Category II QUALITY ASSURANCE PROJECT PLAN
PROJECT TITLE:
EPA PROJECT OFFICER:
EERU PROGRAM DIRECTOR:
PERFORMING ORGANIZATION:
DURATION:
TYPE OF PROJECT:
SUPPORTING ORGANIZATION:
The U.S. Environmental
Protection Agency
Mobile Incinerator System
Pesticide Preproduction Burn
James J. Yezzi, Jr.
Gopa' Gupta
Envi r.Sponse, Inc. - EERU, GSA
Ran an
Depot, Edison, New Jersey
08837
February 1988 to September 1988
Work Order under EPA Contract
68-03-3255
U.S. Environmental Protection
Agency
Hazardous Waste Engineering
Research
Office of Research and
Laboratory Development Releases
Control Branch
APPROVALS:
EI CORPORATION
EPA
NAME: Gopal Gupta
TITLE: Project Manager
SIGNATURE: DATE iktlf? SIGNATURE:
NAME: James J. Yezzi, Jr.
TITLE: Project Officer
Date
NAME: Ramjee Raghavan
TITLE: R&D Section Chief
SIGNATURE: CU*r sc.-
NAME: Joyce Perdek
TITLE: EPA Task Monitor
DATE SIGNATURE:
Date
NAME: James P. Stumbar
TITLE: Test Coordinator
SIGNATURE: (j.
7/ r/ij'.l V
NAME: Guy F. Simes
• . TITLE: QA Officer HWERL
DATE 7/2/1 <43 SIGNATURE:
NAME: Jack Borris
TITLE: QA Officer .
SIGNATURE: PjK DATE W off
Date
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6.6.1
QUALITY ASSURANCE PROJECT PLAN APPROVAL FORM
for
HWERL Contracts/lAGs/Cooperatlve Agreements/lrvhouse Project*
L.b Workman No: Support: Office of
Pestic ides
Project Category: 11
OA ID No: sp ~ 2 3 6 "E
Task Start Date: 1993 - sept 1983
(Tor measurement, data gathering, and/or data gen-
eration activities)
Date QAPP Received:
Task Title: US EPA MobiLe Incinerator Svstpm P^rindp Pr°rnfl"r f i n n—qn r n
( 2 , 4 . 5 -T )
Technical Project Officer. Joyce Perdek
Contractor. Env i response
APPROVALS:
Robert Sawyer
Contractor Project/Task Manager
John Bo r r i s
Contractor OA Manager
/I ScjUs^ sjfaf.
Signature
^ Si
Signature
7/2/^P
7/jLt/ve
Date
TBN
Affiliate Task Manager*
Signature
Oate
Other (as appropriate)
Joyce Perdek
HWERL Technical Project Officer
John S. Fa r Low
HWERL Branch or Staff Chief"
Guy S lmes
HWERL Quality Assurance Officer
Signature
Signature
Signature
Signature
Date
Date
Date
Date
• Approval signature Is required for any ancillary sampling, analytical, or data gathering support
provided by a subcontractor or HWERL principal Investigator.
•• Approval signature from the HWERL Branch or Staff Chief Is required for Category I, 11, and III
extramural pro|ects and for all In-house projects.
HWERL (QAPP AF)
(October 1986)
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1 of 5
CONTENTS
SECTION NO. PAGES
Title Page 1
Table of Contents and Distribution 5
1.0 Project Description 14
2.0 Project Organization and Responsibilities 11
3.0 Quality Assurance Objectives 11
4.0 Sampling Procedures 18
5.0 Analytical Procedures and Calibration 29
6.0 Data Reduction, Validation, and Reporting 9
7.0 Internal Quality Control Checks
and Frequency 6
8.0 Quality Assurance Performance and
System Audits 1
9.0 Calculation of Data Quality Indicators 4
10.0 Corrective Action 4
11.0 Quality Control Reports to Management 1
Appendix A Deliverables Required From
Analytical Subcontractors
Appendix B Procedures for Compositing
Purge Water Samples For
Volatile Organic Analyses
REVISION DATE
5 7-21-88
5
5
5
5
5
5
5
5
5
5
5
7-21-88
7-21-88
7-21-88
7-21-88
7-21-88
7-21-88
7-21-88
7-21-88
7-21-88
7-21-88
7-21-88
7-21-88
Appendix C Field Data Sheets
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TABLES
Table
No.
Page
1-1 Sampling and Analysis Summary For Ash, 1-6
Sludge, and Purge Water Delisting
1-2 Herbicide Compositions 1-11
1-3 QA/QC For Delisting Tests-Spiking Requirements 1-12
2-1 Division of Labor & Analytical Methods for
Preproduction Burn at Denney Farm 2-3
2-2 Personnel List and Line of Responsibility for 2-10
MIS Operation and Sampling During Test Burn
Tests
2-3 Personnel List and Line of Responsibility for 2-11
Trial Burn Sample Analyses
3-1 Quality Assurance Objectives for Combustion 3-2
and Operating Parameters
3-2 Analytical QA Objectives for Precision 3-3
and Accuracy
3-3 Method Detection Limits (MDL) of the Flue 3-8
Gas Component Monitors
3-4 Analytical Methods and Detection Limits 3-9
3-5 PCDD/PCDF Detection Limits 3-11
4-1 Sample Requirements for Preproduction Burn
Analyses 4-2
4-2 Sample Collection Locations, Equipment, and 4-6
Methods
4-3 Preproduction Burn Sample Frequency
and Container Requirements 4-10
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TABLES (Cont'd)
Table
No.
4-4 Preproduction Burn Preservation Requirements
and Holding Times
5-1 GC/MS Instrument Operating Conditions For
Volati1es Analys i s
5-2 Surrogate Compounds and Internal Standards
Used to Analyze Volatiles
5-3 Volatile Organic Calibration Mixture
5-4 BFB Ion Abundance Criteria
5-5 Surrogate Compounds Added to Sample For
Semivolatile Organic Analysis
5-6 GC/MS Operating Conditions For Method 8270
Semivolatile Organic Analysis
5-7 DFTPP Key Ions and Ion Abundance Criteria
5-8 Surrogates and Internal Standards Used to
Calibrate the GC/MS For Extractable Analyses
5-9 Recommended GC Operating Conditions For
Method 8290
5-10 High Resolution Calibration Solutions
Concentrati ons
5-11 GC Operating Conditions For Chlorinated
Herbicide Analyses
5-12 Approximate Concentrations of Calibration Gases
7-1 Analytical QC Measures
Contents
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July 21, 1988
3 of 5
Page
4-12
5-5
5-7
5-8
5-9
5-12
5-12
5-14
5-15
5-18
5-19
5-22
5-29
7-6
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Figure
No.
1.1
2.1
4.1
4.2
4.3
4.4
4.5
4.6
4.7
6.1
6.2
6.3
10.1
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FIGURES
Page
Block Flow Diagram of Mobile Incineration 1-2
System
General Project Organization 2-2
Sampling Locations For Test Burn 4-5
Stack Gas Sampling Ports and Sampling 4-8
Probe Traverse Points
Chain of Custody Record 4-13
Chain of Custody Seal 4-14
Master Log Heading 4-16
Sample Label 4-17
Sample Indentification Tag 4-18
Data Flow and Reporting Scheme 6-7
Measurement Data Flow Scheme 6-8
Analytical Data Reporting Scheme 6-9
Corrective Action Request Form 10-3
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DISTRIBUTION OF TEST BURN QA PROJECT PLAN
ENVI RESPONSE, INC.
J. Stumbar, EERU Test Coordinator
G. Gupta, EERU Project Director & EERU R&D Group Manager
R. Sawyer, MIS Project Manager
G. King
E. Russell, Test Burn Site Supervisor
M. Merdinger, Sampling and Analytical Supervisor
J. Borris, Project Health & Safety & QA Officer
EPA HWERL:
J. J. Yezzi, Jr., EERU Project Officer
J. Perdek, EPA Project Manager
G. F. Simes, HWERL QA Officer
EPA REGION VII:
H. Brown, Region VII Chief
D. I. Bates, Region VII Quality Assurance Officer
Environmental Services Division
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Date: July 21, 1988
Page: 1 of 14
1.0 PROJECT DESCRIPTION
1.1 OVERVIEW
This project covers pesticide preproduction (delisting) test
operations of the U.S. Environmental Protection Agency's
Office of Research and Development's Mobile Incinerator System
by the Environmental Emergency Response Unit (EERU) at the
Denney farm, a site in Barry County in the State of Missouri.
The system operation and planned tests are described below.
1.2 FACILITY DESCRIPTION AND OPERATION
An objective of the incinerator development and testing
project is to demonstrate a mobile thermal oxidation and
incineration system that is capable of destroying/detoxifying
hazardous and toxic organic materials and cleansing the
contaminated soil and debris frequently associated with spills
or uncontrolled hazardous waste disposal sites.
The Mobile Incineration System design includes three heavy
duty semi-trai1ers equipped with the necessary components for
response to remote locations that are accessible by
over-the-road equipment. A fourth trailer includes the
analytical instrumentation for monitoring the combustion and
stack gases generated by the incineration process. A Block
Flow Diagram of the system is shown in Figure 1.1. The four
trailers are equipped as follows:
Trai1er No. 1 is equipped with a control system console,
solids feeder, waste feed nozzle and refractory lined rotary
kiln, the kiln operates in an excess air mode at temperatures
up to 982°C (1800 F) and is capable of providing long
residence time for those solid materials that do not burn or
volatilize readily, and which might tend to release toxic
substances into the gas stream. The kiln has two combustion
burners, one firing with ambient combustion air and the second
firing with pure oxygen. Solid materials are ram fed into the
kiln after being shredded; sludges and viscous fluids are
pumped into the kiln. Residual ash and inert solids are
removed from the discharge end of the kiln while vaporized and
partially burned toxic vapors and gases are carried in exhaust
gases through the self-aligning expansion joint ducting into
the high temperature cyclone. The high temperature cyclone
removes 93% of the dust greater than 20 microns in size. This
dust deposits in a drum collector under the cyclone. The gas
passes into the secondary combustion chamber on trailer No. 2,
where complete detoxification/destruction is achieved.
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—*
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r r
1
ASH
wahr
c
*
c
I
*
see
o
M
(
i.
OUMCH
tlftOW
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WAIIR
_L
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IHANSftN
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FIGURE 1.1 BLOCK FLOW DIAGRAM OF MOBILE INCINERATION SYi/I'EM M
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00
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Trailer No. 2 is equipped with a refractory-1ined Secondary
Combustion Chamber (SCC) designed to operate at 1200°C
(2200°F) and to maintain a minimum two-second gas stream
dwell time with more than 4% oxygen in conformance with the
Federal Toxic Substances Control Act (TSCA) regulations
covering PCB incineration. The gases leaving the secondary
combustion chamber are cooled by quenching in a wetted throat
venturi quench elbow. Acid gas removal starts in the quench
elbow since the process water contains caustic to neutralize
acids. Excess spray drains into a ground-level sump while the
cooled flue gases are ducted to the air pollution control
equipment. The gas passes into the wet electrostatic
precipitator.
Wet Electrostatic Precipitator removes fly ash and sub-micron
particulates such as phosphorous pentoxide. It uses a
water-wetted, electrostatistical1y charged, fiber reinforced
grid as the collection medium. The gas passes into the mass
transfer scrubber on trailer No. 3.
Trailer No. 3 is equipped with air pollution control equipment
designed to complete the neutralization and removal of acid
gases. The gases then pass through a mass transfer (packed
bed) scrubber for SO2, HC1, and other acid gas removal. A
demister is provided before the induced draft
diesel-engine-driven fan. The fan provides the motive force
for gas movement and maintains the negative pressure necessary
to avoid toxic fume escape anywhere in the process. The
cleaned exhaust leaving the induced draft fan is passed
through a sound attenuator and flow straightener before being
discharged from the stack.
Trai1er No. 4 is equipped with a continuous monitoring system
that analyzes the flue and stack gases for combustion
components (carbon monoxide (CO), carbon dioxide(C02) and
oxygen (0?) and emission components (oxides of nitrogen
(NOx), and total hydrocarbons (THC)). Sulfur dioxide
(SO2) is not monitored because the wastes and fuel oil have
low sulfur contents.
Monitoring and recording of flue and stack gas components are
accomplished through the use of: (1) a thermal conductivity
detector GC for analysis of CO? and 62; (2) a methanizer
to flame ionization detector GC for analysis of CO; (3) a
flame ionization detector GC for analysis of THC; and (4) a
chemi1uminescent detector for analysis of N0X. The analyzer
section also has valves and switching to introduce calibration
gas (from cylinders) through the sampling/conditioning units
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to the appropriate analyzer. The analyzers are controlled by
microprocessors to provide automatic sampling and tabulation
of results.
Waste water from the incineration system will be treated by
sedimentation and high-pressure filtering. A "bleed" will be
collected and held for analysis in two 1 5,000-gal1 on tanks.
The waste water will be delisted as a hazardous waste by
petition to MDNR and EPA Region VII and disposed of under an
NPDES permit.
The ash from the rotary kiln drops from the ash discharge
chute directly into steel, 55-gal1 on drums located under the
chute. Once a drum is full, the ash discharge chute is closed
to allow replacement of drums. Full drums are covered and
moved aside on a roller conveyor and allowed to cool to I
ambient temperature. An empty drum is then placed under the t
ash discharge chute and the discharge chute is returned to
automatic operation.
1.3 TEST PROGRAM DESCRIPTION
The incinerator system has undergone trial burns during which
chlorinated liquids and solids were incinerated. Waste feed
will be introduced into the mobile incinerator in two matrix
forms. A solid matrix form will consist of vermiculite
contaminated with 2,4-D, 2,4-DB, 2,4,5-T, and 2,4,5-TP
pesticides (herbicides). The feed rate to the incinerator
will be approximately 650 lb/hr (600-700 lb/hr). A liquid
matrix will consist of 2,4-D, 2,4-DB, 2,4,5-T, and 2,4,5-TP
dissolved in heavy naphtha and diesel oil. This liquid will
be fed to the incinerator at a rate of 150 lbs/hour. The i
purpose of this project is to:
Run a series of delisting tests which would exclude from
the identification as a hazardous waste by CFR 261.3 the
three main byproducts of the MIS generated during the
incineration of the pesticide wastes. Separator sludge
will not be analyzed since it will be recycled through the
process. Thus no separator sludge will be generated.
This exclusion will be based upon the analytical results
of the wastewater (purge water), and kiln ash/cyclone ash
composite.
1.3.1 Test Plan
Waste feeds consist of liquid and solid herbicides whose
registrations have been suspended by the EPA due to
contamination with trace quantities of dioxin. The solid
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waste is composed of over 99.5% WeedoneR granular weed
killer and the liquid waste is composed of over 93% Envert
DT. Remaining materials are other herbicides of similar
composition. Compositions of these materials are presented in
Table 1-2.
Deli sti ng Tests -- The primary analytical requirements shall
be to determine the concentrations of contaminants of the
three main byproducts streams during a test burn using methods
and procedures that will satisfy the Missouri Department of
Natural Resources (MDNR), EPA Region VII and the EPA Office of
Solid Waste. The purpose of the test burn is to provide data
to verify that the incinerator byproducts meet or exceed the
analytical criteria and should therefore be delisted. QA/QC
for these tests will meet Category II requirements.
A summary of the analyses and methods required are given in
Table 1-1.
Four samples of each matrix will be analyzed. In addition, a
Matrix Spike (MS) and Matrix Spike Duplicate (MSD) of each
sample matrix is required. The spiking compounds for each
method are detailed in Table 1-3. The MS/MSD analyses will be
performed on the first set of samples received.
Four replicate eight hour tests are to be completed at the
feedrates given above.
Contingency Tests -- Since the cost of maintaining the
incinerator in a holding mode is high and the delisting
process takes three to four weeks to complete. A second
series of four replicate delisting tests will be executed at
75% of the feed rates given above: i.e., 490 lb/hr of solids
(450-525 lb/hr) and 115 lb/hr of liquids. The residue streams
from these tests will only be analyzed if the residue streams
from the first test series fail to meet the delisting
cri teri a.
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TABLE 1-1 SAMPLING AND ANALYSIS SUMMARY FOR ASH, SLUDGE,
AND PURGE WATER DELISTING
This table summarizes the sampling and analytical requirements for delisting
of the solid and liquid streams as a hazardous waste. The criteria for
delisting presented in this table follow the final rules published in pages
7903-7915 of Vol. 53 No. 48 (March 11, 1988) of the Federal Register.
Sample Matrices: A composite sample of kiln and cyclone ash and a separate
sample of purge water.
Sampling Frequencies and Methods:
Sampling Frequency
Sample Per Test Sampling Method
1. Kiln Ash
and cyclone ash
2. Purge Water
(after carbon
filters)
3. Purge Water
(before carbon
filters)
Sample each drum
during test run and
composite.
Sample at 2 hour
intervals and
composite.
Sample at 2 hour
intervals and
composite.
S007
S004
S004
Since the purge water before the filters has failed to meet the delisting
criteria during previous analyses, the second purge water sample will be
analyzed only if the purge water after the carbon filter passes delisting.
However, volatile analyses must be preformed before holding times are
exceeded.
The following analytical protocol will be followed for each sample:
A. Per 40 CFR 261 Subpart C
Ignitability
Corrosivity
Reactivity
EP Toxicity
Ash and Solids
N.A.1
pH = 2.0-12.
Not reactive
As per 40 CFR,
Table 1, and APP
261.24,
II3
Scrubber Waste Liquids
N.A.2
pH = 2.0-12.5
Not reactive'
ICP scan-heavy metals, as
per 40 CFR, 261.24, Table l3
B. Analyses to be performed for the following criteria^:
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Table 1-1 (cont.)
Toxic Constituent^
Dioxins/Dibenzofurans®
Acetone
Aldrin
Benzene
Benzo(a)pyrene
Benzo(b)fluoranthene
Biphenyl
Bis-(2-ethylhexyl)phthalate
Chlordane
Chlorobenzene
Trichloromethane
(Chloroform)
Chrysene
2,4-Dichlorophenoxy-
acetic acid (2,4-D)
Dibenzo(a,h)anthracene
Dichloromethane
(Methlyene chloride)
1.3-Dichlorobenzene
1.4-Dichlorobenzene
1,2-Dichlorobenzene
1,2-Dichloroethane
2,4-Dichlorphenol
Dichlorvos
Diethyl Phthalate
Disulfaton
Endosulfan I
Ethyl benzene
Fluoranthene
Fluorene
Indeno(l,2,3-c,d)pyrene
Isophorone
Chloromethane
(Methyl chloride)
Methyl parathion
Naphthalene
Nitrosodiphenylamine
Pentachlorophenol
Phenanthrene
Phenol
Polychlorinated biphenyls
Pyrene
Tetrachloroethylene
2,3,4,6-Tetrachlorophenol
Toluene
Concentration
Sol ids Purge Water
5 ppt4
15 ppb
9.7 ppm
0.43 ppm
1.8 ppm
0.002 ppt4
35.3 ppm
18 ppt
44 ppb
27 ppt
0.18 ppb
15.5 ppm
SW-846 |
Method I
8290* I
8240
8080 |
8240
8310 in
8270/831010
8270
0.37 ppm
0.24 ppb
8080
—
8.8 ppm
8240
5.4 ppm
52 ppb
8240
170 ppm
1.8 ppb
8270/8310
3.5 ppm
8150
83 ppb
6.0 ppt
8310
2.4 ppm
42 ppb
8240
—
34 ppm
8270
—
0.66 ppm
8270
—
26.5 ppm
8270
4.1 ppm
44 ppb
8240
480 ppm
0.88 ppm
8270
260 ppm
0.78 ppm
8140
—
4418 ppm
8270
23 ppm
16 ppb
8140
310 ppm
20 ppb
8080
—
35 ppm
8240
—
1.77 ppm
8270
120 ppm
18 ppb
8270
330 ppm
1.8 ppb
8270/8310
—
61.9 ppm
8270
35.3 ppm
8240
210 ppm
99 ppb
8140
—
79.5 ppm
8270
130 ppm
63 ppb
8270
—
8.8 ppm
8270
150 ppm
18 ppb
8270
—
8.8 ppm
8270
0.31 ppm
72 ppt
8080
—
35 ppm
8270
59 ppm
59 ppb
8240
—
8.8 ppm
8270
—
88.4 ppm
8240
L,
(continued)
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Table 1-1 (cont.)
