EPA/600/R-16/114 I July 2016
www.epa.gov/homeland-security-research
United States
Environmental Protection
Agency
oEPA
Analytical Protocol for Measurement of
Extractable Semivolatile Organic
Compounds Using Gas
Chromatography/Mass Spectrometry
Office of Research and Development
Homeland Security Research Program
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EPA/600/R-16/114
July 2016
Analytical Protocol for Measurement
of Extractable Semivolatile Organic
Compounds Using Gas
Chromatography/Mass Spectrometry
United States Environmental Protection Agency
Office of Research and Development
Homeland Security Research Program
Cincinnati, Ohio 45268
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Acknowledgments
This analytical protocol is for the determination and measurement of the semivolatile organic compounds.
The procedures were tested by ALS Environmental (formerly Columbia Analytical Services [CAS]) of
Kelso, Washington, in a single-laboratory study funded by the U.S. Environmental Protection Agency's
Homeland Security Research Program (HSRP). The procedures also were used during a multi-laboratory
exercise funded by the Water Security Division within the U.S. Environmental Protection Agency's
Office of Water. Technical support, data evaluation, and procedure modifications were provided by CSC
Science and Threat Reduction Solutions.
Disclaimer
The United States Environmental Protection Agency through its Office of Research and Development
funded and managed the research described here through EPA Contract No. EP-C-10-060. This
document has been reviewed in accordance with U.S. Environmental Protection Agency policy and
approved for publication. Note that approval does not signify that the contents necessarily reflect the
views of the Agency. Mention of trade names, products, or services does not convey EPA approval,
endorsement, or recommendation.
Questions concerning this document or its application should be addressed to:
Romy Campisano
U.S. Environmental Protection Agency
National Homeland Security Research Center
Office of Research and Development (NG16)
26 West Martin Luther King Drive
Cincinnati, OH 45268
(513) 569-7016
campisano.romv@,epa.gov
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table of Contents
Section Page
I.0 SCOPE AND APPLICATION 1
2.0 SUMMARY OF PROTOCOL 2
3.0 ACRONYMS, ABBREVIATIONS AND DEFINITIONS 3
3.1 Acronyms and Abbreviations 3
3.2 Definitions 4
4.0 INTERFERENCES 7
5.0 SAFETY 7
6.0 EQUIPMENT AND SUPPLIES 7
6.1 Microscale Extraction (MSE) Apparatus 7
6.2 General Equipment 9
6.3 Gas chromatograph/mass spectrometer (GC/MS) System 10
7.0 REAGENTS AND STANDARDS 11
7.1 Reagents 11
7.2 Standards 12
8.0 SAMPLE PRESERVATION, STORAGE, AND TECHNICAL HOLDING TIMES 14
8.1 Sample Preservation 14
8.2 Sample Storage 15
8.3 Procedure for Sample Extract Storage 15
8.4 Technical Holding Times 16
9.0 QUALITY CONTROL (QC) 16
9.1 Initial Demonstration of Capability (IDC) 16
9.2 Initial Precision and Recovery (IPR) Determination 17
9.3 Method Blanks 18
9.4 Matrix Spike and Matrix Spike Duplicate (MS/MSD) 20
9.5 Laboratory Control Sample (LCS) 22
9.6 Instrument Detection Limit (IDL) Determination 23
9.7 Method Detection Limit (MDL) Determination 23
9.8 Quantitation Limit (QL) Determination 24
10.0 CALIBRATION AND STANDARDIZATION 24
10.1 Instrument Operating Conditions 24
10.2 GC/MS Mass Calibration (Tuning) and Ion Abundance 25
10.3 Initial Calibration 26
10.4 Continuing Calibration Verification 28
II.0 ANALYTICAL PROCEDURE 30
11.1 Sample Preparation - General 30
11.2 Preparation of Water Samples 31
11.3 Preparation of Soil/Sediment Samples - General 32
11.4 Preparation of Air Samples 34
11.5 Preparation of Wipe Samples 34
11.6 Final Concentration of Extract by Nitrogen Evaporation Technique 35
11.7 Sample Analysis by Gas Chromatograph/Mass Spectrometer (GC/MS) 35
12.0 CALCULATIONS AND DATA ANALYSIS 36
12.1 Qualitative Identification of Target Compounds 36
12.2 Data Analysis and Calculations of Target Compounds 37
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Analytical Protocol for Extractable Semivolatile Organic Compounds
12.3 Technical Acceptance Criteria for Sample Analysis 41
12.4 Corrective Action for Sample Analysis 42
13.0 ANALYTICAL PROCEDURE PERFORMANCE 44
13.1 Instrument Detection Limit (IDL), Method Detection Limit (MDL) and
Quantitation Limit (QL) 45
13.2 Precision and Recovery in Samples 45
13.3 Problem Analytes 45
14.0 POLLUTION PREVENTION 46
15.0 WASTE MANAGEMENT 46
16.0 REFERENCES 46
APPENDIX: ALTERNATE SAMPLE PREPARATION PROCEDURES A-1
LIST OF TABLES
Table 1. Decafluorotriphenylphosphine (DFTPP) Key Ions and Ion Abundance Criteria 48
Table 2. Internal Standards (IS) with Corresponding Target and Surrogate (S) Compounds Assigned
for Quantitation 48
Table 3. Single-Laboratory Method Detection Limits (MDLs) for Target Compounds in Reagent
Water and Ottawa Sand 49
Table 4. Single-Laboratory Estimated Instrument Detection Limits (IDL), Retention Times (RT), and
Characteristic Ions for Target Compounds, Surrogates (S) and Internal Standards (IS) 50
Table 5. Analyte-specific Dwell Times and Ion Grouping for Selected Ion Monitoring (SIM) Analysis
51
Table 6a. Relative Response Factors (RRF) and Percent RSDs for Initial Calibration of Target
Compounds and Surrogates in Full Scan Mode from a Single-Laboratory Evaluation 52
Table 6b. Relative Response Factors (RRF) and Percent RSDs for Initial Calibration of Target
Compounds and Surrogates in SIM Mode from a Single-Laboratory Evaluation 53
Table 7a. Single-Laboratory Matrix Spike Recovery and Relative Percent Difference (RPD) in Surface
and Drinking Water Samples 54
Table 7b. Single-Laboratory Matrix Spike Recovery and Relative Percent Difference (RPD) in Soils. 55
Table 8a. Single-Laboratory Recovery and Precision in Reagent Water 56
Table 8b. Single-Laboratory Recovery and Precision in Ottawa Sand 57
Table 8c. Single-Laboratory Recovery and Precision in Wipes 58
Table 8d. Single-Laboratory Recovery and Precision in Air Filters 59
Table 9a. Surrogate Recovery in a Single-Laboratory (reagent water and Ottawa sand) 60
Table 9b. Surrogate Recovery in a Single-Laboratory (surface wipes and air filters) 60
Table 10a. Calibration Standard Concentrations (ng/|_iL) for GC/MS Full Scan with Split-Splitless
Injection 61
Table 10b. Calibration Standard Concentrations (ng/|_iL) for GC/MS Selected Ion Monitoring (SIM) with
Split-Splitless Injection 62
Table 11a. Single-Laboratory Quantitation Limit (QL) Results and Low Calibration Standard
Concentrations in Reagent Water Using Full Scan Analysis 63
Table lib. Single-Laboratory Quantitation Limit (QL) Results and Low Calibration Standard
Concentrations in Reagent Water Using SIM Analysis 64
Table 12a. Single-Laboratory Quantitation Limit (QL) Results and Low Calibration Standard
Concentrations in Ottawa Sand Using Full Scan Analysis 65
Table 12b. Single-Laboratory Quantitation Limit (QL) Results and Low Calibration Standard
Concentrations in Ottawa Sand Using SIM Analysis 66
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 13a. Single-Laboratory Study Water Matrix Characterization Data 67
Table 13b. Multi-Laboratory Exercise Water Matrix Characterization Data 67
Table 14. Single-Laboratory Study Soil Matrix Characterization Data 67
Table 15. Multi-laboratory Reagent Water Results for Dichlorvos, Mevinphos,
Tetramethylenedisulfotetramine (TETS) and Associated Surrogates 68
Table 16. Multi-laboratory Drinking Water Results for Dichlorvos, Mevinphos,
Tetramethylenedisulfotetramine (TETS) and Associated Surrogates 68
Table Al. Mean Percent Recovery and Relative Percent Difference (RPD) Results of Duplicate Water
Sample Extractions A-4
Table A2. Mean Percent Recovery and Relative Percent Difference (RPD) Results of Duplicate Ottawa
Sand Sample Extractions A-7
Table A3. Effect of Gel Permeation Cleanup (GPC) on Microscale Solvent Extraction (MSE) of
Georgia Bt2 Soil A-9
LIST OF FIGURES
Figure 1. Gas chromatogram of a midpoint calibration standard 69
Figure 2. Peak requiring manual integration due to peak tailing - dimethylphosphite (DMP) 70
Figure 3. Peak requiring manual integration due to closely eluting isomers - mevinphos 71
Figure 4. Peak requiring manual integration due to closely eluting isomers - phosphamidon 72
Figure 5. Peak requiring manual integration due to closely eluting isomers - chlorfenvinphos 73
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Analytical Protocol for Extractable Semivolatile Organic Compounds
1.0 SCOPE AND APPLICATION
1.1 In 2004, the U.S. Environmental Protection Agency (EPA) Homeland Security Research
Program (HSRP), in collaboration with experts from across EPA and other federal
agencies, identified analytical methods for the analysis of extractable semivolatile
organic compounds (SVOCs) during environmental remediation following a homeland
security event. This protocol is to be applied by the national network of
laboratories that has been recruited to the EPA-established Environmental
Response Laboratory Network (ERLN) so that their analytical results are
consistent and comparable. Summaries of these methods are provided in Selected
Analytical Methods for Environmental Remediation and Recovery (SAM), 2012.1
NHSRC is currently using the SAM methods to develop standard analytical protocols for
laboratory identification and measurement of target agents during site remediation.
These methods will be used to assist in determining the presence of contamination, the
effectiveness of decontamination, and site clearance decisions following
decontamination. SAM applies the following tiers listed below to indicate a level of
method usability for each specific analyte and sample type (SAM Tier definitions and
their application to SAM methods are also available at: http://www.epa.gov/homeland-
securitv-research/sam-chemical-methods-querv):
SAM Tier I: Analyte/sample type is a target of the method(s). Data are available for all
aspects of method performance and quality control (QC) measures supporting its use for
analysis of environmental samples following a contamination event. Evaluation and/or
use of the method(s) in multiple laboratories indicate that the method can be implemented
with no additional modifications for the analyte/sample type.
SAM Tier II: (1) The analyte/sample type is a target of the method(s) and the method(s)
has been evaluated for the analyte/sample type by one or more laboratories, or (2) the
analyte/sample type is not a target of the method(s), but the method has been used by
laboratories to address the analyte/sample type. In either case, available data and/or
information indicate that modifications will likely be needed for use of the method(s) to
address the analyte/sample type.
SAM Tier III: The analyte/sample type is not a target of the method(s), and/or no
reliable data supporting the method's fitness for intended use are available. Data from
other analytes or sample types, however, suggest that the method(s), with significant
modification, may be applicable.
1.2 This analytical protocol is for the determination of the contaminants listed in the table
below. The procedures are based on EPA SW-846 Methods 8270D, 8290A, 3511,
3535A, 3540C/3541, 3545A, and 3570 (References 16.1 - 16.8) and were tested in a
single-laboratory for measurement of the specific SVOCs in water, soil, air filters, and
wipes. The procedures also were tested for dichlorvos, mevinphos and tetramethylene-
disulfotetramine (TETS) in water during a multi-laboratory exercise.
Laboratory performance data are provided in Section 17.0 for the analyte/sample type
combinations listed in the table below. An "X" in the table below indicates that the
protocol meets the SAM Tier II definition of laboratory testing for the analyte/sample
type combination. Shaded areas indicate that the protocol meets the SAM Tier III
1 SAM and its methods are available at: http://www.epa.qov/homeland-securitv-research/sam.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
definition of laboratory testing for the analyte/sample type combination. The entries
shaded in grey with no "X" indicate the analyte/sample type combination meets the SAM
Tier III definition of insufficient supporting data. SAM considers five of the 21 analytes
listed to be "Not of concern" in air.
Target Analytes and Sample Matrices
Semivolatile Compounds
CAS RN'
Matrix **
Water
Sand/Soil
Air Filters
Wipes
Chlorfenvinphos
470-90-6
X
X
X
X
Chlorpyrifos
2921-88-2
X
X
X
X
Dichlorvos
62-73-7
X
X
X
X
Dicrotophos
141-66-2
X
X
X
X
Disulfoton
298-04-4
X
X
X
X
Fenamiphos
22224-92-6
X
X
X
X
Methyl parathion
298-00-0
X
X
X
X
Mevinphos
7786-34-7
X
X
X
X
Parathion
56-38-2
X
X
X
X
Phencyclidine
77-10-1
X
X
X
X
Phorate
298-02-2
X
X
X
X
Phosphamidon
13171-21-6
X
X
X
X
Tetramethylenedisulfotetramine (TETS)
80-12-6
X
X
X
X
Crimidine
535-89-7
X
X
Not a concern
X
1,4-Dithiane
505-29-3
X
X
Not a concern
X
1,4-Thioxane
15980-15-1
X
X
Not a concern
X
Chloropicrin
76-06-2
X
X
Strychnine
57-24-9
X
Not a concern
X
Tetraethyl pyrophosphate (TEPP)
107-49-3
X
Dimethylphosphite
868-85-9
X
X
X
Nicotine
54-11-5
X
Not a concern
X
* Chemical Abstracts Service (CAS) Registry Number
** An "X" indicates that the protocol meets the SAM Tier II definition of laboratory testing for the analyte/sample
type combination. Shaded areas indicate that the protocol meets the SAM Tier III definition of laboratory testing
for the analyte/sample type combination.
1.3 Results described in this protocol are based on use of the procedures in a single
laboratory and may contain high levels of uncertainty. Care should be taken by each
laboratory using the procedures to ensure that a sufficient initial demonstration of
competence is performed by each analyst and that adequate QC acceptance criteria are
established before any results are reported.
2.0 SUMMARY OF PROTOCOL
2.1 This analytical protocol involves solvent extraction of the sample followed by gas
chromatography/mass spectrometry analysis to determine SVOCs. The protocol
describes procedures and provides data for analyses using a mass selective detector
(MSD) in both full scan and selected ion monitoring (SIM) modes. The technique used
will depend on the data quality objectives. The user should keep in mind that, while SIM
offers greater sensitivity, SIM tends to be more affected by interferences than full scan.
2.2 Prior to analysis, aqueous, soil and wipe samples are prepared by microscale solvent
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Analytical Protocol for Extractable Semivolatile Organic Compounds
extraction (MSE). Appendix A provides information regarding additional extraction
procedures that have not been fully tested (solid phase extraction for aqueous samples,
automated Soxhlet extraction for soils, and pressurized fluid extraction (PFE) for soils
and wipes). Sample extracts may require concentration to achieve appropriate detection
and quantitation.
3.0 ACRONYMS, ABBREVIATIONS and DEFINITIONS
Acronyms and Abbreviations
%Recovery
Percent recovery
ACS
American Chemical Society
ASE
Accelerated Solvent Extraction
ASTM
ASTM International
amu
Atomic mass unit
CAS RN
Chemical Abstract Service Registry Number
CCV
Continuing calibration verification
DCM
Dichloromethane (methylene chloride)
DF
Dilution factor
DFTPP
Decafluorotriphenylphosphine
DVB
Divinylbenzene
EI
Electron ionization
EICP
Extracted ion current profile
EPA
U.S. Environmental Protection Agency
FC-43
Perfluoro-tri-«-butylamine
GC
Gas chromatograph
GC/MS
Gas chromatograph/Mass spectrometer
GPC
Gel permeation chromatography
ID
Internal diameter
IDC
Initial demonstration of capability
IDL
Instrument detection limit
IPR
Initial precision and recovery
IS
Internal standard
LCS
Laboratory control sample
LFB
Laboratory fortified blank
LRB
Laboratory reagent blank
MDL
Method detection limit
mEq
Milliequivalent(s)
MS
Mass spectrometer
MS/MSD
Matrix spike/Matrix spike duplicate
MSD
Mass selective detector
MSE
Microscale solvent extraction
NHSRC
National Homeland Security Research Center
NIST
National Institute of Standards and Technology
OSHA
U.S. Occupational Safety and Health Administration
PD
Percent drift
PE
Performance evaluation
PFE
Pressurized fluid extraction
PFK
Perfluorokerosene
PTFE
Polytetrafluoroethylene (Teflon®)
PUF
Polyurethane foam
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Analytical Protocol for Extractable Semivolatile Organic Compounds
QA
QC
QL
RPD
RRF
RRT
RSD
RT
SAM
Quality assurance
Quality control
Quantitation limit
Relative percent difference
Relative response factor
Relative retention time
Relative standard deviation
Retention time
Selected Analytical Methods for Environmental Remediation and
Recovery
Safety data sheet
Selected ion monitoring
Signal-to-noise ratio
Solid phase extraction
Semivolatile organic compound
Triethylamine
Tetraethyl pyrophosphate
Tetramethylenedisulfotetramine
Volatile organic analysis
SDS
SIM
S:N
SPE
SVOC
TEA
TEPP
TETS
VOA
3.2 Definitions
Aliquot - A measured portion of a field sample, standard or solution taken for sample
preparation and/or analysis.
Analytical Batch - A set of samples that is analyzed on the same instrument during a 12-
hour period of operation or after the analysis of 10 samples (whichever comes first). The
analytical batch begins and ends with the analysis of the appropriate Continuing
Calibration Verification (CCV) standards.
Calibration Standard - A solution prepared from the stock standard solution(s) and the
internal standards and surrogate analytes. The calibration standards are used to calibrate
instrument response with respect to analyte concentration.
Continuing Calibration Verification (CCV) Standard - A calibration standard
containing the target analytes. It is analyzed periodically to verify the accuracy of the
existing calibration for those analytes.
Extracted Ion Current Profile (EICP) - A plot of ion abundance versus time (or scan
number) for ion(s) of specified mass(es).
Extraction Batch - A set of up to 20 field samples (not including QC samples) extracted
together by the same person(s) during a work day using the same lot of solid phase
extraction devices, solvents, surrogate solution, and fortifying solutions.
Holding Time - The elapsed time from sample collection until sample extraction or
analysis.
Initial Calibration - Analysis of calibration standards for a series of different specified
concentrations; used to define the quantitative response, linearity, and dynamic range of
the instrument for target analytes.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Initial Demonstration of Capability (IDC) - Procedures performed prior to using the
method to analyze field samples. The IDC is used to demonstrate that the laboratory and
analyst are capable of performing the analysis with acceptable precision, accuracy,
sensitivity and specificity pertaining to that particular method.
Initial Precision and Recovery (IPR) - A set of four aliquots of a clean reference
matrix (i.e., reagent water, Ottawa sand, clean wipe or air filter) to which known
quantities of the target analytes are added. The IPR aliquots are processed and analyzed
exactly like a sample and analyzed prior to the analysis of field samples as part of the
IDC. Their purpose is to determine whether the laboratory is capable of making accurate
and precise measurements.
Instrument Detection Limit (IDL) - The minimum concentration of an analyte that,
when injected into the gas chromatograph/mass spectrometer (GC/MS), produces an
average signal-to-noise ratio (S:N) between 3:1 and 5:1 for at least three replicate
injections.
Instrument Performance Check Solution - A solution of one or more method analytes,
surrogates, internal standards, or other test substances used to evaluate the performance
of the instrument system with respect to a defined set of method criteria.
Internal Standard - A pure analyte added to an extract or standard solution in a known
amount and used to measure the relative responses of target analytes and surrogates. The
internal standard must be an analyte that is not a sample component.
Laboratory Control Sample (LCS) - An aliquot of a clean reference matrix (i.e.,
reagent water, Ottawa sand, clean wipe or air filter) to which known quantities of the
target analytes are added. The LCS, also called a laboratory fortified blank (LFB), is
processed and analyzed exactly like a sample. Its purpose is to determine whether the
analytical process is in control.
Matrix - The predominant material of which the sample to be analyzed is composed.
For the purpose of this protocol, a sample matrix is either aqueous/water,
soil/sediment/sand, wipe or small (e.g., 37 mm) air filter. Matrix is not synonymous with
phase (e.g., liquid or solid).
Matrix Spike/Matrix Spike Duplicate (MS/MSD) - Two aliquots of a field sample
which is fortified, extracted and analyzed exactly like a sample. The purpose of the
MS/MSD is to assess method precision and accuracy for analyses of the sample type and
whether the sample matrix contributes bias to the analytical results. The background
concentrations of the analytes in the sample matrix must be determined in a separate
aliquot and the measured values in the MS/MSD corrected for background
concentrations. The purpose of the MS/MSD is to assess method precision and accuracy
for analyses of the sample type.
Method Blank - An aliquot of a clean reference matrix (reagent water, Ottawa sand,
clean wipe or clean air filter) that is treated exactly as a sample including exposure to all
glassware, equipment, solvents, reagents, sample preservatives, internal standards, and
surrogates that are used in the extraction batch. The method blank, also called a
laboratory reagent blank (LRB), is used to determine whether target analytes or
interferences are present in the laboratory environment, reagents or equipment.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Method Detection Limit (MDL) - The minimum concentration of an analyte that can be
identified, measured and reported with 99 percent confidence that the analyte
concentration is greater than zero. The MDL is a statistical determination (Section 9.7),
and accurate quantitation is not expected at this level.
Percent Difference - The difference between two values divided by one of the values.
Used in this protocol to compare two relative response factor (RRF) values.
Percent Drift (PD) - The difference between the calculated and theoretical value divided
by the theoretical value. Used in this protocol to compare calculated and theoretical
values for calibration by regression techniques.
Quantitation Limit (QL) - The minimum level of quantitation. This concentration must
meet the criteria defined in Section 9.8.
Reagent Water - Water in which an interferent is not observed at or above the low-level
calibration standard for each analyte of interest. The purity of this water must be
equivalent to ASTM International (ASTM) Type II reagent water of Specification
D1193-06, "Standard Specification for Reagent Water" (Reference 16.9).
Relative Percent Difference (RPD) - The difference between two values divided by the
mean of the values. RPD is reported as an absolute value (i.e., always expressed as a
positive number or zero).
Relative Response Factor (RRF) - A measure of the relative mass spectral response of
an analyte compared to its internal standard. RRFs are determined by analysis of
standards and are used in calculating the concentrations of analytes in samples.
Retention Time (RT) - The time an analyte is retained on a GC column before elution.
The RT is dependent on the nature of the column's stationary phase, diameter,
temperature, flow rate, and other parameters.
Relative Retention Time (RRT) - The ratio of the RT of a compound to the RT of a
corresponding internal standard.
Safety Data Sheet (SDS) - Written information provided by vendors concerning a
chemical's toxicity, health hazards, physical properties, flammability, and reactivity data
including storage, spill, and handling precautions.
Stock Standard Solution - A concentrated solution containing one or more target
analytes prepared in the laboratory using assayed reference materials or materials
purchased from a reputable commercial source.
Surrogate - A pure analyte that is unlikely to be found in any sample and that is added to
a sample aliquot in a known amount before extraction or other processing. Surrogates are
measured with the same procedures used to measure other sample components. The
purpose of the surrogate is to monitor method performance with each sample.
Working Standard Solution - A solution containing target analytes prepared from stock
standard solutions. Working standard solutions are diluted as needed to prepare
calibration and spiking solutions.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
4.0 INTERFERENCES
4.1 Contaminants in solvents, reagents, glassware, and other sample processing hardware can
cause interferences such as discrete artifacts and/or elevated baselines in the Extracted
Ion Current Profiles (EICPs). All of the materials must be routinely demonstrated to be
free from interferences under the conditions of the analysis by running laboratory method
blanks. Matrix interferences can be caused by contaminants that are co-extracted from
the sample. The extent of matrix interferences can vary considerably depending on the
sample source.
4.2 For solid samples containing significant matrix interferences, gel permeation
chromatography (GPC) cleanup following the procedures in SW-846 Method 3640
(Reference 16.10) may help improve chromatography. Preliminary evaluation during a
single-laboratory study showed that analyte recoveries in solid sample extracts having
undergone GPC cleanup were comparable with analyte recoveries in sample extracts
having no GPC cleanup (see Appendix A). If GPC is used, a thorough demonstration of
capability is performed for each target analyte before results are reported.
4.3 Laboratory results indicate that improved recovery of alkaline compounds (e.g.,
strychnine, nicotine, crimidine, and phencyclidine) from water may result when
extracting samples under acidic conditions (e.g., pH <2) during the first extraction,
followed by back extraction under basic conditions (Reference 16.11).
