corporate health and safety
practices.

8.0 QUALITY CONTROL

8.1 There are no specific quality assurance activities which apply to the operation of the Photovac. However, the following
general quality assurance procedures applies:

-------
8.1.1 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer,
unless otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to
sampling/operation, and they must be documented.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Photovac 10S Operations Manual, Photovac International, Thornhill, Ontario, Canada L3T 1L3.

-------
ERT Method

PHOTOVAC GC ANALYSIS FOR SOIL. WATER. AND AIR/SOIL GAS

1.0 SCOPE AND APPLICATION

1.1 The purpose of this standard operating procedure (SOP) is to describe a method for a low-cost field laboratory screening
tool for tentative identification and determination of concentration levels on select contaminants for site assessment and health and
safety surveys.

1.2 This method describes the rapid screening of air/soil gas, water, and soil samples using a Photovac portable Gas
Chromatograph (GC) Model 10S series to determine the presence of various volatile organic compounds.

1.3 Data generated allows only rapid evaluation of site conditions and is applied to, but not limited to, the following
activities: extent and degree of contamination; pollutant plume definition; health and safety assessment; and tentative pollutant
identification and quantitation. The data should not be used for site ranking or enforcement purposes since only limited Quality
Assurrance/Quality Control (QA/QC) is required, and the reported data is qualified as tentative.

1.4 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required,
dependent on site conditions, equipment limitations, or limitations imposed by the procedure or other procedure limitations. In all
instances, the ultimate procedures employed should be documented and associated with the final report.

1.5 Mention of trade names or commercial products does not constitute EPA endorsement or recommendation for use.
2.0 SUMMARY OF METHOD

2.1 Air/soil gas, water, or soil samples can be analyzed by the Photovac. Brief method summaries are provided below. All
methods use a Photovac 10S series GC equipped with a 10.6 eV Photoionization Detector (PID), and use external standards to
tentatively identify and quantitate compounds of interest.

2.2 Air/Soil Gas Samples: Ambient air or soil gas samples are collected in one-liter Tedlar bags. An aliquot of each bag
sample is withdrawn using a gas-tight syringe and directly injected into the GC. Vapor from selected samples can then be
absorbed onto Tenax/CMS cartridges for confirmational GC/MS analysis.

2.3 Water Samples: Water samples are collected in 40-ml VOA vials with Teflon-lined silicone septum screw caps. A 20-
ml aliquot of sample is pipetted into a second, clean VOA vial. The vial is capped, shaken vigorously for one minute, and allowed
to stand at room temperature for at least 30 minutes for vapor phase equilibration. An aliquot of the water headspace is then
injected into the GC using a gas-tight syringe.

2.4 Soil Samples: Soil samples are collected in VOA vials. A five gram aliquot of sample is weighed into a second, clean
vial. Enough reagent water is added to bring the total volume of the soil/water extract to 20-ml. The vial is then capped, shaken
vigorously for one minute, and allowed to stand at room temperature for at least one hour for vapor phase equilibration. An aliquot
of the soil headspace is then injected into the GC using a gas-tight syringe.

3.0 INTERFERENCES

3.1 Air/Soil Gas Samples

3.1.1 High concentrations of short chain alkanes and alkenes in samples may interfere with the resolution and detector

sensitivity of early-eluting chlorinated alkenes and aromatic compounds.

3.1.2 Syringe blanks should be run as necessary to ensure against carryover contamination.

-------
3.1.3 Samples can be contaminated by diffusion of volatile organics through the septum seals and the walls of the
sampling bag during shipment and storage. A field blank, a Tedlar bag filled with ultra-zero air carried through sampling and
handling protocol can serve as a check on such contamination.

3.1.4 Teflon or equivalent inert fittings and tubing should be used in all procedures to prevent contamination by off-
gassing.

3.1.5 Parameters are identified by retention time (RT). Samples with response at the same RTs as target compounds are
assumed to be identical, which may not be the case.

3.2 Water and Soil Samples

3.2.1 Liquid samples can not be directly introduced into the GC. Direct injection of liquids, without heated injection
ports, may result in damage to the GC.

3.2.2 Syringe blanks should be run as necessary to ensure against carryover contamination.

3.2.3 Samples can be contaminated by diffusion of volatile organics through the septum seal during shipment and storage.
A field reagent blank, prepared from reagent water and carried through the sampling and handling protocol, can serve as a
check on such contamination.

3.2.4 Some of the sample will volatilize when the vials are opened during sample preparation. This loss is minimized by
proper sample handling.

3.2.5 Parameters are identified by retention time (RT). Samples with response at the same RTs as target compounds are
assumed to be identical, which may not be the case.

APPARATUS AND MATERIALS

4.1 The following equipment is required for Photovac operation and analysis:

4.1.1 Photovac Operation

4.1.1.1 Photovac IPS Series Gas Chromatograph: With manual and power cord.

4.1.1.2 Extra source lamp.

4.1.1.3 Photovac lamp-tuning screwdriver.

4.1.1.4 Extra columns/fittings.

4.1.1.5 Ultra-zero-air carrier gas.

4.1.1.6 Two stage regulator: With quick-connect fitting.

4.1.1.7 One flowmeter per Photovac: Either bubble-meter, rotameter, or Gilibrator.

4.1.1.8 Septa: 6-mm diameter.

4.1.1.9 Syringes: Gas-tight, 10 (iL to 1.0-mL.

4.1.1.10 VOA vials: Filled with activated charcoal (for syringe cleaning).

-------
4.1.1.11	Extra Photovac integrator pens.

4.1.1.12	Extra Photovac integrator paper.

4.1.1.13	Labels.

4.1.1.14	Tools: Large adjustable wrench.

4.1.1.14.1	Wrenches: "5/16" to "9/16".

4.1.1.14.2	Screwdrivers: Flat head and Phillips head.

4.1.1.14.3	Nosepliers.

4.1.1.14.5	Jeweler's screwdrivers.

4.1.1.14.6	Allen wrenches.

4.1.1.15	Duct tape.

4.1.1.16	Teflon tape.

4.1.1.17	Power strip.

4.1.1.18	Snoop.

4.1.1.19	Kimwipes.

4.1.1.20	Pelican cases.

4.2	Soil Gas Analysis

4.2.1	Tedlar bags: One liter.

4.2.2	Summa canisters for holding gas standards.

4.2.3	Extra-large syringe: 100-mL to 500-mL for serial dilutions.

4.3	Tenax/CMS Sampling

4.3.1	Tenax/CMS cartridges: Sealed in, glass ampoules.

4.3.2	Culture tubes (labeled): With glass wool to ship cartridges.

4.3.3	Cotton gloves or cloths: For cartridge handling.

4.3.4	Fitting: To connect syringe to cartridge.

4.3.5	Fitting: To connect cartridge to Tedlar bag.

4.3.6	Silicone O-rings: 1/4", for a tight seal around cartridge.

4.4	Water Headspace Analysis

EMC-m-MDB-3

-------
4.4.1

Headspace standards: Purgeable A and B or equivalent.

4.4.2 1.8-ml vials: For holding standards (either screw-cap or crimp-top vials).

4.4.3 Pasteur pipettes: For transferring standards.

4.4.4 40-mL VOA vials: One per sample plus extras for standards and QA/QC requirements.

4.4.5 10-ml or 20-ml pipettes and pipette bulb.

4.4.6 Liquid standard syringes.

4.4.7 Surgical gloves.

4.5 Soil Headspace Analysis

4.5.1 Same equipment for Water Headspace Analysis, plus:

4.5.1.1 Portable scale: Accurate to ± 0.1 g.

4.5.1.2 Spatulas: Or equivalent, for transferring soil.

5.0 REAGENTS

5.1 Reagent List for Air Sample Analysis

5.1.1 Gas Standards: Certified to ± 2 % level of accuracy, commercially available through Scott Specialty Gas or
equivalent. In-house laboratory preparation of calibration gas standards with confirmational GC/MS analysis is acceptable.

5.1.2 Ultra-zero air carrier gas.

5.2 Reagent List for Water and Soil Sample Analysis

5.2.1 Reagent Water: Organic-free chromatographic grade or equivalent, free of any contaminants which may interfere
with the detection and resolution of target parameters.

5.2.2 Ultra zero air carrier gas.

5.2.3 Stock Standard Solutions: Stock standard solutions may be prepared from pure standard materials or purchased as
certified solutions (e.g., Supelco Purgeable A or B, or equivalent). Reagents to be used as standards may be dependent upon
site specific suspected volatile contaminants.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Air/Soil Gas Samples

6.1.1 Air/soil gas samples are collected and stored in one liter Tedlar gas sampling bags as per ERT SOP #2149, Soil Gas
Sampling. Samples should be kept in a cooler out of direct light and heat. Samples should be analyzed within 48 hours of
collection, preferably within 12 hours.

6.1.2 Alternatively, samples may be collected in Summa canisters. In this case, sample stability may extend up to two
months, depending upon sample matrix.

EMC-m-MDM

-------
6.2 Water Samples

6.2.1 Water samples are collected, in triplicate, in 40-ml VOA vials. One sample is to be analyzed by the Photovac; the
two remaining vials are used for confirmation analysis by another method. All three should be completely filled, with no
visible air bubbles. Samples are stored out of direct light, in a cooler packed with ice immediatly upon collection until
analysis. Sample vials should be protected against breakage. Samples should be analyzed within seven days of collection.

6.3 Soil Samples

6.3.1 Soil samples are collected in 40-ml VOA vials, and stored out of direct light, in a cooler packed with ice (according
to ERT SOP #2012, Soil Sampling). Sample containers should be protected from breakage.

PROCEDURES

7.1 Method Detection Limits

7.1.1 The Method Detection Limit (MDL) is determined just before the analysis with a serial dilution of the standard, and
is the lowest concentration that can be detected at the gain setting selected for the analysis. MDLs are dependent on the type
of analysis performed and the condition of the gas chromatograph. Because of the difference in matrices, air and soil gas
analyses usually have MDLs an order of magnitude above headspace analyses. Factors that can vary the sensitivity of a
Photovac from site to site are the age of the source lamp, detector age, column condition, shipping the GC to the site, and the
location of the field lab. Typical MDLs for soil gas range from 10 ppb to 50 ppb, and headspace MDLs range from 1 ppb to
5 ppb.

7.1.2 If sample concentrations are high, injection volumes may be reduced to obtain on-scale response for parameters of
interest, and to avoid contamination of the GC system. The method detection limit (MDL) for compounds not detected at
reduced injection volumes is calculated by the following;

Vstd X Cstd

MDL = —

Where: Vstd = Lowest volume of standard headspace injected.

Cstd = Concentration of standard.

V = Volume of sample headspace injected.

7.2 Calibration

7.2.1 Photovac analyses are calibrated by the external standard method using the standards described in Section 5. At the
beginning of the analysis, a three-to-five point calibration curve is run to demonstrate linear instrument response over a
specified concentration range. The development of this method has shown the best linearity of the PID response to be from
10 ppb to 1 ppm for air/soil gas analysis and from 1 ppb to 100 ppb for headspace analysis. Most PIDs will be linear above
that range but eventually at high enough concentrations the PID will become saturated. The curve is verified daily by running
a calibration check standard from the middle of the curve.

7.2.2 If the response of any parameter varies from the curve by more than + 25% RSD instrument response has changed
and a new calibration curve should be run.

7.2.3 Air/Soil Gas Calibration

7.2.3.1 The concentrations needed for calibration can be prepared by a serial dilution of the gas standard. For example,
adding 50 mL of a 1 ppm standard and 450 ml of ultra zero carrier gas to a new Tedlar bag gives a 100 ppb calibration
standard. The 100 ppb bag can then be used to make up lower concentration standards.

-------
7.2.3.2 Alternatively, the analyst can construct a calibration curve by varying injection volumes. By designating a 250
(iL injection volume as the 1 ppm standard, a 100 ppb standard is created by injecting 25 (iL of a 1 ppm standard. This
method is more convenient and does not require the large syringes needed for serial dilution, but it has the limitation that
the calibration curve is limited by the sizes of the available syringes.

7.2.4 Water and Soil Calibration

7.2.4.1 Headspace standards can be created at selected concentrations by adding the appropriate volumes of stock
standard into clean 40 ml VOA vials containing 20 ml of reagent water. These volumes (V) are calculated by:

20 mL .„, , .

V = x (Stock conc. )

(Calibrant conc.)

7.2.4.2 From the 200 ppm Purgeable A and B standards, it is advisable to first prepare a 2 ppm stock solution to allow
calibration standards between 1 ppb and 10 ppb to be prepared with the syringes listed in Section 4.

7.3 Operation

7.3.1 Air/Soil Gas Analysis

7.3.1.1 Typical columns used for this method include SE-30 (packed) and CP-Sil 19 (capillary). An example of
compound separation using CP-Sil 19, with typical chromatographic conditions, is shown in Figure I (Appendix A).

7.3.1.2 Standards are injected after every 10-15 samples or every six (6) hours, whichever is more frequent, to bracket
possible parameter RT variations.

7.3.1.3 If sample concentrations are high, injection volumes may be reduced to obtain on-scale response. The method
detection limit (MDL) for compounds not detected at reduced injection volumes is calculated according to Equation 1, in
Section 7.1.

7.3.1.4 Identify the compounds in the sample by comparing the retention time (RT) of the peaks in the sample
chromatogram with those of the peaks in the standard chromatograms. The width of the RT windows used to make
identifications should be based upon measurements of actual RT variations of standards which bracket a series of sample
injections. Three times the standard deviation of a RT can be used to calculate a suggested window size, however, the
experience of the analyst should be a major factor in the interpretation of chromato grams.

7.3.2 Water Sample Analysis

7.3.2.1 Pipet a 20-mL aliquot of sample into a clean 40-ml VOA vial with Teflon-lined septum screw cap. Cap the
vial.

7.3.2.2 Shake the capped vial vigorously by hand for one minute. Allow to stand, inverted, and undisturbed for at least
30 minutes at ambient temperature for vapor phase equilibration. Use a gas-tight syringe to extract an aliquot of
headspace by inserting the syringe needle through the vial septum to a distance approximately half way between the liquid
surface and the septum's Teflon face. Purge the syringe barrel three to five times by withdrawing and expelling a volume
of headspace in slight excess of the volume anticipated to be used for analysis.

7.3.2.3 If sample concentrations are high, injection volumes may be reduced to obtain on-scale response. If sample
headspace injection volume is reduced below the volume of the aqueous calibration standard used to establish the method
detection limit (MDL), the detection limit for target compounds detected at the reduced headspace volume must be
determined. This is accomplished by injecting headspace aliquots at the reduced volume into the GC, beginning with the
10-ppb calibration standard and increasing or decreasing standard concentrations as warranted until a response has been

-------
obtained for all target compounds. The detection limit for parameters detected at the lower headspace injection volume is
then calculated using Equation 1, Section 7.1.

7.3.2.4 Identify the compounds in the sample by comparing the RT of the peaks in the sample chromatogram with
those of the peaks in standard chromatograms. The width of the RT windows used to make identifications should be
based upon measurements of actual RT variations of standards over the course of a day. Three times the standard
deviation of a RT can be used to calculate a suggested window size, however, the experience of the analyst should be a
major factor in the interpretation of chromato grams.

7.3.3 Soil Sample Analysis

7.3.3.1 Place a clean, empty, 40-mL, glass vial on the balance. Zero the balance. Use a clean stainless steel spatula to
add 5.0 g ± 0.1 g of soil sample. Pipet enough reagent water to bring the total volume of the soil and water to 20 ml. Seal
the vial with a Teflon-lined, septum screw cap.

7.3.3.2 Shake the capped vial vigorously for one minute to promote dispersion of the soil sample and increase surface
area. Allow to stand, undisturbed, at ambient temperature for at least one hour for vapor phase equilibrium. Use a gas-
tight syringe to extract an aliquot of headspace by inserting the syringe needle through the vial septum to a distance
approximately half way between the slurry surface and the septum's Teflon face. Purge the syringe barrel three to five
times by withdrawing and expelling a volume of headspace in slight excess of the volume anticipated to be used for
analysis. Wipe the syringe needle with a kimwipe before injection into the GC.

7.3.3.3 Although five gram has worked the best for most soil matrices other amounts, ranging from one gram to 10-g,
have also been used depending on sample concentrations and the consistency of the matrix.

7.3.3.4 If sample concentrations are high, the analyst can either reduce the injection volumes or analyze less soil to
obtain on-scale response. If sample headspace injection volume is reduced below the volume of aqueous calibration
standard used to establish the MDL, follow the procedure in Section 7.2.3 to determine the MDL for target compounds
detected at the reduced headspace volume. Alternatively, the analyst can weigh out as little as 1.0 g, keeping in mind that
this means a 10% error if using a portable balance accurate to ± 0.1 g.

7.3.3.5 Identify the parameters in the sample by comparing the RT of the peaks in the sample chromatogram with those
of the peaks in standard chromato grams. The width of the RT windows used to make identifications should be based upon
measurements of actual RT variations of standards over the course of a day. Three times the standard deviation of a RT
can be used to calculate a suggested window size, however, the experience of the analyst should be a major factor in the
interpretation of chromato grams.

7.4 Calculations

7.4.1 Air/Soil Gas Samples

7.4.1.1 The concentration of individual compounds in each sample is determined by using the following equation:

, , (Area Sample) ( Volume Standard)

[Sample] = —: — ¦— x — — x [Standard]

(Area Standard) ( Volume Sample)

7.4.1.2 "Area Standard" is the average of the areas of the standards run before and after the sample. Concentrations are
reported in ppb or ppm (volume/volume).

7.4.2 Water Samples

7.4.2.1 Concentrations of individual compounds in the sample are determined by the following equation:

-------
, ,	(Area Sample)	(Volume Standard)

[Sample] = —:	—	¦— * _	_ x [Standard]

(Area Standard)	(Volume Sample)

7.4.2.2 This is the same equation as in section 7.4.1.1, except the concentration of the headspace standard is used.
Concentrations are reported in jj.g/1 (ppb).

7.4.3 Soil Samples

7.4.3.1	Concentrations of individual compounds in the sample are determined by the following equation;

, ,	(Area Sample)	(Vol. Standard) (Vol. Headspace)

[Sample] = —:	—	¦— x —	— x _	£.	_ x [Standard]

(Area Standard)	(Vol. Sample)	(Weight Sample)

7.4.3.2	The volume of the headspace is always 20 ml, and the weight of the sample is usually 5 g. Concentrations are
reported in Hg/kg (ppb).

7.5 Health and Safety

7.5.1 When working with potentially hazardous materials, follow US EPA, OSHA, and corporate health and safety
practices. More specifically, it is suggested that the samples should be stored in a cooler, away from the analysis area. In
addition, the analysis area should have adequate ventilation.

8.0 QUALITY CONTROL

8.1 In order to meet the QA2 data quality objectives, at least 10% of all field samples must be confirmed by GC/MS
analysis. The following QA/QC requirements must be followed and provided in the data package submitted:

8.1.1	Chain of custody documentation.

8.1.2	Sample log, including date/time of sample collection, date/time of analysis, and run numbers.

8.1.3	Blanks

8.1.3.1	Air/Soil Gas Analysis: For each day of analysis, Field Standards (Tedlar bags filled with gas standards) and
Field Blanks (Tedlar bags filled with ultra-zero air) must accompany samples through collection, handling, and storage.

8.1.3.2	Water Analysis: Field Blank; duplicate 40-ml VOA vials completely filled with reagent water must
accompany each cooler used for sample collection, storage, and/or shipment.

8.1.3.3	Soil Analysis: Reagent Blank; 20 ml of the reagent water used in the soil analysis is pipetted into a clean 40-
ml VOA vial, allowed to equilibrate, and analyzed prior to sample analysis.

8.1.4	Instrument calibration data.

8.1.5	Syringe blanks: Syringe blanks are to be run prior to each sample analysis. (In practice, there is no need to run
syringe blanks if the previous sample is clean).

8.1.6	Labeling of chromatograms: Each chromatogram must be clearly identified by analysis type (i.e., syringe blank,
sample number, or calibrant concentration), injection volume, run number, date, and time.

-------
8.1.7 Replicate analysis: A replicate sample analysis is to be run after every 10 samples to check method/analyst
precision. The RSD of the area response of any of the compounds should be within 15%.

8.1.8 Retention time/instrument response check: Since compound identification is based upon RT matches, a calibration
standard should be run after every 10-15 samples.

8.1.9 Spikes - Soil and Water Samples Only

8.1.9.1 For every 20 samples, one Matrix Spike (MS) and one Matrix Spike Duplicate (MSD) must be analyzed. If
there are less than 20 samples in a matrix, at least one MS/MSD must be analyzed.

8.1.9.2 The spiked samples should, if possible, have moderate concentrations. The amount spiked should be
equivalent to the middle of the calibration range, or one to five times the sample background concentrations, whichever is
higher.

8.1.9.3 To calculate the percent recovery (%R) of each compound of interest:

Where: A = Concentration of sample and spike;

B = Concentration of sample; and
S = Concentration of the spike.

8.1.9.4 The %R should be 50-90% for a soil matrix, and 80-120% for a water matrix. Due to the complexity of the
soil/water/vapor equilibria, recoveries from soil matrices are consistently below 100%.

8.1.9.5 After the analysis of at least three spiked water samples, calculate the average percent recovery (Pavg) and the
standard deviation of percent recovery (S ). Express the accuracy assessment as the percent recovery interval, from Pavg-
(w)s to Pavg+(2)sp. Update the accuracy assessment for each parameter at each site where at least three accuracy
measurements are made. This step is optional.

8.2 Confirmational Analysis (Air/Soil Gas)

8.2.1 Depending on work plan stipulations, at least 10% of the soil gas samples analyzed by this GC method must be
submitted for confirmational GC/MS analysis (according to modified methods TO-1 [Tenax absorbent] and TO-2 [Carbon
Molecular Sieve (CMS) absorbent]). Each soil gas sample must be absorbed on replicate Tenax/CMS tubes. The volume
absorbed on a Tenax/CMS tube is dependent on the total concentration of the compounds measured by the Photovac:

8.2.2 A range of volumes is given to account for sample variability. The low end of the range should be used for samples
whose total concentrations are primarily one large peak, as too large a volume will overload the GC/MS column when that
peak is confirmed. The high end of the range should be used for multi-peak samples.

9.0 METHOD PERFORMANCE

Information not available.

%r = 100% x —£1
s

Total Concentration fppm)

Sample Volume (mL)

> 10
10
5

Use Serial Dilution
10-50
20-100
100-250

-------
10.0 REFERENCES

1.	EPA Method 601/602.

2.	FASP Method 101, Screening for Volatile Organics in Water.

3.	Chapman, H., Clay, P., Field Investigation Team (FIT) Screening Methods and Mobile Laboratories Complementary to
Contract Laboratory Program (CLP), October 17, 1986.

-------
CSL Method

DETERMINATION OF DETECTION LEVELS FOR
GROSS ALPHA AND GROSS BETA ANALYSES

1.0 SCOPE AND APPLICATION

1.1 This procedure documents the methods used to calculate Lower Limit of Detection (LLD) and Minimum Detectable
Concentration (MDC) values for the gross alpha and gross beta analyses. For the purpose of this procedure, definitions of LLD and
MDC are taken from the Health Pysics Society Committee Report HPSR-1 (1980), Upgrading Environmental Radiation Data.

1.2 The LLD is defined in HPSR-1 as "the smallest amount of sample activity that will yield a net count for which there is a
confidence at a predetermined level that activity is present." The LLD is an "a priori ESTIMATE of the detection capabilities of a
given measurement process." This limit depends only on the detection capability of the measurement process itself, not on the
characteristics of the sample; thus, the LLD is reported in activity units (e.g., pCi).

1.3 The MDC "is a level of activity concentration which is practically achievable by an overall measurement method." The
MDC considers not only the instrument characteristics (background and efficiency), but other sample specific characteristics such
as sample size, counting time, self-absorption and decay corrections, chemical yield, and other factors that are used in the
concentration determination. The MDC is reported in units of activity concentration (e.g., pCi/L).

1.4 This calculation method is applicable to soil samples and water samples taken as composites or grab samples. Both
sample types are radiologically screened to meet Department of Transportation (DOT) and/or CH2M HILL administrative shipping
limits.

2.0 SUMMARY OF METHOD
Information not available.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

Information not available.

5.0 REAGENTS

Information not available.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
Information not avialable.

7.0 PROCEDURE

7.1 LLD Calculations

ffMC-m-«-ll

-------
The following assumptions are used to calculate LLD values for solid and liquid sample analyses by the CSL:

•	Background count rate (B) is determind by counting a blank planchet.

B^aipha) = 0.069 cpm, Bp(bet!l)= 1.008 cpm; and

•	Alpha counting efficiency is determined using a Th-230 standard. Beta counting efficiency is determined using a
Tc-99 standard. Both standards are traceable to the National Institute of Standards and Technology (NIST).

4.66 x S
LLD = 		

Where:	Ex 2.22

4

.66 = Constant providing 5 percent risk of false detection and false nondetection;

Sb = Standard deviation of the background count rate = B/T;

E = Counter efficiency cpm/dpm;

2.22 = Dpm/pci conversion factor (2.22 dpm = 1 pCi);

B = Background count rate (cpm); and
T = Count time = 50 min.

7.1.1 Example. Alpha LLD

7	t t n 4-66 x V°-069 / 50 .

/	LLD = 	1	 = 0.37 pCi

0.21 x 2.22

2

Example. Beta LLD

7	LLP - 4.66 xV1. 008 / 50 ,„,61 ei
3 0.37 x 2.22

MDC

Calculations

The following assumptions are used to calculate MDC values for solid and liquid sample analyses by the CSL:

•	Background count rate for liquid samples is obtained from a deionized water sample processed as a normal sample,
plated on a planchet, and counted for 50 min. The standard duration is obtained by counting this sample 15 times
and calculating the square root of the variance of these counts.

•	The methods described in the MDC calculation approach is consistent with the MDC definition described in the
Nuclear Regulatory Commission (NRC) Regulatory Guide 8.30, Appendix B.

7.3.1 Example. Alpha Background-Soil

-------
Test

X (Count)

X-X

(X-X)2

1

15

-0.5

0.3

2

10

-5.5

30.3

3

15

-0.5

0.3

4

15

-0.5

0.3

5

15

-0.5

0.3

6

13

-2.5

6.3

7

12

-3.5

12.3

8

12

-3.5

12.3

9

13

-2.5

6.3

10

16

0.5

0.3

11

26

10.5

110.3

12

14

-1.5

2.3

13

17

1.5

2.3

14

22

605

42.3

15

17

1.5

2.3

Sum =

232

-0.5

228.5

— 232

X = 	 = 15 . 5 = mean of N counts :

15

Gaussian s = \j 228 . 5 / 14 = 4.0

for minimum detectable concentration, Sb = s/t = 4.0/50 = 0.08
where: s = Standard deviation;

\J < X. ~ X ) 2
s = 		

N - 1

t = Background count time (min); and
N = Number of counts.

Poisson s = ^15.5 =3.9

-------
4.66 x S

MDCa= 	—

2.22 x E x V

where:	MDC = The minimum detectable concentration;

Sb	= The standard deviation of background count rate (count per minute) based on Gaussin statistics = O.i

2.22	= Dpm/pCi;

E	= The counting efficiency (cpm/dpm) = 0.14;

V	= Volume or weight = 0.10 g; and

t = Count time = 50 min.

MDCa =

4.66 x 0.08
2.22 x 0.14 x 0.1

12 pCi / gm

7.3.2 Example. Beta Background-Soil

Test

X (Count)

X-X

(X-X)2

1

152

-6.8

46.2

2

157

-1.8

3.2

3

149

-9.8

96.0

4

161

2.2

4.8

5

148

-10.8

116.6

6

166

7.2

51.8

7

157

-1.8

3.2

8

165

6.2

38.4

9

132

-26.5

718.2

10

160

1.2

1.4

11

178

19.2

368.6

12

177

18.2

331.2

13

158

-0.8

0.6

14

159

0.2

0.04

15

163

4.2

17.6

Sum =

2382

0.0

1797.8

X = ^382 _ ^ j- _ mean ^ counts
15

-------
Gaussian s = ^17 97.8/14 =11.3

for minimum detectable concentration, Sb = s/t = 11.3/50 = 0.23

Poisson s = ^158 . 8 = 12 . 6

-------
4.66 x S

MDCB= 	—

2.22 x E x V

MDC(3

4.66 x 0.23

2.22 x 0.4

0.1

= 12 pCi / gm

7.4 CSL Detectable Concentration "MDC" Method (Water)

The data listed was developed using samples prepared by the CSL. These data sets used the CH2M HILL-supplied D.I.
water and NBS No. 114 uranium solution for counter efficiency.

NOTE: A test was conducted to determine if use of the uranium efficiency was acceptable for determining gross beta
results for samples containing Tc-99. It was determined that the difference between natural uranium and Tc-99
efficiencies for water samples (with low solids) was less than 10 percent. Because this represents a small error and the
CSL is a "screening" lab, it is acceptable to use the natural uranium efficiency for determining gross beta results for water
samples.

-------
HMOMffll-I

-------
— 46

X = 	 = 3.1= mean of N counts

15

Gaussian s = ^36.8/14 =1.6

for minimum detectable concentration, Sb = s/t = 1.6/50 = 0.032
where: s = Standard deviation;

\l < X. ~ X ) 2
N ~ 1

t = Background count time (min); and
N = Number of counts.

Poisson s = \/3 . 1 =1.1

4.66 x S
MDCa-	b

2.22 x E x V x A

where:	MDC = The minimum detectable concentration;

Sb	= The standard deviation of background count rate (count per minute) based on Gaussin statistics = O.i

2.22	= Dpm/pCi;

E	= The counting efficiency (cpm/dpm);

V	= Volume or weight;

t =	Count time = 50 min; and
A = Self-absorption.

MDCa = 	4 . 66 x o . 32	 = 10.3 pCi / L

2.22 x 0.21 x 0.1 x 0.31

-------
7.4.2 Example. Beta Background-D.I.Water

Test

X (Count)

x-"x

(X-X)2

1

52

4.0

16.0

2

61

13.0

169.0

3

55

7.0

49.0

4

40

-8.0

64.0

5

41

-7.0

49.0

6

54

6.0

36.0

7

37

-11.0

121.0

8

61

13.0

169.0

9

40

-8.0

64.0

10

49

1.0

1.0

11

52

4.0

16.0

12

57

9.0

81.0

13

40

-8.0

64.0

14

40

-0.8

64.0

15

41

-7.0

49.0

Sum =

720

0.0

1012.0

— 720

X = 	 = 48 = mean of N counts :

15

for minimum detectable concentration, Sv = s/t = 8.5/50 = 0.17

Poisson s = J48 =6.9

MDCP =

4.66 x S

b

2.22 x E x V x A

MDCP =

4.66 x 0.17

2.22 x 0.37 x 0.1 x 0.665

14 . 5 pCi / L

ffMC-m-«)ii-®

-------
8.0 QUALITY CONTROL

Information not available.
9.0 METHOD PERFORMANCE

Information not available.
10.0 REFERNCES

Information not available.

