PB8A-155845
Sampling and Analysis Methods for Hazardous Waste Combustion
Little (Arthur D.)> Inc., Cambridge, MA
Prepared for
Industrial Environmental Research Lab.
Research Triangle Park, NC
Feb 84
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
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PB84-155845
EPA.-600/8-84-002
February 1984
SAMPLING AND ANALYSIS METHODS
FOR
HAZARDOUS WASTE COMBUSTION
by
Judith C. Harris, Deborah J. Larsen,
Carl E. Rechsteiner, Kathleen E. Thrun
Arthur D. Little, Inc.
Cambridge, Massachusetts 02140
EPA Contracts 68-02-3111 (Task 124) and -3627
EPA Project Officer: Larry D. Johnson
Technical Support Staff
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
Prepared for:
Office of Research and Development
U.S. Environmental Protection Agency
Washington, DC 20460
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/8-84-002
3, RECIPIENT'S ACCESSION-NO.
FB8 4 15 5 8 4 5
4. TITLE AND SUBTITLE
Sampling and Analysis Methods for Hazardous Waste
Combustion
5. REPORT DATE
February 1984
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
J. C. Harris, D. J. Larsen, C. E. Rechsteiner, and
K.E. Thrun
B. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING OROANIZATION NAME ANO ADDRESS
Arthur D. Little, Inc.
Cambridge, Massachusetts 02140
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-3111, Task 124, and
68-02-3627
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 2/82
14. SPONSORING AGENCY CODE
EPA/600/13
is. supplementary notes ierl-rtp project officer is Larry D. Johnson, Mail Drop 62,
919/541-7943.
i6. abstract rep0rt £S a reference document, describing sampling and analysis
methods for measuring the hazardous constituents (as defined in 40 C. F. R., Part
261, Appendix VIII) which might be designated as principal organic hazardous con-
stituents (POHCs) in the various influent and effluent streams of incineration facil-
ities. The methods for these constituents are described in the text. Also included is
a concise summary sheet for each recommended method which states the name and
number of the method, the types of samples and specific analytes to which the method
applies, a brief description of the method, instrument, and operating conditions,
and reference(s) to more detailed descriptions of the procedure. Technician-level
protocols are thus incorporated by reference, rather than by reproduction in this
report. In addition to presenting the methods for sampling and analysis of POHCs
at these facilities, information concerning additional sampling and analysis require-
ments, general strategies for preparing sampling and analysis plans to meet the
regulatory requirements, and guidelines for reporting and documentation are dis-
cussed.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COS AT l Field/Group
Pollution
Incinerators
Organic Compounds
Toxicity
Waste Treatment
Sampling
Analyzing
Measurement
Pollution Control
Stationary Sources
Hazardous Waste
13 B
07C
06T
14B
14G
18. DISTRIBUTION STATEMENT
Release to Public
It. SECURITY CLASS {This Report)
Unclassified
20. SECURITY CLASS (This page)
Unclassified
EPA form 2220-1 (t-73)
i
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NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
ii
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FOREWORD
This report has been produced by EPA's Office of Research and
Development as part of on-going studies in support of regulatory
programs and of EPA's Office of Solid Waste, EPA Regional Offices, and
appropriate State Agencies. The document contains state-of-the-art
sampling and analysis methods for determination of hazardous waste
incinerator performance. It is intended as a reference work to be used
by personnel of the regulatory groups, personnel associated with
engineering R&D, and the regulated community.
Inclusion in this report does not mean that the sampling or analysis
method is an official EPA method. Official test methods for hazardous
waste related programs are published in SW-846 "Test Methods for
Evaluating Solid Waste," as
Frank T. Princiotta
Director
Industrial Environmental Research Laboratory
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TABLE OF CONTENTS
Page
FOREWORD iii
LIST OF FIGURES x
LIST OF TABLES xi
ABBREVIATIONS AND GLOSSARY OF TERMS ..... xiii
ACKNOWLEDGMENT xx
I. ABSTRACT 1
II. INTRODUCTION 2
A. Purpose 2
B. Scope 3
C. Use of Report 4
III. SAMPLING AND ANALYSIS STRATEGY TO MEET REGULATORY
REQUIREMENTS 5
A. Introduction 5
1. General Facility Standards 5
2. Interim Status Standards for Incinerators ... 5
3. Permitting Standards for Incinerators 6
4. Hazardous Waste Permit Program 7
B. Waste Characterization Strategy 8
1. Sampling 8
2. Analysis 9
C. Stack Gas Effluent Characterization Strategy .... 14
D. Additional Effluent Characterization Strategy ... 16
E. Selection of Specific Sampling and Analysis
Methods 16
1. Scenario 16
2. Strategy 17
3. Tactics and Methods 19
4. Results and Calculations 24
Preceding page Nank
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TABLE OF CONTENTS (Continued)
Page
IV. SAMPLING PROCEDURES 30
A. Overview 30
B. Sampling Methods for Influent Streams . 30
1. Sampling Methods for Liquid Wastes 33
2. Sampling Methods for Solid Wastes 34
3. Sampling Methods for Slurry and Sludge
Samples 35
4. Sampling Methods for Water Samples 35
C. Sampling Methods for Effluent Streams . . 36
1. Sampling Methods for Stack Gas . 36
2. Sampling Methods for Solid and Liquid
Effluents 50
D. Health and Safety Precautions 50
E. Collection of Representative Samples 51
1. Gase s 51
2. Liquids 52
3. Solids 52
4. Slurries 52
5. Sample Handling 52
F. Identification of Samples 53
1. Sample Labels 53
2. Field Log Book 53
3. Field Observations ..... 53
G. Sampling Method Summaries 54
V. SAMPLE PREPARATION PROCEDURES 67
A. Overview 67
B. Representative Aliquots from Field Samples
(Methods P001-P003) 67
C. Recovery Measurements (Methods P011-P014) 68
D. Solvent Extraction of Organic Compounds
(Methods P021-P024) ... 72
1. Aqueous Liquids (Method P021) 72
2. Sludges (Method P022) 72
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TABLE OF CONTENTS (Continued)
Page
3. Organic Liquids (Method P023) 73
4. Solids (Method P024) 74
E. Drying and Concentrating of Solvent Extracts
(Method P031) 75
F. Digestion (Method P032) 75
G. Sample Cleanup Procedures (Methods P041-P045) ... 76
H. Sample Preparation Method Summaries 76
VI. ANALYSIS PROCEDURES 97
A. Overview 97
B. Waste Characteristics 97
1. Ignitability (Method C001) 97
2. Corrosivity (Method C002) 98
3. Reactivity (Method C003) 98
4. Extraction Procedure Toxicity (Method C004) . . 99
C. Proximate Analysis 99
1. Moisture, Solid and Ash Content
(Methods A001-A002) 99
2. Elemental Composition (Method A003) 103
3. Total Organic Carbon and Total Organic
Halogen (Method A004) ... 103
4. Viscosity (Method A005) 104
5. Heating Value of the Waste (Method A006) . . . 104
D. Survey Analysis 104
1. Survey Analysis of Organic Content
(Methods A011-A017) 105
2. Survey Analysis of Inorganics (Method A021) . . 116
E. Directed Analysis 116
1. Organic Constituents (Appendix VIII) 118
2. Inorganic Constituents (Appendix VIII) .... 125
3. Directed Organic Analysis Criteria 128
F. Analysis Method Summaries 135
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TABLE OF CONTENTS (Continued)
Pa^e
VII. QUALITY ASSURANCE AND QUALITY CONTROL PROCEDURES .... 215
A. Overview 215
B. Title Page and Table of Contents 216
C. Project Description 216
D. Project Organization and Responsibility 216
E. Quality Assurance Objectives 220
1. Accuracy 220
2. Precision 223
3. Completeness 223
4. Representativeness 223
5. Comparability 223
F. Sampling Procedures 224
G. Sample Custody 224
H. Data Maintenance and Chain-of-Custody 224
I. Calibration Procedures and Frequency 226
1. Sampling 226
2. Analysis 226
J. Analytical Procedures 226
K. Data Reduction, Validation, and Reporting 226
1. Data Reduction 226
2. Data Validation 234
3. Data Reporting 234
L. Internal Quality Control Checks 235
1. Blank Samples 235
2. Analytical Replicates 235
3. Spiked Samples 235
M. Performance and System Audit 236
N. Preventive Maintenance 236
0. Specific Routine Procedures Used to Assess Data
Precision, Accuracy and Completeness 236
1. Calculation of Mean Values and Estimates of
Precision 236
2. Assessment of Accuracy 237
3. Assessment of Causes of Variance 238
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TABLE OF CONTENTS (Continued)
Page
P. Corrective Action 238
Q. Quality Assurance Reports 240
VIII, REFERENCES 242
APPENDIX A - Hazardous Constituents - Physical/Chemical
Data 245
APPENDIX B - Hazardous Constituents - Stack Gas
Sampling Methods 320
APPENDIX C - Hazardous Constituents - Analysis Methods . 344
APPENDIX D - Summary of Method Numbers 368
APPENDIX E - MS - Analytical Ions 375
APPENDIX F - Volatile Organic Sampling Train 392
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LIST OF FIGURES
Figure No. Page
1 Overview of the Analytical Approach for Waste
Characterization 10
2 Overview of an Analysis Scheme for Stack Gas
Samples from a Comprehensive Sampling Train .... 15
3 Modified Method 5 Train (MM5) 38
4 Sorbent Module 39
5 Source Assessment Sampling System (SASS) 41
6 Evacuated Grab Sampling Apparatus (For
Subatmospheric Pressures) . 43
7 Integrated Gas-Sampling Train: Gas Bag 45
8 Volatile Organic Sampling Train (VOST) . 46
9 Apparatus for Flameless Mercury Determination . . . 197
10 Example of Project Organization and
Responsibility 219
11 Samples of Waste Feed and Stack Emissions are Taken
as Composites Over Four-Hour Long Periods. Three
Destruction and Removal Efficiencies (DRE) are
Calculated from the Ratios Ej/Fi, E2/F2, E3/F3 . . . 225
12 Field Sampling Chain-of-Custody Form 227
13 Chain-of-Custody Record 228
14 Record of Analysis Report Form with Acceptable
Documentation 229
15 Diagram of a Sampling and Analysis Procedure Which
Uses Replicate Samples to Provide Information on
Sources of Variance 239
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LIST OF TABLES
Table No. Page
1 Available Information on Composition of
Hypothetical Waste 20
2 Candidate POHCs for Hypothetical Waste 21
3 Recommended Stack Sampling Methods for Candidate
POHCs in Hypothetical Trial Burn Example 22
4 Recommended Analysis Methods for Candidate POHCs
in Hypothetical Trial Burn Example 25
5 Choice of Samplers for Hazardous Wastes 31
6 Sampling Points for Most Waste Containers 32
7 Sorbents and Special Reagents for Specific POHCs . . 48
8 Summary of Procedures for Compositing Samples ... 69
9 Estimated Quantities of Sample Required for
Analysis 70
10 Potential Compounds for Use as Surrogates 71
11 Threshold Levels of Contaminants in the Extraction
Procedure Toxicity Test 100
12 Proximate Analysis Reporting Form ......... 101
13 Summary of Results for Organic Extracts of a SASS
Train Sample 106
14 IR Analysis Report Form 110
15 Categories for Reporting LRMS Data . Ill
16 LRMS Analysis Report Form 113
17 GC/MS Survey Report Form . 114
18 HPLC/IR or HPLC/LRMS Survey Report Form 115
19 Metals Sought in a Survey Analysis 117
20 Sunnary of Determinations of POHCs by the
Generalized HPLC Analysis Method 121
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LIST OF TABLES (Continued)
Table No. Page
21 Characteristic Data for Metals Listed in
Appendix VIII 12 7
22 Tune Criteria for Decafluorotriphenylphosphine
(DFTPP) 131
23 Tune Criteria for Bromofluorobenzene ........ 132
24 Essential Elements of a QA Project Plan 217
25 Precision Goals for Analysis 221
26 Activity Matrix for Calibration of Equipment .... 230
27 Activity Matrix for Calibration of Apparatus .... 231
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ABBREVIATIONS AND GLOSSARY OF TEEMS
AAS Atomic Absorption Spectroscopy
Accuracy The difference between a single value or the
mean of a set of results and the value which
is accepted as the correct (true) value for
the quantity measured.
AF1D Alkali Flame Ionization Detector
amu Atomic Mass Unit (1 amu = 9.314 x 108 eV)
APCD Air Pollution Control Device
Appendix VIII Hazardous Constituent List (40 C.F.R. Part 261)
ASTM American Society for Testing and Materials
atm Atmosphere (1 atm = 1.013 x 10 s Pa = 760 Torr)
Btu/lb British Thermal Unit per Pound
(1 Btu/lb = 2.3244 x 103 J/Kg
= 0.556 x 10 3 kcal/g)
Btu/h British Thermal Unit per Hour
(1 Btu/h « 2.931 x 10-1 VJ)
C Corrosivity Test—RCRA Characteristic
C.F.R. Code of Federal Regulations
CI Chemical Ionization Mode (Mass Spectrometry)
cm Centimeter (10"2m)
CO Carbon Monoxide
Coliwasa Composite Liquid Waste Sampler
CV Coefficient of Variation
2,4-D 2,4-Dichlorophenoxyacetic acid
ODD Dichlorodiphenyldichloroethane
DDE Dichlorodiphenyldichloroethylene
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DDT
D. E. S.
DFTPP
Directed Analysis
DNPH
DRE
dscf
dscm
E
ECD
EI
EP
EPA
ESP
eV
Excess Air
FPD
ft
FT-IR
g
Dichlorodiphenyltrichloroethane
Diethylstilbestrol
Decafluorotriphenylphosphine
Qualitative confirmation of compound presence
and identity. Also, quantitative data of
known quality for a set of constituents that
might reasonably be expected to be present in
the waste based on professional judgment and/or
the results of proximate and survey analyses.
Dinitrophenylhydrazine
Destruction and Removal Efficiency—the measure
of the mass emission rate of a principal organic
hazardous constituent (POHC) in the output stack
gas versus the mass feed rate of the same POHC
in the influent waste.
Dry Standard Cubic Foot (1 dscf » 2.8317 x 10 2 dscm)
Dry Standard Cubic Meter
Extraction Procedure Toxicity Test—RCRA
Characteristic
Electron Capture Detector
Electron Impact Ionization Mode (Mass Spectrometry)
Extraction Procedure
U.S. Environmental Protection Agency
Electrostatic Precipitator
Electron Volt (1 eV - 1.602 x 10~19J)
Air flow rate above that required to achieve
theoretically complete combustion.
Flame Photometric Detector
Foot (1 ft - 3.0480 x 10-1m)
Fourier Transform-Infrared Spectroscopy
Gram (10 3 kg)
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gal Gallon (1 gal = 3.785 x 10 3 m3)
GC Gas Chromatography
GC/AFID Gas Chromatography/Alkali Flame Ionization
Detector
GC/ECD Gas Chromatography/Electron Capture Detector
GC/MS Gas Chromatography/Mass Spectrometry
GC/MS/DS Gas Chromatography/Mass Spectrometry/Data System
GC/NPD Gas Chromatography/Nitrogen-Phosphorus Detector
(Alkali Flame Ionization Detector)
GC/TD Gas Chromatography/Thermionic Detector
gr Grain (1 gr * 6.48 x 10 5 kg)
GRAV Gravimetric Analysis
h Hour
HC1 Hydrochloric Acid
KPLC High Performance Liquid Chromatography
HPLC/UV High Performance Liquid Chromatography/
Ultraviolet Spectroscopy
I Ignitability Test—RCRA Characteristic
ICAP Inductively Coupled Argon Plasma Atomic
Emission Spectroscopy
I.D. Internal Diameter
in Inch (1 in ¦ 2.54 x 10 2m)
IR Infrared Spectroscopy
Isokinetic Sampling Collection of stack gas samples under conditions
such that the linear velocity of gas through the
sampling nozzle is equal to that of the
undisturbed gas stream at the sample point.
Isothermal With or at equal temperatures.
J Joule
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kcal
Kilocalorie (1 kcal = 4.184 x 103J)
K-D
Kuderna-Danish Evaporative Concentrator
kg
Kilogram (103g)
L
Liter (1L = 1.00 x 10~3 m3)
LC
Liquid Chromatography
LC/EC
Liquid Chromatography/Electrochemical Detector
LOD
Loss on Drying
LOI
Loss on Ignition
LRMS
Low Resolution Mass Spectrometry
Vig
Microgram (10 6g)
HL
Microliter (10 6L)
mm
Micrometer (10 6m)
m
Meter
m3
Cubic Meter
M5
Method 5 Sampling Train
mg
Milligram (10 3g)
min
Minute (1 min * 60 sec)
mL
Milliliter (10_3L)
mm
Millimeter (10~3m)
MM5
Modified Method 5 Sampling Train
MS
Mass Spectrometry
mV
Millivolt (10"3V)
MW
Molecular Weight
NDIR
Non-Dispersive Infrared Analyzer
NFPA
National Fire Protection Association
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ng Nanogram (10 9g)
hq Nanometer (10 9m)
NO^ Nitrogen Oxides (NO, NO2, etc.)
N.O.S. Not Otherwise Specified
O.D. Outer Diameter
Opacity Measurement of the optical density of stack
gas emissions of an incinerator.
Pa Pascal
PCB(s) Polychlorinated Biphenyl(s)
POHC(s) Principal Organic Hazardous Constituent(s)
PzOs Phosphorus Pentoxide
ppb Part Per Billion
One part in 109. For gaseous mixtures, a
volume:volume basis is typically used and
1 ppb is on the order of 1 ug/m3:
Ug/m3 - ppb x H
where RT a 22.4 L/mole at 0° and 1 atm
¦ 24.5 L/mole at 25° and 1 atm
For liquid materials, a weight:volume
basis is most commonly used and 1 ppb ¦
1 ug/L (% 1 yg/kg for liquids with density
^ 1). For solid materials, a weight:weight
basis is most commonly used and 1 ppb =
1 pg/kg.
ppm Part Per Million
One part in 10s (see ppb).
1 ppm ^ 1 mg/m3 gaseous streams
1 ppm » 1 mg/L liquid streams
1 ppm ¦ 1 mg/kg solid streams
Precision The reproducibility of measurements within a
set of independent replicate determinations.
The relative standard deviation expressed as
a percentage of the mean is a common measure
of precision.
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Proximate Analysis Provides data relating to the physical form
of the waste and provides an approximate
mass balance as to the composition of the
waste.
psi Pounds Per Square Inch (1 psi = 6.8948 x 103 Pa)
PVC Polyvinyl Chloride
QA Quality Assurance
QC Quality Control
R Reactivity Test—RCRA Characteristic
RCRA Resource Conservation and Recovery Act of 1976
RI Refractive Index Detector
rpm Revolutions Per Minute
RSD Relative Standard Deviation
SASS Source Assessment Sampling System
s Second
SCFM Standard Cubic Feet per Minute
SD Standard Deviation
Segregation Heterogeneity in a sample
Semivolatiles Organic species with moderate vapor pressure
sufficient to allow analysis by gas chromato-
graphy, generally have boiling points of lOO'C
or higher, molecular weights of 100-400, seven
to twenty carbon atoms per molecule.
SO^ Sulfur Oxides (SO2, SO3)
Sparging Removal of the volatile constituents of a
sample by bubbling an inert gas stream
through the sample.
Surrogate A known compound added to a sample which is
chemically similar to a POHC of interest so
that an estimate of the accuracy of the
analytical measurement and an assessment of
the overall efficiency of the analytical
procedures can be made.
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Provides an overall description of the sample
in terms of the major organic compounds and
major inorganic compounds that are present
in the sample. The analysis provides a
qualitative description of the overall
chemistry of the sample.
Transmittance
2,4,5-Trichlorophenoxyacetic acid
Thermal Conductivity Detector
Tetrachlorodibenzo-p-dioxin(s)
Total Chromatographicable Organics
Thermogravimetric Analysis
Tetrahydroxyethylenediamine
Thin Layer Chromatography
Total Organic Carbon Content
Total Organic Halogen Content
2,4,5-Trichlorophenoxypropionic acid
Hazardous Waste Treatment, Storage, and
Disposal Facility
Ultraviolet Spectroscopy
Volt
Volatile Organics Analysis
Organic species with appreciable vapor pressure
at room temperature, generally have boiling
points of 100°C or lower, molecular weights
less than 200, one to seven carbon atoms per
molecule.
Watt
Mass feed rate of one POHC in the waste
stream feeding the incinerator.
Mass emission rate of the same POHC (see W^n)
present in exhaust emissions prior to
release to the atmosphere.
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ACKNOWLEDGMENT
The authors wish to acknowledge the assistance of several people whose
efforts led to the successful production of this report. The authors
especially wish to acknowledge the authorship of Debi J. Sorlin and
Virginia Grady on previous drafts. The assistance of Afaf Wensky of
Battelle Columbus Laboratories and Ruby James and her associates at
Southern Research Institute in their efforts for the preparation of
recommendations for the sampling and analysis methods for many of the
compounds listed was greatly appreciated.
The following people provided valuable comments as external peer reviewers
of previous versions of this report: Bruce N. Colby of S-Cubed,
Alvia Gaskill of Research Triangle Institute, Paul Gorman of Midwest
Research Institute, and Herbert C. Miller of Southern Research Institute.
We are also grateful for constructive criticism received from EPA
reviewers, Jan Jablonski and Edward Martin of the Office of Solid Waste,
Charles Rogers of the Hazardous Waste Incineration Branch, IERL in
Cincinnati, Ohio, and most especially, Larry Johnson of the Technical
Support Staff, IERL in Research Triangle Park, North Carolina.
Many individuals at Arthur D. Little, Inc. contributed to this report.
In particular, the authors wish to thank Katherine Norwood and Anthony
DeMarco for their technical contributions to the associated appendices,
and Philip Levins for his review comments. The authors are also grateful
to Christine McGrail and Patricia Fredriksen for their efforts in the
preparation of this manuscript.
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I. ABSTRACT
As part of the Resource Conservation and Recovery Act of 1976, the
U.S. Environmental Protection Agency (EPA) has proposed regulations
for owners and operators of facilities that treat hazardous wastes by
incineration to ensure that these incinerators will be operated in an
environmentally responsible manner. The primary criterion upon which
the operational specifications are based is the destruction and removal
efficiency (DRE) of the incinerator. The DRE value, defined i«n terms
of waste input and stack output levels of designated principal organic
hazardous constituents (POHCs) must be equal to or greater than 99.99
percent.
In support of the DRE requirement, this report is a reference that
describes the sampling and analysis methods for measuring the hazardous
constituents (as defined in 40 C.F.R. Part 261, Appendix VIII) which
might be designated as POHCs in the various influent and effluent
streams of incineration facilities. The sampling and analysis methods
for these constituents are described in the text. Also included are
concise summary sheets for all recommended methods which state the name
and number of the method, the types of samples and specific analytes to
which the method applies, a brief description of the method, instrument
and operating conditions, and reference(s) to more detailed descriptions
of the procedure. Technician-level protocols are thus incorporated
by reference rather than by reproduction in this report. In addition
to presenting the methods for sampling and analysis of POHCs at these
facilities, information concerning additional sampling and analysis
requirements, general strategies for preparing sampling and analysis
plans to meet the regulatory requirements, and guidelines for reporting
and documentation are discussed.
Appendix A provides physical/chemical data (structure, CAS Registry
Number, molecular weight, melting point, boiling point, and heat of
combustion, when available) for all hazardous constituents listed in
40 C.F.R. Part 261, Appendix VIII (May 20, 1981). Additional appendices
list specific compounds from Appendix VIII, with appropriate sampling
(Appendix B) and analysis (Appendix C) methods. Mass spectral
analytical ions for compounds analyzed by gas chromatography/mass
spectrometry (GC/MS) are tabulated in Appendix E.
This report has been submitted in partial fulfillment of Contract No.
68-02-3111, Technical Directive No. 124, by Arthur D. Little, Inc.
(Case No. 82480-54), under the sponsorship of the U.S. Environmental
Protection Agency/Industrial Environmental Research Laboratory,
Research Triangle Park, North Carolina.