4.4 This protocol includes conditions for collecting mass spectral data using selected ion
monitoring (SIM) operating conditions. Although SIM may be used in cases when there
is a need to address low concentration levels, the procedure is, as with any scan analysis
technique, prone to matrix interference effects with the analyte of interest and may cause
suppression/enhancement of ionization signal relative to the analyte eluting in the
absence of the matrix component. Laboratories should give special attention to all
calibration and quality assurance/quality control (QA/QC) data requirements.
5.0 SAFETY
This protocol does not address all safety issues associated with its use. The laboratory is
responsible for maintaining a safe work environment and a current awareness file of U.S.
Occupational Safety and Health Administration (OSHA) regulations regarding the safe handling
of the chemicals listed in this method. Analysts should wear safety glasses, gloves, and
laboratory coats when working in the laboratory. Analysts also should review the Safety Data
Sheets (SDSs) for all reagents used in this method. A reference file of SDSs must be available to
all personnel involved in these analyses, chemical handling, and contaminated area cleaning, or
who might potentially come in contact with the materials in their workplace.
6.0 EQUIPMENT AND SUPPLIES
Brand names, suppliers, and catalog and part numbers are for illustrative purposes only. No
endorsement is implied. Equivalent performance may be achieved using equipment and supplies
other than those specified in this protocol. Demonstration of equivalent performance meeting the
requirements of this analytical protocol is the responsibility of the laboratory.
6.1 Microscale Extraction (MSE) Apparatus
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Glass vials - 40- or 60-mL (Fisher Scientific Catalog No. 05-719-
400, Westminster, MD, or equivalent) capacity with polytetrafluoro-
ethylene (PTFE)-lined screw caps (Fisher Scientific Catalog No. 05-
719-400, Westminster, MD, or equivalent) OR 50- or 60-mL glass
conical bottom vials or centrifuge tubes (Fisher Scientific Catalog
No. 0553841A, Westminster, MD, or equivalent) with screw caps.
Note: Tubes with conical ends may facilitate the removal of the
bottom methylene chloride layer.
Vials - amber glass, 2-mL, with PTFE-lined screw or crimp top
(Sigma Aldrich Catalog No.SU860033, St. Louis, MO, or
equivalent)
Vortexer - VWR® or equivalent
Water bath - heated, capable of temperature control (± 5 °C). The
bath should be used in a hood.
Pasteur glass pipettes - 1 mL, disposable (Fisher Scientific Catalog
No. NC0541803, Westminster, MD, or equivalent)
Centrifuge - capable of at least 500 G force units (4900 m/s2) and
accommodating 40-mL or 60-mL vials. Accuspin™ Model 400 or
equivalent. CAUTION: Different centrifuge makes and models
have different maximum centrifuge speeds for safe operation. The
maximum safe handling speed of each centrifuge will depend, in
part, on the vials used and should be determined prior to use.
6.1.2 Soil, Wipes and Air Filter Samples
6.1.2.1 Glass powder funnel with glass wool plugging the bottom, used in
filtering soil samples that fail to settle out with centrifugation (Fisher
Scientific Catalog No. CG172305, Westminster, MD, or equivalent)
6.1.2.2 Sonicator - Branson 3510 Ultrasonic Cleaner (Branson Ultrasonic
Corp., Danbury, CT, or equivalent)
6.1.2.3 Rotator/Shaker - Glas-Col® Rotator (Part # 099A-RD50, Glas-Col
Inc., Terre Haute, IN), Glas-Col Shaker (Part # 099A LC1012, Glas-
Col Inc., Terre Haute, IN), Glas-Col Digital Pulse Mixer (Part #
099A DPM12, Glas-Col Inc., Terre Haute, IN, or equivalent). Model
used must be adequately sized to accommodate sample batch.
Note: The Digital Pulse Mixer requires a foam pad for 40-mL
volatile organic analysis (VOA) vials (Part #099A VC0614,
Glas-Col Inc., Terre Haute, IN, or equivalent).
6.1.2.4 Syringes - gastight, contaminant-free, 500 |iL and 25 jxL
(Thermoscientific Part No. NS600911 andNS600511,
ThermoFisher Scientific, Westminster, MD, or equivalent)
6.1.1 General
6.1.1.1
6.1.1.2
6.1.1.3
6.1.1.4
6.1.1.5
6.1.1.6
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Analytical Protocol for Extractable Semivolatile Organic Compounds
6.1.2.5 Glass beads - solvent-rinsed with acetone methylene chloride: ethyl
acetate (1:2:1 v:v:v) and baked in 400 °C oven for approximately one
hour (Fisher Scientific Catalog No. S80024, Westminster, MD, or
equivalent)
6.1.3 Water Samples
6.1.3.1 Syringes - gastight, contaminant-free, 2.0 mL, 1.0 mL (BD Medical
Part No. 512019, 512027, Becton Dickinson, Franklin Lakes, NJ, or
equivalent) and . 10 |iL (Thermoscientific Part No. NS142404 or
equivalent)
6.1.3.2 Class A volumetric pipette - 2 mL (Corning Part No. 7103C-2,
Corning, NY, or equivalent)
6.1.3.3 Beakers - 400 mL
6.1.3.4 Syringes - 2 (iL, 10 (iL, 0.1 mL, 0.2 mL, 0.5 mL, 1 mL, 5 mL,
and 10 mL with Luer-lok® fitting (Hamilton Gas-tight Luer-
lok® syringes, Hamilton Robotics, Reno, NV, or equivalent)
6.1.3.5 Graduated cylinder - Class A, 100 mL
6.1.3.6 Volumetric flasks - Class A, 10 mL
6.2 General Equipment
6.2.1 Spatula - Stainless steel or PTFE
6.2.2 Balances - Analytical, capable of accurately weighing ±0.0001 gram, and one
balance capable of weighing 100 grams (±0.01 gram). The balances must be
calibrated with Class S weights at a minimum of once per month. The balances
also must be calibrated with Class S weights or known reference weights once
per each 12-hour work shift, and be checked annually by a certified technician.
6.2.3 Vacuum Filtration Apparatus
6.2.3.1 Biichner funnel (porcelain or Pyrex®)
6.2.3.2 Filter paper - Whatman® No. 41, Whatman, Maidstone, UK, or
equivalent
6.2.4 Borosilicate glass wool - rinsed with dichloromethane (DCM)
6.2.5 Test Tube Rack
6.2.6 Silicon carbide boiling chips (Troemner Hengar Boiling Granules, Sigma-
Aldrich Catalog No. 902100, St. Louis, MO, or equivalent) - approximately
10/40 mesh. Heat to 400 °C for 30 minutes or clean using DCM and Soxhlet
extraction. PTFE boiling chips that are solvent-rinsed prior to use are acceptable.
6.2.7 Water bath - with concentric ring cover, capable of heating to 80 °C and
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Analytical Protocol for Extractable Semivolatile Organic Compounds
maintaining a temperature control (±5 °C). The bath should be used in a
hood.
6.2.8 Nitrogen evaporation device - Equipped with a water bath that can be
maintained at 35 - 40 °C, a RapidVap® (Labconco Corporation, Kansas City,
MO, or equivalent). To prevent the release of solvent fumes into the laboratory,
the nitrogen evaporator device must be used in a hood.
6.2.9 pH indicator paper - capable of covering a wide pH range (i.e., 1 - 14)
6.2.10 pH meter - with a combination glass electrode. Calibrate prior to each use
according to manufacturer's instructions.
6.2.11 Apparatus for determining percent dry weight
6.2.11.1 Drying oven - capable of maintaining 105 °C
6.2.11.2 Desiccator
6.2.11.3 Crucibles - disposable aluminum or porcelain
6.2.12 Clean cloth or wipes - Kimwipe® (Kimberly-Clark Professional, Roswell, GA) or
equivalent
6.2.13 Air filters - Consisting of glass fiber filter (Pallflex®, Pall Corp., Timonium, MD,
or equivalent) and XAD resin (Supelpak™ 2SV, Sigma Aldrich, St. Louis, MO,
or equivalent)
6.3 Gas chromatograph/mass spectrometer (GC/MS) System
Note: The single-laboratory study was performed using an Agilent® 6890/5973 with
Agilent 7683 Autosampler and a Zebron™ ZB-5MS capillary column from Phenomenex.
6.3.1 Gas Chromatograph -The GC system must be capable of temperature
programming and have a flow controller that maintains a constant column flow
rate throughout the temperature program operations. The system must be
suitable for splitless injection and have all required accessories including
syringes, analytical columns, regulators, and gases. All GC carrier gas lines
must be constructed from stainless steel or copper tubing. Non-PTFE thread
sealants or flow controllers with rubber components are not to be used.
6.3.2 Gas Chromatography Column - Minimum length 30 m x 0.25 mm internal
diameter (ID) (or 0.32 mm) bonded phase silicon coated fused silica capillary
column DB-5 (J&W Scientific, Agilent Technologies, Santa Clara, CA); RTX-5,
RTX-5Sil MS (Restek Corp., Bellefonte, PA); Zebron™ ZB-5 (Phenomenex,
Phenomenex, Inc., Torrance, CA); Zebron™ ZB-5MS (Phenomenex,
Phenomenex, Inc., Torrance, CA), SPB®-5 (Supelco, Sigma-Aldrich, St. Louis,
MO); AT™-5 (Alltech, Grace, Columbia, MD); HP®-5 (Agilent, Agilent
Technologies, Santa Clara, CA); CP™-Sil 8 CB (Chrompack, Raritan, NJ); 007-
2 (Quadrex®, Quadrex, Corp., Bethany, CT); BP-5 (SGE, Trajan Scientific
Americas, Inc., Austin, TX) or equivalent.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Note: This is a minimum requirement for column length. Longer columns may
be used. Although a film thickness of 1.0 micron may be desirable because of its
larger capacity, a film thickness of 0.25 micron also may be used.
A capillary column is considered equivalent if:
• The column does not introduce contaminants that interfere with the
identification and quantification of the compounds listed in Section 1.2.
• The analytical results generated using the column meet the initial and
continuing calibration verification (CCV) technical acceptance criteria and
the quantitation limits listed in Tables 1 la, 1 lb, 12a and 12b.
• The column can accept up to 80 ng of each compound without becoming
overloaded.
• The column provides equal or better resolution of the compounds.
6.3.3 Mass Spectrometer - Must be capable of scanning from 35 to 500 atomic mass
unit (amu) every 1 second or less, using 70 volts (nominal) electron energy in the
electron ionization (EI) mode, and producing a mass spectrum that meets the
tuning acceptance criteria (Section 10.2.4) when 50 ng of decafluorotriphenyl-
phosphine (DFTPP) is injected through the GC inlet. The instrument must be
vented to the outside of the facility or to a trapping system that prevents the
release of contaminants into the instrument room.
6.3.4 GC/MS Interface - The laboratory may use any GC/MS interface that provides
acceptable sensitivity and QC. However, direct insertion of the GC column into
the mass spectrometer source is the recommended interface.
6.3.5 Helium Carrier Gas - Ultra high purity (99.995 % or higher)
7.0 REAGENTS AND STANDARDS
7.1 Reagents
7.1.1 Reagent Water - ASTM Type II reagent water of Specification D1193-06,
"Standard Specification for Reagent Water," (Reference 16.9) or equivalent.
7.1.2 Acetone, DCM, Ethyl Acetate, Triethanolamine (TEA), and Toluene -
Pesticide residue analysis grade or equivalent.
Note: Solvents should be dried prior to use with anhydrous sodium sulfate.
7.1.3 Drying Agent - Powdered or granular anhydrous sodium sulfate,
American Chemical Society (ACS) reagent grade, heated at 400 °C for
four hours in a shallow tray, cooled in a desiccator, and stored in a glass
bottle. See Appendix A for possible alternative drying agents.
7.1.4 Dechlorinating Agents
See Section 8.1.2 for dechlorinating agents recommended for specific analytes.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
7.1.4.1 Ammonium chloride - ACS reagent grade
7.1.4.2 Sodium sulfite - ACS reagent grade
7.1.5 Anhydrous Sodium Chloride - ACS reagent, >99 %. Used to adjust the ionic
strength during MSE of water samples.
7.1.6 Ottawa Sand (Fisher Scientific Catalog No. S25516 or equivalent) - Oven
muffled in a 500-mL, wide mouthed amber bottle. (Oven is muffled to 450 °C
and held for four hours, then ramped back to room temperature.)
7.2 Standards
7.2.1 Introduction
The laboratory must be able to verify that standards are certified. Manufacturers'
certificates of analysis must be retained by the laboratory and presented upon
request. Standard solutions purchased from a chemical supply house as extracts
in sealed, glass ampules may be retained and used until the expiration date
provided by the manufacturer. If no manufacturer's expiration date is provided,
general guidance for similar compounds suggests that unopened ampules of
standard solutions may be retained and used up to two years from the preparation
date (Reference 16.12). Based on this guidance, the expiration date of opened
standards, upon breaking the glass seal, is six months (or sooner, if the standard
has degraded or evaporated). Solutions used for calibration verification ideally
are prepared from a separate source other than the source used to prepare
calibration standards.
7.2.2 Stock Standard Solutions
Stock standard solutions are defined as standards that are used to produce
working standards, and may be in the form of single compounds or mixtures.
Stock standard solutions may be purchased or prepared from neat compounds in
DCM or another suitable solvent.
Note: Combined stock standard solutions can be prepared for most of the target
analytes listed in Section 1.2. Exceptions are tetraethyl pyrophosphate (TEPP)
and strychnine, which are unstable when combined with other target analytes. If
analysis of TEPP and strychnine are required, fresh standards should be prepared
immediately prior to calibration.
7.2.3 Working Standards
7.2.3.1 Surrogate Standard Spiking Solution - Prepare a surrogate standard
spiking solution that contains the appropriate surrogates for the target
compounds (see Table 2). Surrogate standards are added to all
samples and calibration solutions. Additional surrogates may be
added at the laboratory's discretion. Surrogates are added to samples
and blanks at a concentration that is approximately the midpoint of
the calibration range.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Note: It is recommended that all surrogates in Table 2 be added to
all samples and calibration standards. In cases where only certain
analytes are to be measured and/or high throughput is necessary, the
laboratory may add a subset of these surrogates.
7.2.3.2 Matrix Spiking Solution - The matrix spiking solution should
consist of the target compounds prepared at a concentration that,
when added to samples, results in a concentration near the midpoint
of the calibration range for each target compound.
7.2.3.3 Instrument Performance Check Solution - Prepare a solution of
DFTPP such that a 1 -JJ.L injection will contain 50 ng of DFTPP. The
DFTPP may also be included in the calibration standards at this
level.
7.2.3.4 Initial and Continuing Calibration Solutions
7.2.3.4.1 Prepare calibration standards at a minimum of five
concentration levels. Each calibration standard should
contain each target compound, associated surrogate,
and internal standard. (See Section 17.0, Tables 10a
and 10b for suggested concentrations for full scan and
Selected Ion Monitoring (SIM), respectively.)
Note: 1.0 jj.L injections of all calibration standards
should be used. All sample extracts must be injected at
the same volume (1.0 |_iL) as the calibration standards.
Note: The concentrations listed in Section 17.0, Tables
10a and 10b were used during method evaluation in a
single laboratory. For most analytes, the low calibration
standard is set at the expected quantitation level (QL).
The remaining calibration standards should be prepared
at concentrations that meet the specifications in Section
10.3.5.
7.2.3.4.2 The continuing calibration standard is prepared at or
near the midpoint of the calibration curve.
7.2.3.5 Internal Standard Solution - An internal standard solution is
prepared by dissolving 100 mg of each of the following compounds
in lOOmLofDCM: l,4-dichlorobenzene-d4, naphthalene-d8,
acenaphthene-d10, phenanthrene-d10, chrysene-d12 and perylene-d12.
It may be necessary to use 5-10 percent toluene in this solution and
a few minutes of ultrasonic mixing to dissolve all constituents. A
sufficient portion of this solution will be added to each sample
extract just prior to analysis to result in a concentration of 10 ng/(.iL.
Alternatively, internal standard solutions can be purchased from
commercial sources (e.g., Supelco part number 861238 or
equivalent).
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Analytical Protocol for Extractable Semivolatile Organic Compounds
7.2.4 Storage of Standard Solutions
7.2.4.1 Store the stock standard solutions at 4 °C (± 2 °C) in PTFE-lined
screw-cap amber bottles. Prepare fresh standards every six months
at a minimum (or sooner if the expiration date has elapsed).
7.2.4.2 Store the working standards at 4 °C (± 2 °C) or less in PTFE-sealed
containers. Certain analytes (i.e., TEPP and strychnine) may degrade
in as little as two weeks; calibrations for these analytes should be
performed using separate, freshly prepared standard solutions. It is
also recommended that working standard solutions for all analytes be
checked at least weekly for stability. These solutions must be
replaced after six months (or sooner if the stock standard solutions
have expired), or if comparison with QC samples or standards
indicates a problem.
7.2.4.3 Protect all standards from light. Samples, sample extracts, and
standards must be stored separately.
7.2.4.4 The laboratory is responsible for maintaining and verifying the
integrity of standard solutions prior to use. The standards must be
brought to room temperature prior to use, checked for losses, and
checked to ensure that all components have remained in solution.
8.0 SAMPLE PRESERVATION, STORAGE, AND TECHNICAL HOLDING TIMES
Preservation, storage, and holding times for drinking water samples were evaluated in a single-
laboratory. Suggested sample preservation, storage, and holding times for all other sample types
are based on EPA's SW-846 Method 8270D (Reference 16.1). SW-846 preservation techniques
were not evaluated for solids, wipes or air filters.
8.1 Sample Preservation
8.1.1 All samples should be protected from light and cooled to 4 °C (±2 °C).
8.1.2 Water Samples
Existing EPA methods for determination of SVOCs use sodium thiosulfate or
sodium sulfite for dechlorination of water samples. Laboratory results evaluating
the procedures described in this protocol, however, indicated improved analyte
recovery and stability when using ammonium chloride (NH4CI) for sample
dechlorination. Results also indicated improved stability when using sodium
sulfite (Na2SC>3) for sample dechlorination along with hydrochloric acid (HC1)
for sample preservation. This dechlorination/preservation procedure was also
used during a multi-laboratory exercise for three analytes (dichlorvos, mevinphos
and TETS). Recommended dechlorinating agents and preservatives based on
single-laboratory results are provided in the table below (entitled "Recommended
Preservatives/Dechlorinating Agents"). Recommended procedures using
ammonium chloride are provided in Section 8.1.2.1. Recommended procedures
using sodium sulfite, with and without HC1, are provided in Section 8.1.2.2.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Note: Due to low recoveries of nicotine and strychnine, results of this evaluation
could not be used to determine an appropriate treatment for drinking water
samples containing these analytes.
Recommended Preservatives/Dechlorinating Agents
NH4CI
Na2S03
Na2S03 and HCI
No treatment
Chlorfenvinphos
Crimidine
Dichlorvos
Chlorfenvinphos
Chloropicrin
Dicrotophos
Dicrotophos
Chloropicrin
Crimidine
Mevinphos
1,4-Dithiane
Crimidine
Chlorpyrifos
Phencyclidine
Methyl parathion
Fenamiphos
Dichlorvos
Phosphamidon
Mevinphos
Dicrotophos
Dicrotophos
TETS
Phencyclidine
Disulfoton
Disulfoton
Phosphamidon
Fenamiphos
1,4-Dithiane
TEPP
Mevinphos
Methyl parathion
TETS
Parathion
Mevinphos
1,4-Thioxane
Phencyclidine
Parathion
Phorate
Phencyclidine
Phosphamidon
Phorate
TEPP
Phosphamidon
TETS
TEPP
TETS
1,4-Thioxane
Acronyms:
TEPP - tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
8.1.2.1 NH4CI - To each water sample, add a sufficient amount of
ammonium chloride to achieve a concentration of 40 - 50 mg/L (this
may be added as a solid with stirring or shaking until dissolved). Do
NOT add HC1 preservative, as this will decrease the effectiveness of
ammonium chloride as a dechlorinating agent.
8.1.2.2 Na2SC>3/HCl - To each water sample, add a sufficient amount of
sodium sulfite to achieve a concentration of 40 - 50 mg/L (this may
be added as a solid with stirring or shaking until dissolved). If
preservative is required, adjust the pH of the sample with 6 N
hydrochloric acid (HC1) until the pH is ~2.
8.2 Sample Storage
8.2.1 Samples must be protected from light and refrigerated at 4 °C (±2 °C).
8.2.2 Samples must be stored in an atmosphere demonstrated to be free of all potential
contaminants.
8.3 Procedure for Sample Extract Storage
8.3.1 Sample extracts must be protected from light and stored at <6 °C.
8.3.2 Samples, sample extracts, and standards must be stored separately.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
8.4 Technical Holding Times
It is recommended that samples be extracted within 14 days from the time of collection
and that extracts be analyzed within 40 days following extraction.
Note: Laboratory results indicate that water samples to be analyzed for TEPP or
fenamiphos should be extracted and/or analyzed immediately upon receipt. The holding
times for samples containing nicotine and strychnine have not been determined. Until
additional holding time data are available, laboratories are advised to extract all samples
as soon as possible after receipt and to evaluate analyte holding times in matrices
typically analyzed by the laboratory.
9.0 QUALITY CONTROL (QC)
QC requirements for this protocol include the following:
Quality Control (QC) Analyses
Requirement
Section
Frequency
Instrument Detection Limit (IDL)
Determination
Section 9.6
Optional. Performed prior to Method
Detection Limit (MDL) Study
Method Detection Limit (MDL)
Determination
Section 9.7
Performed once, prior to first performing
the method and with each significant
change as part of the Initial Demonstration
of Capability (IDC)
Initial Precision and Recovery (IPR)
Determination
Section 9.2
Quantitation Limit (QL)
Determination
Section 9.8
Method Blanks
Section 9.3
At least one per extraction batch
Matrix Spike and Matrix Spike
Duplicate (MS/MSD)
Section 9.4
One per each batch of 20 samples of the
same matrix or within 24 hours or less
Laboratory Control Sample (LCS)
Section 9.5
At least one per extraction batch
Continuing Calibration Verification
(CCV)
Section 10.4
Prior to the analysis of samples, and after
instrument performance check. Analyzed
once per analytical batch (every 12 hours
or after 10 samples, whichever comes first)
Precision and bias criteria for data generated using this method are currently set at 50 - 150 %
recovery and < 30 % precision (as relative standard deviation [RSD] or relative percent difference
[RPD]). These criteria may change as more laboratory data become available. In cases where
analyses of difficult sample matrices generate results outside these criteria, data should be
flagged, and laboratories should collect additional data to support development of laboratory- and
matrix-specific criteria. Example precision and bias results obtained from laboratories analyzing
spiked reference matrix samples (reagent water, Ottawa sand, and wipes) and field samples
(water and soil) are provided in Section 17.
9.1 Initial Demonstration of Capability (IDC)
An IDC is performed prior to the analysis of any samples and with each significant
change in instrument type, detection technique, personnel or method. An IDC consists of
the following:
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Analytical Protocol for Extractable Semivolatile Organic Compounds
• An demonstration of initial precision and recovery (IPR) determination (Section 9.2)
• A method detection limit (MDL) study (Section 9.7)
• A QL determination (Section 9.8) on a clean matrix (reagent water, Ottawa sand, pre-
cleaned wipe, air filter)
The IPR consists of four replicate samples of a clean matrix spiked with the target
analytes around the midpoint of the calibration curve and carried through the entire
analytical process. Prior to performing the IDC, a valid initial calibration (Section 10.3)
should be established.
9.2 Initial Precision and Recovery (IPR) Determination
9.2.1 Preparation and analysis of IPR samples
9.2.1.1 Water Samples
Prepare four replicate samples consisting of 35 mL of reagent
water. Add a sufficient amount of surrogate standard spiking
solution to result in a surrogate concentration at approximately the
calibration midpoint. Extract, concentrate, and analyze according
to the procedures for water samples (Section 11.2). The total
volume of dichloromethane (DCM) added will be slightly greater
than the 2 mL needed for extraction and includes the volumes
added for spiking target compounds, surrogates, and internal
standards.
9.2.1.2 Ottawa Sand
Prepare four replicate samples consisting of 10 grams of Ottawa sand
and 2.5 grams of sodium sulfate. Add a sufficient amount of the
surrogate standard spiking solution to result in a surrogate
concentration at approximately the calibration midpoint and follow
the appropriate extraction procedure in Section 11.3. Extract,
concentrate and analyze according to procedures for solid samples.
9.2.1.3 Wipes
Prepare four replicate samples of wipes (Section 6.2.14). Add a
sufficient amount of the surrogate standard spiking solution to result
in a surrogate concentration at approximately the calibration
midpoint, and follow the appropriate extraction procedure in Section
11.5. Extract, concentrate and analyze according to procedures for
wipe samples.