-------
CSL Method

RADIOCHEMICAL/RADIOCHEMICAL ANALYSIS EFFICIENCY.
BACKGROUND. AND RECOVERY STANDARDS fCOUNTER) PREPARATION

1.0 SCOPE AND APPLICATION

1.1 This procedure applies to tertiary standards prepared for use in the CSL to assess counting efficiencies, backgrounds and
radiochemical recoveries for the various samples being analyzed by the CSL for gross alpha/beta activity.

1.2 The methods used are modifications of the standard radiochemical procedures and reflect the flexibility necessary to
operate a field laboratory. The CSL has limited analyses capabilities and a 48-hour turnaround requirement for data reporting.

1.3 These methods will meet the "minimum detectable concentration requirements" necessary to ship samples offsite under
the regulations established in the Department of Transportation (DOT) 10CFR49, Part 173.

1.4 These methods also meet the requirements to ship samples to vendor laboratories and CH2M HILL's laboratory.
2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

Information not available.

5.0 REAGENTS

5.1 Standard Solutions: Provided to the CSL by a certified laboratory. These are in solution and traceable to NIST; for
gross alpha/beta in soil/solids; a uranium standard with parent/daughter in equilibrium (NBS No. 114) 375 dpm/mL (alpha and
beta).

5.2 Technetium-99: For water sample (chemical recovery spikes), NBS No.211-45, at 4,440 dpm/mL is provided.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not provided.

7.0 PRODEDURE

7.1 Laboratory counting equipment shall be certified as meeting the manufacturers acceptance procedures before proceeding
to employ these methods.

7.2 The laboratory counting equipment should be rechecked, at a minimum, quarterly and when the P2 counting gas is
changed; to insure continued proper counter operations.

7.3 Soil Efficiency Counting on a 2-inch Stainless Steel Planchet

ffMC-m-«2-ll

-------
7.3.1 Using the electric engraver, engrave the date, type sample, isotope, and dpm/unit on the rear, of the planchet.

Obtain a tare weight; record the weight of the planchet on the analytical balance sheet or radiochemical worksheet (for
appropriate for the sample analysis).

7.3.1.1 Obtain the background soil. Transfer 10 grams of the soil to a weighting tin and place in the drying oven (set at
100°C). Allow to dry for a sufficient time to remove any moisture in the soil.

7.3.1.2 Remove soil and allow to cool. Transfer sufficient soil to a mortar/pestle set and grind sufficiently to pass
through the sample mill.

7.3.1.3 Place a milling sample bottle under the output of the milling unit. Place unit power switch "ON."

7.3.1.4 Carefully transfer the soil into the milling harper and allow the soil to enter the unit rotor. Allow all soil, in the
harper, to pass through the unit. When all the soil has passed through the unit rotor, press the air valve down and remove
the sample bottle. Once bottle is removed, release the air valve and place the power switch in the "OFF" position.

7.3.1.5 Cap the sample bottle. Proceed to clean the milling unit.

7.3.1.6 Place the capped milling bottle and numbered planchet on a sample tray. Obtain a radiochemical analysis
worksheet and proceed to the analytical balance.

7.3.1.7 Press the function bar to power on the balance. When the balance has proceeded through the selfcheck mode
and readout indicates "0.0000" proceed with the weighing.

7.3.1.8 Open the balance glass door and place the empty planchet (using tweezers) on the balance pan, close the glass
door allow balance to reach a stable reading. Record the planchet tare weight.

7.3.1.9 Reopen the balance glass door. Using a microspatula transfer small quantities of the background soil to the
planchet. Continue to transfer the soil until the readout indicates "O. 1000" indicating a 100 mg soil sample by weight.
The weight can vary no greater than 5 percent of the total weight (95-105 mg).

7.3.1.10 Record the weight of the soil on the radiochemistry worksheet. Recap the soil milling bottle and carefully
remove the planchet, with soil, from the balance pan. Place the planchet on the sample tray. NOTE: Do not remove the
planchet when the room heating fan is on.

7.3.1.11 Close the balance glass door and press the function switch up momentarily to power "OFF" the unit.

7.3.2 Standard Sample Preparation:

7.3.2.1 Place the planchet, with soil, in the fume hood. Exhaust fan "OFF". Ensure that the lamp assembly and base are
in place and the base surface is clean.

7.3.2.2 Transfer the planchet to the lamp base surface. Using a wooden applicator carefully spread the soil evenly over
the surface of the planchet.

7.3.2.3 Obtain the NBS standard solution (NBS No. 114 uranium or NBS No. 211-45 Technetium). Using an automatic
pipet with the disposable tip remove 1 mL of the standard solution from the vial.

7.3.2.4 Dropwise, transfer the standard solution to the soil surface (Technique: Begin at the outer edge of the planchet
and with a clockwise motion, apply the solution, working continually toward the center of the planchet). Place the heat
lamp "ON" and allow the soil to dry.

-------
7.3.2.5 To ensure a uniform mix of the soil and the standard and to adhere the soil to the planchet surface, a 1 mL
solution of 2-Propanol (50 percent) is applied.

7.3.2.6 Using an automatic pipet, draw a 1 mL volume of the 2-Propanol from the container. Slowly transfer the
solution to the dried soil. Using the lip of the disposable pipet tip, carefully mix the soil and solution. Ensure that the
sample is removed from the pipet. Rinse the applicator tip with a few drops of D.I. water and allow the soil to dry.

7.3.2.7 Remove the dried sample and allow to cool; reweigh the planchet and record the weight of the planchet, soil and
standard solution in the radiochemist project log.

7.3.2.8 Count the planchet for sufficient time to insure proper counting statistics.

7.4 Water Efficiency Counting Standard (Method D

7.4.1 The NBS traceable solution is for the Water Standard Method I. Place a 250 mL glass beaker in the fume hood and
transfer a 100 mL sample of D.I. water to the beaker. To the beaker add 1 mL of the standard solution (uranium or
technetium).

7.4.2 Obtain a solution of 8N HN03 from the acid storage cabinet and using a squeeze bottle transfer about 10-15 mL of
the acid to the beaker.

7.4.3 Transfer the beaker to the hot plate set on position "3." Allow the solution to dry to wet dryness.

7.4.3.1 Remove the beaker and allow to cool.

7.4.3.2 Obtain the oxidizing solution by (8N HN03 and H202) adding 10 mL of 8N HN03; then 20 mL of H202 (30
percent), if required. Return the beaker to the hot plate and take to wet dryness.

7.4.3.3 Remove the beaker from the hot plate and allow to cool. Obtain a solution using 0.5N HN03 and scrub sides of
beaker with a rubber policeman. Obtain a 2-inch stainless steel planchet; then weigh the planchet; and record the weight.

7.4.3.4 Place the planchet in the fume hood (on the lamp assembly base).

7.4.3.5 Using a squeeze bottle, add about 5 mL of the 0.5N HN03 to the beaker. Using the rubber policeman, scrub the
the beaker; allow to settle. Carefully transfer the solution to the planchet.

7.4.3.6 Place the the heat lamp "ON" and allow to dry.

7.4.3.7 Repeat the procedure a total of three times and each time allow the solution to dry before the next application (to
prevent salt buildup on the side of the planchet).

7.4.3.8 Remove the planchet and allow to cool. Reweigh the planchet and record the weight of the residues on the
planchet.

7.4.3.9 Count and record the data. Calculate the "MDC."

7.5 Water Efficiency Counting Satndard (DOT Shipping Limits Modified Procedure') (Method ID
(Currently Not Used)

7.5.1 Obtain stainless steel planchet and record a tare weight.

7.5.2 Place a 250 mL glass beaker in the fume hood and transfer 20 mL of D.I. water, 1 mL solution of the U-238
standard solution, and about 10 mL of 8N HN03 to the beaker.

-------
7.5.3	Place the beaker on the hot plate and evaporate the solution to wet dryness. Remove beaker and allow to cool. Add
about 5 mL of 8N HN03, and 5 mL of H202 if required; return to the hot plate and take to wet dryness.

7.5.4	Transfer the solution to the planchet, as described in 7.4.3.5.

7.5.5	Reweigh the planchet following drying and cooling. Record the weight of the residue on the radiochemical analysis
report.

7.5.6	Count the sample as in method I.

7.6 The background to use in the calculation is obtained by using procedures given in methods I and II without adding the
standard solutions.

7.6.1	Place the planchet in the fume hood and on the lamp base. Using the procedures defined in method I, dropwise add
the solution to the planchet and allow to dry. Reweigh and record the weight.

7.6.2	Count the planchet as in method I and record the results.

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

-------
CSL

RADIOLOGICAL/DAILY OPERATION OF THE LB 1500 GAS PROPORTIONAL COUNTER

1.0 SCOPE AND APPLICATION

1.1 This procedure is applicable to the operation of the LB5100 Series II Gas Proportional Alpha/Beta Counting System used
in the C SL.

2.0 SUMMARY OF METHODS

2.1	The LB5100 is an automatic Alpha/Beta counting system; with an accompanying software operational system. These
software programs allow the system to be setup under the manufactures acceptance test (HV Setting) with various user defined
parameters input and saved on a diskette.

2.2	The LB5100 Gas Proportional Alpha/Beta Counting System is operated by following the Tennelec Operators Manual for
Rev. 3.3 software.

2.3	The counting system is operated on a firm and sturdy surface.

2.4	The counting system is kept clean and free of dust.

3.0 INTERFERENCES

Information not avaialable.

4.0 APPARATUS AND MATERIALS

4.1	Tennelec LB5100 Series II Counting System.

4.2	Tennelec Sample Carriers: Sample/group carriers.

4.3	Tennelec Stainless Steel Sample Holders: Shallow and deep holders.

4.4	P-10 Counting Gas.

4.5	Alpha/Beta Calibrating Sources.

4.6	Sample Planchets 2-Inch: Aluminum and stainless steel.

4.7	Tennelec Operational Software Rev. 3.3.

4.8	Supply of Low Density DS/DD 5-1/4-inch Diskettes.

4.9	Printer.

4.10	Printer Paper: Tractor feed type, 8-1/2-inch by 11 -inch removal edge.

5.0 REAGENTS

Information not available.

ffMC-m-«)B-ll

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not available.

7.0 PROCEDURE

7.1	An operational sample set is counted, at a minimum, every other day to access counter operation acceptability with
control charts maintained as a part of the QA/QC program, for the CSL. The daily operational sample set is maintained on the
counter as follows:

•	Group end carrier;

•	Blank carrier;

•	Group "a" carrier;

•	Carrier no. 1; carrier with a csl blank 2-inch planchet;

•	Carrier no. 4; carrier with a background soil on a polished planchet

•	Carrier no. 5; carrier with a soil efficiency standard (NBS No. 114 uranium solution)

7.2	Samples are prepared on 2-inch aluminum planchets (soil) and 2-inch stainless steel (water/sediment) for CSL sample
procedures.

7.3	A numbered/coded sample carrer (shallow sample holder) is selected and the planchet with the CH2M HILL sample
number placed on back of planchet is transferred to the holder.

7.4	Select a group carrier appropriate to the sample(s) being counted and load ahead of the first sample to be counted in the
group. NOTE: Group parameters are preset by the operator for each group (using the group setting command) and saved to a
record file (LB5100.IDN) on diskette. The group parameter can be modified by the operator as needed (reference the LB5100
operators manual for complete instructions.)

7.5	A second, third, etc., sample group can be loaded as required by the needs of the CSL sample screening project.

7.6	A end coded carrier is loaded to instruct the system to restack the automatic sample loader and restart the counting
sequence. NOTE: An empty carrier, with sample holder, is placed after the end carrier to keep room dust from settling on the last
sample in the sample set.)

8.0 QUALITY CONTROL

Information not available.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERNCES

Information not available.

-------
CSL MEETHOD

RADIOLOGICAL/SETUP AND OPERATION OF THE COUNTER TOP CENTRIFUGE

1.0 SCOPE AND APPLICATION

1.1	This method covers samples introduced into the CSL requiring the use of the Counter Top Centrifuge.

1.2	A number of samples will be introduced into the CSL requiring centrifugation. These samples will be ground water
samples, surface water or other water samples deemed by the radiochemist to require centrifuging.

2.0 SUMMARY OF METHOD

Information not available.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1	IEC Model HN-SH General Purpose Centrifuge: Model 2355 with horizontal rotor.

4.2	Rotor No. 958 (6 places').

4.3	Trunnion and Ring No. 325.

4.4	Shield Carrier No. 320.

4.5	Centrifuge Bottles with Screw Cap C35 mLY
5.0 REAGENTS

Information not available.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Information not avialable.

7.0 PROCEDURE

7.1	Open the centrifuge cavity and insure the Trunnion Rings are in place.

7.2	Place a set of tube shields in the centrifuge tube holder; check that the rubber spacer and cup are in place.

7.3	Obtain 4 centrifuge bottles and screw type caps and place the bottles in the tube shields.

7.4	To one of the bottles add 35 mL of D.I. water and screw on cap tightly.

7.5	To each of the other 3 bottles transfer an equal volume of the sample to be centrifuged.

ffMC-m-«-ll

-------
7.6 To each of the samples add about 10 drops of 8N HN03; screw cap on tightly and shake the sample; return the sample to
the centrifuge shield.

7.7 Place the tube shields into the certrifuge trunnion rings. For a 100 mL water sample use only 4 rings and place the D.I.
water sample opposite one of the samples to balance the centrifuge load.

7.8 Close and lock the centrifuge top.

7.9 Turn the power switch to "ON".

NOTE: Before truning on the power switch insures that the timer and speed switches are in the off or "O" position.

7.10 Set the Timer Control for 10 minutes.

7.11 Slowly increase the speed control until the centrifuge rotor begins to operate. Allow the unit to come to speed at the
low speed setting; then slowly increase the speed control to the 3/4 setting (this setting will give you approximately 2500 RPM).

NOTE: Do not exceed 2800 rpm using the equipment set-up presently in place. See reference chart 3.3 in the IM201
instruction manual for additional information.

7.12 Allow the sample to centrifuge for 10 minutes; the centrifuge must come to a complete stop before the top is opened.

7.13 When the centrifuge comes to a complete stop; open the top and remove the tube shields one at a time. Place, the tube
shields into the centrifuge tube rack.

7.14 Set the centrifuge rack, with samples, into the fume hood.

7.15 Obtain a 250 mL glass beaker and mark with the sample No. and carefully transfer the liquid phase of the sample for
each centrifuge bottle containing a sample.

7.16 Proceed with CSL procedure for processing liquid and sediment fractions of the water sample.

7.17 Obtain a tared weight tin and mark with the sample No.; using small aliquots of D.I. water and a glass stirring rod
transfer the solid phase of the sample to the weigh tin.

NOTE: When the sediment phase is small the solid sample can be transferred directly to a tared couting planchet. Take
care to not exceed the 100 mg/cm2 total weight for solid samples.

7.18 Place the weighing tin in the drying oven and dry the sediment sample.

NOTE: When sample is transferred directly to a counting planchet dry the sample under the infrared heat lamp.

7.19 Remove the weighing tin and reweigh and record the weight of the sample.

7.20 Obtain a tared counting planchet and mark with the sample number. Transfer 100 milligrams of the sediment and treat
as a solid sample.

7.21 Proceed with the solid phase of CSL procedure.

8.0 QUALITY CONTROL

Information not available.

-------
9.0 METHOD PERFORMANCE

Information not available.
10.0 REFERNCES

Information not available.

-------
ERT Method

SAMPLING EQUIPMENT DECONTAMINATION

1.0 SCOPE AND APPLICATION

1.1 The purpose of this standard operating procedure (SOP) is to provide a description of the methods used for preventing,
minimizing, or limiting cross-contamination of samples due to inappropriate or inadequate equipment decontamination and to
provide general guidelines for developing decontamination procedures for sampling equipment to be used during hazardous waste
operations as per 29 Code of Federal Regulations (CFR) 1910.120. This SOP does not address personnel decontamination.

1.2 These are standard (i.e. typically applicable) operating procedures which may be varied or changed as required,
dependent upon site conditions, equipment limitation, or limitations imposed by the procedure. In all instances, the ultimate
procedures employed should be documented and associated with the final report. Mention of trade names or commercial products
does not constitute U.S. Environmental Protection Agency (U.S. EPA) endorsement or recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Removing or neutralizing contaminants from equipment minimizes the likelihood of sample cross contamination,
reduces or eliminates transfer of contaminants to clean areas, and prevents the mixing of incompatible substances. Gross
contamination can be removed by physical decontamination procedures. These abrasive and non-abrasive methods include the use
of brushes, air and wet blasting, and high and low pressure water cleaning.

2.2 The first step, a soap and water wash, removes all visible particulate matter and residual oils and grease. This may be
preceded by a steam or high pressure water wash to facilitate residuals removal. The second step involves a tap water rinse and a
distilled/deionized water rinse to remove the detergent. An acid rinse provides a low pH media for trace metals removal and is
included in the decontamination process if metal samples are to be collected. It is followed by another distilled/deionized water
rinse. If sample analysis does not include metals, the acid rinse step can be omitted. Next, a high purity solvent rinse is performed
for trace organics removal if organics are a concern at the site. Typical solvents used for removal of organic contaminants include
acetone, hexane, or water. Acetone is typically chosen because it is an excellent solvent, miscible in water, and not a target analyte
on the Priority Pollutant List. If acetone is known to be a contaminant of concern at a given site or if Target Compound List
analysis (which includes acetone) is to be performed, another solvent may be substituted. The solvent must be allowed to
evaporate completely and then a final distilled/deionized water rinse is performed. This rinse removes any residual traces of the
solvent.

2.3 The decontamination procedure described above may be summarized as follows:

2.3.

.1.

Physical removal

2.3.

Non-phosphate detergent wash

2.3.

Tap water rinse

2.3.

Distilled/deionized water rinse

2.3.

10% nitric acid rinse

2.3.

Distilled/deionized water rinse

2.3.

Solvent rinse (pesticide grade)

2.3.

Air dry

2.3.

Distilled/deionized water rinse

EMC-SM4MI-11

-------
2.4 If a particular contaminant fraction is not present at the site, the nine (9) step decontamination procedure specified above
may be modified for site specificity. For example, the nitric acid rinse may be eliminated if metals are not of concern at a site.
Similarly, the solvent rinse may be eliminated if organics are not of concern at a site. Modifications to the standard procedure
should be documented in the site specific work plan or subsequent report.

3.0 INTERFERENCES

3.1 The use of distilled/deionized water commonly available from commercial vendors may be acceptable for
decontamination of sampling equipment provided that it has been verified by laboratory analysis to be analyte free (specifically for
the contaminants of concern).

3.2 The use of an untreated potable water supply is not an acceptable substitute for tap water. Tap water may be used from
any municipal or industrial water treatment system.

3.3 If acids or solvents are utilized in decontamination they raise health and safety, and waste disposal concerns.

3.4 Damage can be incurred by acid and solvent washing of complex and sophisticated sampling equipment.
4.0 APPARATUS AND MATERIALS

Decontamination equipment, materials, and supplies are generally selected based on availability. Other considerations
include the ease of decontaminating or disposing of the equipment. Most equipment and supplies can be easily procured. For
example, soft-bristle scrub brushes or long-handled bottle brushes can be used to remove contaminants. Large galvanized wash
tubs, stock tanks, or buckets can hold wash and rinse solutions. Children's wading pools can also be used. Large plastic garbage
cans or other similar containers lined with plastic bags can help segregate contaminated equipment. Contaminated liquid can be
stored temporarily in metal or plastic cans or drums. The following standard materials and equipment are recommended for
decontamination activities.

4.1 Decontamination Solutions: Non-phosphate detergent, selected solvents (acetone, hexane, nitric acid, etc), tap water,
distilled or deionized water.

4.2 Decontamination Tools/Supplies: Long and short handled brushes, bottle brushes, drop cloth/plastic sheeting, paper
towels, plastic or galvanized tubs or buckets, pressurized sprayers (h2o), solvent sprayers, aluminum foil.

4.3 Health and Safety Equipment: Appropriate personal protective equipment (i.e., safety glasses or splash shield,
appropriate gloves, aprons or coveralls, respirator, emergency eye wash).

4.4 Waste Disposal: Trash bags, trash containers, 55-gallon drums, metal/plastic buckets/containers for storage and disposal
of decontamination solutions.

5.0 REAGENTS

There are no reagents used in this procedure aside from the actual decontamination solutions. Table 1 (Appendix A) lists
solvent rinses which may be required for elimination of particular chemicals. In general, the following solvents are typically
utilized for decontamination purposes:

5.1 10% Nitric Acid: used for inorganic compounds such as metals. An acid rinse may not be required if inorganics are not
a contaminant of concern.

5.2 Acetone (pesticide grade)1-1-1.

5.3 Hexane (pesticide grade)1-1-1.

5.4 Methanol(1)

EMC-3MMD11-2

-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 The amount of sample to be collected and the proper sample container type (i.e., glass, plastic), chemical preservation,
and storage requirements are dependent on the matrix being sampled and the parameter(s) of interest.

6.2 For the soil and water matrices, these are discussed in ERT/REAC SOP #2003, Sample Storage, Preservation and
Handling. For air and waste samples, sample preservation, containers, handling, and storage are discussed in the specific SOPs for
the technique selected.

6.3 More specifically, sample collection and analysis of decontamination waste may be required before beginning proper
disposal of decontamination liquids and solids generated at a site. This should be determined prior to initiation of site activities.

7.0 PROCEDURES

7.1 As part of the health and safety plan, a decontamination plan should be developed and reviewed. The decontamination
line should be set up before any personnel or equipment enter the areas of potential exposure. The equipment decontamination plan
should include:

7.1.1 The number, location, and layout of decontamination stations.

7.1.2 Decontamination equipment needed.

7.1.3 Appropriate decontamination methods.

7.1.4 Methods for disposal of contaminated clothing, equipment, and solutions.

7.1.5 Procedures can be established to minimize the potential for contamination. This may include: (1) work practices
that minimize contact with potential contaminants; (2) using remote sampling techniques; (3) covering monitoring and
sampling equipment with plastic, aluminum foil, or other protective material; (4) watering down dusty areas; (5) avoiding
laying down equipment in areas of obvious contamination; and (6) use of disposable sampling equipment.

(1) Only if sample is to be analyzed for organics.

7.2 Decontamination Methods

All samples and equipment leaving the contaminated area of a site must be decontaminated to remove any contamination
that may have adhered to equipment. Various decontamination methods will remove contaminants by:(l) flushing or other
physical action, or (2) chemical complexing to inactivate contaminants by neutralization, chemical reaction, disinfection, or
sterilization. Physical decontamination techniques can be grouped into two categories: abrasive methods and non-abrasive
methods, as follows:

7.2.1 Abrasive Cleaning Methods: Abrasive cleaning methods work by rubbing and wearing away the top layer of the
surface containing the contaminant. The mechanical abrasive cleaning methods are most commonly used at hazardous waste
sites. The following abrasive methods are available:

7.2.1.1 Mechanical: Mechanical methods of decontamination include using metal or nylon brushes. The amount and
type of contaminants removed will vary with the hardness of bristles, Length of time brushed, degree of brush contact,
degree of contamination, nature of the surface being cleaned, and degree of contaminant adherence to the surface.

7.2.1.2 Air Blasting: Air blasting equipment uses compressed air to force abrasive material through a nozzle at high
velocities. The distance between nozzle and surface cleaned, air pressure, time of application, and angle at which the

EMC-SMMDll-S

-------
abrasive strikes the surface will dictate cleaning efficiency. Disadvantages of this method are the inability to control the
amount of material removed and the large amount of waste generated.

7.2.1.3 Wet Blasting: Wet blast cleaning involves use of a suspended fine abrasive. The abrasive/water mixture is
delivered by compressed air to the contaminated area. By using a very fine abrasive, the amount of materials removed can
be carefully controlled.

7.2.2 Non-Abrasive Cleaning Methods: Non-abrasive cleaning methods work by forcing the contaminant off a surface
with pressure. In general, the equipment surface is not removed using non-abrasive methods.

7.2.2.1 Low-Pressure Water: This method consists of a container which is filled with water. The user pumps air out of
the container to create a vacuum. A slender nozzle and hose allow the user to spray in hard-to-reach places.

7.2.2.2 High-Pressure Water: This method consists of a high-pressure pump, an operator controlled directional nozzle,
and a high-pressure hose. Operating pressure usually ranges from 340 to 680 atmospheres (atm) and flow rates usually
range from 20 to 140 liters per minute.

7.2.2.3 Ultra-High-Pressure Water: This system produces a water jet that is pressured from 1,000 to 4,000 atmospheres.
This ultra-high-pressure spray can remove tightly-adhered surface films. The water velocity ranges from 500
meters/second (m/s) (1,000 atm) to 900 m/s (4,000 atm). Additives can be used to enhance the cleaning action.

7.2.3 Disinfection/Rinse Methods:

7.2.3.1 Rinsing: Contaminants are removed by rinsing through dilution, physical attraction, and solubilization.

7.2.3.2 Damp Cloth Removal: In some instances, due to sensitive, non-waterproof equipment or due to the
unlikelihood of equipment being contaminated, it is not necessary to conduct an extensive decontamination procedure.For
example, air sampling pumps hooked on a fence, placed on a drum, or wrapped in plastic bags are not likely to become
heavily contaminated. A damp cloth should be used to wipe off contaminants which may have adhered to equipment
through airborne contaminants or from surfaces upon which the equipment was set.

7.2.3.3 Disinfection/Sterilization: Disinfectants are a practical means of inactivating infectious agents. Unfortunately,
standard sterilization methods are impractical for large equipment. This method of decontamination is typically performed
off-site.

7.3 Field Sampling Equipment Decontamination Procedures

7.3.1 The decontamination line is setup so that the first station is used to clean the most contaminated item. It progresses
to the last station where the least contaminated item is cleaned. The spread of contaminants is further reduced by separating
each decontamination station by a minimum of three (3) feet. Ideally, the contamination should decrease as the equipment
progresses from one station to another farther along in the line.

7.3.2 A site is typically divided up into the following boundaries: Hot Zone or Exclusion Zone (EZ), the Contamination
Reduction Zone (CRZ), and the Support or Safe Zone (SZ). The decontamination line should be setup in the Contamination
Reduction Corridor (CRC) which is in the CRZ. Figure 1 (Appendix B) shows a typical contaminant reduction zone layout.
The CRC controls access into and out of the exclusion zone and confines decontamination activities to a limited area. The
CRC boundaries should be conspicuously marked. The far end is the hotline, the boundary between the exclusion zone and
the contamination reduction zone. The size of the decontamination corridor depends on the number of stations in the
decontamination process, overall dimensions of the work zones, and amount of space available at the site. Whenever
possible, it should be a straight line.

EMC-SMMDM

-------
7.3.3 Anyone in the CRC should be wearing the level of protection designated for the decontamination crew. Another
corridor may be required for the entry and exit of heavy equipment. Sampling and monitoring equipment and sampling
supplies are all maintained outside of the CRC. Personnel don their equipment away from the CRC and enter the exclusion
zone through a separate access control point at the hotline. One person (or more) dedicated to decontaminating equipment is
recommended.

7.4 Calculations

This section is not applicable to this SOP.

7.5 Health and Safety

7.5.1 When working with potentially hazardous materials, follow OSHA, U.S. EPA, corporate, and other applicable
health and safety procedures.

7.5.2 Decontamination can pose hazards under certain circumstances. Hazardous substances may be incompatible with
decontamination materials. For example, the decontamination solution may react with contaminants to produce heat,
explosion, or toxic products. Also, vapors from decontamination solutions may pose a direct health hazard to workers by
inhalation, contact, fire, or explosion.

7.5.3 The decontamination solutions must be determined to be acceptable before use. Decontamination materials may
degrade protective clothing or equipment; some solvents can permeate protective clothing. If decontamination materials do
pose a health hazard, measures should be taken to protect personnel or substitutions should be made to eliminate the hazard.
The choice of respiratory protection based on contaminants of concern from the site may not be appropriate for solvents used
in the decontamination process.

7.5.4 Safety considerations should be addressed when using abrasive and non-abrasive decontamination equipment.
Maximum air pressure produced by abrasive equipment could cause physical injury. Displaced material requires control
mechanisms.

7.5.5 Material generated from decontamination activities requires proper handling, storage, and disposal. Personal
Protective Equipment may be required for these activities.

7.5.6 Material safety data sheets are required for all decontamination solvents or solutions as required by the Hazard
Communication Standard (i.e., acetone, alcohol, and trisodiumphosphate).

7.5.7 In some jurisdictions, phosphate containing detergents (i.e., TSP) are banned.

8.0 QUALITY CONTROL

8.1 A rinsate blank is one specific type of quality control sample associated with the field decontamination process. This
sample will provide information on the effectiveness of the decontamination process employed in the field. Rinsate blanks are
samples obtained by running analyte free water over decontaminated sampling equipment to test for residual contamination. The
blank water is collected in sample containers for handling, shipment, and analysis. These samples are treated identical to samples
collected that day. A rinsate blank is used to assess cross contamination brought about by improper decontamination procedures.
Where dedicated sampling equipment is not utilized, collect one rinsate blank per day per type of sampling device samples to meet
QA2 and QA3 objectives. For further information, refer to ERT/REAC SOP #2005, Quality Control Samples.

9.0 METHOD PERFORMANCE

Inforamtion not available.

10.0 REFERENCES

EMC-3MMD11-5

-------
1.	Field Sampling Procedures Manual, New Jersey Department of Environmental Protection, February, 1988.

2.	A Compendium of Superfund Field Operations Methods, EPA 540/p-87/001.

3.	Engineering Support Branch Standard Operating Procedures and Quality Assurance Manual, USEPA Region IV, April 1,
1986.

4.	Guidelines for the Selection of Chemical Protective Clothing, Volume 1, Third Edition, American Conference of
Governmental Industrial Hygienists, Inc., February, 1987.

5.	Occupational Safety and Health Guidance Manual for Hazardous Waste Site Activities,

NIO SH/O SHA/USC G/EPA, October, 198

-------
Table 1

RECOMMENDED SOLVENTS FOR SOLUBLE CONTAMINANTS

SOLVENT

SOLUBLE CONTAMINANTS

Water

•	Low-chain hydrocarbons

•	Inorganic compounds

•	Salts

•	Some organic acids and other polar compounds

Dilute Acids

•	Basic (caustic) compounds

•	Amines

•	Hydrazines

Dilute Bases—for example detergent and
soap

•	Metals

•	Acidic compounds

•	Phenol

•	Thiols

•	Some nitro and sulfonic compounds

Organic solevnts—for example, alcohols,
ethers, ketone,aromatics, straight chain
alkanes, and common petroleum
products

• Nonpolar compounds

EME-3MMD11-17

-------
ERT Method

SURFACE WATER SAMPLING

1.0 SCOPE AND APPLICATION

1.1 This standard operating procedure (SOP) is applicable to the collection of representative liquid samples, both aqueous
and non-aqueous from streams, rivers, lakes, ponds, lagoons, and surface impoundments. It includes samples collected from depth,
as well as samples collected from the surface.

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required,
dependent upon site conditions, equipment limitations or limitations imposed by the procedure or other procedure limitations. In
all instances, the ultimate procedures employed should

be documented and associated with the final report. Mention of trade names or commercial products does not constitute U.S.
Environmental Protection Agency (EPA) endorsement or recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Sampling situations vary widely, therefore, no universal sampling procedure can be recommended. However, sampling
of both aqueous and non-aqueous liquids from the above mentioned sources is generally accomplished through the use of one of the
following samplers or techniques:

• Kemmerer bottle

• Bacon bomb sampler

• Dip sampler

• Direct method

2.2 These sampling techniques will allow for the collection of representative samples from the majority of surface watersa
and impounments encountered.