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II. INTRODUCTION
A. PURPOSE
As part of the Resource Conservation and Recovery Act (RCRA), the
EPA has promulgated proposed, interim, and final regulations for
owners/operators of facilities which treat hazardous wastes by
incineration to ensure that the incinerators are operated in an
environmentally responsible manner (1). The regulations cover a
range of activities, including operational performance standards,
waste analysis, trial burns, monitoring and inspections, record-
keeping and reporting, emission control criteria, fugitive emissions
control, and closure of the facility. Details for each incinerator
facility are authorized via facility permits.
In the permitting process, permitting officials use best professional
judgment to determine the performance parameters which must be followed
for each facility. The permit writer makes use of available technical
advisory information contained in the "Guidance Manual for Hazardous
Waste Incinerator Permits" (2) and the "Engineering Handbook for
Hazardous Waste Incineration" (3). These documents provide engineering
information in terms of waste and effluent characterization, Incinerator
design, control technology, facilities requirements, environmental
impacts, and cost evaluations. Additional supporting documentation for
the permit writer and for the incinerator facility owners/operators is
available to address points raised during the permitting process.
This report is considered to be an additional supporting document. The
primary criterion upon which all operational specifications are based
is the destruction and removal efficiency (DRE) of the incinerator.
This value, defined in terms of waste input and stack output levels
of the principal organic hazardous constituent(s) (POHC(s)) designated
in the trial burn permitting process, must be equal to or greater
than 99.99 percent, according to the permitting standards for hazardous
waste incineration. This report addresses the sampling and analysis
methods to be used when measuring the levels of the POHC(s) in the
various streams of an incinerator facility (inlet waste, stack gas,
process water, fly ash, and bottom ash) for the purpose of calculating
a DRE value for the incinerator. This compilation of sampling and
analysis methods expands upon and augments the information contained
in the "Guidance Manual for Hazardous Waste Incinerator Permits" (2).
The purpose of this report was an initial attempt to gather the sampling
and analysis procedures for the benefit of the owners/operators of
hazardous waste incineration units, permit application writers, the
permit reviewer, and the chemical analyst. Since this report is an
initial attempt, the information on sampling techniques and analytical
procedures should be considered more as a guidance rather than a
2
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prescription. These protocols lack definitive data on accuracy and
precision because of limited use within the context of hazardous
waste incineration. As new data are developed, the precision and
accuracy data will be made available through updated versions of this
manual or other documents. It is important that users of these
protocols provide Information on verified techniques, new procedures,
and other relevant matters to the EPA so that updates can be made
available.
B. SCOPE
This report describes the sampling and analysis methods which are
appropriate to the measurement of POHCs in hazardous waste incineration
facility streams. The material in this report has been divided into
sections which address different aspects of the sampling and analysis
approach for hazardous waste incinerators.
Regulatory requirements for the sampling and analysis activities are
briefly reviewed, with emphasis on the data needs for trial burns.
During trial burns, the sampling and analysis methods need to allow
measurement of those POHCs which are expected to be present in the
effluents, the level of particulate matter in the stack exhaust gas,
and (in some cases) the concentration of hydrochloric acid in the
stack gas. Also during trial burns, waste samples must be characterized
to establish limits on the waste compositions which may be incinerated.
During routine facility operations, the incoming wastes are examined
periodically to determine if the composition of the waste has changed.
Some gaseous species, such as carbon monoxide (CO), are monitored
continuously as an indicator of the combustion efficiency of the
process. Periodically, at a frequency not specified in the current
regulations, the influent and effluent streams may be tested to
monitor compliance with the DRE criteria and general incinerator
performance.
Section III explains the strategies involved in preparing sampling
and analysis plans to meet regulatory requirements. These strategies
include approaches to the selection of POHCs which are likely to be
present in the waste streams and combustion effluents. In addition,
other strategies for monitoring of indicator species and characterization
of liquid and solid effluents are included.
This report contains separate sections for sampling methods (Section IV),
preparation methods (Section V), and analysis methods (Section VI), in
terms of the various types of streams and sample media which will be
encountered. Section VII describes general methods which will aid
in the collection of high-quality sampling and analysis data; it
also discusses the reporting and documentation concerns for the
sampling and analysis of incinerator emissions. Other aspects of
the reporting requirements are fully discussed in the permit writer's
guidance document (2).
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C. USE OF REPORT
In this report, the procedures are primarily briefly described with
reference to other documents which contain more detailed procedural
information. Existing collections of sampling and analysis methods,
such as "Test Methods for Evaluating Solid Waste - Physical/Chemical
Methods" SW-846 (4) or "Samplers and Sampling Procedures for
Hazardous Waste Steams" (5), are incorporated into this report
only by reference.
The structure of this report permits quick access for the user.
Concise method summary sheets for each sampling, preparation, and
analysis method are grouped at the end of their respective sections.
Many tables have been prepared which cross-reference specific methods
to the individual hazardous constituents from 40 C.F.R. Part 261,
Appendix VIII. Appendix A summarizes the physical and chemical data
(structure, molecular weight, melting point, boiling point, and heat
of combustion), of each hazardous constituent listed in Appendix VIII,
if available. Appendices B and C reference each hazardous constituent
by recommended sampling and analysis method.
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III. SAMPLING AND ANALYSIS STRATEGY
TO MEET REGULATORY REQUIREMENTS
A. INTRODUCTION
Section 3004 of the Resource Conservation and Recovery Act (RCRA) of
1976 requires the Administrator of the U.S. Environmental Protection
Agency to promulgate such performance standards for owners and operators
of hazardous waste treatment, storage, and disposal facilities (TSDFs)
as may be necessary to protect human health and the environment.
Section 3004 standards not only establish the levels of environmental
protection that hazardous waste TSDFs must achieve, but also mandate
the criteria against which applications for permits must be measured.
The facility standards are thus key elements in the system mandated by
RCRA for management of hazardous wastes.
The RCRA regulations that relate specifically to hazardous waste
incineration are incorporated in the Code of Federal Regulations,
Title 40 (40 C.F.R.) Parts 122, 264, and 265. Under Part 122 which
regulates EPA administered permit programs, Subpart A presents
definitions and general program requirements, while Subpart B
specifies additional requirements for hazardous waste permitting
programs under RCRA. Under Parts 264 (Permitting Standards) and
265 (Interim Status Standards), Subpart B presents general facility
standards, including general waste characterization requirements,
while Subpart 0 relates specifically to incinerators.
1. General Facility Standards
The General Facility Standards as they relate to the sampling and
analysis of hazardous waste are identical in the interim status
(§265.13) and permitting (§264.13) standards. The general waste
analysis requirement is that the owner or operator must obtain a
detailed chemical and physical analysis of a representative sample
of waste. At a minimum, the analysis must generate all information
that is needed to treat, store, or dispose of waste in accordance
with RCRA requirements and/or conditions of an operating permit. In
addition to this detailed analysis of a representative waste sample,
the owner/operator must "inspect" each shipment of waste to determine
whether it matches the identity specified on the manifest. The
sampling and analysis or inspection methods to be used must be
specified in a written plan, which may become part of a RCRA Part B
permit application.
2. Interim Status Standards for Incinerators
In addition to the general waste analysis, the Part 265, Subpart 0,
incinerator standards require that the owner/operator sufficiently
analyze any waste that he has not previously burned in his
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incinerator, so that he can (a) establish steady-state (normal)
operating conditions, and (b) determine the type of pollutants
which might be emitted.
The interim status standards for incinerators specify no explicit
requirements for sampling and analysis of stack exhaust gas, or
other incinerator effluents.
3. Permitting Standards for Incinerators
The Part 264, Subpart 0, incinerator standards include requirements
for waste analysis, three performance standards that include implicit
sampling and analysis requirements, and also some operating/monitoring/
inspection requirements. The waste analysis requirements are cross-
referenced to the Part 122 Hazardous Waste Permit Program regulations
and include analyses to determine the heating value of the waste,
viscosity or physical form, identification of any hazardous constituents
(listed in 40 C.F.R. Part 261, Appendix VIII) present in the waste to
be burned, and an approximate quantification of any hazardous constituents
identified in the waste.
The Part 264 performance standards (§264.343) relate to:
• The destruction and removal efficiency (DRE) for each
principal organic hazardous constituent (POHC) designated
in the permit. The DRE, defined 'in terms of the mass
emission rate of a POHC in the stack exhaust gas vs. the
mass feed rate of the same POHC in the waste, must be
99.99%. The DRE performance standard implicitly requires
sampling and analysis to quantify the designated POHC(s) in
the waste stream and in the stack gas during a trial burn.
A limitation on hydrochloric acid emissions from the stack
of an incinerator. This performance standard implicitly
requires, in some cases, sampling and analysis to quantify
hydrochloric acid in the stack gas and/or to determine the
efficiency of air pollution control devices.
• A limitation on stack emissions of particulate material to
_< 180 mg/dscm (<_ 0.08 gr/dscf), corrected to a standard excess
air level. This performance standard implies measurement of
the particulate emission rate.
The sampling and analysis requirements of the Part 264 performance
standards are described here as implicit because, during routine
operational burns, compliance with specified operating requirements is
acceptable in lieu of actual demonstrated compliance with the performance
standards. The operating requirements (§264.345) and monitoring/
inspection requirements (§264.347), in turn, specify that the carbon
monoxide (CO) level in the stack exhaust gas must be monitored continu-
ously; this is the only explicit chemical sampling and analysis require-
ment imposed on all operating incinerators by the Part 264 regulations.
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On a case-by-case basis, the permit to operate an incinerator may specify
additional operating requirements that necessitate other types of
sampling and analysis on a routine basis. The permit may also include
requirements for sampling and analysis to demonstrate actual compliance
¦with the performance standards oil an annual or other periodic schedule.
4. Hazardous Waste Permit Program
The Part 122, Subpart B, requirements for hazardous waste incineration
permit programs under RCRA mandate that the owner/operator of an
incineration facility must either:
• submit results of a trial burn which demonstrate facility
operating conditions under which the waste can be
incinerated in accordance with the Part 264.343 performance
standards, or
• submit data based on waste analysis and on other trial or
operational burns sufficient to specify operating
conditions under which the waste can be incinerated in
accordance with the Part 264.343 performance standards.
(An exemption to these requirements may be sought in the case of
incineration of waste that is hazardous only because it has the
characteristic(s) of Ignitability, Corrosivity, or Reactivity (in
some cases), as defined in Part 261, Subpart C, of the RCRA regulations
and that contains insignificant concentrations of hazardous components,
as defined by Appendix VIII of Part 261.)
Sampling and analysis requirements for waste characterization are
the same in the case of a trial burn (§122.27) or alternative data
submission (§122.25). The analysis of the waste must include:
• heating value of the waste (in the form and composition
in which it will be burned),
• viscosity or physical form,
• identification and approximate quantification of any
hazardous organic constituents that are listed in
Appendix VIII of Part 261 and are known or suspected
to be present in the waste, and
• quantification of those hazardous constituents that may
be designated as principal organic hazardous constituents
(POHCs) for purposes of demonstrating compliance with the
DRE performance standard.
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Sampling and analysis requirements for incinerator effluent characteri-
zation (stack gas) in the event that a trial burn is conducted include:
• quantitative analysis of the stack exhaust gas for
concentration (mass emissions) of the designated POHC(s),
• quantitative analysis of the stack exhaust gas for the
concentration (mass emissions) of particulate matter,
• quantitative analysis (in some cases) of the stack exhaust
gas for the concentration of hydrochloric acid for purposes
of calculating a removal efficiency and/or emission rate,
• determination of the oxygen concentration in the stack exhaust
gas for the purpose of calculating the excess air level in the
exhaust gas, and
• continuous monitoring of carbon monoxide in the stack exhaust
gas.
It is important to emphasize that most of the sampling and analysis
procedures described in this report relate to trial burns. It is
further important to note that only a small fraction of the procedures
specifically selected to address an individual POHC will generally be
applied in any single trial burn.
For operating burns, the only explicit sampling and analysis require-
ment is the determination of carbon monoxide in the stack gas.
Although the permit writer or the state/local authorities may impose
additional monitoring requirements In some instances, it is not
anticipated that comprehensive sampling of the stack gas effluent
or directed analysis of POHCs will be required except in trial burn
situations.
B. WASTE CHARACTERIZATION STRATEGY
1. Sampling
Acquisition of a representative sample of hazardous waste for subsequent
chemical analysis is accomplished by preparing a composite of several
subsamples of the waste. Sampling tactics for the collection of sub-
samples, as specified in "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (4), generally involve grab sampling
of liter/kilogram-sized portions of waste materials. To ensure that
the bulk of the waste is accurately represented by the composite sample,
the sampling strategy requires collection of a minimum of three subsamples
which provide an integration over both the depth and the surface area
of the waste as contained in drums, tanks, holding ponds, etc. The
composite sample prepared in the field is split into at least three
replicate samples prior to shipment to the analytical laboratory. This
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is primarily a precaution against breakage or loss of a sample, but
it also provides the potential for a check on the homogeneity of the
composite sample.
To ensure that sampling and analysis results will be adequately
documented, chain-of-custody procedures are incorporated into
sampling protocols. The sampling protocols also include explicit
provisions for ensuring the safety of the personnel collecting the
samples.
2. Analysis
The overall strategy for waste characterization includes test procedures
to determine the characteristics of the waste and analysis procedures to
determine the composition of the waste. The analysis procedures for
determining the composition of the waste are divided into three
sections:
• Proximate Analysis
• Survey Analysis
• Directed Analysis
Figure 1 provides an overview of this analytical approach. The
discussion below provides a capsule description of each major element
of this scheme and the utility of the resulting information in the
hazardous waste incineration permitting process.
a. Characteristics
The characteristics of the waste sample in terms of Ignitability (I),
Corrosivity (C), Reactivity (R), and Extraction Procedure Toxicity (E)
are determined according to the procedures and guidelines presented in
40 C.F.R. Part 261, Subpart C, and in SW-846 (4). These tests are
performed on a sample from each waste stream unless there is sufficient
information from the engineering analysis to indicate that the waste
does not meet the I, C, R, and/or E criteria. This information is
relevant to the Part 264, Subpart B, general waste analysis requirement
in that the data affect procedures for safely storing, handling, and
disposing of the waste at the facility. The data are also relevant to
possible exclusion from the trial burn requirements of Part 122. The
1, C, R, and E test data for each hazardous waste to which the tests
are applicable are generally available from the waste generator
and manifest or shipping papers received by the incineration facility
owner/operatar.
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COMPOSITE WASTE SAMPLE
CHARACTERISTICS
Ignitability
Corrosivity
Reactivity
Toxicity (EPTest)
PROXIMATE
ANALYSIS
COMPOSITION
SURVEY
ANALYSIS
DIRECTED
ANALYSIS
Physical Form and
Approximate Mass Balance:
Moisture (Volatile) Content
Solid Content
Ash Content
Elemental Analysis
Heating Value of the Waste
Viscosity (Physical Form)
Overall Description of Sample
With Estimated Quantities of
Major Components:
Total Organic Content
Organic Compound Classes
Specific Major Organic
Components
Specific Major Inorganic
Elements
Identification and Quantification
of the Hazardous Constituents
Selected from the Appendix VIII
List
FIGURE 1 OVERVIEW OF THE ANALYTICAL APPROACH FOR WASTE CHARACTERIZATION
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b. Composition—Proximate Analysis
The proximate analysis provides data relating to the physical form of
the waste and provides an approximate mass balance as to its composition.
This analysis includes determination of:
• moisture (volatile), solid, and ash content;
0 elemental composition (carbon, hydrogen, nitrogen,
sulfur, phosphorus, fluorine, chlorine, bromine, iodine);
• heating value of the waste; and
• viscosity or physical form.
This information meets the waste analysis requirements of the Part 264,
Subpart 0 regulations and is also responsive to the general waste
analysis requirements of Subpart B.
The elemental composition data allow prediction of a high concentration
of potentially significant combustion products (NO , SO , P^Os, hydrogen
halides and halogens). These data also facilitate an informed selection
of the Appendix VIII hazardous constituents that might be present/not
present in the waste by indicating whether the overall waste composition,
and hence the types of components present, are consistent with the
expectations based on best professional judgment. For example, if
bromine were not expected to be present in the waste, the organobromine
compounds from Appendix VIII would have been excluded from the directed
analysis based on professional judgment. If bromine were, in fact,
found in the waste at 0.5 percent level by weight, the list of compounds
sought by directed analysis would be expanded to include the organobromines.
It might also be possible, in some cases, to rule out some categories
of Appendix VIII compounds on the basis of elemental analysis data
when conservative professional judgment could not have excluded them.
c. Composition—Survey Analysis
The survey analysis is designed to provide an overall description of
the sample in terms of (1) the major types of organic compounds, and
(2) the major inorganic elements (metals) that are present. The survey
analysis package includes determination of:
• total organic content by chromatographic (TCO) and
gravimetric (GRAV) procedures,
• organic compound class types present by infrared (IR) and
probe mass spectrometric procedures,
• major organic components by gas chromatographic/mass
spectrometric (GC/MS) or high performance liquid
chromatographic/infrared (HPLC/IR) or high performance
liquid chromatographic/mass spectrometric (HPLC/LRMS)
procedures, and
11
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• metals by inductively coupled argon plasma emission
spectroscopic (ICAP) and atomic absorption spectroscopic
(AAS) procedures.
The type of data generated by the survey analysis allows a qualitative
description of the overall chemistry of the sample. This information
is important in deciding which of the hazardous constituents listed in
Appendix VIII are present in the waste, and may lead to the selection
of alternative, previously unsuspected POHC(s). Knowledge of the
major components of the sample is also important in predicting the
identity of hazardous by-products of combustion, or other emissions
that may require sampling and analysis.
d. Composition—Directed Analysis
The directed analysis portion of the waste characterization scheme pro-
vides qualitative confirmation of the presence and identity of specific
compounds and quantitative data with appropriate quality control measures
for the Appendix VIII constituents that might reasonably be expected to
be present in the waste based on professional judgment and/or on the
results of proximate and survey analysis. It is important to note that
directed analysis does not involve screening of every waste sample
against the complete Appendix VIII hazardous component list. A preli-
minary judgment is made as to the compounds or types of compounds that
are actually present.
For the organic directed analysis, a high resolution separation technique—
fused silica capillary gas chromatography—and a high specificity detec-
tion technique—mass spectrometry—are used wherever possible. This
approach ensures adequate qualitative and quantitative analysis on a
cost-effective basis for a variety of waste types and process chemistries.
Although gas chromatography/mass spectrometry (GC/MS) instrumentation is
sophisticated and the initial capital cost of the instrumentation is
high, the analytical technique is widely available in contractor
laboratories, routine analytical service laboratories, and EPA
laboratories. The combination of highly specific and reliable compound
identification, high sensitivity, good quantitative capability, and
the capability for the determination of multiple components in a
single analysis make GC/MS the analytical method of choice for
both waste and effluent organic analyses. Alternative organic analysis
procedures using gas chromatography with less specific detectors
generally require additional sample preparation and multiple analyses,
and may still prove inadequate in terms of selectivity and elimination
of interferences from non-target compounds.
For the inorganic directed analysis, atomic absorption spectroscopy
(AAS) and inductively coupled argon plasma emission spectroscopy (ICAP)
for metals and ion chromatography (IC) for anions are the primary
analytical procedures.
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The results of the directed analysis establishes that the waste
contains the suspected pollutant(s) and demonstrates the concentration
rate at which the pollutant(s) may be expected to be found. Directed
analysis is also used to confirm and quantify unexpected hazardous
components identified in the survey analysis. These data from the
quantitative analysis of confirmed, identified contaminants of documented
toxicity (Appendix VIII compounds) are essential for the selection of
POHCs and the prediction of hazardous by-products of combustion.
e. Selection of POHC(s)
The criteria for selection of the POHC(s) (typically one to six specific
constituents per waste stream) include:
• the expected difficulty of thermal degradation of the
various hazardous organic constituents in the waste, and
• the concentration of those constituents in the waste.
Designation of the POHC(s) will be negotiated on a case-by-case basis
for each permit application. It is important to note that it is not
necessarily, nor even generally, true that all Appendix VIII compounds
present in the waste will be designated as POHCs for trial burn purposes.
The intent is to select a few specific compounds as indicators of
satisfactory incinerator performance when burning a particular waste.
It is necessary that the compounds selected provide a sufficiently
stringent test of the incinerator performance in terms of the DRE
to ensure that incineration of the waste can be carried out in an
environmentally sound fashion. This criterion mandates selection of
the more thermally stable constituent(s) as the POHC(s). At the same
time, however, it is also necessary that the designated POHC(s) be
present in the waste in sufficiently high concentration that they are
capable of being detected in the stack gas at emission levels corresponding
to £0.01 percent of their mass feed rate in the waste. This is a particularly
important constraint for wastes that are to be incinerated with sub-
stantial quantities of auxiliary fuel which effectively dilutes the
concentration of the POHC(s) in the exhaust gas. Although the burning
of auxiliary fuel might not affect the mass emission rate of the POHC(s),
it would lead to an increased volumetric flow of stack gas and thus to
a decreased concentration of the POHC(s) in the stack exhaust gas. This
lower concentration directly affects the detection limit achievable
for a given stack gas sample size (e.g., 5 or 30 dscm).
It is recommended that, whenever possible, the permit writer select
the POHC(s) present in the waste at 1000 ppm or higher. If it is
considered desirable to designate as a POHC a thermally stable
compound present at the hundreds of parts per million level, the trial
burn permit application must include calculations and supporting data
to indicate that 0.01 percent of the mass feed rate of that component
in the waste could, in fact, be detected in the stack effluent. A waste
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concentration of 100 ppm probably represents a practical lower level
below which determination of 99.99 percent DRE may require extraordinary
sampling, analysis, and quality control procedures, which may significantly
increase the sampling and analysis costs for that trial burn.
For a waste material that is a listed hazardous waste under RCRA
(40 C.F.R. Part 261, Subpart D), the constituents which caused the
Administrator to list the waste as toxic (tabulated in Appendix VII of
40 C.F.R. Part 261) would be logical candidates for designation as
POHC(s) if these constituents were organic chemicals. However, many
of the listed wastes are considered hazardous on the basis of their
content of metals which are not, by definition, POHCs; Appendix VII
contains relatively few organic chemicals.
C. STACK GAS EFFLUENT CHARACTERIZATION STRATEGY
The overall strategy for hazardous waste incinerator stack gas effluent
characterization to determine compliance with the Part 264 performance
standards is to collect replicate 3 to 6 hour (5-30 dscm) samples of
stack exhaust gas, using a comprehensive sampling train, such as a
modified EPA Method 5 (MM5) train (6) or the EPA/IERL-RTP Source
Assessment Sampling System (SASS) (7). Either of these trains provides
a sample sufficient for determination of particulate mass loading,
concentrations of particulate and vapor phase organics, concentration
of HC1, and concentrations of particulate and volatile metals.
Directed analyses for P0HC(s) in the stack exhaust gas samples are
performed on these MM5/SASS samples. The same sample (probe wash and
particulate catch composite) may be used for determination of the
particulate mass loading, determination of the non-volatile metal
content, and subsequent extraction of non-volatile organic components.
The semi-volatile organic components of the stack exhaust gas are
collected in the sorbent trap and condensate portions of the MM5 or
SASS train. More volatile organic constituents require additional
sampling procedures. The extracts of the various parts of the MM5/SASS
train may be combined for analysis of the concentration of POHC(s).
For burns of wastes that could also produce significant emissions of
HC1, a special reagent (caustic) in the impinger solution of a
Method 5, or either a MM5 or SASS train is used to collect the HC1
in the stack exhaust gas; the concentration of HC1 is then quantified
as chloride by ion chromatography. Figure 2 shows an overview of
the analysis scheme for stack gas samples.
The directed analyses shown in Figure 1 are performed on triplicate
samples. Although two samples would allow an average level of a POHC
to be determined, at least three samples should be analyzed in order
to compute an error bound for the measured values. The incremental
cost of the replicate sampling and analysis is warranted by the increased
confidence in the resulting data; quantitative results from a single
sampling and analysis run should not generally be considered as an
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Probe
Wash
I
Concentrate
to
Dryness
Particulate
Catch
Dry
Weigh
W.