Toxic Constituent
2,4,5-TP (Silvex)
1.2.4-Trichlorobenzene
2.4.5-Trichlorophenol
2.4.6-Trichlorophenol
2,4,5-Trichlorophenoxy-
acetic acid
Xylenes (Total)
Metals & Cyanides (EP Toxicity)3
Arsenic8
Chromium
Lead
Silver
Barium
Cadmium
Selenium8
Mercury
Nickel
Cyanides
Concentration
SW-846
Sol ids
Purge Water
Method
110 ppm
88 ppb
8150
6.2 ppm
8270
35 ppm
8270
3.9 ppm
18 ppb
8270
—
0.88 ppm
8150
—
619 ppm
8240
1.6 ppm
0.44 ppm
6010
1.6 ppm
0.44 ppm
6010
1.6 ppm
0.44 ppm
6010
1.6 ppm
0.44 ppm
6010
32 ppm
8.8 ppm
6010
0.3 ppm
0.09 ppm
6010
0.3 ppm
0.09 ppm
6010
0.07 ppm
0.02 ppm
7470
16 ppm
4.4 ppm
6010
6.5 ppm
1.8 ppm
9010
* High Resolution GC/High Resolution MS
Footnotes:
* The ash would not be ignitable after having passed through a kiln
and having reached approximately 750°C at the time of discharge.
2
The scrubber waste liquid (purge water), which is water, is also
not considered to be ignitable.
Analysis will be for the following metals plus total cyanides in
the EP toxicity leachate: Arsenic, Barium, Cadmium, Chromium,
Lead, Nickel, Selenium, Silver, and Mercury. Nickel is not a EP
Toxicity Test requirement.
^ Subjected to the constraints given below and calculated as per the
following formulae.
A conservative estimate of the level of concern is a weighted sum of
'the concentration of tetra-, penta-, and hexachlorinated dioxins and
-dibenzofuran isomers. The weighting factors are given below, and
represent current best estimates of the relative toxicities of the
(continued)
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Table 1-1 (cont.)
"2,3,7,8-substituted" congeners. In the absence of isomer-specific
data, it is prudent to consider all detected isomers in a homologue to
be "2,3,7,8-substituted" isomers.
CDD/CDF Isomers and Their Relative Toxicity
POLYCHLORINATED
DIBENZO-P-DIOXINS
Relative
Isomer Toxicity
POLYCHLORINATED
DIBENZOFURANS
Isomer
Relative
Toxicity
Mono thru Tri CDDs 0
2,3,7,8-TCDD 1
other TCDD 0.01
2,3,7,8-TDCFs
other TDCFs
0.1
0.001
2,3,7,8-Penta CDDs 0.5
other Penta CDDs 0.005
2,3,7,8-Penta CDFs
other Penta CDFs
0.1
0.001
2,3,7,8-Hexa CDDs 0.04
other Hexa CDDs 0.0004
2,3,7,8-Hexa CDFs
other Hexa CDFs
0.01
0.0001
For the residues to pass the delisting analyses, the equivalent
concentration of 2, 3, 7, 8-TCDD as calculated above must be lower than 5
ppt in the waste solids or 0.002 ppt in the purge water or the analyses
must achieve non detects at or below the practical quantitation limits
(PQLs) given below. The laboratory will achieve these PQLs since failure
to achieve them results in failure to pass delisting.
PCDD/PCDF
Homologues
Sol ids
Purge Water
Tetra and Penta = CCD/F
< 15
< 0.12
Hexa - CDD
< 37
< 0.30
All sampling and analysis methods will be defined by SW-846 Test
Methods for Evaluating Solid Waste, third Edition 1987 and ASTM
methods, where applicable.
(continued)
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Table 1-1 (cont.)
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10 of 14
PCDD/PCDF analysis includes the quantification of the following
dioxin and furan compounds (typical for all sample matrices):
1. 2,3,7,8 tetra, penta and hexa chlorodibenzo-p-dioxins
2. 2,3,7,8 tetra, penta and hexa chlorodibenzofurans
3. Total tetra, penta, hexa, hepta, and octa
chlorodibenzo-p-dioxins (each total separately)
4. Total tetra, penta, hexa, hepta, and octa
chlorodibenzofurans (each total separately)
For organic constituents other than dioxins/furans, the constituent
must be below the delisting limit or be not detect.
If arsenic and/or selenium is detected or if the detection limit is
above the delisting criteria. The sample will be rerun using Method
7740 for selenium and Method 7060 for arsenic.
Since the feed materials were commercial household products which
were applied to people's lawns, reactivity tests of the residues are
not a concern and are not required.
Method 8310 will be used for purge water to attain greater
sensitivity for detecting this analyte. Method 8270 is adequate for
the kiln ash/cyclone ash matrix.
-------
Product
Ueedone Granular
Weed KiIler
Envert OT
Emulsavert 100
Emulsamine 2,4,5-T
Emulsaert 248
Dinoxol
Ueedone BK64
Section No: 1.0
Revision: 5
Date: July 21, 1988
Page: 11 of 14
TABLE 1-2 HERBICIDE COMPOSITIONS
Haxttnun Main Inert
Herbicide Concentration (wt)X 2.3.7.8 TCDD Component (ut) X
2,4-0 2,4-DB 2,4,5-T 2,4,5-TP (ppb)
'-22 -- -- 1.61 1.52 93X vermiculite
18.14 17.71 -- 7.83 59* Fuel Oil
11-95 -- 11.95 -- 30.9 5751 Fuel Oil
34.38 -- 9780. 61X Fuel Oil
6-14 -- 12.28 -- 20.2 67% Fuel Oil
32.45 31.68 -- 45 2 36X Fuel OiI
42.26 20.23 -- 20.9 30X Fuel OiI
-------
Section No:
Revision:
Date:
Page:
1.0
5
July 21, 1988
12 of 14
TABLE 1-3 QA/QC FOR DELISTING TESTS-SPIKING REQUIREMENTS
1 matrix spike and 1 matrix spike duplicate per sample matrix
with the following spiking compounds plus required method blank,
surrogate spikes, laboratory control samples, and duplicate
analyses:
SW-846
METHODS
8290
8150
8240
8270
8310
8080
8140
6010
SPIKING COMPOUNDS
All dioxin/furan homologs
All delisting compounds using
method 8150
All delisting compounds using
method 8240
The following compounds:
2,4-Dichlorophenol
Naphth alene
F1uorene
2,4,6-Trichlorophenol
Pentachlorophenol
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
Benzo(a)pyrene
Benzo(b)fluoranthene
All delisting compounds using
Method 8310 in the matrix of
interest
Appropriate Aroclors and
Chlordanes, Aldrin, Endosulfan I
All delisting compounds using
method 8140
Spike all metals at the
regulatory level given
1-1 .
in Table
7470
Spike mercury at the regulatory
level g i ven in Table 1 -1.
-------
Tab! e
SW-846
METHODS
7060
9010
See Table 1-1 for delisting
(3rd Edition) methods. For sp
Section No: 1.0
Revision: 5
Date: July 21, 1988
Page: 13 of 14
1-3 (cont.)
SPIKING COMPOUNDS*
Spike arsenic at the regulatory
1evel gi ven i n Table 1 -1.
Spike cyanides at the regulatory
1evel gi ven i n Table 1 -1.
compounds and specified SW-846
king levels, see Table 3-2.
-------
Section No:
Revision:
Date:
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5
July 21, 1988
14 of 14
1.4 TEST SCHEDULES
The intended schedule of operation of the unit during these
test runs will be as follows:
Delisting Tests: (week of August 22, 1988)
Acti vi tv
Day
Obtain steady
state operation
Perform Run #1 & 2
Perform Run #3 & 4
Perform Run #5 & 6
Perform Run #7 & 8
2
3
4
5
Comments
Test Set-up
Cont i ngency
Cont i ngency
A final report will be issued in September based upon the
anticipated schedule for the analytical laboratory to complete
their work. Preliminary analytical data will be available two
weeks after the preproduction burn.
-------
Section No:
Revision:
Date:
Page:
2.0
5
July 21, 1988
1 of 11
2.0 PROJECT ORGANIZATION AND RESPONSIBILITIES
The overall project organization and reporting relationships
are shown in Fig. 2.1. Enviresponse, Inc., the EPA
Environmental Emergency Response Unit (EERU) operating
contractor, has the total responsibility for the test burns
including the sampling of all matrices, QA management of
subcontractors, the preparation for shipment, and the shipment
of the samples to EPA Region VII Laboratory.
Enviresponse will also be responsible for issuing the final
report to the appropriate regulatory authorities.
The analytical work will be performed by two laboratories: EPA
Region VII and a CLP laboratory. They will be given copies of
this QAPP and will be responsible for carrying out analyses
according to the QAPP. The scope of the analytical work for
each laboratory is presented in Table 2-1. The primary
laboratory is EPA Region VII Laboratory. Region VII
laboratory will perform all analyses except those for
pesticides by SW Method 8140 and will be responsible for:
Providing all bottles, labels, field documents, and
preservatives for the samples. The bottles will be
precleaned by the appropriate procedures.
Dividing samples and shipping them to the appropriate
laboratory for analysis.
Analysis of samples within their scope.
Review, validation and certification of al1 laboratory
data.
The CLP laboratory will be responsible for:
Analysis of all ash and water samples for organo-phosphate
pesticides by SW Method 8140 and for polynuclear aromatic
hydrocarbons by SW Method 8310.
Validation of data produced within their laboratory.
Presenting results, including QA/QC results, to
Enviresponse and EPA Region VII Laboratories within the
required time limits.
-------
El Health and
Safety Officer
J. Borris
El President
J. Sarappo
R&D Sect ion Chief
Copal Gupta
EERU Project Manager
G. Cupta
lest Burn
QA/QC Officer
J. Borris
Asst. Project Manager
J 1ichansky
MIS Project Manager
R Sawyer
St Jt f tng i iillt
A Roubo
Field Superintendent
F Russell
Site Health and
Safety Of 1icer
M III intz
Sampling & Analytical
Supervibor
M Merdinqcr
Instrument technician
P. Farcone
Subcont ractor
AnalysIs
Records
Mechanical lechnicen
0 Kennedy
1
kuool les
Housekeeping
1 Records
I Opciaiions Repair and
H
(V (D —ft"
• • • • U)
-*• O
O 3
3
ro C A rg
c
o
O 3
-h fD
»— fS3
CO
00
00
-------
TABLE 2-1
DIVISION OF LABOR & ANALYTICAL METHOOS FOR DELISTING TESTS
DENNEY FARM
MATRIX
Kiln Ash/ Cyclone Ash
Composite (Solid)
Purge Water filtered (b)
LABORATORY
PARAMETER
ANALYTICAL METHOO
QA/QC
Total Samples
Total Samples
(REGION VII)
(OTHERS)
REGION VIl-ESAT
PCDD/PCDF
8290
MS/MSD
6
REGION Vll-ESAT
Semivolat iles
8270
MS/MSD
6
TBN
PAHs
8310
MS/MSD
6
REGION VII
Volat iles
8240
MS/MSD
6
REGION VII-TAT
Herbicides
8150
MS/MSD
6
TBN
Pesticides
8140
MS/MSD
6
REGION VII
PC8s&Pesticides
8080
MS/MSD
6
REGION VII
Heavy Metals
6010
MS/MSD
6
REGION VII
Mercury
7470
MS/MSD
6
REGION VII
Total Cyanides
9010
MS/MSD
6
Region Vll-ESAT
PCDD/PCDF
8290
MS/MSD/BLANK
6
Region VII-ESAT
Semivolatiles
8270
MS/MSD/BLANK
6
TBN
PAHs
8310
MS/MSD
6
Region VII
Volat iles
8240
MS/MSD/BLANK
6
Region VII-TAT
Herbicides
8150
MS/MSD/BLANK
6
TBN
Pesticides
8140
MS/MSD/BLANK
6
Region VI1
PCBs&Pesticides
8080
MS/MSD/BLANK
6
Region VI1
Heavy Metals
6010
MS/MSD/BLANK
6
Region VI1
Mercury
7470
MS/MSD/BLANK
6
Region VI1
Total Cyanides
9010
MS/MSD/BLANK
6
Continued
at oj (o n>
IT3 rt < fl
(O (ti ft
. . . . CO —I.
o
O =1
w c, cn rv)
c
o —• o
-n*<
h- no
CD
CD
-------
TABLE 2-1 (cont)
DIVISION OF LABOR & ANALYTICAL METHODS FOR DELISTING TESTS
DENNEY FARM
MATRIX
PRIORITY
LABORATORY PARAMETER
ANALYTICAL METHOD QA/QC
Total Samples Total Samples
(REGION VII) (OTHERS)
Purge Water unfUtered (b)
Purge Uater unfiltered
(Prior to Test)
Region VI1-ESAT
PCDD/PCDF
8290
MS/MSD
6
Region VII-ESAT
Semivolatites
8270
MS/MSD
6
TBN
PAHs
8310
MS/MS0
6
Region VII
Volatiles
8240
MS/MSD
6
Region VII-TAT
Herbicides
8150
MS/HS0
6
TBN
Pesticides
8140
MS/MSD
6
Region VII
PCBs&Pesticides
8080
MS/MSD
6
Region VII
Heavy Metals
6010
MS/MSO
6
Region VII
Mercury
7-470
MS/MSD
6
Region VII
Total Cyanides
9010
MS/MSD
6
Region VII-ESAT
PCDD/PCDF
8290
(a)
1
Region VII-ESAT
Semi volatiles
8270
(a)
1
TBN
PAHs
8310
(a)
1
Region VII
Votatiles
8240
(a)
1
Region VII-TAT
Herbicides
8150
(a)
1
TBN
Pesticides
8140
(a)
1
Region VI1
PCBsSPesticides
8080
(a)
1
Region VII
Heavy Metals.
6010
(a)
1
Region VII
Mercury
7470
(a)
1
Region VI1
Total Cyanides
9010
(a)
1
Total
152
38
-a a so on
OJ fP (1>
l£> <-»- < O
» fD rf
.. .. (A —«•
a
O 3
Z3
Continued
C_> l*» fM
c
O —¦ O
-h*<
i—• ro
vo
CO
00
-------
TABLE 2-1 (cont)
DIVISION OF LABOR & ANALYTICAL METHOOS FOR DELISTING TESTS
DENMEY FARM
Number 1 priority to be conpleted within 14 days of receiving sample.
Member 2 priorities to be completed within 21 days of receiving sample.
(a) Purge water prior to run will be analyzed only in case of
a major hit for the analyte(s) associated with the hit.
(b) If filtered purge water samples fail to pass the delisting
then the samples for the contingency runs will be analyzed.
If the MS/MSD for the first samples are within the control limits,
then No MS/MSD is required for the contingency samples.
(c) For volatiles and other analyses, holding times listed in Table 4-4
shall not be exceeded regardless of priority.
-------
Section No:
Revision:
Date:
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5
July 21, 1988
6 of 11
Presenting method deliverables given in Appendix A to EPA
Region VII Laboratories.
The quality assurance officer, Jack Borris, has the primary
responsibility for reviewing and approving the QA Project Plan
and for overseeing the project to assure that the QA
objectives are met.
Jack Borris is responsible for:
Approving the project QA Plan
Reviewing and approving QA plans submitted by the
analytical laboratories
Advising project manager and EI Corporate QA Officer of
any deficiencies or nonconformance to plan
The MIS project manager, R. Sawyer, has overall responsibility
for the mobile incinerator operations including QA/QC. For
this purpose he reports to the EERU R&D project director and
group manager, G. Gupta, and who has the overall
responsibility for the EERU project to the EPA. Some of the
MIS project manager's (R. Sawyer) responsibilities are:
Managing the overall operation of the mobile incinerator.
Included are such activities as obtaining required RCRA,
TSCA, and state permits; readiness preparations of
equipment, personnel, and waste feeds; operating site
preparations; operating and safety procedure; and
maintaining communication with USEPA/HWERL Branch on
activities.
Deciding when test run sampling will be conducted.
Calling to the attention of the quality assurance officer
and others, as appropriate, any problems arising during
the testing that affect this QA Project Plan so that the
problems can be resolved in a timely manner. Responsible
for properly documenting any modifications to this plan.
Issuing a final test burn report to the EPA.
The test coordinator, J. Stumbar, reports to the MIS project
manager and has field operations responsibility for conducting
the planned tests. Some of the test burn coordinator's
respons i bi1i t i es are:
-------
Section No:
Revision:
Date:
Page:
3.0
5
July 21, 1988
8 of 11
TABLE 3-3. METHOD DETECTION LIMITS (MDL) OF THE FLUE GAS COMPONENT MONITORS
Parameter
Method of Measurement
MDL
CO
Continuous non-dispersive
infrared analyzer
1 ppm
co2
Gas chromatograph/thermal
conductivity detector
0.5%
02
Continuous polarographic
detector
0.5%
N0X
Chemiluminescent detector
analyzer
10 ppm
-------
Section No:
Revision:
Date:
Page:
3.0
5
July 21, 1988
9 of 11
TABLE 3-4. ANALYTICAL METHODS AND DETECTION LIMITS
DETECTION
LIMITS
SW-846
Toxic Constituent
Sol ids
Purge Water
Method
Acetone
_ _
100 ug/L
8240
Aldrin
10 ug/Kg
1.0 ug/L
8080
Benzene
5 ug/Kg
5 ug/L
8240
Benzo(a)pyrene
15.4 ug/Kg
0.023 ug/L
8310
Benzo(b)fluoranthene
330 ug/Kg
0.018 ug/L
8270/8310
Biphenyl
-- ug/Kg
10 ug/L
8270
Bis-2-ethylhexyl phthalate
-- ug/Kg
10 ug/L
8270
Chlordane
10 ug/Kg
1.0 ug/L
8270
Chlorobenzene
-- ug/Kg
5 ug/L
8240
Chloroform
5 ug/Kg
5 ug/L
8240
Chrysene
330 ug/Kg
0.150 ug/L
8270/8310
2,4-D
--
1.0 ug/L
8150
Dibenz(a,h)anthracene
20.1 ug/Kg
0.030 ug/L
8310
Dichloromethane
5 ug/Kg
5 ug/L
8240
1,3-Dichlorobenzene
--
10 ug/L
8270
1,4-Dichlorobenzene
--
10 ug/L
8270
1,2-Dichlorobenzene
10 ug/L
8270
1,2-Dichloroethane
5 ug/Kg
5 ug/L
8240
2,4-Dichlorophenol
330 ug/Kg
10 ug/L
8270
Dichlorvos
100 ug/Kg
1.0 ug/L
8140
Diethyl phthalate
--
10 ug/L
8270
Disulfaton
100 ug/Kg
1.0 ug/L
8140
Endosulfan I
10 ug/Kg
1.0 ug/L
8080
Ethyl benzene
--
5 ug/L
8240
Fluoranthene
--
10 ug/L
8270
Fluorene
330 ug/Kg
10 ug/L
8270
Indeno(l,2,3,cd)pyrene
330 ug/Kg
0.043 ug/L
8270/8310
Isophorone
--
10 ug/L
8270
Methyl chloride
--
100 ug/L
8240
Methyl parathion
100 ug/Kg
1.0 ug/L
8140
Napthalene
10 ug/L
8270
Ni trosodi phenyl ami ne
330 ug/Kg
10 ug/L
8270
Pentachlorophenol
10 ug/L
8270
Phenanthrene
330 ug/Kg
10 ug/L
8270
Phenol
10 ug/L
8270
Polychlorinated biphenyls
10 ug/Kg
1.0 ug/L
8080
Pyrene
5 ug/L
8270
Tetrachloroethylene
5 ug/Kg
5 ug/L
8240
2,3,4,6-Tetrachlorophenol
10 ug/L
8270
Toluene
5 ug/L
8240
2,4,5-TP (silvex)
50 ug/Kg
0.1 ug/L
8150
-------
Section No:
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July 21, 1988
10 of 11
TABLE 3-4. ANALYTICAL METHODS AND DETECTION LIMITS
DETECTION LIMITS SW-846
Toxic Constituent Solids Purge Water Method
1,2,4-Trichlorobenzene
10
ug/L
8270
2,4,6-Trichlorophenol
330 ug/Kg
10
ug/L
8270
2,4,5-Trichlorophenol
10
ug/L
8270
2,4,5-Trichlorophenoxyacetic
50
ug/Kg
0.