3.0 INTERFERENCES AND POTENTIAL PROBLEMS

3.1 Cross contamination problems can be eliminated or minimized through the use of dedicated decontamination.

3.2 Improper sample collection can involve using contaminated equipment, disturbance of the stream or impoundment
substrate, and sampling in an obviously disturbed area.

3.3 Following proper decontamination procedures and minimizing disturbance of the sample site will eliminate these
problems.

4.0 APPARATUS AND MATERIALS

4.1 Kemmerer Bottles.

4.2 Bacon Bomb Sampler.

4.3 Dip Sampler.

4.4 Line and Messengers.

4.5 Sample Bottles/preservatives.

FMM
-------
4.6 Ziploc Bags.

4.7 Ice.

4.8 Coolers.

4.9 Chain of Custody Records. Custody Seals.

4.10

Field Data Sheets.

4.11

Decontamination Equipment.

4.12

Maps/plot Plan.

4.13

Safety Equipment.

4.14

Compass.

4.15

Tape Measure.

4.16

Survey Stakes. Flaes. or Buovs and Anchors.

4.17

Camera and Film.

4.18

Loebook/waterproof Pen.

4.19

Sample Bottle Labels.

5.0 REAGENTS

Reagents will be utilized for preservation of samples and for decontamination of sampling equipment. The preservatives
required are specified by the analysis to be performed and are summarized in ERT/REAC SOP #2003, Sample Storage,
Preservation and Handling. Decontamination solutions are specified in ERT/REAC SOP #2006, Sampling Equipment
Decontamination.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Transfer the sample(s) into suitable, labeled sample containers.

6.2 Preserve the sample if appropriate, or use pre-preserved sample bottles. Do not overfill bottles if they are pre-preserved.

6.3 Cap the container, place in a ziploc plastic bag and cool to 4°C.

6.4 Decontaminate all sampling equipment prior to the collection of additional samples with that sampling device.

7.0 PROCEDURES
7.1 Preparation

FfflEKSW&S0X>E-2

-------
7.1.1 Determine the extent of the sampling effort, the sampling methods to be employed, and the types and amounts of
equipment and supplies needed.

7.1.2 Obtain the necessary sampling and monitoring equipment.

7.1.3 Decontaminate or pre-clean equipment, and ensure that it is in working order.

7.1.4 Prepare scheduling and coordinate with staff, clients, and regulatory agency, if appropriate.

7.1.5 Perform a general site survey prior to site entry, in accordance with the site specific Health and Safety Plan.

7.1.6 Use stakes, flagging, or buoys to identify and mark all sampling locations. If required the proposed locations may
be adjusted based on site access, property boundaries, and surface obstructions. If collecting sediment samples, this
procedure may disturb the bottom.

7.2 Representative Sampling Considerations

7.2.1 In order to collect a representative sample, the hydrology and morphometries of a stream or impoundment should be
determined prior to sampling. This will aid in determining the presence of phases or layers in lagoons, or impoundments,
flow patterns in streams, and appropriate sample locations and depths.

7.2.2 Water quality data should be collected in impoundments, and to determine if stratification is present. Measurements
of dissolved oxygen, pH, and temperature can indicate if strata exist which would effect analytical results. Measurements
should be collected at one-meter intervals from the substrate to the surface using the appropriate instrument (i.e., a Hydrolab
or equivalent).

7.2.3 Water quality measurements such as dissolved oxygen, pH, temperature, conductivity, and oxidation-reduction
potential can assist in the interpretation of analytical data and the selection of sampling sites and depths when surface water
samples are collected.

7.2.4 Generally, the deciding factors in the selection of a sampling device for sampling liquids in streams, rivers, lakes,
ponds, lagoons, and surface impoundments are:

• Will the sample be collected from shore or from a boat?

• What is the desired depth at which you wish to collect the sample?

• What is the overall depth and flow direction of river or stream?

• What type of sample will be collected (i.e., water or lagoon liquids)?

7.2.5 The appropriate sampling device must be of a proper composition. Selection of samplers constructed of glass,
stainless steel, PVC or PFTE (Teflon) should be based upon the analyses to be performed.

7.3 Sample Collection

7.3.1 Kemmerer Bottle: A Kemmerer bottle (Figure 1, Appendix A) may be used in most situations where site access is
from a boat or structure such as a bridge or pier, and where samples at depth are required. Sampling procedures are as
follows:

FfflM-<$W$S(mB-3

-------
7.3.1.1 Use a properly decontaminated Kemmerer bottle. Set the sampling device so that the sampling end pieces
(upper and lower stoppers) are pulled away from the sampling tube (body), allowing the substance to be sampled to pass
through this tube.

7.3.1.2 Lower the pre-set sampling device to the predetermined depth. Avoid bottom disturbance.

7.3.1.3 When the Kemmerer bottle is at the required depth, send down the messenger, closing the sampling device.

7.3.1.4 Retrieve the sampler and discharge from the bottom drain the first 10-20 mL to clear any potential contamination
of the valve. Transfer the sample to the appropriate sample container.

7.3.2 Bacon Bomb Sampler: A bacon bomb sampler (Figure 2, Appendix A) may be used in situations similar to those
outlined for the Kemmerer bottle. Sampling procedures are as follows:

7.3.2.1 Lower the bacon bomb sampler carefully to the desired depth, allowing the line for the trigger to remain slack at
all times. When the desired depth is reached, pull the trigger line until taut. This will allow the sampler to fill.

7.3.2.2 Release the trigger line and retrieve the sampler.

7.3.2.3 Transfer the sample to the appropriate sample container by pulling up on the trigger.

7.3.3 Dip Sampler: A dip sampler (Figure 3, Appendix A) is useful in situations where a sample is to be recovered from
an outfall pipe or along a lagoon bank where direct access is limited. The long handle on such a device allows access from a
discrete location. Sampling procedures are as follows:

7.3.3.1 Assemble the device in accordance with the manufacturer's instructions.

7.3.3.2 Extend the device to the sample location and collect the sample by dipping the sampler into the substance.

7.3.3.3 Retrieve the sampler and transfer the sample to the appropriate sample container.

7.3.4 Direct Method

7.3.4.1 For streams, rivers, lakes, and other surface waters, the direct method may be utilized to collect water samples
from the surface directly into the sample bottle. This method is not to be used for sampling lagoons or other
impoundments where contact with contaminants is a concern.

7.3.4.2 Using adequate protective clothing, access the sampling station by appropriate means. For shallow stream
stations, collect the sample under the water surface while pointing the sample container upstream; the container must be
upstream of the collector. Avoid disturbing the substrate. For lakes and other impoundments, collect the sample under the
water surface avoiding surface debris and the boat wake.

7.3.4.3 When using the direct method, do not use pre-preserved sample bottles as the collection method may dilute the
concentration of preservative necessary for proper sample preservation.

7.4 Calculations

This section is not applicable to this SOP.

7.5 Health and Safety

7.5.1 When working with potentially hazardous materials, follow U.S. EPA, OSHA and corporate health and safety
procedures.

FfflEKSW&S«X>»-4

-------
7.5.2 More specifically, when sampling lagoons or surface impoundments containing known or suspected hazardous
substances, adequate precautions must be taken to ensure the safety of sampling personnel. The sampling team member
collecting the sample should not get too close to the edge of the impoundment, where bank failure may cause him/her to lose
his/her balance. The person performing the sampling should be on a lifeline and be wearing adequate protective equipment.
When conducting sampling from a boat in an impoundment or flowing waters, appropriate boating safety procedures should
be followed.

8.0 QUALITY CONTROL

8.1 There are no specific quality assurance (QA) activities which apply to the implementation of these procedures.

However, the following general QA procedures apply:

8.1.1 All data must be documented on field data sheets or within site logbooks.

8.1.2 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer,
unless otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to
sampling/operation and they must be documented.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. U.S. Geological Survey. 1977. National Handbook or Recommended Methods for Water Data Acquisition. Office of Water
Data Coordination Reston, Virginia. (Chapter Updates available).

2. U.S. Environmental Protection Agency. 1984. Characterization of Hazardous Waste Sites - A Methods Manual: Volume II.
Available Sampling Methods, Second Edition. EPA/600/4-84-076.

FMM
-------
ERT Method

SEDIMENT SAMPLING

1.0 SCOPE AND APPLICATION

1.1 This standard operating procedure (SOP) is applicable to the collection of representative sediment samples. Analysis of
sediment may be biological, chemical, or physical in nature and may be used to determine the following:

• toxicity;

• biological availability and effects of contaminants;

• benthic biota;

• extent and magnitude of contamination;

• contaminant migration pathways and source;

• fate of contaminants; and

• grain size distribution.

1.2 The methodologies discussed in this SOP are applicable to the sampling of sediment in both flowing and standing water.
They are generic in nature and may be modified in whole or part to meet the handling and analytical requirements of the
contaminants of concern, as well as the constraints presented by site conditions and equipment limitations. However, if
modifications occur, they should be documented in a site or personal logbook and discussed in reports summarizing field activities
and analytical results.

1.3 For the purposes of this procedure, sediments are those mineral and organic materials situated beneath an aqueous layer.
The aqueous layer may be either static, as in lakes, ponds, and impoundments; or flowing, as in rivers and streams.

1.4 Mention of trade names or commercial products does not constitute U.S. EPA endorsement or recommendation for use.
2.0 SUMMARY OF METHOD

2.1 Sediment samples may be collected using a variety of methods and equipment, depending on the depth of the aqueous
layer, the portion of the sediment profile required (surface vs. subsurface), the type of sample required (disturbed vs. undisturbed),
contaminants present, and sediment type.

2.2 Sediment is collected from beneath an aqueous layer either directly, using a hand held device such as a shovel, trowel, or
auger; or indirectly, using a remotely activated device such as an Ekman or Ponar dredge. Following collection, sediment is
transferred from the sampling device to a sample container of appropriate size and construction for the analyses requested. If
composite sampling techniques are employed, multiple grabs are placed into a container constructed of inert material,
homogenized, and transferred to sample containers appropriate for the analyses requested. The homogenization procedure should
not be used if sample analysis includes volatile organics; in this case, sediment, or multiple grabs of sediment, should be
transferred directly from the sample collection device or homogenization container to the sample container.

3.0 INTERFERENCES

3.1 Substrate particle size and organic matter content are a direct consequence of the flow characteristics of a waterbody.
Contaminants are more likely to be concentrated in sediments typified by fine particle size and a high organic matter content. This
type of sediment is most likely to be collected from depositional zones. In contrast, coarse sediments with low organic matter
content do not typically

concentrate pollutants and are generally found in erosional zones. The selection of a sampling location can, therefore, greatly
influence the analytical results and should be justified and specified in the work plan.

4.0 APPARATUS AND MATERIALS

FMM
-------
4.1 Ziploc Bags.

4.2 Ice.

4.3 Coolers.

4.4 Chain of Custody Records. Custody Seals.

4.5 Field data sheets.

4.6 Decontamination Equipment.

4.7 Maps/plot Plan.

4.8 Safety Equipment.

4.9 Compass.

4.10 Tape Measure.

4.11 Survey Stakes. Flags, or Buovs and Anchors.

4.12 Camera and Film.

4.13 Logbook/waterproof Pen.

4.14 Sample Bottle Labels.

4.15 Stainless Steel. Plastic, or Other Appropriate Composition Bucket.

4.16 4-oz.. 8-oz.. and One-quart Wide Mouth Jars w/Teflon Lined Lids.

4.17 Sample Jar Labels.

4.18 Spade or Shovel.

4.19 Spatula.

4.20 Scoop.

4.21 Trowel.

4.22 Bucket Auger.

4.23 Tube Auger.

4.24 Extension Rods.

4.25 "T" Handle.

4.26 Sediment Coring Device ftube. drive head, eggshell check value, nosecone. acetate tube, extension rods. "T" handle).

4.27 Ponar Dredge.

FMM2-2

-------
4.28 Ekman Dredge.

4.29 Nvlon Rope or Steel Cable.

4.30 Messenger Device.

5.0 REAGENTS

5.1 Reagents are not used for preservation of sediment samples. Decontamination solutions are specified in ERT/REAC
SOP #2006, Sampling Equipment Decontamination.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Chemical preservation of solids is generally not recommended. Cooling to 4°C is usually the best approach,
supplemented by the appropriate holding time for the analyses requested.

6.2 Wide mouth glass containers with Teflon lined caps are utilized for sediment samples. The sample volume is a function
of the analytical requirements and will be specified in the work plan.

6.3 If analysis of sediment from a discrete depth or location is desired, sediment is transferred directly from the sampling
device to a labeled sample container(s) of appropriate size and construction for the analyses requested. Transfer is accomplished
with a stainless steel or plastic lab spoon or equivalent.

6.4 If composite sampling techniques or multiple grabs are employed, equal portions of sediment from each location are
deposited into a stainless steel, plastic, or other appropriate composition (e.g., Teflon) containers. The sediment is homogenized
thoroughly to obtain a composite representative of the area sampled. The composite sediment sample is transferred to a labeled
container(s) of appropriate size and construction for the analyses requested. Transfer of sediment is accomplished with a stainless
steel or plastic lab spoon or equivalent. Samples for volatile organic analysis must be transferred directly from the sample
collection device or pooled from multiple areas in the homogenization container prior to mixing. This is done to minimize loss of
contaminant due to volatilization during homogenization.

6.5 All sampling devices should be decontaminated, then wrapped in aluminum foil. The sampling device should remain in
this wrapping until it is needed. Each sampling device should be used for only one sample. Disposable sampling devices for
sediment are generally impractical due to cost and the large number of sediment samples which may be required. Sampling
devices should be cleaned in the field using the decontamination procedure described in ERT/REAC SOP #2006, Sampling
Equipment Decontamination.

7.0 PROCEDURES

7.1 Preparation

7.1.1 Determine the objective(s) and extent of the sampling effort. The sampling methods to be employed, and the types

and amounts of equipment and supplies required will be a function of site characteristics and objectives of the study.

7.1.2 Obtain the necessary sampling and monitoring equipment.

7.1.3 Prepare schedules, and coordinate with staff, client, and regulatory agencies, if appropriate.

7.1.4 Decontaminate or preclean equipment, and ensure that it is in working order.

7.1.5 Perform a general site survey prior to site entry in accordance with the site specific Health and Safety Plan.

FMM3-3

-------
7.1.6 Use stakes, flagging, or buoys to identify and mark all sampling locations. Specific site factors including flow
regime, basin morphometry, sediment characteristics, depth of overlying aqueous layer, contaminant source, and extent and
nature of contamination should be considered when selecting sample locations. If required, the proposed locations may be
adjusted based on site access, property boundaries, and surface obstructions.

7.2 Sample Collection

Selection of a sampling device is most often contingent upon: (1) the depth of water at the sampling location, and (2) the
physical characteristics of the sediment to be sampled. The following procedures may be utilized:

7.2.1 Sampling Surface Sediment with a Trowel or Scoop from Beneath a Shallow Aqueous Laver: For the purpose of
this method, surface sediment is considered to range from 0 to six (6) inches in depth and a shallow aqueous layer is
considered to range from 0 to 12 inches in depth. Collection of surface sediment from beneath a shallow aqueous layer can
be accomplished with tools such as spades, shovels, trowels, and scoops. Although this method can be used to collect both
unconsolidated/consolidated sediment, it is limited somewhat by the depth and movement of the aqueous layer. Deep and
rapidly flowing water render this method less accurate than others discussed below. However, representative samples can be
collected with this procedure in shallow sluggish water provided care is demonstrated by the sample team member. A
stainless steel or plastic sampling implement will suffice in most applications. Care should be exercised to avoid the use of
devices plated with chrome or other materials; plating is particularly common with garden trowels. The following procedure
will be used to collect sediment with a scoop, shovel, or trowel.

7.2.1.1 Using a decontaminated sampling implement, remove the desired thickness and volume of sediment from the
sampling area.

7.2.1.2 Transfer the sample into an appropriate sample or homogenization container. Ensure that non-dedicated
containers have been adequately decontaminated.

7.2.1.3 Surface water should be decanted from the sample or homogenization container prior to sealing or transfer; care
should be taken to retain the fine sediment fraction during this procedure.

7.2.2 Sampling Surface Sediment with a Bucket Auger or Tube Auger from Beneath a Shallow Aqueous Laver: For the
purpose of this method, surface sediment is considered to range from 0 to six (6) inches in depth and a shallow aqueous layer
is considered to range from 0 to 24 inches in depth. Collection of surface sediment from beneath a shallow aqueous layer can
be accomplished with a system consisting of bucket auger or tube auger, a series of extensions, and a "T" handle (Figure 1,
Appendix A). The use of additional extensions in conjunction with a bucket auger can increase the depth of water from
which sediment can be collected from 24 inches to 10 feet or more. However, sample handling and manipulation increases in
difficulty with increasing depth of water. The bucket auger or tube auger is driven into the sediment and used to extract a
core. The various depths represented by the core are homogenized or a subsample of the core is taken from the appropriate
depth. The following procedure will be used to collect sediment samples with a bucket auger or tube auger.

7.2.2.1 An acetate core may be inserted into the bucket auger or tube auger prior to sampling if characteristics of the
sediments or waterbody warrant. By using this technique, an intact core can be extracted.

7.2.2.2 Attach the auger head to the required length of extensions, then attach the "T" handle to the upper extension.

7.2.2.3 Clear the area to be sampled of any surface debris.

7.2.2.4 Insert the bucket auger or tube auger into the sediment at a Oo to 20o angle from vertical. This orientation
minimizes spillage of the sample from the sampler upon extraction from the sediment and water.

7.2.2.5 Rotate the auger to cut a core of sediment.

7.2.2.6 Slowly withdraw the auger; if using a tub auger, make sure that the slot is facing upward.

FfflEKSW&S0X>3-4

-------
7.2.2.7 Transfer the sample or a specified aliquot of sample into an appropriate sample or homogenization container.
Ensure that non-dedicated containers have been adequately decontaminated.

7.2.3 Sampling Deep Sediment with a Bucket Auger or Tube Auger from Beneath a Shallow Aqueous Laver: For the
purpose of this method, deep sediment is considered to range from six (6) to greater than 18 inches in depth and a shallow
aqueous layer is considered to range from 0 to 24 inches. Collection of deep sediment from beneath a shallow aqueous layer
can be accomplished with a system consisting of a bucket auger, a tube auger, a series of extensions and a "T" handle. The
use of additional extensions can increase the depth of water from which sediment can be collected from 24 inches to five feet
or more. However, water clarity must be high enough to permit the sampler to directly observe the sampling operation. In
addition, sample handling and manipulation increases in difficulty with increasing depth of water. The bucket auger is used
to bore a hole to the upper range of the desired sampling depth and then withdrawn. The tube auger is then lowered down the
borehole, and driven into the sediment to the lower range of the desired sampling depth. The tube is then withdrawn and the
sample recovered from the tube. This method can be used to collect firmly consolidated sediments, but is somewhat limited
by the depth of the aqueous layer, and the integrity of the initial borehole. The following procedure will be used to collect
deep sediment samples with a bucket auger and a tube auger.

7.2.3.1 Attach the bucket auger bit to the required lengths of extensions, then attach the "T" handle to the upper
extension.

7.2.3.2 Clear the area to be sampled of any surface debris.

7.2.3.3 Begin augering, periodically removing any accumulated sediment (i.e., cuttings) from the auger bucket.

Cuttings should be disposed of far enough from the sampling area to minimize cross contamination of various depths.

7.2.3.4 After reaching the upper range of the desired depth, slowly and carefully remove bucket auger from the boring.

7.2.3.5 Attach the tube auger bit to the required lengths of extensions, then attach the "T" handle to the upper extension.

7.2.3.6 Carefully lower tube auger down borehole using care to avoid making contact with the borehole sides and, thus,
cross contaminating the sample. Gradually force tube auger into sediment to the lower range of the desired sampling
depth. Hammering of the tube auger to facilitate coring should be avoided as the vibrations may cause the boring walls to
collapse.

7.2.3.7 Remove tube auger from the borehole, again taking care to avoid making contact with the borehole sides and,
thus, cross contaminating the sample.

7.2.3.8 Discard the top of core (approximately 1 inch); as this represents material collected by the tube auger before
penetration to the layer of concern.

7.2.3.9 Transfer sample into an appropriate sample or homogenization container. Ensure that non-dedicated containers
have been adequately decontaminated.

7.2.4 Sampling Surface Sediment with an Ekman or Ponar Dredge from Beneath a Shallow or Deep Aqueous Laver: For
the purpose of this method, surface sediment is considered to range from 0 to six inches in depth. Collection of surface
sediment can be accomplished with asystem consisting of a remotely activated device (dredge) and a deployment system.

This technique consists of lowering a sampling device (dredge) to the surface of the sediment by use of a rope, cable, or
extended handle. The mechanism is activated, and the device entraps sediment in spring loaded or lever operated jaws. An
Ekman dredge is a lightweight sediment sampling device with spring activated jaws. It is used to collect moderately
consolidated, fine textured sediment. The following procedure will be used for collecting sediment with an Ekman dredge
(Figure 2, Appendix A):

7.2.4.1 Attach a sturdy nylon rope or stainless steel cable through the hole on the top of the bracket, or secure the
extension handle to the bracket with machine bolts.

FfflEKSW&SOX>3-5

-------
7.2.4.2 Attach springs to both sides of the jaws. Fix the jaws so that they are in open position by placing trip cables
over the release studs. Ensure that the hinged doors on the dredge top are free to open.

7.2.4.3 Lower the sampler to a point 4 to 6 inches above the sediment surface.

7.2.4.4 Drop the sampler to the sediment.

7.2.4.5 Trigger the jaw release mechanism by lowering a messenger down the line, or by depressing the button on the
upper end of the extension handle.

7.2.4.6 Raise the sampler and slowly decant any free liquid through the top of the sampler. Care should be taken to
retain the fine sediment fraction during this procedure.

7.2.4.7 Open the dredge jaws and transfer the sample into a stainless steel, plastic or other appropriate composition
(e.g., Teflon) container. Ensure that non-ndedicated containers have been adequately decontaminated. If necessary,
continue to collect additional sediment grabs until sufficient material has been secured to fulfill analytical requirements.
Thoroughly homogenize and then transfer sediment to sample containers appropriate for the analyses requested. Samples
for volatile organic analysis must be collected directly from the bucket before homogenization to minimize volatilization
of contaminants.

A Ponar dredge is a heavyweight sediment sampling device with weighted jaws that are lever or spring activated. It is
used to collect consolidated fine to coarse textured sediment. The following procedure will be used for collecting sediment
with a Ponar dredge (Figure 3, Appendix A):

7.2.4.8 Attach a sturdy nylon rope or steel cable to the ring provided on
top of the dredge.

7.2.4.9 Arrange the Ponar dredge with the jaws in the open position, setting the trip bar so the sampler remains open
when lifted from the top. If the dredge is so equipped, place the spring loaded pin into the aligned holes in the trip bar.

7.2.4.10 Slowly lower the sampler to a point approximately two inches above the sediment.

7.2.4.11 Drop the sampler to the sediment. Slack on the line will release the trip bar or spring loaded pin; pull up
sharply on the line closing the dredge.

7.2.4.12 Raise the dredge to the surface and slowly decant any free liquid through the screens on top of the dredge.

Care should be taken to retain the fine sediment fraction during this operation.

7.2.4.13 Open the dredge and transfer the sediment to a stainless steel, plastic or other appropriate composition (e.g.,
Teflon) container. Ensure that non-dedicated containers have been adequately decontaminated. If necessary, continue to
collect additional sediment until sufficient material has been secured to fulfill analytical requirements. Thoroughly
homogenized and then transfer sediment to sample containers appropriate for the analyses requested. Samples for volatile
organic analysis must be collected directly from the bucket before homogenization to minimize volatilization of
contaminants.

7.2.5 Sampling Subsurface Sediment with a Coring Device from Beneath a Shallow Aqueous Laver: For purposes of this
method, subsurface sediment is considered to range from 6 to 24 inches in depth and a shallow aqueous layer is considered to
range from 0 to 24 inches in depth. Collection of subsurface sediment from beneath a shallow aqueous layer can be
accomplished with a system consisting of a tube sampler, acetate tube, eggshell check valve, nosecone, extensions, and "T"
handler, or drivehead. The use of additional extensions can increase the depth of water from which sediment can be collected
from 24 inches to 10 feet or more. This sampler may be used with either a drive hammer for firm sediment, or a "T" handle
for soft sediment. However, sample handling and manipulation increases in difficulty with increasing depth of water. The

FfflEKSW&SOX>0-6

-------
following procedure describes the use of a sample coring device (Figure 4, Appendix A) used to collect subsurface
sediments.

7.2.5.1 Assemble the coring device by inserting the acetate core into the sampling tube.

7.2.5.2 Insert the "egg shell" check valve into the lower end of the sampling tube with the convex surface positioned
inside the acetate core.

7.2.5.3 Screw the nosecone onto the lower end of the sampling tube, securing the acetate tube and eggshell check valve.

7.2.5.4 Screw the handle onto the upper end of the sampling tube and add extension rods as needed.

7.2.5.5 Place the sampler in a perpendicular position on the sediment to be sampled.

7.2.5.6 If the "T" handle is used, place downward pressure on the device until the desired depth is reached. After the
desired depth is reached, rotate the sampler to shear off the core at the bottom. Slowly withdraw the sampler from the
sediment and proceed to Step 15.

7.2.5.7 If the drive hammer is selected, insert the tapered handle (drive head) of the drive hammer through the drive
head.

7.2.5.8 Drive the sampler into the sediment to the desired depth.

7.2.5.9 Record the length of the tube that penetrated the sample material, and the number of blows required to obtain
this depth.

7.2.5.10 Remove the drive hammer and fit the keyhole-like opening on the flat side of the hammer onto the drive head.
In this position, the hammer serves as a handle for the sampler.

7.2.5.11 Rotate the sampler to shear off the core at the bottom.

7.2.5.12 Lower the sampler handle (hammer) until it just clears the two ear-,like protrusions on the drive head, and
rotate about 90°.

7.2.5.13 Slowly withdraw the sampler from the sediment. If the drivehead was used, pull the hammer upwards and
dislodge the sampler from the sediment.

7.2.5.14 Carefully remove the coring device from the water. Unscrew the nosecone and remove the eggshell check
valve.

7.2.5.15 Slide the acetate core out of the sampler tube. Decant surface water, using care to retain the fine sediment
fraction. If head space is present in the upper end, a hacksaw may be used to shear the acetate tube off at the sediment
surface. The acetate core may then be capped at both ends. Indicate on the acetate tube the appropriate orientation of the
sediment core using a waterproof marker. The sample may be used in this fashion, or the contents transferred to a sample
or homogenization container.

7.2.5.16 Open the acetate tube and transfer the sediment to a stainless steel, plastic or other appropriate composition
(e.g., Teflon) container. Ensure that non-dedicated containers have been adequately decontaminated. If necessary,
continue to collect additional sediment until sufficient material has been secured to fulfill analytical requirements.
Thoroughly homogenize and then transfer sediment to sample containers appropriate for the analyses requested. Samples
for volatile organic analysis must be collected directly from the bucket before homogenization to minimize volatilization
of contaminants.

FfflEKSW&SOX>2-7

-------
7.3 Calculations

This section is not applicable to this SOP.

7.4 Health and Safety

7.4.1 When working with potentially hazardous materials, follow U.S. EPA/OSHA and Corporate health and safety
procedures.

7.4.2 More specifically, when sampling sediment from waterbodies, physical hazards must be identified and adequate
precautions must be taken to ensure the safety of the sampling team. The team member collecting the sample should not get
too close to the edge of the waterbody, where bank failure may cause loss of balance. To prevent this, the person performing
the sampling should be on a lifeline, and be wearing adequate protective equipment. If sampling from a vessel is determined
to be necessary, appropriate protective measures must be implemented.

8.0 QUALITY CONTROL

8.1 There are no specific quality assurance (QA) activities which apply to the implementation of these procedures.

However, the following QA procedures apply:

8.1.1 All data must be documented on field data sheets or within site logbooks.

8.1.2 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer,
unless otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to
sampling/operation, and they must be documented.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Mason, B.J., Preparation of Soil Sampling Protocol: Technique and Strategies. 1983 EPA-600/4-83-020.

2. Barth, D.S. and B.J. Mason, Soil Sampling Quality Assurance User's Guide. 1984 EPA-600/4-84-043.

3. USEPA. Characterization of Hazardous Waste Sites - A Methods Manual: Volume II. Available

4. Sampling Methods, Second Edition. 1984 EPA-600/4-84-076.

5. de Vera, E.R., B.P. Simmons, R.D. Stephen, and D.L. Storm. Samplers and Sampling Procedures for Hazardous Waste
Streams. 1980 EPA-600/2-80-018.

FMM
-------
ERT Method

DRUM SAMPLING

1.0 SCOPE AND APPLICATION

1.1 The purpose of this Standard Operating Procedure (SOP) is to provide technical guidance on safe and cost effective
response actions at hazardous waste sites conataining drums with unknown contents. Container contents are sampled and
characterized for disposal, bulking, recycling, grouping, and/or classification purposes.

2.0 SUMMARY OF METHOD

2.1 Prior to sampling, drums must be inventoried, staged, and opened. An inventory entails recording visual qualities of each
drum and any characteristics pertinent to the contents' classification. Staging involves the organization, and sometimes
consolidation of drums which have similar wastes or characteristics. Opening of closed drums can be performed manually or
remotely. Remote drum opening is recommended for worker safety. The most widely used method of sampling a drum involves
the use of a glass thief. This method is quick, simple, relatively inexpensive, and requires no decontamination.

3.0 INTERFERENCES

3.1 The practice of tapping drums to determine their contents is neither safe nor effective and should not be used if the drums
are visually overpressurized or if shock-sensitive materials are suspected. A laser thermometer may be used instead.

3.2 Drums that have been overpressurized, to the extent that the head is swollen several inches above the level of the chime,
should not be moved. A number of devices have been developed for venting critically swollen drums. One method that has
proven to be effective is a tube and spear device. A light aluminum tube (3 meters long) is positioned at the vapor space of the
drum. A rigid, hooking device attached to the tube goes over the chime and holds the tube securely in place. The spear is inserted
in the tube and positioned against the drum wall. A sharp blow on the end of the spear drives the sharpened tip through the drum
and the gas vents along the grooves. The venting should be done from behind a wall or barricade. This device can be cheaply and
easily designed and constructed where needed. Once the pressure has been relieved, the bong can be removed and the drum
sampled.