9.2.1.4 Air Filters
Prepare four replicate samples of air filters (Section 6.2.15). Add a
sufficient amount of the surrogate standard spiking solution to result
in a surrogate concentration at approximately the calibration
midpoint, and follow the appropriate extraction procedure in Section
11.4. Extract, concentrate and analyze according to procedures for
air filter samples.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
9.2.2 Calculations for IPR
9.2.2.1 Calculate the percent recovery of each compound in each IPR
sample using Equation 11 (Section 12.2.9.1). Calculate an average
percent recovery for each compound.
9.2.2.2 Calculate a percent relative standard deviation (%RSD) for each
compound in the IPR samples.
9.2.3 Technical Acceptance Criteria for IPR
9.2.3.1 The average percent recovery of each compound in the IPR should
be within 50 - 150 %.
9.2.3.2 The %RSD of each compound in the IPR should be less than or
equal to 20 %.
9.2.4 Corrective Action for IPR
If the technical acceptance criteria in Section 9.2.3 are not met, inspect the
system for problems and take corrective action to achieve the acceptance criteria.
Note: The technical acceptance criteria are based on results obtained in a single
laboratory. Until criteria are developed based on multi-laboratory data,
laboratory-specific criteria may be developed and used.
9.3 Method Blanks
A method blank is a volume of a clean reference matrix (e.g., reagent water for water
samples, Ottawa sand for soil/sediment samples, clean sorbent for air samples, or
clean wipe for wipe samples) spiked with a sufficient amount of surrogate standard
spiking solution (Section 7.2.3.1) so that each surrogate is added at a concentration
expected to be at approximately the midpoint of the calibration range. The blank is
carried through the entire analytical procedure used to analyze associated samples.
Internal standard solution is added just prior to full scan analysis by GC/MS to give a
concentration of 10 ng/(.iL for each internal standard. The volume or weight of the
reference matrix must be approximately equal to the volume or weight of the samples
associated with the blank.
9.3.1 Frequency of Method Blanks
A method blank must be extracted each time samples are extracted. The number
of samples extracted with each method blank should not exceed 20 field samples
(excluding Matrix Spike and Matrix Spike Duplicates [MS/MSDs] and
Performance Evaluation [PE] samples). In addition, a method blank is:
• Extracted by the same procedure used to extract samples
• Analyzed on each GC/MS system used to analyze associated samples and
conditions (i.e., GC/MS settings)
9.3.2 Method Blank Preparation
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Analytical Protocol for Extractable Semivolatile Organic Compounds
9.3.2.1 A method blank for water samples consists of an aliquot of reagent
water, of the same volume as the corresponding field samples spiked
with a sufficient amount of the surrogate standard spiking solution to
result in the addition of 10 (.ig of each surrogate (Section 7.2.3.1).
For soil/sediment samples, a method blank consists of an aliquot of
Ottawa sand, of the same weight as the corresponding field samples,
spiked with sufficient amount of the surrogate spiking solution to
result in the addition of 10 (ig of each surrogate. A method blank for
gas-phase samples consists of a clean unused polyurethane foam
(PUF) cartridge (or XAD-2) and filter spiked with a sufficient
amount of the surrogate standard spiking solution to result in the
addition of 10 (ig of each surrogate. A method blank for wipe
samples consists of a clean, unused wipe spiked with a sufficient
amount of the surrogate standard spiking solution to result in the
addition of 10 (ig of each surrogate. Extract, concentrate, and
analyze the blank according to procedure.
9.3.2.2 Under no circumstances should method blanks be analyzed at a
dilution.
9.3.3 Technical Acceptance Criteria for Method Blank Analysis
9.3.3.1 All blanks should be extracted and analyzed at the frequency
described in Section 9.3.1 on a GC/MS system meeting the DFTPP
(Section 10.2.4), initial calibration (Section 10.3.5), and CCV
(Section 10.4.5) technical acceptance criteria.
9.3.3.2 The recovery of each of the surrogates in the blank must be within
50- 150 %.
9.3.3.3 The blank must meet the internal standard acceptance criteria listed
in Sections 12.3.5 through 12.3.6.
9.3.3.4 A method blank for soil, water, air, and wipe samples must not
contain analytes at concentrations at or above the low-level
calibration standard for each analyte of interest.
9.3.4 Corrective Action for Method Blanks
9.3.4.1 If a method blank does not meet the technical acceptance
criteria for method blank analysis, the analytical system is
considered to be out of control.
9.3.4.2 If contamination is the problem, the source of the contamination
should be investigated and appropriate corrective measures taken
before further sample analysis proceeds. It is the laboratory's
responsibility to ensure that interferences caused by contaminants
in solvents, reagents, glassware, and sample storage and processing
hardware that lead to discrete artifacts and/or elevated baselines in
the GC/MS have been eliminated. If possible, samples associated
with the contaminated blank should be re-extracted and
reanalyzed.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
9.3.4.3 If surrogate recoveries in the method blank do not meet the
acceptance criteria Section 9.3.3.2, reanalyze the method blank. If
the surrogate recoveries do not meet the acceptance criteria after
reanalysis, the method blank and all samples associated with that
method blank should be re-extracted if possible, and reanalyzed.
9.3.4.4 If the method blank does not meet internal standard response
requirements listed in Section 12.3.5, follow the corrective action
procedure outlined in Section 12.4.4.1. Resolve the problem before
proceeding with sample analysis.
9.3.4.5 If the method blank does not meet the retention time (RT)
requirements for internal standards (Section 12.3.6), check the
GC/MS instrument for malfunction and recalibrate. Reanalyze the
method blank. Sample analyses cannot proceed until the method
blank meets these requirements.
9.4 Matrix Spike and Matrix Spike Duplicate (MS/MSD)
9.4.1 Summary of MS/MSD - To evaluate the effects of the sample matrix, a mixture
of target compounds is spiked into two aliquots of a water or soil sample and
analyzed in accordance with the appropriate method. MS/MSDs are not
performed on air or wipe samples.
9.4.2 Frequency of MS/MSD Analyses
9.4.2.1 An MS/MSD pair is analyzed with each batch of <20 samples of
each water or solid matrix type. MS/MSDs are not performed on
wipe or air samples.
9.4.2.2 For QA/QC purposes, water rinsate samples and/or field/trip blanks
(field QC) or PE samples may accompany samples that are delivered
to the laboratory for analysis. These field QC or PE samples are not
used for MS/MSD analyses.
9.4.2.3 If the agency requesting the analyses designates a sample to be used
as an MS/MSD, then that sample must be used. If there is
insufficient sample remaining to perform an MS/MSD, then the
laboratory should choose another sample on which to perform an
MS/MSD analysis. At the time the selection is made, the laboratory
should notify the agency that insufficient sample was received and
identify the sample selected for the MS/MSD analysis.
9.4.2.4 If there is insufficient sample remaining in any of the samples in a
batch to perform the requested MS/MSD, then the laboratory must
immediately contact the agency to inform them of the problem.
The agency will either approve that no MS/MSD be performed, or
require that a reduced sample aliquot be used for the MS/MSD
analysis.
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9.4.3 Procedure for Preparing MS/MSD
9.4.3.1 Water Samples
Prepare two additional aliquots of the sample chosen for spiking.
The volume chosen should be equal to that of the associated
samples. Add a sufficient amount of the surrogate standard spiking
solution and the matrix spiking solution to each aliquot to result in
a concentration that is expected to be at approximately the
midpoint of the calibration range. Extract, concentrate, clean up,
and analyze the MS/MSD according to the procedures for water
samples (Section 11.2).
9.4.3.2 Soil/Sediment Samples
Prepare two additional aliquots of the sample chosen for spiking in
the two 400 mL beakers. The amount chosen should be equal to that
of the associated samples. Add twice the weight of anhydrous
powdered sodium sulfate to each aliquot (relative to sample). Mix
well. Add a sufficient amount of the surrogate standard spiking
solution and the matrix spiking solution to each aliquot to result in a
concentration that is expected to be at approximately the midpoint of
the calibration range, and then follow the appropriate extraction
procedure in Section 11.3. Extract, concentrate, clean up, and
analyze the MS/MSD according to the procedures for soil/sediment
samples (Section 11.3).
9.4.4 Dilution of MS/MSD
Before any MS/MSD analysis, analyze the original sample, then analyze the
MS/MSD at the same concentration as the most concentrated extract for
which the original sample results will be reported.
9.4.5 Calculations for MS/MSD
9.4.5.1 Calculate the recovery of each MS/MSD compound in the
MS/MSD sample.
9.4.5.2 Calculate the relative percent difference (RPD) of the recoveries of
each compound in the MS/MSD (Equation 12). Concentrations of
the MS/MSD compounds are calculated using the same equations
as are used for target compounds (Equations 5 through 8).
9.4.6 Technical Acceptance Criteria for MS/MSD
9.4.6.1 All MS/MSDs must be prepared and analyzed at the frequency
described in Section 9.4.2. All MS/MSDs must be analyzed on a
GC/MS system meeting DFTPP, initial and CCV technical
acceptance criteria and the method blank technical acceptance
criteria.
9.4.6.2 The MS/MSD must have an associated method blank meeting the
blank technical acceptance criteria.
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9.4.6.3 The MS/MSD must be extracted and analyzed within the technical
holding time.
9.4.6.4 The RT shift for each of the internal standards must be within ± 30
seconds between the MS/MSD sample and the most recent CCV
standard analysis.
9.4.6.5 MS/MSD compound recovery and RPD limits are 50 - 150 % and
<30 %, respectively. These limits are based on SW-846 methods
and will be updated following method validation in multiple
laboratories.
9.4.7 Corrective Action for MS/MSD
If recovery or RPD limits are not met and the LCS, CCV and method blank are
within acceptable limits, this might be an indication of matrix interferences. If
recovery or RPD limits are not met and the LCS, CCV or method blank are not
within acceptable limits, then the MS/MSD samples should be reanalyzed along
with all appropriate QC samples. If, after reanalysis, MS/MSD recovery limits
cannot be met, flag the results of the associated sample.
9.5 Laboratory Control Sample (LCS)
An LCS consists of an aliquot of clean reference matrix, of the same weight or volume as
the corresponding field samples, and spiked with the same compounds at the same
concentrations used to spike the MS/MSD. When the results of the MS/MSD analysis
indicate a matrix interference might be present, the LCS results are used to verify that the
interferences are due to the sample matrix and not from artifacts introduced in the
laboratory.
9.5.1 Preparation of LCS
An LCS is prepared by spiking reagent water (when analyzing water samples),
clean sand (when analyzing soils), a clean sorbent and filter (when analyzing air
samples), or a clean wipe (when analyzing wipe samples) at a concentration that
is expected to be at approximately the midpoint of the calibration range. The
same spiking levels that are used for the MS/MSD samples should be used for the
LCS. Extract and analyze the LCS according to the procedure(s) in Section 11.2
for water samples, 11.3 for soil/sediment samples, 11.4 for air filter samples, or
11.5 for wipe samples.
Note: Air filters and wipes used for the LCS and method blank should come
from the same manufacturing lot as those used for samples.
9.5.2 Frequency of LCS Analyses
One LCS should be prepared, extracted, analyzed, and reported for every 20 field
samples or fewer extracted in a batch of a similar matrix. The LCS must be
extracted and analyzed concurrently with the samples, using the same extraction
protocol, cleanup procedure (if required), and instrumentation.
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9.5.3 Calculations for LCS
Calculate the recovery of each target and surrogate compound in the LCS.
9.5.4 Technical Acceptance Criteria for LCS Analysis
9.5.4.1 All LCSs should be extracted and analyzed at the frequency
described in Section 9.5.2 on a GC/MS system meeting the tuning,
initial and CCV, and the method blank technical acceptance criteria.
9.5.4.2 LCS compound recovery limits will be established following
laboratory validation of these procedures. Recovery limits of
50-150 % are applied as guidance until laboratory limits are
established.
9.6 Instrument Detection Limit (IDL) Determination
Before any field samples are analyzed, laboratories may determine an IDL for each target
compound on each instrument used for analysis. While determining IDLs is not required,
IDL results can be helpful in determining an appropriate spike level for use in
determining the MDL (Section 9.7). It is recommended that IDLs be verified annually
thereafter or after major instrument maintenance. Major instrument maintenance
includes, but is not limited to: cleaning or replacement of the mass spectrometer source,
mass filters, or electron multiplier; or installing a different GC column type. An IDL is
instrument-specified and independent of sample matrices. An IDL is determined for each
compound as the concentration that produces an average signal-to-noise ratio (S:N)
between 3:1 and 5:1 for at least three replicate injections.
9.7 Method Detection Limit (MDL) Determination
Before any field samples are analyzed, laboratory MDLs should be determined for each
target analyte in appropriate reference matrices (i.e., reagent water, Ottawa sand, clean
wipes or air filters), using the sample preparation and analytical procedures described in
this analytical protocol for each specific matrix (see also 40 CFR Part 136, Appendix B).
9.7.1 The laboratory must use full method procedures to prepare and analyze at least
seven replicates.
9.7.2 Spike each replicate sample at concentrations of 1 - 5 times the IDL
concentration for each analyte and analyze the samples following analytical
protocol procedures.
9.7.3 To determine analyte MDLs, the following equation is applied to the analytical
results (Student's t-factor is dependent on the number of replicates used; 3.14
assumes seven replicates):
EQ. 1. Method Detection Limit Calculation
MDL = 3 .14 xsd
where:
sd = standard deviation for the analytical results, and
3.14 = the Student's t-value for seven replicate samples
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9.7.4 The MDL results calculated using Equation 1 in Section 9.7.3 must meet the
following requirements as well as all other requirements specified in 40 CFR Part
136, Appendix B:
• MDL result must not be greater than the spiking level used for the MDL
determination.
• MDL result must not be less than 0.10 times the spiking level used for
the MDL determination.
If either requirement is not met, the laboratory must adjust the spiking level
appropriately and repeat the MDL determination.
9.8 Quantitation Limit (QL) Determination
A QL determination is recommended for each laboratory/technician performing the
method for the first time, or in cases where new or repaired instrumentation is being used.
Laboratory QLs are determined by first assessing at least four samples containing
concentrations of target analytes at the levels of the lowest calibration standard, against
the criteria listed below. If any of these criteria are not met, samples are assessed at
concentrations of the next (second lowest) calibration standard. These criteria are
provided as guidance. If the criteria cannot be met, the laboratory should consult project
managers to determine if the QL is sufficient to address project needs.
• Results from spikes at the QL should be above the MDL.
• The QL should be at or above the lowest calibration level.
• The QL should be at least two times the MDL.
• The RSD of results from spikes at the QL should be less than 30 %.
• The mean recovery of spikes at the QL should be within 50 - 150 %.
10.0 CALIBRATION AND STANDARDIZATION
10.1 Instrument Operating Conditions
10.1.1 Gas Chromatograph (GC)
10.1.1.1 The following are suggested GC conditions when using an Agilent
6890/5973 mass selective detector (MSD) or equivalent. These
conditions were used during the single-laboratory evaluation of this
protocol, using a Zebron™ ZB-5MS column. Instrument conditions
are the same for SIM and full scan analysis modes. Analyte RTs
using the conditions below are provided in Section 17, Table 4.
Injector Temperature: 250 °C
Injection Volume:
Injector Type:
Column:
1.0 (iL
Grob-type, Splitless
Zebron™ ZB-5MS (95 % dimethyl, 5 %
diphenylpolysiloxane), 30 m, 0.25 mm I.D.,
0.25(im
Oven Temperature 35 °C for 5.5 minutes
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Program: 35 - 270 °C at 10 0C/minute, hold for 2
minutes. 270 - 320 °C at 30 °C/minute, hold
for 5 minutes.
Carrier Gas: 1.0 mL/minute, helium (7.07 psi, 36
cm/second)
10.1.1.2 The conditions below were used during the single-laboratory
evaluation of this analytical protocol, using an Agilent Programmed
Temperature Vaporization injector. These conditions may be
necessary when using a programmed temperature vaporization
injection GC/MS.
Oven Temperature
Program:
40 °C for 4 minutes.
40 - 270 °C at 10 °C/minute, hold for 4
minutes. 270 - 320 °C at 10 °C/minutes,
hold for 2 minutes.
Front Inlet Program:
10.1.2 Mass Spectrometer (MS)
40 °C for 0.10 minute.
40 - 340 °C at 600 °C/minute, hold for 10
minutes. 340 - 170 °C at 10 °C/minute.
The following are the required MS analytical conditions:
Electron Energy 70 electron volts (nominal)
Mass Range 35 to 500 daltons
Ionization Mode Electron ionization (EI)
Scan Time Not to exceed 1 second per scan
For SIM ion groupings and dwell times, see Table 5 (Section 17).
10.2 GC/MS Mass Calibration (Tuning) and Ion Abundance
10.2.1 Summary of GC/MS Instrument Performance Check
The GC/MS system must be tuned to meet the manufacturer's specifications,
using a suitable calibration such as perfluoro-tri-«-butylamine (FC-43) or
perfluorokerosene (PFK). The mass calibration and resolution of the GC/MS
system are verified by the analysis of the instrument performance check solution
(Section 7.2.3.3). Prior to the analysis of any samples, including MS/MSDs,
blanks, or calibration standards, the laboratory must establish that the GC/MS
system meets the mass spectral ion abundance criteria for the instrument
performance check solution (Table 1) containing DFTPP.
10.2.2 Frequency of GC/MS Instrument Performance Check
10.2.2.1 The instrument performance check solution must be analyzed
once at the beginning of each 12-hour period during which
samples or standards are analyzed.
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10.2.2.2 The 12-hour period for the instrument performance check and
initial or CCV begins at the moment of injection of the DFTPP.
10.2.3 GC/MS Instrument Performance Check
The analysis of the instrument performance check solution may be performed as
an injection of 50 ng or less of DFTPP into the GC/MS or by adding a sufficient
amount of DFTPP to the calibration standards to result in an on-column amount
of 50 ng or less of DFTPP (Section 7.2.3.3) and analyzing the calibration
standard.
10.2.4 Technical Acceptance Criteria for GC/MS Instrument Performance Check
10.2.4.1 The GC/MS system tune must be verified or the instrument must be
tuned at the frequency described in Section 10.2.2.
10.2.4.2 The abundance criteria listed in Table 1 must be met. The mass
spectrum of DFTPP must be acquired using an average of three scans
(the peak apex scan and the scans immediately preceding and
following the apex). Background subtraction is required and must be
accomplished using a single scan acquired no more than 20 scans
prior to the elution of DFTPP. The background subtraction should
be used only to eliminate column bleed or instrument background
ions. Do not subtract part of the DFTPP peak.
Note: All subsequent standards, samples, MS/MSDs, and
blanks associated with a DFTPP analysis must use the identical
GC/MS instrument run conditions.
10.2.5 Corrective Action for GC/MS Instrument Performance Check
10.2.5.1 If the GC/MS instrument performance check technical acceptance
criteria are not met, re-tune the GC/MS system. It may be
necessary to perform maintenance to achieve the criteria.
10.2.5.2 The instrument performance check technical acceptance criteria in
Section 10.2.4 must be met before any standards, samples (including
QC samples), or required blanks are analyzed.
10.2.6 Selected Ion Monitoring (SIM)
SIM analysis can be used to achieve lower detection and quantitation levels.
Instrument conditions for SIM analysis are the same as those for full scan.
Analyte-specific dwell times and ion groupings are provided in Table 5.
10.3 Initial Calibration
10.3.1 Summary of Initial Calibration
Prior to the analysis of samples and after the instrument performance check
technical acceptance criteria have been met, each GC/MS system must be
calibrated at a minimum of five concentrations (Section 7.2.3.4.1 and Tables 10a
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and 10b) to determine instrument sensitivity and the linearity of the GC/MS
response for the target and surrogate compounds.
10.3.2 Frequency of Initial Calibration
10.3.2.1 Each GC/MS system should be calibrated whenever the laboratory
takes corrective action that might change or affect the initial
calibration criteria, or if the CCV technical acceptance criteria have
not been met.
10.3.2.2 If time remains in the 12-hour period that defines an analysis batch
after meeting the technical acceptance criteria for the initial
calibration, samples may be analyzed. It is not necessary to analyze
a continuing calibration standard within this 12-hour time period.
10.3.3 Procedure for Initial Calibration
10.3.3.1 Prepare calibration standards containing the target compounds
and associated surrogates at the concentrations described in
Tables 10a (full scan) and 10b (SIM).
10.3.3.2 Add a sufficient amount of internal standard solution (Section
7.2.3.5) to aliquots of calibration standards to result in 10 ng/(.iL of
each internal standard. Standards specified in Section 7.2.3.5
should permit most of the target compounds to have relative
retention times (RRTs) of 0.80 to 1.20, using the assignments of
internal standards to target compounds given in Table 2.
10.3.3.3 Analyze each calibration standard by injecting 1.0 |_iL of standard.
10.3.4 Calculations for Initial Calibration
10.3.4.1 Calculate the relative response factors (RRFs) for each target
compound and surrogate using Equation 2 and the primary
characteristic ions found in Table 4. Assign the target
compounds and surrogates to the internal standard according to
Table 2. For internal standards, use the primary ion listed in
Table 4 unless interferences are present. Unless otherwise
stated, the area response of the primary characteristic ion is the
quantitation ion.
EQ. 2. Relative Response Factor (RRF) Calculation
a r
RRF = —— x ——
A, Cx
where:
Ax = Area of the characteristic ion for the compound to be measured
(Table 4)
Ais = Area of the characteristic ion for specific internal standard
(Table 4)
Cis = Amount of the internal standard injected (ng)
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Cx = Amount of the target compound or surrogate injected (ng)
Note: Phosphamidon and chlorfenvinphos exist as two and three
isomers, respectively; therefore, RRF for these analytes is calculated
as the sum of the peak areas of the individual isomers.
10.3.4.2 The Mean Relative Response Factor (RRF ) for the Initial
Calibration
RRF must be calculated for all compounds. Calculate the %RSD of
the RRF values for the initial calibration. If linear regression or
quadratic curve fitting is needed, consult SW-846 Method 8000C
(Reference 16.13) for guidance on the appropriate calculations.
10.3.5 Technical Acceptance Criteria for Initial Calibration
10.3.5.1 All initial calibration standards should be analyzed at the
concentration levels described in Section 7.2.3.4.1 and at the
frequency described in Section 10.3.2 on a GC/MS system meeting
the instrument performance technical acceptance criteria.
10.3.5.2 The RRF for each target compound and surrogate should be greater
than or equal to 0.01.
10.3.5.3 The %RSD of the RRFs over the initial calibration range for each
target compound and surrogate should be less than or equal to 20. If
%RSD for a target analyte or surrogate cannot meet the acceptance
criteria, curve fitting by linear or quadratic regression may be used,
provided the R2 value is greater than or equal to 0.99 (linear) or
0.995 (quadratic). Single-laboratory calibration results are provided
in Table 6a (full scan) and Table 6b (SIM).
Note: Percent drift (PD) criteria may be added to the initial
calibration following a multi-laboratory study and/or updates to SW-
846 Method 8000C (Reference 16.13).
10.3.5.4 Excluding those ions in the solvent front, no quantitation ion may
saturate the detector.
10.3.6 Corrective Action for Initial Calibration
10.3.6.1 If any technical acceptance criteria for initial calibration are not met,
inspect the system for problems and take corrective actions to
achieve the acceptance criteria.
10.3.6.2 Initial calibration technical acceptance criteria must be met before
any samples or required blanks are analyzed.
10.4 Continuing Calibration Verification (CCV)
10.4.1 Summary of Continuing Calibration Verification
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Prior to the analysis of samples, and after instrument performance check
technical acceptance criteria and initial calibration technical acceptance criteria
have been met, each GC/MS system must be routinely checked by analyzing a
CCV standard to ensure that the instrument continues to meet the instrument
sensitivity and linearity requirements. The CCV standard contains all the target
compounds, surrogates, and internal standards. The same injection volume must
be used for all standards, samples, and blanks.
10.4.2 Frequency of Continuing Calibration Verification - Each GC/MS used for
analysis must be checked once per analytical batch for every 12-hour period of
operation or after the analysis of 10 samples, whichever comes first. The 12-
hour period of operation begins with the injection of DFTPP for full scan or the
analysis of the CCV.
10.4.3 Procedure for Continuing Calibration Verification
10.4.3.1 Add a sufficient amount of internal standard solution (Section
7.2.3.5) to an aliquot of CCV standard to result in a concentration of
0.5 ng/(.iL for SIM analyses, and 10 ng/(.iL for full scan analyses.
The concentration of the CCV should fall near the mid-point of the
calibration curve.