1
ug/L
8150
acid
Xylenes (total)
--
50
ug/L
8240
Corrosivity
--
--
7.2
EP Toxicity
1310
Arsenic1
2
mg/Kg
53
ug/L
6010
Barium
40
mg/Kg
200
ug/L
6010
Cadmium
1
mg/Kg
5
ug/L
6010
Chromium
2
mg/Kg
10
ug/L
6010
Lead
1
mg/Kg
42
ug/L
6010
Nickel
8
mg/Kg
40
ug/L
6010
Selenium1
1
mg/Kg
75
ug/L
6010
Silver
2
mg/Kg
10
ug/L
6010
Mercury
0.1 mg/Kg
0.
2
ug/L
7470
TDS
--
1
mg/L
160.1
TSS
1
mg/L
160.2
T0C
--
0.
5
mg/L
9060
PH
0.
1
pH units
9040
Total Cyanides (in EP
0.5 mg/Kg
10
ug/L
9010
toxicity leachate)
If arsenic and/or selenium is detected or if the detection limit
is above the delisting criteria. The sample will be rerun using
SW Method 7740 for selenium and Method 7060 for arsenic.
-------
Section No: 3.0
Revi sion: 5
Date: July 21, 1988
Page: 11 of 11
TABLE 3-5. PCDD/PCDF PRACTICAL DETECTION LIMITS*
Compound Ash (ppt) Water (ppt)
2,3,7,8-TCDF 15.0 0.12
Tetra Furans 15.0 0.12
Penta Furans 15.0 0.12
Hexa Furans 37.0 0.30
Hepta Furans 37.0 0.30
Octa Furans 50.0 0.50
2,3,7,8-TCDD 15.0 0.12
Tetra Di oxi n 15.0 0.12
PentaDioxin 15.0 0.12
Hexa Dioxin 37.0 0.30
Hepta Dioxin 37.0 0.30
Octa Dioxin 50.0 0.50
* Per final rule given in the Federal Register/Vol. 53.
No. 48, March 11, 1988 pages 7903-7915
-------
Section No: 4.0
Revi s i on: 5
Date: July 21, 1988
Page: 1 of 18
4.0 SAMPLING PROCEDURES
This section details the planned sampling procedures for this
test program. Currently, the program consists of a
preproduction burn for delisting purposes consisting of four
replicate eight hour tests conducted on consective days.
Sampling requirements for these tests are listed in Table
4-1. Enviresponse will have sufficient equipment and sample
containers to conduct ten tests.
During each test burn run, the pesticide contaminated wastes
will be burned in the incinerator for a period of 8 to 10
hours. All sampling for the run will be performed during this
time period except as follows:
o Kiln ash and cyclone ash, which require cooling, will
be sampled approximately 12 hours after the test.
4.1 COMBUSTION PARAMETERS
The sampling and data collection procedures for waste flow
rate, fuel flow rate, water flow rate, temperature, CO, CO?,
NOx, 02, and air flow rate are described below.
The waste solids feed rate to the rotary kiln is controlled by
a weigh cell and a mechanical timer/sequencer that cycles a
hydraulic feed ram. The desired feed rate is obtained by
adjustment of the weigh cell controller to give the desired
weight per cycle and the cycle time of the ram feeder to give
the desired frequency. The weigh cell controller will send a
weight signal to a printer to record the weight of each charge
and a totalized weight.
The waste oil feed will be measured with an EXAC Model 2100
flow meter. This flow meter has a digital display for the
instantaneous flow rate, lb/hr, and the totalized flow. The
2100 model has a maximum readable rate of 720 lb/hr with an
accuracy of +0.15%. This unit will be field-calibrated with
fuel oil before the test. The waste oil feed rate will be
displayed on the instrument. The incinerator operator will
-------
Section No: 4.0
Revision: 5
Date: July 21, 1988
Page: 2 of 18
4-1. SAMPLE REQUIREMENTS FOR PREPRODUCTION BURN ANALYSES
BYPRODUCT STREAMS
ANALYSIS
SAMPLE
1. Kiln Ash/Cyclone Ash
Dioxins/Furans
1-1 iter bottle
composite
Metals/Mercury/Cyanide
1-liter bottle
Herbicides/BNAs
1-1 iter bottle
PAHs
1-1 iter bottle
Organophosphate Pesticides
1-1 iter bottle
Pesticides/PCBs
1-liter bottle
Volatile Organics
2-40 mL VOA vials
2. Purge Water
EP Toxicity Metals/Mercury
1-1 iter cubitainer
(after filters)
Total Metals
1-liter cubitainer
Cyanide
1-1 iter cubitainer
Volatile Organics
2-40 mL VOA vials
BNAs/Herbicides
1-gallon bottle
PAHs
1-gal 1 on bottle
Organophosphate Pesticides
1-gallon bottle
Pesticides/PCBs
1-gallon bottle
Dioxins/Furans
2-gallon bottle
3. Purge Water
EP Toxicity Metals/Mercury
1-1 iter cubitainer
(before filters)
Total Metals
1-1 iter cubitainer
Cyanide
1-1 iter cubitainer
Volatile Organics
2-40 mL VOA vials
BNAs/Herbicides
1-gallon bottle
PAHs
1-gallon bottle
Organophosphate Pesticides
1-gallon bottle
Pesticides/PCBs
1-gallon bottle
Dioxins/Furans
2-gallon bottle
4. Purge Water before
EP Toxicity Metals/Mercury
1-liter cubitainer
test run (before filters)
Total Metals
1-1 iter cubitainer
Cyanide
1-1 iter cubitainer
Volatile Organics
2-40 mL VOA vials
BNAs/Herbicides
1-gallon bottle
PAHs
1-gallon bottle
Organophosphate Pesticides
1-gallon bottle
Pesticides/PCBs
1-gallon bottle
Dioxins/Furans
2-gallon bottle
NOTE: Amount of sample to be sufficient to supply two laboratories.
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Section No:
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4.0
5
July 21, 1988
3 of 18
also manually record the rate on the log sheet every 15
minutes. The totalized flow for each test will be recorded
every 15 minutes to check that the instantaneous flow rates
are consistent, and the feed tank levels will be also
measured, using a sight level gage, to verify the quantity
fed.
The flue gas composition (02, CO, C02 and N0X) will be
continuously monitored at two locations. The first location
is in the quench elbow at the SCC outlet immediately upstream
of the water spray. This location will have two gas sample
probes. One will supply the sample to the non-dispersive
infrared/polarographic primary monitoring system and the other
will supply the sample to the chromatograph backup monitoring
system. The second sampling location is at the stack. One
advantage of monitoring at these two points is that the amount
of air in-leakage from the air pollution control equipment can
be calculated.
The gaseous samples are withdrawn from the center of the ducts
through a 1/2-in. Inconel probe. The extracted sample passes
through a ceramic inertial filter, located inside the probe,
to remove particulate material (greater than 100 micron) from
the gas sample. There is another filter at the Perma Pure
dryer. Filtration is required for instrument protection.
Next, the filtered gas is partially cooled in an air-air heat
exchanger to lower the temperature to approximately 38°C
(100°F). Entrained liquids are collected in a liquid trap
at the bottom of the exchanger. The gas sample then passes
through a vaporizer ( 1 200C) to ensure that any entrained
liquids from the process are vaporized before entering the gas
drying unit. Gas drying will be accomplished in a Perma Pure
dryer (hygroscopic, ion-exchange membrane) that removes water
vapor from the gas sample without using a condensation process
since condensation often removes key gaseous components from
the sample. The cooled and dried gas sample is then
transported to the gas chromatographic/chemi1uminescent or the
nondispersive infrared/polarographic analyzers through Teflon
tubing. The sampling and sample transport functions are all
controlled by a microprocessor. The sampling function of the
gas monitoring system continuously operates to provide fresh,
up-to-date gas samples to the analyzers for stack and flue gas
analysis.
The temperatures at the rotary kiln and SCC outlets will be
monitored with thermocouples, ANSI, type S (Pt/Pt-Rh), in
direct contact with the flue gases. The thermocouples are
shielded from the burner flames to eliminate temperature
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Section No:
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5
July 21, 1988
4 of 18
measurement error associated with flame radiation. The
millivolt thermocouple signal is converted to a (4-20 mA)
signal and is recorded on a strip chart recorder which is in
the control panel on the kiln trailer.
The fuel flow rates will be read from rotameters and the air
flow rates will be read from indicators. These data will be
recorded every 30 minutes in the log sheets. These
instruments will be calibrated before the test burn program
according to manufacturers' recommendations. Wastewater
collected during a test is measured by a flow meter and also
will be measured at the end of each test by the change in
liquid level in the wastewater tank.
4.2 SAMPLING PERIODS
Each eight hour sampling period will begin when the
incineration system is at steady-state. The project manager
will determine when sampling may begin, based on a review of
data from the continuous monitoring equipment. During
sampling, the test coordinator will periodically verify that
steady-state conditions exist. Steady-state operation is
defined as consistent operation during a 30 minute period with
less than 5% drift during 30 minutes for the SCC temperature
and less than 10% drift for waste feed, and flue gas 02
concentrations. These parameters will be checked at least
every 30 minutes. If a transient condition develops during
sampling, the test coordinator will decide whether to
temporarily interrupt or to terminate sampling.
4.3 SAMPLING LOCATIONS AND PROCEDURES
The locations where solid, liquid, and gaseous samples are
collected from the Incineration System are shown in Fig. 4-1.
Materials supplied to the incineration process including
liquid and solid waste feeds, are sampled at locations 2 and
3. Samples of process solids (ash) and liquid (purge water)
effluents are collected at locations 4 and 6. The composition
of the combustion gases is continuously monitored at the exit
duct from the SCC (locations 11 and 12) and at the stack
(location 13).
The sampling equipment and the procedures for collecting
samples at each location are summarized in Table 4-2.
Sampling frequency and reference methods are included in the
table. Additional details regarding each sampling location
are discussed below.
-------
fMOCIU
VAVKR
HCONOART
COMfeUSIlOM
chi— m
cvciome
•OtB
«MU
¦> FAN
PURUE WAIER
94.UOQE
"O O 50 <~>
(D CD
tfl rt< n
(O n> —«• c+
• • • • (/)
— o
O 3
cn c_« in .f*
c
o —* o
-hVc
m no
00 •—
iO
00
00
riCUKL 4-1. iik"j locations lor To:.,t. lum
-------
Section No: 4.0
Revision: 5
Oste: July 21, 1988
Page: 6 of 18
TABLE 4-2. SAMPLE COLLECTION LOCATIONS, EQUIPMENT, AND METHOOS
description/Location Access Equipment General Procedures/Frequency Reference Methods3
1. Ki In and Cyclone
Ash Container
(4a,4b)
Open top
Spoon; glass
bottle
Composite grab samples
collected from druns for
each run
S007, SU846
2. Purge water line Tap
downstream of
carbon filters (6)
3. Purge water line Tap
upstream of
carbon filters (6)
4. SCC exit duct 4-in.
(10) port
5. SCC exit duct 4-in.
(10) port
Glass bottle
Glass bottle
Sample extra-
l on/condi Hon-
ing system
Sample extra-
lon/condition-
mg system
Sample continuously
during run (2 hour
intervals) and composite
Sample continuously
during run (2 hour
intervals) and composite
Continuously filters, cools
drys, and transports combustion
gases to instrunents for 0
N0x, COj and CO analyses
Continuously filters, cools
drys, and transports combustion
gases to instrinents for 0^
and CO analyses
S004, SU846
S004, SU846
6. Stack (12) 4-in. Sample extra- Continuously filters, cools
port lon/condition- drys, and transports combustion
ing system gases to instrunents for 02,
N0x, COj and CO analyses
Prefix S refers to Sampling and Analysis Methods for Hazardous Waste Combustion. EPA-600/8-84-002.
SU refers to Test Methods for Evaluating Solid Waste. SW846, Third Ed., 1987.
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Section No: 4.0
Revision: 5
Date: July 21, 1988
Page: 7 of 18
Kiln and Cyclone Ash (4) -- Bulk ash will be collected from
the kiln and cyclone in open-top containers, covered, and
allowed to cool. A scoop will be used to collect a sample
from each container. The samples collected during each
replicate test run will be composited in a stainless steel
mixing apparatus.
Purge Mater (6) -- Samples will be taken from taps in the
discharge line downstream and upstream of the carbon filters.
Before the first run, a sample upstream of the carbon filters
will be collected to provide a blank sample. Samples will
then be taken at 1 hour intervals after test start, and ending
with test completion. The samples for volatile organic
analysis will be composited as described in the procedure
given in Appendix B. The other samples will be composited as
per ASTM Method D-3370. It
4.4 Flue Gas Samp!i no
-v3
-1
Continuous emission monitors will be utilized for measuring
the concentration of the following gases: oxygen, carbon
dioxide, carbon monoxide, oxides of nitrogen, and total
hydrocarbons during all tests. A side view of the exhaust
stack is shown in Figure 4-2. The stack is 2 foot by 2 foot
square and the top of the stack is approximately 40 ft above
ground 1 evel . -2.
The continuous emission monitoring system (CEM) probe is
located in a port hole located 2 feet above the stack
silencer. Other stack sampling is not required because the
program is solely for purposes of delisting byproducts streams
as hazardous wastes.
The CEM system will monitor the stack during the entire test
peri od.
4.5 SAMPLING PROGRAM OPERATIONS
All field activities will be conducted per the guidance of
Section 3.0 in the (OSWER) Guidance Directive 9355.0-14 for
implementing field activities. This will include Sections 3.2
(Control of Fieldwork Generated Contaminated Material), 3.3
(Organization of the Field Team), 3.4 (Decontamination), and
3.5 (General Health and Safety Considerations).
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Section No: 4.0
Rev i s i on: 5
Date: July 21, 1988
Page: 8 of 18
FIGURE 4-2.
Stack gas sampling ports and sampling probe traverse points.
2'
MM8PORT§
(9)
CONTINUOUS
MONITORING
PORT
(12)
VOST
PORT'
(8)
ooooo
p-f I
SILENCER
« 42'
10'
T
2'
J L
r
VOST
PORT
LJ LJ LJ LJ LJ
MMS POA
TRAVERSE -:>(NT DISTANCE FROM PRONT WAU
I
Z
1
4
5
a
2.0"
8.0"
10.0"
M.0"
18 0"
22 0"
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Section No: 4.0
Revi s i on : 5
Date: July 21, 1988
Page: 9 of 18
4.6 SAMPLE CONTAINERS AND PRESERVATION REQUIREMENTS
Table 4.3 summarizes the container requirements for the
samples. Table 4-4 summarizes preservation requirements and
presents holding times for the samples. Precleaned sample
bottles will be obtained for I-Chem Research (415/782-3905) in
California (presently the official bottle repository for the
Superfund Program).
4.7 SAMPLE CONTROL
The purpose of sample control is to maintain the quality of
samples during collection, transportation and storage for
analysis. Sample control in the field will be per OSWER
directive 9355.0-14 Sections 4.0 and 6.2. Information
detailed in these sections include:
o Records (OSWER Section 4.5)
o Procedures for sample indentification tags, sample
traffic reports, chain-of-custody records, receipt-
for-samples forms, custody seals and field notebooks
(Section 4.6)
o Packaging, labeling and shipping (Section 6.2)
4.7.1 Chain of Custody
Chain of custody procedures will be followed to ensure a
documented, traceable link between any given measurement
results and the sample and parameter which is represents.
These procedures are intended to provide a legally acceptable
record of sample preparation, storage, and analysis.
To track sample custody transfers before ultimate disposition,
sample custody will be documented using the form shown in
Figure 4.3. A chain of custody seal is shown in Figure 4.4.
In addition, a master logbook will be used as a centralized
mechanism for documenting project activities.
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Section No: 6.0
Revision: 5
Date: July 21, 1988
Page: 10 of 18
TABLE 4-3. PREPROOUCTION BURN SAMPLE
FREQUENCY AMD CONTAINER REQUIREMENTS
Total Total Total
Containers Sample Sample
For Containers Containers
Process Stream Sampling Frequency Compositing Shipped Required Sanple Container Description
Kiln ash/Cyclone ash One grab per drun
composite and composite
Scrubber Purge
Water (after
carbon fiIter)
One grab every 2
hours during run
and composite
2
0
2
0
1
0
3
5
0
6 1000 irt. wide-mouth glass bottles w/tefIon-Iined
screw cap
2 40 irt. glass vials w/ teflon-Iined screw cap
1 12" x 24" shallow stainless steel pan
10 40 nl glass vials w/tefIon-Iined screw cap
1 1000 nl glass Erlermeyer flask
1 125 mL amber glass bottle w/tefIon-Iined
screw cap
8 1000 nl a fiber glass bottles w/tef Ion-1 ined
screw cap
3 1000 irL cubitai ner w/tef Ion-1 ined
screw cap
5 1 gallon amber glass bottle w/tefIon-Iined
screw cap
1 32 oz wide mouth jar
'C- I
'3
(continued)
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Section No: 4.0
Revision: 5
Date: July 21, 1988
Page: 11 of 18
TABLE 4-3. PREPRODUCTION BURN SAHPIE FREQUENCY AND CONTAINER REQUIREMENTS (COTlt.)
Total Total Total
Containers Sanple Sample
For Containers Containers
Process Stream Sampling Frequency Compositing Shipped Required Sanple Container Description
Scrubber Purge
Water (before
carbon fiIter)
Scrifcber Purge
Water (Collected
prior to run)
One grab every 2
hours during run
and conposi te
One grab taken prior
to any waste feed
going to incinerator
8
1
0
8
0
0
1
0
0
0
8
0
1
2
0
1
0
3
5
0
2
1
3
0
5
0
10 40 rrt_ glass vials w/teflon-lined screw cap
1 1000 irt. glass Erlenmeyer flask
1 125 ml artier glass bottle u/tefIon-lined
screw cap
8 1000 nt antoer glass bottles w/tefIon-lined
screw cap
3 1000 nt cubitainer w/tefIon-lined
screw cap
5 1 gallon amber glass bottle w/tefIon-lined
screw cap
1 32 oz wide mouth jar
2 40 nt glass vials w/teflon-lined screw cap
1 125 ml amber glass bottle w/tefIon-1ined
screw cap
3 1000 nt cubitainer w/tefIon-Iined
screw cap
8 1000 nt antoer glass bottles w/tefIon-lined
screw cap
5 1 gallon amber glass bottle w/tefIon-Iined
screw cap
1 32 oz wide mouth jar
'5
3
U
NOTE: Basis is for 1 run. Equipment for ten rins is required.
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Section No:
Revision:
Date:
Page:
4.0
5
July 21, 1988
12 of 18
TABLE 4-4. PREPRODUCTION BURN PRESERVATION
REQUIREMENTS AND HOLDING TIMES
Analyses
Preservati on
Hoi ding Times
Di oxi ns/Furans1
Metals
Mercury
Cyan i de
BNAs1
PAHs1
Organochlorj ne
Pesti ci des1
Pesticides
PCBs
Vol. Org.
TOC
TDS, TSS
1
Cool to <4°C
HN03 to pH <2
HN03 to pH <2
Cool <4°C
NaOH to pH 12
0.6 g ascorbic acid
Cool <4°C
Cool <4°C
Cool <4°C
Cool <4°C
Cool <4°C
Cool <4°C
4 drops cone
Cool <4°C
HC1 to pH <2
Cool <4°C
HC1
7 days until
extraction
6 mos.
13 days
14 days
7 days until
extraction
7 days until
extract i on
7 days until
extraction
7 days unti1
extraction
7 days until
extract i on
14 days
28 days
48 hours
Note:
1. Analysis within 30 days after extraction.
-------
Section No
Revi s i on:
Date:
Page:
4.0
5
July 21, 1988
13 of 18
FIGURE 4.3
CHAIN OF CUSTOOY RECORD
N? 05002
ENVIRESPONSE, INC.
CHAIN OF CUSTOOT fteCOAO
MOrfCf ««¦(.