4.0 APPARATUS AND MATERIALS

4.1 The following are standard materials and equipment required for sampling:

4.1.1 Personal protection equipment;

4.1.2 Wide-mouth glass jars with Teflon cap liner, approximately 500 mL volume;

4.1.3 Uniquely numbered sample identification labels with corresponding data sheets;

4.1.4 1 -gallon covered cans half-filled with absorbent (vermiculite);

4.1.5 Chain of custody forms;

4.1.6 Decontamination materials;

4.1.7 Glass thief tubes or Composite Liquid Waste Samplers (COLIWASA)

4.1.8 L aser thermometer

4.2 Drum Opening Devices

-------
4.2.1 Bung wrench: A common method for opening drums manually is using a universal bung wrench. These wrenches
have fittings made to remove nearly all commonly encountered bungs. They are usually constructed of cast iron, brass, or a
bronze-beryllium, non-sparking alloy formulated to reduce the likelihood of sparks. The use of a non-sparking bung wrench
does not completely eliminate the possibility of a spark being produced. (See Figure 1, Appendix B.)

4.2.2 Drum deheader: When a bung is not removable with a bung wrench, a drum can be opened manually by using a
drum deheader. This tool is constructed of forged steel with an alloy steel blade and is designed to cut the lid of a drum off
or part way off by means of a scissors-like cutting action. A limitation of this device is that it can be attached only to closed
head drums. Drums with removable heads must be opened by other means. (See Figure 2, Appendix B.)

4.2.3 Hand pick, pickaxe, and hand spike: These tools are usually constructed of brass or a non-sparking alloy with a
sharpened point that can penetrate the drum lid or head when the tool is swung. The hand picks or pickaxes that are most
commonly used are commercially available; whereas the spikes are generally uniquely fabricated 4-foot long poles with a
pointed end. (See Figure 3, Appendix B.)

4.2.4 Backhoe spike: The most common means used to open drums remotely for sampling is the use of a metal spike
attached or welded to a backhoe bucket. In addition to being very efficient, this method can greatly reduce the likelihood of
personal exposure. (See Figure 4, Appendix B.)

4.2.5 Hydraulic drum opener: Another remote method for opening drums is with remotely operated hydraulic devices.
One such device uses hydraulic pressure to pierce through the all of a drum. It consists of a manually operated *phmp which
pressurizes soil through a length of hydraulic line. (See Figure 5, Appendix B.)

4.2.6 Pneumatic devices: A pneumatic bung remover consists of a compressed air supply that is controlled by a heavy-
duty, two-stage regulator. A high-pressure air line of desired length delivers compressed air to a pneumatic drill, which is
adapted to turn a bung fitting selected to fit the bung to be removed. An adjustable bracketing system has been designed to
position and align the pneumatic drill over the bung. This bracketing system must be attached to the drum before the drill can
be operated. Once the bung has been loosened, the bracketing system must be removed before the drum can be sampled.

This remote bung opener does not permit the slow venting of the container, and therefore appropriate precautions must be
taken. It also requires the container to be upright and relatively level. Bungs that are rusted shut cannot be removed with this
device. (See Figure 6, Appendix B.)

5.0 REAGENTS

5.1 Reagents are not typically required for preserving drum samples. However, reagents are used for decontaminating sampling
equipment. Decontamination solutions are specified in ERT SOP #2006, Sampling Equipment Decontamination.

6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING

6.1 Samples collected from drums are considered waste samples. No preservatives should be added since there is a potential
reaction of the sample with the preservative. Samples should, however, be cooled to 4°C and protected from sunlight in order to
minimize any potential reaction due to the light sensitivity of the sample.

6.2 Sample bottles for collection of waste liquids, sludges, or solids are typically wide-mouth amber jars with Teflon-lined screw
caps. Actual volume required for analysis should be determined in conjunction with the laboratory performing the analysis.

6.3 Follow these waste sample handling procedures:

6.3.1 Place sample container in two Ziploc plastic bags;

6.3.2 Place each bagged container in a 1-gallon covered can containing absorbent packing material. Place the lid on the
can;

HMC-W^BBn-2

-------
6.3.3 Mark the sample identification number on the outside of the can;

6.3.4 Place the marked cans in a cooler, and fill remaining space with absorbent packing material;

6.3.5 Fill out chain of custody form for each cooler, place in plastic, and affix to inside lid of cooler;

6.3.6 Secure and custody seal the lid of cooler; and

6.3.7 Arrange for the appropriate transportation mode consistent with the type of hazardous waste involved.
7.0 PROCEDURES

7.1 Preparation

7.1.1 Determine the extent of the sampling effort, the sampling methods to be employed, and which equipment and
supplies are needed.

7.1.2 Obtain necessary sampling and monitoring equipment.

7.1.3 Decontaminate or preclean equipment, and ensure that it is in working order.

7.1.4 Prepare scheduling and coordinate with staff, clients, and regulatory agency, if appropriate.

7.1.5 Perform a general site survey prior to site entry in accordance with the site-specific health and safety plan.

7.1.6 Use stakes, flagging, or buoys to identify and mark all sampling locations. If required, the proposed locations may
be adjusted based on site access, property boundaries, and surface obstructions.

7.2 Drum Inspection

7.2.1 Appropriate procedures for handling drums depend on the contents. Thus, prior to any handling, drums should be
visually inspected to gain as much information as possible about their contents. Those in charge of inspections should be on
the look-out for:

• drum condition, corrosion, rust, and leaking contents;

• symbols, words, or other markings on the drum indicating hazards (i.e., explosive, radioactive, toxic, flammable);

• signs that the drum is under pressure; and

• shock sensitivity.

7.2.2 Monitor around the drums with radiation instruments, organic vapor monitors (OVA) and combustible gas
indicators (CGI).

7.2.3 Classify the drums into categories, for instance:

• radioactive;

• leaking/deteriorating;

• bulging;

HMC-W^BBn-3

-------
• drums containing lab packs; or

• explosive/shock sensitive.

7.2.4 All personnel should assume that unmarked drums contain hazardous materials until their contents has been
categorized, and that labels on drums may not accurately describe their contents.

7.2.5 If it is presumed that there are buried drums onsite, geophysical investigation techniques such as magnetometry,
ground penetrating radar, and metal detection can be employed in an attempt to determine depth and location of the drums.
See ERT SOP #2159, General Surface Geophysics.

7.3 Drum Staging

7.3.1 Prior to sampling, the drums should be staged to allow easy access. Ideally, the staging area should be located just
far enough from the drum opening area to prevent a chain reaction if one drum should explode or catch fire when opened.

7.3.2 While staging, physically separate the drums into the following categories: those containing liquids, those
containing solids, lab packs, or gas cylinders, and those which are empty. This is done because the strategy for sampling and
handling drums/containers in each of these categories will be different. This may be achieved by:

7.3.2.1 Visual inspection of the drum and its labels, codes, etc. Solids and sludges are typically disposed of in open-top

drums. Closed-head drums with a bung opening generally contain liquid; and

7.3.2.2 Visual inspection of the contents of the drum during sampling followed by restaging, if needed.

7.3.3 Once a drum has been excavated and any immediate hazard has been eliminated by overpacking or transferr the
drum's contents, affix a numbered tag to the drum and transfer it to a staging area. Color-coded tags, labels, or bands should
be used to mark similar waste types. Record a description of each drum, its condition, any unusual markings, and the
location where it was buried or stored, on a drum data sheet (Appendix A). This data sheet becomes the principal
recordkeeping tool for tracking the drum onsite.

7.3.4 Where there is good reason to suspect that some drums contain radioactive, explosive, and shocksensitive materials,
these drums should be staged in a separate, isolated area. Placement of explosives and shock-sensitive materials in diked and
fenced areas will minimize the hazard and the adverse effects of any premature detonation of explosives.

7.3.5 Where space allows, the drum opening area should be physically separated from the drum removal and drum staging
operations. Drums are moved from the staging area to the drum opening area one at a time using forklift trucks equipped with
drum grabber or a barrel grappler. In a large-scale drum handling operation, drums may be conveyed to the drum opening area
using a roller conveyor.

7.4 Drum Opening

7.4.1 There are three basic techniques available for opening drums at hazardous waste sites:

• Manual opening with non-sparking bung wrenches;

• Drum deheading; and

• Remote drum puncturing or bung removal.

7.4.2 The choice of drum opening techniques and accessories depends on the number of drums to be opened, their waste
contents, and physical condition. Remote drum opening equipment should always be considered in order to protect worker
safety. Under OSHA 1910.120, manual drum opening with bung wrenches or deheaders should be performed only with

HMIC-W^BBn-4

-------
structurally sound drums having contents that are known to be (1) not shock sensitive, (2) non-reactive, (3) non-explosive,
and (4) nonflammable.

7.4.3 Manual Drum Opening with a Bung Wrench: Manual drum opening with bung wrenches (Figure 1, Appendix B)
should not be performed unless the drums are structurally sound (no evidence of bulging or deformation) and their contents
are known to be non-explosive. If opening the drum with bung wrenches is deemed reasonably costeffective and safe, then
follow these procedures to minimize the hazard.

7.4.3.1 Fully outfit field personnel with protective gear.

7.4.3.2 Position drum upright with the bung up, or, for drums with bungs on the side, lay the drum on its side with the

bung plug up.

7.4.3.3 Wrench the bung with a slow, steady pulling motion across the drum. If the length of the bung wrench handle

provides inadequate leverage for unscrewing the plug, attach a "cheater bar" to the handle to improve leverage.

7.4.4 Manual Drum Opening with a Drum Deheader: Drums are opened with a drum deheader (Figure 2, Appendix B) by
first positioning the cutting edge just inside the top chime and then tightening the adjustment screw so that the deheader is
held against the side of the drum. Moving the handle of the deheader up and down while sliding the deheader along the
chime will cut off the entire top. If the top chime of a drum has been damaged or badly dented, it may not be possible to cut
off the entire top. Since there is always the possibility that a drum may be under pressure, make the initial cut very slowly to
allow for the gradual release of any built-up pressure. A safer technique would be to use a remote method to puncture the
drum prior to using the deheader. Self-propelled drum openers which are either electrically or pneumatically driven can be
used for quicker and more efficient deheading.

7.4.5 Manual Drum Opening with a Hand Pick. Pickaxe, or Spike: When a drum must be opened and neither a bung
wrench nor a drum deheader is suitable, the drum can be opened for sampling by using a hand pick, pickaxe, or spike (Figure
3, Appendix B). Often the drum lid or head must be hit with a great deal of force in order to penetrate it. The potential for
splash or spraying is greater than with other opening methods and, therefore, this method of drum opening is not
recommended, particularly when opening drums containing liquids. Somes spikes used have been modified by the addition
of a circular splash plate near the penetrating end. This plate acts as a shield and reduces the amount of splash in the
direction of the person using the spike. Even with this shield, good splash gear is essential. Since drums cannot be opened
slowly with these tools, spray from drums is common requiring appropriate safety measures. Decontaminate the pick or
spike after each drum is opened to avoid cross-contamination and/or adverse chemical reaction from incompatible materials.

7.4.6 Remote Drum Opening with a Backhoe Spike: Remotely operated drum opening tools are the safest available
means of drum opening. Remote drum opening is slow, but is much safer compared to manual methods of opening. Drums
should be "staged" or placed in rows with adequate aisle space to allow ease in backhoe maneuvering. Once staged, the
drums can be quickly opened by punching a hole in the drum head or lid with the spike. The spike (Figure 4, Appendix B)
should be decontaminated after each drum is opened to prevent cross-contamination. Even though some splash or spray may
occur when this method is used, the operator of the backhoe can be protected by mounting a large shatter-resistant shield in
front of the operator's cage. This, combined with the required level of personal protection gear, should be sufficient to protect
the operator. Additional respiratory protection can be afforded by providing the operator with an on-board airline system.

7.4.7 Remote Drum Opening with Hydraulic Devices: A piercing device with a metal point is attached to the end of a
hydraulic line and is pushed into the drum by hydraulic pressure (Figure 5, Appendix B). The piercing device can be attached
so that the sampling hole can be made on either the side or the head of the drum. Some of the metal piercers are hollow or
tube-like so that they can be left in place if desired and serve as a permanent tap or sampling port. The piercer is designed to
establish a tight seal after penetrating the container.

7.4.8 Remote Drum Opening with Pneumatic Devices: Pneumatically - operated devices utilizing compressed air have
been designed to remove drum bungs remotely (Figure 6, Appendix B).

HMC-WS-QfflDll-S

-------
7.5 Drum Sampling

7.5.1 After the drum has been opened, monitor headspace gases using an explosimeter and organic vapor analyzer. In most
cases it is impossible to observe the contents of these sealed or partially sealed vessels. Since some layering or stratification is
likely in any solution left undisturbed over time, take a sample that represents the entire depth of the vessel.

7.5.2 When sampling a previously sealed vessel, check for the presence of a bottom sludge. This is easily accomplished by
measuring the depth to the apparent bottom, then comparing it to the known interior depth.

7.5.3 Glass Thief Sampler: The most widely used implement for sampling is a glass tube commonly referred to as a glass
thief (Figure 7, Appendix B). This tool is simple, cost effective, quick, and collects a sample without halving to decontaminate.
Glass thieves are typically 6mm to 16mm I.D. and 48 inches long.

7.5.3.1 Remove cover from sample container.

7.5.3.2 Insert glass tubing almost to the bottom of the drum or until a solid layer is encountered. About one foot of tubing
should extend above the drum.

7.5.3.3 Allow the waste in the drum to reach its natural level in the tube.

7.5.3.4 Cap the top of the sampling tube with a tapered stopper or thumb, ensuring liquid does not come into contact with
stopper.

7.5.3.5 Carefully remove the capped tube from the drum and insert the uncapped end in the sample container.

7.5.3.6 Release stopper and allow the glass thief to drain until the container is approximately 2/3 full.

7.5.3.7 Remove tube from the sample container, break it into pieces and place the pieces in the drum.

7.5.3.8 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.5.3.9 Replace the bung or place plastic over the drum.

7.5.3.10 Log all samples in the site logbook and on field data sheets.

7.5.3.11 Package samples and complete necessary paperwork.

7.5.3.12 Transport sample to decontamination zone to prepare it for transport to the analytical laboratory.

In many instances a drum containing waste material will have a sludge layer on the bottom. Slow insertion of the sample tube
down into this layer and then a gradual withdrawal will allow the sludge to act as a bottom plug to maintain the fluid in the
tube. The plug can be gently removed and placed into the sample container by the use of a stainless steel lab spoon.

It should be noted that in some instances disposal of the tube by breaking it into the drum may interfere with eventual plans
for the removal of its contents. This practice should be cleared with the project officer or other disposal techniques evaluated.

7.5.4 COLIWASA Sampler: Some equipment is designed to collect a sample from the full depth of a drum and maintain it
in the transfer tube until delivery to the sample bottle. These designs include primarily the Composite Liquid Waste Sampler
(COLIWASA) and modifications thereof. The COLIWASA (Figure 8, Appendix B) is a much cited sampler designed to permit
representative sampling of multiphase wastes from drums and other containerized wastes. One configuration consists of a 152
cm by 4 cm I.D. section of tubing with a neoprene stopper at one end attached by a rod running the length of the tube to a locking
mechanism at the other end. Manipulation of the locking mechanism opens and closes the sampler by raising and lowering the
neoprene stopper. One model of the COLIWASA is shown in Appendix B; however, the design can be modified and/or adapted

-------
somewhat to meet the needs of the sampler. The major drawbacks associated with using a COLIWASA concern decontamination
and costs. The sampler is difficult, if not impossible to decontaminate in the field and its high cost in relation to alternative
procedures (glass tubes) make it an impractical throwaway item. It still has a applications, however, especially in instances where
a true representation of a multiphase waste is absolutely necessary.

7.5.4.1 Put the sampler in the open position by placing the stopper rod handle in the T-position and pushing the rod down
unt*u the handle sits against the sampler's locking block.

7.5.4.2 Slowly lower the sampler into the liquid waste. Lower the sampler at a rate that permits the levels of the liquid
inside and outside the sampler tube to be about the same. If the level of the liquid in the sample tube is lower than that outside
the sampler, the sampling rate is too fast and will result in a non-representative sample.

7.5.4.3 When the sampler stopper hits the bottom of the waste container, push the sampler tube downward against the
stopper to close the sampler. Lock the sampler in the closed position by turning the T-handle until it is upright and one end
rests tightly on the locking block.

7.5.4.4 Slowly withdraw the sample from the waste container with one hand while wiping the sampler tube with a disposable
cloth or rag with the other hand.

7.5.4.5 Carefully discharge the sample into a suitable sample container by slowly pulling the lower end of the T-handle away
from the locking block while the lower end of the sampler is positioned in a sample container.

7.5.4.6 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.5.4.7 Replace the bung or place plastic over the drum.

7.5.4.8 Log all samples in the site *logbook and on field data sheets.

7.5.4.9 Package samples and complete necessary paperwork.

7.5.4.10 Transport sample to decontamination zone to prepare it for transport to the analytical laboratory.

7.6 Calculations

This section is not applicable to this SOP.

7.7 Health and Safety

7.7.1 When working with potentially hazardous materials, follow U.S. EPA, OSHA, and specific health and safety
procedures.

7.7.2 The opening of closed containers is one of the most hazardous site activities. Maximum efforts should be made to ensure
the safety of the sampling team. Pr*eDper protective equipment and a general awareness of the possible dangers will minimize
the risk inherent in sampling operations. Employing proper drum-opening techniques and equipment will also safeguard
personnel. Use remote sampling equipment whenever feasible.

8.0 QUALITY CONTROL

8.1 The following general quality assurance procedures apply.

8.1.1 Document all data on standard chain of custody forms, field data sheets, or within site logbooks.

HMIC-W^BBn-77

-------
8.1.2 Operate all instrumentation in accordance with operating instructions as supplied by the manufacturer, unless otherwise
specified in the work plan. Equipment checkout and calibration activities must occur prior to sampling/operation, and they must
be documented.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

Information not available.

HM!E-W&«)ll-«

-------
ERT Method

TANK SAMPLING

1.0 SCOPE AND APPLICATION

1.1 The purpose of this standard operating procedure (SOP) is to provide technical guidance for the implementation of sampling
protocols for tanks and other confined spaces from outside the vessel.These are standard (i.e., typically applicable) operating procedures
which may be varied or changed as required, dependent on site conditions, equipment limitations or limitations imposed by the
procedure or other procedure limitations. In all instances, the ultimate procedures employed should be documented and associated with
the final report.

1.2 Mention of trade names or commercial products does not constitute EPA endorsement or
recommendation for use.

2.0 SUMMARY OF METHOD

2.1 The safe collection of a representative sample should be the criteria for selecting sample locations. A representative sample
can be collected using techniques or equipment that are designed for obtaining liquids or sludges from various depths. The structure
and characteristics of storage tanks present problems with collection of samples from more than one location; therefore, the selection
of sampling devices is an important consideration.

2.2 Depending on the type of vessel and characteristics of the material to be sampled, one can choose a bacon bomb sampler,
sludge judge, subsurface grab sampler, glass thief, bailer or Composite Liquid Waste Sampler (COLIWASA) to collect the sample.
A sludge judge, bacon bomb or COLIWASA can be used to determine if the tank consists of various strata. Various other custom-made
samplers may be used depending on the specific application.

2.3 All sample locations should be surveyed for air quality prior to sampling. At no time should sampling continue with an LEL
reading greater than 25%.

3.0 INTERFERENCES

3.1 Sampling a storage tank requires a great deal of manual dexterity, often requiring climbing to the top of the tank upon a
narrow vertical or spiral stairway or ladder while wearing protective clothing and carrying sampling equipment.

3.2 Before climbing onto the vessel, a structural survey should be performed. This will ensure appropriate consideration of safety
and accessibility prior to initiation of any field activities.

3.3 As in all opening of containers, extreme caution should be taken to avoid ignition or combustion of volatile contents. All
tools used must be constructed of a non-sparking material and electronic instruments must be intrinsically safe.

3.4 All sample locations should be surveyed for air quality prior to sampling. At no time should sampling continue with a lower
explosive limit (LEL) reading greater than 25%.

4.0 APPARATUS AND MATERIALS

4.1 Storage tank materials include liquids, sludges, still bottoms, and solids of various structure. The type of sampler chosen
should be compatible with the waste. Samplers commonly used for tanks include: a bacon bomb sampler, sludge judge, glass thief,
bailer, COLIWASA, and subsurface grab sampler.

-------
4.2 Sampling Plan.

4.3 Safety Equipment.

4.4 Tape Measure.

4.5 Weighted Tape Line. Measuring Stick or Equivalent.

4.6 Camera/film.

4.7 Stainless Steel Bucket or Bowl.

4.8 Sample Containers.

4.9 Ziplock Plastic Bags.

4.10 Logbook.

4.11 Labels.

4.12 Field Data Sheets.

4.13 Chain of Custody Forms.

4.14 Flashlight (explosion proof).

4.15 Coolers.

4.16 Ice.

4.17 Decontamination Supplies.

4.18 Bacon Bomb Sampler.

4.19 Sludge Judge.

4.20 Glass Thieves.

4.21 Bailers.

4.22 COLIWASA.

4.23 Subsurface Grab Sampler.

4.24 Water/oil Level Indicator.

4.25 OVA (organic vapor analyzer or equivalent).

4.26 Explosimeter/oxvgen Meter.

4.27 High Volume Blower.

5.0 REAGENTS

HM!E-W&«)12-2

-------
5.1 Reagents are not typically required for the preservation of waste samples. However, reagents will be utilized for
decontamination of equipment. Decontamination solutions required are specified in ERT SOP #2006, Sampling Equipment
Decontamination.

6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING

6.1 Samples collected from tanks are considered waste samples. No preservatives should be added since there is a potential
reaction of the sample with the preservative. Samples should, however, be cooled to 4°C and protected from sunlight in order to
minimize any potential reaction due to the light sensitivity of the sample.

6.3 Follow these waste sample handling procedures:

6.3.1 Place sample container in two Ziploc plastic bags;

6.3.2 Place each bagged container in a 1-gallon covered can containing absorbent packing material. Place the lid on the can;

6.3.3 Mark the sample identification number on the outside of the can;

6.3.4 Place the marked cans in a cooler, and fill remaining space with absorbent packing material;

6.3.5 Fill out chain of custody form for each cooler, place in plastic, and affix to inside lid of cooler;

6.3.6 Secure and custody seal the lid of cooler; and

6.3.7 Arrange for the appropriate transportation mode consistent with the type of hazardous waste involved.
7.0 PROCEDURE

7.1 Preparation

7.1.1 Determine the extent of the sampling effort, the sampling methods to be employed, and which equipment and supplies
are needed.

7.1.2 Obtain necessary sampling and monitoring equipment.

7.1.3 Decontaminate or preclean equipment, and ensure that it is in working order.

7.1.4 Prepare scheduling and coordinate with staff, clients, and regulatory agency, if appropriate.

7.1.5 Perform a general site survey prior to site entry in accordance with the site-specific health and safety plan.

7.1.6 Use stakes, flagging, or buoys to identify and mark all sampling locations. If required, the proposed locations may be
adjusted based on site access, property boundaries, and surface obstructions.

7.2 Preliminary Inspection

7.2.1 Inspect the external structural characteristics of each tank and record in the site logbook. Potential sampling points
should be evaluated for safety, accessibility and sample quality.

7.2.2 Prior to opening a tank for internal inspection, the tank sampling team shall:

-------
7.2.2.1 Review safety procedures and emergency contingency plans with the Safety Officer;

7.2.2.2 Ensure that the tank is properly grounded; and

7.2.2.3 Remove all sources of ignition from the immediate area.

7.2.3 Each tank should be mounted using appropriate means. Remove manway covers using non-nsparking tools.

7.2.4 Collect air quality measurements for each potential sample location using an explosimeter/oxygen meter for a lower
explosive limit (LEL/O^ reading and an OVA/HNU for an organic vapor concentration. Both readings should be taken from the
tank headspace, above the sampling port, and in the breathing zone.

7.2.5 Prior to commencing sampling, the tank headspace should be cleared of any toxic or explosive vapor concentration using
a high volume explosion proof blower. No work shall start if LEL readings exceed 25%. At 10% LEL, work can continue but
with extreme caution.

7.3 Sampling Procedure

7.3.1 Determine the depth of any and all liquid, solid, and liquid/solid interface, and depth of sludge using a weighted tape
measure, probe line, sludge judge, or equivalent.

7.3.2 Collect liquid samples from one (1) foot below the surface, from mid-depth of liquid, and from one (1) foot above the
bottom sludge layer. This can be accomplished with a subsurface grab sampler or bacon bomb. For liquids less than five (5) feet
in depth, use a glass thief or COLIWASA to collect the sample.

7.3.3 If sampling storage tanks, vacuum trucks, or process vessels, collect at least one sample from each compartment in the
tank. Samples should always be collected through an opened hatch at the top of the tank. Valves near the bottom should not be
used, because of their questionable or unknown integrity. If such a valve cannot be closed once opened, the entire tank contents
may be lost to the ground surface. Also, individual strata cannot be sampled separately through a valve near the bottom.

7.3.4 Compare the three samples for visual phase differences. If phase differences appear, systematic iterative sampling should
be performed. By halving the distance between two discrete sampling points, one can determine the depth of the phase change.

7.3.5 If another sampling port is available, sample as above to verify the phase information.

7.3.6 Measure the inside diameter of the tank and determine the volume of wastes using the depth measurements (Appendix
A). Measuring the external diameter may be misleading as some tanks are insulated or have external supports that are covered.

7.3.7 Sludges can be collected using a bacon bomb sampler, glass thief, or sludge judge.

7.3.8 Record all information on the sample data sheet or site logbook. Label the container with the appropriate sample tag.

7.3.9 Decontaminate sampling equipment as per ERT/REAC SOP #2006, Sampling Equipment Decontamination.

7.4 Sampling Devices

7.4.1 Bacon Bomb Sampler: The bacon bomb sampler (Figure 1, Appendix B) is designed for the collection of material from
various levels within a storage tank. It consists of a cylindrical body, usually made of chrome-plated brass and bronze with an
internal tapered plunger that acts as a valve to admit the sample. A line attached to the top of the plunger opens and closes the
valve. A line is attached to the removable top cover which has a locking mechanism to keep the plunger closed after sampling.

7.4.1.1 Attach the sample line and the plunger line to the sampler.

HME-W&4M2-41

-------
7.4.1.2 Measure and then mark the sampling line at the desired depth.

7.4.1.3 Gradually lower the sampler by the sample line until the desire level is reached.

7.4.1.4 When the desired level is reached, pull up on the plunger line and allow the sampler to fill before releasing the
plunger line to seal off the sampler.

7.4.1.5 Retrieve the sampler by the sample line being careful not to pull up on the plunger line and thereby prevent accidental
opening of the bottom valve.

7.4.1.6 Rinse or wipe off the exterior of the sampler body.

7.4.1.7 Position the sampler over the sample container and release its contents by pulling up on the plunger line.

7.4.1.8 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.4.1.9 Replace the flange or manway or place plastic over the tank.

7.4.1.10 Log all samples in the site logbook and on field data sheets and label all samples.

7.4.1.11 Package samples and complete necessary paperwork.

7.4.1.12 Transport sample to decontamination zone for preparation for transport to analytical laboratory.

7.4.2 Sludge Judge: A sludge judge (Figure 2, Appendix B) is used for obtaining an accurate reading of settleable solids in
any liquid. The sampling depth is dependent upon the length of the sludge judge. The sampler consists of 3/4" plastic pipe in
5-ft. sections, marked at 1 -ft. increments, with screw-type fittings.

7.4.2.1 Lower the sludge judge to the bottom of the tank.

7.4.2.2 When the bottom has been reached, the pipe is allowed to fill to the surface level. This will seat the check valve,
trapping the column of material.

7.4.2.3 When the unit has been raised clear of the tank liquid, the amount of sludge in the sample can be read using the one
foot increments marked on the pipe sections.

7.4.2.4 By touching the pin extending from the bottom section against a hard surface, the material is released from the unit.

7.4.2.5 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.4.2.6 Replace the flange or manway or place plastic over the tank.

7.4.2.7 Log all samples in the site logbook and on field data sheets and label all samples.

7.4.2.8 Package samples and complete necessary paperwork.

7.4.2.9 Transport sample to decontamination zone for preparation for transport to analytical laboratory.

7.4.3 Subsurface Grab Sampler: Subsurface grab samplers (Figure 3, Appendix B) are designed to collect samples of liquids
at various depths. The sampler is usually constructed of aluminum or stainless steel tubing with a polypropylene or teflon head
that attaches to a 1 -liter sample container.

7.4.3.1 Screw the sample bottle onto the sampling head.

HMIC-\P&«)12--5

-------
7.4.3.2 Lower the sampler to the desired depth.

7.4.3.3 Pull the ring at the top which opens the spring-loaded plunger in the head assembly.

7.4.3.4 When the bottle is full, release the ring, lift sampler, and remove sample bottle.

7.4.3.5 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.4.3.6 Replace the flange or manway or place plastic over the tank.

7.4.3.7 Log all samples in the site logbook and on field data sheets and label all samples.

7.4.3.8 Package samples and complete necessary paperwork.

7.4.3.9 Transport sample to decontamination zone for preparation for transport to analytical laboratory.

7.4.4 Glass Thief: The most widely used implement for sampling is a glass tube commonly referred to as a glass thief (Figure
4, Appendix B). This tool is simple, cost effective, quick, and collects a sample without having to decontaminate. Glass thieves
are typically 6mm to 16mm I.D. and 48 inches long.

7.4.4.1 Remove cover from sample container.

7.4.4.2 Insert glass tubing almost to the bottom of the tank or until a solid layer is encountered. About one foot of tubing
should extend above the drum.

7.4.4.3 Allow the waste in the tank to reach its natural level in the tube.

7.4.4.4 Cap the top of the sampling tube with a tapered stopper or thumb, ensuring liquid does not come into contact with
stopper.

7.4.4.5 Carefully remove the capped tube from the tank and insert the uncapped end in the sample container. Do not spill
liquid on the outside of the sample container.

7.4.4.6 Release stopper and allow the glass thief to drain until the container is approximately 2/3 full.

7.4.4.7 Remove tube from the sample container, break it into pieces and place the pieces in the tank.

7.4.4.8 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.4.4.9 Replace the bung or place plastic over the tank.

7.4.4.10 Log all samples in the site logbook and on field data sheets and label all samples.

7.4.4.11 Package samples and complete necessary paperwork.

7.4.4.12 Transport sample to decontamination zone for preparation for transport to analytical laboratory.

In many instances a tank containing waste material will have a sludge layer on the bottom. Slow insertion of the sample tube
down into this layer and then a gradual withdrawal will allow the sludge to act as a bottom plug to maintain the fluid in the tube.
The plug can be gently removed and placed into the sample container by the use of a stainless steel lab spoon.

7.4.5 Bailer: The positive-displacement volatile sampling bailer (Figure 5, Appendix B) (by GPI) is perhaps the most
appropriate for collection of water samples for volatile analysis. Other bailer types (messenger, bottom fill, etc.) are less

-------
desirable, but may be mandated by cost and site conditions. Generally, bailers can provide an acceptable sample, providing that
the sampling personnel use extra care in the collection process.

7.4.5.1 Make sure clean plastic sheeting surrounds the tank.

7.4.5.2 Attach a line to the bailer.

7.4.5.3 Lower the bailer slowly and gently into the tank so as not to splash the bailer into the tank contents.

7.4.5.4 Allow the bailer to fill completely and retrieve the bailer from the tank.

7.4.5.5 Begin slowly pouring from the bailer.

7.4.5.6 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.4.5.7 Replace the flange or manway or place plastic over the tank.