Note: The laboratory should analyze a CCV standard at a
concentration near the mid-point of the calibration range. It is
recommended that the laboratory also analyze a CCV standard at the
low end of the calibration range. For example, analyze a mid-point
CCV at the beginning of an analytical batch and a low-point CCV at
the end of the analytical batch.
10.4.3.2 Analyze the CCV standard by injecting 1.0 |_iL of standard.
10.4.4 Calculations for CCV
10.4.4.1 Calculate an RRF for each target compound and surrogate
using Equation 2 and the primary characteristic ions found in
Table 4.
10.4.4.2 Calculate the Percent Difference (%Difference) between
the RRF, from the most recent initial calibration and the
continuing calibration verification RRF for each target
compound and surrogate using Equation 3 a.
EQ. 3a. Relative Response Factor Percent Difference Calculation
RRF — RRF
%DifferenceRRF = c —Lxl00
RRF,
where:
RRFi= Mean Relative Response Factor from the most recent
initial calibration meeting technical acceptance criteria
RRFc = Relative Response Factor from CCV standard
10.4.5 Technical Acceptance Criteria for CCV
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10.4.5.1 The CCV standard should be analyzed at the frequency described in
Section 10.4.2, on a GC/MS system meeting the instrument
performance check and the initial calibration technical acceptance
criteria.
10.4.5.2 The RRF for each target compound and surrogate should be >
0.01.
10.4.5.3 The RRF percent difference for each target compound should
be within the range of ±50 %.
Note: This range may be updated following additional laboratory
testing of the method.
If regression techniques are used for the initial calibration, the
CCV should be evaluated in terms of PD using concentrations
(see Equation 3b). The PD for each target compound should
be within the range of ±50 %.
EQ. 3b. Percent Drift (PD) Calculation for CCV
Calculated Concentration-Theoretical Concentration
lJL) = xl00%
Theoretical Concentration
10.4.5.4 Excluding those ions in the solvent front, no quantitation ion may
saturate the detector.
10.4.6 Corrective Action for CCV
10.4.6.1 If the CCV technical acceptance criteria in Section 10.4.5 are not
met, recalibrate the GC/MS instrument according to Section 10.3.
10.4.6.2 CCV technical acceptance criteria should be met before any samples,
MS/MSDs, or required blanks are analyzed. If CCV criteria are not
met, flag associated samples and blanks accordingly.
11.0 ANALYTICAL PROCEDURE
11.1 Sample Preparation - General
11.1.1 If an insufficient sample amount (less than 90 % of the required amount) is
received to perform the analyses, use a reduced amount and adjust
calculations accordingly.
11.1.2 If multi-phase samples (e.g., a two-phase liquid sample, oily sludge/sandy soil
sample) are received, the laboratory should contact the agency requesting the
analyses. If some or all phases of the sample are amenable to analysis, the
agency may require the laboratory to do any of the following:
• Mix the sample and analyze an aliquot from the homogenized sample
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• Separate the phases of the sample and analyze each phase separately
• Separate the phases and analyze one or more but not all of the phases
• Do not analyze the sample
11.2 Preparation of Water Samples
Microscale extraction (MSE) has been evaluated for precision and bias in a single-
laboratory and is the suggested procedure for preparing water samples. Single-laboratory
data are provided in Section 17.0, Table 7a and 8a. See Appendix A for alternative
preparation techniques, such as solid phase extraction (SPE).
11.2.1 Approximately 35 mL of a water sample is required for this
extraction. If extraction is to be performed in the sample receipt vial,
remove any excess sample so that a total sample volume of 35 mL is
retained and recap the vial. Weigh the capped vial. Record the
weight to the nearest 0.1 gram. Alternatively, 35 mL of sample can
be transferred by pipette into the vial and the weighing step
eliminated.
Note: The conical bottoms of centrifuge vials may allow the DCM
layer to be removed more easily than from VOA vials.
11.2.2 Add a sufficient volume of each surrogate to the sample to yield a concentration
approximating the mid-calibration level in the VOA vial.
11.2.3 Add 2.0 mL of DCM using a Class A volumetric pipette or gastight syringe (or
equivalent) and approximately 12 grams of anhydrous sodium chloride to the
sample. Replace the vial cap.
Note: During a multi-laboratory exercise using this protocol for analysis of
dichlorvos, mevinphos and TETS in water, two laboratories used less salt (8.8
and 10 grams) and one laboratory found it was easier to dissolve the salt if it was
added prior to adding the DCM. These modifications, as well as other solvent
delivery systems, such as a repeating solvent dispenser, may be used provided
that equivalent performance can be demonstrated.
11.2.4 Shake the vial vigorously or vortex for approximately 2 minutes or until the
sodium chloride dissolves completely.
11.2.5 Briefly allow the phases to settle. If the phases do not separate, then centrifuge
at 500 times the force of gravity (500 G force units) for 5-15 minutes.
CAUTION: The maximum safe handling speed of each centrifuge will depend,
in part, on the vials used and should be determined prior to use. Adding an
additional volume of DCM may also help separate the phases.
Note: If additional DCM is used, calculations must be adjusted to account for the
additional volume.
11.2.6 Using a 2.0 -mL gastight syringe, transfer approximately 1.5 mL of the lower
(DCM) layer to a 2-mL vial with a PTFE-lined screw cap, taking precautions to
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exclude any water from the syringe. Add a small amount (-50 mg) of anhydrous
sodium sulfate to the vial, then cap, and shake for 2 minutes.
11.2.7 Using a 1. 0-mL gastight syringe, transfer 1.0 mL of the dried extract to a 2-mL
vial with a PTFE-lined screw cap.
11.2.8 Discard the remaining contents of the VOA vial according to laboratory waste
disposal guidelines. Shake off the last few drops with short, brisk movements. If
needed, rinse the vial with a water-soluble solvent to ensure the extraction
solvent is removed. If the vial was pre-weighed (i.e., exact sample volume used
in Section 11.2.1 is unknown), reweigh the capped vial, and record the weight to
the nearest 0.1 grams. The difference between this weight and the weight
determined in Section 11.2.1 is equal to the volume of water extracted in
milliliters. As the density of water is 1.00 g/mL (at 20 °C), the volume of water
extracted may be assumed to be equal to the weight of water extracted.
11.2.9 Proceed to Section 11.6.
11.3 Preparation of Soil/Sediment Samples - General
MSE was evaluated for precision and bias in a single-laboratory and is recommended
for analysis of soil or sediment samples. Laboratory results are provided in Tables 7b
and 8b. See Appendix A for alternative techniques.
11.3.1 Soil/Sediment Samples - Decant and discard any water layer on a sediment
sample. Mix samples thoroughly, especially composited samples. Discard any
foreign objects such as sticks, leaves, and rocks.
11.3.2 pH Determination - If pH determination is requested, transfer a 1:1 (w:w) ratio
of sample:water to a 100-mL beaker and stir for one hour. Determine the pH of
the sample with a pH meter or wide-range pH paper, and document this value in
the data narrative. Discard this portion of the sample.
11.3.3 Percent Moisture Determination
If percent moisture determination is requested, immediately after weighing the
sample for extraction, weigh 5-10 grams of the soil/sediment into a tared
crucible. Determine the Percent Moisture (%Moisture) by drying overnight at
103-105 °C. Allow the sample to cool in a desiccator before weighing.
EQ. 4. Percent Moisture Calculation
grams of wet sample - grams of dry sample
%Moisture = x 100
grams of wet sample
11.3.4 Perform the following steps rapidly to avoid loss of the more volatile
compounds. Weigh 10 grams of sample to the nearest 0.1 gram, and place in
a 400-mL beaker. Add double the weight (relative to the sample) of
anhydrous powdered or granulated sodium sulfate and mix well.
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11.3.5 Microscale Solvent Extraction (MSE)
Note: The extraction solvent of choice is dependent on the analyte that is to be
measured. For most target analytes, the extraction solvent that gave the best
results in a single-laboratory was acetone:DCM:ethyl acetate (1:2:1 v:v:v). If
nicotine, crimidine, phencyclidine, or strychnine is to be measured, the extraction
solvent giving the best results was 5 % TEA in ethyl acetate. Results of a single-
laboratory preliminary evaluation of alternate solvent mixtures are provided in
Appendix A.
11.3.5.1 Add approximately 2.5 grams of anhydrous sodium sulfate to a pre-
cleaned extraction tube (e.g., 40-mL VOA vial with PTFE screw
cap). Also add 5-10 pre-cleaned glass beads (Section 6.1.2.5).
11.3.5.2 Weigh 10 grams of sample into the tared extraction tube. Wipe the
lip and threads of the tube with a clean cloth (e.g., Kimwipe®,
Kimberly-Clark Professional, Roswell, GA, or equivalent). Cap
tightly, and record the weight to the nearest 0.0 lg.
11.3.5.3 Add 10 (ig of the surrogate standard compounds in DCM directly to
the sample. If the surrogate compounds in the spiking solution are at
a concentration of 100 |ig/m L. add 0.1 mL of the spiking solution.
11.3.5.4 Add 15 mL of the extraction solvent (see Note in Section 11.3.5 for
solvent choice) to the tube, and cap tightly. For certain sample types,
15 mL of solvent will not be sufficient to completely immerse the
sample. For these situations, add the minimal amount of solvent so
that the sample is completely immersed. The additional volume of
solvent should be reported in the narrative.
11.3.5.5 Shake the tubes vigorously until the slurry is free-flowing. Break up
any chunks with a metal spatula, working quickly but gently. Cap
immediately when finished. Add more sodium sulfate and manually
mix as necessary to produce a free-flowing, finely divided slurry.
11.3.5.6 Extract the samples by rotating end-over-end for at least 1 hour or by
sonicating, in a water bath, for at least 30 minutes.
11.3.5.7 Vortex each sample for 30 seconds. Add ~ lg anhydrous, sodium
sulfate to each sample. Cap and shake briefly or vortex to ensure
thorough mixing. Allow the solids to settle or centrifuge for 1-2
minutes at 1000 rpm. If the solid is still unsettled, repeat the
centrifuge step, but increase speed to 2500 rpm. CAUTION:
Different centrifuge makes and models have different maximum
centrifuge speeds that are recommended for safe operation. The
maximum safe handling speed of each centrifuge will depend, in
part, on the vials used and should be determined prior to centrifuging
samples. Repeat until the solid is completely settled. If after
repeating the centrifuging steps several times the solid is still
unsettled, proceed to Section 11.3.5.8. Once the solid has settled,
decant or pipette the solvent layer into a pre-cleaned, 40-mL VOA
vial with PTFE-lined screw cap and proceed to Section 11.3.5.9.
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Note: For solids that have difficulty settling, pipetting is
recommended.
11.3.5.8 If solids are not settled out by centrifugation (Section 11.3.5.7), filter
by placing a small plug of glass wool into a small glass funnel. Add
anhydrous sodium sulfate to cover the glass wool plug. Wet the
sodium sulfate thoroughly with DCM. Decant the sample solvent
layer into the funnel. Rinse the sodium sulfate with 2-3 mL of
DCM as soon as the surface is exposed, not allowing it to dry.
Note: Due to the potential for analyte loss, filtration should be used
only as a last resort in cases where centrifugation does not work.
11.3.5.9 Extract the sample twice more by adding approximately 10 mL of
the extraction solvent to the sample, capping the extraction tube
tightly, and shaking vigorously by hand for 2 minutes. Be certain to
wipe the lip and threads of the extraction tube clean before capping
each time. More sodium sulfate can be added as necessary to dry the
extract and break up any clumps that may have formed.
Note: Less than three extractions may be needed and can be used
provided all surrogate and MS/MSD performance criteria are met.
11.3.5.10 After each extraction, repeat procedures in Section 11.3.5.6 -
11.3.5.8.
11.3.5.11 If a sample requires extraction by both solvent systems, repeat
procedures in Sections 11.3.5.3 - 11.3.5.9, using the other extraction
solvent. Extracts are not combined and are analyzed separately.
11.3.5.12 Proceed to Section 11.6.
11.4 Preparation of Air Samples
MSE of spiked air filters has been evaluated in a single-laboratory and is the suggested
procedure. Data characterizing pressurized fluid extraction (PFE) efficiency is limited
and the procedure is provided as a possible alternative for analytes exhibiting poor results
by MSE. Follow the procedure in Section 11.3.5 replacing the soil sample with the air
filter and using the acetone:DCM:ethyl acetate (1:2:1 v:v:v) solvent system. Once
extraction is complete, proceed to Section 11.6.
Note: If PUF is the sorbent, the extraction solvent is 10 % diethyl ether in hexane. If
XAD-2 resin is the sorbent, the extraction solvent is DCM.
11.5 Preparation of Wipe Samples
MSE of spiked wipe samples was evaluated in a single-laboratory and is the suggested
procedure for preparing wipe samples. Laboratory results are provided in Table 8c.
See Appendix A for alternative preparation techniques. Follow the procedure in Section
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11.3.5 replacing the soil sample with a surface wipe and using the acetone:DCM:ethyl
acetate (1:2:1 v:v:v) solvent system. Once extraction is complete, proceed to Section
11.6.
11.6 Final Concentration of Extract by Nitrogen Evaporation Technique
11.6.1 Place the concentrator tube in a warm water bath (30 - 35 °C recommended) and
evaporate the solvent volume to just below 1 mL by blowing a gentle stream of
clean dry nitrogen (filtered through a column of activated carbon) above the
extract. CAUTION: Gas lines from the gas source to the evaporation apparatus
should be stainless steel, copper, or PTFE tubing. Plastic tubing must not be
used between the carbon trap and the sample since plastic tubing may introduce
interferences. The internal wall of the concentrator tube must be rinsed down
several times with DCM. During evaporation, the tube solvent level must be
kept below the water level of the bath. The extract must never be allowed to
become dry.
11.6.2 Final Extract Volumes
The final extract volumes in Sections 11.6.2.1 through 11.6.2.4 are
recommended volumes. If more sensitive GC/MS systems are used, the larger
extract volumes (less concentrated extracts) may be used provided that the QLs
for all target compounds can be achieved, and that all surrogates and internal
standards have an expected extract concentration that is at the mid-point of the
calibration curve. Once extract volumes are obtained, transfer the extract to a
PTFE-sealed screw-cap vial (approximately 2.0 mL). Label the vial and store
at 6 °C or less.
11.6.2.1 Water - As concentration of the sample extract is not needed for
these sample matrices, no adjustment of the final extract volume is
required. The nominal volume of DCM added to water samples is
2.0 mL. Target compound and surrogate spiking solutions also
contain DCM; therefore, the total volume of DCM added may be
slightly greater than 2.0 mL. The actual total volume of DCM added
should be used in the calculations in Section 12.2.
11.6.2.2 Solids - Adjust the final volume for solid samples to a final volume
of 1.0 mL with DCM or another appropriate solvent.
11.6.2.3 Air Filters - Adjust the final volume for air filter samples to a final
volume of 1.0 mL with DCM or another appropriate solvent.
11.6.2.4 Wipes - Adjust the final volume for wipe samples to 1.0 mL with
DCM or another appropriate solvent.
11.7 Sample Analysis by Gas Chromatograph/Mass Spectrometer (GC/MS)
11.7.1 Analyze extracts only after the GC/MS system has met the instrument
performance check (Section 10.2.4), initial calibration (Section 10.3.5), and CCV
requirements (10.4.5). The same instrument conditions used for calibration must
be used for the analysis of samples.
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11.7.2 Add a sufficient amount of the internal standard solution (Section 7.2.3.5) to each
accurately measured aliquot of sample extract to result in 10 ng/(.iL concentration
of each internal standard in the extract volume. If sample extracts are to be
diluted, add internal standards after dilution.
11.7.3 Inject 1.0 |_iL of the sample extract into the GC/MS.
Note: The injection volume used for sample extracts must be the same as the
injection volume used for the calibration standards.
11.7.4 Sample Dilutions
11.7.4.1 If the response of any target compound in any sample exceeds the
response of the same target compound in the high standard of the
initial calibration, that sample extract must be diluted. Add the
internal standard solution to the diluted extract for a concentration of
10 ng/(.iL of each internal standard, and analyze the diluted extract.
11.7.4.2 Use the results of the original analysis to determine the approximate
Dilution Factor (DF) required to achieve the largest analyte peak
within the calibration range. The DF chosen must keep the response
of the largest peak for a target compound in the upper half of the
calibration range of the instrument.
12.0 CALCULATIONS AND DATA ANALYSIS
12.1 Qualitative Identification of Target Compounds
12.1.1 Target compounds should be identified by an analyst competent in the
interpretation of mass spectra by comparison of the sample mass spectrum to the
mass spectrum of the standard of the suspected compound. Two criteria must be
satisfied to verify the identifications:
• Elution of the sample analyte within the Gas Chromatograph (GC) RRT
unit window established from the 12-hour calibration standard
• Correspondence of the sample analyte and calibration standard
component mass spectra
12.1.2 For establishing correspondence of the GC RRT, the sample component RRT
must compare within ±0.06 RRT units of the RRT of the standard component.
For samples analyzed during the same 12-hour time period as the initial
calibration standards, compare the analyte RTs to those from the midpoint initial
calibration standard. Otherwise, use the corresponding CCV standard. If
coelution of interfering components prohibits accurate assignment of the sample
component RRT from the total ion chromatogram, the RRT should be assigned
by using EICPs for ions unique to the component of interest.
12.1.3 For comparison of standard and sample component mass spectra, mass spectra
obtained from a calibration standard on the laboratory's GC/Mass Spectrometer
(GC/MS) meeting the daily instrument performance requirements for DFTPP are
required. Once obtained, these standard spectra may be used for identification
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purposes only if the laboratory's GC/MS meets the DFTPP daily instrument
performance requirements.
12.1.4 The requirements for qualitative verification by comparison of mass spectra are
as follows:
All ions present in the standard mass spectrum at a relative intensity greater than
10 % (most abundant ion in the spectrum equals 100 %) must be present in the
sample spectrum. The relative intensities of ions must agree within ±20 %
between the standard and sample spectra (e.g., for an ion with an abundance of
50 % in the standard spectra, the corresponding sample ion abundance must be
between 30 and 70 %). Ions greater than 10 % in the sample spectrum but not
present in the standard spectrum must be considered and accounted for by the
analyst making the comparison. The verification process should favor false
positives. All compounds meeting the identification criteria must be reported
with their spectra. When target compounds are below QLs but the spectrum
meets the identification criteria, report the concentration with a "J". For example,
if the QL is 5.0 (ig/L and concentration of 3.0 (ig/L is calculated, report as "3.0J."
12.1.5 If a compound cannot be verified by all of the spectral identification criteria in
Sections 12.1.1- 12.1.4, but in the technical judgment of the mass spectral
interpretation specialist the identification is correct, then the laboratory should
report the identification and proceed with quantitation.
12.2 Data Analysis and Calculations of Target Compounds
12.2.1 Target compounds identified are quantitated by the internal standard method.
The internal standard used should be the one assigned to that analyte for
quantitation (Table 2). The EICP area of primary characteristic ions of
analytes listed in Table 4 are used for quantitation.
12.2.2 It is expected that situations will arise when the automated quantitation
procedures in the GC/MS software provide inappropriate quantitations. This
normally occurs when there is compound coelution, baseline noise, or matrix
interference. In these circumstances, the laboratory should perform a manual
quantitation. Manual quantitations are performed by integrating the area of the
quantitation ion of the compound. This integration includes only the area
attributable to the specific target compound. The area integrated must not
include baseline background noise, and must not extend past the point where the
sides of the peak intersect with the baseline noise. Manual integration is not to
be used solely to meet QC criteria, nor is it to be used as a substitute for
corrective action on the chromatographic system.
12.2.3 In some instances, the data system report may have been edited or manual
integration or quantitation may have been performed. In all such instances, the
GC/MS operator should identify such edits or manual procedures by initialing
and dating the changes made to the report, and include the integration scan range.
The GC/MS operator should also mark each integrated area on the quantitation
report.
12.2.4 The requirements listed in Sections 12.2.1 - 12.2.3 apply to all standards,
samples, and blanks.
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12.2.5 The Mean Relative Response Factor (RRF ) from the initial calibration is used to
calculate the concentration in the sample. Secondary ion quantitation is allowed
ONLY when there are sample interferences with the primary ion. If linear
regression is used, a regression curve must be used to calculate the concentration
in samples. Refer to Section 12.2.7 for calculating sample concentration using
linear regression techniques.
12.2.6 Calculate the concentration in the sample using the RRF and Equations 5-8.
12.2.6.1 Water
EQ. 5. Concentration of Water Sample
(Ax)(Is)(Vt)(DF)
Concentration (ug/L) = ¦
(A1S )(RRF)(Vo )(V1)
where:
Ax = Area of the characteristic ion for the compound to be measured
A1S = Area of the characteristic ion for the internal standard
Is = Amount of internal standard injected in ng
V0 = Volume of water extracted in mL
V| = Volume of extract injected in (.iL
Vt = Volume of the concentrated extract in (.iL
RRF = Mean Relative Response Factor determined from the initial
calibration standard
DF = Dilution Factor
The DF for analysis of water samples is defined as follows:
|iL most conc. extract used to make dilution + |iL clean solvent
DF = -
|iL most conc. extract used to make dilution
If no dilution is performed, DF = 1.0.
12.2.6.2 Soil/Sediment
EQ. 6. Concentration of Soil/Sediment Sample
Eq. 6 includes a %moisture factor (D) for those cases when data are
to be reported on the basis of dry sample weight. In cases where
results are reported in terms of sample weight, this factor is deleted
from the equation.
(A )(I )(V )(DF)
Concentration mg / Kg (Dry weight basis) =
1000(A. g )(V. )(RRF)( W§ )(D)
where:
Ax, Is, A1S, V15 Vt are as given for water, above.
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_ 100 - %Moisture
100
%Moisture is as given in EQ. 4
Ws = Weight of sample extracted in grams
RRF = Mean Relative Response Factor determined from the initial
calibration standard
DF = Dilution Factor
12.2.6.3 Air
EQ. 7. Concentration of Gas Phase Sample
Concentration jLig / nr =
3 _ (Ax )(IS )(Vt )(DF)
1000(AlsW0Wt)(RRF)
where:
Ax = area response for the compound to be measured, counts
A1S = area response for the internal standard, counts
Is = amount of internal standard, ng
RRF = the mean RRF from the most recent initial calibration,
dimensionless
V0 = volume of air sampled, std m3
Vt = volume of final extract, (.iL
V| = volume of extract injected, (.iL
DF = dilution factor for the extract. If there was no dilution, DF
equals 1. If the sample was diluted, the DF is greater than 1.
12.2.6.4 Wipes
EQ. 8. Concentration of Wipe Sample
2 (Ax)(Is)(Vt)(DF)
Concentration jug/ cm =
(AJiAreaXV^RRF)
where:
Ax = area response for the compound to be measured, counts
Ais = area response for the internal standard, counts
Is = amount of internal standard, |_ig
RRF = mean RRF from the most recent initial calibration,
dimensionless
Area = area of surface wiped, cm2. If concentration is reported as
(ig/wipe, area= 1 wipe.
Vt = volume of final extract, (.iL
V, = volume of extract injected, (.iL
DF = dilution factor for the extract. If there was no dilution, DF
equals 1. If the sample was diluted, the DF is greater than 1.
12.2.7 Calculate the concentration in the sample using linear regression. Refer to SW-
846 Method 8000C (Reference 16.13) if calibration curves were determined
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Analytical Protocol for Extractable Semivolatile Organic Compounds
using quadratic equations.
12.2.7.1 Set y = (Peak Area of Target/Peak Area of Internal Standard) and x =
(Theoretical Concentration of Target/Theoretical Concentration of
Internal Standard).
12.2.7.2 Plot (Peak Area of Target/Peak Area of Internal Standard [Y-axis])
vs. (Theoretical Concentration of Target/Theoretical Concentration
of Internal Standard).
12.2.7.3 Determine the slope of the line (m) and the y-intercept (b).
12.2.7.4 Rearrange the line equation to solve for x: x = (y-b)/m.
12.2.7.5 Multiply x by the concentration of the internal standard to get
concentration of target in extract.
12.2.7.6 Multiply the concentration of target analyte in the extract by the
extract volume and divide by the sample volume to get the
concentration of target analyte in the sample.
12.2.8 QL Calculations
12.2.8.1 Water Samples
EQ. 9. Aqueous Adjusted QL
Adjusted QL = Method QL x )(DF)
(V0)(VC)
where:
Vt, DF, and V0 are as given in Equation 5.
Vx = Method sample volume (35 mL).
Vc = Method concentrated extract volume.