IMI^I
04 H
i o
1
1
1
'0 H
COllIC M 0
• 0 0'
>m i
i icrioa
¦ IM
i
' '¦*
canctio*
covins
i
m a
• •
• ¦1
3
i
•» «*•!
«r>o»Mf>oa 'on oiooin .
. 3»'C
3«'C
•(C(|«10 •* Utf .
•cctivto rr mtwt .
:*'!" m
-m «. i5«i
-------
Section No: 4.0
Revi s i on : 5
Date: July 21, 1988
Page: 14 of 18
FIGURE 4.4
>jnitu6»s
"IV3S AOOlSftO V, ^
x)Q>S X**
>no v„
^ CUSTODY SEAL
J Dau
Sigrviturt
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Section No:
Rev i s i on :
Date:
Page:
4.0
5
July 21, 1988
15 of 18
4.7.2 Logbooks
Field notebooks and a master sample log will be used to record
sampling activities and information. Field notebooks will be
bound field survey books. Notebooks will be surrendered to
the field sampling task leader upon completion of the
assignment. The cover of each logbook will contain:
o The name of the person to whom the book is assigned
o The book number;
o The project name;
o Entry start date; and
o Entry completion date.
Entries will include general sampling information to
reconstruct the site activities without reliance on memory.
The beginning of each entry will include the date, sampling
site, start time, weather conditions, field personnel present,
and level of personal protection. Other possible entries
would be names and purpose of any visitors to the vicinity
during sampling, unusual conditions which might impact the
interpretation of the subsequent sampling data, or problems
with the sampling equipment. All entries will be in ink with
no erasures. Incorrect entries will be crossed out with a
single strike and initialed.
A master sample log will be maintained on site for all samples
taken. A full description of the sample, its origin, and
condition will be included in the master log entry. An
example of the master log heading is shown in Figure 4.5.
4.7.3 Sample Labels
Each sample will be assigned a unique identification number.
Examples of a sample label and a sample Identification Tag are
shown in Figures 4.6 and 4.7.
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Section No:
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Date:
Page:
FIGURE 4.5
4.0
5
July 21, 1988
16 of 18
Example of Master Logbook Format
II #•.
Call«CI
T»M
iaalfla*
fllaatio lv«
••¦a
laiiUla
¦wit*
Bala
Tim
lilt
-------
Section No:
Revision:
Date:
Page:
FIGURE 4.6
4.0
5
July 21, 1988
17 of 18
EPA REG ION VII tS V0LATILF5
ABC LAW ILL WCC/HOUSER
EPAi: K09ZA00I S(10#: WCC/H0USE*
11 / /B6 TIME?
DEPTH:
CSLOR:~CTYm,
LOCATION!
«- !
EPA REGION VII *, VOLATILES
ABC LANDFILL ^wcC/HOUSER
EPA#: K09ZA001 SMO#j
11/ /B6 TIME?
DEPTH:
COLOR: 'limi
LOCATION:
EPA REGION VII *X VOLATILES
efa#^£;^ wcc/houser
EFA#. K09ZA001 SflOi:
117 '2* TIME?
CEF Tl-;
CI'i-OF: |_Ti~MI
LOCATION:
]
1
EDA REGION VII tr METALS-TOTAL
ABC LANEr rLL ir.'CC 'HCUSER
EPA#: K09ZA0O1 SMO#:
11/ /s^ TmE?::::::
D€PTH: LOCATION:
COLOR: WHITE
EPA REGION VII ft METALS-FILTERED
ABC L AfILL WCCHOUSER
EFA#; K09ZA001 SMO#:
J1/ -- TIME?
i' '
~
CEPT -
col:-
C- R; ^ V
-OCATION:
-------
Section No: 4.0
Revision: 5
July 21, 1988
Pa9e: is of 18
FIGURE 4.7
I
J
J
1
J
1
Q
* a»e »¦»
tm ~ m« a
AMMTta
800 kmm
S«M« ithi (tq«i «¦
»
COO. TOC NutnrtQ
U(IM
fti intf Gram
Orfincs GC/MJ
^nofliv hffunmi
Vodbit Or u^a
!
I
r I1UUU91
UutiCtmetff
Bsoinaioo
AtmirfeK
3 50966
O
««
"3
7!
a
s
v
M
o
s
*
2
LU
cd2
-------
Section No:
Revi sion
Date:
Page:
5.0
5
July 21, 1988
1 of 29
5.0 ANALYTICAL PROCEDURES AND CALIBRATIONS
This section delineates the analytical protocols which will be
used to analyze samples at the laboratories.
As discussed in Sections 1.0 and 4.0, the following process
streams will be sampled: _2
o Kiln ash,
o Cyclone ash,
o Purge water downstream of carbon filter,
- 2.
o Purge water upstream of carbon filter, and
o Stack gases.
C02, 02, N0X, THC
These samples will be analyzed for the parameters previously
discussed in Section 4.0 using appropriate laboratory
analytical techniques described in this section and outlined
i n Table 3-4.
5.1 INORGANIC ANALYSIS
5.1.1 Total Dissolved & Total Suspended Solids
Purge water upstream of the carbon filter will be analyzed for
Total Dissolved Solids by Method 160.1 and Total Suspended
Solids according to Method 150.2 of "Methods for Chemical
Analyses of Water and Wastes", EPA 500/4-79-020. Measurements
are to be performed with an analytical balance which has been
calibrated using standardized weights traceable to the
National Bureau of Standards and capable of weighing to the
nearest milligram (mg).
5.1.2 &H
The pH of the purge water upstream and downstream of the
carbon filters will be determined according to EPA Method 9040
(SW-846, 3rd Edition). The meter is calibrated to a pH of 7.0
and 10.0 using two buffer solutions.
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Section No:
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5.0
5
July 21, 1988
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5.1.3 Total Organic Carbon
Total organic carbon content will be determined for the purge I
water upstream of the carbon filters following the procedures I
outlined in Method 9060 (SW-846, 3rd Edition). The analyses
will be performed on a Dohrman DC80 TOC Analyzer the
instrument will be calibrated daily with standard solutions of
potassium hydrogen phthalate over the expected concentration
range, 0, 0.25 and 0.50% TOC.
5.1.4a Metals - (Total)
Samples of purge water (downstream and upstream of the carbon
filters) from the incineration system will be analyzed for
total metals prior to the analysis for EP toxicity. If the
target analytes meet the delisting criteria then the EP
toxicity test is unnecessary for the target analytes. The
samples for the total metals analysis will be acidified in the
field with 5 mL/L of reagent grade HNO3. The samples will
be extracted in the laboratory using SW Method 3005 and the
extract will be analyzed by ICP according to Method 6010 of
U.S. EPA SW-846. The calibration for ICP and the separate
analysis by SW Method 7470 required for mercury are discussed
in Section 5.1.4b.
5.1.4b Metals - (EP Toxicity & Nickel^
Samples of purge water (downstream and upstream of the carbon
filters) from the incineration system and kiln ash/cyclone ash
composite will be submitted for metals determination in
accordance with delisting requirements (arsenic, barium,
cadmium, chromium, lead, mercury, nickel, selenium, and
silver). Extraction procedures will follow those outlined in
40 CFR Chapter 1, Part 261, Appendix II for EP toxicity test
procedures. After extraction is complete, the extracts will
be acid digested per procedures discussed below and analyzed.
The analyses will be performed by ICP according to Method 6010 I
of U.S. EPA SW-846 with the exception of Mercury. Mercury
will be analyzed by Method 7470 (cold vapor). If selenium
and/or arsenic is detected or if matrix interferences raise
the method detection limits above the delisting criteria for
these compounds, the sample will be rerun using atomic
adsorption Method 7740 for selenium and Method 7060 for
arsenic. Detection limits are provided in Table 3-4.
Digestion For ICP - The EP Toxicity extract will be digested
according to the procedure given in Method 3010. This
consists of an acid digestion with concentrated nitric acid
(HNO3) under gentle reflux conditions until the digestate is
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Section No
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5.0
5
July 21, 1988
3 of 29
light in color and does not change in appearance. This is
followed by addition of 1:1 hydrochloric acid (HC1) and
dilution to 100 mL with dionized water (ASTM Type II).
Digestion For Methods 7060 and 7740 - The EP Toxicity extract
will be digested according to the procedure given in section
7.1 of the method description. This consists of an acid
digestion with 30% hydrogen peroxide solution (H202) and
concentrated nitric acid (HNO3). This is followed by
addition of 1% nickel nitrate solution and dilution with Type
II water.
Dissolution Procedure For Method 7470 (Hal - The EP Toxicity
extract will be digested according to the procedure given in
section 7.1 of the method description. This consists of
addition of sulfuric acid (H2S04) and concentrated HNO3
followed by addition of 5% potassium permanganate solution and
5% potassium persulfate solution. Sodium
chloride-hydroxylamine sulfate solution is then added to
reduce excess permanganate. Finally, stannous sulfate
solution is added and the sample bottle is immediately
attached to the aeration apparatus for Hg analysis.
Calibration For ICP - Prepare mixed calibration standard
solutions combining appropriate volumes of stock solutions.
Five different sets of mixed solutions are required as
specified in Method 6010. Each set should be prepared at
three different concentration levels. The concentrations
should span the linear range of the instrument and bracket the
target concentrations for delisting (Table 1-1). Establish
the calibration curve by running the blank first and then
working toward the highest standard.
Calibration For Methods 7060 (As). 7470 (Hg) and 7740 (Se) -
The calibration will be made according to section 8.2 of the
respective method description using appropriate standard
solutions as described above. A calibration curve will be
constructed by analyzing a blank and three standard
concentrations. A new calibration curve will be constructed
after each hour of continuous sample requirements.
5.1.5 Total Cyanides
Total cyanides will be analyzed in liquid matrices using
Method 9010 of SW-846 which is a colorimetric technique. Per
the Federal Register requirement, cyanides in the EP toxicity
leachate from the solid sample will also be measured by Method
9010.
-------
ENVIRESPONSE, INC.
ENVIRONMENTAL EMERGENCY RESPONSE UNIT
GSA RARITAN DEPOT, WOODBRIOGE AVENUE BUILDING 209 BAY F EDISON. N J 08037
(201) 548 9660
DATE: July 21, 1988
TO: Joyce Perdek
Project Officer, HWERL
FROM: James P. Stumbar
SUBJECT: QA ID No. SP-236-E
Lab Work Plan No. Support Office of Pesticides
Project Category II
Title: "USEPA Mobile Incinerator System Pesticide
Preproduction Burn (2,4,5-T)
Prepared by: Enviresponse, Inc.
CC: Guy Simes
Revision 5 of QAPP SP-236-E is attached. This contains minor changes to the
previously approved Revision 4. These changes are described below:
1. SW-846 Method 8310 has been specified for those polynuclear aromatic
hydrocarbons (PAHs) for which the delisting criteria require lower
detection limits than achievable with Method 8270.
Affected pages: Section 1 pages 7, 10, and 12
Section 2 pages 1, 3, and 4
Section 3 pages 4, 6, and 9
Section 4 pages 10 and 11
Section 5 pages 25 and 26
2. Minor revisions and corrections have been made to the holding times and
preservation requirements in Table 4-4 to reflect SW-846 requirements. A
30 day maximum holding time has been specified to expedite results for
semivolatiles, PAHs, etc.
Affected page: Section 4 page 12
3. Method 8080 write-up has been changed to reflect external standardization
used by the analytical laboratory.
Affected page: Section 5 page 24
-------
Category II QUALITY ASSURANCE PROJECT PLAN
PROJECT TITLE:
EPA PROJECT OFFICER:
EERU PROGRAM DIRECTOR:
PERFORMING ORGANIZATION:
DURATION:
TYPE OF PROJECT:
SUPPORTING ORGANIZATION:
The U.S. Environmental
Protection Agency
Mobile Incinerator System
Pesticide Preproduction Burn
James J. Yezzi, Jr.
Gopal Gupta
Enviresponse, Inc. - EERU, GSA
Raritan
Depot, Edison, New Jersey
08837
February 1988 to September 1988
Work Order under EPA Contract
68-03-3255
U.S. Environmental Protection
Agency
Hazardous Waste Engineering
Research
Office of Research and
Laboratory Development Releases
Control Branch
APPROVALS:
EI CORPORATION
EPA
NAME: Gopal Gupta
TITLE: Project Manager
SIGNATURE: DATE ikijtff SIGNATURE:
NAME: James J. Yezzi, Jr.
TITLE: Project Officer
Date
NAME: Ramjee Raghavan
TITLE: R&D Section Chief
SIGNATURE: r v<—
NAME: Joyce Perdek
TITLE: EPA Task Monitor
DATE U2/&T SIGNATURE:
Date
NAME: James P. Stumbar
TITLE: Test .Coordinator
SIGNATURE: !i P rJ'it \
NAME: Jack Borns
TITLE: QA Officer
SIGNATURE:
NAME: Guy F. Simes
. TITLE: QA Officer HWERL
DATE f'ZttVB SIGNATURE:
P./K DATE VjJjdg
Date
-------
6.6.1
QUALITY ASSURANCE PROJECT PLAN APPROVAL FORM
for
HWERL Contracts/lAGs/Cooperatlve Agreementajln-house Pro|ects
Lab Workplan No: Support: office o f Task $urt Date: 1933 - sept 1983
Pesticides (for measurement, data gathering, and/or data gen-
eration activities)
Project Category: 11
OA 10 No: sp ~ 236 ~s Date QAPP Received:
Task Title: USEPA Mobile Incinerator Svstpm Ppstinrif. P ° n r oH n m n n Rn>-n
(2,4, 5 - T)
Technical Project Officer. Joyce Perde't
Contractor Enviresponse
APPROVALS:
Robert Sawyer
Contractor Project/Task Manager
John Boms
Contractor OA Manager
TBN
Affiliate Task Manager*
A.
Signature
^ Ji
Signature
Signature
7/»di?
7/1/ !SS
Date
Oate
Other (as appropriate)
Joyce Perdek
HWERL Technical Project Officer
John S. Far low
HWERL Branch or Staff Chief**
Guy Simes
HWERL Quality Assurance Officer
Signature
Signature
Signature
Signature
Date
Oate
Date
Date
• Approval signature Is required for any ancillary sampling, analytical, or data gathering support
provided by a subcontractor or HWERL principal Investigator.
*" Approval signature from the HWERL Branch or Staff Chief Is required for Category I, II, and III
extramural projects and for all In-house projects.
HWERL (QAPP AF)
(October 1966)
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Section No:
Revi sion
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5.0
5
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5.2 VOLATILE ORGANICS
5.2.1 Analysis for Volatile Qrqanics
The samples of kiln ash/cyclone ash composites and purge water
downstream and upstream of the carbon filters for volatiles
analysis will be conducted using Method 8240 of EPA SW-846.
These samples will be analyzed for acetone,
1,2-dichloroethane, chloroform, tetrachloroethylene, methyl
chloride, methylene chloride, xylenes, benzene, ethyl benzene,
toluene, and ch1orobenzene. Detection limits are presented in
Table 3-4. A portion of the ash samples will be dispersed in
methanol to dissolve the volatile organic constituents. An
aliquot of the methanol solution will be combined with organic
free water in the purging chamber. Methanol is freely
miscible with water in all proportions.
Approximately 1 gram of the sample will be transferred into a
preweighed 50 mL glass centrifuge tube or 20 mL glass vial,
with Teflon-lined caps, containing 15 mL methanol. The capped
centrifuge tube and methanol will be reweighed on an
analytical balance to determine the sample weight. Care will
be taken not to touch the sample transfer implement to the
methanol. The sample will be dispersed in the methanol as
expeditiously as possible to prevent loss of volatiles from
the sample. After the sample weight has been determined,
additional methanol will be added to the 20 mL mark of the
centrifuge tube or glass vial. The sample container will be
securely recapped and then vigorously agitated for 1 minute.
The mixture will be agitated manually or with the aid of a
vortex mixer. If the sample does not disperse during the
process, the mixture will be sonicated in an ultrasonic bath
for 30 minutes. The mixture will be allowed to stand until a
clear supernatant is obtained. Centrifugation may be
necessary to facilitate phase separation. The supernatant
solution will then be analyzed or stored for future analytical
needs in a 10 mL screw cap vial with Teflon cap line at 4°C.
Analysis of the methanol extract will proceed by taking an
appropriate aliquot of the methanol solution using a
microsyringe. An aliquot of the methanol solution extract
will be dispersed directly into 5 mL reagent water in the
purging device. The sample will then be purged according to
Method 5030 of SW-846 for GC/MS analysis.
Aqueous samples will be analyzed by the same method as the
methanol extracts. Table 5-1 provides the GC/MS operating
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TABLE 5-1. GC/MS INSTRUMENT OPERATING CONDITIONS FOR VOLATILES ANALYSIS
GC/MS Conditions
Instrument
Hewlett-Packard 5985 or Finnigan OWA
GC Conditions
Column
Temperature
Injector temperature
Carrier flow
1% SP-1000 on Carbopack B,
6 ft x 2 mm ID column
45° C held for 3 min, then 8°/min to
220°C and held
200 - 225°C
Helium at 30 cm/sec or hydrogen
50 cm/sec
MS Conditions
Emission
Ionization
Scan time
300 ua
70 eV
5 scans/peak but not to exceed
7 scans/peak
Mass interval
35-260 amu
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conditions for these analyses. Surrogate compounds and
internal standards shown in Table 5-2 will be injected prior
to GC/MS analysis.
5.2.2 Calibration Standards for Volatile Orqanics
Stock standard solutions will be prepared from pure standard
materials or purchased certified solutions. The stock
standards will be prepared in methanol by serially diluting
EPA EMSL (Las Vegas, Nevada) standard solutions. Because of
the toxicity of some of the organohalides, primary dilutions
of these materials will be prepared in a hood.
Fresh standards will be prepared at least weekly for volatile
compounds with boiling points at <30°C. All other standards
will be replaced monthly, or sooner if comparison with check
standards indicates a problem. Table 5-3 lists the compounds
in the calibration mixture along with internal standards and
surrogate compounds.
Secondary dilution standards in methanol will be prepared from
stock standard solutions which contain the compounds of
interest, at concentrations such that the desorbed calibration
standards will bracket the working range of the analytical
system.
Calibration standards will be prepared at a minimum of five
concentration levels. The calibration standards will be
prepared in reagent water.
5.2.3 Tuning for Volatile Analysis
The GC/MS will be tuned at the beginning of each day. The
instrument tuning will be verified using a direct injection of
bromf1uorobenzene (8FB), using the criteria presented in Table
5-4.
If the performance criteria listed above are not met, the
analyst will retune the instrument and repeat the performance
check. The performance criteria will be met before any
standards, blanks, or samples are analyzed.
After allowing the column to cool, a Laboratory Control
Sample, consisting of an EPA EMSL Quality Assurance (QA)
spike, will be analyzed. If the measured value departs from
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TABLE 5-2. SURROGATE COMPOUNDS AND INTERNAL
STANDARDS USED TO ANALYZE VOLATILES
Surrogate Compounds
dg-toluene
Bromofluorobenzene
d4-l,2-dichloroethane
Internal Standards
Bromochloromethane
1,4-d i f1uorobenzene
d 5 -c h1orobenzene
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1
2
3
4
5
1
2
3
4
1
2
3
4
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TABLE 5-3. VOLATILE ORGANIC CALIBRATION MIXTURE
Typical
relative
Compound retention times
Chlorobromomethane (internal standard) 1.0
d^-l,2-dichloroethane (surrogate) 1.2
Methylene chloride 0.73
Chloroform 1.17
1,2-dichloroethane 1.23
1,4-difluorobenzene (internal standard) 1.0
dg-toluene (surrogate) 1.17
Trichloroethene 0.87
Benzene 0.89
dg-chlorobenzene (internal standard) 1.0
Bromofluorobenzene (surrogate) 1.23
Tetrachloroethylene 0.91
Toluene 0.96
Clorobenzene 1.01
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TABLE 5-4. BFB ION ABUNDANCE CRITERIA
Mass Ion abundance criteria
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 Base peak, 100% relative abundance
95 5 to 9% of mass 95
173 less than 2% of mass 174
174 less than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95% but less than 101% of mass 174
177 5 to 9% of mass 176
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the true value by more than two standard deviations as listed
on the EMSL specification sheet, corrective action will be
taken before further analyses will be performed.