Combine extracts
Aliquot (~1Q%t
1-*
tn
Metal analysis .
by ICAP
-------
acceptable indicator of performance. The survey analysis, which is a
qualitative screen of the collected material to ensure that potentially
hazardous, but unexpected, emissions are not overlooked, need be
performed, on no more than one stack gas sample.
During a trial burn, the oxygen level in the stack gas is measured
using an Orsat analyzer, as detailed in 40 C.F.R. Part 60, Appendix A,
Method 3 (6), so that the particulate loading may be corrected to a
standard excess air level.
For both trial and operating burns, on-line monitors (non-dispersive
infrared instruments) are used to provide continuous readings of the
carbon monoxide (CO) level in the incinerator effluent.
D. ADDITIONAL EFFLUENT CHARACTERIZATION STRATEGY
The basic strategy for sampling scrubber water, ash, and other residues
(if any) is to prepare composite samples from grab subsamples, collected
using the same types of sampling devices and tactics used for waste
characterization. This sampling is required only during trial burns
in accordance with 40 C.F.R. Part 122.27. These additional effluent
samples are analyzed for the designated POHC(s) to determine appropriate
disposal or subsequent treatment methods, and to ensure that significant
discharges of the POHC(s) in other media do not go undetected. A target
detection limit of 0.01-0.5 percent of the mass feed rate of each POHC
in the waste should be achievable with a reasonable sample size.
E. SELECTION OF SPECIFIC SAMPLING AND ANALYSIS METHODS
The preceding discussion has briefly described the RCRA regulations
that define the sampling and analysis requirements for hazardous waste
Incineration and presented an overview of the strategic sampling .
and analysis approaches that have been developed to meet these require-
ments. Subsequent sections of this document present descriptions of the
sampling, sample preparation, and analysis methods that are recommended
for implementation of this strategy. This portion of Section III
illustrates, by means of a hypothetical example, the transition from
strategy, as described, to the tactics and methods described in the
following chapters. The example is somewhat oversimplified in the
interest of clarity, but it should demonstrate how to use this
document in the development and evaluation of a hazardous waste
incineration trial burn plan. The following discussion deals with
sampling and analysis considerations only and does not address
adequacy of incinerator design, operating conditions, or other
engineering considerations.
1. Scenario
The owner/operator of an incineration facility seeks a RCRA permit to
treat chlorinated organic waste material.
16
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The facility is a liquid-injection incinerator with a capacity of
10 x 10 Btu/h (2.931 x 106 W); it is equipped with a wet scrubber
for acid gas removal. A waste oil (<0.1% chlorine) is burned as
auxiliary fuel. The proposed operating conditions for hazardous
waste incineration include: combustion zone temperature of 2000°F
(1100°C), residence time of 2 s with 150 percent excess air.
The waste is still bottom from the production of tetrachloroethene
(tetrachloroethylene). Based on engineering analysis, it is expected
to be a non-viscous organic liquid with a heating value <5000 Btu/lb
(<1.163 x 107 J/kg). The major components of the waste are expected
to be highly chlorinated species such as hexachlorobenzene, hexa-
chlorobutadiene, and the like.
2. Strategy
It is hypothesized that there are insufficient data from other trial
or operating burns to specify operating conditions under which this
type of facility has been demonstrated as being in compliance with
the Part 264 performance criteria when burning this type of waste.
Therefore, a trial bum will be required.
It is also hypothesized that there are data available from the waste
generator which are sufficient to develop the trial burn plan. There-
fore, additional analysis of the waste will not be necessary to
support the trial burn permit application. The POHC(s) for which
destruction and removal efficiencies are to be demonstrated in the
trial burn must be designated, based on review of existing information
and/or additional analysis of a representative sample of the waste.
Since the owner/operator plans to operate his facility under one set
of temperature-residence time-excess air conditions when treating
hazardous waste, the trial burn will consist of three replicate tests
under that set of operating conditions.
The trial burn sampling and analysis strategy must address:
• the waste analysis requirements of 40 C.F.R. Part 122,
• the performance standards of 40 C.F.R. Part 264,
Subpart 0, and
• the monitoring requirements of 40 C.F.R. Part 264,
Subpart 0.
a. Sampling Strategy
During each of the three replicate tests, the following samples must
be obtained:
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• one composite sample of the waste actually treated,
• one time-averaged (3-4 hour) sample of stack gas, and
• one composite sample of spent scrubber water.
No bottom ash or fly ash streams (other than the stack particulate
emissions) are expected to be generated as effluents from this
facility.
b. Analysis Strategy
The waste must be analyzed to determine:
*
• heating value of the waste,
*
• viscosity or physical form,
•k
• quantity of organically-bound chlorine (this analysis
is not mandatory; however, the data obtained may be
helpful in determining a potential for HC1 emissions),
• identity and approximate quantity of known or suspected
Appendix VIII constituents,* and
• quantity of the designated POHC(s) for the trial burn.
The stack gas must be analyzed to determine:
• quantity of the designated POHC(s) for the trial burn,
• quantity of particulate matter emissions,
• quantity of hydrochloric acid emissions,
• carbon monoxide level, and
• oxygen level (excess air level determination).
The scrubber water must be analyzed to determine:
• quantity of the designated POHC(s) for the trial burn.
It has been hypothesized, for this example, that this information was
available from the waste generator. Some or all of these determinations
may be repeated on the actual composite waste sample.
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3. Tactics and Methods
a. Selection of POHC3
Table 1 summarizes the information that is hypothetically available
from the generator of the waste in this example. The major organic
components that appear to be candidates for selection as the POHC(s)
are listed in Table 2, along with their relevant physical/chemical
properties (from Appendix A).
It is hypothesized that the permit writer designates hexachlorobutadiene,
hexachlorobenzene, and hexachloroethane as the POHCs. All three species
are present in significant concentration in the waste and will remain
at >1000 ppm concentration, even if the waste were cut by as much as
1:10 with auxiliary fuel in order to limit the total chlorine feed
rate and to maintain an adequate heating value in the total incinerator
feed. Fully chlorinated species, such as these, are generally considered
to be highly resistant to thermal degradation, and thus provide a set
of "worst case" POHCs for DRE determination.
b. Selection of Sampling Methods
For sampling of wastes, as well as the liquid and solid effluents, the
choice of method is based primarily on the nature of the medium. Review
of available methods indicates that dipper (Method S002) and tap
sampling (Method S004) is appropriate for collection of discrete sub-
samples of waste feed and of spent scrubber water, respectively, at
regular time intervals over the duration of each trial burn. These
subsamples are then combined to form the corresponding composite
samples for each test.
For sampling of stack gas, both the nature of the medium and the
nature (volatility, stability) of the POHC(s) and other target species
affects the choice of a sampling method. Appendix B lists recommended
sampling methods for each candidate POHC. Table 3 summarizes these
recommendations for the candidate POHCs in this hypothetical example.
The MM5/SASS approach collects all the candidate POHCs and also
suffices to determine compliance with the two other performance
standards of 40 C.F.R. Part 264. The particulate matter emission
rate is determined from the mass of material collected in the probe
wash, cyclone (if any), and filter of the MM5 train, prior to extraction
for POHC analysis. The hydrochloric acid emission rate is determined
by using a caustic scrubbing solution in the impinger portion of the
MM5 train and determining the hydrochloric acid level, as chloride, by
ion chromatography.
In addition to the procedures chosen for the collection of the POHCs,
it is necessary to specify procedures to accomplish the required
monitoring for carbon monoxide and excess air (oxygen determination)
levels in the stack gas.
19
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TABLE 1
AVAILABLE INFORMATION ON COMPOSITION
OF HYPOTHETICAL WASTE
Visual Inspection: The waste is a pitch black, non-viscous liquid
with obvious particulate loading. It has a pungent odor and fumes
slightly when the cap is removed.
Loss on Ignition: Ignition at 600°C resulted in a 99.8% loss of
mass.
Higher Heating Value: The waste does not burn in a bomb calorimeter;
its higher heating value is estimated at ^2000 Btu/lb (^1.11 kcal/g).
Combustion Analysis: The waste was found to contain: 21.35% C;
0.13% H; 0.07% N; 0.02% S; 75.52% CI.
Infrared Spectrum: The IR shows no -COOH, -OH, -NH, or C"0
functionality. Most of the spectral peaks can be attributed to
hexachlorobutadiene. Hexachlorobenzene peaks are also present.
LRMS: The major components identified are mass 258, 6 Cl's, C^C^ or
hexachlorobutadiene and, less abundant, mass 282, 6 Cl's, C6C16 or
hexachlorobenzene.
GC/MS: This analysis confirms that hexachlorobutadiene is the major
component and hexachlorobenzene is present at about 10% of the C^Cls
concentration. Other peaks in the chromatogram correspond to
hexachloroethane (*v4%), tetrachloroethanes (^3%), tetrachloroethene
(^0.1%) plus four others at about 0.5% concentration of the CHC16
concentration.
Summary: All of the available evidence suggests that this waste
contains essentially no tetrachloroethene, that hexachlorobutadiene
makes up about 65% of the waste, and that there are perhaps a
dozen other components at 1-5% concentration. All of the minor
components appear to be chlorinated, with hexachlorobenzene the
most abundant.
20
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TABLE 2
CANDIDATE POHCs FOR HYPOTHETICAL WASTE
AH1
Approximate B.P. kcal/mol2 MW
Compound Concentration in Waste (°C) (kcal/g) (g/mol)
Hexachlorobutadiene3 65 % 215 553 260.74
(2.12)
Hexachlorobenzene3 6 % 323- 510 284.76
326 (1.79)
Hexachloroethane3 2 % 186.8 109 236.72
(0.46)
Tetrachloroethane
1,1,1,2- ) 1.5% 130.5 233 167.84
(1.39)
1,1,2,2- ) 146.5 233 167.84
(1.39)
Tetrachloroethene 0.1% 121.0 197 165.82
(Tetrachloroethylene) (1.19)
x
Standard Enthalpy of Combustion
21 kcal/g = 1.8 x 103 Btu/lb
designated as POHC for the trial burn
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TABLE 3
RECOMMENDED STACK SAMPLING METHODS FOR CANDIDATE
POHCs IN HYPOTHETICAL TRIAL BURN EXAMPLE
Candidate POHC
Hexachlorobutadiene1
Hexachlorobenzene1
Hexachloroe thane1
Tetrachloroethane(s)
Tetrachloroethene
(Tetrachloroethylene)
Number
S0082
S0082
S0082
S0082
S0082
Stack Sampling Method
Description
MM5 - Sorbent
MM5 - Particulate and Sorbent
MM5 - Sorbent
MM5 - Sorbent
MM5 - Sorbent
'''Designated as a POHC for the trial burn.
2Method S009 (SASS) could also be selected. A specially fabricated
glass-lined SASS train might be necessary to withstand the hydro-
chloric acid concentration expected in the stack gas.
22
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c. Selection of Sample Preparation Methods
The procedures used in the preparation of field samples for subsequent
analysis of the designated POHC(s) and other target species are
determined both by the nature of the sample medium and the nature of
the species sought.
The samples which have been collected for Test No. 1 of the trial burn
include a composite sample of still bottom waste (organic liquid/
sludge), one composite sample of spent scrubber water (aqueous liquid),
and one time-integrated stack gas sample collected with a MM5
comprehensive sampling train. The stack gas sample is composed of
several discrete subsamples (Figure 2) which are prepared individually—
probe wash and filter catch (solid), sorbent trap (solid), condensate
(aqueous liquid), and impinger solution (aqueous liquid).
Representative aliquots of samples must be obtained prior to subsequent
extraction procedures. Method P001 is appropriate for obtaining
representative aliquots of both the waste and scrubber water samples.
For the various MM5 samples, aliquots are not necessary since the
entire sample is usually extracted. The target species (hexachloro-
butadiene, hexachlorobenzene, and hexachloroethane) require the
addition, prior to extraction, of a surrogate to monitor the recovery
of the neutral extractable organics (Method PQ14). (For the probe
wash and filter catch samples, the surrogate(s) are added after the
samples have been dried to constant weight, and the particulate
loading obtained.)
The appropriate extraction procedure is primarily determined by the
sample medium. Review of available extraction procedures suggests
that liquid/liquid extraction (Method P021a) is appropriate for aqueous
liquid samples (scrubber water and MM5 train condensate), solvent
dilution (Method P023) for organic liquids (still bottom waste), and
liquid/solid extraction in a Soxhlet apparatus (Method P024b) for
the solid samples (combined probe wash and filter catch and the sorbent
trap from the MM5 train). The resulting sample extracts are then
concentrated (Method P031) for subsequent analysis procedures,
assuming further cleanup procedures (Methods P041-P045) are not needed
to remove interferences. All extracts from the MM5 train samples
(probe wash/filter catch, sorbent, and condensate) are combined prior
to the concentration step to yield one sample extract for analysis.
A representative aliquot (Method P001) of the impinger solution is
removed for analysis of chloride by ion chromatography.
d. Selection of Analysis Methods
The analytical procedures used for qualitative identification and
quantitative determination of POHC(s) and other target species are
determined primarily by the nature (volatility, polarity) of the
species sought.
23
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Appendix C lists recommended analysis methods for each candidate
POHC after the appropriate sample preparation steps (described in
Section IV) have been performed. Table 4 summarizes the recommended
analysis methods for the candidate POHCs in this hypothetical example.
Note that a single analytical method suffices to determine all of the
hexachloro- species of concern here, while an additional method would
be recommended if it were desired to include the tetrachloroethanes
and tetrachloroethene.
4. Results and Calculations
Chapter VI includes formats for reporting the results of specific
analyses and Chapter VII deals with overall reporting and documentation
procedures. This section of Chapter III supplements these discussions
and those available in other resources (2-5), by showing the calculations
of DRE, corrected particulate loading, and HCl emissions for the
hypothetical example described above. Again, this example has been
somewhat oversimplified for purposes of illustration.
According to 40 C.F.R. Part 264, the DRE for each POHC is calculated as:
DRE - Wln„ W°Ut x 100%
in
where:
W - mass feed rate of one POHC in the waste stream feeding
the incinerator, and
W ¦ mass emission rate of the same POHC present in stack
out exhaust gas emissions.
a. Calculation of W,
C x FR
win - "^Too ~
where:
C ¦ concentration of POHC in waste (%), and
w
FRw - mass feed rate of waste to the incinerator (lb/h).
Assume that quantitative analysis of a representative aliquot drawn
from the composite waste sample from Test No. 1 of the trial burn
gave the following concentrations:
24
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TABLE 4
RECOMMENDED ANALYSIS METHODS FOR CANDIDATE
POHCs IN HYPOTHETICAL TRIAL BURN EXAMPLE
Candidate POHC
Hexachlorobutadiene1
Hexachlorobenzene1
Hexachloroethane1
Tetrachloroethane(s)
Tetrachloroethene
(Tetrachloroethylene)
Number
A121
A121
A121
A101
A101
A101
Analysis Method
Description
GC/MS Extractables
GC/MS Extractables
GC/MS Extractables
GC/MS Volatiles
GC/MS Volatiles
GC/MS Volatiles
1Designated as POHC for the trial burn.
25
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hexachlorobutadiene: 63.0%
hexachlorobenzene: 9.4%
hexachloroethane: 1.1%
Further, assume that the 10 x 10s Btu/h thermal capacity of the
facility was met by blending waste 1:10 with waste oil to give a
feed mixture that was 7.5% chlorine and had a heating value of
16,400 Btu/lb (3.8 x 107 J/kg). The total mass feed rate to the
incinerator was therefore 600 lb/h (272.2 kg/h), 540 lb/h (245 kg/h)
of which was auxiliary fuel (waste oil) and 60 lb/h (27 kg/h) was
chlorinated waste.
The W. values for the three POHCs are therefore:
in
W,
POHC in
hexachlorobutadiene (.630 x 60) 37.8 lb/h
hexachlorobenzene (.094 x 60) 5.64 lb/h
hexachloroethane (.011 x 60) 0.66 lb/h
b. Calculation of W
out
W (lb/h) = C x ER x 1.32 x 10 *
out s s
where:
C ¦ concentration of POHC in the stack gas effluent
s (mg/dscm),
ER ¦ volumetric flow rate of stack gas (dscm/min),
s and
1.32 x 10 4 » conversion factor from mg/min to lb/h.
Assume that quantitative analysis of the extract prepared from the
time-integrated comprehensive sampling train sample from Test No. 1
of the trial burn gave the following concentrations in the sampled
gas:
hexachlorobutadiene 0.080 mg/dscm
hexachlorobenzene 0.020 mg/dscm
hexachloroethane £0.004 mg/dscm
Further, assume that the average measured volumetric flow of stack
gas during Test No. 1 of the trial burn was 3200 dscf/min (90 dscm/min)
26
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The W values for the three POHC therefore would be:
out
POHC
W
out
hexachlorobutadiene
hexachlorobenzene
hexachloroethane
0.080 x 90 x 1.32 x 10"" 9.5 x 10_'f lb/h
0.020 x 90 x 1.32 x 10_if 2.4 x 10_'t lb/h
<0.004 x 90 x 1.32 x 10"'t < .48 x 10 * lb/h
c. Calculation of PRE
f W
in
W
DRE =¦
out
x 100Z
W
in
POHC
DRE
hexachlorobutadiene
hexachlorobenzene
hexac hioroe than e
99.997%
99.996%
>99.993%
Note that compliance with a four-nines DRE performance standard could
not have been demonstrated in this particular example for a component
present at <1% in the waste itself (or <1000 ppm in the 1:10 waste:fuel
blend fed to the incinerator), unless the detection limit for that
component in the stack gas were <4 ug/dscm.
In this hypothetical example, compliance with a >99.99% DRE performance
standard has been demonstrated, in one test, for each of the three
POHCs. If these results were supported by data from the other two
replicate trial burn tests, the four-nines DRE could be considered
to have been established.
d. Calculation of HCl Emissions
An incinerator which burns highly chlorinated hazardous waste capable
of producing significant stack gas emissions of hydrogen chloride
(HCl) must be monitored and/or controlled for the HCl emissions.
The hypothetical waste in this example contains approximately 75 percent
chlorine by weight (Table 1). At the proposed 60 lb/h feed rate of
waste (blended 1:10 with auxiliary fuel for a total feed of 600 lb/h
or 9.8 x 106 Btu/h), the maximum HCl emission rate would be 45 lb/h
(chlorine basis) or 46 lb/h (21 kg/h) as HCl. This is sufficiently high
to warrant concern for potential HCl emissions and to indicate the
necessity for stack measurement of HCl.
27
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The stack emission rate of HC1 can be calculated from:
HC1 (lb/h) - C. x ER x 1.32 x 10_1+
out in s
where:
C. = concentration of HC1 (as CI ) in the stack gas
n effluent and collected in the impingers,
ER = volumetric flow rate of the stack gas (dscm/min),
S and
1.32 x lO-1* = conversion factor from mg/min to lb/h.
Assume that quantitative analysis of the impinger/condensate solution
from the time-integrated comprehensive sampling train from Test No. 1
of the trial burn gave 34 mg/dscm HC1 in the stack gas effluent.
The stack emission rate of HC1 is calculated by:
HC1 ¦ 34 mg/dscm (90 dscm/min) (1.32 x 10 l+)
out
=0.40 lb/h HC1
This emission level is <1% of the 46 lb/h of HC1 potentially generated
from the waste, indicating that the removal efficiency of the wet
scrubber was >99%, and the incinerator is shown to be in compliance with
the Part 264 performance standard which limits HC1 emissions from the
stack.
e. Calculation of Particulate Loading
An incinerator burning hazardous waste must not emit particulate
matter in excess of 180 milligrams per dry standard cubic meter
when corrected to a standard excess air level (7 percent oxygen)
in the stack gas according to the performance standard outlined in
40 C.F.R. Part 264.
Assume that prior to chemical analysis, particulate samples from the
stack effluent of the hypothetical waste (from probe washes and
filter catches of the time-integrated comprehensive sampling train)
were dried and weighed. The hypothetical particulate loading from
these measurements was calculated to be 80 mg/dscm at the actual
excess air level of the stack exhaust gas. The excess air level was
determined to be 150 percent based on a measured oxygen level of
12.8 percent.
28
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The measured oxygen level is corrected to a standard excess air level
and a corrected particulate loading calculated as specified in the
Part 264 regulations, according to the following formula:
P (mg/dscm) = P x 14
c m ZX - X
where:
P^ = corrected concentration of particulate matter (mg/dscm),
P^ » measured concentration of particulate matter (mg/dscm), and
Y - measured concentration of oxygen in the stack gas using the
Orsat method for oxygen analysis of dry flue gas (%).
The corrected particulate loading is then 140 mg/dscm (0.06 gr/dscf).
Therefore, it is determined that this total particulate emission level
is in compliance with the Part 264 performance standard which specifies
that particulate emissions cannot exceed 180 mg/dscm (0.08 gr/dscf).
f. Summary
It is apparent that this sample of hypothetical waste when burned under
these conditions complies with the Part 264, Subpart 0, incinerator
performance standards as they relate to:
• destruction and removal efficiency-
All three POHCs showed compliance with the >99.99%
DRE performance standard;
¦ limitation on HCl emissions-
The HCl emission rate of 0.40 lb/h shows compliance
with a ^99% removal standard for HCl; and
• limitation on stack emissions of particulate material-
The corrected particulate loading of 140 mg/dscm shows
compliance with the 180 mg/dscm standard for particulate
loading (corrected to a standard excess air level).
If these results are supported by data from two replicate hypothetical
waste samples, compliance could be considered to have been established.
29
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IV. SAMPLING PROCEDURES
A. OVERVIEW
The sampling methods which are required for the ultimate analysis of
POHCs in hazardous wastes and incinerator effluents during trial burns
may be required to address a variety of media. The hazardous waste
prior to incineration may be a solid, liquid, slurry, or sludge.
Following combustion, POHCs may be found in solids (e.g., bottom
ash, fly ash/ESP catches), liquids (scrubber water), or the stack
gas with its entrained particulate material. In this discussion,
the sampling methods appropriate to each influent and effluent stream
of a hazardous waste incinerator are discussed. Each sampling method
is described in an outline which also indicates the sample matrix
and the general hardware requirements for the sampling method.
Reference to a primary source, where a complete detailed description
of the method can be found, is also included.
Liquid and gaseous sampling methods are likely to be most important
for both routine and trial burn monitoring. It is expected that most
hazardous wastes to be incinerated will be liquids, sludges, or
slurries. Often these wastes will be contained in drums following
transportation from the generator to the disposal facility. Such
wastes are amenable to sampling with a Coliwasa (composite liquid
waste sampler). During trial burns, the calculation of the destruction
and removal efficiency (DRE) value for the designated POHC(s)
requires the measurement of the POHC(s) in the stack gas following
all emission control devices. The required DRE value, 99.99 percent
minimum, for each POHC places severe constraints on the sampling
system for stack exhaust gases. It should be remembered that only
during the trial burn does specific POHC sampling occur. During
routine incinerator operation, sampling requirements are significantly
less.
B. SAMPLING METHODS FOR INFLUENT STREAMS
The preferred sampling method for the influent streams to a hazardous
waste incinerator depends upon the exact form of the influent (solid,
sludge, liquid, etc.). This section presents a summary description of
the general methods which are to be used for the sampling of the
influent streams to a hazardous waste incinerator. Table 5 summarizes
the sampling devices appropriate for hazardous waste sampling and
Table 6 summarizes typical sampling points for most waste containers.
The basic strategy for sampling of influent waste streams to a hazardous
waste incinerator during a trial burn is the compositing of individual
grab samples of the influent waste. To obtain a representative sample
of the waste, the number and frequency of the grab samples collected
30
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TABLE 5
CHOICE OF SAMPLERS FOR HAZARDOUS WASTES
Waste Type
Liquids, sludges
and slurries in
drums, vacuum
trucks, barrels,
and similar con-
tainers
Liquids and
sludges in
ponds, pits or
lagoons
Wastes in
storage tanks
Powdered or
granular solids
in bags, drums,
or containers
Dry wastes (in
shallow con-
tainers) and
surface soil
Sampler
Coliwasa
a) Plastic
b) Glass
a) Dipper
b) Weighted
Bottle
Weighted
Bottle
a) Thief
b) Trier
Trowel
Limitations/Comments
Not for containers >1.5m deep.