12.2.8.2 Soil/Sediment Samples
EQ. 10. Soil/Sediment Adjusted QL
Adjusted QL = Method QL x (W; )(V')(°F)
(WS)(VC)(D)
where:
Vt and DF are as given in Equation 5
Ws and D are as given in Equation 6
Wx = Method sample weight (10 grams for soil/sediment samples)
Vc = Method concentrated extract volume
12.2.9 Surrogate Recoveries
12.2.9.1 Calculate surrogate recoveries for all samples, blanks, and
MS/MSDs using Equation 11.
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EQ. 11. Percent Recovery
r
Recovery = %R = — x 100
where:
Cs = Measured concentration of the spiked sample aliquot.
Cn = Nominal (theoretical) concentration increase that results from
spiking the sample, or the nominal concentration of the spiked
aliquot (for LCS).
12.2.9.2 Calculate the RPD of the concentrations of each compound in the
MS/MSD using Equation 12. Concentrations of the MS/MSD
compounds are calculated using the same equations used for target
compounds (Equation 5 for water samples and Equation 6 for solid
samples in Section 12.2.6).
EQ. 12. Relative Percent Difference (RPD) Calculation
RPD = jCl ~C2j x 100
^c1+c2j
where
Ci = Measured concentration of the first sample aliquot
C2 = Measured concentration of the second sample aliquot
Note: The vertical bars in the equation above indicate the
absolute value of the difference.
12.2.9.3 Calculate the concentrations of the surrogates using the same
equations as used for the target compounds. Calculate the
recovery of each surrogate.
12.3 Technical Acceptance Criteria for Sample Analysis
12.3.1 Samples must be analyzed on a GC/MS system meeting the instrument
performance check, initial calibration, CCV, and blank technical acceptance
criteria.
12.3.2 The sample must be extracted and analyzed within the technical holding times.
12.3.3 The sample must have an associated method blank meeting the blank technical
acceptance criteria.
12.3.4 Percent recoveries of the surrogates in a sample must be within the recovery
limits of 50-150 % .
Note: Surrogate recovery requirements do not apply to samples that have
been diluted.
12.3.5 The instrumental response (EICP area) for each of the internal standards in the
sample must be within the range of 50.0 % - 200 % of the response of the
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internal standard in the most recent CCV standard analysis.
12.3.6 The RT shift for each of the internal standards must be within ±0.50
minutes (30 seconds) between the sample and the most recent CCV
standard analysis.
12.3.7 Excluding those ions in the solvent front, no ion may saturate the detector. No
target compound concentration may exceed the upper limit of the initial
calibration range unless a more dilute aliquot of the sample extract is also
analyzed according to the procedures in Section 11.7.4.
12.4 Corrective Action for Sample Analysis
12.4.1 The sample technical acceptance criteria must be met before data are reported.
12.4.2 Corrective action for failure to meet instrument performance checks and
initial calibration and CCV must be completed before the analysis of
samples.
12.4.3 Corrective Action for Surrogate Recoveries that Fail to Meet Their Acceptance
Criteria (Section 9.3.3.2).
12.4.3.1 If the surrogate recoveries in a sample fail to meet the acceptance
criteria, check calculations, sample preparation logs, surrogate
standard spiking solutions, and the instrument operation.
• If the calculations were incorrect, correct them and verify that
the surrogate recoveries meet their acceptance criteria.
• If the sample preparation logs indicate that the incorrect amount
of surrogate standard spiking solution was added to the sample,
then re-extract (if possible) and reanalyze the sample after
adding the correct amount of surrogate standard spiking solution.
• If the surrogate standard spiking solution was improperly
prepared, concentrated, or degraded, re-prepare the solution, and
re-extract the sample (if possible) and re-analyze the samples.
• If the instrument malfunctioned, correct the instrument problem
and reanalyze the sample extract. Verify that the surrogate
recoveries meet their acceptance criteria.
• If the instrument malfunction affected the calibrations,
recalibrate the instrument before reanalyzing the sample extract.
12.4.3.2 If the above actions do not correct the problem, then the problem
might be due to a sample matrix effect. To determine if there was
matrix effect, take the following corrective action steps:
12.4.3.2.1 Re-extract (if possible) and reanalyze the sample.
Note: Samples with corresponding MS and MSDs
should be re-extracted and reanalyzed only if
surrogate recoveries in a sample were considered
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unacceptable, and the surrogate recoveries met the
acceptance criteria in both the corresponding MS
and MSD.
12.4.3.2.2 If the surrogate recoveries meet acceptance
criteria in the re-extracted/reanalyzed sample, then
the problem was within the laboratory's control.
12.4.3.2.3 Submit data from both analyses. Distinguish
between the initial analysis and the
extraction/reanalysis on all data.
12.4.4 Corrective Action for Internal Standard Compound Responses that Fail to
Meet Their Acceptance Criteria (Sections 12.3.5 and 12.3.6).
12.4.4.1 If the internal standards in a sample fail to meet their
acceptance criteria, check calculations, internal standard
solutions, and instrument operation.
• If the calculations were incorrect, correct them, and verify that
the internal standard responses meet their acceptance criteria.
• If the internal standard solution was improperly prepared,
concentrated, or degraded, re-prepare solutions and reanalyze
another aliquot of the sample extract (if possible) after adding
the correct amount of the freshly prepared internal standard
solution.
• If the instrument malfunctioned, correct the instrument problem
and reanalyze the sample extract.
• If the instrument malfunction affected the calibration, recalibrate
the instrument before reanalyzing the sample extract.
12.4.4.2 If the above actions do not correct the problem, then the problem
might be due to a sample matrix effect. To determine if there was
matrix effect, take the following corrective action steps:
12.4.4.2.1 Reanalyze the sample extract.
Note: Samples with corresponding MS and MSDs
should be re-extracted and reanalyzed only if internal
standard recoveries in a sample were considered
unacceptable, and the internal standard recoveries met
the acceptance criteria in both the corresponding MS
and MSD.
12.4.4.2.2 If the internal standard compound recoveries
meet acceptance criteria in the reanalyzed sample
extract, then the problem was within the
laboratory's control.
12.4.4.2.3 Submit data from both analyses. Distinguish
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Analytical Protocol for Extractable Semivolatile Organic Compounds
between the initial analysis and the reanalysis on
all data.
12.4.5 Corrective Action for Internal Standard Compound RTs Outside
Acceptance Criteria (Section 12.3.6)
12.4.5.1 If the internal standard compound RTs are not within their
acceptance criteria, check the instrument for malfunctions. If the
instrument malfunctioned, correct the instrument problem and
reanalyze the sample extract. If the instrument malfunction affected
the calibration, recalibrate the instrument before reanalyzing the
sample extract.
12.4.5.2 If the above actions do not correct the problem, then the problem
may be due to a sample matrix effect. To determine if there was
matrix effect, take the following corrective action steps:
12.4.5.2.1 Reanalyze the sample extract.
Note: Samples with corresponding MS and MSDs
should be re-extracted and reanalyzed only if internal
standard RTs in a sample were considered
unacceptable, and the internal standard RTs met the
acceptance criteria in both the corresponding MS and
MSD.
12.4.5.2.2 If the internal standard compound RTs are within
the acceptance criteria in the reanalyzed sample
extract, then the problem was within the
laboratory's control.
12.4.5.2.3 Submit data from both analyses. Distinguish
between the initial analysis and the reanalysis on
all deliverables.
13.0 ANALYTICAL PROCEDURE PERFORMANCE
Performance of this protocol was evaluated in a single laboratory for all analyte/matrix
combinations listed in the table in Section 1.2 (except those labeled "Not a concern"). Reagent
water and Ottawa sand were used as reference matrices throughout the study. Surface and tap
water were obtained by the laboratory from Germany Creek, Washington, and from the tap at
ALS Environmental (formerly Columbia Analytical Services [CAS] in Kelso Washington),
respectively. Pre-characterized EPA Georgia Bt2 and EPA Nebraska Ap soils were provided to
the laboratory for use as environmental soil matrices, and the laboratory procured Clinisorb 2-
inch x 2-inch (CliniMed, Ltd., Buckinghamshire, UK), non-woven sterile sponges and XAD-2
(Sigma-Aldrich, St. Louis, MO) polymeric adsorbent resin for use in evaluation of precision and
bias in wipes and air collection material, respectively. MSE was used to extract analytes from the
reagent, surface and laboratory tap water, Ottawa sand, Georgia Bt2 red clay and Nebraska Ap
soil, surface wipes, and spiked air sorbents and filters. Resulting detection and quantitation levels
are listed in Tables 3, 1 la, 1 lb, 12a and 12b. Resulting precision and recovery for target analytes
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Analytical Protocol for Extractable Semivolatile Organic Compounds
are listed in Tables 7a, 7b and 8a - 8d. Surrogate recovery ranges are listed in Tables 9a and 9b.
Figure 1 shows an example chromatogram of the analysis of a midpoint calibration standard.
Figures 2-5 show the chromatograms and mass spectra for analytes that required manual
integration. Characterization information for the water and soils is provided in Tables 13a and 14,
respectively.
Performance of this protocol was evaluated in nine laboratories for dichlorvos, mevinphos, and
TETS in reagent water and drinking water. Characterization information for the water samples
used is provided in Table 13b. Characterization of the drinking water used in this evaluation is
listed in Table 13b. Drinking water was spiked with the three analytes and dechlorinated and
preserved with Na2SC>3 and HC1. Resulting precision and recovery for target analytes and
surrogates are listed in Tables 15 and 16, respectively.
13.1 Instrument Detection Limit (IDL), Method Detection Limit (MDL) and Quantitation
Limit (QL)
Table 4 lists single-laboratory estimated IDLs (Section 9.6), RTs, and quantitation ions
for all target analytes. The mass spectra generated from full scan analyses for the
analytes were verified by comparison with the spectra in the National Institute of
Standards and Technology (NIST) 98 library (http://www.nist.gov/srd/nistla.cfm').
For SIM mode, only a few selected ions were monitored, therefore the NIST library was
not applied. RTs and quantitation ions were established using the instrument conditions
listed in Section 10.1. MDLs listed in Table 3 were established using the procedures
outlined in Section 9.7. Single-laboratory QLs listed in Tables 1 la and 1 lb (reagent
water) and Tables 12a and 12b (Ottawa sand) were established using the procedures and
criteria provided in Section 9.8.
13.2 Precision and Recovery in Samples
Single-laboratory study samples were spiked at 1, 2, 5 and/or 10 times the QL with either
2, 3 or 4 replicates at each concentration level. Results of precision and recovery for
clean reference sample types (reagent water, Ottawa sand, and clean wipes) and non-
reference sample types (tap water, surface water, and Nebraska Ap and Georgia Bt2
soils) are presented in Section 17.0, Tables, 7a, 7b, and 8a - 8d. Reagent water samples
in the multi-laboratory exercise were spiked with dichlorvos, mevinphos, and TETS at
28.6 and 571 (ig/L, with seven and four replicates prepared at each concentration level,
respectively. The drinking water samples in the exercise were spiked at 114 and 571 (ig/L
in drinking water, with four replicates prepared at each concentration level. Multi-
laboratory precision and bias results are presented in Section 17.0, Tables 15 and 16.
13.3 Problem Analyte s
13.3.1 During the single-laboratory study, TEPP and strychnine showed instability when
combined with other analytes in standard solutions and exhibited improved
linearity and coefficients of determination when run separately. For this reason,
separate standards are prepared for these analytes (see Section 7.2.2).
13.3.2 Dimethylphosphite was not recovered from spiked water samples using any of
the extraction procedures that were evaluated (i.e., SPE at pH = 4 and pH = 8, or
MSE at pH = 4).
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Analytical Protocol for Extractable Semivolatile Organic Compounds
13.3.3 Nicotine had low recoveries (<50 %) and poor precision (RSDs > 20 %) in
reagent and non-reference waters when using MSE. Preliminary results using
SPE at pH = 8 gave higher recoveries (see Appendix A).
13.3.4 Chloropicrin and TEPP had consistently low recoveries and poor precision in
Ottawa sand, non-reference soils and wipes. None of the extraction procedures
evaluated resulted in recoveries between 50 - 150 % and RSD of less than 20 %.
14.0 POLLUTION PREVENTION
14.1 Pollution prevention encompasses any technique that reduces or eliminates the quantity
and/or toxicity of waste at the point of generation. Numerous opportunities for pollution
prevention exist in laboratory operation. EPA has established a preferred hierarchy of
environmental management techniques that places pollution prevention as the option of
first choice. Whenever feasible, laboratory personnel should use pollution prevention
techniques to address their waste generation. When wastes cannot be feasibly reduced at
the source, the Agency recommends recycling as the next best option.
14.2 For information about pollution prevention that might be applicable to laboratories and
research institutions, consult Less is Better: Laboratory Chemical Management for Waste
Reduction, available from the American Chemical Society's Department of Government
Relations and Science Policy, 1155 16th St., N.W. Washington, D.C. 20036, (202) 872-
4477.
15.0 WASTE MANAGEMENT
EPA requires that laboratory waste management practices be conducted in a manner consistent
with all applicable rules and regulations. The Agency urges laboratories to protect the air, water,
and land by minimizing and controlling all releases from hoods and bench operations, complying
with the letter and spirit of any sewer discharge permits and regulations, and by complying with
all solid and hazardous waste regulations, particularly the hazardous waste identification rules
and land disposal restrictions. For further information on waste management, consult The Waste
Management Manual for Laboratory Personnel, available from the American Chemical Society
at the address listed in Section 14.2.
16.0 REFERENCES
16.1 U.S. Environmental Protection Agency. Semivolatile Organic Compounds by Gas
Chromatography/Mass Spectrometry (GC/MS). SW-846, Method 8270D. Revision 4.
February 2007. [In: Test Methods for Evaluating Solid Waste, Physical/Chemical
Methods. EPA publication SW-846. Washington DC: U.S. Environmental Protection
Agency, Office of Land and Emergency Management (formerly, Office of Solid Waste
and Emergency Response).]
16.2 U.S. Environmental Protection Agency. Poly chlorinated Dibenzo-p-Dioxins (PCDDS)
and Poly chlorinated Dibenzofurans (PCDFs) by High-Resolution Gas
Chromatography/High Resolution Mass Spectrometry (HRGC/HRMS). SW-846 Method
8290A, Revision 1. February 2007. Washington DC: U.S. Environmental Protection
Agency, Office of Land and Emergency Management.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
16.3 U.S. Environmental Protection Agency. Organic Compounds in Water by
Microextraction.SW-846 Method 3511, Revision 0. November 2002. Washington DC:
U.S. Environmental Protection Agency, Office of Land and Emergency Management.
16.4 U.S. Environmental Protection Agency. SW-846, Solid Phase Extraction (SPE).
Method 3535A, Revision 1. February 2007. Washington DC: U.S.
Environmental Protection Agency, Office of Land and Emergency Management.
16.5 U.S. Environmental Protection Agency. Soxhlet Extraction. SW-846 Method 3540C,
Revision 3. December 1996. Washington DC: U.S. Environmental Protection Agency,
Office of Land and Emergency Management.
16.6 U.S. Environmental Protection Agency. Automated Soxhlet Extraction. SW-846
Method 3541, Revision 0. September 1994. Washington DC: U.S. Environmental
Protection Agency, Office of Land and Emergency Management.
16.7 U.S. Environmental Protection Agency. Pressurized Fluid Extraction (PFE). SW-
846 Method 3545A, Revision 1. February 2007. Washington DC: U.S.
Environmental Protection Agency, Office of Land and Emergency Management.
16.8 U.S. Environmental Protection Agency. Microscale Solvent Extraction (MSE). SW-
846 Method 3570, Revision 0. November 2002. Washington DC: U.S. Environmental
Protection Agency, Office of Land and Emergency Management.
16.9 ASTM. 2011. Method D 1193-06: Standard Specification for Reagent Water. 2011
annual book of ASTM standards. Vol. 11.01: Water and environmental technology.
American Society for Testing and Materials, Philadelphia, PA, pp. 163 - 178.
16.10 U.S. Environmental Protection Agency. Gel-Permeation Cleanup. SW-846 Method
3640A, Revision 1. September 1994. Washington DC: U.S. Environmental Protection
Agency, Office of Land and Emergency Management.
16.11 Patnaik, P. Handbook of Environmental Analysis. Chemical Pollutants in Air, Water,
Soil, and Solid Wastes, Second Edition. 2010. CRC Press, Boca Raton, FL, pp. 593-594.
16.12 U.S. Environmental Protection Agency. EPA Contract Laboratory Program Statement of
Work for Organic Superfund Methods Multi-Media, Multi-Concentration SOM02.3.
Exhibit D-Semivolatile Organic Compounds Analysis. September 2015.
http://www.epa.gov/clp/epa-contract-laboratorv-program-statement-work-organic-
superfund-methods-multi-media-multi-0 (accessed 05/31/2016)
16.13 U.S. Environmental Protection Agency. Determinative Chromatographic Separations.
SW-846 Method 8000C, Revision 3. March 2003. Washington DC: U.S. Environmental
Protection Agency, Office of Land and Emergency Management.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
17.0 TABLES and FIGURES
Table 1
Decafluorotriphenylphosphine (DFTPP) Key Ions and Ion Abundance Criteria
Note: All ion abundances MUST be normalized to m/z of base peak (either 198 or 442).
Mass
Ion Abundance Criteria
51
10.0 - 80.0 % of mass 198
68
Less than 2.0 % of mass 69
69
Present
70
Less than 2.0 % of mass 69
127
10.0 - 80.0 % of mass 198
197
Less than 2.0 % of mass 198
198
Present (see Note, above)
199
5.0-9.0 % of mass 198
275
10.0 - 60.0 % of mass 198
365
Greater than 1.0 % of base peak (198 or 442)
441
Present but less than mass 443
442
Present (see Note)
443
15.0-24.0 %of mass 442
Table 2
Internal Standards (IS) with Corresponding Target and Surrogate (S) Compounds
Assigned for Quantitation
Note: Not all target compounds have been assigned to an internal standard.
(S) = Surrogate
1,4-Dichlorobenzene-d4
Naphthalene-ds
Acenaphthene-dio
Chloropicrin
Dimethylphosphite
1,4-Dithiane
1,4-Thioxane
Bromoform-di (S)
Nitrobenzene-ds (S)
Dichlorvos
Crimidine
Mevinphos
Nicotine
TEPP
2-Fluorobiphenyl (S)
Nicotine-d4 (S)
Phenanthrene-dio
Chrysene-di2
Perylene-di2
Chlorfenvinphos
Chlorpyrifos
Dicrotophos
Disulfoton
Methyl parathion
Parathion
Phencyclidine
Phorate
Phosphamidon
Tetramethylenedisulfotetramine (TETS)
Phencyclidine-ds (S)
Triphenyl phosphate (S)
Terphenyl-di4 (S)
Fenamiphos
Strychnine
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 3
Single-Laboratory Method Detection Limits (MDLs) for Target Compounds in Reagent
Water and Ottawa Sand
Note: Parenthetical data represent cases where the spike level used is greater than 10 times the resulting MDL.
D = Dropped from matrix due to poor performance (see Section 1.2).
Full Scan
Selected Ion Monitoring (SIM)
Analyte
Reagent Water
Ottawa Sand
Reagent Water
Ottawa Sand
(MQ/L)
(|jg/kg)
(HQ"-)
(|jg/kg)
MDL
MDL
MDL
MDL
Chlorfenvinphos
(0.79)
16
0.36
0.63
Chloropicrin
3.6
(18)
0.512
7.0
Chlorpyrifos
0.89
3.8
0.107
0.107
Crimidine
(0.91)
2.1
0.141
0.34
Dichlorvos
0.79
3.2
0.032
0.31
Dicrotophos
(2.2)
9.9
0.086
2.86
Dimethylphosphite
D
93.5
D
12
Disulfoton
0.92
(1.9)
0.100
0.172
1,4-Dithiane
0.79
1.9
0.089
0.180
Fenamiphos
(0.92)
(3.0)
0.141
0.70
Methyl parathion
(1.4)
3.4
0.45
0.63
Mevinphos
(0.92)
2.3
0.165
0.65
Nicotine
4.1
10.0
1.09
15.4
Parathion
(1.3)
3.4
0.34
0.94
Phencyclidine
1.2
3.2
0.091
0.32
Phorate
0.79
1.6
0.031
0.42
Phosphamidon
(1.4)
9.6
0.081
0.047
Strychnine
(9.0)
(32.1)
0.97
1.02
TEPP
2.2
D
1.45
D
TETS
0.89
2.5
0.030
0.058
1,4-Thioxane
0.89
3.9
0.138
0.180
Acronyms:
TEPP-tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 4
Single-Laboratory Estimated Instrument Detection Limits (IDL), Retention Times (RT),
and Characteristic Ions for Target Compounds, Surrogates (S) and Internal Standards
(IS)
Analyte
Quant
Ions
Qualifier
Ions
Full Scan
Selected Ion
Monitoring (SIM)
Retention
Time (RT)
IDL111
(ppm)
Signal:
Noise
(S:N)
RT
IDL'11
(ppm)
S:N
Chlorfenvinphos
267
269, 323, 295
25.57
0.15
6.17
25.55
0.02
4.13
Chloropicrin
117
119, 82, 47
6.04
0.20
4.17
6.02
0.01
5.16
Chlorpyrifos
197
314, 97, 258
24.72
0.09
5.10
24.70
0.01
4.53
Crimidine
142
156, 171, 120
19.58
0.13
3.83
19.60
0.02
4.27
Dichlorvos
109
185, 79, 145
16.01
0.09
3.77
16.09
0.01
4.70
Dicrotophos
127
67, 109, 193
21.43
0.30
5.30
21.50
0.02
3.97
Dimethylphosphite
79
80, 95
7.88
2.00
4.40
9.72
0.1
4.13
Disulfoton
88
97, 142, 186
23.03
0.15
4.13
23.02
.005
4.13
1,4-Dithiane
120
CD
CO
13.18
0.05
4.63
13.16
0.003
4.10
Fenamiphos
303
154, 288, 217
26.36
0.30
4.50
26.37
0.02
3.67
Methyl parathion
109
125, 263, 79
23.91
0.25
4.10
23.91
.02
4.40
Mevinphos
127
192, 109, 67
18.52
0.20
6.43
18.58
0.02
4.23
Nicotine
162
161, 133
17.66
0.20
6.20
17.65
0.04
4.27
Parathion
109
97, 291, 139
24.88
0.20
3.97
24.86
0.02
3.73
Phencyclidine
200
242, 186, 91
24.20
0.09
6.30
24.21
0.005
4.43
Phorate
75
260, 121
21.76
0.13
6.33
21.75
0.005
5.10
Phosphamidon
127
264, 72, 109
23.60
0.25
5.33
23.60
0.02
4.57
Strychnine
334
120, 130, 162
34.84
3.00
5.10
34.83
0.1
4.07
TEPP
161
263, 179, 235
20.20
0.30
4.50
20.19
0.05
3.50
TETS
212
240, 132, 121
22.09
0.10
5.53
22.08
0.002
4.67
1,4-Thioxane
104
46, 61
9.33
0.09
4.93
9.34
0.005
3.60
Bromoform-di (S)
174
93
9.29
NA
NA
9.31
NA
NA
Nitrobenzene-ds (S)
82
128, 54, 70
13.41
NA
NA
13.41
NA
NA
Nicotine-d4 (S)
166
165,136
17.52
NA
NA
17.52
NA
NA
2-Fluorobiphenyl (S)
172
171, 170, 85
17.74
NA
NA
17.74
NA
NA
Phencyclidine-ds (S)
205
171
24.13
NA
NA
24.12
NA
NA
Terphenyl-di4 (S)
244
212, 182
26.76
NA
NA
26.76
NA
NA
Triphenyl phosphate (S)
326
122
28.50
NA
NA
28.47
NA
NA
1,4-Dichlorobenzene-d4 (IS)
152
150
12.08
NA
NA
12.08
NA
NA
Naphthalene-ds (IS)
136
68
15.09
NA
NA
15.08
NA
NA
Acenaphthene-dio (IS)
164
162
19.28
NA
NA
19.27
NA
NA
Phenanthrene-dio (IS)
188
94
22.83
NA
NA
22.81
NA
NA
Chrysene-di2 (IS)
240
120,236
29.18
NA
NA
29.15
NA
NA
Perylene-di2 (IS)
264
260,265
32.69
NA
NA
32.66
NA
NA
Acronyms:
NA = Not available
TEPP-tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
(1) Estimated instrument detection limits (IDLs) were determined in a single laboratory based on concentrations
producing a signal-to-noise (S:N) ratio of at least 3:1.