5.2.4 Calibration for Volatile Analysis
After all system criteria have been met, the GC/MS will be
initially calibrated to determine response by generating a
five-point calibration curve. System calibration will be
accomplished by the analysis of reagent water spiked with the
compounds of interest. Spiked solutions will be prepared for
at least five concentration levels and responses of the
compounds at these levels will be recorded to form a
calibration curve. One of the concentration levels will be at
a concentration near, but above, the method detection limit
found in real samples. The remaining concentration levels
should correspond to the concentration levels found in real
samples or not exceed the working range of the GC/MS system.
On every day that samples are analyzed, verification of the
five-point calibration curve is necessary. A standard set of
solutions with concentrations of the compounds of interest
between the low and high points of the calibration curve will
be analyzed. If the response varies by more than + 25
percent, the calibration check procedure will be repeated. A
second failure indicates the calibration curve is invalid and
the instrument must be recalibrated. Calibration will be
performed a minimum of once per calendar week.
The GC/MS data system will be programmed to operate in the
Total Ion Current Profile (TCIP) mode collecting the mass
spectra for each of the compounds of interest. The peak for
the major ion of each compound will be measured versus
concentration at five levels of calibration.
The information regarding response ratio versus area ratio for
each standard is stored in the computer and used to calculate
sample concentration. The response factor (RF) for each
compound is calculated using the following equation:
RF = (Ax . Cis)
(Ais)(Cx)
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where: Ax = Area of the prime characteristic ion for the
compound to be measured.
Ais = Area of the primary characteristic ion of the
internal standard.
Cjs = Concentration of the specific internal
standard.
Cx = Concentration of the compound to be measured.
5.3 SEMIVOLATILE ORGANIC COMPOUNDS BY METHOD 8270
5.3.1 Analysis for Semivolatile Organic Compounds
Samples of the purge water (downstream and upstream of the
carbon filters), and kiln ash/cyclone ash composite will be
sent to the laboratory for analysis of delisting requirement
organic extractable compounds by EPA Method 8270 of SW-846.
For Method 8270 the compounds of interest include: phenol,
chlorinated phenols, d i - and tri- chlorobenzenes, polynuclear
aromatic hydrocarbons and phthalates. Detection limits are
presented in Table 3-4.
Aqueous samples will be spiked with the surrogate compounds
shown in Table 5-5, then serially extracted with methylene
chloride at a pH greater than 11 and again at pH less than 2,
using a separatory funnel. The methylene chloride extract is
dried and subsequently concentrated to a volume of 1 to 2 mL.
The concentrated extract is then analyzed by gas
chromatography/mass spectrometry using the operating
conditions shown is Table 5-6.
Qualitative identification is performed using the retention
time data and spectral matches to standards. Quantitative
analysis will be performed using an internal standard method
of quanti fication .
The potential for contamination introduced as a result of
sample handling and analysis procedures will be assessed by
analyzing daily method blanks. These consist of deionized
water taken from the Laboratory System to detect contamination
introduced by extraction and sample handling.
Preparation of ash samples for semivolatile organic analysis
will be conducted in accordance with Method 3540 of EPA
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TABLE 5-5. SURROGATE COMPOUNDS ADDED TO SAMPLE
FOR SEMIVOLATILE ORGANIC ANALYSIS
d 5 -N itrobenzene
2 -f1uorob i phenyl
dj4-terphenyl
dg-phenol
2 -f1uorophenol
2,4,6-tri bromophenol
TABLE 5-6. GC/MS OPERATING CONDITIONS FOR METHOD 8270
SEMIVOLATILE ORGANIC ANALYSES
Instrument
GC Conditions
Column
Temperature program
Injector type
Injector temperature
Injection volume
Column flow
MS Conditions
Electron energy
Scan rate
Mass range
Source temperature
Hewlett-Packard 5985 or 5988A,
Quadrupole Mass Spectrometer
DB5 30M fused silica capillary
or equivalent
40°C held for 4 min, then
10°/min to 270°C and held
Grob type
250° - 300°C
1-2 uL, splitless
Helium at 30 cm/sec or hydrogen
at 50 cm/sec
70 eV
1.0 sec/scan
35 - 500 amu
According to manufacturer
speci fi cations
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SW-846. The solid sample is mixed with anhydrous sodium
sulfate, placed in an extraction thimble, and extracted first
with methylene chloride in a Soxhlet extractor. The methylene
chloride extract is dried, concentrated and analyzed by gas
chromatography/mass spectrometry in accordance with the GC/MS
procedures of Method 8270 in SW-846. The operating conditions
are shown in Table 5-6.
5.3.2 Instrument Tuning
At the beginning of each working day, the system will be tuned
by injecting bis-decaf1uorotriphenylphospene (DFTPP) to obtain
a spectrum. The GC/MS will be tuned to meet all the key ion
criteria shown in Table 5-7.
5.3.3 Calibration Standards
The GC/MS unit will be calibrated to the analytes of concern
and the internal standards and surrogates shown in Table 5-8.
Calibration standards will be prepared at five concentration
levels by adding volumes of stock EMSL standards to a
volumetric flask and diluting to volume with acetone or other
suitable solvent. These calibration standards will cover the
working range of 20 to 200 ppb in the pre-extracted samples.
Each new set of standards will be verified by analyzing
EPA/EMSL QA samples of base, neutral, and acid extractable
compounds.
5.3.4 Instrument Calibration
Internal standards, shown in Table 5-8, will be used to
calibrate the instrument. One (1) of each calibration mixture
will be analyzed and the area of the primary characteristic
ion will be tabulated against the concentration for each
compound and internal standard. A response factor, defined in
Section 5.2.4 will then be calculated.
A five-point calibration curve will be constructed by plotting
the response factor against the standard concentration. The
concentration of the standards will be in the range of 20 to
160 ug/mL.
The working calibration curve or response factor will be
verified on each working day by measurement of the calibration
standards. The working calibration curve will be considered
valid if the criteria specified in Section 7.4 of the method
description for Calibration Check Compounds (CCC) and System
Performance Check Compounds (SPCC) are met and 90% of the
semi vol ati1es have an actual response within + 25 percent of
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TABLE 5-7. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA*
Mass
Ion
abundance criteria
51
30 -
60% of mass 198
68
less
than 2% of mass 69
70
less
than 2% of mass 69
127
40 -
60% of mass 198
197
less
than 1% of mass 198
198
base
peak, 100% relative abundance
199
5 -
9% of mass 198
275
10 -
30% of mass 198
365
greater than 1% of mass 198
441
present but less than mass 443
442
greater than 40% of mass 198
443
17 23% of mass 442
* For the following instrumental parameters:
electron energy: 70 volts (nominal); mass range
35-450 amu; scan time: at least 5 scans/peak but
not greater than 7 seconds per scan.
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TABLE 5-8. SURROGATES AND INTERNAL STANDARDS USED TO
CALIBRATE THE GC/MS FOR EXTRACTABLE ANALYSES
Parameter Relative retention
ti me
Region 1
d^-1,4-dichlorobenzene (IS)* 1.0
dg-phenol 0.94
2-f1uorophenol 0.69
Region 2
dg-naphthalene (IS) 1.0
d5-nitrobenzene 0.84
Region 3
djq-acenaphthene (IS) 1.0
2 - r1uorobiphenyl 0.90
Region 4
dig-phenanthrene (IS) 1.0
2,4,6-tribromophenol 0.91
Region 5
d J 2-chrysene 1.0
d^-terphenyl 0.90
Region 6
d 12-pery1ene 1.0
* IS - Internal Standard.
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the predicted response. If this criterion is not met, the
test will be repeated using a fresh calibration standard.
Alternatively, a new calibration curve will be prepared.
5.3.5 Calibration Procedures
1. The instrument will be calibrated using five
calibration (working) standards when it has failed to
pass verification.
2. A laboratory control sample will then be analyzed.
If the reported values are within control limits of
the expected values, analysis will proceed.
3. All instrument operating conditions and quality
control results will be entered in the instrument
1ogbook.
5.4 PCDD/PCDF BY METHOD 8290
Samples submitted for Polychlorinated Dibenzo-p-dioxins and
Polychlorinated Dibenzofurans analysis will be processed
according to Method 8290, U.S. EPA EMSL (Las Vegas), a method
for the determination of tetra-, penta-, hepta, and
octa-chlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans
(PCDFs) in chemical wastes including still bottoms, fuel oils,
sludges, fly ash, reactor residues, soil and water.
Method 8290 uses a matrix-specific extraction, analyte- c
specific cleanup, and high-resolution capillary column gas
chromatography/high resolution mass spectrometry (HR6C/HRMS)
techniques.
Because of the extreme toxicity of these compounds, the
analyst must take necessary precautions to prevent exposure to
himself, or to others, of materials know or believed to
contain PCDDs or PCDFs.
5.4.1 Sample Preparation and Extraction
Fly ash samples are extracted by placing a sample (e.g. lOg)
and an equivalent amount of anhydrous sodium sulfate in a
Soxhlet extraction apparatus charged with 100 mL of toluene
(benzene) and extracted for 16 hours using a three cycle per
hour schedule. The toluene extract is cooled and filtered
through a glass fiber filter paper into a 500 mL round bottom
flask. The filter is then rinsed with 5 mL of toluene. The
combined toluene solution is then concentrated to near dryness
and transferred to a separatory funnel with hexane.
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The solvent is partitioned with a basic solution and an acidic
solution and placed on an alumina column and eluted with
methylene chloride in hexane. The sample is then cleaned up
on a carbon column.
Aqueous samples are extracted with methylene chloride for a
25-hour period then dried through anhydrous sodium sulfate.
Samples are concentrated on a water bath and the solvent
exchanged to hexane. The solvent is then partitioned and
cleaned as described above.
5.4.2 GC/MS Analysis
Response factors are calculated for standard relative to 7
internal standards. The recovery standards
(1JCi2-l,2,3,4-TCDD and c 1 2-1,2,3,7,8,9-HxCDD) are
added to the samples prior to injection. The TCDD standard is
used to determine the percent recoveries of the tetra- and
pentachlorinated PCDD/PCDF congeners while the HxCDD standard
is used for the determination of hexa, hepta and octa-
chlori nated PCDD/PCDF congeners percent recoveries. The
concentration of the recovery standard in the sample extract
will be the same as that in the calibration standards used to
measure the response factors. The GC operating conditions and
temperature programs are listed in Table 5-9. The high
resolution calibration solution concentrations are listed in
Table 5-10.
5.4.3 Initial Cali brati on
Initial calibration is required before any samples are
analyzed for PCDDs and PCDFs. Initial calibration is also
required if any routine calibration (Section 5.4.4) does not
meet the required criteria. All seven high-resolution
concentration calibration solutions listed in Table 5-10 will
be used for the initial calibration. The instrument will be
tuned with PFK molecular leak to meet the minimum resolving
power of 10,000. The instrument is then injected with 2 uL of
the GC column performance check solution to acquire the SIM
mass spectral data. The total cycle time must be less than or
equal to 1 second. The laboratory will not perform any
further analysis until it is demonstrated and documented that
the criterion listed in the reference method are met.
Using the same GC and mass spectrometer conditions that
produced acceptable results with the column performance check
solution, a 2-uL portion of each of the seven concentration
calibration solutions is then analyzed.
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TABLE 5-9. RECOMMENDED GC OPERATING CONDITIONS
FOR METHOD 8290
Column coating DB-5
Film thickness 0.25 urn
Column dimension 60 m x 0.32 mm
Injector temperature 270°C
Splitless value time 45 s
Interface temperature Function of the final temperature
TEMPERATURE PROGRAM
Stage Init. Temp. Init. Hold. Temp. Fin. Temp. Fin.
(° C) Time (min) Ramp (° C) Hold.
(° C/min) Time
1 200 2
2
3
5 220 16
5 235 7
5 330 5
Total time: 60 min
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TABLE 5-10. HIGH RESOLUTION CALIBRATION SOLUTIONS CONCENTRATIONS
Concentration (pq/uLl
Compound HRCC
7
6
5
4
3
2
1
Unlabeled Analvtes
2,3,7,8-TCDD
200
100
50
25
10
5
2.5
2,3,7,8-TCDF
200
100
50
25
10
5
2.5
1,2,3,7,8-PeCDD
200
100
50
25
10
5
2.5
1,3,4,7,8-PeCDF
200
100
50
25
10
5
2.5
2,3,4,7,8-PeCDF
200
100
50
25
10
5
2.5
1,2,3,4,7,8-HxCDD
500
250
125
52.5
25
12.5
6.25
1,2,3,6,7,8-HxCDD
500
250
125
62.5
25
12.5
6.25
1,2,3,7,8,9-HxCDD
500
250
125
62.5
25
12.5
6.25
1,2,3,4,7,8-HxCDF
500
250
125
62.5
25
12.5
6.25
1,2,3,6,7,8-HxCDF
500
250
125
62.5
25
12.5
6.25
1,2,3,7,8,9-HxCDF
500
250
125
62.5
25
12.5
6.25
2,3,4,6,7,8-HxCDF
500
250
125
62.5
25
12.5
6.25
1,2,3,4,6,7,8-HpCDD
500
250
125
62.5
25
12.5
6.25
1,2,3,4,6,7,8-HpCDF
500
250
125
62.5
25
12.5
6.25
1,2,3,4,7,8,9-HpCDF
500
250
125
62.5
25
12.5
6.25
OCDD
1,000
500
250
125
50
25
12.5
OCDF
1,000
500
250
125
50
25
12.5
Internal Standards
13r
13^12
13r12
13r12
13^12
13c12
13c12
13r12
13?12
l12
-2,3,7,8-TCDD
-2,3,7,8-TCDF
¦1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
-1,2,3,6,7,8-HxCCD
¦1,2,3,4,7,8-HxCDF
•1,2,3,4,6,7,8-HpCDD
-1,2,3,4,6,7,8-HpCDF
¦OCDD
Recovery Standards
^0,2-1,2,3,4-TCDD(a)
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
125
250
250
250
250
250
250
250
50
125
50
125
50
125
50
125
50
125
50
125
50
125
(a)used for recovery determinations of TCDD, TCDF, PeCDD and PeCDF
internal standards
' 'Used for recovery determinations of HxCDD, HxCDF, HpCDD, HpCDF, and
OCDD internal standards.
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o The criteria listed below for acceptable calibration
must be me before the analysis is performed.
o The percent relative standard deviations for the mean
response factors [RRF(n) and RRF(m)] from each of the
26 determinations (17 for the unlabeled standards and
9 for the labeled reference compounds) must be less
that 20 percent.
o The S/N for the GC signals present in every SICP
(including the ones for the labeled standards) must
be > 2.5.
o The isotopic ratios must be within the specified
control limits.
5.4.4 Routine Calibration (Continuing Calibration Check)
Routine calibrations must be performed at the beginning of a
12-hour period after successful mass resolution and GC
resolution performance checks. A routine calibration is also
required at the end of a 12-hour shift.
The routine calibration is completed by injecting 2 uL of the
concentration solution HRCC-3 containing 10 pg/uL of tetra-
and pentachlorinated congeners, 25 pg/uL of hexa- and
heptachlorinated congeners, 50 pg/uL of octachlorinated
congeners, and the respective internal and recovery standards
(Table 5-10).
The measured RRFs [RRF(n) for the unlabeled standards]
obtained during the routine calibration runs must be within 20
percent of the mean values established during the initial
cali brati on.
The following criteria will be met before further analysis is
performed. If these criteria are not met, corrective action
will be taken.
The measured RRFs [RRF(m) for the labeled standards] obtained
during the routine calibration runs must be within 20 percent
of the mean values established during the initial calibration.
The ion - abundance ratios must be within the allowed control
1i mi ts.
If either of the first two above criteria is not satisfied,
the entire initial calibration process must be repeated If
the ion - abundance ratio is not satisfied corrective action
will be taken.
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5.5 CHLORINATED HERBICIDE ANALYSIS BY METHOD 8150
Chlorinated Herbicide analyses on the kiln ash/cyclone ash
composite and the purge waters will be performed according to
Method 8150 of U.S. EPA SW-846, a GC/ECD Method for
determining the concentration of 2,4-D, 2,4-DB, 2,4,5-T, and
2,4,5-TP.
5.5.1 Summary of Method
Method 8150 provides extraction, esterification, and gas
chromatographic conditions for the analysis of chlorinated
acid herbicides. The esters are hydrolyzed with potassium
hydroxide, and extraneous organic material is removed by a
solvent wash. After acidification, the acids are extracted
with solvent and converted to their methyl esters using the
diazomethane as the derivatizing agent. After excess reagent
is removed, the esters are determined by gas chromatography
employing an electron capture detector, microcoulometric
detector, or electrolytic conductivity detector (Goerlitz and
Lamar, 1967). The results are reported as the acid
equi valents.
Based upon the specific herbicides to be quantified, a Type la
GC column will be used, as defined in the method. The GS
operating conditions for the herbicide analyses are listed in
Table 5-11.
5.5.2 External Calibration Standards
Calibration standards at a minimum of five concentration
levels for each analyte of interest will be prepared through
dilution of the stock standards with diethyl ether. One of
the concentration levels will be at a concentration near, but
above, the method detection range of concentrations found in
real samples or should define the working range of the GC.
Calibration solutions must be replaced after six months, or
sooner if comparison with check standards indicates a problem.
The results will be used to prepare a calibration curve for
each analyte or if appropriate, the ratio of response to
amount injected or calibration factor (CF) will be calculated
for each analyte at each standard calculation. If the percent
relative standard deviation (% RSD) of the calibration factor
is less than 20% over the working range, linearity through the
range will be assumed and the average calibration factor can
be used in place of the calibration curve.
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TABLE 5-11. GC OPERATING CONDITIONS FOR
CHLORINATED HERBICIDE ANALYSES
GC Conditions
Column
8m x 4mm ID glass, packed
with 1.5% SP-2250/1 .95%
SP-2410 on Supelcoport
(100/200 mesh)
Temperature
185°C isothermal
Column flow
5% methane/95% argon at
70 ml/mim
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CF = Total Area of Peak or Peaks (multiple response)
Mass injected (ng)
5.5.3 Calibration Verification
The working calibration curves or calibration factors will be
verified on each working day by injection of one or more
calibration standards. If the response for any analyte varies
by more than + 15% from the predicted response, a new
calibration curve will be prepared for that analyte.
Rj - f*2 x 100
Percent Difference =
R1
where:
Rj = Calibration factor form first analysis.
R2 = Calibration factor from succeding analyses.
5.5.4 Surrogate Standards
The analyst will monitor the performance of the extraction,
cleanup (when used), and analytical system and the
effectiveness of the method in dealing with each sample matrix I
by spiking each sample, standard, and reagent water blank with I
dicamba herbicide. Deuterated analogs of analytes will not be
used as surrogates for gas chromatographic analysis due to
coelution problems.
5.6 ORGANOCHLORIDE PESTICIDES AND PCBS BY METHOD 8080
Samples of the purge water (downstream and upstream of the I
carbon filters), kiln ash/cyclone ash composites, and the
separator sludge will be sent to the laboratory for analysis
of the delisting requirement pesticides and PCBs by Method
8080 of SW-846. For Method 8080 the compounds of interest are
Aldrin, Chlorodane, Endosulfan I, and total PCBs which are
calculated as the sum of all PCB Arochlor mixtures contained
in the method.
Method 8080 provides gas chromatographic conditions for the
detection of ppb levels of certain organochlorine pesticides
and PCBs. Prior to the use of this method, solid matrices
will be extracted using either Method 3540 or 3550. The purge
water will be extracted at a neutral or as is pH with
methylene chloride using either Method 3510 or 3520. The
extraction solivent is then exchanged to hexane and the
extract is concentrated prior to injection into a gas
chromatograph. The extract will be analyzed by direct
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injection. A 2- to 5-uL sample is injected into a gas
chromatograph (GC) using the solvent flush technique, and
compounds in the GC effluent are detected by an electron
capture detector (ECD) or a halogen specific detector (HSD).
The analysis will be performed with a gas chromatograph
suitable for on-column injections and all required
accessories. The columns and detectors to be used are as
follows:
Column 1: Supelcoport (100/120 mesh) coated with 1.5%
SP-2250/1.95% SP-2401 packed in a 1.8-m x 4-mm I.D. glass
column or equivalent.