7.4.5.8 Log all samples in the site logbook and on field data sheets and label all samples.

7.4.5.9 Package samples and complete necessary paperwork.

7.4.5.10 Transport sample to decontamination zone for preparation for transport to analytical laboratory.

7.4.6 COLIWASA: Sampling devices are available that allow collection of a sample from the full depth of a tank and
maintain its integrity in the transfer tube until delivery to the sample bottle. The sampling device is known as a Composite Liquid
Waste Sampler (COLIWASA) (Figure 6, Appendix B). The COLIWASA is a much cited sampler designed to permit
representative sampling of multiphase wastes from tanks and other containerized wastes. One configuration consists of a 152
cm by 4 cm I.D. section of tubing with a neoprene stopper at one end attached by a rod running the length of the tube to a locking
mechanism at the other end. Manipulation of the locking mechanism opens and closes the sampler by raising and lowering the
neoprene stopper. The major drawbacks associated with using a COLIWASA concern decontamination and costs. The sampler
is difficult if not impossible to decontaminate in the field, and its high cost in relation to alternative procedures (glass tubes) make
it an impractical throwaway item. However, disposable COLIWASA's are a viable alternative. It still has applications, however,
especially in instances where a true representation of a multiphase waste is absolutely necessary.

7.4.6.1 Put the sampler in the open position by placing the stopper rod handle in the T-position and pushing the rod down
until the handle sits against the sampler's locking block.

7.4.6.2 Slowly lower the sampler into the liquid waste. Lower the sampler at a rate that permits the levels of the liquid inside
and outside the sampler tube to be about the same. If the level of the liquid in the sample tube is lower than that outside the
sampler, the sampling rate is too fast and will result in a non-representative sample.

7.4.6.3 When the sampler stopper hits the bottom of the waste container, push the sampler tube downward against the
stopper to close the sampler. Lock the sampler in the closed position by turning the T-handle until it is upright and one end
rests tightly on the locking block.

7.4.6.4 Slowly withdraw the sample from the waste container with one hand while wiping the sampler tube with a disposable
cloth or rag with the other hand.

7.4.6.5 Carefully discharge the sample into a suitable sample container by slowly pulling the lower end of the T-handle away
from the locking block while the lower end of the sampler is positioned in a sample container.

7.4.6.6 Cap the sample container tightly and place prelabeled sample container in a carrier.

HME-W&4M2-77

-------
7.4.6.7 Replace the bung or place plastic over the tank.

7.4.6.8 Log all samples in the site logbook and on field data sheets and label all samples.

7.4.6.9 Package samples and complete necessary paperwork.

7.4.6.10 Transport sample to decontamination zone for preparation for transport to analytical laboratory.

7.5 Calculations

There are no specific calculations for these procedures. Refer to Appendix A regarding calculations utilized in determining
tank volumes.

7.6 Health and Safety

7.6.1 When working with potentially hazardous materials, follow USEPA, OSHA, and corporate health and safety procedures.
More specifically, the hazards associated with tank sampling may cause bodily injury, illness, or death to the worker. Failure
to recognize potential hazards of waste containers is the cause of most accidents. It should be assumed that the most unfavorable
conditions exist, and that the danger of explosion and poisoning will be present. Hazards specific to tank sampling are:

7.6.1.1 Hazardous atmospheres which are either flammable, toxic, asphyxiating, or corrosive;

7.6.1.2 If activation of electrical or mechanical equipment would cause injury, each piece of equipment should be manually
isolated to prevent inadvertent activation while workers are occupied;

7.6.1.3 Communication is of utmost importance between the sampling worker and the standby person to prevent distress
or injury going unnoticed; and

7.6.1.4 Proper procedures to evacuate a tank with forced air and grounding of equipment and tanks should be reviewed.
8.0 QUALITY CONTROL

8.1 There are no specific quality assurance activities which apply to the implementation of these procedures. However, the
following general QA procedures apply:

8.1.1 All data must be documented on field data sheets or within site logbooks.

8.1.2 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer, unless
otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to sampling/operation and
they must be documented.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Guidance Document for Cleanup of Surface Tank and Drum Sites, OSWER Directive 9380.0-3.

2. Drum Handling Practices at Hazardous Waste Sites, EPA-600/2-86-013.

HME-W$-(M2-88

-------
ERT Method

CHIP. WIPE. AND SWEEP SAMPLING

1.0 SCOPE AND APPLICATION

1.1 This standard operating procedure (SOP) outlines the recommended protocol and equipment for collection of representative
chip, wipe, and sweep samples to monitor potential surficial contamination.

1.2 This method of sampling is appropriate for surfaces contaminated with non-volatile species of analytes (i.e., PCB, PCDD,
PCDF, metals, cyanide, etc.) Detection limits are analyte specific. Sample size should be determined based upon the detection limit
desired and the amount of sample requested by the analytical laboratory. Typical sample area is one square foot. However, based upon
sampling location, the sample size may need modification due to area configuration.

1.3 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required, dependent
on site conditions, equipment limitations or limitations imposed by the procedure or other procedure limitations. In all instances, the
ultimate procedures employed should be documented and associated with the final report.

1.4 Mention of trade names or commercial products does not constitute EPA endorsement or recommendation for use.
2.0 SUMMARY OF METHOD

2.1 Since surface situations vary widely, no universal sampling method can be recommended. Rather, the method and
implements used must be tailored to suit a specific sampling site. The sampling location should be selected based upon the potential
for contamination as a result of manufacturing processes or personnel practices.

2.2 Chip sampling is appropriate for porous surfaces and is generally accomplished with either a hammer and chisel, or an electric
hammer. The sampling device should be laboratory cleaned and wrapped in clean, autoclaved aluminum foil until ready for use. To
collect the sample, a measured and marked off area is chipped both horizontally and vertically to an even depth of 1/8 inch. The sample
is then transferred to the proper sample container.

2.3 Wipe samples are collected from smooth surfaces to indicate surficial contamination; a sample location is measured and
marked off. While wearing a new pair of surgical gloves, a sterile gauze pad is opened, and soaked with solvent. The solvent used
is dependent on the surface being sampled. This pad is then stroked firmly over the sample surface, first vertically, then horizontally,
to ensure complete coverage. The pad is then transferred to the sample container.

2.4 Sweep sampling is an effective method for the collection of dust or residue on porous or non-porous surfaces. To collect such
a sample, an appropriate area is measured off. Then, while wearing a new pair of disposable surgical gloves, a dedicated brush is used
to sweep material into a dedicated dust pan. The sample is then transferred to the proper sample container.

2.5 Samples collected by all three methods are then sent to the laboratory for analysis.

3.0 INTERFERENCES

3.1 This method has few significant interferences or problems. Typical problems result from rough porous surfaces which may
be difficult to wipe, chip, or sweep.

4.0 APPARATUS AND MATERIALS

4.1 Lab Clean Sample Containers of Proper Size and Composition.

-------
4.2

Site Logbook.

4.3 Sample Analysis Request Forms.

4.4 Chain of Custody Records.

4.5 Custody Seals.

4.6 Field Data Sheets.

4.7 Sample Labels.

4.8 Disposable Surgical Gloves.

4.9 Sterile Wrapped Gauze Pad (3 in. x 3 in.).

4.10 Appropriate Pesticide fHPLQ Grade Solvent.

4.11 Medium Sized Laboratory Cleaned Paint Brush.

4.12 Medium Sized Laboratory Cleaned Chisel.

4.13 Autoclaved Aluminum Foil.

4.14 Camera.

5.0 REAGENTS

5.1 Reagents are not required for preservation of chip, wipe or sweep samples. However, reagents will be utilized for
decontamination of sampling equipment. Decontamination solutions are specified in ERT SOP #2006, Sampling Equipment
Decontamination.

5.2 Hexane (pesticide/HPLC grade).

5.3 Iso-octane.

5.4 Distilled/deionized water.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Samples should be stored out of direct sunlight to reduce photodegredation, cooled to 4oC and shipped to the laboratory
performing the analysis. Appropriately sized laboratory cleaned, glass sample jars should be used for sample collection. The amount
of sample required will be determined in concert with the analytical laboratory.

7.0 PROCEDURES

7.1 Preparation

7.1.1 Determine the extent of the sampling effort, the sampling methods to be employed, and the types and amounts of
equipment and supplies needed.

7.1.2 Obtain necessary sampling and monitoring equipment.

-------
7.1.3 Decontaminate or preclean equipment, and ensure that it is in working order.

7.1.4 Prepare scheduling and coordinate with staff, clients, and regulatory agency, if appropriate.

7.1.5 Perform a general site survey prior to site entry in accordance with the site specific Health and Safety Plan.

7.1.6 Mark all sampling locations. If required the proposed locations may be adjusted based on site access, property
boundaries, and surface obstructions.

7.2 Chip Sample Collection

7.2.1 Sampling of porous surfaces is generally accomplished by using a chisel and hammer or electric hammer. The sampling
device should be laboratory cleaned or field decontaminated as per ERT SOP# 2006, Sampling Equipment Decontamination.
It is then wrapped in cleaned, autoclaved aluminum foil. The sampler should remain in this wrapping until it is needed. Each
sampling device should be used for only one sample.

7.2.2 Choose appropriate sampling points; measure off the designated area. Photo documentation is optional.

7.2.3 Record surface area to be chipped.

7.2.4 Don a new pair of disposable surgical gloves.

7.2.5 Open a laboratory-cleaned chisel or equivalent sampling device.

7.2.6 Chip the sample area horizontally, then vertically to an even depth of approximately 1/8 inch.

7.2.7 Place the sample in an appropriately prepared sample container with a Teflon lined cap.

7.2.8 Cap the sample container, attach the label and custody seal, and place in a plastic bag. Record all pertinent data in the
site logbook and on field data sheets. Complete the sampling analysis request form and chain of custody record before taking
the next sample.

7.2.9 Store samples out of direct sunlight and cool to 4°C.

7.2.10 Follow proper decontamination procedures then deliver sample(s) to the laboratory for analysis.

7.3 Wipe Sample Collection

7.3.1 Wipe sampling is accomplished by using a sterile gauze pad, adding a solvent in which the contaminant is most soluble,
then wiping a pre-determined, pre-measured area. The sample is packaged in an amber jar to prevent photodegradation and
packed in coolers for shipment to the lab. Each gauze pad is used for only one wipe sample.

7.3.2 Choose appropriate sampling points; measure off the designated area. Photo documentation is optional.

7.3.3 Record surface area to be wiped.

7.3.4 Don a new pair of disposable surgical gloves.

7.3.5 Open new sterile package of gauze pad.

7.3.6 Soak the pad with solvent of choice.

7.3.7 Wipe the marked surface area using firm strokes. Wipe vertically, then horizontally to insure complete surface coverage.

-------
7.3.8 Place the gauze pad in an appropriately prepared sample container with a Teflon-flined cap.

7.3.9 Cap the sample container, attach the label and custody seal, and place in a plastic bag. Record all pertinent data in the
site logbook and on field data sheets. Complete the sampling analysis request form and chain of custody record before taking
the next sample.

7.3.10 Store samples out of direct sunlight and cool to 4°C.

7.3.11 Follow proper decontamination procedures, then deliver sample(s) to the laboratory for analysis.

7.4 Sweep Sample Collection

7.4.1 Sweep sampling is appropriate for bulk contamination. This procedure utilizes a dedicated, hand held sweeper brush
to acquire a sample from a pre-measured area.

7.4.2 Choose appropriate sampling points; measure off the designated area. Photo documentation is optional.

7.4.3 Record the surface area to be swept.

7.4.4 Don new pair of disposable surgical gloves.

7.4.5 Sweep the measured area using a dedicated brush; collect the sample in a dedicated dust pan.

7.4.6 Transfer sample from dust pan to sample container.

7.4.7 Cap the sample container, attach the label and custody seal, and place in a plastic bag. Record all pertinent data in the
site log book and on field data sheets. Complete the sampling analysis request form and chain of custody record before taking
the next sample.

7.4.8 Store samples out of direct sunlight and cool to 4°C.

7.4.9 Leave contaminated sampling device in the sample material, unless decontamination is practical.

7.4.10 Follow proper decontamination procedures, then deliver sample(s) to the laboratory for analysis.

7.5 Calculations

7.5.1 Results are usually provided in mg/g, ug/g, mass per unit area, or other appropriate measurement. Calculations are
typically done by the laboratory.

7.6 Health and Safety

7.6.1 When working with potentially hazardous materials, follow USEPA, OSHA and corporate health and safety procedures.
8.0 QUALITY CONTROL

8.1 All data must be documented on standard chain of custody forms, field data sheets or within the site logbook.

8.2 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer, unless
otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to sampling/operation, and they
must be documented.

-------
8.3 For wipe samples, a blank should be collected for each sampling event. This consists of a sterile gauze pad, wet with the
appropriate solvent, and placed in a prepared sample container. The blank will help identify potential introduction of contaminants via
the sampling methods, the pad, solvent or sample container. Spiked wipe samples can also be collected to better assess the data being
generated. These are prepared by spiking a piece of foil of known area with a standard of the analyte of choice. The solvent containing
the standard is allowed to evaporate, and the foil is wiped in a manner identical to the other wipe samples.

8.4 Specific quality assurance activities for chip and sweep samples should be determined on a site specific basis.
9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. USEPA, A Compendium of Superfund Field Operation Methods. EPA/540/5-87/001.

2. NJDEP Field Sampling Procedures Manual, February, 1988.

-------
ERT Method
WASTE PILE SAMPLING

1.0 SCOPE AND APPLICATION

1.1 The objective of this standard operating procedure (SOP) is to outline the equipment and methods used in collecting
representative samples from waste piles, sludges or other solid or liquid waste mixed with soil.

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required, dependent
on site conditions, equipment limitations or other procedure limitations. In all instances, the ultimate procedures employed should be
documented and associated with the final report.

1.3 Mention of trade names or commercial products does not constitute U.S. EPA endorsement or recommendation for use.
2.0 SUMMARY OF METHOD

2.1 Stainless steel shovels, trowels, or scoops should be used to clear away surface material before samples are collected. For
depth samples, a decontaminated auger may be required to advance the hole, then another decontaminated auger used for sample
collection. For a sample core, thin-wall tube samplers or grain samplers may be used. Near surfaces, samples can be collected with
a clean stainless steel spoon or trowel.

2.2 All samples collected, except those for volatile organic analysis, should be placed into a Teflon lined or stainless steel pail
and mixed thoroughly before transfer to appropriate sample container.

3.0 INTERFERENCES AND POTENTIAL PROBLEMS

3.1 There are several variables involved in waste sampling, including shape and size of piles, compactness, and structure of the
waste material. Shape and size of waste material or waste piles vary greatly in areal extent and height. Since state and federal
regulations often require a specified number of samples per volume of waste, the size and shape must be used to calculate volume and
to plan for the correct number of samples. Shape must also be accounted for when planning physical access to the sampling point and
the equipment necessary to successfully collect the sample at that location.

3.2 Material to be sampled may be homogeneous or heterogeneous. Homogeneous material resulting from known situations may
not require an extensive sampling protocol. Heterogeneous and unknown wastes require more extensive sampling and analysis to ensure
the different components (i.e. layers, strata) are being represented.

3.3 The term "representative sample" is commonly used to denote a sample that has the properties and composition of the
population from which it was collected and in the same proportions as found in the population. This can be misleading unless one is
dealing with a homogenous waste from which one sample can represent the whole population.

3.4 The usual options for obtaining the most "representative sample" from waste piles are simple random sampling or stratified
random sampling. Simple random sampling is the method of choice unless: (1) there are known distinct strata; (2) one wants to prove
or disprove that there are distinct strata; or (3) one is limited in the number of samples and desires to statistically minimize the size of
a "hot spot" that could go unsampled. If any of these conditions exist, stratified random sampling would be the better strategy.

3.5 Stratified random sampling can be employed only if all points within the pile can be accessed. In such cases, the pile should
be divided into a three-dimensional grid system with, the grid cubes should be numbered, and the grid cubes to be sampled should be
chosen by random number tables or generators. The only exceptions to this are situations in which representative samples cannot be
collected safely or where the investigative team is trying to determine worst case conditions.

-------
3.6 If sampling is limited to certain portions of the pile, a statistically based sample will be representative only of that portion,
unless the waste is homogenous.

4.0 APPARATUS AND MATERIALS

4.1 Waste pile solids include powdered, granular, or block materials of various sizes, shapes, structure, and compactness. The
type of sampler chosen should be compatible with the waste. Samplers commonly used for waste piles include: stainless steel scoops,
shovels, trowels, spoons, and stainless steel hand augers, sampling triers, and grain samplers.

4.2 Sampling Plan.

4.3 Maps/plot Plan.

4.4 Safety Equipment, as Specified in the Health and Safety Plan.

4.5 Compass.

4.6 Tape Measure.

4.7 Survey Stakes or Flags.

4.8 Camera and Film.

4.9 Stainless Steel. Plastic, or Other Appropriate Homogenization Bucket or bowl.

4.10 Appropriate Size Sample Jars.

4.11 Ziplock Plastic Bags.

4.12 Logbook.

4.13 Labels.

4.14 Chain of Custody Forms and Seals.

4.15 Field Data Sheets.

4.16 Coolerfsl.

4.17 Ice.

4.18 Decontamination Supplies/equipment.

4.19 Canvas or Plastic Sheet.

4.20 Spade or Shovel.

4.21 Spatula.

4.22 Scoop.

4.23 Plastic or Stainless Steel Spoons.

-------
4.24

Trowel.

4.25 Continuous Flight (screw) Augers.

4.26 Bucket Auger.

4.27 Post Hole Auger.

4.28 Extension Rods.

4.29 T-Handle.

4.30 Thin-wall Tube Sampler with Cutting Tips.

4.31 Sampling Trier.

4.32 Grain Sampler.

5.0 REAGENTS

5.1 No chemical reagents are used for the preservation of waste pile samples; however, decontamination solutions may be
required. If decontamination of equipment is required, refer to ERT/REAC SOP #2006, Sampling Equipment Decontamination, and
the site specific work plan.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Chemical preservation of solids is generally not recommended. Refrigeration to 4oC is
supplemented by a minimal holding time, depending on contaminants of concern.

6.2 Wide mouth glass containers with Teflon lined caps are typically used for waste pile samples,
a function of the analytical requirements and should be specified in the work plan.

7.0 PROCEDURES

7.1 Preparation

7.1.1 Review all information available on the waste pile and expected or unknown contaminants.

7.1.2 Determine the extent of the sampling effort, the sampling methods to be employed, and the types and amounts of
equipment and supplies required.

7.1.3 Obtain necessary sampling and monitoring equipment.

7.1.4 Decontaminate or pre-clean equipment, and ensure that it is in working order.

7.1.5 Prepare schedules, and coordinate with staff, client, and regulatory agencies, if appropriate.

7.1.6 Perform a general site survey prior to site entry in accordance with the site specific Health and Safety Plan.

7.1.7 Use stakes or flagging to identify and mark all sampling locations. Specific site factors, including extent and nature of
contaminant should be considered when selecting sample locations. If required, the proposed locations may be adjusted based
on site access, property boundaries, and surface obstructions.

usually the best approach,

Sample volume required is

-------
7.2 Sample Collection

7.2.1 Sampling with Shovels and Scoops: Collection of samples from surface portions of the pile can be accomplished with
tools such as spades, shovels, and scoops. Surface material can be removed to the required depth with this equipment, then a
stainless steel or plastic scoop, or equivalent can be used to collect the sample. Accurate, representative samples can be collected
with this procedure depending on the care and precision demonstrated by sample team members. Use of a flat, pointed mason
trowel to cut a block of the desired material can be helpful when undisturbed profiles are required. A stainless steel scoop, lab
spoon, plastic spoon, or equivalent will suffice in most other applications. Care should be exercised to avoid the use of devices
plated with chrome or other materials. Plating is particularly common with implements such as garden trowels.

7.2.1.1 Carefully remove the top layer of material to the desired sample depth with a pre-cleaned spade.

7.2.1.2 Using a pre-cleaned stainless steel scoop, plastic spoon, trowel, or equivalent remove and discard a thin layer of
material from the area which came in contact with the spade.

7.2.1.3 If volatile organic analysis is to be performed, transfer the sample into an appropriate, labeled sample container with
a stainless steel lab spoon, or equivalent, and secure the cap tightly. Place the remainder of the sample into a stainless steel,
plastic, or other appropriate homogenization container, and mix thoroughly to obtain a homogenous sample representative of
the entire sampling interval. Then, either place the sample into appropriate, labeled containers and secure the caps tightly;
or, if composite samples are to be collected, place a sample from another sampling interval into the homogenization container
and mix thoroughly. When compositing is complete, place the sample into appropriate, labeled containers and secure the caps
tightly.

7.2.2 Sampling with Bucket Augers and Thin-Wall Tube Samplers: These samplers consist of a series of extensions, a "T"
handle, and a bucket auger or thin-wall tube sampler (Appendix A, Figure 1). The auger is used to bore a hole to a desired
sampling depth, and is then withdrawn. The sample may be collected directly from the bucket auger. If a core sample is to
becollected, the auger tip is then replaced with a thin-wall tube sampler. The sampler is then lowered down the borehole, and
driven into the pile to the completion depth. The sampler is withdrawn and the core collected from the thin-wall tube sampler.
Several augers are available. These include: bucket, continuous flight (screw), and post hole augers. Bucket augers are better
for direct sample recovery since they provide a large volume of sample in a short time. When continuous flight augers are used,
the sample can be collected directly from the flights, which are usually at five (5) foot intervals. The continuous flight augers
are satisfactory for use when a composite of the complete waste pile column is desired. Post hole augers have limited utility for
sample collection as they are designed to cut through fibrous, rooted, swampy areas.

7.2.2.1 Attach the auger bit to a drill rod extension, and attach the "T" handle to the drill rod.

7.2.2.2 Clear the area to be sampled of any surface debris. It may be advisable to remove the first three (3) to six (6) inches
of surface material for an area approximately six (6) inches in radius around the drilling location.

7.2.2.3 Begin augering, periodically removing and depositing accumulated materials onto a plastic sheet spread near the
hole. This prevents accidental brushing of loose material back down the borehole when removing the auger or adding drill
rod extensions. It also facilitates refilling the hole, and avoids possible contamination of the surrounding area.

7.2.2.4 After reaching the desired depth, slowly and carefully remove the auger from the borehole. When sampling directly
from the auger, collect the sample after the auger is removed from the borehole and proceed to Step 10.

7.2.2.5 Remove auger tip from drill rods and replace with a pre-cleaned thin-wall tube sampler. Install proper cutting tip.

7.2.2.6 Carefully lower the tube sampler down the borehole. Gradually force the tube sampler into the pile. Care should
be taken to avoid scraping the borehole sides. Avoid hammering the drill rod extensions to facilitate coring as the vibrations
may cause the borehole walls to collapse.

7.2.2.7 Remove the tube sampler, and unscrew the drill rod extensions.

-------
7.2.2.8 Remove the cutting tip and the thin-wall tube sampler.

7.2.2.9 Discard the top of the core (approximately one-inch), as this represents material collected before penetration of the
layer of concern. Place the remaining core into the appropriate labeled sample container. Sample homogenization is not
required.

7.2.2.10 If volatile organic analysis is to be performed, transfer the sample into an appropriate, labeled sample container
with a stainless steel lab spoon, or equivalent and secure the cap tightly. Place the remainder of the sample into a stainless
steel, plastic, or other appropriate homogenization container, and mix thoroughly to obtain a homogenous sample representative
of the entire sampling interval. Then, either place the sample into appropriate, labeled containers and secure the caps tightly;
or, if composite samples are to be collected, place a sample from another sampling interval into the homogenization container
and mix thoroughly. When compositing is complete, place the sample into appropriate, labeled containers and secure the caps
tightly.

7.2.2.11 If another sample is to be collected in the same hole, but at a greater depth, reattach the bucket auger to the drill
and assembly, and follow steps 3 through 11, making sure to decontaminate the bucket auger and thin-wall tube sampler
between samples.

7.2.3 Sampling with a Trier: This sampling device consists of a trier, and a "T" handle. The trier is driven into the waste pile
and used to extract a core sample from the appropriate depth.

7.2.3.1 Insert the trier (Appendix A, Figure 2) into the material to be sampled at a 0° to 45° angle from horizontal. This
orientation minimizes spillage of the sample. Extraction of the samples might require tilting of the sample containers.

7.2.3.2 Rotate the trier once or twice to cut a core of material.

7.2.3.3 Slowly withdraw the trier, making sure that the slot is facing upward.

7.2.3.4 If volatile organic analysis is to be performed, transfer the sample into an appropriate, labeled sample container with
a stainless steel lab spoon, plastic lab spoon, or equivalent and secure the cap tightly. Place the remainder of the sample into
a stainless steel, plastic, or other appropriate homogenization container, and mix thoroughly to obtain a homogenous sample
representative of the entire sampling interval. Then, either place the sample into appropriate, labeled containers and secure
the caps tightly; or, if composite samples are being collected, place samples from the other sampling intervals into the
homogenization container and mix thoroughly. When compositing is complete, place the sample into appropriate, labeled
containers and secure the caps tightly.

7.2.4 Sampling with a Grain Sampler: The grain sampler (Appendix A, Figure 3) is used for sampling powdered or granular
wastes or materials in bags, fiber drums, sacks, similar containers or piles. This sampler is most useful when the solids are no
greater than 0.6 cm (1/4") in diameter. This sampler consists of two slotted telescoping brass or stainless steel tubes. The outer
tube has a conical, pointed tip at one end that permits the sampler to penetrate the material being sampled. The sampler is opened
and closed by rotating the inner tube. Grain samplers are generally 61 to 100 cm (24 to 40 in.) long by 1.27 to 2.54 cm (1/2 to
1 in.) in diameter and are commercially available at laboratory supply houses.

7.2.4.1 With the sampler in the closed position, insert it into the granular or powdered material or waste being sampled from
a point near a top edge or corner, through the center, and to a point diagonally opposite the point of entry.

7.2.4.2 Rotate the sampler inner tube into the open position.

7.2.4.3 Wiggle the sampler a few times to allow material to enter the open slots.

7.2.4.4 Place the sampler in the closed position and withdraw from the material being sampled.

7.2.4.5 Place the sampler in a horizontal position with the slots facing upward.

-------
7.2.4.6 Rotate the outer tube and slide it away from the inner tube.

7.2.4.7 If volatile organic analysis is to be performed, transfer the sample into an appropriate, labeled sample container with
a stainless steel lab spoon, plastic lab spoon, or equivalent and secure the cap tightly. Place the remainder of the sample into
a stainless steel, plastic, or other appropriate homogenization container, and mix thoroughly to obtain a homogenous sample
representative of the entire sampling interval. Then, either place the sample into appropriate, labeled containers and secure
the caps tightly; or, if composite samples are to be collected, place a sample from another sampling interval into the
homogenization container and mix thoroughly. When compositing is complete, place the sample into appropriate, labeled
containers and secure the caps tightly.

7.3 Calculations

This section is not applicable to this SOP.

7.4 Health and Safety

7.4.1 When working with potentially hazardous materials, follow U.S. EPA/OSHA and corporate health and safety procedures.
8.0 QUALITY CONTROL

8.1 There are no specific quality assurance activities which apply to the implementation of these procedures. However, the
following QA procedures apply:

8.1.1 All data must be documented on field data sheets or within site logbooks.

8.1.2 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer, unless
otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to sampling/operation, and
they must be documented.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Test Methods for Evaluating Solids Waste (SW-846), Third Edition, Vol. II Field Manual U.S. EPA Office of Solid Waste and
Emergency Response, Washington, D.C. November, 1986.

2. Engineering Support Branch Standard Operating Procedures and Quality Assurance Manual, U.S. Environmental Protection
Agency, Region IV, April 1, 1986.

3. Field Sampling Procedures Manual, New Jersey Department of Environmental Protection, February, 1988.

-------
ERT Method

SOIL SAMPLING

1.0 SCOPE AND APPLICATION

1.1 The purpose of this standard operating procedure (SOP) is to describe the procedures for the collection of representative soil
samples. Analysis of soil samples may determine whether concentrations of specific pollutants exceed established action levels, or
if the concentrations of pollutants present a risk to public health, welfare, or the environment.

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required, dependent
upon site conditions, equipment limitations or limitations imposed by the procedure. In all instances, the ultimate procedures employed
should be documented and associated with the final report.

1.3 Mention of trade names or commercial products does not constitute U.S. Environmental Protection Agency (EPA)
endorsement or recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Soil samples may be collected using a variety of methods and equipment. The methods and equipment used are dependent
on the depth of the desired sample, the type of sample required (disturbed vs. undisturbed), and the soil type. Near-surface soils may
be easily sampled using a spade, trowel, and scoop. Sampling at greater depths may be performed using a hand auger, continuous flight
auger, a trier, a split-spoon, or, if required, a backhoe.

3.0 INTERFERENCES

3.1 There are two primary interferences or potential problems associated with soil sampling. These include cross contamination
of samples and improper sample collection. Cross contamination problems can be eliminated or minimized through the use of dedicated
sampling equipment. If this is not possible or practical, then decontamination of sampling equipment is necessary. Improper sample
collection can involve using contaminated equipment, disturbance of the matrix resulting in compaction of the sample or inadequate
homogenization of the samples where required, resulting in variable, non-representative results.

4.0 APPARATUS AND MATERIALS

4.1 Sampling Plan.

4.2 Maps/plot Plan

4.3 Safety Equipment, as Specified in the Health and Safety Plan.

4.4 Survey Equipment.

4.5 Tape Measure.

4.6 Survey Stakes or Flags.

4.7 Camera and Film.

4.8 Stainless Steel. Plastic, or Other Appropriate Homogenization Bucket. Bowl or Pan.

4.9 Appropriate Size Sample Containers.

FMC-B&-001-1

-------
4.10 Ziplock Plastic Bags.

4.11 Logbook.

4.12 Labels.

4.13 Chain of Custody Forms and Seals.

4.14 Field Data Sheets.

4.15 Coolerfsl.

4.16 Ice.

4.17 Vermiculite.

4.18 Decontamination Supplies/equipment.

4.19 Canvas or Plastic Sheet.

4.20 Spade or Shovel.

4.21 Spatula.

4.22 Scoop

4.23 Plastic or Stainless Steel Spoons

4.24 Trowel.

4.25 Continuous Flight (screw) Auger.

4.26 Bucket Auger.

4.27 Post Hole Auger.

4.28 Extension Rods.

4.29 T-handle.

4.30 Sampling Trier.

4.31 Thin Wall Tube Sampler.

4.32 Split Spoons.

4.33 Vehimever Soil Sampler Outfit:

4.33.1 Tubes.

4.33.2 Points.

4.33.3 Drive head.

FMC-B&-001-2

-------
4.33.4 Drop hammer.

4.33.5 Puller jack and grip.

4.34 Backhoe.

5.0 REAGENTS

5.1 Reagents are not used for the preservation of soil samples. Decontamination solutions are specified in ERT/REAC SOP
#2006, Sampling Equipment Decontamination, and the site specific work plan.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Chemical preservation of solids is not generally recommended. Samples should, however, be cooled and protected from
sunlight to minimize any potential reaction. The amount of sample to be collected and proper sample container type are discussed in
ERT/REAC SOP #2003, Sample Storage, Preservation and Handling.