Not for wastes containing
ketones, nitrobenzene,
dimethylformamide, mesityl
oxide, or tetrahydrofuran (5).
Not for wastes containing
hydrofluoric acid and
concentrated alkali solutions.
Cannot be used to collect
samples beyond 3.5m; dip and
retrieve sampler slowly to
avoid bending the tubular
aluminum handle.
May be difficult to use on
viscous liquids; the bottle
may also be used as the sample
container.
May be difficult to use on
viscous liquids; the bottle
may also be used as the sample
container.
Limited application for sampling
moist and sticky solids and
when the diameter of the solids
is greater than 0.6 cm.
May incur difficulty in retaining a
core sample of very dry granular
materials during sampling.
Not applicable to sampling deeper
Chan 8 cm. Difficult to obtain a
reproducible sample mass.
Waste piles
Waste Pile Not applicable to sampling solid
Sampler wastes with dimensions greater
than one-half the diameter of
the sampling tube.
Source—References 2, 4, and 5.
31
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TABLE 6
SAMPLING POINTS FOR MOST WASTE CONTAINERS
Container
Drum (bung on one end)
Drum (bung on side)
Barrels, fiberdrums,
buckets, sacks, or bags
Sampling Point
Vacuum truck (or
similar)
Ponds, pits, lagoons
Waste piles
Storage tanks
Soils
Withdraw sample through the bung opening.
Lay drum on side with bung up; withdraw sample
through the bung opening.
Withdraw samples through the top of barrels,
fiberdrums, buckets, and similar containers,
or through fill openings of bags and sacks;
withdraw sample through the center of the
containers and to different points diagonally
opposite the point of entry.
Withdraw sample through open hatch; sample all
other hatches.
•k
Divide surface area into an imaginary grid;
take three samples, if possible: one sample
near surface, one sample at mid-depth or at
center, and one sample at the bottom; repeat
the sampling at each grid over the entire
pond or site.
Withdraw subsurface sample through at least three
different points near the top of pile to points
diagonally opposite the point of entry.
Withdraw sample from the top through the sampling
hole.
•fa
Divide the surface area into an imaginary grid;
sample each grid.
The number of grids is determined by the desired number of samples to be
collected which, when combined, will give a representative sample of the
waste.
Source—References 2, 4, and 5.
32
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will vary, depending upon the engineering design of the waste feed
system. In general, a minimum of three individual grab samples will
be composited to ensure adequate integration over time (for continuous
feed processes) or over mass (for batch feed processes).
1. Sampling Methods for Liquid Wastes
a. Coliwasa (Method SQQ1)
The most important liquid sampler for use in sampling hazardous wastes
is the composite liquid waste sampler (Coliwasa). The design of this
device is both simple and inexpensive, and permits the sampling of both
free-flowing liquids and slurries, including multiphase wastes. Coli-
wasa samples may be collected rapidly, thus minimizing the exposure of
the sample collector to the potential hazards of the waste. In addition,
although not commercially available, the Coliwasa sampler is simple to
fabricate and inexpensive enough that contaminated parts may be discardec
after a single use if the parts cannot be easily cleaned.
The fabrication of a Coliwasa has been thoroughly documented (5), with
the selection of the sampling tube material (PVC or borosilicate glass
tubing) for a particular waste determined by the components of the waste,
as described in Table 5. To collect a waste sample, the Coliwasa
is slowly lowered into the waste container, a liquid sample is removed
from the waste, and the waste sample is transferred to a storage
container. This process is repeated until the requisite quantity of
sample has been collected. The primary limitation on the use of a
Coliwasa is that the sample depth cannot exceed 1.5m. However, most
of the liquid hazardous wastes which will be sent to incinerator
facilities will probably be contained in drums, barrels, and tanks
where this limitation will not be important.
b. Dipper or Pond Sampler (Method S0Q2)
The dipper or pond sampler, permits collection of liquid samples in
ponds, pits, lagoons, and tanks with open tops. The sampler consists
of an adjustable clamp attached to the end of a multiple-piece telescoping
aluminum tube; the clamp is used to secure a sampling beaker or bucket.
This device ia not sold commercially, but the pieces may be obtained from
hardware or swimming pool stores (for the telescoping tube) and
laboratory supply houses (for the clamp and beaker).
Dipper samples can be collected from open streams such as sluices or
from open tanks where there is sufficient access to permit the insertion
and removal of the dipper apparatus. A sample is collected by inverting
the beaker and then slowly lowering it into the liquid to be sampled.
At the appropriate depth, a rapid push-pull motion will rotate the
beaker opening toward the surface and allow a waste sample to be
collected. This device may be used to obtain samples as far as 3.5m
from the edge of the tank and at different depths.
33
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c. Weighted Bottle Sampler (Method S003)
The weighted bottle sampler usually consists of a glass bottle, a weight
sinker, a bottle stopper, and a line which is used to raise and lower
the bottle during sampling, as well as to open the bottle at the appropriate
sampling depth. Descriptions of this device are found in ASTM Methods
D-270 (8) and E-300 (9). These methods use a metallic bottle basket
which also serves as the weight sinker. These devices may be either
fabricated or purchased.
The use of a weighted bottle to sample liquids contained in storage tanks,
wells, sumps, or other containers which cannot be adequately sampled
with the other liquid sampling devices, involves lowering the bottle to
the appropriate depth, uncapping it, and after completely filling it,
withdrawing the sampler. Once out of the waste, the bottle may be
capped, rinsed off, and used as the sample storage container. The
sampler cannot be used to collect liquids that are incompatible with,
or chemically react with, the weight sinker or the control lines.
d. Tap Sampling (Method S004)
Tap sampling is the appropriate method for sampling liquid wastes in
pipes or ducts. Coliwasa sampling is not appropriate to the collection
of liquids from moving streams. For liquids in motion, such as scrubber
water which mixes while being recycled, a simple tap, either in the pro-
cess line or in the storage reservoir, allows collection of a repre-
sentative sample. For this method, a sampling line is attached to the
tap and inserted into the sampling bottle. The tap is opened to permit
a flow such that the sample fill-time exceeds five minutes. Both the
sampling line and bottle are flushed several times prior to isolation
of the sample. Excess waste should be returned to the feed tank or
disposed of in accordance with facility procedures. This method is
described fully in ASTM Method D-270 (8).
2. Sampling Methods for Solid Wastes
A wide variety of sampling tools are available for the sampling of solid
materials. The most suitable of these methods for the sampling of
hazardous waste are the grain sampler (thief), the sample corer (trier),
and the trowel (scoop). The use of each sampler is described in detail
in SW-846 (4).
a. Thief or Grain Sampler (Method S005)
The grain sampler, also called a thief, consists of two slotted tele-
scoping tubes, usually made of brass or stainless steel. The outer
tube has a conical pointed tip on one end which permits the sampler
to penetrate the material being sampled. The sampler is opened and
closed by rotating the inner tube. While open, the sampler is shaken
to permit the free-flowing sample to fill the interior of the sampler.
34
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b. Trier or Sample Corer/Waste Pile Sampler (Method S006)
A typical trier or sample corer consists of a long tube with a slot
that extends almost the entire length of the tube. The waste pile
sampler is essentially a large sample corer. While not commercially
available, these samplers can be easily fabricated from sheet metal or
plastic (PVC) pipe. The tip and edges of the tube slot are sharpened
to allow the corer to cut a core of the material to be sampled when
rotated after insertion into the material. The sampler is inserted
into the waste at. an oblique angle and withdrawn with the open portion
pointed upwards. Sample corers are usually made of stainless steel
with wooden handles, and can be purchased from laboratory equipment
suppliers. Its use is similar to that of the grain sampler as discussed
above. However, the trier is preferred over the grain sampler when
the powdered or granular material to be sampled is moist or sticky.
The waste pile sampler is used to sample wastes in large heaps, with
cross-sectional diameters greater than lm. In addition, this sampler
can be used to sample granular or powdered wastes in large bins, silos
or barges where the grain sampler and corer are not long enough. This
sampler will not collect representative samples when the diameter of
the solid particles in the waste exceeds one-half the diameter of the
tube.
c. Trowel or Scoop (Method S007)
A trowel looks like a small shovel. A laboratory scoop is similar to
the trowel except that the blade on the trowel is usually more curved
and has a closed upper end to permit the containment of material.
A trowel can be purchased from hardware stores; the scoop can be
purchased from laboratory equipment suppliers. An ordinary zinc-plated
garden trowel can be used in some cases to sample dry granular or
powdered materials in bins or other shallow containers. The laboratory
scoop, however, is a better device because it is usually made of
materials less subject to corrosion or chemical reactions, thus
lessening the probability of sample contamination.
3. Sampling Methods for Slurry and Sludge Samples
Slurries and sludges may be sampled employing the methods described
previously (such as the Coliwasa). Free-flowing sludges and slurries
may be appropriately sampled as liquids. For compacted sludges, i.e.,
non-free-flowing, the solid waste samplers used for moist samples (such
as corers and trowels) are appropriate.
4. Sampling Methods for Water Samples
Scrubber water and other liquid hazardous waste influents to a hazardous
waste incinerator are usually sampled by the dipper or tap sampling
method.
35
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C. SAMPLING METHODS FOR EFFLUENT STREAMS
Sampling of the effluent streams of a hazardous waste incinerator serves
several purposes. During trial burns, the measurement of POHCs in the
stack gas effluent is an integral part of the calculation of DRE values
to determine whether the incinerator meets its performance criteria.
In addition, other effluent streams such as scrubber waters and solids,
have to be monitored periodically to ensure that these effluents are
disposed of in an environmentally acceptable manner.
1. Sampling Methods for Stack. Gas
The sampling of stack gas components is most important to the hazardous
waste incinerator permitting process. In general, the sampling apparatus
for collecting stack gas effluents includes three major components:
(a) an extractive probe which must be resistant to physical and chemical
reactions with the gas being sampled; (b) one or more thermostatted
compartments to maintain the gas at a temperature consistent with the
collection medium, usually hot (200°C) for particulate collection and
cool (20°C) for sorbent collection of the more volatile constituents;
and (c) the sample collector. Some of the sampling devices integrate
all three components into a single unit, while other methods require
the addition of one or more components before they are suitable for use.
In general, the deployment of stack gas sampling trains for the measure-
ment of emissions from a hazardous waste incinerator should parallel
the procedures specified in EPA Methods 1-5 (6) for particulate emissions
testing. Criteria for selection of sampling port locations and number,
location of sampling points within a stack, and assurance of isokinetic
sampling rates are comparable with the Modified Method 5 train and
SASS train. These criteria are discussed in both EPA Methods (6) and
in "Air Pollution (Volume III)" (10).
In addition to the Modified Method 5 and SASS trains, a volatile
organic sampling train (VOST) has recently been developed for the
collection of volatile POHCs at low concentrations in stack gas
effluents.
a. Modified Method 5 Train (Method S008)
The Modified Method 5 (MM5) sampling train is one of the comprehensive
sampling systems which is used to sample stack gas effluents. This
system is based upon the design of units which normally are employed
for sampling under EPA Method 5 (6). The modified system consists of
a probe, an optional cyclone, a high-efficiency glass or quartz fiber
filter stage, a sorbent module, four impingers, and some control hard-
ware. The sorbent module, the modification to the basic system which
permits trapping of volatile organic vapors, is mounted vertically atop
the first impinger of the train. This impinger is empty and is used to
collect the condensate which percolates through the sorbent resin module.
36
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A diagram of this system is shown in Figure 3. Physical construction
details and assembly details of this system have been described by
Martin (11) and maintenance procedures have been described by Rom (12).
This system may be used for either stack gas sampling or combustion
zone sampling with differences only in the type of probe utilized.
For stack gas sampling, either medium-wall Pyrex glass tubing (for probes
less than 2.1m (7 ft) in length) or 1.6 cm O.D. Inconel 825 tubing
(for probes greater than 7 ft long) is wrapped with heating wire and a
stainless-steel jacket. Samples are collected while the probe is heated
to a gas temperature above the dew point of the stack gas. If sampling
of combustion zone vapors is necessary or desirable for a particular trial
burn, a water-cooled, quartz-lined sampling probe is used (13). A stain-
less-steel jacket surrounds the quartz probe liner, and the water cooling
decreases the temperature of the exiting gas to about 205°C (40Q°F).
The ball or spherical joint of the probe connects to a glass cyclone with
a collection flask attached. The use of the glass cyclone is optional.
The purpose of the cyclone is to remove large quantities of particulates
and prevent plugging of the filter. In gas streams where the particulate
loading is expected to be minimal, the cyclone may be replaced with a
glass tube connecting the probe to a glass filter holder. If the cyclone
is not used, the cyclone outlet is connected to the glass filter holder.
This holder is equipped with a very coarse, fritted glass filter support
and a tared glass or quartz fiber filter. The cyclone, flask, and filter
holder are contained in an electrically heated enclosed box which is
thermostatically maintained at a temperature of 120°C + 12°C (250°F + 25"?)
which is sufficient to prevent water condensation in this portion of
the train.
Downstream of the heated filter, the sampled gas passes through a water-
cooled module and then to a sorbent module that is filled with XAD-2
resin. The XAD-2 sorbent is a porous polymer resin with the capability
of adsorbing a broad range of organic species. The sorbent module is
expected to give efficient collection of vapor phase organic materials
with boiling points >_1009C (200®F) (14,15,16,17).
A diagram of a suitable sorbent module is shown in Figure 4. Alternative
designs in which the cooling and sorbent portions are separate components
are also acceptable and may be more conveniently cleaned. Before the
sampled gas reaches the sorbent resin, it ia cooled to a temperature
of 20°C (70°F). This may cause some of the water vapor in the sampled
stream to condense and, in turn, some organic vapor may become entrained
in the condensate. For this reason, the condensate is allowed to
percolate through the resin bed prior to being discharged into a
collection vessel.
37
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Probe
Reverse-Type Pitot Tube
U>
00
Thermometer
Heated Area
Filter Holder \ ^
Sorbent Trap
Silica Gel
p
Temperature Sensor . | | Stack Wall
Thermometer
Check Valve
Pitot Manometer
Recirculation Pump
Thermometers
Vacuum Line
Orifice
Impingers Ice Bath
By-Pass Valve
Main Valve
Dry Gas Meter Air-Tight Pump
FIGURE 3 MODIFIED METHOD S TRAIN (MM5)
-------
u>
vo
28/12 8«U Joint
Glut Water Jacket
Flow Olfaction
8 mm Glass Cooling Coil
Glass rrlttad Disc
Retaining Spring
Glass Wool Plug
Frittad Stalniass Steal Disc
16 mm Solv-Saal Joint
(or 28/12 Sockat Joint)
FIGURE 4 SORBENT MODULE
-------
At the downstream side of the sorbent module, four impingers are
connected in series and immersed in an ice bath. The first impinger,
connected to the outlet of the sorbent module, Is modified to have a
very short stem, so that the sampled gas does not bubble through the
collected condensate. An oversized impinger may be required for
sampling high moisture streams since the first impinger collects the
condensate, which passes through the sorbent module, for subsequent
organic analysis. The second impinger is a modified version of a
Greenberg-Smith design; initially it is filled with scrubbing solution.
The selection of scrubbing solution is contingent upon the type of
vapors that are suspected of being contained in the stack gas. A
caustic solution such as sodium hydroxide or sodium acetate, is used
to collect acidic gases such as HC1. (Sodium acetate may be used to
prevent depletion of scrubbing reagent by carbon dioxide.) For
collecting volatile metals (mercury, arsenic, selenium), a strongly
oxidizing solution (such as the SASS silver-catalyzed ammonium
persulfate) must be used. The third impinger is a Greenberg-Smith
impinger with a tip; it is also filled with an appropriate scrubbing
solution. The fourth impinger is typically filled with silica gel
to absorb any moisture in the stack gas. Moisture removal is
important to ensure accurate gas flow measurements and to prevent
damage to the pumping system.
During operation, the MM5 train typically collects a 4-6 $|y standard
cubic meter (dscm) sample over a sampling time of 3-5 hours. A near
isokinetic sampling rate is maintained throughout the sample collection.
b. Source Assessment Sampling System (SASS) (Method S009)
The Source Assessment Sampling System (SASS) is an alternative
integrated stack gas sampling system. In many respects, the SASS train
is about a five-fold scale-up of the MM3 train and collects a larger
sample, typically 30 dscm over a 3-hour sampling period. This sampling
train is appropriate whenever a large sample of stack gas (greater
than 10 dscm) is required to ensure adequate detection limits.
The SASS train consists of a stainless-steel probe that connects to
three cyclones and a filter in an oven module, a gas treatment section,
and an impinger series (Figure 5). Size fractionation is accomplished
in the cyclone portion of the SASS train, which incorporates three
cyclones in series to provide large collection capacities for
particulate matter nominally size-classified into three ranges:
(a) >10 ym, (b) 3 ym to 10 ym, and (c) 1 urn to 3 ym. By means of a
standard 142 or 230 mm filter, a fourth cut, <1 ym, can also be obtained.
The gas treatment system follows the oven unit and is composed of four
primary components: the gas cooler, the sorbent trap, the aqueous
condensate collector, and a temperature controller. Volatile organic
material is collected in a cartridge or "trap" containing XAD-2
sorbent, a macroreticular resin with the capability of adsorbing a
broad range of organic species. The XAD-2 cartridge in the SASS train
40
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Heat Controller
Isolation Ball Valve
Convection Oven
_z___
Filter
Gas Cooler
Stack T.C.
I
SS Probe
lO*
Gas
Temperature T.C.
S-Type Pitot
(®:
/o~3\
Oven T.C.
Sorbent Cartridge
Imp/Cooler Trace
Element Collector
Condensate Collector
Impinger T.C.
Dry Gas Meter/Orifice Meter
Centralized Temperature
and Pressure Readout
Control Module
Two 10 ft^/min Vacuum Pumps
FIGURE 5 SOURCE ASSESSMENT SAMPLING SYSTEM (SASS)
-------
is sized to ensure efficient collection of vapor phase organic materials
with boiling points _> 100°C (200°F). Volatile inorganic elements are
collected in a series of impingers that follow the condenser and
sorbent system. Trapping of some inorganic species also may occur
in the sorbent module. The last impinger in the series contains
silica gel for moisture removal.
This train was not designed for traversing a stack or for sampling at
stack gas temperatures above 260°C (500°F), although it could be
adapted, with suitable modifications, to these sampling situations.
In routine stack sampling, the stack to be sampled is velocity-traversed
once to locate a position near the center of the stack which has an
average stream velocity. The velocity at the sampling point, the stack
temperature, and moisture content are used to calculate the size of the
probe nozzle which will give approximately isokinetic sampling conditions
(10). The appropriately sized nozzle is attached to the probe for the
subsequent sampling effort.
c. Gas Bulb and Gas Bag Sampling Systems (Methods S010. SOU)
In addition to the stack gas sample collected with the comprehensive
sampling system, other gas phase stack samples may have to be collected
during some particular trial burns if volatile organic species are
among the designated POHCs for the purpose of calculating the DRE
performance. This type of sample is required because the sorbent
module and filter units contained within the comprehensive sampling
system (MM5 or SASS) are not efficient for the collection of organic
material with boiling points below 100°C (200°F), Therefore, organic
materials with high volatility may pass through the comprehensive
sampling system without being collected quantitatively.
To collect volatile POHC species, gas bulb samples of the stack
exhaust gas should be obtained during each trial burn when constituent(s)
of high volatility are designated as the POHC(s). The gas bulb may be
either directly coupled to a point that is downstream from the sorbent
module in a MM5 or SASS sampling train, or to a separate sampling line
within the stack. The latter alternative is preferred since the flow
in the comprehensive sampling system would not be disturbed.
For gas bulb sampling, the bulb is evacuated prior to connection to the
sample line and then it is allowed to fill with stack gag effluent (or
combustion zone effluent, if desired). Once the bulb is filled, the
sample valve is closed and firmly sealed. The bulb is removed and
shipped to the laboratory for analysis. A diagram of a typical gas
bulb collection system is shown in Figure 6. An outer styrofoam
container is used for thermal insulation during handling and for sample
safety during shipping.
42
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Styrofoam Protector
Side Bleed Control
Pyrex Wool Plug
2-Liter Vessel
ZZZZZ
Duct
Flow
/// >////////////*///////777-rrr,
FIGURE 6 EVACUATED GRAB SAMPLING APPARATUS (FOR SUBATMOSPHERIC PRESSURES)
-------
The amount of sample which has to be collected is a function of the
limit of detection requirements for the POHC(s) which is being monitored.
An alternative approach is to use gas bag sampling with an integrated
sampling train, as shown in Figure 7. The gas bag collects a 10 to 30L
gas sample which can be integrated over a reasonably long sampling
time (e.g., 3 hours).
For gas bag sampling, a nonreactive probe is inserted into the stack
and the gas sample is first bled or drawn through the probe, and then
through an air-cooled condenser, or equivalent, at a rate which is
regulated by a small diaphragm pump. The condenser serves to remove
excess moisture from the gas stream and to cool the gas to a temperature
which is compatible with the physical characteristics of the bag. A
flow rate meter is used to adjust and measure the gas flow into the
bag. Gas bag sampling should only be used for those components for
which it is validated. Also, it is important that field blank gas
bag samples (i.e., gas bags filled with air drawn from a cylinder) are
collected at the same time that the field samples are collected.
d. Volatile Organic Sampling Train (VOST) (Method S012)
After reviewing previous editions of this document and also the results
of previous hazardous waste incineration trial burns, it seems that
the volatile hazardous constituents are important components in
incinerator effluents. Thus, the need to develop a better and more
sensitive sampling and analysis technique for these volatile
constituents is apparent. Therefore, the concept of a volatile organic
sampling train (VOST) was developed as an alternative to the use of the
integrated gas bag sampling system, or the gas bulb sampling system
for the collection of volatile POHCs. The VOST has since been
evaluated by Midwest Research Institute (Kansas City, Missouri). A
paper which describes the equipment and procedures used during a
laboratory evaluation of the VOST, data from the collection, and
analysis of four volatile constituents taken during the laboratory
evaluation, a description of a field version of the VOST, and conclusions
and recommendations from the study, has been included as Appendix F
of this report.
The VOST which was evaluated consisted of a system designed to draw
effluent gas at a flow rate of lL/min through two traps (1.6 cm in
diameter x 10 cm) in series (Figure 8). The first trap contained
Tenax and was preceded by a gas cooler/condenser and followed
by an impinger for condensate collection. A second trap, containing
a section of Tenax and a section of charcoal, was located after the
impinger. The purpose of the second trap was to collect very volatile
compounds (e.g., vinyl chloride) which readily break through a Tenax
trap. The concept also involved replacing both pairs of traps with
fresh traps every 20 minutes (20L sample) over a 2 hour sampling period,
for a total of six pairs of traps. The collection of several pairs of
traps assures that the more volatile components will not break through
44
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Air-Cooled Condenser
Probe
Quick Disconnect
Filter (Glass Wool)
Rigid Container
FIGURE 7
INTEGRATED GAS-SAMPLING TRAIN: GAS BAG
-------
Glass Wool
Particulate Filter
Exhaust t litar/mln
Critical Orifice
pq
Stack
(or Test System)
Pump
Tanax
Dry Gas Matar
Charcoal Backup
rlfWfiV-
Empty
Trap Impinger
NOTE:
Both traps should ba changed out every
20 minutes over 2-hour period.
FIGURE 8
VOLATILE ORGANIC SAMPLING TRAIN (VOST)
-------
both the front (Tenax) and back (Tenax/charcoal) traps. Also, a
range of POHC concentrations are obtained since the contents of one
or all pairs of traps can be combined for analysis.
Prior to sampling it may be useful to spike the Tenax and Tenax/charcoal
traps with the compounds of interest to ensure that they can be thermally
desorbed at the time of analysis. A set of blank traps should also be
analyzed to determine background levels.
e. Specific Sorbent/Reagent Methods
Specific sorbents and reagents are used to collect POHCs which are
subject to reaction or loss when collected using the previously
described approaches. The use of specific sorbent/reagent sample
collection methods requires devices similar to that shown previously
for integrated gas bag samples. A nonreactive probe is inserted
into the stack gas stream and gas collected at a controlled rate.