Column 2: Supelcoport ( 100/120 mesh) coated with 3% 0V-1
in a 1.8-m x 4-mm I.D. glass column or equivalent.
Detectors: Electron capture (ECD) or halogen specific
(HSD) (i.e., electrolytic conductivity detector).
5.6.1 External Cali bration
Calibration standards at a minimum of five concentration
levels for each parameter of interest are prepared through
dilution of the stock standards with isooctane. One of the
concentration levels will be at a concentration near, but
above, the method detection limit. The remaining
concentration levels will correspond to the expected range of
concentrations found in real samples or should define the
working range of the GC. Calibration solutions will be
replaced after six months, or sooner, if comparison with check
standards indicates a problem.
5.6.2 Surrogate standards
The analyst will monitor the performance of the extraction,
cleanup (when used), and analytical system and the
effectiveness of the method in dealing with each sample matrix
by spiking each sample, standard, and reagant water blank with
pesticide surrogates. Because GC/ECD data are much more
subject to interference than GC/MS, a secondary surrogate is
to be used when sample interference is apparent.
Dibutylchlorendate (DBC) is also subject to acid and base
degradation. Therefore, two surrogate standards are added to
each sample; however, only one need be calculated for
recovery. DBC is the primary surrogate and should be used
whenever possible. However, if DBC recovery is low or
compounds interfere with DBC, then the
2 , 4, 5, 6 - tetrachloro-meta-xylene should be evaluated for
acceptance. Corrective action will be taken when both
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surrogates are out of limits for a sample as defined in Method
8080. Method 3500 indicates the proper procedure for
preparing these surrogates.
5.7 POLYNUCLEAR AROMATIC HYDROCARBONS (PAHs) BY METHOD 8310
Samples of the purge waters, and kiln ash/cyclone ash
composites will be sent to the laboratory for analysis of the
specified delisting requirement PAHs by Method 8310 of
SW-846. Method 8310 provides high performance liquid
chromatographic (HPLC) conditions for the detection of ppb
levels of PAHs. For Method 8310 the compounds of interest are
listed in Table 1-1.
Prior to analysis, solid matrices will be extracted using
either Method 3540 or 3550. The purge water will be extracted
at a neutral pH with methylene chloride using either Method
3510 or 3520. The extraction solvent is then exchanged to
acetonitrile with a Kuderna-Danish (K-D) procedure and the
extract is concentrated prior to injection into a gas
chromatograph.
The extract will be analyzed by direct injection. A 2- to
5-uL aliquot of the extract is injected into a gas
chromatograph, using the solvent flush technique, and
compounds in the GC effluent are detected by a fluorescene
detector.
The analysis will be performed with a gas chromatograph
suitable for on-column injections and all required
accessories. The columns and detectors to be used are as
fol1ows:
Fluorescence Detector: For excitation at 280-nm and
emission greater than 389-nm cutoff (Corning 3-75 or
equivalent). Fluormeters will have dispersive optics for
excitation and will utilize either filter or dispersive
optics at the emission detector.
5.7.1 External Cali brat i on
Calibration standards at a minimum of five concentration
levels for each analyte of interest are prepared through
dilution of the stock standards with acetonitrile. One of the
concentration levels will be at a concentration near, but
above, the method detection limit. The remaining
concentration levels will correspond to the expected range of
concentrations found in real samples or should define the
working range of the GC. Calibration solutions will be
replaced after six months, or sooner, if comparison with check
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standards indicates a problem. Calibration factors are to be
generated and verified as discussed in Sections 5.5.2 and
5.5.3.
5.7.2 Surrogate standards
The analyst will monitor the performance of the extraction,
cleanup (when used), and analytical system and the
effectiveness of the method in dealing with each sample matrix
by spiking each sample, standard, and reagent water blank with
decaf1uorobiphenyl and anthracene or other PAH not expected to
be present in the sample. These surrogates encompass the
range of temperature program to target analytes. Deuterated
analogs of analytes will not be used due to coelution
problems.
5.8 ORGANOPHOSPHOROUS PESTICIDES BY METHOD 8140
Samples of the purge waters, and kiln ash/cyclone ash
composites will be sent to the laboratory for analysis of the
delisting requirement by Method 8140 of SW-846. For Method
8140 the compounds of interest are Dichlorvos, Disulfaton, and
Methyl parathion.
Method 8140 provides gas chromatographic conditions for the
detection of ppb levels of organophosphorous pesticides.
Prior to analysis, appropriate sample extraction techniques
will be used for the solid matrices. The purge water will be
analyzed by direct injection. A 2- to 5-uL aliquot of the
extract is injected into a gas chromatograph, and compounds in
the GC effluent are detected with a flame photometric or
thermionic detector.
The analysis will be performed with a gas chromatograph
suitable for on-column injections and all required
accessories. The columns and detectors to be used are as
fol1ows:
Column: 1.8-m x 2-mm I.D. glass, packed with 5% SP-2401
on Supelcoport, 100/120 mesh (or equivalent)
Detector: Phosphorous-specific, Nitrogen/Phosphorous
(N/P) operated in the phosphorous sensitive mode or Flame
Photometric (FPD)
5.8.1 External Cali bration
Calibration standards at a minimum of five concentration
levels for each analyte of interest are prepared through
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dilution of the stock standards with acetonitri1e. One of the
concentration levels will be at a concentration near, but
above, the method detection limit. The remaining
concentration levels will correspond to the expected range of
concentrations found in real samples or should define the
working range of the GC. Calibration solutions will be
replaced after six months, or sooner, if comparison with check
standards indicates a problem. Calibration factors are to be
generated and verified as discussed in Sections 5.5.2 and
5.5.3.
5.7.2 Surrogate standards
The analyst will monitor the performance of the extraction,
cleanup (when used), and analytical system and the
effectiveness of the method in dealing with each sample matrix
by spiking each sample, standard, and reagent water blank with
tetrachlorvinphos, dimeton 0, and ethoprop.
5.9 CALIBRATION OF CRITICAL COMBUSTION PARAMETER MEASUREMENT
SYSTEMS
The critical combustion parameter measurements are the kiln
and SCC exit temperatures, the waste solid and liquid feed
rates and the combustion gas monitoring systems. The
calibration procedures and frequency are detailed below.
5.9.1 Temperature Monitoring System
The thermocouple converter and recorder are calibrated by
inputting a millivolt signal which corresponds to a given
temperature signal according to ANSI Standard Thermocouple
Tables. The output signal is then adjusted to a proper
temperature reading. The temperature monitoring system cannot
be calibrated during the operation of the mobile incinerator,
so calibration of the instrument will be done before the start
of the testing program. If the calibrations show a
significant drift (greater than 2%) in the accuracy of the
temperature monitor, the deviation will be recorded and the
instrument recalibrated.
5.9.2 Contaminated Waste Organic Liquid Flow Rate
The EXAC Model #2100 unit will be field-calibrated with fuel
oil. Calibration will be done by gravimetric changes in a
separate feed container with time. The liquid waste feed rate
will be manually recorded by the kiln operator every 15
minutes. The total flow will be recorded to confirm that the
instantaneous flow rates are consistent. The periodic
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recording of flow rates will be used to evaluate the
steady-state operation of the incinerator before and during
each test.
5.9.3 Waste Solids Feed Rate
The weigh cell will be calibrated according to the
manufacturer's specifications, and the cycle time will be
checked with a watch prior to the start of the testing
program.
5.9.4 CO, COo. N0y. THC and Oo Stack and SCC Gas
M o n i t o~r s ~ —
The gas chromatographs, chemi1uminescent detector analyzer,
nondispersive infrared analyzer, and the polarographic
detector analyzer will be calibrated by selectively opening
valves on certified gas standards that direct calibrated gas
mixtures into the sampling probe assemblies on the
incinerator. The calibration gas passes through the same
sample conditioning and transfer systems to the analyzers as
the actual incinerator samples. This technique not only
calibrates the analyzers but corrects for losses that can
occur during sample conditioning. The calibration of the
analyzers generates a four-point calibration curve for each
gas component using a zero gas (pure nitrogen) and three
standard gases. Approximate concentrations of standard gases
are listed in Table 5-12. The four-point calibration will be
performed prior to the start of the testing program for CO,
CO2, 0?» and NO.,. Zero and span calibration gases will
be analyzed daily for CO, COo, 0o, and N0X or will be
analyzed during each run if the tests are run consecutively.
If the zero-span gas analysis data show an analyzer response
drift greater than 5%, a new four-point calibration will be
performed. The gas mixtures used for calibration will be
certified gas standards traceable to the National Bureau of
Standards where possible. The concentrations of the
calibration standard gases used will be close to and will span
the expected values in the gas stream.
Both the primary and backup monitoring systems must be
operational and calibrated before a test is started. Failure
of one system during a test, however, will not be a cause for
interrupting a sampling run because both systems have equal
status in activating alarms, safety interlocks, or waste feed
shutdown and will provide the required gas composition data.
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TABLE 5-12 Approximate Concentrations of
Calibration Gases
Consti tuent Zero Low Mid Span
Carbon monoxide (vppm) 0 25 90 500
Total hydrocarbons (vppm) 0 10 50 100
Oxygen (vol %) 0 4.5 8.0 18.0
Carbon dioxide (vol %) 0 5.0 13.0 19.5
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Preparing, obtaining approval of, and distributing the QA
Project Plan for the mobile incinerator operations.
Managing the incinerator test operations and sampling.
Monitoring to see that field QC and sampling procedures
are carried out.
Deciding when test run sampling must be interrupted or
termi nated.
Reviewing operating logs, stack sampling report, and
analytical reports for completeness and transferring all
test data and reports to the project manager.
Making weekly telephone calls to the three analytical
laboratories to monitor performance and progress.
Assisting in the interim test burn report preparation.
The site supervisors have the responsibility for the field
operation of the mobile incinerator according to directives
during their shift. Some of the site supervisor's
responsibi1ities are:
Assuring that equipment and instrument calibrations are
performed and recorded.
Assuring that the process conditions (temperatures,
pressures, flowrates, etc.) established for the test are
set and maintained.
Ensuring that the required operating data are recorded,
collected, and delivered to the test coordinator.
Monitoring and coordinating with the sample coordinator
the taking of all test samples.
The test burn sample coordinator, M. Merdinger, has the
overall responsibilities for field activities pertaining to
sample collection, handling, packaging, and shipping. The
analytical laboratory will supply the required supplies such
as the resin columns for the stack sampling, sample
containers, and field sample preservation reagents. Some of
the test burn sample manager's responsibilities are:
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Ensuring that appropriate sampling equipment, sample
containers, and field blanks are supplied by the
subcontractor at the test site.
Reviewing the assignment and recording of sample numbers.
Directing sample collection activities.
Overseeing sample preservation in the field.
Documenting sampling activities in field log book.
Ensuring chain of custody of samples in the field.
Overseeing the preparation samples for shipping and
shipping them to Region VII Laboratory.
The remaining members of the test burn field test team are
identified in Table 2-2 along with their lines of
responsibility.
The analytical laboratory directors and the laboratories lines
of responsibility are shown on Table 2-3. The laboratory
analysis coordinator, has the overall responsibility for the
test burn samples and sample analyses. Some of the analysis
coordinator's responsibilities include:
Training and qualifying laboratory personnel in the
analytical procedures specified in the test burn plan,
prior to receiving the test samples.
Directing the distribution of the samples for analyses.
Monitoring and verifying that the specified analytical and
QC procedures are being followed.
Insuring that analytical personnel have the required
information to perform the analyses in accordance with
this Quality Assurance Project Plan.
Reviewing the analytical and QC data as soon as each major
group is analyzed and notifying the project manager if
data quality appears to warrant repeat analyses of some or
all samples.
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If for any reason, any personnel assigned to this project are
lost to it before completion, they will be replaced with
others of equal or better qualifications.
Byproduct streams will be sampled by Enviresponse. Region VII
Laboratory will be the prime subcontractor for analytical
activities. Reporting requirements of the subcontractors to
the main contractor, Enviresponse, Inc., are included in
Section 6.0.
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Table 2-2. Personnel List and Line of Responsibility for MIS
Operation and Sampling During Test Burns
Position Person
R&D Group Manager/EPA Liaison
G. Gupta
Project Manager
R. Sawyer
Assistant Project Manager
J. Tichansky
Test Coordinator
J. Stumbar
Site Supervisors
E. Russell
H. Gragg
J. Irwin
S. Jones
1 '2
Incinerator/APC System Operators
T. Miller
R. L. Turner
J. Collins
R. B. Turner
'i
Waste Feed Handlers
a
Ash Handlers
a
Electrical/Utility
D. Weigel
C. Webb
J. Wheeler
P. Wilson
u
Monitoring System Operator
TBN
G. Tieman
K. Schaedel
G. Thompson
'3
4
Sample Coordinator
Field Team Leader
M. Merdinger I,
M. Merdinger/ ,
J. Stumbar I3
a Local personnel trained and experienced in handling same or similar
hazardous wastes, and who are under a medical surveillance program.
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Table 2-3 Personnel List and Line of Responsibility for Test Burn
Sample Analyses
Position
Person
MIS Project Manager
Prime Analytical Laboratory Region VII
Analytical Laboratory Director
Analysis Coordinator
Volatiles
Herbicides
Di oxins/Furans/Semi volati1es
Metals
Subcontracting Laboratory - TBN
Analytical Laboratory Director
Analysis Coordinator
Organo phosphate pesticides
R. Sawyer
Dr. Harold Brown
Wi11iam Bunn
Diane Easley
Audra Gier
Dr. Tenkasi S.
Viswanathan
Dr. Harold Brown
TBN
TBN
TBN
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3.0 QUALITY ASSURANCE OBJECTIVES
3.1 PRECISION, ACCURACY AND COMPLETENESS
The collection of data to characterize the waste feed,
kiln and cyclone ash, purge water and stack gas requires that
sampling and analysis procedures be conducted with properly
operated and calibrated equipment by trained personnel.
Precision and accuracy goals for this program are presented in
Tables 3-1 and 3-2. Table 3-1 presents precision, accuracy
and completeness goals for field measurements which consist of
process measurements and flue gas composition measurements.
Table 3-2 lists the goals for analysis of process stream
samples.
Precision is defined as the degree of mutual agreement
among measurements made under prescribed conditions. Accuracy
is the degree of agreement of a measurement with an accepted
reference or true value. Completeness is defined as the
percent of samples judged to be valid compared to the total
number of samples collected. Every attempt will be made to
have all data generated to be valid data. However,
realistically, some samples may be lost in laboratory
accidents and some results may be deemed questionable based on
internal QC procedures. Enviresponse anticipates that some 10
percent of the recovery values will be outside the QC limits
owing to matrix interferences. In the event of gross matrix
interferences, revised QA objectives will be submitted for
approval. The objective will be to have 90 percent of the
data valid.
3.2 REPRESENTATIVENESS AND COMPARABILITY
It is recognized that the usefulness of the data is also
contingent upon meeting the criteria for representativeness
and comparability. Wherever possible, reference methods and
standard sampling procedures will be used. The QA objective
is that all measurements be representative of the media and
operation being evaluated. The detailed requirements for the
continuous monitoring, EPA Methods (3A, 6C, 7E, 10, and 25A),
will be followed to ensure representative sampling of flue
gases. The frequent grab sampling of ash and the composite
sampling of process water during each test run will provide
representative samples of these media.
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- 2,
TABLE 3-1. QUALITY ASSURANCE OBJECTIVES FOR
COMBUSTION AND OPERATING PARAMETERS
Method of Precision Accuracy Completeness
Parameter Measurement (%)a (%)b (%)*
Rotary kiln gas
temperature
SCC temperature
Waste oil flow
rate
Waste soil flow
rate
CO
CO,
Thermocouple
Thermocouple
NOv
Electronic flow meter 5
Weigh cell 10
Continuous non-dispersive
infrared analyzer^
15e
Gas chromatograph/
thermal conductivity
detector 5
Continuous polaroaraphic
detector analyzer
5
Chemiluminescent
detector analyzer 10e
5
5
5
10
15e
5
5
10e
90
90
90
90
90
90
90
90
Expressed in terms of the relative standard deviation as defined in Section
IP-
Expressed as the percentage difference from the true (standard) value.
cExpressed as the amount of valid data obtained compared to the total amount
expected.
^Backup is a methanizer coupled to a gas chromatograph/flame ionization
detector.
eBased on results of the previous trial burn, the level of CO and NOx in
the combustion gases was very low. Precision and accuracy will need to be with
t 15% or 5 ppm for CO and ± 10% or 10 ppm for NO^, whichever is greater.
rBackup is a gas chromatograph/thermal conductivity detector.
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TABLE 3-2. ANALYTICAL QA OBJECTIVES FOR PRECISION AND ACCURACY^)
Spiking
Parameter Matrix Precision Accuracy Level
(RPD) [% Recovery) ug/L or ug/kg
olatiles(b)
Acetone
Aqueous
<
25(c)
50-150(c)
500
Soli d(d)
NA
NA
0
Benzene
Aqueous
<
20
76-127
50
Sol id
<
21
66-142
50
Chlorobenzene
Aqueous
<
20
75-130
50
Sol id
NA
NA
0
Chloromethane
Aqueous
<
37
5-204
500
(methyl chloride)
Solid(d)
NA
NA
0
1,2-Dichloroethane
Aqueous
<
20
61-145
50
Sol id
<
22
59-172
50
Ethyl benzene
Aqueous
<
20
59-141
50
Solid(d)
NA
NA
0
Dichloromethane
Aqueous
<
20
24-140
50
(methlylene chloride)
Sol id
<
25
14-150
50
Trichloromethane
Aqueous
<
20
27-133
50
(chloroform)
Solid
<
25
17-143
50
Toluene
Aqueous
<
20
76-125
50
Solid(d)
NA
NA
0
Tetrachloroethylene
Aqueous
<
20
74-127
60
Sol id
<
20
64-137
60
;mi-volatiles(b)
2,4-Dichlorophenol
Aqueous
<
40
27-123
50
Sol id
<
50
25-102
1600
Naphthalene
Aqueous
<
25
36-120
50
Sol id(d)
NA
NA
0
Fluorene
Aqueous
<
20
72-110
50
Solid
<
25
62-120
1600
(cont.)
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TABLE 3-2. ANALYTICAL QA OBJECTIVES FOR PRECISION AND ACCURACY(a> (cont)
Spiking
Parameter Matrix Precision Accuracy Level
(RPD) (% Recovery) ug/L or ug/kg
2,4,6 Trichlorophenol
Aqueous
<
30
52-129
50
Sol id
<
35
42-139
1600
Pentachlorophenol
Aqueous
<
50
9-103
50
Solid(d)
NA
NA
0
Phenanthrene
Aqueous
<
20
65-109
60
Sol id
<
25
55-119
1600
Pyrene
Aqueous
<
31
26-127
50
Soli d(d)
NA
NA
0
1,4-Dichlorobenzene
Aqueous
<
28
36-97
50
Solid(d)
NA
NA
0
1,2,4-Trichlorobenzene
Aqueous
<
28
39-98
50
Solid(d)
NA
NA
0
Benzo(b)fluoranthene
Aqueous
<
26
42-140
50
Solid
<
31
32-150
1600
>AHs(b)
Benzo(a)pyrene
Aqueous
<
38
5-128
10
Solid
<
43
5-138
400
Benzo(b)fluoranthene
Aqueous
<
20
6-150
10
Sol id
<
NA
NA
NA
Chrysene
Aqueous
<
30
5-159
10
Sol id
<
NA
NA
NA
Dibenzo(a,h)anthracene
Aqueous
<
25
5-110
10
Solid
<
30
5-120
100
Indeno(l,2,3-c,d)pyrene
Aqueous
<
29
5-116
10
Sol id
<
NA
NA
NA
cont.)
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TABLE 3-2. (cont.)