7.0 PROCEDURES

7.1 Preparation

7.1.1 Determine the extent of the sampling effort, the sampling methods to be employed, and the types and amounts of
equipment and supplies required.

7.1.2 Obtain necessary sampling and monitoring equipment.

7.1.3 Decontaminate or pre-clean equipment, and ensure that it is in working order.

7.1.4 Prepare schedules, and coordinate with staff, client, and regulatory agencies, if appropriate.

7.1.5 Perform a general site survey prior to site entry in accordance with the site specific Health and Safety Plan.

7.1.6 Use stakes, flagging, or buoys to identify and mark all sampling locations. Specific site factors, including extent and
nature of contaminant should be considered when selecting sample location. If required, the proposed locations may be adjusted
based on site access, property boundaries, and surface obstructions. All staked locations will be utility-cleared by the property
owner prior to soil sampling.

7.2 Sample Collection

7.2.1 Surface Soil Samples: Collection of samples from near-surface soil can be accomplished with tools such as spades,
shovels, trowels, and scoops. Surface material can be removed to the required depth with this equipment, then a stainless steel
or plastic scoop can be used to collect the sample. This method can be used in most soil types but is limited to sampling near
surface areas. Accurate, representative samples can be collected with this procedure depending on the care and precision
demonstrated by the sample team member. A stainless steel scoop, lab spoon, or plastic spoon will suffice in most other
applications. The use of a flat, pointed mason trowel to cut a block of the desired soil can be helpful when undisturbed profiles
are required. Care should be exercised to avoid use of devices plated with chrome or other materials. Plating is particularly
common with garden implements such as potting trowels. The following procedure is used to collect surface soil samples.

7.2.1.1 Carefully remove the top layer of soil or debris to the desired sample depth with a pre-cleaned spade.

FMC-B&-001-3

-------
7.2.1.2 Using a pre-cleaned, stainless steel scoop, plastic spoon, or trowel, remove and discard a thin layer of soil from the
area which came in contact with the spade.

7.2.1.3 If volatile organic analysis is to be performed, transfer the sample directly into an appropriate, labeled sample
container with a stainless steel lab spoon, or equivalent and secure the cap tightly. Place the remainder of the sample into a
stainless steel, plastic, or other appropriate homogenization container, and mix thoroughly to obtain a homogenous sample
representative of the entire sampling interval. Then, either place the sample into appropriate, labeled containers and secure
the caps tightly; or, if composite samples are to be collected, place a sample from another sampling interval or location into
the homogenization container and mix thoroughly. When compositing is complete, place the sample into appropriate, labeled
containers and secure the caps tightly.

7.2.2 Sampling at Depth with Augers and Thin Wall Tube Samplers: This system consists of an auger, or a thin-wall tube
sampler, a series of extensions, and a "T" handle (Figure 1, Appendix A). The auger is used to bore a hole to a desired sampling
depth, and is then withdrawn. The sample may be collected directly from the auger. If a core sample is to be collected, the auger
tip is then replaced with a thin wall tube sampler. The system is then lowered down the borehole, and driven into the soil to the
completion depth. The system is withdrawn and the core is collected from the thin wall tube sampler. Several types of augers
are available; these include: bucket type, continuous flight (screw), and posthole augers. Bucket type augers are better for direct
sample recovery since they provide a large volume of sample in a short time. When continuous flight augers are used, the
sample can be collected directly from the flights. The continuous flight augers are satisfactory for use when a composite of the
complete soil column is desired. Post hole augers have limited utility for sample collection as they are designed to cut through
fibrous, rooted, swampy soil and cannot be used below a depth of three feet. The following procedure will be used for collecting
soil samples with the auger.

7.2.2.1 Attach the auger bit to a drill rod extension, and attach the "T" handle to the drill rod.

7.2.2.2 Clear the area to be sampled of any surface debris (e.g., twigs, rocks, litter). It may be advisable to remove the first
three (3) to six (6) inches of surface soil for an area approximately six inches in radius around the drilling location.

7.2.2.3 Begin augering, periodically removing and depositing accumulated soils onto a plastic sheet spread near the hole.
This prevents accidental brushing of loose material back down the borehole when removing the auger or adding drill rods.
It also facilitates refilling the hole, and avoids possible contamination of the surrounding area.

7.2.2.4 After reaching the desired depth, slowly and carefully remove the auger from boring. When sampling directly from
the auger, collect the sample after the auger is removed from the boring and proceed to Step 10.

7.2.2.5 Remove auger tip from drill rods and replace with a pre-cleaned thin wall tube sampler. Install the proper cutting
tip.

7.2.2.6 Carefully lower the tube sampler down the borehole. Gradually force the tube sampler into soil. Care should be
taken to avoid scraping the borehole sides. Avoid hammering the drill rods to facilitate coring as the vibrations may cause
the boring walls to collapse.

7.2.2.7 Remove the tube sampler, and unscrew the drill rods.

7.2.2.8 Remove the cutting tip and the core from the device.

7.2.2.9 Discard the top of the core (approximately 1 inch), as this possibly represents material collected before penetration
of the layer of concern. Place the remaining core into the appropriate labeled sample container. Sample homogenization is
not required.

FMC-B&-001-4

-------
of the entire sampling interval. Then, either place the sample into appropriate, labeled containers and secure the caps tightly;
or, if composite samples are to be collected, place a sample from another sampling interval into the homogenization container
and mix thoroughly. When compositing is complete, place the sample into appropriate, labeled containers and secure the caps
tightly.

7.2.2.11 If another sample is to be collected in the same hole, but at a greater depth, reattach the auger bit to the drill and
assembly, and follow steps 3 through 11, making sure to decontaminate the auger and tube sampler between samples.

7.2.2.12 Abandon the hole according to applicable State regulations. Generally, shallow holes can simply be backfilled with
the removed soil material.

7.2.3 Sampling at Depth with a Trier: The system consists of a trier, and a "T" handle. The auger is driven into the soil to
be sampled and used to extract a core sample from the appropriate depth. The following procedure will be used to collect soil
samples with a sampling trier.

7.2.3.1 Insert the trier (Figure 2, Appendix A) into the material to be sampled at a 0° to 45° angle from horizontal. This
orientation minimizes the spillage of sample.

7.2.3.2 Rotate the trier once or twice to cut a core of material.

7.2.3.3 Slowly withdraw the trier, making sure that the slot is facing upward.

7.2.3.4 If volatile organic analysis is to be performed, transfer the sample into an appropriate, labeled sample container with
a stainless steel lab spoon, or equivalent and secure the cap tightly. Place the remainder of the sample into a stainless steel,
plastic, or other appropriate homogenization container, and mix thoroughly to obtain a homogenous sample representative of
the entire sampling interval. Then, either place the sample into appropriate, labeled containers and secure the caps tightly;
or, if composite samples are to be collected, place a sample from another sampling interval into the homogenization container
and mix thoroughly. When compositing is complete, place the sample into appropriate, labeled containers and secure the caps
tightly.

7.2.4 Sampling at Depth with a Split Spoon (Barrel') Sampler: The procedure for split spoon sampling describes the collection
and extraction of undisturbed soil cores of 18 or 24 inches in length. A series of consecutive cores may be extracted with a split
spoon sampler to give a complete soil column profile, or an auger may be used to drill down to the desired depth for sampling.
The split spoon is then driven to its sampling depth through the bottom of the augured hole and the core extracted. When split
spoon sampling is performed to gain geologic information, all work should be performed in accordance with ASTM D 1586-67
(reapproved 1974). The following procedures will be used for collecting soil samples with a split spoon.

7.2.4.1 Assemble the sampler by aligning both sides of barrel and then screwing the drive shoe on the bottom and the head
piece on top.

7.2.4.2 Place the sampler in a perpendicular position on the sample material.

7.2.4.3 Using a well ring, drive the tube. Do not drive past the bottom of the head piece or compression of the sample will
result.

7.2.4.4 Record in the site logbook or on field data sheets the length of the tube used to penetrate the material being sampled,
and the number of blows required to obtain this depth.

7.2.4.5 Withdraw the sampler, and open by unscrewing the bit and head and splitting the barrel. The amount of recovery
and soil type should be recorded on the boring log. If a split sample is desired, a cleaned, stainless steel knife should be used
to divide the tube contents in half, longitudinally. This sampler is typically available in 2 and 3 1/2 inch diameters. However,
in order to obtain the required sample volume, use of a larger barrel may be required.

FMC-B&-001-5

-------
7.2.4.6 Without disturbing the core, transfer it to appropriate labeled sample container(s) and seal tightly.

7.2.5 Test Pit/Trench Excavation: These relatively large excavations are used to remove sections of soil, when detailed
examination of soil characteristics (horizontal, structure, color, etc.) are required. It is the least cost effective sampling method
due to the relatively high cost of backhoe operation. The following procedures will be used for collecting soil samples from test
pit/trench excavations.

7.2.5.1 Prior to any excavation with a backhoe, it is important to ensure that all sampling locations are clear of utility lines,
subsurface pipes and poles (subsurface as well as above surface).

7.2.5.2 Using the backhoe, a trench is dug to approximately three feet in width and approximately one foot below the cleared
sampling location. Place excavated soils on plastic sheets. Trenches greater than five feet deep must be sloped or protected
by a shoring system, as required by OSHA regulations.

7.2.5.3 A shovel is used to remove a one to two inch layer of soil from the vertical face of the pit where sampling is to be
done.

7.2.5.4 Samples are taken using a trowel, scoop, or coring device at the desired intervals. Be sure to scrape the vertical face
at the point of sampling to remove any soil that may have fallen from above, and to expose fresh soil for sampling. In many
instances, samples can be collected directly from the backhoe bucket.

7.2.5.5 If volatile organic analysis is to be performed, transfer the sample into an appropriate, labeled sample container with
a stainless steel lab spoon, or equivalent and secure the cap tightly. Place the remainder of the sample into a stainless steel,
plastic, or other appropriate homogenization container, and mix thoroughly to obtain a homogenous sample representative of
the entire sampling interval. Then, either place the sample into appropriate, labeled containers and secure the caps tightly;
or, if composite samples are to be collected, place a sample from another sampling interval into the homogenization container
and mix thoroughly. When compositing is complete, place the sample into appropriate, labeled containers and secure the caps
tightly.

7.2.5.6 Abandon the pit or excavation according to applicable state regulations. Generally, shallow excavations can simply
be backfilled with the removed soil material.

7.3 Calculations

This section is not applicable to this SOP.

7.4 Health and Safety

When working with potentially hazardous materials, follow U.S. EPA, OHSA and corporate health and safety procedures.
8.0 QUALITY CONTROL

8.1 There are no specific quality assurance (QA) activities which apply to the implementation of these procedures. However,
the following QA procedures apply.

8.1.1 All data must be documented on field data sheets or within site logbooks.

8.1.2 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer, unless
otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to sampling/operation, and
they must be documented.

9.0 METHOD PERFORMANCE

FMC-B&-001-6

-------
Information not available.

10.0 REFERENCES

1. Mason, B.J., Preparation of Soil Sampling Protocol: Technique and Strategies. 1983 EPA-600/4-83-020.

2. Barth, D.S. and B.J. Mason, Soil Sampling Quality Assurance User's Guide. 1984 EPA-600/4-84-043.

3. U.S. EPA. Characterization of Hazardous Waste Sites - A Methods Manual: Volume II. Available Sampling Methods, Second
Edition. 1984 EPA-600/4-84-076.

4. de Vera, E.R., B.P. Simmons, R.D. Stephen, and D.L. Storm. Samplers and Sampling Procedures for Hazardous Waste Streams.
1980 EPA-600/2-80-018.

5. ASTM D 1586-67 (reapproved 1974), ASTM Committee on Standards, Philadelphia, PA.

FMC-B&-001-7

-------
ERT Method

SOIL GAS SAMPLING

1.0 SCOPE AND APPLICATION

1.1 Soil gas monitoring provides a quick means of waste site evaluation. Using this method, underground contamination can
be identified, and the source, extent, and movement of the pollutants can be traced.

1.2 This procedure outlines the methods used by EPA/ERT in installing soil gas wells; measuring organic levels in the soil gas
using an HNU PI 101 Portable Photoionization Analyzer and/or other air monitoring devices; and sampling the soil gas using Tedlar
bags, Tenax sorbent tubes, and Summa canisters.

2.0 SUMMARY OF METHOD

2.1 A 3/8" diameter hole is driven into the ground to a depth of four to five feet using a commercially available " slam bar". (Soil
gas can also be sampled at other depths by the use of a longer bar or bar attachments.) A 1/4" O.D. stainless steel probe is inserted into
the hole. The hole is then sealed at the top around the probe using modeling clay. The gas contained in the interstitial spaces of the
soil is sampled by pulling the sample through the probe using an air sampling pump. The sample may be stored in Tedlar bags, drawn
through sorbent cartridges, or analyzed directly using a direct reading instrument.

2.2 The air sampling pump is not used for Summa canister sampling of soil gas. Sampling is achieved by soil gas equilibration
with the evacuated Summa canister. Other field air monitoring devices, such as the combustible gas indicator (MSA CGI/02 Meter,
Model 260) and the organic vapor analyzer (Foxboro OVA, Model 128), can also be used dependent on specific site conditions.
Measurement of soil temperature using a temperature probe may also be desirable. Bagged samples are usually analyzed in a field
laboratory using a portable Photovac GC.

2.3 Power driven sampling probes may be utilized when soil conditions make sampling by hand unfeasible (i.e., frozen ground,
very dense clays, pavement, etc.). Commercially available soil gas sampling probes (hollow, 1/2 = O.D. steel probes) can be driven
to the desired depth using a power hammer (e.g., Bosch Demolition Hammer). Samples can be drawn through the probe itself, or
through Teflon tubing inserted through the probe and attached to the probe point. Samples are collected and analyzed as described
above.

3.0 INTERFERENCES

3.1 HNU Measurements

3.1.1 A number of factors can affect the response of the HNU PI 101. High humidity can cause lamp fogging and decreased
sensitivity. This can be significant when soil moisture levels are high, or when a soil gas well is actually in groundwater. High
concentrations of methane can cause a downscale deflection of the meter. High and low temperature, electrical fields, FM radio
transmission, and naturally occurring compounds, such as terpenes in wooded areas, will also affect instrument response.

3.1.2 Other field screening instruments can be affected by interferences. Consult the manufacturers manuals.

3.2 Factors Affecting Organic Concentrations in Soil Gas

3.2.1 Concentrations in soil gas are affected by dissolution, adsorption, and partitioning. Partitioning refers to the ratio of
component found in a saturated vapor above an aqueous solution to the amount in the solution; this can, in theory, be calculated
using the Henry's Law constants. Contaminants can also be adsorbed onto inorganic soil components or "dissolved" in organic
components. These factors can result in a lowering of the partitioning coefficient.

3.2.2 Soil "tightness" or amount of void space in the soil matrix, will affect the rate of recharging of gas into the soil gas well.

FMC-B&-002-1

-------
3.2.3 Existence of a high, or perched, water table, or of an impermeable underlying layer (such as a clay lens or layer of buried
slag) may interfere with sampling of the soil gas. Knowledge of site geology is useful in such situations, and can prevent
inaccurate sampling.

3.3 Soil Probe Clogging

3.3.1 A common problem with this sampling method is soil probe clogging. A clogged probe can be identified by using an
in-line vacuum gauge or by listening for the sound of the pump laboring. This problem can usually be eliminated by using a wire
cable to clear probe (see Section 7.1.3.).

3.4 Underground Utilities

3.4.1 Prior to selecting sample locations, an underground utility search is recommended. The local utility companies can be
contacted and requested to mark the locations of their underground lines. Sampling plans can then be drawn up accordingly. Each
sample location should also be screened with a metal detector or magnetometer to verify that no underground pipes or drums exist.

4.0 APPARATUS AND MATERIALS

4.1 Slam Bar Method

4.1.1 Slam Bar (1 per sampling team).

4.1.2 Soil gas probes, stainless steel tubing, 1/4" O.D., 5 ft length.

4.1.3 Flexible wire or cable used for clearing the tubing during insertion into the well.

4.1.4 "Quick Connect" fittings to connect sampling probe tubing, monitoring instruments, and Gilian pumps to appropriate
fittings on vacuum box.

4.1.5 Modeling clay.

4.1.6 Vacuum box for drawing a vacuum around Tedlar bag for sample collection (1 per sampling team).

4.1.7 Gilian pump Model HFS113A adjusted to approximately 3.0 L/min (1 to 2 per sample team).

4.1.8 1/4" Teflon tubing, 2 ft to 3 ft lengths, for replacement of contaminated sample line.

4.1.9 Tedlar bags, 1.0 L, at least 1 bag per sample point.

4.1.10 Soil Gas Sampling labels, field data sheets, logbook, etc.

4.1.11 HNU Model P1101, or other field air monitoring devices, (1 per sampling team).

4.1.12 Ice chest, for carrying equipment and for protection of samples (2 per sampling team).

4.1.13 Metal detector or magnetometer, for detecting underground utilities/pipes/drums (1 per sampling team).

4.1.14 Photovac GC, for field-lab analysis of bagged samples.

4.1.15 Summa canisters (plus their shipping cases) for sample, storage and transportation.

4.2 Power Hammer Method

4.2.1 Bosch demolition hammer.

FMC-B&-002-2

-------
4.2.2 1/2" O.D. steel probes, extensions, and points.

4.2.3 Dedicated aluminum sampling points.

4.2.4 Teflon tubing, 1/4".

4.2.5 "Quick Connect" fittings to connect sampling probe tubing, monitoring instruments, and Gilian pumps to appropriate
fittings on vacuum box.

4.2.6 Modeling clay.

4.2.7 Vacuum box for drawing a vacuum around Tedlar bag for sample collection (1 per sampling team).

4.2.8 Gilian pump Model HFS113A adjusted to approximately 3.0 L/min (1 to 2 per sample team).

4.2.9 1/4" Teflon tubing, 2 ft to 3 ft lengths, for replacement of contaminated sample line.

4.2.10 Tedlar bags, 1.0 L, at least 1 bag per sample point.

4.2.11 Soil Gas Sampling labels, field data sheets, logbook, etc.

4.2.12 HNU Model PI 101, or other field air monitoring devices, (1 per sampling team).

4.2.13 Ice chest, for carrying equipment and for protection of samples (2 per sampling team).

4.2.14 Metal detector or magnetometer, for detecting underground utilities/pipes/drums (1 per sampling team).

4.2.15 Photovac GC, for field-lab analysis of bagged samples.

4.2.16 Summa canisters (plus their shipping cases) for sample, storage and transportation.

4.2.17 Generator with extension cords.

4.2.18 High lift jack assembly for removing probes.

5.0 REAGENTS

5.1 HNU Systems Inc. Calibration Gas for HNU Model PI 101. and/or calibration gas for other field air monitoring devices.

5.2 Deionized organic-free water, for decontamination.

5.3 Methanol. HPLC grade, for decontamination.

5.4 Ultra-zero grade compressed air, for field blanks.

5.5 Standard gas preparations for Photovac GC calibration and Tedlar bag spikes.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Tedlar Bags: Soil gas samples are generally contained in 1.0-L Tedlar bags. Bagged samples are best stored in coolers to
protect the bags from any damage that may occur in the field or in transit. In addition, coolers insure the integrity of the samples by
keeping them at a cool temperature and out of direct sunlight. Samples should be analyzed as soon as possible, preferably within 24
- 48 hours.

FMC-B&-002-3

-------
6.2 Tenax Tubes: Bagged samples can also be drawn onto Tenax or other sorbent tubes to undergo lab GC/MS analysis. If Tenax
tubes are to be utilized, special care must be taken to avoid contamination. Handling of the tubes should be kept to a minimum and only
while wearing nylon or other

lint-free gloves. After sampling, each tube should be stored in a clean, sealed culture tube; the ends packed with clean glass wool to
protect the sorbent tube from breakage. The culture tubes should be kept cool and wrapped in aluminum foil to prevent any
photodegradation of samples (see Section 7.4.).

6.3 Summa Canisters: The Summa canisters used for soil gas sampling have a 6 liter sample capacity and are certified clean
by GC/MS analysis before being utilized in the field. After sampling is completed, they are stored and shipped in travel cases.

7.0 PROCEDURES

7.1 Soil Gas Well Installation

7.1.1 Initially a hole slightly deeper than the desired depth is made. For sampling up to 5 feet, a 5-ft single piston slam bar
is used. For deeper depths, a piston slam bar with threaded 4-foot-long extensions can be used. Other techniques can be used,
so long as holes are of narrow diameter and no contamination is introduced.

7.1.2 After the hole is made, the slam bar is carefully withdrawn to prevent collapse of the walls of the hole. The soil gas
probe is then inserted.

7.1.3 It is necessary to prevent plugging of the probe, especially for deeper holes. A metal wire or cable, slightly longer than
the probe, is placed in the probe prior to inserting into the hole. The probe is inserted to full depth, then pulled up three to six
inches, then cleared by moving the cable up and down. The cable is removed before sampling.

7.1.4 The top of the sample hole is sealed at the surface against ambient air infiltration by using modeling clay molded around
the probe at the surface of the hole.

7.1.5 If conditions preclude hand installation of the soil gas wells, the power driven system may be employed. The generator
powered demolition hammer is used to drive the probe to the desired depth (up to 12' may be attained with extensions). The
probe is pulled up 1-3 inches if the retractable point is used. No clay is needed to seal the hole. After sampling, the probe is
retrieved using the high lift jack assembly.

7.1.6 If semi-permanent soil gas wells are required, the dedicated aluminum probe points are used. These points are inserted
into the bottom of the power driven probe and attached to the Teflon tubing. The probe is inserted as in step 5. When the probe
is removed, the point and Teflon tube remain in the hole, which may be sealed by backfilling with sand, bentonite, or soil.

7.2 Screening with Field Instruments

7.2.1 The well volume must be evacuated prior to sampling. Connect the Gilian pump, adjusted to 3.0 L/min, to the sample
probe using a section of Teflon tubing as a connector. The pump is turned on, and a vacuum is pulled through the probe for
approximately 15 seconds. Longer time is required for sample wells of greater depths.

7.2.2 After evacuation, the monitoring instrument(s) is connected to the probe using a Teflon connector. When the reading
is stable, or peaks, the reading is recorded.

7.2.3 Of course, readings may be above or below the range set on the field instruments. The range may be reset, or the
response recorded as a greater than or less than figure. Recharge rate of the well with soil gas must be considered when
resampling at a different range setting.

7.3 Tedlar Bag Sampling

FMC-B&-002-4

-------
7.3.1 Follow step 7.2.1 to evacuate well volume. If air monitoring instrument screening was performed prior to sample taking,
evacuation is not necessary.

7.3.2 Use the vacuum box and sampling train (Figure 1) to take the sample. The sampling train is designed to minimize the
introduction of contaminants and losses due to adsorption. All wetted parts are either Teflon or stainless steel. The vacuum is
drawn indirectly to avoid contamination from sample pumps.

7.3.3 The Tedlar bag is placed inside the vacuum box, and attached to the sampling port. The sample probe is attached to the
sampling port via Teflon tubing and a "Quick Connect" fitting.

7.3.4 A vacuum is drawn around the outside of the bag, using a Gilian pump connected to the vacuum box evacuation port,
via Tygon tubing and a "Quick Connect" fitting. The vacuum causes the bag to inflate, drawing the sample.

7.3.5 Break the vacuum by removing the Tygon line from the pump. Remove the bagged sample from the box and close valve.
Label bag, record data on data sheets or in logbooks. Record the date, time, sample location ID, and the HNU, or other
instruments reading(s) on sample bag label. CAUTION: Labels should not be pasted directly onto the bags, nor should bags
be labeled directly using a marker or pen. Inks and adhesive may diffuse through the bag material, contaminating the sample.
Place labels on the edge of the bags, or tie the labels to the metal eyelets provided on the bags. Markers with inks containing
volatile organics (i.e., permanent ink markers) should not be used.

7.4 Tenax Tube Sampling

Samples collected in Tedlar bags may be sorbed onto Tenax tubes for further analysis by GC/MS.

7.4.1 Additional Apparatus:

7.4.1.1 Syringe with a luer-lock tip capable of drawing a soil gas or air sample from a Tedlar bag onto a Tenax/CMS sorbent
tube. The syringe capacity is dependent upon the volume of sample begin drawn onto the sorbent tube.

7.4.1.2 Adapters for fitting the sorbent tube between the Tedlar bag and the sampling syringe. The adapter attaching the
Tedlar bag to the sorbent tube consists of a reducing union (1/4" to 1/16" O.D. — Swagelok cat. # SS-400-6-IL V or equivalent)
with a length of 1/4" O.D. Teflon tubing replacing the nut on the 1/6" (Tedlar bag) side. A 1/4" I.D. silicone O-ring replaces
the ferrules in the nut on the 1/4" (sorbent tube) side of the union.

7.4.1.3 The adapter attaching the sampling syringe to the sorbent tube consists of a reducing union (1/4" to 1/16" O.D. —
Swagelok Cat. # SS-400-6-ILV or equivalent) with a 1/4" I.D. silicone O-ring replacing the ferrules in the nut on the 1/4"
(sorbent tube) side and the needle of a luer-lock syringe needle inserted into the 1/16" side. (Held in place with a 1/16"
ferrule.) The luer-lock end of the needle can be attached to the sampling syringe. It is useful to have a luer-lock on/off valve
situated between the syringe and the needle.

7.4.1.4 Two-stage glass sampling cartridge (1/4" O.D. x 1/8" I.D. x 5 1/8") contained in a flame-sealed tube (Manufacturer:
Supelco Custom Tenax/Spherocarb Tubes) containing two sorbent sections retained by glass wool:

Front section: 150 mg of Tenax-GC

Back section: 150 mg of CMS (Carbonized Molecular Sieve)

Sorbent tubes may also be prepared in the lab and stored in either Teflon capped culture tubes or stainless steel tube
containers. Sorbent tubes stored in this manner should not be kept more than two weeks without reconditioning. (See
"Standard Operating Procedure for Tenax/CMS Sorbent Tube Preparation").

7.4.1.5 Teflon-capped culture tubes or stainless steel tube containers for sorbent tube storage. These containers should be
conditioned by baking at 120 degrees C for at least two hours. The culture tubes should contain a glass wool plug to prevent

FMC-B&-002-5

-------
sorbent tube breakage during transport. Reconditioning of the containers should occur between uses or after extended periods
of disuse (i.e., two weeks or more).

7.4.1.6 Nylon gloves or lint-free cloth. (Hewlett Packard Part # 8650-0030 or equivalent.)

7.4.2 Sample Collection:

7.4.2.1 Handle sorbent tubes with care, using nylon gloves (or other lint-free material) to avoid contamination.

7.4.2.2 Immediately before sampling, break one end of the sealed tube and remove the Tenax cartridge. For in-house
prepared tubes, remove cartridge from its container.

7.4.2.3 Connect the valve on the Tedlar bag to the sorbent tube adapter. Connect the sorbent tube to the sorbent tube adapter
with the Tenax (white granular) side of the tube facing the Tedlar bag.

7.4.2.4 Connect the sampling syringe assembly to the CMS (black) side of the sorbent tube. Fittings on the adapters should
be finer-tight.

7.4.2.5 Open the valve on the Tedlar bag.

7.4.2.6 Open the on/off valve of the sampling syringe.

7.4.2.7 Draw a predetermined volume of sample onto the sorbent tube (may require closing the syringe valve, emptying
the syringe and then repeating the procedure, depending upon the syringe capacity and volume of sample required).

7.4.2.8 After sampling, remove the tube from the sampling train with gloves or a clean cloth. DO NOT LABEL OR
WRITE ON THE TENAX/CMS TUBE

7.4.2.9 Place the sorbent tube in a conditioned stainless steel tube holder or culture tube. Culture tube caps should be sealed
with Teflon tape.

7.4.3 Sample Labeling:

7.4.3.1 Each sample tube container (not tube) must be labeled with the site name, sample station number, date sampled, and
volume sampled.

7.4.3.2 Chain of custody sheets must accompany all samples to the laboratory.

7.4.4 Quality Assurance:

7.4.4.1 Before field use, a QA check should be performed on each batch of sorbent tubes by analyzing a tube by thermal
desorption/cryogenic trapping GC/MS.

7.4.4.2 At least one blank sample must be submitted with each set of samples collected at a site. This trip blank must be
treated the same as the sample tubes except no sample will be drawn through the tube.

7.4.4.3 Sample tubes should be stored out of UV light (i.e., sunlight) and kept on ice until analysis.

7.4.4.4 Samples should be taken in duplicate, when possible.

7.5 Summa Canister Sampling

FMC-B&-002-6

-------
7.5.1 Follow step 7.2.1 to evacuate well volume. If HNU analysis was performed prior to taking a sample, evacuation is not
necessary.

7.5.2 Attach a certified clean, evacuated 6-liter Summa canister via the 1/4" Teflon tubing.

7.5.3 Open valve on Summa canister. The soil gas sample is drawn into the canister by pressure equilibration. The
approximate sampling time for a 6 liter canister is 20 minutes.

7.5.4 Site name, sample location, number, and date must be recorded on a chain of custody form and on a blank tag attached
to the canister.

7.6 Calculations

7.6.1 Field Screening Instruments: Instrument readings are usually read directly from the meter. In some cases, the
background level at the soil gas station may be subtracted.

Final Reading = Sample Reading - Background

7.6.2 Photovac GC Analysis: Calculations used to determine concentrations of individual components by Photovac GC
analysis are beyond the scope of this SOP and are covered ERT/REAC SOP #2109, Photovac GC Analysis for Soil Water and
Air/Soil Gas.

7.7 Health and Safety

7.7.1 Due to the remote nature of sampling soil gas, special considerations can be taken with regard to health and safety.
Because the sample is being drawn from underground, and no contamination is introduced into the breathing zone, soil gas
sampling usually occurs in Level D. Ambient air is constantly monitored using the HNU PI 101 to obtain background readings
during the sampling procedure. As long as the levels in ambient air do not rise above background, no upgrade of the level of
protection is needed. Also, an underground utility search should be performed prior to sampling. (See Section 4.4).

8.0 QUALITY CONTROL

8.1 Field Instruments Calibration

8.1.1 It is recommended that the manufacturers' manuals be consulted for correct use and calibration of all instrumentation.

8.2 Gilian Model HFS113A Air Sampling Pumps Calibration

8.2.1 Flow should be set at approximately 3.0 L/min; accurate flow adjustment is not necessary. Pumps should be calibrated
prior to bringing into the field.

8.3 Sample Probe Contamination

8.3.1 Sample probe contamination is checked between each sample by drawing ambient air through the probe via a Gilian
pump and checking the response of the HNU PI 101. If HNU readings are higher than background, replacement or
decontamination is necessary.

8.3.2 Sample probes may be decontaminated simply by drawing ambient air through the probe until the HNU reading is at
background. More persistent contamination can be washed out using methanol and water, then air drying. Having more than one
probe per sample team will reduce lag times between sample stations while probes are decontaminated.