A gas cooler is located before the sorbent or reagent collector to
reduce the temperature of the gas stream to levels compatible with
the collector. The sorbent appropriate to the POHC of interest is
mounted in place of the gas bag shown in Figure 7. Special reagent
solutions in impingers may be placed following the selected sorbent,
as appropriate, to remove other POHCs and corrosive gases from the gas
stream prior to the flow controllers. Table 7 summarizes the sorbents
and special reagents to be used for the sampling of the specific
POHCs.
These special-purpose sorbents/reagents may be incorporated into the
Modified Method 5 or SASS train modules if the substitution for standard
train components does not adversely affect collection of other POHCs.
Alternatively, a separate MM5/SASS train to collect the compound types
listed in Table 7 may be used.
f. Monitoring of Gaseous Combustion Products
As part of the routine documentation of the combustion performance of
a hazardous waste incinerator, several parameters are monitored con-
tinuously in the incinerator stack. The primary component which needs
to be monitored on a continuous basis, or with high frequency (once per
hour), i3 the level of carbon monoxide (CO) in the stack effluent. This
measurement is needed during trial burns as well as during routine
incinerator operation. Plume color and plume opacity may also be
measured frequently for control purposes, although routine documentation
is not required.
In addition, the oxygen level in the incinerator effluent must be
determined to allow correction of the measured particulate loading
to a standard excess air level. It may also be necessary, in some
cases, to measure the incinerator effluent for hydrochloric acid
for the purpose of calculating a removal efficiency.
47
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TABLE 7
SORBENTS AND SPECIAL REAGENTS FOR SPECIFIC POHCs
Compound Type
Sorbent
General-purpose—organics
General-purpose—organics
General-purpose—chlorinated organics
General-purpose—nonpolar organics
General-purpose—polar organics
(better than XAD-2 resin for
polar compounds)
General-purpose—polar organics
XAD-2 resin
Tenax GC
Florisil
Ambersorb XE-340
XAD-8 resin
Ambersorb XE-347
Compound Type
Special Reagent
Acidic compounds
Basic compounds
Volatile metals
Aldehydes
Dilute caustic (such as 1% NaOH)
Dilute acid (such as 1% HC1)
Oxidizing reagents (such as ammonium
persulfate)
2,4-Dinitrophenylhydrazine in 2N HC1
(or 2,3,4,5,6-Pentachlorobenzylhydrazine)
48
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• Gaseous Sample Conditioner
On-line, continuous monitoring instrumentation for incinerator
effluents involves a sample delivery system which provides a properly
conditioned representative sample to the instrumentation for measure-
ment. The sample delivery system needs to include a sampling probe and
a gas conditioner. For stack gas sampling, Pyrex glass or stainless-
steel probes may be used for the collection of particulates or gases.
A gas conditioning process is generally required to remove particulate,
cool, dilute and/or dehumidify the effluent prior to continuous
analysis by instruments, such as carbon monoxide monitors.
• Carbon Monoxide Measurement
For measurement of the level of carbon monoxide (CO) in the incinerator
effluent, a nondispersive infrared (NDIR) analyzer is recommended as
the preferred analytical procedure (EPA Method 10 (6)). Selection of
this instrument is consistent with the need to continuously monitor
combustion efficiency by monitoring CO. Many commercial NDIR
analyzers for CO are available; however, selection should be based on
the EPA specifications described in EPA Method 10 (6). Such
specifications are required to provide suitable quality control of
the collected data by requiring that instrumentation meet certain
criteria with regard to response time, span stability, and zero .
stability.
• Plume Color and Plume Opacity
The color and opacity of the incinerator plume can be measured by EPA
Method 9 (6). EPA Method 9 involves the visual determination of plume
opacity by a qualified observer. Commercially available smoke
generators are available which can be used to provide calibration of
the observer during the certification procedures defined in EPA
Method 9 (6).
• Oxygen Measurement
The oxygen level in the incinerator effluent must be determined to
allow correction of the measured particulate loading to a standard
excess air level. EPA Method 3 (6) involves the collection of a
gas sample, and subsequent analysis of the oxygen level by an Orsat
analyzer.
• Hydrogen Halide Measurement
Several wet chemical methods are available for the measurement of hydrogen
halides in stack gas effluents. These methods generally involve the
collection of the hydrogen halides in impingers containing water or dilute
caustic (0.1 N NaOH). A filter is utilized upstream of the impingers to
remove particulates.
49
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Analysis for the hydrogen halides by a specific ion electrode
method is the preferred analysis method due to potential interferences.
Recent research into the suitability of ion chromatography as a reliable
tool for analysis of several anions corroborates the suitability of this
technique for the analysis of hydrogen halides in stack gas samples. It
is recommended that this technique, or the selective electrode technique,
be used for the analysis of hydrogen halide in testing incinerator
effluents. Both techniques will permit analysis of effluent concentrations
as low as 1 ppm.
2. Sampling Methods for Solid and Liquid Effluents
The solid and liquid effluents from a hazardous waste incineration
facility, including bottom ash or fly ash/ESP catches, may be sampled
by the methods discussed previously for the influent waste streams.
Solid effluents will be sampled using scoops, corers, etc., as
appropriate. Liquid effluents, primarily scrubber water, may be
sampled by a variety of grab techniques including Coliwasa, dipper,
and tap samplers.
D. HEALTH AND SAFETY PRECAUTIONS
Proper safety precautions to protect the field crew from general and
specific hazards of sampling hazardous wastes should be a major focus
of any site-specific sampling plan. Proper safety precautions must be
observed when sampling any hazardous wastes.
In all cases, the field crew collecting a sample should be aware that
wastes can be corrosive, flammable, explosive, toxic and/or capable of
releasing acutely poisonous gases. Background information about the
waste is necessary in deciding the extent of safety precautions to be
observed in the choice of protective equipment to be used during
sampling.
If full protection is indicated, the person collecting the sample should
use a self-contained breathing apparatus, protective clothing, hard hat,
neoprene rubber gloves, goggles, and rubber boots. The self-contained
breathing apparatus should consist of an air-tight face mask and a supply
of air in a pressure tank which is equipped with a pressure regulator.
Protective clothing should consist of a long-sleeved neoprene rubber
coat and pants or long-sleeved coverall and an oil and acid proof
apron (5).
Once work begins at a field location, the sampling team leader, or an
individual designated by him and approved by the Safety Officer, should
have authority and responsibility for the implementation of the safety
regulations.
50
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The following precautions should be employed by all field crew members:
• Steel-toed safety shoes or boots should be worn.
a Eye protection should be worn at all times.
¦ Hard hats should be worn.
• Adequate protective clothing should be worn to prevent burns
from heat or chemicals or exposure to severe environmental
conditions. As necessary, a supply of gloves (both rubber
and cotton), shirts, pants, lab coats, aprons, jackets,
rain slickers, and parkas should be available for use.
• In general, all field work should be performed within the
view (or hearing) of at least one other individual. At
remote locations, this means that there should be at least
two field crew members.
• Upon arrival at the field site, the team leader or his
designated alternate should become familiar with the
locations of all the safety equipment offered at the
facility. If any equipment is unfamiliar to him, he
should ask for instructions on its use and transmit all
information regarding these safety items to each member
of the field crew.
¦ Either prior to departure for the field site, or immediately
upon arriving there, the field leader should identify all
local emergency assistance facilities and record their
telephone numbers for future reference, including fire
departments, rescue squads, poison information centers,
and hospital emergency facilities. Home telephone numbers for
all team members should also be recorded by the team
leader in case of need for emergency notification of
relatives.
E. COLLECTION OF REPRESENTATIVE SAMPLES
1. Gases
The representativeness of all gas samples is ensured by the integrated
sampling approaches presented previously. Stack gas samples taken by
MM5, SASS, or VOST represent collections obtained over a period of
several hours at or near the isokinetic sampling point. Hence, these
stack gas samples contain the average composition of the stack gas
during the time period sampled. Bag samples are also collected over
a period of several hours and thus any fluctuations in the levels of
specific components are integrated, yielding an average- composition
sample.
51
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2. Liquids
Each sample collected should be prepared in strict accordance with a
specified procedure. When sampling nonvolatile liquid products, the
sampling apparatus should be filled and allowed to drain before
drawing the actual sample. If the actual sample is to be transferred
to another container, the sample container should be rinsed with
some of the product to be sampled and drained before it is filled
with the actual sample.
3. Solids
The sampling procedure for solids should allow for some element of
randomness in the selection of subsamples since a variation in the
quality of the material is possible. Generally, where segregation
is known to exist and random variation of quality is not possible,
the sampling should be designed to allow for this status. The
sampler should always be on the alert for possible biases arising
from the use of a particular sampling device, or from unexpected
segregation in the material. Procedures for avoiding bias in the
sampling of solid materials, including pattern sampling of bulk
materials and procedures for blending and reducing samples to uniform
subsamples given in EPA manuals (4,5) should be used to ensure
adequately representative samples.
4. Slurries
The sampling of slurries with any degree of accuracy is difficult.
This is particularly true when sampling a normally static system
such as a storage tank or vat. Thus, arrangements should be made to
agitate thoroughly the contents of such storage units prior to
sampling. The most desirable and convenient place to sample a
slurry is from a pipeline as the material moves through the line.
Even in a pipe, it is difficult to obtain a representative sample
since slurries subjected to shearing will tend to change in composition
due to loss of liquid.
If only a portion of a slurry sample is needed for analysis, the
sample should be shaken and a portion more than adequate for analysis
dumped out. Attempts to pour a predetermined volume of a heterogeneous
sample for analysis are unsatisfactory, since the solids have time to
separate during pouring. The more frequently subsamples are taken,
the more accurately will the sample represent the total stream.
5. Sample Handling
After a sample has been transferred into the proper sample container,
the container must be tightly capped as quickly as possible to prevent
the loss of volatile components and to exclude possible oxidation from
the atmosphere.
52
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The use of a preservative or additive is not generally recommended.
However, if only one or two components of a waste are of interest and
these components are known to rapidly degrade or deteriorate chemically
or biochemically, the sample may be refrigerated at 4-6°C and/or
treated with preservatives.
To split or withdraw an aliquot of a sample, considerable mixing,
homogenization, or quartering is required to ensure that representative
or identical portions are obtained. When transferring a sample
aliquot, the container should be kept open as briefly as possible.
F. IDENTIFICATION OF SAMPLES
Each sample must be labeled and sealed properly immediately after
collection.
1. Sample Labels
Sample labels are necessary to prevent misidentification of samples.
Gummed paper labels or tags are adequate. The label must include at
least the following information:
Name of Collector (individual and affiliation)
Date and Time of Collection
Place of Collection
Collector's Sample Number which uniquely identifies the sample.
2. Field Log Book
All information pertinent to a field survey and/or sampling must be
recorded in a log book. This must be a bound book, with pages numbered
consecutively. Entries in the log book should include the following:
Location of Sampling (e.g., hauler, disposal site, etc.) and Address
Name and Address of Field Contact
Producer of Waste and Address
Type of Process Producing Waste (if known)
Type of Waste (e.g., sludge, wastewater, etc.)
Description of Sampling Point
Date and Time of Collection
Collector's Sample Identification Number(s)
Sample Distribution (e.g., laboratory, hauler, etc.).
3. Field Observations
Any field observations should also be incorporated into the log book.
Sampling situations vary widely. No general rule can be given as to
the extent of information that must be entered in the log book. A
good rule, however, is to record sufficient information so that
others may consistently reconstruct the sampling situation without
reliance on the memory of the sample collector.
53
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G. SAMPLING METHOD SUMMARIES
The sampling methods described in the previous portions of this section
are presented in a summary form. Each of the numbered methods is
presented as a summary table which includes the method name and number,
appropriate sample matrix, the general procedure to be used, and
literature references. In each case, the cited reference(s) provide
a complete description of the procedure with a level of detail suitable
for direct use by the sampling and analysis team.
54
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Method Number:
S001
Method Name:
Coliwasa
Basic Method:
Liquid Grab Sample
Matrix:
Liquids
Apparatus:
Coliwasa sampler, as described in SW-846 (4).
Sampling Method Parameters:
The Coliwasa sampler will be inserted in the closed position
into the liquid. The sampler will then be opened, filled,
capped, and removed.
References: U.S. Environmental Protection Agency/Office of Solid
Waste, Washington, D.C., "Test Methods for Evaluating
Solid Waste - Physical/Chemical Methods," SW-846 (1980).
deVera, E.R., B.P. Simmons, R.D. Stephens and
D.L. Strom, "Samplers and Sampling Procedures for
Hazardous Waste Streams," EPA-600/2-80-018
(January 1980). NTIS No. PB80-135353.
55
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Method Number:
S002
Method Name:
Dipper (Pond Sampler)
Basic Method:
Liquid Grab Sample
Matrix:
Liquids
Apparatus:
Beaker attached to telescoping pole, as
described in SW-846 (4).
Sampling Method Parameters:
The beaker will be inserted into the liquid with the opening
downward, until the desired depth is reached. The beaker
will then be turned right side up, filled with sample, the
dipper raised, and the sample transferred to a storage vessel.
A 2-4L sample will be collected.
References: U.S. Environmental Protection Agency/Office of Solid
Waste, Washington, D.C., "Test Methods for Evaluating
Solid Waste - Physical/Chemical Methods," SW-846 (1980).
deVera, E.R., B.P. Simmons, R.D. Stephens and
D.L. Strom, "Samplers and Sampling Procedures for
Hazardous Waste Streams," EPA-600/2-80-018 (January 1980).
NTIS No. PB80-135353.
56
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Method Number:
S003
Method Name:
Weighted Bottle
Basic Method:
Liquid Grab Sample
Matrix:
Liquids
Apparatus:
Weighted bottle, constructed as described
in ASTM D-270 (8) and ASTM E-300 (9).
Sampling Method Parameters:
A stoppered bottle will be lowered to the appropriate depth,
the stopper removed, and a sample collected. After the bottle
is filled, the sample bottle will be capped and wiped off.
References: U.S. Environmental Protection Agency/Office of Solid
Waste, Washington, D.C., "Test Methods for Evaluating
Solid Waste - Physical/Chemical Methods," SW-846 (1980).
American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards,"
Method D-270 (1975).
American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards,"
Method E-300 (1973).
57
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Method Number:
S004
Method Name:
Tap
Basic Method:
Liquid Grab Sample
Matrix:
Liquids
Apparatus:
Tap Valves
Sample Line (washed teflon)
Collection Bottles
Sampling Method Parameters:
A sample line will be inserted into the collection vessel.
The sample line and bottle must be thoroughly rinsed with the
liquid waste prior to isolating the sample. (This waste
must be disposed of in an appropriate manner.) A 2L (minimum)
sample will be collected over a sampling time which exceeds
5 min.
References: Lentzen, D.E., D.E. Wagoner, E.D. Estes and W.F. Gutknecht,
"EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment (Second Edition)," EPA-600/7-78-201
(October 1978). NTIS No. PB293795/AS.
American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards,"
Method D-270 (1975).
58
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Method Number:
S005
Method Name: Thief (Grain Sampler)
Basic Method: Solid Grab Sample
Matrix: Solids
Apparatus: Thief (available from laboratory supply
houses)
Sampling Method Parameters:
The thief will be inserted into the solid to be sampled, the
inner tube rotated to open the sampler, and then agitated to
encourage flow of the sample. The sampler will be closed, and
the sample withdrawn.
Reference: U.S. Environmental Protection Agency/Office of Solid
Waste, Washington, D.C., "Test Methods for Evaluating
Solid Waste - Physical/Chemical Methods," SW-846 (1980).
59
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Method Number:
S006
Method Name:
Basic Method:
Matrices:
Apparatus:
Trier (Sample Corer/Waste Pile Sampler)
Solid Grab Sample
Sludges
Solids
Sample corer (trier), fabricated from
PVC pipe or sheet metal, as described in
SW-846. (The waste pile sampler is a
larger scaled version.)
Sampling Method Parameters:
The sampler will be inserted into the solid material at an
angle of 0-45°, rotated to cut a core of the solid or sludge,
and removed with the concave side upward.
Reference: U.S. Environmental Protection Agency/Office of Solid
Waste, Washington, D.C., "Test Methods for Evaluating
Solid Waste - Physical/Chemical Methods," SW-846 (1980)
60
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Method Number:
S007
Method Name:
Trowel (Scoop)
Basic Method:
Solid Grab Sample
Matrix:
Solids
Apparatus:
Stainless steel or polypropylene
laboratory scoop (7 x 15 cm)
Sampling Method Parameters:
Prior to collecting a sample, the top-half inch of the solid
must be removed. Kg-sized samples will be obtained by combining
subsamples taken at several locations.
References: U.S. Environmental Protection Agency/Office of Solid
Waste, Washington, D.C., "Test Methods for Evaluating
Solid Waste - Physical/Chemical Methods," SW-846 (1980).
deVera, E.R., B.P. Simmons, R.D. Stephens and
D.L. Strom, "Samplers and Sampling Procedures for
Hazardous Waste Streams," EPA-600/2-80-018 (January 1980).
NT1S No. PB80-135J53.
61
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Method Number:
S008
Method Name:
MM5 Train
Basic Method:
Matrix:
Apparatus:
Comprehensive Sampling Train (filter-
sorbent-impinger)
Stack Gas (particulate plus vapor phase
material)
RAC or equivalent sampling train, modified
to include sorbent module as shown in
Figure 3
Filter - glass fiber filter
Sorbent - XAD-2 resin or as necessary for
collection of target species (Table 7)
Impinger reagent - as necessary for
collection of target species (Table 7)
Sampling Method Parameters:
The stack, will be traversed to determine the point of average
velocity and a gas sample collected at isokinetic conditions, as
specified in EPA Methods 1-5 (6). A 5 dscm sample will be collected
at a sampling rate of approximately 0.75 ft3/min.
As a check on recovery, the filter/sorbent and/or impinger
solutions must be spiked before or immediately after sampling
with a known quantity of the deuterated or fluorinated analog(s)
of the target compound(s).
References: Title 40, Code of Federal Regulations, Part 60,
Appendix A, Methods 1-5 (1980).
Martin, R.M., "Construction Details for Isokinetic
Source Sampling Equipment," EPA-APTD-0581 (1971).
NTIS No. PB209060.
Rom, J.J., "Maintenance, Calibration and Operation of
Isokinetic Source Sampling Equipment," EPA-APTD-0576
(1972). NTIS No. PB209022.
62
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Method Number:
S009
Method Name:
SASS Train
Basic Method:
Comprehensive Sampling Train (filter-
cyclone-sorbent-impinger)
Matrix:
Stack Gas (particulate plus vapor phase
material)
Apparatus:
Acurex or equivalent sampling train
Filter - glass fiber filter
Sorbent - XAD-2 Resin (or as necessary
for collection of target species) (Table 7)
Impinger reagent - as necessary for
collection of target species (Table 7)
Cyclone cutoffs - 10 ym, 3 um, 1 ym
Sampling Method Parameters:
The stack will be traversed to determine the point of average
velocity and a gas sample collected under isokinetic conditions,
as specified in EPA Methods 1-5 (6). A 30 dscm sample will
be collected at approximately 4 ft3/min.
As a check on recovery, the filter/sorbent and/or impinger
solutions must be spiked before or immediately after sampling
with a known quantity of a deuterated or fluorinated analog(s)
of the target compound(s).
References: Lentzen, D.E., D.E. Wagoner, E.D. Estes and
W.F. Gutknecht, "EPA/IERL-RTr Procedures Manual:
Level 1 Environmental Assessment (Second Edition),"
EPA-600/7-78-201 (October 1978). NT1S No. PB293795/AS.
Title 40, Code of Federal Regulations, Part 60,
Appendix A, Methods 1-5 (1980).
63
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Method Number:
S010
Method Name:
Gas Bulb
Basic Method:
Gas Grab Sample (reactive gases)
Matrix:
Stack Gas
Apparatus:
2L glass bulb in styrofoam package
Glass wool for particulate removal
Side bleed gas control mounted perpendicular
to duct
Sampling Method Parameters:
A gas bulb will be purged with a 20L gas sample at 0.5 L/min
prior to isolating sample. The bulb will then be re-evacuated,
the valve opened, a 2L gas sample collected, and the valve
closed.
References: Lentzen, D.E., D.E. Wagoner, E.D. Estes and
W.F. Gutknecht, "EPA/IERL-RTP Procedures Manual
Level 1 Environmental Assessment (Second Edition),"
EPA-600/7-78-201 (October 1978). NTIS No. PB293795/AS.
Title AO, Code of Federal Regulations, Part 60,
Appendix A, Method 7 (1980).
64
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Method Number:
SOU
Method Name:
Gas Bag
Basic Method:
Gas Grab Sample (unreactive gases)
Matrix:
Stack Gas
Apparatus:
Integrated gas sampling train (including
probe with filter, condenser, flow
controllers, meters, and pumps)
Sampling Method Parameters:
The probe will be inserted into the center of the stack, and
a 30L gas sample collected at a sampling rate of 0.5 L/min.
References: Lentzen, D.E., D.E. Wagoner, E.D. Estes and
W.F. Gutknecht, "EPA/IERL-RTP Procedures Manual:
Level 1 Environmental Assessment (Second Edition),"
EPA-600/7-78-201 (October 1978). NTIS No. PB293795/AS.
Title 40, Code of Federal Regulations, Part 60,
Appendix A, Method 3 (1980).
65
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Method Number:
Method Name:
Basic Method:
Matrix:
Apparatus:
S012
VOST
Sampling Train
Stack Gas
Integrated gas sampling train including
probe with condensers
Tenax trap
Tenax/charcoal trap
Condensate trap impingers
Sampling Method Parameters:
A 20L gas sample will be collected through a sorbent tube at a
flow rate of 1 L/min. Sorbent traps will be changed every
20 min over a 2 h sampling period.
Reference: Appendix F.
66
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V. SAMPLE PREPARATION PROCEDURES
A. OVERVIEW
The sample preparation procedures for use with hazardous waste influents
and effluents involve a number of steps. The collected sample, whether
gaseous, liquid, or solid, must be converted into a matrix which is
compatible with the final analysis methods needed for measurement of
the designated POHC(s). The sample preparation scheme for analysis of
organic components may require extraction of the sample, concentration
of an extract, and cleanup of the sample extract to remove potential
interferences. Surrogate and standard addition methods are required
for better precision in assessing the POHC level(s) by determining
recoveries for the POHC(s) of interest. Digestion of a sample is
necessary prior to analysis of inorganic constituents.
This section describes the sample preparation steps appropriate for
the hazardous constituents identified in 40 C.F.R. Appendix VIII
(May 20, 1981). The sample preparation methods were chosen to be as
widely applicable as possible. Preparation methods (e.g., extraction
and concentration for organics and digestion for inorganic species)
are not necessarily optimized for each specific POHC. Rather, they
have been generalized to encompass a large number of compounds.
(Method description summaries are compiled at the end of the chapter.)
The types of samples which could be collected during the evaluation
of a hazardous waste incinerator include:
• Permanent gases (reactive and nonreactive) and stack gas
samples collected as comprehensive sampling train
components (particulate catch, sorbent, impinger reagents);
• Aqueous liquids (including process waters, scrubber
waters, etc.) and organic liquids;
• Sludges, including suspensions, slurries, and gels; and
• Solids, including particulates on filters, solid
residues, and sorbents.
B. REPRESENTATIVE AL1QU0TS FROM FIELD SAMPLES (Methods P001-P003)
Combination and preparation of representative aliquots (composites) of
collected samples are appropriate for all solid and liquid grab samples.
Samples of gases collected with the bag sampling approach and stack
gas samples collected via the MM5 or SASS train and VOST already
represent time-averaged sample collections. In effect, the sampling
approach has composited the gas sample on a time-averaged basis. Other
67
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grab samples (liquids and solids) will be homogenized prior to withdrawal
of aliquots for analysis. Individual aliquots are composited to form
a single sample for subsequent preparation and analysis procedures.