Parameter
Matrix
Precision
(RPD)
Accuracy
{% Recovery)
Spiking
Level
ug/L or ug/kg
Hebicides(b)
PCDD/PCDFs(b,f)
PCBs (as Arochlors)
and organochlorine
pesticides
Organophosphorous
pesticides
Metals(e)
PH
Total Suspended/
Dissolved Solids
Cyanides (c)
Aqueous
Sol id
Aqueous
Sol id
Aqueous
Solid
Aqueous
Solid
Aqueous
Sol id
Aqueous
25
25
25
25
20
25
< 20
< 25
< 15
< 20
< 10
50-130
50-130
40-120
40-120
70-130
50-150
40-140
40-140
85-115
80-120
+ 10%
Aqueous No matrix
spike or matrix spike duplicate required
100
250
5
50
20
500
Aqueous < 20
non-aqueous < 30
80-120
70-130
NOTE: All precision and accuracy objectives are based upon historical
laboratory results.
a - Accuracy will be measured as percent recovery of a matrix spike
compounds. Precision will be estimated as the relative percent
difference of a matrix spike duplicate.
(cont.)
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TABLE 3-2. (cont.)
b - Precision and accuracy targets wre determined as follows:
When applicable values were taken from tables for water and
soil MS/MSD recovery in Chapter 1 of the 3rd Ed. SW-846.
Minimum precision of 20% was assumed to be adequate since most
compounds will be nondetect and proof of the ability to
recover compounds present in the matrices is the most
important QC objective.
For constituents not listed in the above tables, the data,
presented in Tables 6 and 7 of the SW Methods 8240 & 8270
write-ups, and in Table 3 and 4 of the SW Method 8310 write-up
were used to estimate target values for water.
Target values for soil were obtained from water target values
by adding 5% to the precision value and increasing the range
of recoveries by 20%.
c - Targets are estimated.
d - NA means that the constituent will not be spiked in the solid
matrix because, analysis in not required for delisting purposes.
e - Accuracy will be determined as percent recovery of matrix spikes
when appropriate or the percent recovery of a QC sample if spiking
is inappropriate. Precision will be determined as relative percent
difference of duplicate spikes, or duplicate sample if spiking is
inappropriate.
f - From PCDD/PCDF spiking requirements see Table 5-10.
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The combustion parameters for which representativeness could
be a problem are the rotary kiln and SCC gas temperatures and
the flue gas component concentrations. The thermocouples for
temperature measurement will be shielded from flame radiation
and will have combustion gases circulated around them. The
sampling points for flue gas compounds will be located in the
center of the ducts. At test conditions the gas flow at the
sample points will be turbulent, ensuring complete mixing.
3.3 METHOD DETECTION LIMITS
The objectives for the method detection limits (MDL) for the
flue gas component monitors are listed in Table 3-3. These
detection limits have been selected based upon instrument
vendor information, system analysis range and prior operating
experience. Since the MDL for these instruments are
significantly below any system alarm/shutdown condition or
typical operating conditions, the verification of these MDL's
will not be included as part of this testing program.
The method detection limits for the various analytical methods
are listed in Table 3-4. The method detection limits for
dioxin analyses will be calculated using the procedure given
in Method 8290. For other analytes, method detection limits
will be determined by the procedure given in Section 1.3 of
the third edition of SW-846. The method detection limits for
PCDD and PCDF analysis are listed in Table 3-5.
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6.0 DATA REDUCTION, VALIDATION AND REPORTING
Extensive QC measures will be used to ensure the generation of
reliable data from sampling and analysis activities. Proper
collection and organization of accurate information followed
by clear and concise reporting of the data is a primary goal
in all projects.
6.1 FIELD DATA REDUCTION
Appendix C of this QA Plan presents the standardized forms
that will be used to record field data. The data collected
will be reviewed in the field by at least two field crew
members. Errors or discrepancies will be noted in the field
log book. Flue gas data will be treated as follows:
o Continuous Monitoring Data--the monitoring data will
be reduced and presented in terms of 30 minute
averages for the parameters listed below:
Oxides of nitrogen--ppm, lb/hr
Carbon monoxide--ppm, lb/hr
Carbon dioxide--percent
Oxygen — percent
Total Hydrocarbons--ppm, lb/hr
6.2 LABORATORY ANALYSIS DATA REDUCTION
Analytical results will be reduced to concentration units
specified by Enviresponse, Inc. or the analytical procedure,
using the equations given in the analytical procedures. If
units are not specified, data from the analysis of water
samples will be converted to units of mg/L using the following
equat ion:
Xw = Xv x W x DF / Vs
where Xw = reported value, mg/L
Xv = reported sample value, mg/kg
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Vs = sample volume, L
DF = dilution factor
W = sample weight, kg
Data from the analysis of gas samples will be reported as
ug/m . This will be calculated by dividing the total weight
of the substance detected by the volume of gas sampled.
The concentration of compounds identified in a sample will be
calculated using either the internal standard or external
standard method. The internal standards are similar in
analytical behavior to compounds of interest. The calculated
concentrations is based upon the chromatographic peak areas
and response factors obtained from the calibration standards
according to the following equation:
Cx = (Ax C.jS DF) for aqueous samples
(Ai s RF Vs)
Cx = (Ax Cis DF) for solid samples
(Ai s RF W)
where: Cx = concentration of analyte x in ug-C/L (aqueous
or ug - c/kg (sol id)
Ax = peak area for analyte x
RF = response factor for the appropriate
quantitative standard in area counts ug-C/L.
(RF is defined in Section 5).
DF = dilution factor.
The concentration of compounds identified by the external
standard method will be determined by calculating the amount
of standard purged or injected from the peak response using
the calibration curve or the calibration factor given in
Section 5.0 according to the following equations:
Cx = (Ax Cs Vt DF) for aqueous samples
(As Vi Vs)
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Cx = (Ax Cs Vt DF) for solid samples
(As Vi W)
where: Ax, Cx, Vs, W, and DF are defined above.
C$ = Amount of standard injected or purged, ng.
Vt = Volume of total extract, uL.
= Volume of extract injected, uL.
The data generated will include the following information:
o Compound; and
o Concentration.
6.3 DATA VALIDATION
6.3.1 Combustion Parameters
Backup measurements will help validate the primary data. The
total contaminated solids fed during each test will be
measured by counting the number of bags of pesticide fed and
multiplying by the weight of each bag. This backup
measurement for contaminated solids quantity used must agree
within + 10% of the primary measurement during the test to be
valid.
The change in the contaminated organic liquid waste feed tank
level during the test will be measured with a dip stick as a
check on the primary mass flow readings. The backup
measurement for these feeds must agree within + 10% to meet
the test objective. Failure to meet this objective will be
discussed in the final report.
6.3.2 Analytical Parameters
Data validation is the process of filtering data and accepting
or rejecting it on the basis of sound criteria. Laboratory
supervisory and QC personnel will use validation methods and
criteria appropriate to the type of data and the purpose of
the measurement. Records of all data will be maintained, even
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that judged to be an"outlying" or spurious value. The persons
validating the data will have sufficient knowledge of the
technical work to identify questionable values.
Field sampling data will be validated by the Field Team Leader
and/or the Field QC Coordinator based on their judgment of the
representativeness of the sample, maintenance and cleanliness
of sampling equipment and the adherence to an approved,
written sample collection procedure.
Region VII Laboratory (ENSV) will evaluate all analytical
data. Analytical subcontractor, the CLP laboratory, will
provide data deliverables required of EPA Contract Laboratory
Program laboratories. Appendix A presents requirements for
general deliverables, and additional method deliverables for:
(1) PCDD/PCDF, (2) GC/MS, (3) GC, and (4) ICP/Furnace methods.
Analytical data will be validated by the laboratory QC or
supervisory personnel using criteria outlined in the QA
Project Plan. The laboratory uses results from field and
laboratory method blanks, replicate samples and internal QC
samples to validate analytical results. Analytical results on
field blanks and replicate field samples are valuable for
validation of sample collection also.
The following criteria will be used to evaluate the field
sampling data:
o Use of approved test procedures
o Proper operation of the process being tested
o Use of properly operating and calibrated equipment
o Leak checks conducted before and after tests
o Use of reagents that have conformed to QC specified
cri teri a
o Proper chain-of-custody maintained
The criteria listed below will be used to evaluate the
analytical data:
o Use of approved analytical procedures
o Use of properly operating and calibrated
i nstrumentat i on
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o Acceptable results from analyses of QC samples (i.e.,
the reported values should fall within the 95 percent
confidence interval for these samples)
o Precision and accuracy achieved should be comparable
to that achieved in previous analytical programs and
consistent with objectives stated in Section 3.0 of
this QAPP
6.4 IDENTIFICATION AND TREATMENT OF OUTLIERS
Any data point which deviates markedly from others in its set
of measurements will be investigated; however, the suspected
outlier will be recorded and retained in the data set while it
is investigated. One or both of the following tests will be
used to identify outliers.
Dixon's test for extreme observations is an easily computed
procedure for determining whether a single very large or very
small value is consistent with the remaining data. The
one-tailed t-test for difference may also be used in this
case. It should be noted that these tests are designed for
testing a single value. If more than one outlier is suspected
in the same data set, other statistical sources will be
consulted and the most appropriate test of hypothesis will be
used and documented.
Since an outlier may result from unique circumstances at the
time of sample analysis or data collection, those persons
involved in the analysis and data reduction will be
consulted. This may provide an experimental reason for the
outlier to determine its effect on the conclusions. In many
cases, two data sets will be reported, one including, and one
excluding the outlier.
In summary, every effort will be made to include the outlying
values in the reported data. If the value is rejected, it
will be identified as an outlier, reported with its data set
and its omission noted.
6.5 DATA REPORTING
6.5.1 Combustion Parameters
The incinerator operators' log sheets and the continuous
monitoring system operators' logs will be used for reporting
data to the project manager. Calibration check results will
be recorded in the "Remarks" sections of the log sheets. The
results of calibration checks for all instruments will be
reported along with the data in the final report.
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6.5.2 Figure 6-1 shows the sampling, analysis, and
reporting responsibilities for the demonstration
test.
6.5.3 Analytical Data
A flow chart depicting a proposed measurement data reporting
scheme is shown in Figure 6-2. Figure 6-3 presents the
analytical data validation and reporting scheme routinely used
at the laboratory. The Work Assignment Organization Chart
identifies the supervisory and QC personnel who will validate
the data.
All data will be reported in standard units depending on the
measurement and the ultimate use of the data. The bulk of the
data will be computer processed and reported as follows:
o Continuous monitoring data (30 minute averages)
Oxides of nitrogen--to nearest 1.0 ppm N0X
Carbon dioxide--to nearest 1.0 percent COp
Oxygen--to nearest 1.0 percent 02
Carbon monoxide--to nearest 1.0 ppm CO
Dry molecular weight--to nearest tenth gram
Total Hydrocarbons--to nearest 1.0 ppm
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PROJECT RESULTS AND REPORTING
- Destruction and Removal
Efficiencies
- Heat and Material Balances
- Operating Suimaries
- Reports
ANALYSIS
FIELD SAMPLING
EMISSIONS RESULTS
Test Coordinator
Jim St unbar
OPERATIONS LOGS
OPERATORS
CONTINUOUS MONITOR
LOGS OPERATORS
REPORTS TO MANAGEMENT AMD EPA
KILN
OPERATORS
SOURCE SAMPLING AND ANALYSIS
- Stack Gas Sampling
- Waste Feed Composition
- Kiln and Cyclone Ash
- Scrubber Liquid
- Lab Audit Samples
OPERATIONS AND MONITORING
- System Conditions
- Waste Feed Flow
- Combustion Temperature
(continuous monitoring)
- Field Audit Samples
FIGURE 6-1 DATA FLOW AND REPORTING SCHEME
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TEST CONDUCTED
DATA SHEET COMPLETED
DATA CHECKED BY TWO
FIELD CREW MEMBERS
DATA SUBMITTED TO
FIELD TEAM LEADER'
1
. ERRORS AND OUTLIERS
NOTED IN FIELD LOG BOOK
PRELIMINARY DATA REDUCTION
CONDUCTED AND CROSS-CHECKED
IN THE FIELD
SAMPLES SHIPPED TO
4
SAMPLES LOGGED IN
i
SAMPLES AND DATA-
RETURNED TO
ENVIRESPONSE
SAMPLES SHIPPED TO
ANALYSIS PERFORMED
1
RESULTS SUBMITTED TO
LABORATORY PRINCIPAL
INVESTIGATOR
FINAL REPORT «-
WRITTEN
SAMPLING AND PROCESS
DATA SUBMITTED TO FIELD
PRINCIPAL INVESTIGATOR
DATA CHECKED AND
TRANSFERRED TO
COMPUTER SHEETS
I
COMPUTER SHEETS
SUBMITTED AND KEYPUNCHED
1
RESULTS RECEIVED FROM
COMPUTER. INPUT NUMBERS
CROSS-CHECKED
1
CORRECTIONS MADE AND
RESUBMITTED TO COMPUTER
1
FINAL RESULTS RECEIVED
FIGURE 6-2. MEASUREMENT DATA FLOW SCHEME
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QC RESULTS
UNACCEPTABLE
QC RESULTS
ACCEPTABLE
YES
DATA UNACCEPTABLE
DATA
ACCEPTABLE
REVIEW QC
DATA
SAMPLE PREPARATIONS
REVIEW DATA,
REANALYZE
IF NECESSARY
REVIEW DATA,
REANALYZE
IF NECESSARY
REVIEW DATA,
REANALYZE
IF NECESSARY
PRECISION AND
ACCURACY
ACHIEVED?
DATA REVIEWED BY
TASK MANAGER OR
SECTION HEAD
1. VALIDATED DATA
ENTERED INTO
PROJECT FILE
2. DATA REPORTED
PROCEED WITH DATA
REDUCTION, REPORT
ALL VALUES IN
APPROPRIATE UNITS
FIGURE 6-3 ANALYTICAL DATA REPORTING SCHEME
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7.0 INTERNAL QUALITY CONTROL CHECKS AND FREQUENCY
Quality control checks will be performed to ensure the
collection of representative samples and the generation of
valid analytical results on these samples. These checks will
be performed by project participants through the program under
the guidance of the QA Director and Field and Laboratory QC
Coordinators.
7.1 DATA COLLECTION AND SAMPLING QC PROCEDURES
Subcontractors' QC checks for the process data collection and
sampling aspects of this program will include, but not be
limited to, the following:
1. Use of standardized checklists and field notebooks to
ensure completeness, traceabi1ity, and comparability
of the process information and samples collected.
2. Field checking of standardized forms by a second
person to ensure accuracy and completeness.
3. Strict adherence to the sample chain-of-custody
procedures outlined in Section 5.0 of the QAPP.
4. Submission of field biased blanks.
Duplicate samples will not be collected during the project
because the scoping burn does not require this level of QC and
the preproduction burn esesntially gives four duplicate
samples because the unit operating conditions will be the same
over the entire preproduction burn.
7.1.1 Sampling Equipment QC Checks and Frequency
Calibration of the field sampling equipment will be performed
prior to and at the conclusion of the field sampling effort.
Copies of the calibration sheets will be submitted to the
field team leader to take on site for reference, and to the
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project file. Calibrations will be performed as described in
the EPA publication "Quality Assurance Handbook for Air
Pollution Measurement Systems, Volume III, Stationary Source
Specific Method;" Section 3 presents acceptance limits.
Leak checks of the sample trains will be conducted in
accordance to the protocol called out for each method. Leak
checks will be conducted prior to and at the end of sample
collection.
7.1.2 Span Drift Check of Continuous Monitors
The continuous monitoring equipment will be checked at the
beginning and end of each test period by inputting a
combination span gas through the probe for analysis. The
responses obtained from these span checks will be reduced into
units of concentration using the appropriate calibration
equation. These data will be plotted on a control chart to
determine if a significant drift has occurred. These limits
were determined by using the 24-hour drift criteria (contained
in PST No. 2: 2.5 percent of span). Data falling outside the
chart limits will necessitate corrective actions.
7.1.3 Sample Collection QC Checks
Field-biased blanks of reagent and collection media (deionized
water, etc.) will be placed in appropriately cleaned and sized
sample containers in the field and handled in the same way as
actual field samples, to provide a QC check on sample
handli ng.
Sample collection QC checks and frequency for samples to be
analyzed in the laboratory are listed below:
o Scrubber Water Sampling:
One field-biased blank (i.e., DI water) for the
first sampling day for volatile organic
compounds.
o Ash Sampli ng:
No duplicates.
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Method blanks will also be provided with the various sample
sets. These blanks are portions of analytical reagents,
filters, and recovery reagents set aside and not transported
to the field. Method blanks will be obtained for each reagent
and sampling media lot.
Field duplicate samples will not be included as QC samples for
this project because they are inappropriate and unnecessary.
Duplicated samples are inappropriate because previous sampling
history has shown that most compounds are none detected. For
such a case the use of matrix spikes and matrix spike
duplicates provides the necessary estimates of accuracy and
precision. Duplicate samples are unnecessary because the
preproduction runs consist of tests which are essentially
under the same process conditions. Hence, the repetition of
four tests should provide the "duplicate field samples".
7.2 ANALYTICAL QC PROCEDURES FOR SAMPLES TO BE ANALYZED IN
THE LABORATORY
7.2.1 Quality Control Samples and Blanks
The Quality Control program for laboratory analysis makes use
of a number of different types of QC samples to document the
validity of the generated data. The following types of QC
samples are used routinely:
7.2.1.1 Method Blanks - Method blanks contain all the
reagents used in the preparation and analysis of
samples and are processed through the entire
analytical scheme to assess spurious
contamination arising from reagents, glassware,
and other materials used in the analysis.
7.2.1.2 Calibration Check Samples - One of the working
calibration standards which is periodically used
to check that the original calibration is still
vali d.
7.2.1.3 Replicate Samples and Spiked Samples - Analysis
of replicate samples is used to enable
estimation of the precision of the analytical
procedure. Replicate aliquots of project
samples are spiked with components of interest
and carried through the entire preparative and
analytical scheme.
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7.2.1.4 Laboratory Control Samples (LCS1 - These samples
are prepared from EPA EMSL concentrates or NBS
standard reference materials. The LCS are used
to establish that an instrument or procedure is
in control. An LCS is normally carried through
the entire sample preparation and analysis
procedure also.
7.2.1.5 Surrogate Spikes - Samples requiring analysis by
GC/MS are routinely surrogate-spiked with a
series of deuterated analogues of the components
of interest. It is anticipated that these
compounds would assess the behavior of actual
components in individual program samples during
the entire preparative and analysis scheme.
7-2.1.6 "Blind" Quality Control Samples - Blind quality
control samples are inserted in the sample load
in a fashion unrecognizable to the analyst.
These samples may be blanks, duplicate or spiked
project samples, or prepared or purchased
reference material samples.
7.2.1.7 Matrix Spikes/Matrix Spike Duplicates (MS/MSD1
A MS/MSD pair will be run for each different
matrix analyzed. These pairs will be spiked
with the target compounds of concern for that
matrix (e.g., 2,4-D, 2,4-DB, 2,4,5-T, 2,4,5-TP
and PCDD/PCDF for ash samples).
All values which fall outside the QC limits, given in Table
3-2, and described in the Analytical Method will be noted.
Enviresponse anticipates that some of these recovery values
will be outside the QC limit owing to matrix interferences.
The following guidelines will be used:
1. All recovery data are evaluated to determine if the
QC limits are appropriate and if a problem may exist
even though the limits are being achieved (e.g., one
compound that is consistently barely within the lower
limit).
2. All recovery data which are outside the established
limits are evaluated. This evaluation will include
an independent check of the calculation.
3. Corrective action will be performed if any of the
following are observed:
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o All recovery values in any one analysis are
outside the established limits,
o Over 50 percent of the values for a given sample
set are outside limits, or
o One compound is outside the limits in over 50
percent of the samples.
The type and frequency of use of each of these QC measure is
listed in Table 7-1. An analysis batch is defined as a group
of 10 or fewer samples carried through the entire preparation
and analysis procedure in one batch.
Reagents used in the laboratory are normally of analytical
reagent grade or higher purity; each lot of acid or solvent
used is checked for acceptability prior to lab use. All
reagents are labeled with the date received and ate opened.
The quality of the laboratory deionized water is routinely
checked. All glassware used in the sampling and analysis
procedures will be precleaned according to the method
requirements. Standard laboratory practices for laboratory
cleanliness, personnel training and other general procedures
are used.