8.4 Sample Train Contamination

FMC-B&-002-7

-------
8.4.1 The Teflon line forming the sample train from the probe to the Tedlar bag should be changed on a daily basis. If visible
contamination (soil or water) is drawn into the sampling train, it should be changed immediately. When sampling in highly
contaminated areas, the sampling train should be purged with ambient air, via a Gilian pump, for approximately 30 seconds
between each sample. After purging, the sampling train can be checked using an HNU, or other field monitoring device, to
establish the cleanliness of the Teflon line.10.3HNU Calibration The HNU should be calibrated at least once a day.

8.5 Field Blanks

8.5.1 Each cooler containing samples should also contain one Tedlar bag of ultra-zero grade air, acting as a field blank. The
field blank should accompany the samples in the field (while being collected) and when they are delivered for analysis. A fresh
blank must be provided to be placed in the empty cooler pending additional sample collection. One new field blank per cooler
of samples is required. A chain of custody sheet must accompany each cooler of samples and should include the blank that is
dedicated to that group of samples.

8.6 Trip Standards

8.6.1 Each cooler containing samples should contain a Tedlar bag of standard gas to calibrate the analytical instruments
(Photovac GC, etc.). This trip standard will be used to determine any changes in concentrations of the target compounds during
the course of the sampling day (e.g., migration through the sample bag, degradation, or adsorption). A fresh trip standard must
be provided and placed in each cooler pending additional sample collection. A chain of custody sheet should accompany each
cooler of samples and should include the trip standard that is dedicated to that group of samples.

8.7 Tedlar Bag Check

8.7.1 Prior to use, one bag should be removed from each lot (case of 100) of Tedlar bags to be used for sampling and checked
for possible contamination as follows: the test bag should be filled with ultra-zero grade air; a sample should be drawn from the
bag and analyzed via Photovac GC or whatever method is to be used for sample analysis. This procedure will ensure sample
container cleanliness prior to the start of the sampling effort.

8.8 Summa Canister Check

8.8.1 From each lot of four cleaned Summa canisters, one is to be removed for a GC/MS certification check. If the canister
passes certification, then it is re-evacuated and all four canisters from that lot are available for sampling.

8.8.2 If the chosen canister is contaminated, then the entire lot of four Summas must be recleaned, and a single canister is
re-analyzed by GC/MS for certification.

8.9 Options

8.9.1 Duplicate Samples: A minimum of 5% of all samples should be collected in duplicate (i.e., if a total of 100 samples are
to be collected, five samples should be duplicated.) In choosing which samples to duplicate, the following criteria applies: if,
after filling the first Tedlar bag and evacuating the well for 15 seconds, the second HNU (or other field monitoring device being
used) reading matches or is close to (within 50%) the first reading, a duplicate sample may be taken.

8.9.2 Spikes: A Tedlar bag spike and Tenax tube spike may be desirable in situations where high concentrations of
contaminants other than the target compounds are found to exist (landfills, etc.). The additional level of QA/QC attained by
this practice can be useful in determining the effects of interferences caused by these non-target compounds. Summa canisters
containing samples are not spiked.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

FMC-B&-002-8

-------
1. Gilian Instrument Corp., Instruction Manual for Hi Flow Sampler: HFS113, HFS 113 T, HFS 113U, HFS 113 UT, 1983.

2. HNU Systems, Inc., Instruction Manual for Model PI 101 Photoionization Analyzer, 1975.

3. N.J.D.E.P., Field Sampling Procedures Manual, Hazardous Waste Programs, February, 1988.

4. Roy F. Weston, Inc., Weston Instrumentation Manual, Volume I, 1987.

5. U.S.E.P.A., Characterization of Hazardous Waste Sites - A Methods Manual: Volume II, Available Sampling Methods, 2nd
Edition, EPA-600/4-84-076, December, 1984.

FMC-B&-002-9

-------
ERT Method

GROUNDWATER WELL SAMPLING

1.0 SCOPE AND APPLICATION

1.1 The objective of this standard operating procedure (SOP) is to provide general reference informationon sampling of ground
water wells. This guideline is primarily concerned with the collection of water samples from the saturated zone of the subsurface.
Every effort must be made to ensure that the sample is representative of the particular zone of water being sampled. These procedures
are designedto be used in conjunction with analyses for the most common types of ground water contaminants(e.g., volatile and
semi-volatile organic compounds, pesticides, metals, biological parameters).

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required, dependent
upon site conditions, equipment limitations or limitations imposed by the procedure or other procedure limitations. In all instances,
the ultimate procedures employed shouldbe documented and associated with the final report.

1.3 Mention of trade names or commercial products does not constitute U.S. Environmental Protection Agency (EPA)
endorsement or recommendation for use.

2.0 SUMMARY OF METHOD

2.1 Prior to sampling a monitor well, the well must be purged to remove water that may have been stagnant in the well, and to
introduce fresh groundwater into the well for sampling. This may be achieved with one of a number of instruments. The most common
of these are the bailer, submersible pump, non-contact gas bladder pump, inertia pump and suction pump. At a minimum, three
wellvolumes should be purged, if possible. Equipment must be decontaminated prior to use and between wells. Once purging is
completed and the correct laboratory-cleaned sample containers have been prepared, sampling may proceed. Sampling may be
conducted with any of the above instruments, and need not be the same as the device used for purging. Care should be taken when
choosing the sampling device as some will affect the integrity of the sample. Sampling equipment must also be decontaminated.
Sampling should occur in a progression from the least to most contaminated well,if this information is known.

3.0 INTERFERENCES

3.1 General

3.1.1 The primary goal in performing ground water sampling is to obtain a representative sample of the ground water body.
Analysis can be compromised by field personnel in two primary ways: (1) taking an unrepresentative sample, or (2) by incorrect
handling of the sample. There are numerous ways of introducing foreign contaminants into a sample, and these must be avoided
by following strict sampling procedures and utilizing trained field personnel.

3.2 Purging

3.2.1 In a nonpumping well, there will be little or no vertical mixing of the water, and stratification will occur. The well water
in the screened section will mix with the ground water due to normal flow patterns, but the well water above the screened section
will remain isolated, become stagnant, and may lack the contaminants representative of the ground water. Persons sampling
should realize that stagnant water may contain foreign material inadvertently or deliberately introduced from the surface, resulting
in an unrepresentative sample. To safeguard against collecting nonrepresentative stagnant water, the following guidelines and
techniques should be adhered to during sampling:

• As a general rule, all monitor wells should be pumped or bailed prior to sampling. Purge water should be containerized
on site or handled as specified in the site specific project plan. Evacuation of a minimum of one volume of water in the well
casing, and preferably three to five volumes, is recommended for a representative sample. In a high-yielding ground water
formation and where there is no stagnant water in the well above the screened section, evacuation prior to sample withdrawal

FKTOGGMSHJMl-l

-------
is not as critical. However, in all cases where the monitoring data is to be used for enforcement actions, evacuation is
recommended;

• When purging with a pump (not a bailer), the pump should be set at the screened interval, or if the well is an open-rock
well, it should be set at the same depth the sample will be collected. When sampling a screened well, the sample should also
be collected from the same depth the pump was set at;

• The well should be sampled as soon as possible after purging;

• Analytical parameters typically dictate whether the sample should be collected through the purging device, or through
a separate sampling instrument;

• For wells that can be pumped or bailed to dryness with the equipment being used, the well should be evacuated and
allowed to recover prior to sample withdrawal. If the recovery rate is fairly rapid and time allows, evacuation of more than
one volume of water is preferred. If recovery is slow, sample the well upon recovery after one evacuation; and

• A non-representative sample can also result from excessive pre-pumping of the monitoring well. Stratification of the
leachate concentration in the ground water formation may occur, or heavier-than-water compounds may sink to the lower
portions of the aquifer. Excessive pumping can dilute or increase the contaminant concentrations from what is representative
of the sampling point of interest.

3.3 Materials

3.3.1 Materials of construction for samplers and evacuation equipment (bladders, pump, bailers, tubing, etc.) should be limited
to stainless steel, Teflon, and glass in areas where concentrations are expected to be at or near the detection limit. The tendency
of organics to leach into and out of many materials make the selection of materials critical for trace analyses. The use of
plastics, such as PVC or polyethylene, should be avoided when analyzing for organics. However, PVC may be used for
evacuation equipment as it will not come in contact with the sample, and in highly contaminated wells, disposable equipment
(i.e., polypropylene bailers) may be appropriate to avoid cross-contamination.

3.4 Table 1 discusess the advantage and disadvantages of certain equipment.

FM003MSH)iM22

-------
Table 1

ADVANTAGE AND DISADVANTAGES OF VARIOUS GROUNDWATER SAMPLING DEVICES

Device

Advantages

Disadvantages

Bailers

• Only practical limitations on size and materials.

• No power source needed.

• Portable.

• Inexpensive, so it can be dedicated and hung in a
well, thereby reducing the chances of cross
contamination.

• Minimal outgassing of volatile organics while
sample is in bailer.

• Readily available.

• Removes stagnant water first.

• Rapid, simple method for removing small volumes
of purge water.

• Time-consuming to flush a large well of stagnant
water.

• Transfer of sample may cause aeration.

Submersible
Pumps

• Portable and can be transported to several wells.

• Depending upon the size of the pump and the
pumping depths, relatively high pumping rates are
possible.

• Generally very reliable and does not require
priming.

• Potential for effects on analysis of trace organics.

• Heavy and cumbersome to deal with, particularly in
deeper wells.

• Expensive.

• Power source needed.

• Sediment in water may cause problems with the
pumps.

• Impractical in low yielding or shallow wells.

Non-Contact Gas
Bladder Pumps

• Maintains integrity of sample.

• Easy to use.

• Difficulty in cleaning, though dedicated tubing and
bladder may be used.

• Only useful to about 100 feet.

• Supply of gas for operation, gas bottles and/or
compressors are often difficult to obtain and are
cumbersome.

• Relatively low pumping rates.

• Requires air compressor or pressurized gas source and
control box.

Suction Pumps

• Portable, inexpensive, and readily available.

• Restricted to areas with water levels within 20 to 25
feet of the ground surface.

• Vacuum can cause loss of dissolved gasses and
volatile organics.

• Pump must be primed and vacuum is often difficult to
maintain during initial stages of pumping.

Inertia Pumps

• Portable, inexpensive, and readily available.

• Offers a rapid method for purging relatively
shallow wells.

• Restricted to areas with water levels within 70 feet of
the ground surface.

• May be time consuming to purge wells with these
manual pumps.

• Labor intensive.

• WaTerra pumps are only effective in 2-inch diameter
wells.

FM003MSH)iM3-3

-------
4.0 APPARATUS AND MATERIALS
4.1 General

4.1.1 Water level indicator:

• electric sounder;

• steel tape;

• transducer;

• reflection sounder; and

• airline.

4.1.2 Depth sounder.

4.1.3 Appropriate keys for well cap locks.

4.1.4 Steel brush.

4.1.5 HNU or OVA (whichever is most appropriate).

4.1.6 Logbook.

4.1.7 Calculator.

4.1.8 Field data sheets and samples labels.

4.1.9 Chain of custody records and seals.

4.1.10 Sample containers.

4.1.11 Engineer's rule.

4.1.12 Sharp knife (locking blade).

4.1.13 Tool box (to include at least: screwdrivers, pliers, hacksaw, hammer, flashlight, adjustable wrench).

4.1.14 Leather work gloves.

4.1.15 Appropriate Health & Safety gear.

4.1.16 5-gallon pail.

4.1.17 Plastic sheeting.

4.1.18 Shipping containers.

4.1.19 Packing materials.

4.1.20 Bolt cutters.

4.1.21 Ziploc plastic bags.

4.1.22 Containers for evacuation liquids.

4.1.23 Decontamination solutions.

4.1.24 Tap water.

FM003MSHJM44

-------
4.1.25 Non phosphate soap.

4.1.26 Several brushes.

4.1.27 Pails or tubs.

4.1.28 Aluminum foil.

4.1.29 Garden sprayer.

4.1.30 Preservatives.

4.1.31 Distilled or deionized water.

4.2 Bailers

4.2.1 Clean, decontaminated bailers of appropriate size and construction material.

4.2.2 Nylon line, enough to dedicate to each well.

4.2.3 Teflon coated bailer wire.

4.2.4 Sharp knife.

4.2.5 Aluminum foil (to wrap clean bailers).

4.2.6 5-gallon bucket.

4.3 Submersible Pump

4.3.1 Pump(s).

4.3.2 Generator (110, 120, or 240 volt) or 12 volt battery if inaccessible to field vehicle - amp meter is useful

4.3.3 1" black PVC coil pipe - enough to dedicate to each well.

4.3.4 Hose clamps.

4.3.5 Safety cable.

4.3.6 Tool box supplement:

• pipe wrenches;

• wire strippers;

• electrical tape;

• heat shrink;

• hose connectors; and

• Teflon tape.

4.3.7 Winch, pulley or hoist.

4.3.8 Gasoline for generator/gas can.

4.3.9 Flow meter with gate valve.

4.3.10 1" nipples and various plumbing (i.e., pipe connectors).

4.4 Non-Gas Contact Bladder Pump

FM0GGMSH)iM5-5

-------
4.4.1 Non-gas contact bladder pump.

4.4.2 Compressor or nitrogen gas tank.

4.4.3 Batteries and charger.

4.4.4 Teflon tubing - enough to dedicate to each well.

4.4.5 Swagelock fitting.

4.4.6 Toolbox supplements - same as submersible pump.

4.4.7 Control box (if necessary).

4.5 Suction Pump

4.5.1 Pump.

4.5.2 Black coil tubing - enough to dedicate to each well.

4.5.3 Gasoline - if required.

4.5.4 Toolbox.

4.5.5 Plumbing fittings.

4.5.6 Flow meter with gate valve.

4.6 Inertia Pump

4.6.1 Pump assembly (WaTerra pump, piston pump).

4.6.2 Five gallon bucket.

5.0 REAGENTS

5.1 Reagents may be utilized for preservation of samples and for decontamination of sampling equipment. The preservatives
required are specified by the analysis to be performed and are summarized inERT/REAC SOP #2003, Sample Storage, Preservation,
and Handling. Decontamination solutions are specified in ERT/REAC SOP #2006, Sampling Equipment Decontamination.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 The type of analysis for which a sample is being collected determines the type of bottle, preservative, holding time, and
filtering requirements. Samples should be collected directly from the sampling device into appropriate laboratory cleaned containers.
Check that a Teflon liner is present in the cap, if required. Attach a sample identification label. Complete a field data sheet, a chain
of custody form, and record all pertinent data in the site logbook.

6.2 Samples shall be appropriately preserved, labelled, logged, and placed in a cooler to be maintainedat 4°C. Samples must
be shipped well before the holding time is up and ideally should be shipped within 24 hours of sample collection. It is imperative that
these samples be shipped or delivered daily to the analytical laboratory in order to maximize the time available for the laboratory to
perform the analyses. The bottles should be shipped with adequate packing and cooling to ensure that they arriveintact.

6.3 Certain conditions may require special handling techniques. For example, treatment of a sample for volatile organic (VOA)
analysis with sodium thiosulfate preservative is required if there is residual chlorine in the water (such as in a public water supply) that
could cause free radical chlorination andchange the identity of the original contaminants. However, sodium thiosulfate should not be
used if chlorine is not present in the water. Special requirements must be determined prior to conducting field work.

FKf0GGMSH)M&6

-------
7.0 PROCEDURE

7.1 Preparation

7.1.1 Determine the extent of the sampling effort, the sampling methods to be employed, and the types and amounts of
equipment and supplies needed (i.e, diameter and depth of wells to be sampled).

7.1.2 Obtain necessary sampling and monitoring equipment, appropriate to type of contaminant being investigated.

7.1.3 Decontaminate or preclean equipment, and ensure that it is in working order.

7.1.4 Prepare scheduling and coordinate with staff, clients, and regulatory agency, if appropriate.

7.1.5 Perform a general site survey prior to site entry in accordance with the site specific Health and Safety Plan.

7.1.6 Identify and mark all sampling locations.

7.2 Field Preparation

7.2.1 Start at the least contaminated well, if known.

7.2.2 Lay plastic sheeting around the well to minimize likelihood of contamination of equipment from soil adjacent to the
well.

7.2.3 Remove locking well cap, note location, time of day, and date in field notebook or appropriate log form.

7.2.4 Remove well casing cap.

7.2.5 Screen headspace of well with an appropriate monitoring instrument to determine the presence of volatile organic
compounds and record in site logbook.

7.2.6 Lower water level measuring device or equivalent (i.e., permanently installed transducers or airline) into well until water
surface is encountered.

7.2.7 Measure distance from water surface to reference measuring point on well casing or protective barrier post and record
in site logbook. Alternatively, if no reference point, note that water level measurement is from top of steel casing, top of PVC
riser pipe, from ground surface, or some other position on the well head.

7.2.8 Measure total depth of well (at least twice to confirm measurement) and record in site logbook or on field data sheet.

7.2.9 Calculate the volume of water in the well and the volume to be purged using the calculations in Section 7.8

7.2.10 Select the appropriate purging and sampling equipment.

7.3 Purging

7.3.1 The amount of flushing a well receives prior to sample collection depends on the intent of the monitoring program as
well as the hydrogeologic conditions. Programs where overall quality determination of water resources are involved may require
long pumping periods to obtain a sample that is representative of a large volume of that aquifer. The pumped volume can be
determined prior to sampling so that the sample is a collected after a known volume of the water is evacuated from the aquifer,
or the well can be pumped until the stabilization of parameters such as temperature, electrical conductance, or pH has occurred.

7.3.2 However, monitoring for defining a contaminant plume requires a representative sample of a small volume of the aquifer.
These circumstances require that the well be pumped enough to remove the stagnant water but not enough to induce flow from
other areas. Generally, three well volumes are considered effective, or calculations can be made to determine, on the basis of
the aquifer parameters and well dimensions, the appropriate volume to remove prior to sampling.

FM003MSHJM7-7

-------
7.3.3 During purging, water level measurements may be taken regularly at 15-30 second intervals. This data may be used
to compute aquifer transmissivity and other hydraulic characteristics.

7.3.4 The following well evacuation devices are most commonly used. Other evacuation devices are available, but have been
omitted in this discussion due to their limited use.

7.3.5 Bailers: Bailers are the simplest purging device used and have many advantages. They generally consist of a rigid
length of tube, usually with a ball check-valve at the bottom. A line is used to lower the bailer into the well and retrieve a volume
of water. The three most common types of bailer are PVC, Teflon, and stainless steel. This manual method of purging is best
suited to shallow or narrow diameter wells. For deep, larger diameter wells which require evacuation of large volumes of water,
other mechanical devices may be more appropriate. Equipment needed will include a clean decontaminated bailer, Teflon or
nylon line, a sharp knife, and plastic sheeting.

7.3.5.1 Determine the volume of water to be purged as described in 7.2, Field Preparation.

7.3.5.2 Lay plastic sheeting around the well to prevent contamination of the bailer line with foreign materials.

7.3.5.3 Attach the line to the bailer and slowly lower until the bailer is completely submerged, being careful not to drop the
bailer to the water, causing turbulence and the possible loss of volatile organic contaminants.

7.3.5.4 Pull bailer out ensuring that the line either falls onto a clean area of plastic sheeting or never touches the ground.

7.3.5.5 Empty the bailer into a pail until full to determine the number of bails necessary to achieve the required purge
volume.

7.3.5.6 Thereafter, pour the water into a container and dispose of purge waters as specified in the site specific sampling plan.

7.3.6 Submersible Pumps: Submersible pumps are generally constructed of plastics, rubber, and metal parts which may
affect the analysis of samples for certain trace organics and inorganics. As a consequence, submersible pumps may not be
appropriate for investigations requiring analyses of samples for trace contaminants. However, they are still useful for presample
purging. However, the pump must have a check valve to prevent water in the pump and the pipe from rushing back into the well.
Submersible pumps generally use one of two types of power supplies, either electric or compressed gas or air. Electric powered
pumps can run off a 12 volt DC rechargeable battery, or a 110 or 220 volt AC power supply. Those units powered by compressed
air normally use a small electric or gas-powered air compressor. They may also utilize compressed gas (i.e., nitrogen) from
bottles. Different size pumps are available for different depth or diameter monitoring wells.

7.3.6.1 Determine the volume of water to be purged as described in 7.2, Field Preparation.

7.3.6.2 Lay plastic sheeting around the well to prevent contamination of pumps, hoses or lines with foreign materials.

7.3.6.3 Assemble pump, hoses and safety cable, and lower the pump into the well. Make sure the pump is deep enough so
all the water is not evacuated. (Running the pump without water may cause damage.)

7.3.6.4 Attach flow meter to the outlet hose to measure the volume of water purged.

7.3.6.5 Use a ground fault circuit interrupter (GCFI) or ground the generator to avoid possible electric shock.

7.3.6.6 Attach power supply, and purge well until specified volume of water has been evacuated (or until field parameters,
such as temperature, pH, conductivity, etc, have stabilized). Do not allow the pump to run dry. If the pumping rate exceeds
the well recharge rate, lower the pump further into the well, and continue pumping.

7.3.6.7 Collect and dispose of purge waters as specified in the site specific sampling plan.

7.3.7 Non-Contact Gas Bladder Pumps: For this procedure, an all stainless-steel and Teflon Middleburg-squeeze bladder
pump (e.g., IEA, TIMCO, Well Wizard, Geoguard, and others) is used to provide the least amount of material interference to the
sample (Barcelona, 1985). Water comes into contact with the inside of the bladder (Teflon) and the sample tubing, also Teflon,

FKM03MSMIW8-8

-------
that may be dedicated to each well. Some wells may have permanently installed bladder pumps, (i.e., Well Wizard, Geoguard),
that will be used to sample for all parameters.

7.3.7.1 Assemble Teflon tubing, pump and charged control box.

7.3.7.2 Procedure for purging with a bladder pump is the same as for a submersible pump (Section 7.3.6).

7.3.7.3 Be sure to adjust flow rate to prevent violent jolting of the hose as sample is drawn in.

7.3.8 Suction Pumps: There are many different types of suction pumps. They include: centrifugal, peristaltic and diaphragm.
Diaphragm pumps can be used for well evacuation at a fast pumping rate and sampling at a low pumping rate. The peristaltic
pump is a low volume pump that uses rollers to squeeze the flexible tubing thereby creating suction. This tubing can be dedicated
to a well to prevent cross contamination. Peristaltic pumps, however, require a power source.

7.3.8.1 Assembly of the pump, tubing, and power source if necessary.

7.3.8.2 Procedure for purging with a suction pump is exactly the same as for a submersible pump (Section 7.3.6).

7.3.9 Inertia Pumps: Inertia pumps such as the WaTerra pump and piston pump, are manually operated. They are most
appropriate to use when wells are too deep to bail by hand, or too shallow or narrow (or inaccessible) to warrant an automatic
(submersible, etc.) pump. These pumps are made of plastic and may be either decontaminated or discarded.

7.3.9.1 Determine the volume of water to be purged as described in 7.2, Field Preparation.

7.3.9.2 Lay plastic sheeting around the well to prevent contamination of pumps or hoses with foreign materials.

7.3.9.3 Assemble pump and lower to the appropriate depth in the well.

7.3.9.4 Begin pumping manually, discharging water into a 5 gallon bucket (or other graduated vessel). Purge until specified
volume of water has been evacuated (or until field parameters such as temperature, pH, conductivity, etc. have stabilized).

7.3.9.5 Collect and dispose of purge waters as specified in the site specific project plan.

7.4 Sampling

7.4.1 Sample withdrawal methods require the use of pumps, compressed air, bailers, and samplers. Ideally, purging and
sample withdrawal equipment should be completely inert, economical to manufacture, easily cleaned, sterilized, reusable, able
to operate at remote sites in the absence of power resources, and capable of delivering variable rates for sample collection.

7.4.2 There are several factors to take into consideration when choosing a sampling device. Care should be taken when
reviewing the advantages or disadvantages of any one device. It may be appropriate to use a different device to sample than that
which was used to purge. The most common example of this is the use of a submersible pump to purge and a bailer to sample.

7.4.3 Bailers: The positive-displacement volatile sampling bailer is perhaps the most appropriate for collection of water
samples for volatile analysis. Other bailer types (messenger, bottom fill, etc.) are less desirable, but may be mandated by cost
and site conditions.

7.4.3.1 Surround the monitor well with clean plastic sheeting.

7.4.3.2 Attach a line to a clean decontaminated bailer.

7.4.3.3 Lower the bailer slowly and gently into the well, taking care not to shake the casing sides or to splash the bailer into
the water. Stop lowering at a point adjacent to the screen.

7.4.3.4 Allow bailer to fill and then slowly and gently retrieve the bailer from the well avoiding contact with the casing, so
as not to knock flakes of rust or other foreign materials into the bailer.

FM003MSH)iM99

-------
7.4.3.5 Remove the cap from the sample container and place it on the plastic sheet or in a location where it won't become
contaminated. See Section 7.7 for special considerations on VOA samples.

7.4.3.6 Begin slowly pouring from the bailer.

7.4.3.7 Filter and preserve samples as required by sampling plan.

7.4.3.8 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.4.3.9 Replace the well cap.

7.4.3.10 Log all samples in the site logbook and on field data sheets and label all samples.

7.4.3.11 Package samples and complete necessary paperwork.

7.4.3.12 Transport sample to decontamination zone for preparation for transport to analytical laboratory.

7.4.4 Submersible Pumps: Although it is recommended that samples not be collected with a submersible pump due to the
reasons stated in Section 3, there are some situations where they may be used.

7.4.4.1 Allow the monitor well to recharge after purging, keeping the pump just above screened section.

7.4.4.2 Attach gate valve to hose (if not already fitted), and reduce flow of water to a manageable sampling rate.

7.4.4.3 Assemble the appropriate bottles.

7.4.4.4 If no gate valve is available, run the water down the side of a clean jar and fill the sample bottles from the jar.

7.4.4.5 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.4.4.6 Replace the well cap.

7.4.4.7 Log all samples in the site logbook and on the field data sheets and label all samples.

7.4.4.8 Package samples and complete necessary paperwork.

7.4.4.9 Transport sample to decontamination zone for preparation for transport to the analytical laboratory.

7.4.4.10 Upon completion, remove pump and assembly and fully decontaminate prior to setting into the next sample well.
Dedicate the tubing to the hole.

7.4.5 Non-Contact Gas Bladder Pumps: The use of a non-contact gas positive displacement bladder pump is often mandated
by the use of dedicated pumps installed in wells. These pumps are also suitable for shallow (less than 100 feet) wells. They are
somewhat difficult to clean, but may be used with dedicated sample tubing to avoid cleaning. These pumps require a power
supply and a compressed gas supply (or compressor). They may be operated at variable flow and pressure rates making them
ideal for both purging and sampling. Barcelona (1984) and Nielsen (1985) report that the non-contact gas positive displacement
pumps cause the least amount of alteration in sample integrity as compared to other sample retrieval methods.

7.4.5.1 Allow well to recharge after purging.

7.4.5.2 Assemble the appropriate bottles.

7.4.5.3 Turn pump on, increase the cycle time and reduce the pressure to the minimum that will allow the sample to come
to the surface.

7.4.5.4 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.4.5.5 Replace the well cap.

FKM03MSMID4KIO

-------
7.4.5.6 Log all samples in the site logbook and on field data sheets and label all samples.

7.4.5.7 Package samples and complete necessary paperwork.

7.4.5.8 Transport sample to decontamination zone for preparation for transport to analytical laboratory.

7.4.5.9 On completion, remove the tubing from the well and either replace the Teflon tubing and bladder with new dedicated
tubing and bladder or rigorously decontaminate the existing materials.

7.4.5.10 Nonfiltered samples shall be collected directly from the outlet tubing into the sample bottle.

7.4.5.11 For filtered samples, connect the pump outlet tubing directly to the filter unit. The pump pressure should remain
decreased so that the pressure build up on the filter does not blow out the pump bladder or displace the filter. For the Geo tech
barrel filter, no actual connections are necessary so this is not a concern.

7.4.6 Suction Pumps: In view of the limitations of these type pumps, they are not recommended for sampling purposes.

7.4.7 Inertia Pumps: Inertia pumps may be used to collect samples. It is more common, however, to purge with these pumps
and sample with a bailer (Section 7.4.3).

7.4.7.1 Following well evacuation, allow the well to recharge.

7.4.7.2 Assemble the appropriate bottles.

7.4.7.3 Since these pumps are manually operated, the flow rate may be regulated by the sampler. The sample may be
discharged from the pump outlet directly into the appropriate sample container.

7.4.7.4 Cap the sample container tightly and place prelabeled sample container in a carrier.

7.4.7.5 Replace the well cap.

7.4.7.6 Log all samples in the site logbook and on field data sheets and label all samples.

7.4.7.7 Package samples and complete necessary paperwork.

7.4.7.8 Transport sample to decontamination zone for preparation for transport to the analytical laboratory.

7.4.7.9 Upon completion, remove pump and decontaminate or discard, as appropriate.

7.5 Filtering

7.5.1 For samples requiring filtering, such as total metals analysis, the filter must be decontaminated prior to and between
uses. Filters work by two methods. A barrel filter such as the "Geotech" filter works with a bicycle pump, used to build up
positive pressure in the chamber containing the sample which is then forced through the filter paper (minimum size 0.45 /im)
into ajar placed underneath. The barrel itself is filled manually from the bailer or directly via the hose of the sampling pump.
The pressure must be maintained up to 30 lbs/in2 by periodic pumping.

7.5.2 A vacuum type filter involves two chambers; the upper chamber contains the sample and a filter (minimum size 0.45
jUm) divides the chambers. Using a hand pump or a Gilian type pump, air is withdrawn from the lower chamber, creating a
vacuum and thus causing the sample to move through the filter into the lower chamber where it is drained into a sample jar.
Repeated pumping may be required to drain all the sample into the lower chamber. If preservation of the sample is necessary,
this should be done after filtering.

7.6 Post Operation

After all samples are collected and preserved, the sampling equipment should be decontaminated prior to sampling another
well to prevent cross-contamination of equipment and monitor wells between locations.

FKM03MSMID41-11

-------
7.6.1 Decontaminate all equipment.

7.6.2 Replace sampling equipment in storage containers.

7.6.3 Prepare and transport water samples to the laboratory. Check sample documentation and make sure samples are properly
packed for shipment.

7.7 Special Considerations for VOA Sampling

7.7.1 The proper collection of a sample for volatile organics requires minimal disturbance of the sample to limit volatilization
and therefore a loss of volatiles from the sample.

7.7.2 Sample retrieval systems suitable for the valid collection of volatile organic samples are: positive displacement bladder
pumps, gear driven submersible pumps, syringe samplers and bailers (Barcelona, 1984; Nielsen, 1985). Field conditions and
other constraints will limit the choice of appropriate systems. The focus of concern must be to provide a valid sample for
analysis, one which has been subjected to the least amount of turbulence possible.

7.7.3 The following procedures should be followed.

7.7.3.1 Open the vial, set cap in a clean place, and collect the sample during the middle of the cycle. When collecting
duplicates, collect both samples at the same time.

7.7.3.2 Fill the vial to just overflowing. Do not rinse the vial, nor excessively overflow it. There should be a convex
meniscus on the top of the vial.

7.7.3.3 Check that the cap has not been contaminated (splashed) and carefully cap the vial. Place the cap directly over the
top and screw down firmly. Do not overtighten and break the cap.