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 5
Analyte-specific Dwell Times and Ion Grouping for Selected Ion Monitoring (SIM)
Analysis
Ion
Group
Plot
Ion
Scan Rate
(cycles/second)
Ions
Dwell Time
(milliseconds)
1
117.0
2.33
61.0, 66.0, 71.0, 79.0, 80.0, 82.0, 93.0, 94.0, 99.0,
104.0, 117.0, 119.0, 120.0, 128.0, 150.0, 152.0, 174.0
10
2
136.0
4
61.0, 67.0, 68.0, 94.0, 109.0, 136.0, 185.0
20
3
162.0
2.63
67.0, 94.0, 127.0, 133.0, 136.0, 142.0, 156.0, 161.0,
162.0, 164.0, 166.0, 171.0, 172.0, 192.0, 263.0
10
4
127.0
2.17
67.0, 75.0, 94.0, 121.0, 127.0, 212.0, 240.0
50
5
188.0
2.33
88.0, 94.0, 97.0, 109.0, 127.0, 188.0, 197.0, 200.0,
205.0, 242.0, 246.0, 263.0, 264.0, 267.0, 291.0, 314.0,
232.0
10
6
326.0
3.51
120.0, 122.0, 217.0, 240.0, 244.0, 303.0, 325.0, 326.0
20
7
264.0
3.03
120.0, 130.0, 260.0, 264.0, 334.0
50
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 6a
Relative Response Factors (RRF) and Percent RSDs for Initial Calibration of Target
Compounds and Surrogates in Full Scan Mode from a Single-Laboratory Evaluation
Analyte
Calibration
Range
(ppm)
Mean RRF'11
%RSD 121
R2 (3)
Mean RT
Chlorfenvinphos
3.0-20.0
0.182
18.4
0.998
28.02
Chloropicrin
0.5-20.0
0.191
10.0
-
6.01
Chlorpyrifos
0.5-20.0
0.090
14.8
-
24.71
Crimidine
0.5-20.0
0.169
10.4
-
19.57
Dichlorvos
0.5-20.0
0.347
16.1
0.999
15.97
Dicrotophos
3.0-20.0
0.347
20.0
0.998
21.40
Dimethylphosphite
6.0-40.0
0.703
12.2
-
7.28
Disulfoton
0.5-20.0
0.347
16.0
-
23.02
1,4-Dithiane
0.5-20.0
0.596
4.9
-
13.17
Fenamiphos
7.0-20.0
0.172
18.1
0.999
26.36
Methyl parathion
2.0-20.0
0.057
23.0
0.997
23.89
Mevinphos
0.5-20.0
0.117
21.6
0.999
18.49
Nicotine
0.5-20.0
0.084
19.2
0.999
17.51
Parathion
3.0-20.0
0.084
20.9
0.998
24.87
Phencyclidine
0.5-20.0
0.457
16.8
-
24.18
Phorate
0.5-20.0
0.423
16.5
-
21.75
Phosphamidon
3.0-20.0
0.210
21.8
0.997
23.58
Strychnine
10.0-60.0
0.176
13.5
-
34.82
TEPP
1.0-20.0
0.237
20.7
0.998
20.19
TETS
0.5-12.0
0.233
6.9
-
22.08
1,4-Thioxane
0.5-20.0
0.551
7.2
-
9.31
Bromoform-di (S)
0.5-20.0
0.646
8.6
-
9.83
Nitrobenzene-ds(S)
0.5-20.0
1.08
7.2
-
13.89
Nicotine-d4(S)
0.5-20.0
0.090
19.6
-
18.01
2-Fluorobiphenyl (S)
0.5-20.0
1.383
5.5
-
18.22
Phencyclidine-ds(S)
0.5-20.0
0.457
12.4
-
24.63
Terphenyl-d4(S)
0.5-20.0
0.930
7.6
-
27.27
Triphenyl phosphate (S)
0.5-20.0
0.349
20.4
0.999
29.00
Acronyms:
RSD - relative standard deviation
RT - retention time
S - surrogate
TEPP - tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
(1) Mean RRF values calculated as the average of the RRFs for the calibration levels listed in Table 10a. The RRFs
were generated using EQ. 2.
(2)%RSD values are based on single initial calibration (using non-shaded calibration points in Table 10a).
(3) Coefficient of determination or R2 values were calculated by linear regression (see Method 8000C for guidance
based on single replicate analyses across the calibration range) using all shaded and non-shaded calibration points
in Table 10a.
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Table 6b
Relative Response Factors (RRF) and Percent RSDs for Initial Calibration of Target
Compounds and Surrogates in SIM Mode from a Single-Laboratory Evaluation
Analyte
Calibration
Range
(ppm)
Mean RRF111
%RSD 121
Mean RT
Chlorfenvinphos
0.02-1.4
0.116
9.3
25.77
Chloropicrin
0
1
4^
0.051
14.9
6.19
Chlorpyrifos
0.02-1.4
0.078
6.6
24.92
Crimidine
0.01 - 1.4
0.152
9.5
19.77
Dichlorvos
0.01 - 1.4
0.270
9.6
16.20
Dicrotophos
0.05-1.4
0.149
11.6
21.61
Dimethylphosphite
O
LO
I
00
o
0.293
12.4
10.82
Disulfoton
0.01 - 1.4
0.252
8.7
23.32
1,4-Dithiane
0.01 - 1.4
0.588
5.9
13.38
Fenamiphos
0.02-1.4
0.072
7.8
26.57
Methyl parathion
0.02-1.4
0.048
8.3
24.10
Mevinphos
0.05-1.4
0.398
13.8
18.73
Nicotine
0.05-1.4
0.092
10.7
17.77
Parathion
0.02-1.4
0.038
11.7
25.07
Phencyclidine
0.01 - 1.4
0.432
9.1
24.40
Phorate
0.02-1.4
0.316
12.9
21.96
Phosphamidon
0.02-1.4
0.123
8.9
23.69
Strychnine
2.0-15.0
0.110
16.3
34.81
Tetraethyl pyrophosphate (TEPP)
0.2-1.2
0.081
19.9
20.17
Tetramethylenedisulfotetramine (TETS)
0.004-0.8
0.276
6.0
22.29
1,4-Thioxane
0.01 - 1.4
0.530
1.9
9.57
Bromoform-di (S)
0.01 - 1.4
0.585
6.9
9.56
Nitrobenzene-ds(S)
0.01 - 1.4
0.905
5.1
13.64
Nicotine-d4(S)
O
I
4^
0.066
13.6
17.75
2-Fluorobiphenyl (S)
0.01 - 1.4
1.597
4.3
17.97
Phencyclidine-ds(S)
0.01 - 1.4
0.423
5.7
24.38
Terphenyl-d4(S)
0.01 - 1.4
0.907
6.8
27.02
Triphenyl phosphate (S)
0.01 - 1.4
0.324
10.6
28.74
Acronyms:
RSD - relative standard deviation
RT - retention time
S - surrogate
SIM - selected ion monitoring
(1) Mean RRF values calculated as the average of the RRFs for the non-shaded calibration levels listed in Table 10b.
The RRFs were generated using EQ. 2.
(2) %RSD values are based on single replicate analyses across the calibration range (using non-shaded calibration
points in Table 10b).
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Table 7a
Single-Laboratory Matrix Spike Recovery and Relative Percent Difference (RPD) in
Surface and Drinking Water Samples
Note: Matrix spike %recovery and relative percent difference (RPD) ranges are based on the results of 8 samples of
each water type (two replicates at each of two concentration levels in surface and drinking waters).
Analyte
Non-Reference Waters
Full Scan
Selected Ion Monitoring (SIM)
Spike
Level
(HQ"-)
%
Recovery
Range
%
RPD Range
Spike
Level
(MQ/L)
%
Recovery
Range
%
RPD Range
Chlorfenvinphos
172/200
33.3-146
3.1 -48.6
2.86/5.7
61.5-81.1
4.5-27.5
Chloropicrin
28.6/57.1
66.1 - 127
8.4-38.8
2.86/11.4
62.9-126
10.5-41.5
Chlorpyrifos
28.6/57.1
0-154
6.8-21.7
2.86/5.7
42.7-79.3
0.6-43.1
Crimidine
28.6/57.1
52.1 - 105
9.0-20.5
5.7/11.4
75.5-98.2
5.2-10.3
Dichlorvos
28.6/57.1
42.0-93.0
3.8-22.0
2.86/5.7
58.7-77.6
1.8-12.3
Dicrotophos
172/286
22.0-123
7.4-20.6
2.86/5.7
37.8-72.5
0.3-22.1
Disulfoton
28.6/57.1
38.0-112
3.9-57.9
2.86/5.7
54.9-74.5
5.6-17.3
1,4-Dithiane
28.6/57.1
69.9-108
2.8-16.1
0.46/0.9
91.3-104
0-9.1
Fenamiphos
572/686
37.8 - 109
1.8-24.3
2.86/5.7
48.6-71.1
1.1 - 15.4
Methyl parathion
114/286
30.2-141
0.6 37.4
2.86/5.7
55.9-85.1
3.0-22.3
Mevinphos
57.2/114
46.0-104
6.0-27.9
5.7/11.4
56.4-87.4
4.6-14.2
Nicotine
28.6/114
3.5-55.9
3.5-120
5.7/11.4
0-47.1
17.5-56.8
Parathion
286/400
30.3-128
1.3-60.9
2.86/5.7
42.7-78.6
8.0-25.7
Phencyclidine
28.6/57.1
77.1 - 128
-3"
I
o
CO
5.7/11.4
69.6-101
3.0-19.4
Phorate
28.6/57.1
35.0-102
1.9-55.6
2.86/5.7
53.5-76.2
1.2-16.8
Phosphamidon
172/286
36.7-130
0-21.9
2.86/5.7
76.7-140
4.9-24.3
Strychnine
172/343
41.7-210
2.5-28.7
114/229
32.8-108
0.9-41.3
TEPP
57.2/114
0-150
0
1
CD
4^
11.5/22.9
0-157
0.3
TETS
28.6/57.1
45.5-150
7.9-67.5
0.23/0.5
54.7-96.1
6.8-16.2
1,4-Thioxane
28.6/57.1
52.1 - 101
3.0-20.6
2.86/11.4
70.9-84.6
3.3-13.2
Acronyms:
TEPP -tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
54
July 2016
-------
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 7b
Single-Laboratory Matrix Spike Recovery and Relative Percent Difference (RPD) in Soils
Note: Matrix spike %recovery and relative percent difference (RPD) ranges are based on the results of 8 samples of
each soil type (two replicates at each of two concentration levels in EPA Nebraska AP and EPA Georgia Bt2 soils).
Analyte
Non-Reference Soils
Full Scan
Selected Ion Monitoring (SIM)
Spike Level
(mg/kg)
%Recovery
Range
%RPD
Range
Spike Level
(Mg/kg)
%Recovery
Range
%RPD
Range
Chlorfenvinphos
0.3/0.5
90.8-125
0-1.4
5/10
107-294
5.4-25.3
Chloropicrin
5.0/10
11.8-34.5
4.4-47.4
40/80
0-81.5
20.6-200
Chlorpyrifos
0.05/0.1
75.4-107
1.7-12.8
5/10
100-314
0.8-39.2
Crimidine'1'
0.05/0.1
58.9-77.2
1.2-14.2
10/20
49.9-78.0
7.9-9.6
Dichlorvos
0.3/0.5
15.4-87.6
3.1 - 17.0
5/10
26.4-112
4.6-32.9
Dicrotophos
10.0/12.0
0-30.8
0-5.4
5/10
32.3-218
0.3-87.8
Dimethylphosphite
0.3/0.5
4.4-86.7
0.8-15.9
40/80
0
0
Disulfoton
0.01/0.02
59.7-201
0-7.0
5/10
74.2 - 302
1.5-116
1,4-Dithiane
0.05/0.1
58.5-73.1
1.9-12.6
5/10
87.5-122
3.8-33.0
Fenamiphos
1.0/1.2
63.3-87.5
0.4-8.8
5/10
90.8-216
0.9-29.3
Methyl parathion
0.3/0.5
95.7-137
1.7-6.8
50/60
110-348
0.9-84.0
Mevinphos
0.1/0.2
51.5-89.5
2.6-7.1
10/20
57.5-140
5.5-17.1
Nicotine'1'
0.05/0.1
22.8-84.8
1.9-7.4
5/10
66.6-151
0.3-7.6
Parathion
0.3/0.5
72.0-117
0.5-3.7
10/20
141 -221
4.9-15.1
Phencyclidine'1'
0.3/0.5
8.2-63.5
3.8-22.0
5/10
20.5-75.0
2.0-17.4
Phorate
0.05/0.1
59.8-85.4
1.0-9.5
5/10
301 -838
5.7-20.0
Phosphamidon
0.3/0.5
44.1 - 153
0.2-10.1
5/10
57.8-194
6.5-83.0
Strychnine'1'
2.0/3.0
0-26.8
0-5.0
300/600
0-59.8
0.8-19.2
TETS
0.05/0.1
64.4-92.0
0.5-13.8
0.4/1.0
0-69.5
6.9-10.6
1,4-Thioxane
0.05/0.1
43.8-58.8
2.1 - 10.6
5/10
47.7-58.6
3.6-4.9
Acronyms:
TETS - tetramethylenedisulfotetramine
(1) Determined using 2-solvent system (5 % TEA in ethyl acetate).
55
July 2016
-------
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 8a
Single-Laboratory Recovery and Precision in Reagent Water
Analyte
Reagent Water
Full Scan (n=8)
Selected Ion Monitoring (SIM) (n=8)
Spike Level
(HQ"-)
%Recovery
Range
%RSD
Spike Level
(HQ"-)
%Recovery
Range
%RSD
Chlorfenvinphos
172/200
68.2-140
CO
I
LO
LO
2.86/5.7
58.5-94.4
8.8-19.3
Chloropicrin
28.6/57.1
44.1 - 107
15.2-25.9
2.86/11.4
42.2-158
13.0-18.1
Chlorpyrifos
28.6/57.1
66.0-108
2.6-19.6
2.86/5.7
68.5-101
6.1 -9.9
Crimidine
28.6/57.1
67.8-105
4.1 -7.4
5.7/11.4
84.0-116
9.0-9.2
Dichlorvos
28.6/57.1
64.0-98.1
CD
I
CO
LO
2.86/5.7
71.1 -86.3
LO
CO
I
CD
CD
Dicrotophos
172/286
47.3-110
O
CD
I
O
CO
2.86/5.7
48.5-133
5.1 - 19.5
Disulfoton
28.6/57.1
75.1 - 101
3.5-12.4
2.86/5.7
70.3-95.3
CM
I
LO
1,4-Dithiane
28.6/57.1
84.0-108
2.2-2.7
0.46/0.9
99.1 - 119
3.5-10.8
Fenamiphos
572/686
91.8-114
4.0-9.8
2.86/5.7
63.6-88.9
4.9-11.0
Methyl parathion
114/286
116-136
00
CD
I
"3"
2.86/5.7
77.4-147
00
I
00
Mevinphos
57.2/114
59.0-109
co
I
CO
LO
5.7/11.4
54.8-132
5.8-19.2
Nicotine
28.6/114
40.5-168
3.9-11.6
5.7/11.4
29.2-71.8
14.2-1 6.5
Parathion
286/400
71.0-120
4.4-10.3
2.86/5.7
69.0-177
cn
k)
I
CD
Phencyclidine
28.6/57.1
112-164
(J)
CD
I
CO
CO
5.7/11.4
84.5-103
5.0-9.1
Phorate
28.6/57.1
72.0-102
7.1 - 13.2
2.86/5.7
69.6-101
4.9-10.3
Phosphamidon
172/286
70.5-129
3.9-5.9
2.86/5.7
51.0-101
6.2-25.3
Strychnine
172/343
56.9-132
-3"
co
I
CO
CO
114/229
23.1 -59.2
7.8-11.2
TEPP
57.2/114
96.7-152
cn
I
b
11.5/22.9
175-200
o
c\i
I
CM
TETS
28.6/57.1
85.0-133
4.8-11.1
0.23/0.5
30.2-52.8
1.9-11.1
1,4-Thioxane
28.6/57.1
58.0-98.1
4.2-5.4
2.86/11.4
42.8-88.8
CD
I
CD
Acronyms:
RSD - relative standard deviation
TEPP - tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
56
July 2016
-------
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 8b
Single-Laboratory Recovery and Precision in Ottawa Sand
Analyte
Ottawa Sand
Full Scan (n=8
Selected Ion Monitoring (SIM) (n=8)
Spike Level
(mg/kg)
%Recovery
Range
%RSD
Spike Level
(M9'kg)
%Recovery
Range
%RSD
Chlorfenvinphos
0.3/0.5
71.7-110
2.9-15.0
5/10
93.0-111
00
LO
I
CD
Chloropicrin
5.0/10
13.0-25.5
20.7-26.0
40/50
35.5-57.4
10.3-19.5
Chlorpyrifos
0.05/0.1
69.0-78.0
3.5-5.2
5/10
77.2-87.8
2.5-5.3
Crimidine'1'
0.05/0.1
73.0-96.0
3.9-5.2
5/10
70.5-95.8
7.5-11.1
Dichlorvos
0.3/0.5
77.0-89.2
3.6-6.2
5/10
71.8-86.4
3.1 -4.7
Dicrotophos
0.3/0.5
43.0-90.6
8.3-15.0
40/80
53.2-94.2
7.1 - 10.4
Dimethylphosphite
10.0/12.0
91.7-159
6.8-9.5
5/10
41.8-88.1
18.5-19.2
Disulfoton
0.01/0.02
130-210
1.9-2.8
5/10
60.6-69.4
4.6-5.8
1,4-Dithiane
0.05/0.1
66.0-78.0
5.0-5.6
5/10
64.2-74.2
1.8-5.7
Fenamiphos
1.0/1.2
67.4-81.0
3.4-5.2
5/10
52.4-76.0
6.2-8.7
Methyl parathion
0.3/0.5
46.7-71.8
9.7-15.7
50/60
60.6-92.3
7.4-7.6
Mevinphos
0.1/0.2
62.0-77.0
(J)
CO
I
00
LO
10/20
67.6-89.5
3.9-8.9
Nicotine'1'
0.05/0.1
73.0-110
2.4-4.0
5/10
78.9-170
13.9-23.7
Parathion
0.3/0.5
67.3-95.0
5.4-10.6
10/20
66.8-88.0
8.1 -8.6
Phencyclidine'1'
0.3/0.5
64.0-77.0
2.6-5.3
5/10
67.1 -98.6
5.7-6.1
Phorate
0.05/0.1
62.0-70.0
4.4-4.9
5/10
56.0-61.2
2.5-4.3
Phosphamidon
0.3/0.5
33.7-63.0
8.0-13.0
5/10
62.4-103
4.8-18.3
Strychnine11'
2.0/3.0
1.0-4.3
15.5-26.1
300/600
27.1 -51.3
18.0-21.5
TETS
0.05/0.1
74.0-91.0
4.3-8.6
0.4/1.0
76.2-95.3
4.1 -7.1
1,4-Thioxane
0.05/0.1
54.0-67.0
5.2-6.4
5/10
52.4-60.2
3.2-6.3
Acronyms:
RSD - relative standard deviation
TETS - tetramethylenedisulfotetramine
(1) Determined using 2-solvent system (5 % TEA in ethyl acetate).
57
July 2016
-------
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 8c
Single-Laboratory Recovery and Precision in Wipes
Note: Four replicates were analyzed at each of two concentration levels. Ranges of recovery and RSD reflect
evaluations at both concentration levels.
Analyte
Full Scan
Selected Ion Monitorinc
(SIM)
Spike
Levels
(mg/kg)
%Recovery
Range
RSD
Spike Levels
(Mg/kg)
%Recovery
Range
RSD
Chlorfenvinphos
3.0/5.0
77-121
2.5-3.0
0.05/0.10
121 - 159
8.8-13.2
Chlorpyrifos
1.0/2.0
83.0-111
1.5-3.4
0.05/0.10
82.0-99.5
2.8-7.8
Crimidine
0.5/1.0
74.0-84.0
3.7-4.1
0.10/0.20
81.5-105
6.7-10.7
Dichlorvos
0.5/1.0
79.0-84.0
1.2-3.0
0.05/0.10
85.8-103
6.7-8.0
Dicrotophos
3.0/5.0
75.3-116
4.1 4.1
0.05/0.10
94.6-134
5.1 - 17.1
Dimethylphosphite
100/150
72.8-149
3.5-4.2
0.4/0.8
48.6-90.3
10.6-24.4
Disulfoton
0.1/0.5
70.0-80.0
2.2-7.7
0.05/0.10
65.6-77.5
3.4-6.9
1,4-Dithiane
0.5/1.0
72.0-80.0
1.9-3.0
0.05/0.10
75.5-92.8
2.9-6.1
Fenamiphos
10/12.0
87.5-103
1.6-1.9
0.05/0.10
89.6-124
5.6-17.0
Methyl parathion
0.5/1.0
75.0-176
2.4-4.4
0.50/0.60
77.2-107
5.9-16.8
Mevinphos
1.0/2.0
77.0-86.5
1.8-4.2
0.10/0.20
93.1 - 118
8.2-12.3
Nicotine
0.5/1.0
73.0-210
CM
CD
I
O
CO
0.05/0.10
87.9-118
5.4-11.8
Parathion
3.0/5.0
70.0-104
2.9-4.3
0.10/0.20
73.8-114
6.9-20.3
Phencyclidine
0.5/1.0
80.0-140
0.0-1.0
0.05/0.10
84.6-101
5.0-8.7
Phorate
0.5/1.0
73.0-78.0
1.5-2.9
0.05/0.10
59.6-72.6
4.1 -5.2
Phosphamidon
3.0/5.0
78.3-104
3.9-4.3
0.05/0.10
119-168
5.6-11.9
Strychnine
5.0/40.0
73.0-131
2.8-3.6
3.00/6.00
78.7-117
8.9-16.4
TETS
0.5/1.0
90.0-199
8.5-12.2
0.004/0.010
61.8-81.5
1.8-11.5
1,4-Thioxane
0.5/1.0
58.0-62.0
2.1 -3.8
50/100
53.5-89.6
12.5-18.6
Acronyms:
RSD - relative standard deviation
TETS - tetramethylenedisulfotetramine
58
July 2016
-------
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 8d
Single-Laboratory Recovery and Precision in Air Filters
Note: Four replicates were analyzed at each of two concentration levels. Ranges of recovery and RSD reflect
evaluations at both concentration levels.
Analyte
Full Scan
Selected Ion Monitoring (SIM)
Spike
Levels
(mg/kg)
%Recovery
Range
RSD
Spike Levels
(Mg/kg)
%Recovery
Range
RSD
Chlorfenvinphos
3.0/5.0
69.7-122
6.6-13.6
0.05/0.10
86.0-116
5.0-15.1
Chloropicrin
200/250
42.2-68.0
6.2-22.5
0.40/0.50
38.4-67.5
20.8-26.9
Chlorpyrifos
1.0/2.0
71.0-112
6.6-7.7
0.05/0.10
74.6-86.8
1.7-7.1
Dichlorvos
0.5/1.0
67.0-82.0
CD
I
CD
0.05/0.10
70.8-82.6
2.9-7.0
Dicrotophos
3.0/5.0
64.4-96.0
2.3-17.3
0.05/0.10
83.8-105
3.7-9.5
Dimethylphosphite
100/150
52.8-173
4.5-18.9
0.40/0.80
58.1 -85.3
7.3-11.7
Disulfoton
0.1/0.5
48.0-60.0
5.1 - 10.5
0.05/0.10
45.4-54.8
2.1 -5.1
Fenamiphos
10.0/12.0
66.3-93.4
CO
I
CD
c\i
0.05/0.10
56.4-76.5
4.1 - 11.0
Methyl parathion
0.5/1.0
45.0-166
2.4-15.4
0.50/0.60
73.6-92.3
2.3-9.4
Mevinphos
1.0/2.0
65.5-77.5
6.2-7.7
0.10/0.20
78.3-99.0
5.1 -6.7
Parathion
3.0/5.0
61.0-86.8
7.5-14.2
0.10/0.20
67.9-86.0
2.6-10.0
Phencyclidine
0.5/1.0
60.0-144
LO
LO
I
00
0.05/0.10
54.8-78.8
4.2-16.8
Phorate
0.5/1.0
52.0-86.0
3.8-12.8
0.05/0.10
52.8-60.8
LO
CO
I
CO
Phosphamidon
3.0/5.0
57.4-99.0
15.1 - 16.3
0.05/0.10
95.8-109
3.3-4.7
TETS
0.5/1.0
92.0-221
CO
CT»
I
CD
CD
0.004/0.010
73.8-87.3
CO
I
CO
Acronyms:
RSD - relative standard deviation
TETS - tetramethylenedisulfotetramine
59
July 2016
-------
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 9a
Surrogate Recovery in a Single-Laboratory (reagent water and Ottawa sand)
Note: Percent recoveries in this table represent the range of recoveries achieved in a single laboratory for reagent
water (n=8) and Ottawa sand (n=8) samples spiked near the midpoint of the calibration range.