The procedures appropriate for aliquoting and compositing samples are
summarized in Table 8.
The aliquot sizes that are taken from each type of field sample for
the various analytical procedures are specified in Table 9. These
are default values which may be increased or decreased in specific
instances, depending on target detection limits and/or suspected
concentrations based on professional judgment.
All sample aliquots removed for organic analysis are stored in glass
containers with teflon-lined screw caps, and the sample aliquots for
volatile organic analysis are stored so that there is no headspace above
the sample. Sample aliquots for inorganic analysis are stored in high-
density, linear, polyethylene containers.
C. RECOVERY MEASUREMENTS (Methods P011-P014)
It is important to monitor the recovery of the POHC(s) during sample
preparation as an estimate of the accuracy of the analytical measure-
ment and an assessment of the overall efficiency of the analytical
procedures. Two methods are used for these purposes: (1) the addition
of surrogate compounds which are chemically similar to the POHCs of
interest, and (2) the addition of POHCs themselves in their stable
isotopically labeled forms. These compounds are added to the various
samples immediately after return to the analytical laboratory.^
Table 10 lists some potential compounds for use as surrogates. For
stack gas samples, injection of the surrogate compounds directly into
the bulb or bag or onto the filter or sorbent from the MM5 or SASS
train, is appropriate.
The spiking levels used in each instance are selected after consider-
ation of the target detection limits for potential hazardous constituents,
and the expected concentrations of organic components, based on
professional judgment. Concentrations for surrogate standards on
the order of 50-1000 ppm are expected to be added to waste samples,
depending on the total organic content of the waste. For incinerator
effluent samples, spiking levels for surrogate standards are chosen
to correspond to 2 to 10 times the detection limit required to measure
99.99 percent DRE of the designated POHC(s).
To avoid interferences with conventional detectors, it is important
that the deuterated and 13C-surrogates are added only to those
samples that are to be taken for mass spectrometric analysis.
68
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TABLE 8
SUMMARY OF PROCEDURES FOR COMPOSITING SAMPLES
Method
P001
Physical Form
Liquids
Proportioning Method
Homogenize and pour aliquot.
Compositing Method
Combine aliquots in
container and shake.
POO 2
POO 3
Sludges
Solids
<3\
VO
Homogenize and use dipper
to take three portions.
Grind, if necessary, to
reduce particle size (20
mesh screen), using agate
or alumina equipment, and
riffle through steel or
aluminum riffler.
Combine aliquots in
container and mix.
Combine aliquots,
cone-blend three
times, roll-blend,
and cone and quarter.
Sources: American Society for Testing and Materials, Philadelphia, Pennsylvania, Annual Book of ASTM
Standards, Method No. E-300-73, Parts 29 and 30 (1973).
Berl, W.G. (ed.), Physical Methods in Chemical Analysis, Academic Press, New York, Vol. Ill,
pp. 183-217 (1956).
Kennedy, W.R., and J.F. Woodruff (eds.), Symposium on Sampling Standards and Homogeneity,
Los Angeles, California, June 25-30, 1972, American Society for Testing and Materials,
Philadelphia, Pennsylvania (1973).
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TABLE 9
ESTIMATED QUANTITIES OF SAMPLE REQUIRED FOR ANALYSIS
-j
o
Analysis/Sample Type
PROXIMATE ANALYSIS
Moisture, Solid and
Ash Content
Macroscale
Technique
Microscale
Technique
Elemental Composition
TOC, TOX
SURVEY ANALYSIS
Inorganics
Organics
DIRECTED ANALYSIS
Inorganics
Organics
Aqueous Liquids
100
NA
mL
50-300 mg
(solid content)
<100
mL
50-300 mg
(solid content)
1
1
L
L
Sludges
25
50
mg
50-300 mg
(solid content)
20
mL
50-300 mg
(solid content)
100
100
100
mL
8
mL
Organic Liquids
Solids
50
mL
mg
50-300 mg
(solid content)
NA
50-300 mg
(solid content)
1 mL
100
1
mL
mL
10
50
mg
50-300 mg
(solid content)
NA
50-300 mg
(solid content)
20
100
50
Minimum quantity for a single analysis.
NA = Not Applicable.
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TABLE 10
POTENTIAL COMPOUNDS FOR USE AS SURROGATES
Volatile Organlcs (Method P011)
Chloroform-13C
Diethylether-d j 0
1,2-Dichloroethane-d^
Benzene-dg
Bromoform-13C
Bromomethane-d3
Ethylbenzene-dj 0
Basic Extractable Organlcs (Method P012)
m-Fluoroaniline
Acridine-dg
Acidic Extractable Organlcs (Method P013)
2-Chlorophenol-3,4,5,6-d^
Pentachlorophenol-13Ce
Phenol-d5
Bromophenol
2,4,-Dini trophenol-3,5,6-d 3
Benzoic acid-d5
Benzoic acid-13C
Neutral Extractable Organics (Method P014)
Hexachlorobutadiene-1-13C
Octafluorobiphenyl
Naphthalene-d8
1-Fluoronaphthalene
2,6-Dinitrotoluene-a-a-a-d3
1,2-Dichlorobenzene-d^
Di-n-butylphthalate-3,4,5,6-d^
Hexachlorobenzene-13C6
Benz(a)anthracene-di2
9-Phenylanthracene
71
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D. SOLVENT EXTRACTION OF ORGANIC COMPOUNDS (Methods P021-P024)
Solid and liquid samples are extracted at acidic and basic conditions
(except for extractions using a Soxhlet apparatus). The extracts are
generally combined prior to analysis, unless information from the
engineering study suggests that species from the acid and base/neutral
fractions will react. In this case, the acidic and basic extracts
will be analyzed separately.
1. Aqueous Liquids (Method P021)
Method P021 procedures apply to (a) spent scrubber liquor or other
wastewater from the incineration facility, (b) incinerator influent
waste streams that are highly aqueous, and (c) aqueous condensate
collected from the stack gas effluent in the Modified Method 5 or
SASS trains (Figure 2).
a. Semivolatiles (Method P021a)
An aliquot (usually 1L) is taken for liquid/liquid extraction. If the
aqueous aliquot is initially neutral or basic, the pH of the sample is
adjusted to >11 using 6N NaOH and the sample extracted with three
successive 60-mL portions of methylene chloride. The pH of the aqueous
sample is then adjusted to <2 using 6N H2SO4 and the sample again
extracted with three 60-mL portions of methylene chloride. If the
aqueous aliquot is initially acidic, the sample is extracted first
at pH <2. Subsequently it is adjusted to pH >11 for the second
extraction. All extracts (ca. 360 mL) are combined in a labeled amber
glass bottle. If less than 51 mL (85%) of the methylene chloride
organic phase is recovered for each individual extraction, the aqueous
phase is centrifuged at 3000 rpm for 15 min and the recovered organic
phase then added to the combined extracts in the bottle.
b. Volatiles (Method P021b)
An aliquot (20 mL) of an aqueous liquid sample is placed in a 125-mL
separatory funnel with carbon disulfide (2 mL) and methanol (20 yL)
containing 1,2-dichloropropene (200 yg) as an internal standard. The
contents are shaken for 2 minutes and the layers are then allowed to
settle. The sample extract is transferred to a labeled container (the
transfer need not be quantitative).
2. Sludges (Method P022)
The Method P022 procedures apply to incinerator influent waste streams
that are sludges, slurries, or gels. They could also be applied to
any sludges or slurries produced by stack gas pollution control
devices.
72
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a. Semivolatiles (Method P022a)
An aliquot (100 mL) is taken for liquid/liquid extraction using homo-
genization and methylene chloride (100 mL) is added to the sample in
a glass container. If the sludge is known or expected to contain
>1% by weight of extractable organics, 200 mL of methylene chloride
are used for each extraction. The mixture is homogenized using a
blender or impeller for 45 to 60 seconds (maximum). The homogenized
mixture is transferred with a 100-mL pipette to a labeled amber
glass bottle. The extraction/homogenization/centrifugation is
repeated twice.
For sludge/slurry samples suspected of containing >80% water (based
on professional judgment), the pH is adjusted to _>11 with 6N NaOH
prior to extraction. (Note: if precipitation is observed when NaOH
is added, the sample will be made slightly acidic with 6N H2S0i,, and
CO2 evolution allowed to cease before adjusting the pH to _>11.) If
the sludge/slurry aliquot is initially acidic, the sample is extracted
first at pH <2, and subsequently it is adjusted to pH >11 for the
second extraction.
After extraction with three 100-mL volumes of methylene chloride, the
pH is adjusted to <2 with 6N HaSOit and the extraction repeated with
three additional 100-mL portions of methylene chloride. All extracts
are combined in a labeled amber glass bottle.
b. Volatiles (Method P022b)
An aliquot (2g, wet weight) is placed in a 50-mL centrifuge tube.
Water (20 mL), carbon disulfide (2 mL), and methanol (20 yL) containing
200 yg of 1,2-dichloropropene internal standard is added. If the
sludge is known, or expected, to contain >20 mg/g by weight of extractable
organics, the sample is placed in a 100-mL centrifuge tube and the volumes
of carbon disulfide are increased to 20 mL (or more). The tube is
capped and the contents agitated for 1 minute using a vortex mixer.
The mixture is then centrifuged at 3000 rpm for 15 minutes and the
extract transferred to a labeled container.
3. Organic Liquids (Method P023)
The Method P023 procedure applies to incinerator influent waste streams
that consist of organic liquids. An aliquot (1 mL) is diluted to 100 mL
with methylene chloride. If it is apparent that a portion of the
sample is insoluble in methylene chloride, a separate 100-mL aliquot
is taken and treated as a sludge sample.
73
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4. Solids (Method P024)
The Method P024 procedures apply to (a) incinerator waste influent
streams that are solid, (b) ash collected from flue gas cleaning
systems, or from the incinerator itself, and (c) particulate material
and solid sorbent samples collected from either (MM5/SASS) stack
gas sampling train.
a. Semivolatiles (Method P024a,b)
Two procedures are used for extraction of solid samples. Homogenization
(for non-abrasive materials) is used for most wastes. Extraction
using a Soxhlet apparatus is used for abrasive samples and for the
particulate material and solid sorbent portions of the comprehensive
stack gas sampling systems.
• Semivolatiles by Homogenization (Method P024a)
A 40g aliquot is weighed into a 250-mL centrifuge tube, and 40 mL of
10% sodium chloride in reagent water (deionized, distilled water with
organics removed by carbon adsorption) is added and the pH adjusted
to >11. Methylene chloride (60 mL) is added and a probe device
(SDT tissue mixer) used to disperse the sample for a total of 1 minute.
Then the mixture is centrifuged for 15 minutes at 1400 rpm, and the
methylene chloride phase is withdrawn with a 50-mL syringe. If the
emulsion interface between layers is more than one-half the volume of
the solvent layer, a 120-mL portion of methylene chloride is used for
the extraction. The extraction and dispersion are repeated for a total
of three extractions, using 60-mL aliquots of methylene chloride each
time.
The pH of the aqueous/solid mixture is then adjusted to <2 with 6N
H2S0i4 (added slowly to prevent foaming). The contents of the centrifuge
bottle are extracted and centrifuged with three additional 60-mL
portions of methylene chloride. The extracts (ca. 360 mL) are then
combined in a labeled sample container.
0 Semivolatiles by Soxhlet Extraction (Method P024b)
The MM5/SASS particulate materials or solid adsorbent (XAD-2), or a
20-g aliquot of a solid waste sample, combined with 20g of anhydrous
sodium sulfate are placed in a glass or ceramic extraction thimble.
(If high levels of water are present in the waste sample and the
temperature of the sample rises when sodium sulfate is added, the
sample is suspended in methylene chloride prior to adding the sodium
sulfate.) Sorbent or particulate samples on filters are placed directly
in the thimble after weighing. A pre-extracted glass wool plug is
placed on top of the sample. A 200-mL portion of methylene chloride
is placed in the 500-mL round bottom flask containing a teflon boiling
chip. The flask is attached to the extractor and the solids are
extracted for 16 hours (3-4 turnovers per hour). The extract is
finally transferred to a labeled amber glass bottle.
74
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b. Volatlles (Method P024c)
A 2g (wet weight) aliquot of solid waste sample is placed in a 50-mL
centrifuge tube. Water (20 mL), carbon disulfide (2 mL) , and methanol
(20 mL) containing 200 ug of 1,2-dichloropropene internal standard,
is added. If the solid is known to contain >20 mg/g by weight
extractable organics, the sample is placed in a 100-mL centrifuge tube,
and the volume of carbon disulfide is increased to 20 mL (or more).
The tube is then capped, and the contents agitated for 1 minute using
a vortex mixer. The mixture is then centrifuged at 3000 rpm for
15 minutes and the extract transferred to a labeled container. (This
procedure does not apply to MM5/SASS particulate or sorbent.)
E. DRYING AND CONCENTRATING OF SOLVENT EXTRACTS (Method P031)
Aliquots of each methylene chloride sample extract are taken for
analysis of the total chromatographicable content (TC0) (Method A011)
prior to concentration. Sample extracts are passed through a short
column of anhydrous sodium sulfate which has been prerinsed with
the extracting solvent (methylene chloride) into a 500-mL Kuderna-
Danish (K-D) flask fitted with a 10-mL calibrated receiving tube
containing a teflon boiling chip. The extract is evaporated rapidly
to 5 to 10 mL in the 500-mL K-D apparatus fitted with a three-ball
Snyder column. The K-D apparatus is allowed to cool, and the column
and receiver are rinsed with solvent. The three-ball Snyder column
and 500 mL-K-D receiver are removed and the boiling chip replaced.
A microSynder column is then attached to the 10-mL receiver tube
and the extract is evaporated to less than 1 mL. (The sample extract
is not allowed to go to dryness.) The final extract volume is adjusted
to 1 mL (if possible), or to a volume such that the extract contains
1% to 5% total extractable organics, based on the TCO analysis
(Method A011).
F. DIGESTION (Method P032)
The preparation procedures for all samples which contain metals include
a digestion step. Its purpose is to convert all of the metal-containing
species into an inorganic form for subsequent metals analysis. There
are numerous digestion procedures which may be applied to different
types of samples to convert metals in organic and bound compounds to
a readily analyzable inorganic form. For illustration, nitric acid
digestion procedure is outlined below as the typical digestion method.
An aliquot from a well-mixed field sample, such as an aqueous liquid,
sludge, or solid, is prepared for metals analysis. The sample is placed
in a beaker and concentrated nitric acid added to the beaker. The
sample is then heated on a hotplate and evaporated without boiling to
near dryness. A second addition of nitric acid is made to the beaker
upon cooling. The beaker is covered and heated with additions of nitric
75
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acid until the material becomes light in color. This completes the
digestion of the sample. The sample may then be transferred quantitatively
to volumetric glassware for analysis of the metal of interest.
G. SAMPLE CLEANUP PROCEDURES (Methods P041-P045)
For some samples, the level of interfering compounds is sufficiently
high to preclude successful analysis for the POHCs of interest. For
such samples, one or more cleanup steps have to be included in the
sample preparation procedures. Because of the wide variation in the
physical and chemical properties of the listed POHCs, no single sample
cleanup method has been demonstrated to be appropriate for all of the
listed POHCs. A number of different cleanup methods, such as size
exclusion chromatography, liquid column chromatography using columns
filled with silica gel, Florisil, activated alumina, etc., solvent
partitioning, and filtration may be used alone, or in combination, to
cleanup samples for analysis.
Florisil column chromatography is generally the method chosen for
preparing a sample that requires cleanup prior to analysis. Additional
cleanup procedures may be necessary if high background levels of
interferences remain after Florisil chromatography. These include
BioBeads SX-3 (Sephadex LH-20), silica gel, or alumina column chroma-
tography or liquid/liquid extraction.
Separation of the components in a sample using BioBeads SX-3 column
chromatography is based on size exclusion. High molecular weight
compounds elute first from the column and, subsequently, lower
molecular weight compounds are eluted. If necessary, this cleanup
procedure is used following elution of the sample from a Florisil
column.
If BioBeads SX-3 fraction is not adequate to improve the detection of
the constituents of concern in the sample matrix, then silica gel or
alumina column chromatography is employed. These sorbents allow
fractionation of the sample constituents based upon their molecular
activity (polarity, functional groups). The less active constituents
elute first and the more active constituents are retained and eluted
in a later fraction. Again, these cleanup methods are used, if
necessary, after Florisil and/or BioBeads SX-3 column chromatography.
If the sample matrix still prevents the components of interest from
being detected, then the EPA permit assistance team should be
consulted for alternative modes of sample preparation.
H. SAMPLE PREPARATION METHOD SUMMARIES
The preparation procedures (designated with a P) appropriate to the
hazardous constituents from Appendix VIII are summarized in tabular
form on the following pages.
76
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Method Numbers: P001-P003
Method Name: Representative Aliquots from Field Samples
Matrices: Aqueous Liquids (P001)
Organic Liquids (P001)
Sludges (P002)
Solids (P003)
Method Parameters:
P001 - Liquids (aqueous and organic)
Samples will be homogenized and an aliquot removed. Appropriate
aliquots will be combined in a container and shaken.
P002 - Sludges
Samples will be homogenized and aliquots removed. Aliquots will
then be combined and mixed.
P003 - Solids
If necessary, the sample will be ground to reduce the particle
size (20 mesh screen) using agate or alumina equipment. The
sample will then be riffled through a steel or aluminum riffler;
appropriate aliquots combined, cone-blended three times, roll-
blended, and coned and quartered.
References: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Method No.
E-300-37, Parts 29 and 30 (1973).
Berl, W.G. (ed.), Physical Methods in Chemical Analysis,
Academic Press, New York, Vol. Ill, 183-217 (1956).
Kennedy, W.R. and Woodruff, J.F. (eds.), Symposium on
Sampling Standards and Homogeneity, Los Angeles, California,
June 25-30, 1972, American Society for Testing and Materials,
Philadelphia, Pennsylvania (1973).
77
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Method Numbers:
P011-P014
Method Name: Surrogate Addition to Sample Aliquots for
Organic Analysis
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Method Parameters:
Surrogate compounds will be added to sample aliquots taken for
the analysis of volatile and nonvolatile organic compounds in
order to assess the overall recovery of the analytical procedures.
To avoid interferences with conventional detectors, it is important
that the isotopically-labeled surrogates are only added to those
samples that are taken for mass spectrometric analysis. The
surrogate compounds will include, but not necessarily be limited
to, the following:
Volatile Organics (Method P011)
Chloroform-13C
Diethylether-dio
1,2-Dichloroethane-dt»
Broraomethane-d 3
Benzene-d6
Ethylbenzene-d10
Bromoform-13C
Basic Extractable Organics (Method P012)
m-Fluoroaniline
Acridine-d9
Acidic Extractable Organics (Method P013)
2-Chlorophenol-3,4,5,6-di|
Benzoic Acid-ds
Phenol-d6
2,4-Dinitrophenol-3,5,6-d 3
Bromophenol
Benzoic Acid-13C
78
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Neutral Extractable Organics (Method P014)
Hexachlorobutadiene-1-13C
Octafluorobiphenyl
Naphthalene-d 3
1-Fluoronaphthalene
2,6-Dinitrotoluene-2,2,2-d 3
Di-n-butylphthalate-3,4,5,6-du
Benz(a)anthracene-di2
9-Phenylanthracene
The spiking levels used in each instance will be selected after
consideration of target detection limits for potential hazardous
constituents, and expected concentrations of organic components
based on professional judgment. It is expected that surrogate
concentrations on the order of 50-1000 ppm will be added to the
waste samples, depending on the total organic content of the
waste. For incinerator effluent samples, spiking levels for
surrogate standards will be chosen to correspond to 2 to 10
times the detection limits required to measure 99.99% DRE
of the designated POHC(s).
79
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Method Number:
P02La
Method Name: Extraction of Semivolatiles from Aqueous Liquids
Basic Method: Liquid/Liquid Extraction
Matrix: Aqueous Liquids
Method Parameters:
A 1L aliquot will be taken for liquid/liquid extraction. If the
aqueous aliquot is initially neutral or basic, the pH will be
adjusted to 11 using 6N NaOH and the sample extracted with
three successive 60-mL portions of methylene chloride. The pH
of the aqueous sample will then be adjusted to £ 2 using 6N H2SOi«
and the sample again extracted with three 60-mL portions of
methylene chloride. All extracts (ca. 360 mL total) will be
combined in a labeled amber glass bottle. If < 300 mL (85%) of
methylene chloride is recovered, the aqueous phase will be
centrifuged at 3000 rpm for 15 min and the recovered organic
phase added to the combined extracts in the bottle.
If the aqueous aliquot is initially acidic, the sample will be
extracted first at pH <¦ 2 and subsequently adjusted to pH > 11
for the second extraction. ~
Reference: U.S. Environmental Protection Agency, Federal Register,
44, 69464-69575 (December 3, 1979).
80
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Method Number:
P021b
Method Name:
Extraction of Volatiles from Aqueous Liquids
Basic Method:
Liquid/Liquid Extraction
Matrix:
Aqueous Liquids
Method Parameters:
A 20-mL aliquot of an aqueous liquid sample will be placed in
a 125-mL separatory funnel with carbon disulfide (2 mL) and
methanol (20 yL) containing 200 yg of 1,2-dichloropropene
internal standard. The contents will be shaken for 2 min
and the layers allowed to settle. The sample extract will be
transferred to a labeled container (the transfer need not be
quantitative).
Reference: McKown, M.M., J.S. Warner, R.M. Riggin, M.P. Miller,
R.E. Heffelfinger, B.C. Garrett, G.A. Jungclaus and
T.A. Bishop, "Development of Methodology for the
Evaluation of Solid Wastes," Report prepared for
U.S. Environmental Protection Agency/Effluent Guide-
lines Division, Washington, D.C., by Battelle
Columbus Laboratories, Columbus, Ohio under
Contract No. 68-03-2552 (January 1981).
81
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Method Number:
P022a
Method Name:
Extraction of Semivolatiles from Sludges
Basic Method:
Liquid/Liquid Extraction
Matrix:
Sludges (including gels and slurries)
Method Parameters:
A 100-mL aliquot will be taken for liquid/liquid extraction
with homogenization. A 100-mL portion of methylene chloride will
be added to the waste sample in a glass container. If the sludge
is known or expected to contain > 1% by weight of extractable
organics, a 200~mL portion of methylene chloride will be used
for each extraction. The mixture will be homogenized using a
blender or impeller for 45 to 60 s (maximum). The homogenized
mixture will be centrifuged for 30 min at 3000 rpm. The organic
phase will be transferred with a 100-mL pipette to a labeled
amber glass bottle. The extraction/homogenization/centrifugation
will be repeated two more times.
For sludge/slurry samples suspected to contain > 80% water
¦ (based on professional judgment), the pH will be adjusted to
> 11 with 6N NaOH prior to extraction. (Note: if precipitation
Ts observed when NaOH is added, the sample will be made slightly
acidic with 6N H2SO4 and C02 evolution allowed to cease before
adjusting the pH to 11.)
After extraction with 3 x 100 mL of methylene chloride, the pH
will be adjusted to <_ 2 with 6N ^SO,* and the extraction repeated
with 3 additional 100-mL portions of solvent. All extracts
will be combined in a labeled amber glass bottle.
If the sludge/slurry aliquot is initially acidic, the sample
will be extracted first at pH _< 2 and subsequently adjusted to
pH 11 for the second extraction.
Reference: McKown, M.M., J.S. Warner, R.M. Riggen, M.P. Miller,
R.E. Heffelfinger, B.C. Garrett, G.A. Jungclaus and
T.A. Bishop, "Development of Methodology for the
Evaluation of Solid Wastes," Report prepared for
U.S. Environmental Protection Agency/Effluent Guide-
lines Division, Washington, D.C., by Battelle
Columbus Laboratories, Columbus, Ohio under
Contract No. 68-03-2552 (January 1981).