7.7.3.4 Invert the vial and tap gently. Observe vial for at least ten (10) seconds. If an air bubble appears, discard the
sample and begin again. It is imperative that no entrapped air is in the sample vial.

7.7.3.5 Immediately place the vial in the protective foam sleeve and place into the cooler, oriented so that it is lying on
its side, not straight up.

7.7.3.6 The holding time for VOAs is seven days. Samples should be shipped or delivered to the laboratory daily so as
not to exceed the holding time. Ensure that the samples remain at 4oC, but do not allow them to freeze.

7.8 Calculations

There are no calculation necessary to implement this procedure.

7.9 Health and Safety

7.9.1 When working with potentially hazardous materials, follow USEPA, OSHA or Corporate health andsafety guidelines.
More specifically, depending upon the site specific contaminants, various protectiveprograms must be implemented prior to
sampling the first well. The site health and safety planshould be reviewed with specific emphasis placed on the protection
program planned for the wellsampling tasks. Standard safe operating practices should be followed such as minimizing contact
withpotential contaminants in both the vapor phase and liquid matrix through the use of respirators anddisposable clothing.

7.9.2 When working around volatile organic contaminants:

• Avoid breathing constituents venting from the well;

• Pre-survey the well head-space with an FID/PID prior to sampling; and

• If monitoring results indicate organic constituents, sampling activities may be conducted in Level C protection. At a
minimum, skin protection will be afforded by disposable protective clothing.

FKM031WSMID41-2 2

-------
7.9.3 Physical hazards associated with well sampling:

• Lifting injuries associated with pump and bailers retrieval; moving equipment;

• Use of pocket knives for cutting discharge hose;

• Heat/cold stress as a result of exposure to extreme temperatures and protective clothing;

• Slip, trip, fall conditions as a result of pump discharge;

• Restricted mobility due to the wearing of protective clothing; and

• Electrical shock associated with use of submersible pumps is possible. Use a ground fault circuit interrupter (GCFI) or
a copper grounding stake to avoid this problem.

8.0 QUALITY CONTROL

8.1 There are no specific quality assurance activities which apply to the implementation of these procedures. However, the
following general QA procedures apply:

8.1.1 All data must be documented on field data sheets or within site logbooks.

8.1.2 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer, unless
otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to sampling/operation and
they must be documented.

8.1.3 The collection of rinsate blanks is recommended to evaluate potential for cross contamination from the purging and/or
sampling equipment.

8.1.4 Trip blanks are required if analytical parameters include VOAs.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Barcelona, M.J., Helfrich, J.A., Garske, E.E., and J.P. Gibb, Spring 1984. "A Laboratory Evaluation of Groundwater Sampling
Mechanisms," Groundwater Monitoring Review, 1984 pp. 32-41.

2. Barcelona, M.J., Helfrich, J.A., and Garske, E.E., "Sampling Tubing Effects on Groundwater Samples", Analy. Chem., Vol. 57,
1985 pp. 460-463.

3. Driscoll, F.G., Groundwater and Wells (2nd ed.) Johnson Division, UOP Inc., St. Paul, Minnesota, 1986, 1089 pp.

4. Gibb, J.P., R.M. Schuller, andR.A. Griffin,. Monitoring Well Sampling and Preservation Techniques, EPA-600/9-80-010, 1980.
March, 1980.

5. Instrument Specialties Company, (January). Instruction Manual, Model 2100 Wastewater Sampler, Lincoln, Nebraska, 1980.

6. Keely, J.F. and Kwasi Boateng, Monitoring Well Installation, Purging and Sampling Techniques - Part I: Conceptualizations,
Groundwater V25, No. 3, 1987 pp. 300-313.

7. Keith, Lawrence H., Principles of Environmental Sampling, American Chemical Society, 1988.

FKM031WSMID41-3 3

-------
8. Korte, Nic, and Dennis Ealey,. Procedures for Field Chemical Analyses of Water Samples, U.S. Department of Energy,
GJ/TMC-07, Technical Measurements Center, Grand Junction Project Office, 1983.

9. Korte, Nic, and Peter Kearl,. Procedures for the Collection and Preservation of Groundwater and Surface Water Samples and
for the Installation of Monitoring Wells: Second Edition, U.S. Department of Energy, GJ/TMC-08, Technical Measurements Center,
Grand Junction Projects Office, 1985.

10. National Council of the Paper Industry for Air and Stream Improvement, Inc.,. A Guide to Groundwater Sampling, Technical
Bulletin No. 362, Madison, New York. January, 1982.

11. Nielsen, David M. and Yeates, Gillian L., Spring. "A Comparison of Sampling Mechanisms Available for Small-Diameter
Groundwater Monitoring Wells," Groundwater Monitoring Review, 1985, pp. 83-99.

12. Scalf, et al. (M.J. Scalf, McNabb, W. Dunlap, R. Crosby, and J. Fryberger),. Manual for Groundwater Sampling Procedures. R.S.
Kerr Environmental Research Laboratory, Office of Research and Development. 1980, Ada, OK.

13. Sisk, S.W. NEIC Manual for Ground/Surface Investigations at Hazardous Waste Sites, EPA-330/9-81-002, 1981.

14. U.S. Department of the Interior, National Handbook of Recommended Methods for Water-Data Acquisition, Reston, Virginia.

15. U.S. Environmental Protection Agency, 1977. Procedures Manual for Groundwater Monitoring at Solid Waste Disposal Facilities.
EPA-530/SW-611. August, 1977.

16. U.S. Code of Federal Regulations, 49 CFR Parts 100 to 177, Transportation revised November 1, 1985.

17. U.S. Environmental Protection Agency, 1982. Handbook for Chemical and Sample Preservation of Water and Wastewater,
EPA-600/4-82-029, Washington, D.C.

18. U.S. Environmental Protection Agency, 1983. Methods for Chemical Analysis of Water and Waste, EPA-600/4-79-020,
Washington, D.C.

19. U.S. Environmental Protection Agency, 1984. Test Methods for Evaluation of Solid Waste, EPA-SW-846, Second Edition,
Washington, D.C.

20. U.S. Environmental Protection Agency, 1981. Manual of Groundwater Quality Sampling Procedures, EPA-600/2-81-160,
Washington, D.C.

21. U.S. Environmental Protection Agency, 1985. Practical Guide for Groundwater Sampling, EPA-600/2-85/104, September, 1985.

22. U.S. Environmental Protection Agency, 1986. RCRA Groundwater Monitoring Technical Enforcement Guidance Document,
OSWER-9950-1, September, 1986.

23. Weston, 1987. Standard Operations Procedures for Monitor Well Installation. MOUND IGMP/RIP.

FKM031WSMID41-4 4

-------
FASP Method F93012
COLLECTION OF GASEOUS SAMPLES BY USING TEDLAR BAGS

1.0 SCOPE AND APPLICATION

1.1 This method covers the collection of gaseous samples by using Tedlar bags. Tedlar bag sampling may be applied to collection
of air, soil gas, or other type of gaseous samples containing volatile or semivolatile analytes. The specific determinative procedures
are contained in other FASP SOPs.

2.0 SUMMARY OF METHOD

2.1 The FASP Tedlar bag sampling system consists of a Tedlar bag equipped with a valve suitable for connection to the sample
collection tubing, a container large enough to house the Tedlar bag and suitable for partial evacuation, and a pumping system capable
of creating a reduced pressure in the bag container.

2.2 The sample is collected by placing the Tedlar bag in the container, connecting the bag to the sample source, and connecting
the vacuum pump to the bag container as shown in Figure 1. The pressure is reduced in the container around the bag and the sample
gas is drawn into the bag.

3.0 INTERFERENCES

Information not available.

4.0 APPARATUS AND MATERIALS

4.1 Tedlar Bags: Sufficient for two days of sampling.

4.2 Pump: Capable of evacuation of bag container, Gilian Personnel Sampling Pump or equivalent.

4.3 Bag Container. Desiccator: I.D.240 mm, Height 311 mm, with two openings or equivalent.

5.0 REAGENTS

Information not available.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

6.1 Tedlar bag samples should be analyzed within 48 hours of collection. Samples are stored in clean, opaque trash bags to
prevent photodegradation.

7.0 PROCEDURE

7.1 Collection of Tedlar Bag Samples

7.1.1 Place a Tedlar bag in desiccator so that the sample introduction valve is accessible to the sample train tubing and attach
the vacuum system to the desiccator valve.

7.1.2 Seal the desiccator and, with the bag valve closed, open the valve to connect the bag and the sample train tubing.

7.1.3 Draw a vacuum on the desiccator and allow the bag to fill until equilibrium with atmospheric pressure as indicated on
the line pressure gauge.

7.1.4 Close the bag valve, release the vacuum in the desiccator, remove the bag, and store the sample in a cool, dark place.

7.2 Decontamination of Tedlar Bags

FMC-flJS-OTl-l

-------
7.2.1 To prepare bags used for samples in which no contaminants were detected, flush the bags once with Ultra pure nitrogen
of equivalent.

7.2.2 To prepare bags used for samples in which contaminants were detected, flush the bags three times with Ultra pure
nitrogen, analyze last rinse. If no contaminants are detected the bag may be evacuated and reused.

7.2.3 For bags which are not free of contaminants after flushing three times, heat the bags in a vacuum oven under reduced
pressure for 30 minutes. Remove the bags, fill with Ultra pure nitrogen, and analyze the contents by the same method employed
for the target analytes. If there are still detectable contaminants, throw the bag away.

7.2.4 Prior to returning bags to the samplers, slightly overfill the bag with reagent air or nitrogen and check for leaks using
electronic leak detector.

8.0 QUALITY CONTROL

8.1 Field Blanks are collected daily or at a frequency of 1 per 20 field samples, whichever is most frequent. Field blanks are
collected by filling a Tedlar bag with Ultra Pure nitrogen at a specified sample location.

8.2 Equipment Blanks are collected at a frequency of 1 per 20 field samples. A sample of Ultra Pure nitrogen is collected in a
manner identical to the collection of field samples.

9.0 METHOD PERFORMANCE

Information not available.

10.0 REFERENCES

1. Tedlar Bag Sampling: SOP # 2050, in Compendium of ERT Air Sampling Procedures, USEPA, PB92-963406

FMC-flJS-OTl-2

-------
ERT Method

QUALITY ASSURANCE/QUALITY CONTROL SAMPLES

1.0 SCOPE AND APPLICATION

1.1 The purpose of this Standard Operating Procedure (SOP) is to describe typical Quality Assurance/Quality Control
(QA/QC) samples that are collected in the field, or prepared for or by the laboratory. The QA/QC samples identified in this SOP
are representative for soil, water and air matrices.

1.2 These are standard (i.e., typically applicable) operating procedures which may be varied or changed as required,
dependent upon site conditions, equipment limitations or other procedure limitations. In all instances, the ultimate procedures
employed should be documented and associated with the final report.

1.3 Mention of trade names or commercial products does not constitute U.S. Environmental Protection Agency (U.S. EPA)
endorsement or recommendation for use.

2.0 SUMMARY OF METHOD

2.1 QA samples are used as an assessment tool to determine if environmental data meet the quality criteria established for a
specific application. QC samples are generally used to establish intra-laboratory or analyst specific precision and bias or to assess
the performance of all or a portion of the measurement system. The goal of including QA/QC samples with any sampling or
analytical event is to be able to identify, measure and control the sources of error that may be introduced from the time of sample
bottle preparation through analysis.

2.2 Accuracy is defined as the closeness or agreement between an observed value and an accepted reference value. When
applied to a set of matrix spike/matrix spike duplicate (MS/MSD) results, accuracy will be affected by a combination of random
error and systematic error (or bias). However, only bias can be measured. Bias is defined as the deviation of a measured value
from a reference value or a known spiked amount, and is determined by calculating percent recovery. Precision is a measure of the
closeness of agreement among individual measurements. Precision is determined by calculating the relative standard deviation or
the coefficient of variation for at least eight matrix spike samples.

3.0 INTERFERENCES

3.1 QA/QC samples are collected and analyzed in addition to environmental samples to assist in identifying the origin of
both field and laboratory contamination. In order to provide useful information, QA/QC samples must be prepared and analyzed
appropriately.

4.0 APPARATUS AND MATERIALS

4.1 With the exception of some types of blank and performance evaluation samples, the equipment/apparatus required to
collect QA/QC samples is the same as the equipment/apparatus required to collect the environmental samples. This is determined
on a site specific basis. Due to the wide variety of sampling equipment available, refer to the specific SOPs for sampling
techniques which include lists of the equipment/apparatus required for sampling. Sampling equipment/apparatus are generally not
required for field, trip, or lot blanks or performance evaluation samples.

5.0 REAGENTS

5.1 Reagents may be utilized for preservation of samples and for decontamination of sampling equipment. The
preservatives required are specified by the analysis to be performed and are summarized in ERT/REAC SOP #2003, Sample
Storage, Preservation, and Handling. Decontamination solutions are specified in ERT/REAC SOP #2006, Sampling Equipment
Decontamination.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

-------
6.1 The amount of sample to be collected, and the proper sample container type (i.e., glass, plastic), chemical preservation,
and storage requirements are dependent on the matrix being sampled and the parameter(s) of interest, and are discussed in
ERT/REAC SOP #2003, Sample Storage, Preservation, and Handling, for the soil and water matrices. Sample preservation,
containers, handling, and storage for air and waste samples are discussed in the specific SOPs for air and waste sampling
techniques.

7.0 PROCEDURE

7.1 QA/QC samples for soil, water and air matrices are discussed below. Each type of sample is defined and a preparation
procedure is outlined. In addition, the suggested minimum frequency of collection of these QA/QC samples is discussed.

7.1.1 Soil OA/OC Samples

7.1.1.1 Field Replicates

7.1.1.1.1 Field replicates are field samples obtained from one location, homogenized, and divided into separate
containers. They are treated as separate samples throughout the remaining sample handling and analytical processes.
These samples are used to assess error (precision) associated with sample heterogeneity, sample methodology and
analytical procedures. Field replicates may be collected on a site-specific basis and may not be collected at all sites
investigated.

7.1.1.1.2 Field replicates may be used when determining total error (precision) for critical samples with
contamination concentrations at or near the action level. This procedure is useful in determining total (sampling and
analytical) error because it evaluates sample collection, sample preparation, and analytical procedures. A minimum of
eight replicate samples is required in order for a valid statistical analysis to be performed.

NOTE: The terms "field duplicate" or "duplicate sample" have been replaced by the term "field replicate".

7.1.1.2 Collocated Samples

7.1.1.2.1 Collocated samples are collected adjacent to the routine field sample to determine variability of the soil
and contaminant(s) at the site within a small area. Typically, collocated samples are collected about one-half to three
feet away from the routine field sample location. Analytical results from collocated samples can be used to assess site
variation, but only in the immediate sampling area. Due to the non-homogenous nature of soil at sites, collocated
samples should not be used to assess variability across a site and are not recommended for assessing error.

Applicability and frequency of collocated samples should be determined on a site-specific basis.

7.1.1.3 Background Samples

7.1.1.3.1 Background samples are collected from area(s), either on- or off-site where there is little or no chance of
contamination. Background samples are collected in an attempt to determine the natural composition of the soil
(especially important in areas with high concentrations of naturally-occurring metals) and are considered "clean"
samples. They provide a basis for comparison of contaminant concentration levels with samples collected on site. At
least one background soil sample should be collected; however, more are warranted when site-specific factors such as
natural variability of local soil, multiple on-site contaminant source areas, or off-site facilities potentially contributing
to soil contamination exist. Background samples may be collected for all QA objectives, in order to evaluate potential
error associated with sampling design, sampling methodology, and analytical procedures.

7.1.1.3.2 Background samples may be used to determine bias and precision if at least eight replicates are spike
with the analyte of interest at a concentration equal to the action level and then analyzed.

7.1.1.4 Rinsate Blanks

7.1.1.4.1 For the soil matrix, rinsate blanks are not required because the aqueous rinse does not simulate the cross-
contamination mechanism that would occur.

7.1.1.5 Field Blanks

-------
7.1.1.5.1 Field blanks are prepared in the field by filling the appropriate sample container with certified clean sand
or soil and are then submitted to the laboratory for analysis. A field blank is primarily used to evaluate contamination
error associated with field operations and shipping but may also be used to evaluate contamination error associated with
laboratory procedures. Submit field blanks at a rate of one per day to meet QA2 and QA3 objectives.

7.1.1.6 Trip Blanks

7.1.1.6.1 Trip blanks are only required if volatile organics are a concern and are prepared prior to going into the
field. Trip blanks consist of certified clean sand or soil and are handled, transported, and analyzed in the same manner
as the other volatile organic samples acquired that day. Trip blanks are used to evaluate contamination error associated
with sampling, sample handling and shipment, or laboratory handling and analysis. Utilize trip blanks to meet QA2 and
QA3 objectives for volatile organic analyses only. The minimum frequency of trip blanks is one per container used to
transport volatile organic samples.

7.1.1.7 Performance Evaluation Samples

7.1.1.7.1 Performance evaluation (PE) samples evaluate the overall bias of the analytical laboratory and detect any
error in the analytical method used. These samples are usually prepared by a third party, using a quantity of analyte(s)
which is known to the preparer but unknown to the laboratory. The analyte(s) used to prepare the PE sample is the
same as the analyte(s) of concern. Laboratory procedural error is evaluated by the percentage of analyte identified in
the PE sample (percent recovery). Even though they are not available for all analytes, PE samples are required to
achieve QA3 objectives. Where PE samples are unavailable for an analyte of interest, QA2 is the highest QA objective
achievable. When analyzed, the minimum frequency of PE samples is one per analyte of interest per matrix.

7.1.1.8 Matrix Spike Samples

7.1.1.8.1 Matrix spike and matrix spike duplicate samples (MS/MSDs) are environmental samples that are spiked
in the laboratory with a known concentration of a target analyte(s) to verify percent recoveries. MS/MSDs are
primarily used to check sample matrix interferences. They can also be used to monitor laboratory performance.
However, a dataset of at least three or more results is necessary to distinguish between laboratory performance and
matrix interference. For ERT/REAC sampling events, the minimum frequency of MS/MSDs is 10% of the total
number of samples being analyzed for the target analyte(s).

7.1.1.8.2 MS/MSDs are also used to evaluate error due to laboratory bias and precision. One MS/MSD pair
should be analyzed and the average percent recovery should be calculated to assess bias. To assess precision, at least
eight matrix spike replicates from the same sample should be analyzed and the standard deviation and coefficient of
variation should be determined. Bias and precision calculations are optional for QA2 objectives and required to meet
QA3 objectives.

7.1.2 Aqueous QA/QC Samples

7.1.2.1 Field Replicates

7.1.2.1.1 Field replicates are field samples obtained from one location and divided into separate containers. They
are treated as separate samples throughout the remaining sample handling and analytical processes. These samples are
used to assess error (precision) associated with sample heterogeneity, sample methodology and analytical procedures.
Field replicates may be collected on a site-specific basis and may not be collected at all sites investigated.

7.1.2.1.2 Field replicates may be used when determining total error (precision) for critical samples with
contamination concentrations at or near the action level. This procedure is useful in determining total (sampling and
analytical) error because it evaluates the sample collection, samples preparation, and the analysis. A minimum of eight
replicate samples is required in order for a valid statistical analysis to be performed.

NOTE: The terms "field duplicate" or "duplicate samples" have been replaced by the term "field replicate".

7.1.2.2 Background Samples

-------
7.1.2.2.1 Background samples are collected from area(s), either on- or off-site where there is little or no chance of
contamination. Background samples determine the natural composition of the aqueous matrix and are considered
"clean" samples. They provide a basis for comparison of contaminant concentration levels with samples collected on
site. At least one background sample should be collected; however, more are warranted when site-specific factors such
as multiple on-site contaminant source areas, or off-site facilities potentially contributing to contamination exist.
Background samples may be collected for all QA objectives, in order to evaluate potential error associated with
sampling design, sampling methodology, and analytical procedures.

7.1.2.2.2 Background samples may be used to determine bias and precision if at least eight replicates are spiked
with the analyte of interest at a concentration equal to the action level and then analyzed.

7.1.2.3 Rinsate Blanks

7.1.2.3.1 Rinsate blanks are samples obtained by running distilled/deionized water over decontaminated sampling
equipment to test for residual contamination. The blank water is collected in sample containers for handling, shipment,
and analysis. These samples are treated identical to the samples collected that day. A rinsate blank is used to assess
cross-contamination brought about by improper decontamination procedures. Where dedicated sampling equipment is
not utilized, collect one rinsate blank per type of sampling device per day to meet QA2 and QA3 objectives.

7.1.2.4 Field Blanks

7.1.2.4.1 Field blanks are prepared in the field by filling the appropriate sample container with distilled/deionized
water and are then submitted to the laboratory for analysis. A field blank is primarily used to evaluate contamination
error associated with field operations and shipping but may also be used to evaluate contamination error associated with
laboratory procedures. Submit field blanks at a rate of one per day to meet QA2 and QA3 objectives.

7.1.2.5 Trip Blanks

7.1.2.5.1 Trip blanks are only required if volatile organics are a concern and are prepared prior to going into the
field. Trip blanks consist of distilled/deionized water and are handled, transported, and analyzed in the same manner as
the other volatile organic samples acquired that day. Trip blanks are used to evaluate contamination error associated
with sampling, sample handling and transport, or laboratory handling and analysis. Utilize trip blanks to meet QA2 and
QA3 objectives for volatile organic analyses only. The minimum frequency of trip blanks is one per container used to
transport volatile organic samples.

7.1.2.6 Performance Evaluation Samples

7.1.2.6.1 Performance evaluation (PE) samples evaluate the overall bias of the analytical laboratory and detect any
error in the analytical method used. These samples are usually prepared by a third party, using a quantity of analyte(s)
which is known to the preparer but unknown to the laboratory. The analyte(s) used to prepare the PE sample is the
same as the analyte(s) of concern. Laboratory procedural error is evaluated by the percentage of analyte identified in
the PE sample (percent recovery). Even though they are not available for all analytes, PE samples are required to
achieve QA3 objectives. Where PE samples are unavailable for an analyte of interest, QA2 is the highest QA objective
achievable. When analyzed, the minimum frequency of PE samples is one per analyte of interest per matrix.

7.1.2.7 Matrix Spike Samples

7.1.2.7.1 MS/MSDs are environmental samples that are spiked in the laboratory with a known concentration of a
target analyte(s) to verify percent recoveries. MS/MSDs are primarily used to check sample matrix interferences. They
can also be used to monitor laboratory performance. However, a dataset of at least three or more results is necessary to
distinguish between laboratory performance and matrix interference. For ERT/REAC sampling events, the minimum
frequency of MS/MSDs is 10% of the total number of samples being analyzed for the target analyte(s).

7.1.2.7.2 MS/MSDs are also used to evaluate error due to laboratory bias and precision. One MS/MSD pair
should be analyzed and the average percent recovery should be calculated to assess bias. To asses precision, at least
eight matrix spike replicates from the same sample should be analyzed and the standard deviation and coefficient of
variation should be determined. Bias and precision calculations are optional for QA2 objectives and required to meet
QA3 objectives.

S«C-fMin4

-------
7.1.3 Air QA/QC Samples

7.1.3.1 Duplicate/Collocated Samples

7.1.3.1.1 Duplicate or collocated samples are collected by placing two identical samplers next to each other and,
either: (1) air is drawn from one source and split with a manifold; or (2) two pumps are set adjacent to each other and
each collect a sample at the same flow rate. Depending upon the methods used to collect and analyze the samples,
duplicate/collocated samples can determine the variation due to both sampling error and precision in the analyses (e.g.,
using thermally desorbed adsorbent tubes), or to isolate the variation due to sampling error only (e.g., using solvent-
extracted tubes and Summa canisters). The minimum frequency of duplicate/collocated samples is 5% or one per
sampling event for all QA levels.

7.1.3.2 Field Blanks

7.1.3.2.1 Field blanks are samples that undergo the full handling and shipping process of an actual sample. Field
blanks are designed to detect potential sample contamination that may occur during field operations or during shipment.
The field blank is opened with the other sampling media, resealed and carried through the sampling process. The field
blank must be associated with an actual sampling period. Submit field blanks at a rate of 5% of the total samples or a
minimum of one per sampling event to meet QA2 and QA3 objectives.

7.1.3.3 Trip Blanks

7.1.3.3.1 Trip blanks detect whether samples are contaminated during shipping. It is typically used in conjunction
with field blanks to isolate sources of sample contamination already noted in previous field blanks. The trip blank is
prepared and added to the site samples after sampling has been completed, just prior to shipping samples for analysis.
If the absorbent tubes were sealed from the manufacturer, their seals should be broken at this point. For absorbent
tubes that have been recycled and resealed by the laboratory, there is no need to break these temporary seals prior to
shipping. Canister trip blanks are evacuated containers that are shipped to and from the site with the canisters used for
air sampling. A trip blank for an impinger-based sampling method consists of an aliquot of impinger reagent that is
shipped back to the laboratory with the samples. Submit trip blanks at a rate of 5% of the total samples or a minimum
of one per sampling event to meet QA2 and QA3 objectives.

7.1.3.4 Lot Blanks

7.1.3.4.1 A lot blank detects contamination producing false positive results strictly due to the sampling medium
itself. It consists of a sample collector from the same lot as the sample collectors used during a particular day or time
period. It comes from the manufacturer or laboratory with the seal intact. The lot blank is included with the samples
when they are delivered to the laboratory. Whenever a set of canisters is cleaned by the laboratory for reuse, the
previously most contaminated canister should be re-analyzed as a lot blank at least 24 hours later, in order to check the
cleanliness of that lot of "cleaned" canisters. Whenever a new sampler system (e.g., Anderson stainless steel bellows
pump) is initially received from the manufacturer or from a laboratory, a lot blank should be pulled off the system using
humidified zero air or humidified nitrogen. In a similar manner, whenever a sampler system is cleaned, at a minimum,
the sampler(s) that had generated the most contaminated canister sample(s) should be checked with humidified zero air.
Submit lot blanks at a rate of 10% of the total samples or a minimum of one per sampling event to meet QA1, QA2, and
QA3 objectives.

7.1.3.5 Breakthrough Sample

7.1.3.5.1 Breakthrough samples detect false negative results and significant negative biases in the data. These
problems can arise when compounds elute from the sampling media before the sampling run is completed. The two
types of breakthrough samples are serial media samples and spiked media samples. To collect a serial media sample, a
sampling train is set up with a primary sampling device and backed by a secondary sampling device. A spiked media
breakthrough sample is obtained by pulling air through a sampling train that was either spiked in the field with a
standard solution or was spiked in the laboratory prior to being shipped into the field. The spiked media breakthrough
sample is always collected next to and concurrent with an upwind/background sample.

7.1.3.5.2 The breakthrough sample typically is used to determine whether the first sampling device has retained all
of the compounds of concern. It should be collected in the first batch of samples. When mixed-bed adsorbent tubes are

-------
being used, serial media samples are not recommended. Instead, spike medium samples or distributed volume samples
should be collected. Breakthrough samples are recommended to be collected to meet QA2 and QA3 objectives;
however, the rate of collection is method dependent.

7.1.3.6 Reagent/Method Blank

7.1.3.6.1 A reagent/method blank is a reagent sample used in sample analyses. Unlike field and trip blanks, a
reagent/method blank is prepared in the laboratory and is designed to detect contamination that could arise from the
reagents and laboratory equipment used in the analysis. This would include the reagents used in preparing impinger
solutions and the reagents used in the extraction and cleanup of solvent extracted adsorbent media. Reagent/method
blanks should be analyzed at a rate of one per sample batch to meet QA2 and QA3 objectives.

7.1.3.7 Performance Evaluation Sample/Blind Spike

7.1.3.7.1 A PE sample evaluates the overall accuracy of the analytical laboratory and detects any bias in the
analytical method being used. The PE sample contains a quantity of analyte(s) which is known to the sampling team
but unknown to the laboratory. It is usually prepared by a third party and always undergoes some type of certification
analysis. The analyte(s) used to prepare the PE sample is the same as the analyte(s) of concern. The laboratory's
accuracy is evaluated by comparing the percentage of analyte identified in the PE sample with the analytical results of
the site samples.

7.1.3.7.2 A blind spike is a rarely used proficiency sample that is prepared and sent "blind" to a laboratory for the
same analyses as the other samples. A blind spike is used when: (1) the desired frequency of check samples for the
laboratory exceeds the number of available PE samples; (2) the background matrix of the PE does not truly reflect the
background matrix of the samples (e.g., high summer-time humidity or the exhaust from soil vapor extraction or
methane gas collection systems); or (3) many or all of the compounds of concern are not readily available in a PE
sample. In the latter case, because of uncertainties in the stability and half-lives of "new" compounds in or on the
sample media, the preparing laboratory must both certify the blind spikes which will be shipped to the field, and hold
back a few spike samples for re-certification analyses in the same time period as the actual sample analyses. A blind
spike should be prepared by an individual who is proficient in its preparation. PE samples/blind spikes are required to
achieve QA3 objectives, and are optional for QA2 objectives. The minimum frequency of PE samples/blind spikes is
one per parameter.

7.1.3.8 Surrogate Spike

7.1.3.8.1 A surrogate spike, which is typically used only with Gas Chromatography (GC), Gas
Chromatography/Mass Spectrometry (GC/MS), and High Performance Liquid Chromatography (HPLC)-based
methods, is designed to detect potential quantitative errors in the actual analyses of each sample. The surrogate
compounds, which are usually non-target compounds that elute throughout the analyses, are typically spiked into each
sample prior to its analysis. The surrogate results are used to check retention times, concentrations, percent recovery,
and matrix interferences.

7.1.3.9 Matrix Spike

7.1.3.9.1 A matrix spike is designed to test the ability of the method to detect known concentrations of the target
compounds. As a laboratory-prepared sample, it contains known concentrations of the target compounds which are
spiked into a sample prior to its analysis. The matrix spike results are used to verify retention times and percent
recoveries in the extraction procedure and to determine the degree to which matrix interferences will affect the overall
identification and quantification of the target compounds.

7.2 Calculations

7.2.1 This section is not applicable to this SOP.

7.3 Health and Safety

7.3.1 When working with potentially hazardous materials, follow U.S. EPA, OSHA, and corporate health and safety
procedures.

-------
8.0 QUALITY CONTROL

8.1 The following general QA procedures apply when preparing QC samples:

8.1.1 All data must be documented on field data sheets or within site logbooks and on chain of custody forms.

8.1.2 All instrumentation must be operated in accordance with operating instructions as supplied by the manufacturer,
unless otherwise specified in the work plan. Equipment checkout and calibration activities must occur prior to
sampling/operation, and they must be documented.

9.0 METHOD PERFORMANCE
Information not available.

10.0 REFERENCES

1. U.S. EPA Office of Emergency and Remedial Response. April, 1990. Quality Assurance/Quality Control Guidance for

Removal Activities: Sampling QA/QC Plan and Data Validation Procedures. Interim Final. EPA/540/G-90/004.

2. U.S. EPA. Office of Emergency and Remedial Response. June, 1991. Removal Program Representative Sampling

Guidance. Volume 1 - Soil. Interim Final. OWSER Directive 9360.4-10.

3. U.S. EPA Quality Assurance Management Staff. Quality Assurance Glossary and Acronyms. Draft. February 8, 1991.

-------