Surrogate
Reagent Water (% Recovery)
Ottawa Sand (% Recovery)
Full Scan
Selected Ion
Monitoring (SIM)
Full Scan
Selected Ion
Monitoring (SIM)
Min
Max
Min
Max
Min
Max
Min
Max
Bromoform-di
84.8
93.2
72.4
88.4
60.2
73.7
46.2
54.9
Triphenyl
phosphate
74.3
102
52.3
60.0
72.9
82.0
57.7
71.6
Phencyclidine-ds
83.6
119
84.4
104
66.6C)
82.2CD
65.3C)
98.6C)
2-Fluorobiphenyl
76.4
89.6
70.0
80.4
70.0
80.1
67.9
79.9
Nitrobenzene-ds
87.8
107
78.4
97.6
76.2
89.0
62.3
74.5
p-Terphenyl-d-M
60.0
109
60.8
90.4
76.4
80.4
71.7
81.2
Nicotine-d4
35.6
98.6
42.9
76.4
76.0C)
92.0C)
104(1)
1140)
(1) Determined using 2-solvent system (5 % TEA in ethyl acetate).
Table 9b
Surrogate Recovery in a Single-Laboratory (surface wipes and air filters)
Note: Percent recoveries in this table represent the range of recoveries achieved in a single laboratory for surface
wipes (n=8) and air filters (n=8) samples spiked near the midpoint of the calibration range.
Surrogate
Surface Wipes (% Recovery)
Air Filters (% Recovery)
Full Scan
SIM
Full Scan
SIM
Min
Max
Min
Max
Min
Max
Min
Max
Bromoform-di
51.2
90.6
21.9
49.4
51.4
78.0
52.9
57.2
Triphenyl phosphate
77.3
95.7
74.6
89.6
71.7
88.3
60.6
78.5
Phencyclidine-ds
81.3
98.9
76.0
103
64.2
77.9
54.6
76.1
2-Fluorobiphenyl
71.6
95.8
60.5
80.1
63.0
87.6
70.1
77.8
Nitrobenzene-ds
79.6
92.4
56.6
79.1
65.5
78.4
62.3
70.6
p-Terphenyl-d-M
71.9
95.3
75.7
89.1
65.2
83.4
66.2
79.8
Nicotine-d4
101
133
77.0
120
80.2
110
39.9
67.9
60
July 2016
-------
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 10a
Calibration Standard Concentrations (ng/|jL) for GC/MS Full Scan
with Split-Splitless Injection
Notes: Shaded cells indicate calibration points that were removed to improve calibration linearity or due to a low S:N
(<10:1). Linearity was achieved by linear regression using all calibration points (both shaded and unshaded cells).
Internal standards are added at a concentration of 10ppm to each calibration standard (see Table 2).
Analyte
Calibration Standard Concentrations (ppm)
1
2
3
4
5
6
7
8
9
10
11
Chlorfenvinphos
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17
20.0
Chloropicrin
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Chlorpyrifos
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Crimidine
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Dichlorvos
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Dicrotophos
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Dimethylphosphite
-
-
-
6.0
10.0
14.0
20.0
24.0
30.0
34.0
40.0
Disulfoton
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
1,4-Dithiane
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Fenamiphos
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Methyl parathion
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Mevinphos
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Nicotine
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Parathion
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Phencyclidine
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Phorate
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Phosphamidon
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Strychnine
3.0
5.0
10.0
15.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
TEPP
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
TETS
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
-
-
1,4-Thioxane
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Bromoform-di (S)
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Nitrobenzene-ds(S)
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Nicotine-d4(S)
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
2-Fluorobiphenyl (S)
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Phencyclidine-ds (S)
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Terphenyl-d4(S)
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Triphenyl phosphate
(S)
0.5
1.0
2.0
3.0
5.0
7.0
10.0
12.0
15.0
17.0
20.0
Acronyms:
TEPP -tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
(S) = Surrogate
61
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 10b
Calibration Standard Concentrations (ng/|jL) for GC/MS Selected Ion Monitoring (SIM)
with Split-Splitless Injection
Notes: Shaded cells indicate calibration points that were removed to improve calibration linearity or due to a low
Signal:Noise (S:N) (<10:1).
Internal standards are added at a concentration of 10ppm to each calibration standard (see Table 2).
Analyte
Calibration Standard Concentration (ppm)
1
2
3
4
5
6
7
8
9
10
11
12
Chlorfenvinphos
-
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Chloropicrin
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Chlorpyrifos
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Crimidine
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Dichlorvos
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Dicrotophos
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Dimethylphosphite
0.4
0.8
1.6
2.0
2.4
3.0
3.4
4.0
4.4
5.0
-
-
Disulfoton
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
1,4-Dithiane
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Fenamiphos
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Methyl parathion
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Mevinphos
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Nicotine
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Parathion
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Phencyclidine
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Phorate
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Phosphamidon
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Strychnine
0.5
1.0
2.0
4.0
6.0
8.0
10.0
12.0
15.0
-
-
-
TEPP
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
-
-
-
TETS
0.004
0.01
0.02
0.05
0.1
0.2
0.3
0.4
0.5
0.6
0.8
-
1,4-Thioxane
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Bromoform-d (S)
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Nitrobenzene-ds(S)
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Nicotine-d4(S)
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
2-Fluorobiphenyl (S)
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Phencyclidine-ds(S)
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Terphenyl-d4(S)
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Triphenyl phosphate (S)
0.01
0.02
0.05
0.1
0.2
0.4
0.5
0.6
0.8
1.0
1.2
1.4
Acronyms:
TEPP-tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
(S) - Surrogate
62
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 11a
Single-Laboratory Quantitation Limit (QL) Results and Low Calibration Standard
Concentrations in Reagent Water Using Full Scan Analysis
Analyte
Low
Calibration
Standard 111
(HQ"-)
QL121
(Hg'L)
%Recovery
Range at QL
Precision at QL
(%RSD)
Chlorfenvinphos
171
171
68.2-77.5
5.5
Chloropicrin
28.6
57.1
57.1 - 107
25.9
Chlorpyrifos
28.6
28.6
99.8-106
2.6
Crimidine
28.6
28.6
67.8-80.1
7.4
Dichlorvos
28.6
28.6
64.0-75.9
7.6
Dicrotophos
171
286
47.3-54.0
6.0
Disulfoton
28.6
28.6
78.0-84.0
3.5
1,4-Dithiane
28.6
28.6
84.0-87.8
2.2
Fenamiphos
400
571
91.8-114
9.8
Methyl parathion
114
114
120-123
1.4
Mevinphos
28.6
57.1
59.0-68.9
7.3
Nicotine
28.6
ND
ND
ND
Parathion
171
286
71.0-78.7
4.4
Phencyclidine
28.6
57.1
112-120
3.3
Phorate
28.6
28.6
72.0-83.9
7.1
Phosphamidon
171
171
70.5-81.0
5.9
Strychnine
571
571
122- 132(3)
3.3(3)
TEPP
57.1
57.2
96.7-99.0
1.5
TETS
28.6
28.6
105-133
11.1
1,4-Thioxane
28.6
28.6
58.0-64.0
4.2
Acronyms:
ND - not determined (at least one of the criteria described in Section 9.8 was not met)
TEPP - tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
C) Low calibration standard adjusted to reflect sample concentration assuming 100 % extraction efficiency.
(2) QL meets all criteria described in Section 9.8.
(3) Precision and recovery correspond to 171 |jg/L for strychnine. Strychnine showed good precision and recovery
at this level; however, the level was well below the lowest calibration point used.
63
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 11b
Single-Laboratory Quantitation Limit (QL) Results and Low Calibration Standard
Concentrations in Reagent Water Using SIM Analysis
Analyte
Low
Calibration
Standard 111
(HQ"-)
QL121
(Hg'L)
%Recovery
Range at QL
Precision at QL
(%RSD)
Chlorfenvinphos
1.14
2.86
81.8-94.4
00
CO
Chloropicrin
5.71
ND
NA
NA
Chlorpyrifos
1.14
2.86
68.5-79.4
6.1
Crimidine
2.86
5.71
96.3-116
9.2
Dichlorvos
0.57
2.86
73.8-85.0
6.6
Dicrotophos
2.86
2.86
118-133
5.1
Disulfoton
0.57
2.86
70.3-82.5
7.2
1,4-Dithiane
0.57
0.57
99.1 - 124
10.8
Fenamiphos
1.14
2.86
63.6-80.1
11.0
Methyl parathion
1.14
2.86
132-147
4.8
Mevinphos
2.86
5.71
115-132
5.8
Nicotine
2.86
5.71
50.6-71.8
14.2
Parathion
1.14
5.71
69.0-85.3
9.1
Phencyclidine
0.57
5.71
87.7-99.1
5.0
Phorate
1.14
2.86
69.6-84.3
10.3
Phosphamidon
1.14
2.86
88.5-101
6.2
Strychnine
114
ND
ND
ND
Tetraethyl pyrophosphate (TEPP)
11.4
ND
ND
ND
Tetramethylenedisulfotetramine (TETS
0.23
0.46
50.0-52.8
1.9
1,4-Thioxane
0.57
2.86
80.4-88.8
4.6
Acronyms:
ND - not determined (at least one of the criteria described in Section 9.8 was not met.)
RSD - relative standard deviation
SIM - selected ion monitoring
(1) Low calibration standard adjusted to reflect sample concentration assuming 100 % extraction efficiency.
(2) QL meets all criteria described in Section 9.8.
64
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 12a
Single-Laboratory Quantitation Limit (QL) Results and Low Calibration Standard
Concentrations in Ottawa Sand Using Full Scan Analysis
Analyte
Low
Calibration
Standard
(1)
(mg/kg)
QL'21
(mg/kg)
%Recovery
Range at QL
Precision at QL
(%RSD)
Chlorfenvinphos
0.3
0.3
71.7-96.7
15.0
Chloropicrin
0.05
ND
ND
ND
Chlorpyrifos
0.05
0.05
69.0-75.0
3.5
Crimidine
0.05
0.05C4)
86.0-96.0
5.2
Dichlorvos
0.05
0.3
80.7-87.7
3.6
Dicrotophos
0.3
0.5
74.8-90.6
8.3
Dimethylphosphite
0.6
12.0
91.7-108
6.8
Disulfoton
0.05
0.05
130- 135C3)
1.9(3)
1,4-Dithiane
0.05
0.05
70.0-78.0
5.0
Fenamiphos
0.7
1.0
67.4-72.0
3.4
Methyl parathion
0.2
0.5
58.2-71.8
9.7
Mevinphos
0.05
0.1
65.0-69.0
5.8
Nicotine
0.05
0.05C4)
100-110
4.0
Parathion
0.3
0.3
67.3-83.7
10.6
Phencyclidine
0.05
O.3C4)
73.0-77.0
2.6
Phorate
0.05
0.05
62.0-70.0
4.9
Phosphamidon
0.3
0.5
52.8-63.0
8.0
Tetramethylenedisulfotetramine (TETS)
0.05
0.05
74.0-90.0
8.6
1,4-Thioxane
0.05
0.05
54.0-62.0
6.4
Acronyms:
ND - not determined (at least one of the criteria described in Section 9.8 was not met.)
RSD - relative standard deviation
(1) Low calibration standard adjusted to reflect sample concentration assuming 100 % extraction efficiency.
(2)QL meets all criteria described in Section 9.8.
(3) Precision and recovery correspond to 0.02 mg/kg. Disulfoton showed good precision and recovery at this level;
however, the level was below the lowest calibration point used. The QL should be at or above the concentration of
the lowest calibration standard. Recovery and precision at a spike of 0.02 mg/kg are shown for illustrative
purposes.
(4) Determined using 2-solvent system (5 % TEA in ethyl acetate).
65
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 12b
Single-Laboratory Quantitation Limit (QL) Results and Low Calibration Standard
Concentrations in Ottawa Sand Using SIM Analysis
Analyte
Low
Calibration
Standard 111
(Hg/kg)
QL'21
(Hg"
-------
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 13a
Single-Laboratory Study Water Matrix Characterization Data
Information
Reagent Water
Matrix
Surface Water
Drinking Water
Source Name
Deionized Water
Germany Creek,
WA
Tap Water
Source Location
Columbia Analytical,
WA
Germany Creek,
WA
Columbia Analytical,
WA
Collection Date
8/6/2009
8/6/2009
12/1/2009
Weight/Volume
500 mL
5 gallons
500 mL
pH
6.52
7.96
7.14
Total Organic Carbon (TOC) Content
<0.5 mg/L
1.5 mg/L
0.78 mg/L
Chlorine
<0.2 mg/L
5.7 mg/L™
0.9-1.1 mg/L <2'
Total Suspended Solids (TSS)
<5.0 mg/L
<5.0 mg/L
<5.0 mg/L
(1) High level of CI" reported for this matrix is possibly due to tidal effects.
(2) Range of CI" reported over a five-day period after study completion.
Table 13b
Multi-Laboratory Exercise Water Matrix Characterization Data
Information
Value
Source Name
Lab Tap Water
Source Location
ERA Laboratory, Golden, CO
Collection Date
6/19/2014
Alkalinity as CaCC>3
42.7 mg/L
Calcium Hardness as CaCC>3
49.3 mg/L
Specific Conductance at 25 °C
209 mg/L
pH
7.84
Total Hardness as CaCC>3
68.0 mg/L
Total Organic Carbon (TOC)
2.68 mg/L
Total Residual Chlorine
0.04 mg/L
Table 14
Single-Laboratory Study Soil Matrix Characterization Data
Information
Georgia Bt2 soil
Nebraska Ap soil
Calcium
NA
15.4 mEq/100g
Magnesium
NA
4.9 mEq/100g
Cation Exchange Capacity
NA
26.3 mEq/100g
PH
5.0
5.6
Total Organic Carbon (TOC)
0.2 %
2.1 %
Sand
46 %
6 %
Silt
22 %
60 %
Clay
32 %
34 %
Acronyms: NA- not available
67
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table 15
Multi-laboratory Reagent Water Results for Dichlorvos, Mevinphos,
Tetramethylenedisulfotetramine (TETS) and
Associated Surrogates
Analyte
Spike
Concentration
(Mfl/L)
n(1>
Avg Recovery
(%)
Minimum
Recovery
(%)
Maximum
Recovery
(%)
Pooled RSD
(%)
Low-Level Spike
Dichlorvos
28.6
49
102
54.0
150
7.3
Mevinphos
28.6
48
112
65.9
161
9.7
TETS
28.6
49
101
76.9
140
8.0
Mid-Level Spike(2)
Dichlorvos
571
40
106
70.6
140
5.0
Mevinphos
571
41
99.3
71.9
124
5.8
TETS
571
40
98.2
81.8
126
5.0
Surrogate
Spike
Concentration
(jig/Lp
n<4>
Avg Recovery
(%)
Minimum
Recovery
(%)
Maximum
Recovery
(%)
RSD (%)
2-Fluorobiphenyl
571
80
102
61.6
137
20.9
Nitrobenzene-ds
571
80
98.9
66.3
131
16.1
Terphenyl-di4
571
81
110
64.3
140
19.3
(1) Number of analyte results used to develop performance data, after outlier removal.
(2> Four replicates from one laboratory were spiked at 286 |jg/L.
(3) Surrogates were spiked at this level in all low-and mid-level samples.
(4> Number of surrogate results across both analyte spike levels, after outlier removal.
Table 16
Multi-laboratory Drinking Water Results for Dichlorvos, Mevinphos,
Tetramethylenedisulfotetramine (TETS) and
Associated Surrogates
Analyte
Spike
Concentration
(HQ"-)
n(1>
Avg Recovery
(%)
Minimum
Recovery
(%)
Maximum
Recovery
(%)
Pooled RSD
(%)
Low-Level Spike
Dichlorvos
114
32
59.0
38.6
83.1
10.6
Mevinphos
114
32
97.3
53.5
153
13.6
TETS
114
32
91.4
75.6
114
5.7
Mid-Level Spike
Dichlorvos
571
31
62.1
44.0
83.5
14.1
Mevinphos
571
32
103
76.0
155
14.6
TETS
571
31
87.2
72.5
103
12.8
Surrogate
Spike
Concentration
(Mg/Lp
n(3)
Avg Recovery
(%)
Minimum
Recovery
(%)
Maximum
Recovery
(%)
RSD (%)
2-Fluorobiphenyl
571
80
106
73.7
131
10.9
Nitrobenzene-ds
571
80
102
71.9
127
12.0
Terphenyl-di4
571
80
113
81.4
158
10.2
(1> Number of analyte results used to develop performance data, after outlier removal.
(2) Surrogates were spiked at this level in all low-and mid-level samples.
(3> Number of surrogate results across both analyte spike levels, after outlier removal.
68
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Abundance
2100000
2000000
1900000
1800000
1700000
1600000
1500000
1400000
1300000
1200000
1100000
1000000
900000
800000
700000
600000
500000
400000
300000
200000
100000
oW
rime->
CO J2
9-
c H
o Q)
2-'^
2 o.
II
o o.
si
e .2
i:-
o
.2 CD
x: jo
.t: o
Q -t
4 iz
6.00 8.00 10.00 12.00 14 00 16 00
1800
— CL
CL 0)
n «=-
fM?
20 00
o x:
!E O
JJ.
-M
Lr4-r
2200 2400 2600 28.00 30.00 32.00 34.00 3600
Acronyms:
T - Target
S - Surrogate
I - Internal standard
TETS - tetramethylenedisulfotetramine
TEPP - tetraethyl pyrophosphate
Concentrations of all analytes as described in Table 10a, Calibration Level 7.
Figure 1.
Gas chromatogram of a midpoint calibration standard.
69
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Top image: Expanded view of DMP peak from chromatogram of Calibration Level 7 (see Table 10a), with DMP
spiked at 20 pg/mL. Manual integration set from 5.80 to around 6.80 minutes.
Bottom image: Mass spectral fragmentation pattern for DMP, showing abundance ratios for quantitation ion (79 m/z)
and qualifier ions (80 and 90 m/z). Exp% = Experimental ion abundance percentage based on NIST library data.
Act% = Actual ion abundance percentage based on analysis of calibration standard.
Figure 2.
Peak requiring manual integration due to peak tailing - dimethylphosphite (DMP).
70
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Abundance
250000|
200000j
150000;
100000
50000 j
ol
Time-->
1648
15.40
15.60 15.80
1 ''I '
16.00
I i ' ' 1 I 1 ' 1 ' I 1 1 ' ' I 1
16.20 16.40 16.60 16.80 17.00 17.20
17.40
17,60
Abundance
150000
100000
127
50000
109
192
n/z~>
30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230
(17) Mevinphos (T)
16.48min 11,55ug/ml m
response 291760
Ion Exp% Act%
127.10 100 100
192.10 27.30 27.29
109.10 26.10 26.09
6710 14.00 1402
Top image: Expanded view of mevinphos peaks from chromatogram of Calibration Level 7 (see Table 10a). with
mevinphos spiked at 10 pg/mL. Manual integration set from 15,98 to around 16.98 minutes combining two isomers of
mevinphos (retention times of 16.43 and 16.48).
Bottom image: Mass spectral fragmentation pattern for mevinphos (both isomers), showing abundance ratios for
quantitation ion (127.1 m/z) and qualifier ions (192.1, 109.1 and 67.1 m/z). Exp% = Experimental ion abundance
percentage based on NIST library data. Act% = Actual ion abundance percentage based on analysis of calibration
standard.
Figure 3.
Peak requiring manual integration due to closely eluting isomers - mevinphos.
71
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Abundance
120000!
100000 J
800001
60000 J
40000
21.58
20000 {
O'iO I I ~ T r ¦ i ... r 1—T T^i Tr I ' ~r 'T - "I r ^ ]
A
rime~> 19.80 20.00 20.20 20.40 20.60 20.80 21.00 21.20 21.40 21.60 21.80 22.00 22.20 22.40 22.60
Abundance
70000'
60000
50000
40000
30000
20000
10000
0
i;:7
43
-t1!#.',-, r-t1
119 ,
I'l'l I I iTJ'!1!
264
138
147
rrti-n-
158
172
I1] i l'i 111'l'i
193
227
236
•'I'1'' I' •1 ti i ¦ " | i
Tl/z-> 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270
(25) Phosphamidon (T)
21.58min 15 74ug/ml m
response 165797
Ion Exp% Act%
127.10 100 100
264.10 42.40 42.37
72.20 38.70 38.65
109.10 28.80 28.78
Top image: Expanded view of phosphamidon peaks from chromatogram of Calibration Level 7 (see Table 10a), with
phosphamidon spiked at 10 pg/mL. Manual integration set from 21.08 to around 22.08 minutes combining two
isomers of phosphamidon (retention times of 21.58 and 21.90).
Bottom image: Mass spectral fragmentation pattern for phosphamidon (both isomers), showing abundance ratios for
quantitation ion (127.1 m/z) and qualifier ions (264.1, 72.2 and 109,1 m/z). Exp% = Experimental ion abundance
percentage based on NIST library data. Act% = Actual ion abundance percentage based on analysis of calibration
standard.
Figure 4.
Peak requiring manual integration due to closely eluting isomers - phosphamidon.
72
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Abundance
140000!
120000!
100000 <
80000
60000:
40000
20000!
0>.
Time—>
23.56
-A-
~r
~T~
22.40
22.60 22.80 23.00 23.20
23.40
23.60 23.80 24.00 24.20 24.40 24 60
Abundance
80000
60000;
40000I
20000!
267
323
81
109
91
45
65
7lfe-->
40
60
80
V1
123
I, 135
JjL, &
170
295
145
159
193 206
feoU
l, 222 235 249
284
100 120
140 160 180 200 220 240 260 280 300 320
358
340 360
(32) Chlorfenvinphos (T)
23.56min 13.80ug/ml m
response 151495
Ion Exp% Act%
267.00 100 100
269.00 65 90 65.92
323.00 65 00 64.97
295 00 20,70 20.69
Top image: Expanded view of chlorfenvinphos peaks from chromatogram of Calibration Level 7 (see Table 10a), with
chlorfenvinphos spiked at 10 pg/mL. Manual integration set from 23.06 to around 24.06 minutes combining three
isomers of chlorfenvinphos (retention times of 23.35, 23.49 and 23.56).
Bottom image: Mass spectral fragmentation pattern for chlorfenvinphos (all three isomers), showing abundance ratios
for quantitation ion (267.0 m/z) and qualifier ions (269,0, 323.0 and 295.0 m/z). Exp% = Experimental ion abundance
percentage based on NIST library data. Act% = Actual ion abundance percentage based on analysis of calibration
standard.
Figure 5.
Peak requiring manual integration due to closely eluting isomers - chlorfenvinphos.
73
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
APPENDIX: ALTERNATE SAMPLE PREPARATION PROCEDURES
Appendix A is provided as an addendum to the procedures and equipment described in the analytical
protocol, and provides a description of alternative equipment and procedures that have undergone
preliminary evaluation in a single laboratory or have not been evaluated at all, but may be appropriate for
certain analytes, based on other methods or studies. Results using some of these procedures are provided
for informational purposes.
A1.0 EQUIPMENT
Note: The equipment listed in Appendix A is needed specifically for the procedures described in
the appendix, in addition to equipment listed in Section 6.0 of the protocol. Manufacturer
instruction manuals should be consulted if using equipment other than the equipment specified in
this appendix.
A1.1 Pressurized Fluid Extraction (PFE) Device for Soils, Wipes, and Air Filters - Dionex®
Accelerated Solvent Extractor (ASE-300; Thermo Fisher Scientific Inc., Sunnyvale,
CA) or equivalent, with appropriately sized extraction cells. Currently, 100-mL cells
are available that will accommodate samples greater than 30 grams. Cells should be
made of stainless steel or other material capable of withstanding the pressure
environments (2000+ psi) necessary for this procedure. Other system designs may be
used, provided that adequate performance can be demonstrated for the analytes and
matrices of interest.
A1.2 Automated Soxhlet Extraction System for Soils
A1.2.1 Automated Soxhlet extraction system with temperature controlled bath, such as
Soxtec™ HT 6 (Foss, Eden Prairie, MN) or equivalent
A1.2.2 Cellulose or glass extraction thimble - 26 mm ID x 60 mm, contamination
free
A1.2.3 Glass extraction cups (80 mL) - compatible with extraction system
A1.2.4 Thimble adapters - compatible with extraction system
A1.2.5 Viton seals - compatible with extraction system
A1.3 Solid-phase Extraction (SPE) for Water Samples
Note: A manual system with syringe adaptors that fit the top of the SPE tubes is
recommended for accurate control of pressure (flow).