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Method Number:
P022b
Method Name:
Extraction of Volatiles from Sludges
Basic Method:
Liquid/Liquid Extraction
Matrix:
Sludges (including gels and slurries)
Method Parameters:
A 2g (wet weight) aliquot will be placed in a 50-mL centrifuge
tube. Water (20 mL), carbon disulfide (2 mL), and methanol (20 uL)
containing 200 ug of 1,2-dichloropropene internal standard will
be added. If the sludge is known or expected to contain > 20 mg/g
by weight extractable organics, the sample will be placed in a
100-mL centrifuge tube and the volume of carbon disulfide
increased to 20 mL (or more). The tube will be capped and the
contents agitated for 1 min using a vortex mixer. The mixture
will then be centrifuged at 3000 rpm for 15 min and the extract
transferred to a labeled container.
Reference: McKown, M.M., J.S. Warner, R.M. Riggen, M.P. Miller,
R.E. Heffelfinger, B.C. Garrett, G.A. Jungclaus and
T.A. Bishop, "Development of Methodology for the
Evaluation of Solid Wastes," Report prepared for
U.S. Environmental Protection Agency/Effluent Guide-
lines Division, Washington, D.C., by Battelle
Columbus Laboratories, Columbus, Ohio under
Contract No. 68-03-2552 (January 1981).
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Method Number:
P023
Method Name:
Semivolatiles from Organic Liquids
Basic Method:
Solvent Dilution
Matrix:
Organic Liquids
Method Parameters:
A 1-mL aliquot will be diluted to 100 mL with methylene chloride.
If it is apparent that a significant portion of the sample is
insoluble in methylene chloride, a separate 100~mL aliquot
will be taken and treated as a sludge sample (Method P022a).
Reference: McKown, M.M., J.S. Warner, R.M. Riggen, M.P. Miller,
R.E. Heffelfinger, B.C. Garrett, G.A. Jungclaus and
T.A. Bishop, "Development of Methodology for the
Evaluation of Solid Wastes," Report prepared for
U.S. Environmental Protection Agency/Effluent Guide-
lines Division, Washington, D.C., by Battelle
Columbus Laboratories, Columbus, Ohio under
Contract No. 68-03-2552 (January 1981).
84
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Method Number:
P024a
Method Name:
Extraction of Semivolatiles from Solids
Basic Method:
Liquid/Solid Extraction
Homogenization
Matrix:
Solids (nonabrasive materials)
Method Parameters:
A 40g aliquot will be weighed into a 250-mL centrifuge tube.
A 40-mL portion of 10% sodium chloride in deionized, distilled
water with organics removed by carbon adsorption will be added
and the pH adjusted to >_ 11. A 60-mL portion of methylene
chloride will be added and a probe device (SDT tissue mixer)
used to disperse the sample for a total of 1 min. The mixture
will then be centrifuged for 15 min at 1400 rpm and the
methylene chloride phase withdrawn with a 50-mL syringe. If
the emulsion interface between layers is more than one-half
the volume of the solvent layer, a 120-mL aliquot of methylene
chloride will be used for the extraction. The extraction
and dispersion will be repeated a total of three times, with a
60-mL aliquot of methylene chloride used each time.
The pH of the aqueous/solid mixture will then be adjusted to
pH <_ 2 with 6N H2S0i, (added slowly to prevent foaming). The
contents of the centrifuge bottle will be extracted and
centrifuged with three additional 60-mL portions of methylene
chloride.
The extracts (ca. 360 mL) will be combined in a labeled sample
container.
Reference: Miller, H.C., R.H. James and W.R. Dickson, "Evaluated
Methodology for the Analysis of Residual Wastes,"
Report prepared for U.S. Environmental Protection
Agency/Effluent Guidelines Division, Washington, D.C.,
by Southern Research Institute, Birmingham, Alabama
under Contract No. 68-02-2685 (December 1980).
85
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Method Number:
P024b
Method Name:
Extraction of Semivolatiles from Solids
Basic Method:
Liquid/Solid Extraction
Soxhlet Apparatus
Matrix:
Solids (abrasive materials)
XAD-2 Resin from sorbent module
Method Parameters:
A 20g aliquot (or the entire contents of sorbent module) will
be combined with 20g anhydrous sodium sulfate and placed in a
glass or ceramic extraction thimble. (Small quantities of
solid sample on filters may be placed directly in the thimble
after weighing.) A pre-extracted glass wool plug will be placed
on top of the sample. A 300-mL portion of methylene chloride
will be placed in the 500-mL round bottom flask containing a
teflon boiling chip. The flask will be attached to the extractor
and the solids extracted for 16 h (3-4 turnovers per h). The
extract will be transferred to a labeled amber glass bottle.
Reference: Miller, H.C., R.H. James and W.R. Dickson, "Evaluated
Methodology for the Analysis of Residual Wastes,"
Report prepared for U.S. Environmental Protection
Agency/Effluent Guidelines Division, Washington, D.C.,
by Southern Research Institute, Birmingham, Alabama
under Contract No. 68-02-2685 (December 1980).
86
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Method Number:
P024c
Method Name:
Extraction of Volatiles from Solids
Basic Method:
Liquid/Liquid Extraction
Matrix:
Solids
Method Parameters:
A 2g (wet weight) aliquot will be placed in a 50-mL centrifuge
tube. Water (20 mL), carbon disulfide (2 mL), and methanol
(20 yL) containing 200 yg of 1,2-dichloropropene internal
standard will be added. If the solid is known to contain > 20 mg/g
by weight of extractable organics, the sample will be placed in a
100-mL centrifuge tube, and the volume of carbon disulfide
increased to 20 mL (or more). The tube will be capped and the
contents agitated for 1 min using a vortex mixer. The mixture
will then be centrifuged at 3000 rpm for 15 min and the extract
transferred to a labeled container.
Reference: McKown, M.M., J.S. Warner, R.M. Riggin, M.P. Miller,
R.E. Heffelfinger, B.C. Garrett, G.A. Jungclaus and
T.A. Bishop, "Development of Methodology for the
Evaluation of Solid Wastes," Report prepared for
U.S. Environmental Protection Agency/Effluent Guide-
lines Division, Washington, D.C., by Battelle Columbus
Laboratories, Columbus, Ohio under Contract No.
68-03-2552 (January 1981).
87
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Mechod Number:
P031
Mechod Name: Drying and Concentrating Solvent Extracts
Basic Method: Kuderna-Danish Concentration
Matrix: Sample Extracts
Method Parameters:
Aliquots of all sample extracts will be taken for TCO analysis
(Method A001) prior to concentration.
Sample extracts will be passed through a short column of anhydrous
sodium sulfate, prerinsed with extracting solvent (methylene
chloride) into a 500-mL Kuderna-Danish (K-D) flask fitted with
a 10-mL calibrated receiver tube containing a teflon boiling
chip.
The extract will be evaporated rapidly to 5-10 mL in the 500-mL
K-D apparatus fitted with a 3-ball Snyder column. The K-D
apparatus will be allowed to cool and the column and receiver
rinsed with the solvent.
The 3-ball Snyder column and 500-mL K-D receiver will be removed
and the boiling chip replaced. A micto-Snyder column will
be attached to the 10-mL receiver tube and the extract evaporated
to less than 1 mL. (The sample extract will not be allowed to
go to dryness.) The final extract volume will be adjusted to
1 mL (if possible) or to a volume such that the extract contains
1-27c total extractable organics as determined by the TCO analysis
(Method AQ01).
Reference: U.S. Environmental Protection Agency,'Federal Register,
44, 69464-69575 (December 3, 1979).
88
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Method Number:
P032
Method Name:
Digestion Procedures for Metals
Basic Method:
Acid Digestion
Matrices:
Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic Species from Appendix VIII to which the method may be applied:
Antimony (Sb)
Arsenic (As)
Barium (Ba)
Beryllium (Be)*
Cadmium (Cd)
Chromium (Cr)
Lead (Pb)
Mercury (Hg)
Nickel (Ni)
Osmium (Os)*
Selenium (Se)
Silver (Ag)
Strontium (Sr)*
Thallium (Th)*
Vanadium (V)*
Method Parameters:
Aliquots (100 g (5-10g if sample is primarily solid) or 100 mL)
from well- mixed field samples (Methods P001-P003), will be used
for the analysis of metals.
Most samples will be prepared for analysis by general HNO3
digestion procedures as specified in the methods for Sb, Ba,
Cd, Cr, Pb, Hg, Ni, and Ag in SW-846, Section 8, Methods
8.50 to 8.60 and by HNO3-H2O2 for As and Se. Waste samples
containing high levels of organic materials, such as oil,
greases, or waxes, will be prepared by dissolving the sample in
an appropriate organic solvent or digesting the sample in nitric
acid, sulfuric acid, hydrogen peroxide, and hydrochloric acid
as specified in SW-846, Section 8, Pages 8.49-7 to 8.49-11.
Special precautions, however, should be taken if BaSOi*, PbS0i»,
or AgCl precipitate.
*
These elements are not included in the SW-846 reference; it is
believed that this digestion procedure would also be applicable
to them.
89
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References: U.S. Environmental Protection Agency/Office of Solid
Waste, Washington, D.C., "Test Methods for Evaluating
Solid Waste - Physical/Chemical Methods," SW-846
(1980), and SW-846, Revision A (August 8, 1980), and
SW-846, Revision B (July 1981).
Kopp, J.F. and G.D. McKee, "Methods for Chemical
Analysis of Water and Wastes," EPA-600/4-79-020
(March 1979). NTIS No. PB 297686/AS.
Bock, R., A Handbook of Decomposition Methods in
Analytical Chemistry. International Textbook Company,
London (1979).
Dolezal, J., Povondra P., and Svick, Z., Decomposition
Techniques in Inorganic Analysis, Iliffe Books Ltd.,
London (1968).
Gorsuch, T.T., The Destruction of Organic Matter,
Pergamon Press, Oxford (1970).
90
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Method Number:
P0A1
Method Name: Florisil Column Chromatography
Matrix: Sample Extracts
Method Parameters:
Florisil (60/100 mesh PR grade) will be used. Due to the fact
that the adsorption capacity of Florisil may vary, the lauric
acid value of each manufactured lot of Florisil should be
determined. The amount of Florisil to be used for each column
will be calculated by the formula:
100 * lauric acid value x 20g Florisil per column.
This amount of Florisil will be weighed out and each preweighed
portion will be heated for more than 5 h at 130°C. The warm
Florisil will be added directly to a glass chromatography
column and allowed to cool with tapping to settle the adsorbent
bed.
A one-half inch of dried, cleaned sodium sulfate will be added
to the top of the Florisil. The column will be pre-eluted
with the initial solvent to be used for chromatographing the
sample extract. This eluent will be discarded. An aliquot
of the sample extract (P021-P030) will be added to the top of
the column.
Reference: U.S. Environmental Protection Agency, Federal Register,
44, 69464-69575 (December 3, 1979).
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Method Number: P042
Method Name: BioBeads SX-3
Matrix: Sample Extracts
Method Parameters:
A 20-25g aliquot of BioBeads SX-3 (200/400 mesh, BioRad
Laboratories 152-2750) will be placed in a 200-mL beaker
covered with methylene chloride and allowed to swell overnight.
The swelled beads will be placed into a 500 mm x 10 mm I.D.
chromatographic column, containing a glass wool plug at the
bottom. The column will then be rinsed with methylene chloride.
A glass wool plug followed by a layer of glass beads will be
placed on top of the BioBeads, and the column pre-eluted with
an additional 200 mL of methylene chloride.
A 5-mL portion of the GPC calibration solution (100 mg corn oil,
2 mg bis(2-ethylhexyl)phthalate, 2 mg pentachlorophenol in 1 mL
methylene chloride) will be transferred to the BioBeads SX-3
column. The column will be drained into a 12~mL graduated
cylinder tube until the liquid is just above the surface of
the GPC packing, and eluted with 200 mL methylene chloride.
10~mL fractions will be collected. Aliquots of these fractions
will be analyzed for bis(2-ethylhexyl)phthalate and penta-
chlorophenol by GC/FID on a IX SP1240 DA GC column. The corn
oil elution pattern will be determined by evaporating an
aliquot of each of the fractions to dryness and determining
the weight of the residue. The concentration of each component
in each fraction will be plotted versus the total eluent volume.
From this plot, the range of eluent volumes to be collected
will be determined as follows:
Initial Volume =
Eluent Volume at which _> 85% of the corn oil is eluted.
Final Volume =
Eluent Volume at which 100% of the phenol and phthalate
is eluted + 50 mL.
For a typical calibration, the first 60 mL (85% corn oil) will
be discarded and the next 110 mL retained for sample analysis.
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An aliquot volume of the sample extract (P021-P030) equivalent
to 200 mg (determined by Method A012-GRAV) will be transferred
to the calibrated GPC column. A 200-mL portion of methylene
chloride will be used to elute the column. The eluent volume
determined above will be collected and concentrated as
described in Method P031.
Reference: Miller, H.C., R.H. James and W.R. Dickson, "Evaluated
Methodology for the Analysis of Residual Wastes,"
Report prepared for the U.S. Environmental Protection
Agency/Effluent Guidelines Division, Washington, D.C.,
by Southern Research Institute, Birmingham, Alabama,
under Contract No. 68-02-2685 (December 1980).
93
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Method Number:
P043
Method Name: Silica Gel Chromatography
Matrix: Sample Extracts
Method Parameters:
Silica gel is typically used as a secondary cleanup procedure
to other preparation techniques such as derivatization. The
procedure described below follows the Level 1 approach. Other
procedures are described in the Federal Register, as referenced
below.
Silica gel (Davison, 60-200 mesh, Grade 950) which has been
activated at 130°C for > 5 h will be stored in a dessicator
until used. A 10 mm I.D, chromatographic column will be slurry
packed with 6.0g activated silica gel in n-pentane, Approximately
3 ± 0.2g clean, anhydrous sodium sulfate will be added to the
top of the silica gel layer. The column will be pre-eluted
with 20 mL n-pentane (pesticide grade) and the eluent discarded
just prior to exposure of the sodium sulfate layer to air.
2 mL of sample in cyclopentane will be pipetted onto the column.
The following solvents will be used to elute the constituents
in the sample from the silica gel:
Fraction 1 pentane (25 mL)
Fraction 2 20% methylene chloride in pentane (10 mL)
Fraction 3 50% methylene chloride in pentane (10 mL)
Fraction 4 methylene chloride (10 mL)
Fraction 5 5% methanol in methylene chloride (10 mL)
Fraction 6 20% methanol in methylene chloride (10 mL)
Fraction 7 50% methanol in methylene c.hloride (10 mL) .
References: Lentzen, D.E., D.E. Wagoner, E.D. Estes and W.F. Gutknecht,
"EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment (Second Edition)," EPA-600/7-78-201
(October 1978). NTIS No. PB293795/AS.
U.S. Environmental Protection Agency, Federal Register,
44, 69464-69575 (December 3, 1979).
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Method Number:
P044
Method Name: Alumina Column Chromatography
Matrix: Sample Extracts
Method Parameters:
Chromatography on alumina is typically used after sample
extraction and Florisil chromatography.
A previously-prepared extract which has, in most cases, already
been subjected to Florisil column separation will be evaporated
to dryness and redissolved in <_ 10 mL of chloroform (pesticide
grade). An alumina column will be prepared by adding 3 inches
of activated alumina (Woelm neutral, Alupharm Chemicals, New
Orleans, Louisiana, or equivalent, deactivated to 3% water)
to a liquid chromatography column, 100 x 20 mm with a teflon
stopcock.
The chloroform solution containing the organic(s) of interest
will be transferred to the column. The column will be eluted
with the appropriate solvents, as given in the reference below.
Reference: U.S. Environmental Protection Agency, Federal Register,
44, 69464-69575 (December 3, 1979).
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Method Number: P045
Method Name: Liquid/Liquid Extraction
Matrix: Sample Extracts
Method Parameters:
A lOg aliquot of the sample extract (Methods P021-P030) or an
organic liquid sample will be diluted in 20 ml of an appropriate
solvent. A 20-mL portion of distilled water, adjusted to pH 12-13
with 6N NaOH, will be added. This sample/aqueous mixture will
be shaken in a 125-mL separatory funnel for 1 min. The phases
will be allowed to settle for 10 min and the aqueous phase
removed. The organic solvent layer will be extracted two
additional times with distilled water at pH 12-13.
Reference: U.S. Environmental Protection Agency/Office of Solid
Waste, Washington, D.C., "Test Methods for Evaluating
Solid Waste - Physical/Chemical Methods," SW-846
(1980).
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VI. ANALYSIS PROCEDURES
A. OVERVIEW
The overall strategy for analyzing hazardous wastes includes both test
procedures to determine the characteristics of the waste, and analysis
procedures to determine the composition of the waste. This section
summarizes the test procedures for determining the characteristics of the
waste. It also describes analysis methods appropriate to the various
hazardous constituents of interest in waste, stack gas effluents, and other
effluents during a trial burn. Both the preparation and analysis methods
were chosen to be as widely applicable as possible. Analysis procedures,
both specific and survey, were selected on the basis of their appropriateness
to a large number of compounds, and were not necessarily optimized for
each individual constituent. The primary rationale behind this approach
was to minimize the cost of providing assessments of the levels of POHCs,
while still meeting the constraints of the permitting process.
The test procedures used to determine the characteristics of the waste
and the steps involved in the proximate analysis of the waste are performed
on a waste sample prior to any sample preparation procedures. Both the
survey and directed analysis procedures will involve at least some of the
sample preparation steps outlined in the preceding chapter. These
analyses generally require either a sample extract for organic analysis
or a digested sample for inorganic analysis.
B. WASTE CHARACTERISTICS
The characteristics of the waste are defined in terms of Ignitability (I),
Corrosovity (C), Reactivity (R), and Extraction Procedure Toxicity (E).
The test procedures specified in "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980), SW-846 Revision A (August 8,
1980), and SW-846 Revision B (July 1981), are used to determine whether
the wastes exhibit the characteristics of a hazardous waste, as defined
by Section 3001 of RCRA.
1. Ignitability (Method C001)
The objective in determining the ignitability characteristic is to (a)
identify wastes which present fire hazards due to being ignitable under
routine storage, disposal, and transportation procedures, and (b) identify
wastes capable of severely exacerbating a fire once it is started.
A solid waste is considered to exhibit the characteristic of ignitability
if a representative sample of the waste has any of the following
properties:
97
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• it is a liquid, other than an aqueous solution, containing
less than 24 percent alcohol by volume, and has a flash point
of less than 60°C;
• it is not a liquid but is capable, under standard temperature
and pressure, of causing fire through friction, absorption of
moisture or spontaneous chemical changes and, when ignited,
burns vigorously;
• it is an ignitable compressed gas; or
• it is an oxidizer.
2. Corrosivity (Method C002)
The objective in determining the corrosivity characteristic, as defined
in 40 C.F.R. Part 261.22, is to identify wastes which might pose a hazard
to human health or the environment due to their ability to mobilize toxic
metals if discharged into a landfill environment. In addition, a secondary
objective is to identify wastes that would require handling, storage,
transportation, and management equipment to be fabricated of specially
selected materials of construction. Also, corrosivity tests identify
wastes that might destroy human or animal tissue in the event of
inadvertent contact.
A solid waste is considered to exhibit the characteristic of corrosivity
if a representative sample has either of the following properties:
• it is aqueous and has a pH £ 2 or > 1^.5; or
• it is liquid and corrodes steel at a rate > 6.35 mm per
year at a test temperature of 55°C.
3. Reactivity (Method C0Q3)
The definition of a waste as "reactive" is intended to identify wastes
which, because of their extreme instability and tendency to react
violently or explode, would pose a problem at all stages of the waste
management process. This definition is a paraphrase of the narrative
definition used by the National Fire Protection Association.
A solid waste is considered to exhibit the characteristic of reactivity
if it shows any of the following properties:
• it readily undergoes violent chemical changes;
• it reacts violently or forms potentially explosive mixtures
with water;
• it generates toxic fumes when mixed with water or, in the
case of cyanide or sulfide bearing wastes, when exposed to
mildly acidic or basic conditions;
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• it explodes when subjected to a strong initiating force; or
• it fits within the Department of Transportation's forbidden
explosives, Class A explosives, or Glass B explosives
classification.
Reactivity is determined by applying best professional judgment to
the available data. There are no explicit experimental test procedures
for determining this characteristic.
4. Extraction Procedure Toxicity (Method C004)
The Extraction Procedure Toxicity Test (E) is designed to simulate the
leaching a waste would undergo if it were disposed in an improperly
designed sanitary landfill. It is a laboratory test in which a representative
sample of a waste is extracted with distilled water maintained at a pH
of 5 with acetic acid. The extract obtained, the "EP extract," is then
analyzed to determine if any of the thresholds established for eight
elements (viz., arsenic, barium, cadmium, chromium, lead, mercury, selenium,
and silver), four pesticides (viz., endrin, lindane, methoxychlor, and
toxaphene), and two herbicides (viz., 2,4,5-trichlorophenoxypropionic
acid (2,4,5-T), and 2,4-dichlorophenoxyacetic acid (2,4,-D)) have been
exceeded.
A solid waste is considered "EP toxic" if the threshold levels (Table 11)
designated in 40 C.F.R. Part 261.24, are exceeded in the "EP extract."
C. PROXIMATE ANALYSIS
The initial analysis of all waste samples will involve an analysis of
the approximate composition of the sample. Such an analysis includes
determination of physical properties, such as moisture, solid, and ash
content, as well as determination of such chemical properties as the
amount of total organic carbon, total organic halogen, elemental compo-
sition, viscosity, and heating value of the waste. A description of each
method follows:
The type of data generated by the proximate analysis is indicated on the
Proximate Analysis Reporting Form, shown as Table 12.
1. Moisture, Solid and Ash Content (Methods A001-A002)
a. Macro-scale Technique (Method A001)
• Loss on Drying—LOP (Method AOOla)
An aliquot (Table 9) of a well mixed sample is transferred to a tared
porcelain, platinum, or Vycor evaporating dish (previously ignited at
600°C for 1 hour and cooled in a desiccator). The sample and dish are
weighed and then heated on a hot plate to evaporate the sample without
99
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TABLE 11
THRESHOLD LEVELS OF CONTAMINANTS IN THE EXTRACTION PROCEDURE TOXICITY TEST
Threshold Level
Contaminant (mg/L)
Metals
Arsenic 5.0
Barium 100.0
Cadmium 1 • 0
Chromium (Cr +6) 5.0
Lead 5.0
Mercury 0 • 2
Selenium 1.0
Silver 5.0
Pesticides
Endrin 0.02
Lindane 0.4
Me thoxychlor 10.0
Toxaphene 0.5
Herbicides
2,4-Dichlorophenoxyacetic acid 10.0
2,4,5-Trichlorophenoxypropionic acid 1.0
100
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TABLE 12
PROXIMATE ANALYSIS REPORTING FORM
Sample
Moisture, Solid, and Ash Content Analyst and/or Date
Laboratory
% Moisture
% Solids
% Ash
Elemental Composition
% Carbon
% Nitrogen
% Sulfur
% Phosphorus
g % Fluorine
% Chlorine
% Bromine
% Iodine
Total Organic Carbon
Total Organic Halogens
Heating Value of Waste
Viscosity
-------
boiling, to near dryness. The sample and dish are then transferred to a
103°C oven to complete the evaporation. Periodically (at intervals usually
greater than or equal to 1 hour), the sample is removed from the oven,
cooled in a desiccator and weighed. The drying is considered complete
when the loss of weight in a given interval is less than 4 percent of
the previous weight.
The percent solids are calculated as follows:
Solids (%) = Pnal ^ht:~Tale x 100.
Initial Weight—Tare
The percent moisture is calculated as follows:
Moisture (%) = 100 - % Solids.
It should be noted here that the moisture content determination involves
heating a sample at 103°C for a prolonged time period, and it is probable
that the volatile organic content would be lost along with the moisture
content. The loss of volatile organic components would also be applicable
to the micro-scale moisture content determination.
• Loss on Ignition—LOI (Method AOOlb)
After removal of an aliquot (<10% of the solid residue) for elemental
analysis, the weighed solids in the evaporating dish are ignited for
30 minutes at approximately 600°C. The ash is then cooled in a
desiccator, and weighed.