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TABLE 7-1. ANALYTICAL QC MEASURES
QA Measure
Minimum frequency
Method Blank
Each sample
samples
Laboratory
Each sample
Duplicate sample
matrix
Spiked sample
Each sample
matrix when
Laboratory control sample
Each sample
Calibration check sample
Daily
Surrogate spike (GC/MS
Each sample
analysis)
Matrix Spike/Matrix Spike
Each matrix
Duplicate
as given in
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8.0 QUALITY ASSURANCE PERFORMANCE AND SYSTEM AUDITS
The laboratory's Quality Assurance Program includes both
performance and system audits as independent checks on the
quality of data obtained from sampling, analysis, and data
gathering activities. Every effort is made to have the audit
assess the measurement process in normal operation. Either
type of audit may show the need for corrective action.
8.1 PERFORMANCE AUDITS
The sampling, analysis, and data handling segments of a project
are checked in performance audits. Blind QC samples are used
or a different operator/analyst performs these audit operations
to ensure the independence of the quantitative results.
EPA Quality Control Concentrates and NBS Standard Reference
Materials will be used to assess the analytical work. The
Chemistry Divisoin QC Coordinator will direct the inclusion in
the sample load of QC samples appropriate to the analyses
performed in each batch of 20 or fewer samples so that they are
not recognizable to the analyst. In addition, any appropriate
interlaboratory study samples which are available during this
program will be analyzed to further audit the analytical work.
8.2 SYSTEM AUDITS
A system audit is a qualitative review to ensure that the
quality measures outlined in the Project QA Plan are in place.
The Director of Quality Assurance selects projects representing
different types of measurement activities for audit by the QA
staff; this project may be audited under that policy (to ensure
the integrity of system audits, it is not known in advance
whether such an audit will be performed). If it is,, a written
audit report will be submitted as noted in Section 11.0.
8.3 EXTERNAL AUDITS
The laboratory will cooperate fully in any performance of
system audits conducted or arranged by EPA or Enviresponse.
The QA Director and Division QC Coordinators are available to
aid in scheduling such audits.
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9.0 CALCULATION OF DATA QUALITY INDICATORS
9.1 PRECISION
9•1•1 Reference Method Testing and Analytical Measurements
Precision will be determined trough the analysis of replicate
or replicate spiked samples and will be expressed as either
relative standard deviation (RSD) or relative percent
difference (RPD). The following equations will be sued when
three or more measurements are made:
xi = individual measurement
N = number of measurements
Precision of duplicate analyses will be calculated as follows:
RSD = 100 ( S- )
X
where x = arithmetic mean
s = standard deviation
Standard deviation will be determined as follows:
N
2
RPD
Value 1 - Value 2
Arithmetic mean of
values 1 and 2
X 100
9.1.2 Continuous Monitoring System
Precision will be estimated from the periodic span check data
for each monitor using mid-span Manufacturer's Certified gases
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as noted in section 7.1. The following equations will be used
to estimate precision from at least five data points:
Percent difference (dj)
(Yi " xi)
di = (100)
xi
where: = Monitor indicated concentration from the i-th
span check.
Xi = The span check reference concentration for the
i-th precision check.
Mean percent difference (d^)
J
n
_J_ Cd i
dj = n i=l
where: n = number of valid precision checks made during the
test period j.
Standard deviation of the percent difference (Sj)
Sj = \/ n-1 i=l i=l
Upper and lower 95 percent probability limits (UPL and LPL)
will be computed as follows:
UPL = dj + 1.96 Sj
LPL = dj - 1.96 Sj
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9.2 ACCURACY
9-2.1 Reference Method Tests and Analytical Measurements
Accuracy will be estimated from the analysis of matrix spiked
samples and/or laboratory control samples, whose true values
are known to the analyst, and the analysis of "Blind" QC
samples whose values are known to the Chemistry Division QC
Coordinator. Accuracy will be expressed as percent recovery
or as relative error. The formulas to calculate these values
are:
(cm - cs)
Percent Recovery = 100 x ^sp
where:
r
m = Measured value in spiked sample
r
s = Measured value in sample
r
usp = Known value of spike added
. Measured Value - True Value
Relative Error = 100 x I True Value '
9.2.2 Continuous Monitoring System
Relative accuracy will be estimated using blind audit
cylinders or comparison with Reference test procedures. The
cylinder value will be sued as the reference value. The
following equations will be used.
The arithmetic differences will be computed as follows:
where: is the the difference between the current
concentration and previous calibration value
Cm is the monitor indicated concentration
Cr is the reference value concentration
Next, the arithmetic mean of the individual differences will
be calculated:
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-r\
i = i
X n
where: X is the mean of the difference
X ^ is the individual differences
n is the number of data points
The confidence interval at the 95 percent confidence level
will be calculated as follows:
t / -n 2 ^2
• 975 / V V
CI95 = n(n-l) V n ^ Xi - ( . XJ
i=i i 1
where: CI95 is the 95 percent confidence interval
*.975 is a statistical "t factor"
n is the number of data points
X^ are the individual differences
The Relative Accuracy (R.A.) will be calculated from the
preceding values:
X + [ CI ]
95
R.A. = Cr
9.3 COMPLETENESS
Completeness will be reported as the percentage of all
measurements made whose results are judged to be valid. The
procedures to be used for validating data and determination of
outliers are contained in Section 6.0 of this QA Plan. The
following formula will be used to estimate completeness:
( _V_ )
C = 100 T
percent completeness
number of measurements judged valid
total number of measurements
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10.0 CORRECTIVE ACTION
The acceptance limits for the sampling and analyses to be
conducted in this program will be those stated in the method
or defined previously in this QA Project Plan. The corrective
actions are likely to be immediate in nature and most often
will be implemented by the analyst or Project Manager; the
corrective action will usually involve recalculation,
reanalysis, or repeating a sample run. The laboratory's
ongoing corrective action policy is described here.
10.1 IMMEDIATE CORRECTIVE ACTION
Specific QC procedures and checklists are designed to help
analysts detect the need for corrective action. Often the
person's experience will be more valuable in alerting the
operator to suspicious data or malfunctioning equipment.
If a corrective action can be taken at this point, as part of
normal operating procedures, the collection of poor quality
data can be avoided. Instrument and equipment malfunctions
are amenable to this type of action and the laboratory's QC
procedures include troubleshooting guides and corrective
action suggestions. The actions taken should be noted in
field or laboratory notebooks but no other formal
documentation is required, unless further corrective action is
necessary. These on-the-spot corrective actions are an
everyday part of the QA/QC system.
Corrective action during the field sampling portion of a
program is most often a result of equipment failure or an
operator oversight and may require repeating a run. When
equipment is discovered to be defective (i.e., pre- and post-
sampling leak check) it is repaired or replaced and a
corrective factor is established as per the EPA method. If a
correction factor is unacceptable the run is repeated.
Operator oversight is best avoided by having field crew
members audit each others' work before and after a test.
Every effort is made by the field team leader to ensure that
all QC procedures are followed. Economically, it is preferred
to repeat a run during a particular field trip rather than
return at a later date.
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Corrective action for the continuous monitors will involve
constructing a new 3-point calibration equation. In order to
minimize the time that the analyzer is offline, the span gases
will be sampled intermittently (e.g., zero, flue gas, mid
span, flue gas, high span).
Corrective action for analytical work would include
recalibration of instruments, reanalysis of known QC samples
and, if necessary, of actual field samples.
If the problem is not solved in this way, more formalized
long-term corrective action may be necessary.
10.2 LONG-TERM CORRECTIVE ACTION
The need for this action may be identified by standard QC
procedures, control charts, performance or, system audits. Any
quality problem which cannot be solved by immediate corrective
action falls into the long-term category. The laboratory uses
a system to ensure that the condition is reported to a person
responsible for correcting it who is part of the closed-loop
action and follow-up plan.
The essential steps in the closed-loop corrective action
system are:
o Identify and define the problem.
o Assign responsibility for investigating the problem.
o Determine a corrective action to eliminate the
problem.
o Assign and accept responsibility for implementing the
corrective action.
o Establish effectiveness of the corrective action and
implement it.
o Verify that the corrective action has eliminated the
problem.
Documentation of the problem is important to the system. A
Corrective Action Request Form (shown in Figure 10-1) is
filled out by the person finding the quality problem. This
form identifies the problem, possible causes and the person
responsible for action on the problem. The responsible person
may be an analyst, field team leader, Division QC coordinator
or the QA Director. If no person is identified as responsible
for action, the QA Director investigates the situation and
determines who is responsible in each case.
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Section No:
Revision:
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10.0
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July 21, 1988
3 of 4
CORRECTIVE ACTION REQUEST FORM NO.
Originator Date
Person Responsible Contract
for Replying Involved
Description of problem and when identified:
State cause of problem, if known or suspected:
Sequence of Corrective Action: (If no responsible person is identified,
notify QA Director immediately. Submit all CA forms to QA Director for
initial approval of CA.)
State Date, Person, and Action Planned:
CA Initially Approved By: DATE
Follow-up Dates
Final CA Approval By: DATE
Information copies to:
Responsible Person/Division QC Coordinator:
QA Director:
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10.0
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July 21, 1988
4 of 4
The Corrective Action Request Form includes a description of
the corrective action planned and the date it was taken, and
space for follow-up. The QA Director checks to be sure that
initial action has been taken and appears effective and, at an
appropriate later date, checks again to see if the problem has
been fully solved. The QA Director receives a copy of all
Corrective Action Forms and then enters them in the Corrective
Action Log. This permanent record aids the QA Director in
follow-up and makes any quality problems visible to
management; the log may also prove valuable in listing a
similar problem and its solution.
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Section No:
Rev is i on :
Date:
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11.0
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July 21, 1988
1 of 1
11.0 QUALITY ASSURANCE REPORTS TO MANAGEMENT
11.1 INTERNAL REPORTS
The Chemistry Division QC Coordinator and the Air and Process
Engineering Division QC Coordinator prepare written monthly
reports on QC activities for their Division Manager and the QA
Director. These reports detail the results of quality control
procedures, problems encountered and any corrective action
which may have been required.
All Corrective Action Forms are submitted to the QA Director
for initial approval of the corrective action planned and a
copy is provided to the Division Manager. All system audit
reports are provided to the project manager, Division Manager
and the laboratory President.
11.2 REPORTS TO CLIENT
Each data transmittal will contain a summary of QA/QC
activities; this summary will include:
o Estimates of precision, accuracy and completeness of
reported data
o Reports of performance and system audits
o Quality Control problems found
o Corrective actions taken
The final report will include a section summarizing QA/QC
activities during the program. The Chemistry and Air and
Process Engineering Division QC Coordinators and the QA
Director will participate in preparing this section.
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APPENDIX A
DELIVERABLES REQUIRED FROM ANALYTICAL SUBCONTRACTORS
-------
APPENDIX B
PROCEDURES FOR COMPOSITING PURGE WATER SAMPLES
FOR VOLATILE ORGANIC ANALYSES
-------
APPENDIX C
FIELD DATA SHEETS
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APPENDIX D
COMMENTS ON REGION VII VARIATION OF METHOD 8290
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COMMENTS ON REGION VII VARIATION OF METHOD 8290
From: Robert D. Kloepfer, Ph.D.
Chief, Laboratory Branch, ENSV
Date: April 1,1988
The comments of ESAT chemist, Mr. Saleh Arghestani on the
differences between the 8290 and Region VII methods for the
analysis of PCDDs and PCDFs is attached. I discussed the
status of the RCRA method 8290 with Mr. Werner Beckert
(EMSL-LV/EPA) on March 10, 1988. He informed me that this
method is still in the single laboratory evaluation stage and
that the projected completion date for this activity is
September 1988. Apparently, the information that appeared in
the March 11 Federal Register on this method is inaccurate. A
few changes are also proposed for this method after this
evaluation. The method will be subjected to a
multi-1aboratory evaluation in 1989. Although the Region VII
method has not been tested on a multi-1aboratory basis, it has
been peer-reviewed by a numberof scientists with expertise in
this area and has been used for the analysis of up to 30
batches of environmental samples in the last 18 months.
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APPENDIX A
DELIVERABLES REQUIRED FROM ANALYTICAL SUBCONTRACTORS
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GENERAL DELIVERABLES
Please note that some elements are method, technique, op parameter
specific and, therefore, additional deliverables may be required.
Additional deliverables will be outlined on method/parameter specific
attachments to this document.
I. PACKAGE NARRATIVE
1. Method(s) used (citations acceptable 1f commonly available)
2. Summary of problems and/or decision tree processes utilized
to complete the analyses.
II. QUALITY CONTROL
1. Listing of the In-house control limits used as a basis for
corrective action for each of the QC elements.
2. Summary of QC results for reagent blanks, field blanks, matrix
spikes, duplicates, and laboratory control standards analyzed.
a. Matrix Spike: Tabulated results of X recovery
b. Duplicates: Tabulated results for SRSO or ttPD
c. Lab Control Standard: Tabulated results and true values
rtS*'4" or -<4«/l*c
3. Raw QC data chromatograms, quantitation reports, Instrument
readout records, ICP/AA printouts, strip chart recordings,
logbook entries of meter readings. All raw data must be
clearly labeled with the sample ID number and the parameter.
III. SAMPLE DATA PACKAGE
1. Holding time information (date/time sampled and analyzed)
2. Sample results summary
3. Raw sample data chromatograms, instrument readout records,
ICP/AA printouts, strip chart recordings, or logbook entries of
meter readings. All raw data must be clearly labeled with the
sample ID number and the parameter.
4. Quantitation reports
o1? fllian
b. Dilution factors usea
t. Calculations used to determine sample results
5. Percent solids determination for soil data
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STANOARDS OATA PACKAGE
1. listing of laboratory detection limits
2. Initial calibration data
3. Continuing calibration check data
4. Raw standards' data chromatograms, quantitation reports. Aid
instrument readout records, tCP/AA printouts, strip chart
Tier read,n9S. All standards' raw data nust
JfnJ f 1abe1ed as t0 Para
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¦ ieliverab'as ire
tQ the General Oel'ver^uie
ADDITIONAL
PCDD/PCDF Method Deliverables
SAMPLE DATA PACKAGE
1. Listing of ions monitored for each compound along with
area responses found, if any, per sample.
STANDARDS DATA PACKAGE
Initial Calibration:
1. List of retention time (RT) windows established for
each homolog group for both dioxins and furans along
with ions monitored for each compound.
2. All Selected Ion iMonitoring (SIM) reconstructed ion
chromatograms and ion responses for each analyte
in the initial calibration analyses. All raw data
must be clearly labeled as to parameter and concen-
tration they represent.
3. SIM chromatograms for the per:crmance check mixture.
4. % Valley tabulation for rescl-rion between 2,3,7,8- and
1,2,3,4-TCDD.
5. Signal to noise for m/z 320 (2,3,7,3-TCDD) for the low
level calibration standard.
6. Tabulated RRF for each compound in the initial
calibration along with the average RRF and IRSD
calculated based results from tr.e multiple point
initial calibration.
Routine Calibration:
1. SIM chromatograms for the performance check mixture.
2. % Valley tabulation for resolution between 2,3,7,8-
and 1,2,3,4-TCDD.
3. SIM chromatograms and ion responses for the routine
calibration analysis.
4. Tabulated RRF for each compound plus % Difference
between initial calibration RRFs and routine cali-
bration RRFs.
-------
SPECIAL NOTE
For 2,3 ,.7, 8-substituted PCDD/PCDF analysis (versus total
PCDD/PCDF plus 2,3,7,8-TCDD), we also require that each of the
2.3,7,8-PCDD/PCDF analytes be analyzed in the calibration
standard and that RT windows for each analyte be submitted.
-------
These del 1verables are 1
to the General Deliverable-
ADDITIONAL
GC/MS Method Deliverables
I. QUALITY CONTROL
1. Summary of QC results for surrogate compounds.
a. Tabulated % recovery for each surrogate used.
2. Summary of internal standard responses.
a. Listing of area response for each internal standard
compound in che daily calibration solution as weii
as area responses for the internal standard
compounds in each associated sample analysis.
3. Summary of ion abundances for tuning compounds.
a. Tabulated ion abundance results for BFB (volatiles)
and/or DFTPP (semi-volatiles).
b. Raw data mass listing of ion abundances.
II. SAMPLE DATA PACKAGE
1. Mass spectra for all positive -its including reference
spectrum.
III. STANDARDS DATA PACKAGE
Initial Calibration:
1. Tabulated RRFs for each compound plus average RRF
and %RSD for multiple point initial calibration.
Continuing Calibration:
1. Tabulated RRF for each compound plus % Difference
between initial calibration RRF and daily calibra
tion RRF.
-------
ADOITIONAL
GC Method Deliverables
QUALITY CONTROL
1. Summary of QC results for surrogate compounds
a. Tabulated % recovery for each surrogate used.
SAMPLE & STANDAP.D DATA PACKAGE
1. Summary of instrument operating conditions, temperature programs,
and column type or packing.
2. Second or confvmatory column chromatograms and integration printouts
for all samples having positive hits for compounds of Interest including
all standard runs.
3. All chromatograms must be clearly labelled with the sample number
and any peaks representing compounds of interest must be labelled
with the compound name. A corresponding integration printout
must be submitted for each sample which also contains the sample
number, retention time of all peaks, and peak area response.
Each retention time representing a peak corresponding to a compound
of interest must be so labelled on tre integration printout.
-------
ADDITIONAL
ICP/Furnace Method Deliverables
QUALITY CONTROL
1. Tabulated results and raw data for all blanks including
initial calibration blank, continuing calibration bianx,
and preparation blanks.
2. Tabulated results and raw data for ICP Interference
Check Sample analysis.
SAMPLE DATA PACKAGE
Furnace AA;
1. Duplicate m]ection results for all furnace work.
2. MSA data results for all furnace parameters.
3. Tabulated correlation coefficients for MSA results.
-------
APPENDIX B
PROCEDURES FOR COMPOSITING PURGE WATER SAMPLES
FOR VOLATILE ORGANIC ANALYSES
-------
PROCEDURE rQR THE COLLc-.IuN uF A FE== ESENT.;!; vg. ,,,QA SAnFL£ DUp £ nG .
9-1= HOUR SAMPLING FEF.iCD F RCM A SOURCE CF WftT^ ^£T IS GREATER 7m
temperature than ambient ,MAT 13 bRE*TER in
This mathod is written for us# in the collaction of a vQA sample frZ
a BOUTC0 tha^ IS hot and reprsssnt .iti ve of a time period of several
hour*.
EQUIPMENT
•lOml vOA vials, cleaned and baked out and known to be free of
contamination
1000ml Erlenmever {Ias^ cashed and baked out at 130 degrees
centigrade tor 1 hour and coded to ream temperature before use.
A r sf r i ger at or used for the c ;o 1 i n ij o-f tr. a samples.
A source of organic free water to be used for blanks.
PROCEDURE
From a suitable svit port. ]ui:Uv fill one 40 ml VQA vial completel
Cap with the teflon lined septum facing the water layer. Label witf
sample number, time and date of collection. Coal. Collect all
required portions of the sample using the same sample number and
recording the time and date. Cool all portions of the sample.
During the cooling of the sample, a cizzl* of air will form in the
vial. This is normal and snould not ;e o- concern.
After the samples have been cooled. r = -io/-5 all portions of the sampl
from the re+rigerator.
Composite in erlenmeyer flask bv emptying the contents of all vials
that make up the sample. swirl 7 tines and then quicklv fill two
clean JO ml VQA vials full with tne sample. Lafcel and date, noting
the time frame of the composite, eg OZ/o^/33, 3:'.'nam to 4:30cm.
Pack the VGA vials in a plastic cubitainer ~ith an extractor tube
filled with activated charcoal and ref r: gerat-s.
Ship to the analytical laboratorv with the appropriate paperwork.
CLEANING PROCEDURE FCR FEUSABLE GLASSWARE
Rinse with tap water
Wash with hot water and detergent
Rinsa with tap water
Rinse with distilled /iatsr
Bake'in an oven for one hour at 130 degrees centigrade
Cool to room temperature before use
~A/QC Samples
-------
One comoosite blanl. should be preoared for each set of 20 samples
collected. This would mean filling tne aoprcoriat* number of vials
with organic free water. Ref ngerat ing
-------
APPENDIX C
FIELD DATA SHEETS
-------
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