A1.3.1 Horizon SPE-DEX® 4790 Automated Solid Phase Extractor (Horizon
Technology, Salem, NH) or equivalent
A1.3.2 SPE disks - JT Baker® divinylbenzene (DVB) (Avantor Performance Materials,
Center Valley, PA) or equivalent
A-l
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
A1.3.3 Multilayer glass microfiber filter - Whatman GMF 150 or equivalent
A2.0 REAGENTS
Note: The reagents listed in Appendix A are needed specifically for the procedures described in
the appendix, in addition to reagents listed in Section 7.0 of the protocol.
A2.1 Methanol (used in SPE Procedure)
A2.2 Solutions for adjusting the pH of samples before extraction
Note: Check the pH of water samples prior to adding acid or base solution as acid
preservation may have been performed in the field.
A2.2.1 Sulfuric acid (H2SO4) solution (1:1 v/v) - Slowly add 50 mL of concentrated
sulfuric acid (specific gravity 1.84) to 50 mL of organic-free reagent water.
A2.2.2 Sodium hydroxide (NaOH) solution (ION) - Dissolve 40 grams NaOH in
organic-free reagent water and dilute to 100 mL.
A2.3 Hydromatrix™ (recommended drying agent for PFE) - Diatomaceous earth-based
material rinsed with dichloromethane (DCM) and dried at 400 °C for 4 hours in a shallow
tray, cooled in a desiccator, and stored in a glass bottle. (Hydromatrix is a product of
Agilent Technologies, Santa Clara, CA.)
A-3.0 ALTERNATE WATER SAMPLE PREPARATION TECHNIQUES (i.e., SOLID-
PHASE EXTRACTION [SPE])
A3.1 Preparation of Water Samples by Solid Phase Extraction (SPE)
Data characterizing the procedure described for SPE of water samples are limited. The
procedure is provided as an alternative in the event that larger sample volumes are
necessary to address lower concentrations.
Note: Preliminary evaluations showed poor extraction of chloropicrin, nicotine,
phencyclidine, TEPP, and 1,4-thioxane. For this reason, SPE was not thoroughly
evaluated during the single-laboratory study.
A3.1.1 Measure 1 L of sample and adjust the pH to ~4 using small amounts of H2SO4
(1:1 v/v in water) or 10N NaOH solution.
Note: Preliminary single-laboratory results have shown that adjusting the pH to
8 improves the recoveries for the following compounds: chloropicrin, nicotine,
phencyclidine and tetraethyl pyrophosphate (TEPP). Therefore, it is
recommended that the pH be adjusted to 8 if analyzing for these compounds.
A3.1.2 Place a Whatman® GMF 150 (Whatman, Maidstone, UK) on top of the
divinylbenzene (DVB) disk prior to clamping the glass reservoir into the filter
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
apparatus. Wash the extraction apparatus and disk with 25 mL of each solvent
(see Prep/Rinse program below) rinsing down the sides of the reservoir. Pull a
small amount of solvent through the disk with a vacuum. Turn off the vacuum
and allow the disk to soak for approximately one minute. Pull the remaining
solvent through the disk and allow the disk to dry.
Sample Prep/Rinse Program:
Solvent Soak Time Dry Time
Prewet 1 - DCM 1:30 minutes 0:30 minute
Prewet 1 - DCM 1:30 minutes 0:30 minute
Prewet 2 - Acetone 1:30 minutes 0:30 minute
Prewet 3 - Methanol 1:30 minutes 0:30 minute
Prewet 4 - Deionized (DI) Water 0:10 minute 0:10 minute
A3.1.3 Add the sample to the reservoir. Under full vacuum, filter as quickly as the
vacuum will allow, but for a minimum of 10 minutes. After the sample has
passed through the disk, dry the disk by maintaining vacuum for an additional 5
minutes.
A3.1.4 Remove the entire filter assembly without dismantling from the manifold. Insert
a collection tube with sufficient capacity to hold the elution solvents and prevent
splattering when the vacuum is applied.
A3.1.5 Add 8.0 mL of acetone to the disk. Allow the acetone to spread evenly over the
disk. Quickly turn the vacuum on and off to pull the first few drops of acetone
through the disk. Allow the disk to soak for 15 to 20 seconds before proceeding.
CAUTION: From this point until the extraction is completed, the surface of the
disk should not be allowed to go dry.
A3.1.6 Add 8.0 mL of DCM to the sample bottle (or container used to measure sample
volume). Rinse thoroughly, transferring the contents to the acetone soaked disk
using a disposable pipette and rinsing down the sides of the reservoir in the
process. Draw approximately one-half the solvent through the disk and then
release the vacuum. Allow the remaining solvent to soak the disk and any
particulate matter present for approximately one minute before applying a
vacuum to draw the remaining solvent through the disk.
A3.1.7 Repeat Step A3.1.6 with an additional 8.0 mL of DCM, collecting the solvent in
the same collection tube.
A3.1.8 Proceed to Section 11.6 for extract concentration.
A3.2 Single-laboratory Results for SPE
Table A1 provides a comparison of results for reagent water extraction using the
procedures described in A3.1 (SPE at pH = 4 and pH = 8) and Section 11.2.1 (microscle
solvent extraction [MSE]). For a majority of the analytes, MSE procedures gave the
highest recoveries; however, SPE (pH = 4) gave better recoveries for chlorpyrifos,
disulfoton, methyl parathion, parathion, and phorate. SPE (pH = 8) gave the best results
for nicotine.
A-3
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table A1.
Mean Percent Recovery and Relative Percent Difference (RPD) Results of Duplicate Water Sample
Extractions
Note: Bold entries indicate recovery was within 70-130 % and RPD was less than 25.
SPE (pH = 4)
SPE (pH = 8)
MSE (pH = 4) I
Analyte
Spike
(Hg'L
)
Mean %
Recovery
RPD
Spike
(M9'L)
Mean %
Recovery
RPD
Spike
(Hg'L
)
Mean %
Recovery
RPD
4-Aminopvridine
25.0
Not detected
25.0
Not detected
714
Not detected I
Chlorfenvinphos
12.0
79.5
7.9
12.0
72.8
5.8
343
68 I
3
3-MCPD
20.0
Not detected
20.0
Not detected
571
Not detected I
Chloropicrin
10.0
Not detected
10.0
6.2
110
286
71
1
Chlorpvrifos
10.0
96.0
6.8
10.0
78.6
6.9
286
80
5
Crimidine
10.0
78.6
2.4
10.0
74.8
9.9
286
93
10
Dichlorvos
10.0
77.4
5.9
10.0
66.9
7.2
286
92
10
Dicrotophos
12.0
64.8
13.6
12.0
47.0
6.7
343
51
4
Dimethvlphosphite
20.0
Not detected
20.0
Not detected
571
Not detected I
Disulfoton
10.0
93.9
5.8
10.0
79.4
8.3
286
80
0
1,4-Dithiane
10.0
69.9
1.4
10.0
61.1
11.3
286
77
34
Fenamiphos
15.0
79.0
0.8
15.0
68.7
5.8
429
80
8
Methyl parathion
10.0
114
12.4
10.0
64.9
7.7
571
62
0
Mevinphos
10.0
85.0
2.7
10.0
72.2
15.5
286
87
12
Nicotine
10.0
Not detected
10.0
60.3
0.8
286
49
8
Parathion
12.0
90.8
11.0
12.0
68.6
6.0
343
64
0
Phencvclidine
10.0
7.3
16.4
10.0
57.2
18.0
286
102
6
Phorate
10.0
91.7
5.3
10.0
77.6
10.8
286
80
1
Phosphamidon
12.0
70.0
6.8
12.0
69.5
6.4
343
82
5
Strychnine
50.0
Not detected
50.0
Not detected
1430
Not detected I
TEPP
20.0
16.0
34.6
20.0
31.2
10.6
571
87
0
TETS
5.0
80.8
1.5
5.0
71.5
11.5
143
98
8
1,4-Thioxane
10.0
13.2
33.3
10.0
12.4
15.4
286
78
3
All Analytes
53.0 ±40.5
52.0 ±28.7
69 ± 27
Bromoform-di
10
67.0
4.0
10.0
1.0
6.9
286
94
5
Nitrobenzene-ds
10
98.0
5.1
10.0
83.4
10.0
286
122
8
Nicotine-d4
10
Not detected I
10.0
68.8
4.9
286
57
4
2-Fluorobiphenyl
10
I 88.3
I 4.4 |
10.0
75.4
8.1
286
91
0
Phencvlidine-ds
10
Not detected I
10.0
52.1
21.3
286
97
4
Terphenvl-di4
10
71.1
2.4
10.0
35.7
3.4
286
73
9
Triphenvl phosphate
10
75.1
3.6
10.0
29.6
2.4
200
33
11
All Surrogates
68.6 ±29.8
43.4 ± 31.9
77 ± 30
Number of Target Analytes Within 70-130 % Recovery
Target Recovery
SPE (pH 4)
SPE (pH 8)
MSE (pH 4)
Range (70-130 %)
12
6
14
Acronyms:
MSE - microscale solvent extraction
SPE - solid phase extraction
TEPP-tetraethyl pyrophosphate
TETS - tetramethylenedisulfotetramine
A-4
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
A4.0 ALTERNATE SOIL SAMPLE PREPARATION TECHNIQUES
A4.1 Preparation of Solid Samples by Automated Soxhlet Extraction
A4.1 1 The laboratory may use either automated or non-automated Soxhlet extraction.
Check the heating oil level in the automated Soxhlet unit and add oil if needed.
Follow the manufacturer's instructions to set the temperature on the service unit.
Open the cold water tap for the flux condensers and adjust the flow to prevent
solvent loss through the condensers. Transfer the entire sample, including
sodium sulfate drying agent (2:1 w/w drying agent:sample), to the thimble. Add
a sufficient amount of the surrogate standard spiking solution to result in the
addition of 10 (ig of each surrogate to the sample.
A4.1.2 Immediately transfer the thimbles containing the weighed samples into the
condensers. Adjust the heat to boil the solvent. Position the thimble just below
the condenser valve. Insert the extraction cups containing boiling chips, and load
each cup with appropriate volume of extraction solvent (1:1 v/v DCM/acetone).
Clamp the cups into position.
Note: The Viton® seals must be pre-rinsed or pre-extracted with extraction
solvent prior to initial use.
A4.1.3 Immerse the thimbles in DCM/acetone (1:1 v/v). Set the timer for 60 minutes.
The condenser valves must be in the "OPEN" position. Extract for the preset
time. Move the thimbles to rinsing position above the solvent surface. Set the
timer for 60 minutes, leaving the condenser valves open. Extract for the preset
time. After rinse time has elapsed, close the condenser valves. When all but 2 -
5 mL of the solvent have been collected, open the system and remove the cups.
Transfer the contents of the cups to graduated, conical-bottom glass tubes.
Rinse the cups with DCM and add the rinsates to the glass tubes. Proceed to
Section 11.6.
A4.2 Preparation of Solid Samples by Pressurized Fluid Extraction (PFE)
A4.2.1 Transfer the entire sample, including Hydromatrix drying agent (1:1 w/w drying
agent: sample) (Section A2.3), to an extraction cell of the appropriate size for
the aliquot. Add sufficient amount of the surrogate standard spiking solution to
result in the addition of 10 (ig of each surrogate to the sample.
A4.2.2 Place the extraction cell into the instrument or autosampler tray, as described by
the instrument manufacturer. Place a pre-cleaned collection vessel in the
instrument for each sample, as described by the instrument manufacturer. The
total volume of the collected extract will depend on the specific instrument and
the extraction procedure recommended by the manufacturer, and may range
from 0.5 - 1.4 times the volume of the extraction cell. Ensure that the
collection vessel is sufficiently large to hold the extract. The following are
recommended extraction conditions:
Oven temperature:
Pressure:
100 °C
1500-2000 psi
A-5
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Nitrogen purge:
60 seconds at 150 psi (purge time may be extended for
larger cells)
60 % of the cell volume
2
Flush volume:
Static cycles:
Static time:
10 minutes (after 5 minutes, pre-heat equilibration)
A4.2.3 Optimize the extraction conditions as needed, according to the manufacturer's
instructions. An appropriate amount of 1:1 (v/v) acetone/DCM should be used to
achieve the extraction conditions detailed in the preceding paragraph. Once
established, the same pressure should be used for all samples in the same batch.
Begin the extraction according to the manufacturer's instructions. Collect each
extract in a clean vial. Allow the extracts to cool after the extractions are
complete. Proceed to Section 11.6.
A4.3 Single-Laboratory Results for Alternate Soil Preparation Techniques
Table A2 provides a comparison of results for Ottawa sand extractions by microscale
solvent extraction (MSE; see protocol Section 11.3.5) and automated Soxhlet extraction
(A4.1), each using two different solvent systems, and by PFE (A4.2). The procedure for
MSE (2-solvent) involved extraction with only 5 % triethylamine (TEA)/ethyl acetate,
while the procedure for MSE (3-solvent) involved extraction with acetone:DCM:ethyl
acetate (1:2:1) followed by extraction with 5 % TEA/ethyl acetate. Note that the results
for MSE (3-solvent) in Table A2 were generated using the procedure described in
protocol Section 11.3.5 (triplicate extraction using the 3-solvent system, followed by
single extraction using the 2-solvent system). The procedure for automated Soxhlet
extraction using the 2-solvent system is described in A4.1. Automated Soxhlet extraction
was also evaluated using this procedure with a 3-solvent system (acetone:DCM:ethyl
acetate). The procedure used for PFE is described in A4.2. Automated Soxhlet
extraction and PFE procedures are provided as possible alternatives for analytes that have
demonstrated improved extraction efficiency as compared to MSE. Analytes with
improved extraction efficiency using automated Soxhlet extraction include dicrotophos,
phosphamidon, and strychnine; analytes with improved efficiency using PFE include
dicrotophos, 1,4-dithiane, methyl parathion, and 1,4-thioxane.
A-6
July 2016
-------
Analytical Protocol for Extractable Semivolatile Organic Compounds
Table A2. Mean Percent Recovery and Relative Percent Difference (RPD) Results of Duplicate Ottawa Sand Sample Extractions
Note: Bold entries indicate recovery was within 70-130 % and RPD was less than 25 %.
Analyte
Sample
mg/kg
Microscale Solvent Extraction (MSE)
Automated Soxhlet Extraction
Pressurized Fluid
Extraction (PFE)
2-solvent
3-solvent
2-solvent
3-solvent
Mean %
Recovery
RPD
Mean %
Recovery
RPD
Mean %
Recovery
RPD
Mean %
Recovery
RPD
Mean %
Recovery i
RPD
i
4-Aminopvridine
2.5
Not Detected
43.0
4.7
69.0
4.1
43.0
4.7
Not Detected
Chlorfenvinphos
1.2
56.3 | 8.0
64.4
15.1
67.1
2.6
64.4
15.1
67.5 | 3.0
3-MCPD
2.0
Not Detected
44.0
6.0
24.8
108.9
44.0
6.0
Not Detected
Chloropicrin
1.0
Not Detected
0.9
200
Not Detected |
Chlorpyrifos
1.0
69.6
4.0
77.2
6.9
77.5
1.8
77.2
6.9
76.5
4.3
Crimidine
1.0
64.8
4.3
71.8
2.2
71.4
4.6
71.8
2.2
81.2
3.8
Dichlorvos
1.0
27.0
27.4
61.9
4.8
52.0
61.5
61.9
4.8
36.7
37.6
Dicrotophos
1.2
56.0
7.0
56.3
24.1
81.4
4.8
56.3
24.1
72.8
15.6
Dimethylphosphite
2.0
Not Detected
27.0
15.9
18.0
200.0
27.0
15.9
Not Detected |
Disulfoton
1.0
71.0
2.5
75.5
5.4
80.8
0.5
75.5
5.4
80.7
7.9
1,4-Dithiane
1.0
41.9
1.0
46.0
12.4
32.0
200.0
46.0
12.4
69.5
5.9
Fenamiphos
1.5
68.0
2.0
69.4
9.5
83.0
0.8
69.4
9.5
85.0
0.8
Methyl parathion
1.0
14.1
86.8
68.5
1.5
74.6
12.9
68.5
1.5
88.0
14.0
Mevinphos
1.0
51.5
2.1
60.2
1.8
64.9
6.6
60.2
1.8
56.8
16.2
Nicotine
1.0
65.4
4.3
69.1
10.0
60.4
49.2
69.1
10.0
80.9
18.2
Parathion
1.2
63.6
0.0
72.5
13.2
79.8
0.9
72.5
13.2
82.4
4.4
Phencyclidine
1.0
77.1
9.6
69.4
1.2
75.2
1.7
69.4
1.2
80.9
9.8
Phorate
1.0
67.3
1.5
72.2
4.3
79.5
3.5
72.2
4.3
80.4
7.6
Phosphamidon
1.2
27.8
25.2
45.0
23.7
62.7
6.1
45.0
23.7
51.4
14.3
Strychnine
5.0
48.7
41.5
57.1
13.7
82.6
41.6
57.1
13.7
41.0
23.4
Tetraethyl pyrophosphate (TEPP)
2.0
13.9
6.8
Not Detected
4.9
109.9
Not Detected
1.1
200.0
Tetramethylenedisulfotetramine (TETS)
0.5
66.7
8.7
86.0
2.3
80.8
1.5
86.0
2.3
84.8
7.1
1,4-Thioxane
1.0
32.9
7.6
39.3
12.0
25.3
200.0
39.3
12.0
60.0
0.2
Mean Target Analyte Recovery
45.6 ±25.7
56.1 ± 22.4
56.4 ± 22.2
56.1 ± 19.5
56.5 ± 32.5
Bromoform-di
1.0
29.7
00
CO
38.7
10.1
23.9
200.0
44.9
6.0
Not Detected
Nitrobenzene-ds
1.0
58.4
5.1
62.9
11.1
46.3
174.1
75.4
0.4
94.0
6.9
Nicotine-d4
1.0
77.5
0.4
80.8
00
CO
318.7
142.1
84.0
2.1
96.3
18.6
2-Fluorobiphenyl
1.0
54.0
7.0
60.5
6.1
202.9
124.4
66.9
2.4
87.2
10.0
Terphenyl-di4
1.0
74.5
1.9
82.6
6.1
88.2
0.0
73.1
0.7
87.5
5.6
Triphenyl phosphate
0.8
55.3
6.7
63.9
6.3
71.6
2.4
54.6
1.3
215.1
4.1
Mean Surrogate Recovery
69.7 ±16.2
64.9 ± 14.6
60.4 ± 21.0
67.2 ± 13.3
86 ± 6
Number of Target Analytes Within 70-130 % Recovery
Target Recovery Range
(70 -130 %)
MSE (2-solvent)
MSE (3-solvent)
ASE (3-solvent)
ASE
PFE
3
9
11
6
12
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
A5.0 ALTERNATE WIPE SAMPLES PREPARATION TECHNIQUES
Preparation of Wipe Samples by PFE - Follow the procedure in A4.2, replacing the soil sample
with a surface wipe (Section 6.2.14). Once extraction is complete, proceed to Section 11.6.
A6.0 GEL PERMEATION CHROMATOGRAPHY (GPC) CLEANUP
The equipment, reagents and procedure for GPC cleanup can be found in EPA SW-846 Method
3640A (Reference 16.10). Prior to GPC cleanup, the soils were extracted by three different
extraction procedures (solvent systems):
• (Extraction 1)5% TEA in ethyl acetate
• (Extraction 2) 1:2:1 (v:v:v) acetone:DCM:ethyl acetate
• (Extraction 3) Extraction 2 followed by Extraction 1, with extracts combined prior to
analysis
Preliminary results in Georgia Bt2 soil showed no significant improvement in recoveries when
GPC cleanup was performed; however, there is historical precedent that recoveries for analytes in
certain soil types might be improved using this cleanup technique. Table A3 provides a
comparison of results for duplicate Georgia Bt2 soil extractions using MSE with and without
GPC cleanup.
A-8
July 2016
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Analytical Protocol for Extractable Semivolatile Organic Compounds
Table A3. Effect of Gel Permeation Cleanup (GPC) on Microscale Solvent Extraction (MSE) of Georgia Bt2 Soil
Note: Bold entries indicate recovery was within 70-130 % and RPD was less than or equal to 25 %.
Analyte
Spike
Level
(mg/kg)
MSE with no GPC
MSE with GPC
Solvent111
System
RPD
Werage % F
Solvent121
System
iecove
RPD
¦y
Solvent131
System
RPD
Solvent111
System
RPD
verage % R
Solvent'21
System
ecover
RPD
y
Solvent131
System
RPD
Chloropicrin
0.5
ND
Dimethylphosphite
1
ND
1,4-Thioxane
0.5
26.4
19.7
40.0
14.0
36.7
0.5
30.2
41.1
45.4
0.9
42.2
23.7
1,4-Dithiane
0.5
34.2
29.2
56.3
6.0
46.5
12.5
40.0
36.0
57.4
0.7
56.4
25.5
Dichlorvos
0.5
ND
15.9
18.8
3.2
25.0
ND
14.5
21.3
3.2
50.0
Nicotine
0.5
59.2
9.5
ND
11.3
1.8
54.0
7.4
ND
Mevinphos
0.5
17.7
28.2
48.4
5.8
36.0
1.1
16.8
42.9
36.4
13.2
36.2
12.2
Crimidine
0.5
50.5
2.8
1.9
10.5
7.0
11.4
45.4
0.9
1.0
40.0
6.0
0.0
Dicrotophos
0.5
2.1
47.6
8.2
0.0
15.9
3.8
1.2
66.7
3.2
25.0
14.0
11.4
Phorate
0.5
46.8
41.9
61.6
10.4
58.1
2.4
42.8
56.1
60.0
6.7
57.6
8.3
Tetramethylenedisulfotetramine
(TETS)
0.1
99.5
3.0
82.0
2.4
103
1.9
101
5.9
86.0
4.7
111
12.6
Phosphamidon
0.6
30.0
61.1
75.5
3.1
50.8
11.5
27.2
57.7
60.5
0.6
47.8
0.7
Disulfoton
0.5
47.7
35.6
64.2
4.4
62.1
2.3
48.6
45.3
62.2
3.2
61.6
5.2
Methyl parathion
0.5
17.6
22.7
74.4
0.5
18.3
16.4
30.0
21.3
74.0
6.5
32.8
2.4
Phencyclidine
0.5
82.6
6.8
ND
19.2
2.1
70.8
9.0
ND
20.8
7.7
Chlorpyrifos
0.5
54.1
41.0
76.9
2.9
71.7
3.1
53.2
48.1
74.0
2.2
68.0
10.6
Parathion
0.6
39.1
54.2
61.5
1.1
52.5
5.1
33.0
60.6
51.0
3.9
45.0
5.9
Chlorfenvinphos
0.6
57.7
46.2
83.3
0.6
84.2
4.0
51.8
46.9
78.7
0.8
83.5
7.6
Fenamiphos
0.75
44.8
51.2
64.6
2.7
67.3
3.2
31.9
61.1
47.1
2.8
57.1
8.4
Strychnine
1.25
89.7
16.1
ND
32.3
6.9
110
8.0
ND
50.3
2.2
Bromoform-di
2.5
27.6
66.7
48.2
0.8
31.2
12.8
27.6
72.5
44.4
9.0
28.8
33.3
Nitrobenzene-ds
2.5
29.2
57.5
45.6
5.3
40.8
31.4
29.2
79.5
38.4
12.5
44.8
39.3
Nicotine-d4
2.5
69.6
17.2
ND
16.0
100
64.0
10.0
Not Detected
2-Fluorobiphenyl
2.5
32.6
52.8
51.6 | 6.2
44.4
30.6
31.2
71.8
43.2 | 7.4
48.4
41.3
Phencyclidine-ds
2.5
64.6
8.0
ND
11.4
10.5
54.8
1.5
Not Detected
6.8
11.8
Terphenyl-di4
2.5
36.8
56.5
49.8
7.2
49.0
13.9
35.6
60.7
46.4
10.3
50.8
23.6
Triphenyl Phosphate
1.25
54.8
59.9
84.0
7.6
80.4
14.9
50.4
66.7
76.8
8.3
82.4
21.4
Number of Target Analytes Within 70-130 % Recovery
Recovery Target Range
(70-130 %)
Solvent System
Solvent System
Solvent System 3
Solvent System
Solvent System
Solvent System
3
5
3
3
4
2
Acronyms:
RPD - relative percent difference
ND - not detected
(1) 5 % TEA in ethyl acetate (2) 1:2:1 (v:v:v) acetone: DCM:ethyl acetate (3) Extraction 2 followed by Extraction 1, with extracts combined prior to analysis.
A-9
July 2016
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United States
Environmental Protection
Agency
PRESORTED STANDARD
POSTAGE & FEES PAID
EPA
PERMIT NO. G-35
Office of Research and Development (8101R)
Washington, DC 20460
Official Business
Penalty for Private Use
$300
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