The ash content is calculated as follows:
Weight of Solid after Ignition »
Ash (%) 35 height 0f Sample before Drying X
If ash content is <0.1%, the result will be reported as ppm ash:
Ash (ppm) = 101* x % Ash.
b. Micro-scale Technique (Method A002)
Thermogravimetric analysis (TGA) may also be used for micro-scale
determination of moisture, solid, and ash content of non-aqueous
liquid samples and solid samples when insufficient sample is available
for the macro-scale analysis of these parameters.
A sample aliquot (<50 mg) is placed in the sample boat of the TGA
instrument and heated at the rate of 10°C/min in air to 500°C. The results
of the TGA analysis are reported as a plot of weight (mg) vs. temperature
(°C). The moisture, solid, and ash content are estimated from the
curve as follows:
102
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„ , . , Weight at 125 C
Solids U) = _ .. . . „ x 100
Initial Weight
Moisture (%) =¦ 100 - % Solids
Ash (7) = Final Weight at 500°C Q
U; Initial Weight
It is preferable that the thermal instrument be capable of presenting
weight loss directly in percent. The values can then be determined
directly from the curve as follows:
Moisture (%) = Value at 125°C
Solids (%) = 100 - Value at 125°C
Ash (%) = 100 - Value at 500°C
A faster method involves two isothermal measurements, one at 125°C
and another one at 500°C. Instrument recordings may be made by either
of the two methods above. A 2-rnin equilibration period is allowed at
each isothermal temperature.
2. Elemental Composition (Method A003)
Aliquots of organic liquid wastes, solid wastes, or of the dried solids
(from the LOD determination of aqueous wastes or sludges) are analyzed
to determine the concentration (%) of the following elements: carbon,
nitrogen, phosphorus, sulfur and halogens (i.e., iodine, chlorine, fluorine,
bromine). A number of service laboratories perform these analyses on a
routine basis.
3. Total Organic Carbon and Total Organic Halogen (Method A004)
The levels of total organic carbon (T0C) and total organic halogen (TOX)
are measured in much the same way as carbon and halogens are measured in
Method A003. The total organic carbon is measured by combustion of the
sample to form CO2 (with or without subsequent conversion to CHO
and measurement of the CO2 and CHi» formed during combustion. For organic
halogens, the sample is combusted to form the halide which is trapped in
solution. Potentiometric titration against silver is then performed to
determine a total halogen concentration (except fluorine).
Determination of the total organic carbon and total organic halogens is
more useful than the elemental composition determination if the sample
is primarily an aqueous liquid.
103
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4. Viscosity (Method A005)
The viscosity of liquid wastes affects the feasibility of destroying those
wastes at a particular incineration facility. This fact can be attributed,
in part, to the limits on the feed rate of the waste imposed by the viscosity
of the waste. The viscosity of the waste is determined by measuring the
time (in seconds) it takes for a fixed volume of the liquid waste to flow
through the capillary of a calibrated viscometer. Both the head pressure
on the waste and the temperature of the viscometer are controlled. The
kinematic viscosity is the product of the flow time and the calibration
constant of the viscometer. The dynamic viscosity—the value of interest
for incineration processes—is obtained by multiplication of the measured
kinematic viscosity by the density of the liquid waste.
5. Heating Value of the Waste (Method AQ06)
The heating value of a waste corresponds to the quantity of heat released
when the waste is burned (commonly expressed in Btu/lb). Since combustion
reactions are exothermic, all organic wastes have some finite heating
value. However, the magnitude of this heating value must be considered
in establishing an energy balance for the combustion chamber and in
assessing the need for auxiliary fuel firing. To maintain combustion,
the amount of heat released by burning the waste must be sufficient to
heat the incoming waste to its ignition temperature and to provide the
necessary activation energy for the combustion reactions to occur.
Activation energy (expressed as Btu/lb or the equivalent) is the quantity
of heat needed to destabilize molecular bonds and create reactive
intermediates so that the exothermic reaction with oxygen will then proceed.
The experimental determination of the heating value for the waste influents
is measured by calorimetry.
D. SURVEY ANALYSIS
The survey analysis methods are designed to provide an overall description
of the chemistry of a sample during a trial burn in terms of both the major
types of organic compounds and the inorganic elements that are present.
The additional characterization of the waste influent stream or the
effluent streams by survey methods during a trial burn provides a check
on the manifest listing of components in the waste, permits identification
of high priority POHCs in the wastes or in the effluents which may be
unexpected, and supplements the chemical information obtained during the
directed analysis of those POHCs specified in the facility permit.
A survey analysis approach, which is compatible with the preparation
procedures presented and is consistent with the environmental goals described
previously, is an adaptation of the Level 1 Environmental Assessment
procedures (7) developed by the EPA's Process Measurements Branch as
part of a phased approach to environmental assessment. For POHCs, the
survey analysis methods include determination of:
104
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• organic content by chromatographic (TCO) and gravimetric
(GRAV) procedures,
• organic compound class type by infrared (IR) and probe mass
spectrometric procedures (LRMS), and
• specific major organic components by gas chromatography/
mass spectrometric (GC/MS) analysis.
For inorganic-containing species in Appendix VIII, the survey analysis
methods include determination of the elemental composition of the sample.
1. Survey Analysis of Organic Content (Methods A011-A017)
The survey analysis methods for organic components provide information for
identifying the major classes of organic compounds present in the waste,
the facility process streams, and the stack gas. There is also sufficient
information for estimating the concentrations of the compound classes
in the various streams. An example of the information obtained from a
survey analysis of an integrated stack gas sample collected by the SASS
sampling method is presented in Table 13. The concentration estimates
are intended to be accurate to within a factor of 2 or 3 and are generally
reported to one significant figure.
a. Organic Content by TCP (Method A011)
The chromatographable organics (TCO.) value provides a quantitative measure
of the amount of organic material in the sample which have boiling points
between 100 and 300°C. This method is based on gas chromatography.
An aliquot (1-5 uL) of the organic extract prepared according to the
procedures in Methods P021 to P030 of this manual is taken for gas
chromatographic TCO analysis. The analysis is made using the Level 1
GC conditions (10% OV-101 on 100/120 mesh support; 30°C (6 min)
@ 20°C/min -*¦ 250°C (hold); FID). Normal hydrocarbons are used for
qualitative retention time and for quantitative detector response
calibration. The TCO results are reported as mg of TCO range organics
(b.p. 100-300°C) per mL of extract and also per L (kg) of waste. The
chromatograms, which contain "fingerprint" data beyond the TCO values,
should be retained.
Data from the TCO analysis are reported on a form such as delineated
below:
105
-------
TABLE 13
SUMMARY OF RESULTS FOR ORGANIC EXTRACTS OF A SASS TRAIN SAMPLE
I (mg/m3)
Particulate Module
Categories
Aliphatic hydrocarbons
Aromatic hydrocarbons—
benzenes
Fused aromatics, MW <216
Fused aromatics,' MW >216
Rinses
>3 ym
<0.06
0.25
0.25
<3 ym
0.04
0.15
0.15
Sorbent Module
Resin
0.3
6.3
4.2
Rinse
0.8
22.0
21.0
Condensate
Total
1.1
0.6
29.0
26.0
o
Heterocyclic N
Heterocyclic S
Heterocyclic 0
Phenols
Esters
0.31
<0.06
<0.06
0.06
0.18
0.19
<0.04
<0.04
0.04
0.11
0.6
0.4
0.2
0.1
0.1
19.0
2.0
2.0
0.1
20.0
2.4
2.2
0.2
0.5
0.6
0.2
0.1
0.3
0.1
X o
Rinses corresponded to 0.03 mg/m of organics and were not subjected to LC-IR-LRMS analysis.
No condensate was collected for this sample.
***
Rounded results.
Source: Reference 7.
Carboxylic acids <0.60 <0.04 0.3 0.3
Sulfur 0.2
Inorganics 0.1
Unclassified 0.06 <0.04 0.2
Silicones 0.06 0.04
-------
Sample Number
TC0 in Extract
(mg/mL)
TCO in Waste
(mg/L or mg/kg)
b. Organic Content by GRAV (Method A012)
The gravimetric (GRAV) value provides a quantitative measure of the
amount of organic material in the sample which have boiling points in
excess of 300°C.
An aliquot corresponding to one-tenth of the concentrated sample extract
is taken for gravimetric analysis. The aliquot is then transferred to
a clean, tared aluminum weighing dish and evaporated in a desiccator
at room temperature to constant weight (±0.1 mg). The GRAV results
are reported as mg of GRAV range organics (b.p. >300°G) per mL of
extract and also per L (kg) of waste.
Data from the GRAV analysis are reported on a form such as that delineated
below:
Sample Number
GRAV in Extract
(mg/mL)
GRAV in Waste
(mg/L or mg/kg)
c. Organic Content—Volatiles (Method A013)
The volatile organic content value provides an estimate of the level of
volatile materials present in the sample with boiling points below 100°C.
An aliquot (0.5 yL) of the carbon disulfide extract prepared according
to Methods P021b, P022b, or P024c, or of the waste iself if it is an
organic liquid, is taken for survey analysis of the volatile organic
content by gas chromatography with flame ionization detection (GC/FID).
A packed column, 0.2% Carbowax 1500/Carbopack C 60/80 mesh, is used with a
107
-------
temperature program of 47°C (3 min) ->¦ @ 8°C/rain -*¦ 220°C (15 min). If
the GC/FID analysis reveals the presence of peaks from volatile sample
components at levels higher than the internal standard (i.e., concentrations
of _> 10 ppm in liquid samples, or >_ 100 ppm in solid samples), a separate
aliquot of the sample should be taken for GC/MS analysis, according to
the procedures presented in Method A016. The total FID intensity is
used to guide selection of an appropriate sample size for the GC/MS
analysis. If GC/FID analysis shows no peaks higher than that of the
internal standard, the results are reported as:
Estimated volatile organic content < 10 ppm (for liquids), and
<100 ppm (for solids).
d. Compound Class Type by Infrared Analysis (Method A014')
The infrared analysis provides information on the functional groups
present in the samples. The identified functional groups provide a
description of the chemistry of the sample and the major chemical classes
present.
An aliquot corresponding to 2-5 mg of the total organic content (TCO
and GRAV) of a sample extract (Methods A011, P021-P030), or neat organic
liquid waste, is analyzed by infrared (IR) spectrometry. IR spectra
are obtained on samples held between two NaCl plates or on KBr pellets.
Sample size is adjusted, so that the signal of the strongest sample
peak is less than 1.0 absorbance unit. IR instrument conditions used for
most samples are given below. Variations, if necessary, should be
documented. The recommended conditions are as follows:
1) Dispersive Instrument:
• Resolution: The width of the spectral slit should not exceed
4 cm 1 through at least 80 percent of the wave number range.
• Wave number accuracy: ±4 cm 1 below 2000 cm"1 and ±15 cm"1
above 2000 cm 1.
• Noise level: No more than 2 percent peak to peak.
• Baseline flatness: The I0 or 100% line must be flat to
within 5 percent across the recorded spectrum.
• Energy: The instrument should be purged with dry gas or
evacuated so that atmospheric water bands do not exceed
the allowable noise level (2 percent) when the instrument
is used in a double beam mode.
• Spectral range: Spectra should be recorded, without gaps,
over'the spectral range (3800-600 cm .
• False radiation: Not to exceed 2 percent.
108
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2) Fourier Transform (FT) Instrument:
The Fourier Transform instrument conditions are generally designed to meet
the criteria stated above for dispersive instruments. In an FT-IR
analysis, 64 scans average, or the number necessary to achieve a signal-to-
noise ratio on the order of 0.5 percent T average, are accumulated. All
spectra in a related sample set should be acquired using the same
apodization function to allow spectral subtraction. FT-IR spectra are
plotted in the transmission mode to facilitate comparison with standard
spectra.
A report such as that shown in Table 14 provides a convenient format for
reporting the functional groups identified by the infrared analysis. These
data are combined with the mass spectral data (Methods A015 and A016) to
characterize the sample in terms of the major chemical classes present.
e. Mass Spectrometric Analysis (Method A015)
The low resolution mass spectrometric (LRMS) analysis provides specific
compound identifications (non-isomer specific) which may be integrated
with other survey analysis information to identify the major chemical
classes which are present/not present in the sample in terms of the
major chemical components identified.
A sample aliquot (100 pL) of the organic extract (Method P021 to P030)
or neat sample is dried at room temperature on the direct insertion probe
of the mass spectrometer. Spectra are then acquired over a probe temperature
range of 50°C to 400°C.
The ionization mode used for the direct LRMS analysis is the same as that
used for the GC/MS analysis to facilitate comparison of the spectra.
The mode may be either electron impact (EI) or chemical ionization (18).
In the EI mode, an ionization voltage of 70 eV is used to obtain spectra
for comparison with standard reference spectra ionization. Voltages of
8-20 eV are used to obtain spectra with reduced fragmentation. A mass
spectrometer capable of attaining a true resolution of 1 part In 600
minimum should be used to ensure that it is possible to identify
heteroelement compositions.
Spectra are interpreted according to the procedures described by
Stauffer (18). The results are reported as a list of the compound types
that appear to be present in the sample. The Level 1 list of reporting
categories (Table 15) will be used and supplemented as necessary to
incorporate multifunctional organics and other specific categories of
interest. For each category, the molecular weight range is specified.
The relative abundance of each category is indicated on a three-point
logarithmic scale:
100 •= major component
10 ¦ minor component
1 » trace component
109
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TABLE 14
IR ANALYSIS REPORT FORM
Contractor
Sample ID Number
Sample Description^
Analyst Responsible
Instrument_
Observations
Results
Frequencies on which
Manor Functional Groups Assignments are Based
Date Analyzed Time
Sample Cell Type
110
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TABLE 15
CATEGORIES FOR REPORTING
Category
(Subcategory)
Aliphatic hydrocarbons
(Alkanes)
(Alkenes)
(Alkynes)
Halogenated aliphatics
(Saturated)
(Unsaturated)
Aromatic hydrocarbons
(Benzenes)
Halogenated aromatic hydrocarbons
Nitro aromatic hydrocarbons
Fused alternate, nonalternate hydrocarbons
MW < 216 (methyl pyrene)
MW > 216
Ethers
(Halogenated ethers)
Epoxides
Aldehydes
Heterocyclic oxygen compounds
Nitriles
(Aliphatic)
(Aromatic)
Alcohols
(Primary, secondary, tertiary)
(Glycols)
LRMS DATA
Category
(Subcategory)
Phenols
(Alkyl, etc.)
(Halogenated phenols)
(Nitrophenols)
Esters
(Phthalates)
Ketones
Amines
(Primary, secondary, tertiary)
(Hydrazines, azo compounds)
(Nitrosoamines)
Heterocyclic nitrogen compounds
(Indoles, carbazoles)
(Quinolines, acridines)
Alkyl sulfur compounds
(Mercaptans)
(Sulfides, disulfides)
Heterocyclic sulfur compounds
(Benzothiophenes)
Sulfonic acids, sulfoxides
Amides
Carboxylic acids
Silicones
Phosphates
-------
Specific notation is made of any compound categories which make their
first appearance at elevated probe temperatures (>200°C) since these low
volatility materials are less likely to be detected in the complementary
GC/MS analysis. An estimate is made and reported as to the percentage of
any of the sample that did not vaporize into the MS from the direct
insertion probe.
Table 16 shows an example of a LRMS analysis report form.
f. Specific Major Components by GC/MS (Method A016)
In addition to being the primary analytical tool for the directed analysis
of organic POHCs, gas chromatography/mass spectrometry (GC/MS) may be
used as a survey analysis technique. For a survey analysis, the GC/MS
is operated in the full mass range scanning mode with electron impact
ionization. The concentrated extract (Method P031), with or without
additional cleanup procedures (Methods P041 to P045) of the semivolatile
fraction of the sample, is spiked with a retention time standard, such as
dio-phenanthrene. The total ion chromatogram for the sample is examined
for the 20 most intense peaks, or for all peaks with an intensity of more
than 1 percent of the total ion intensity (after eliminating background
due to the GC column). Qualitative identification is attempted for all
of the designated peaks by either computerized library searching or manual
spectral interpretation. Qualitative identification and quantification
protocols are detailed later in this chapter.
The results of this analysis are reported as a list of specific compounds
identified, the relative retention time (vs. d10-phenanthrene) and
relative intensity of the peak, and an indication of the goodness of fit
of the sample spectrum to a standard spectrum. The latter is indicated
by P=xxx for a purity criterion, F=xxx for a fit criterion, RF«xxx for
a reverse fit criterion when computerized matching procedures are employed,
and M=strong or M=tentative for a manual identification or confirmation.
Table 17 shows an example report form.
r. Specific Major Components by HPLC/IR or HPLC/LRMS (Method A017)
Samples known or suspected to contain substantial quantities of non-
volatile organic components (i.e., GRAV:TC0 ratio ^20:1) and/or to
contain organic compound categories not amenable to gas chromatography
are analyzed by HPLC in a survey mode. A reversed phase C^-HPLC column
is used with an acetonitrile/water or a methanol/water solvent system.
Fractions of the eluent corresponding to the ten most intense peaks as
recorded by a 254-nm UV detector, are collected and analyzed by IR
(Method A014) or probe LRMS (Method A015) after evaporation of solvent.
The results of this analysis are reported as a list of specific compounds,
functional groups, and/or compound classes identified in the HPLC fractions.
An indication of the confidence of the assignment(s) is provided by the
designations "M=strong" or "M=tentative" for manual identification or
confirmation. Table 18 shows an example report form.
112
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TABLE 16
LRMS ANALYSIS REPORT FORM
Contractor
Sample ID Number
Sample Description
Analyst Responsible Date Analyzed Time
Ins t rument
Observations
Results
Major Categories, Subcategories, Specific Compounds:
Intensity
Category
MW Range
113
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TABLE 17
GC/MS SURVEY REPORT FORM
Contractor
Sample ID Number
Sample Description
Analyst Responsible Date Analyzed
Instrument ——
Column
GC Temperature Program .
Observations
Results:
Compound
Identified
Peak
Goodness of
Fit Criterion
RRT
(min)
Relative
Intensity (%)
114
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TABLE 18
HPLC/IR OR HPLC/LRMS SURVEY REPORT FORM
Contractor
Sample ID Number
Sample Description_
Analyst Responsible
HPLC Column
HPLC Solvent System_
IR Instrument Used
LRMS Instrument Used
Observations
Results
Compound
Functional Group
or Class Identified
HPLC DATA
Retention AUFS
Time at
Window 254 nm
Identi
IR
fied by:
LRMS
Confidence
Rating
Date Analyzed Time
Detector Sensitivity
115
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2. Survey Analysis of Inorganics (Method A021)
A survey analysis is conducted to determine the possible presence in
the waste of ppm levels of the metals listed in Table 19. This list
includes the metals for which primary and secondary drinking water criteria
exist, the priority pollutant metals, and the additional metals that can
be determined at no incremental cost in the survey analysis by inductively
coupled argon plasma (ICAP) emission spectroscopy. The ICAP analysis can
provide survey data on 26 metals; additional metals are determined by
atomic absorption spectroscopy (AAS), since ICAP is insufficiently sensitive
for their determination.
A portion of the waste sample corresponding to 50-300 mg of solid content
(as determined by Method AOOla or A002) is taken for survey analysis by
ICAP. Separate aliquots are taken for the AAS determinations of antimony,
arsenic, lead, mercury, and selenium. Samples are digested, using the
procedures indicated in Method P032, prior to analysis. The AAS analyses
of digested samples are performed, as described in Method A221 to A235
of this report.
The results of the survey analysis for metals are reported as a table of
metals found in the digested sample and their concentrations in the digested
solution as analyzed and in the original sample. It is anticipated that
detection limits for the metals would be on the order of 10-100 ppm in
the waste for this survey analysis. Accuracy, precision, and recovery
data are not generally obtained for the survey analysis of metals.
E. DIRECTED ANALYSIS
The directed analysis methods presented here allow the measurement of the
levels of permit-designated POHCs in samples collected during a trial
burn. The compounds listed in Appendix VIII of 40 C.F.R. Part 261
have been sorted into groups, the members of which share a common analytical
method for their measurement. In part, these groupings are based on
similar chemistry. For example, the analysis methods which are appropriate
to a single alcohol P0HC are appropriate to other alcohol POHCs. By
grouping the P0HC compounds in this way, the costs incurred during the
directed analysis activities may be minimized.
Whenever possible, a fused silica capillary column GC/MS has been specified
as the analytical method of choice. This specification is based on the
high sensitivity/selectivity of such systems, coupled with their generally
good quantification ability. In those instances in which GC/MS is not
appropriate, HPLC methods have been designated whenever possible.
Appendix C provides cross-reference information for each hazardous
constituent in Appendix VIII and its method number.
116
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TABLE 19
METALS SOUGHT IN A SURVEY ANALYSIS
Metal
Drinking
Water Priority
Standard Pollutant
Method
Alternative Method
Name Number Name
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Cobalt
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Osmium
Phosphorus
Potassium
Selenium
Silicon
Silver
Sodium
Strontium
Thallium
Thorium
Titanium
Vanadium
Zinc
Zirconium
/
/
/
/ (2°)
/ (2°)
/
/ (2°)
/
/
/
/
/
/
~
/
/
7
/
/
/ (2°)
I CAP
AAS
AAS
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
AAS
ICAP
ICAP
ICAP
ICAP
ICAP
AAS
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
ICAP
A021
A221
A222
A021
A021
A021
A021
A021
AO 21
A021
A021
A021
A021
A021
A021
A228
A021
A021
A021
A021
A021
A231
A021
A021
A021
A021
A021
A021
A021
A021
A021
A021
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
Number
A223
A224
A225
A226
A227
A229
A230
A232
A233
A234
A235
117
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1. Organic Constituents (Appendix VIII)
a. Volatiles (Method A101)
The analysis method for volatile organic POHCs is that specified in SW-846
(4) and EPA Method 624 (19). This method utilizes a purge-and-trap
procedure to remove the volatile organics from the sample matrix and
collect the volatiles on a sorbent cartridge for subsequent analysis.
The collected sample is then thermally desorbed from the sorbent cartridge
onto a packed GC column with subsequent MS detection of the volatile
species. For volatile gases which were collected on special-purpose
sorbents, the sorbent cartridge is thermally desorbed onto a packed GC
column for analysis. The analytical finish specified in this method
is also suitable for direct application to grab samples collected in gas-
sampling bulbs.
In addition to the analytical considerations involved in the transmission
of the volatile POHCs through the GC/MS instrumentation, the efficiency
of the purge-and-trap system at separating the POHCs from the bulk waste
or water (for scrubber waters) is crucial to the accurate measurement
of the POHC levels. There is a wide range of purge efficiencies for the
various volatile POHCs. This disparity in efficiencies is due in part
to the solubility characteristics of the individual constituents. To
compensate for differing purging efficiencies, recovery checks must be
made in order to compensate for incomplete sparging of each POHC.
b. Extractable Species (Method A121)
The analytical method'for the extractable POHCs is essentially that
found in SW-846 (4) or EPA Method 625 (19), with the substitution of a
fused silica SE-54 coated capillary GC column for the SP 2250 DB packed
column. This substitution increases the specificity and sensitivity of
the analysis procedure due to the higher resolution and inertness of the
fused silica capillary GC column. The method for the extractable hazardous
constituents is outlined below.
Following extraction, an aliquot of the combined acidic and basic extracts
is injected onto a fused silica capillary GC column, using either on-column,
splitless, or split injection techniques (the latter only for concentrated
extracts or neat liquid organic wastes). The sample is eluted with a
temperature program such as that found in Method A121, using either
hydrogen (preferred) or helium as the carrier gas. Electron impact (EI)
ionization at 70 eV is utilized to produce mass spectra. Alternatively,
chemical ionization (CI) conditions may be used to produce mass spectra,
although the significant ions for POHC identification are different from
those for EI ionization. The qualitative and quantitative criteria for
identifying and measuring the POHCs in this category are found later in
this chapter. The MS ions and their abundance ratios have been tabulated
in Appendix E.
118
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c. Compounds by HPLC (Methods A122, A123)
HPLC analysis procedures (20) were developed by Southern Research
Institute for several organic compounds listed in Appendix VIII (40
C.F.R. Part 261) that could not be determined by gas chromatography with
mass spectrometric (GC/MS) detection. Several compounds have been
included that are amenable to analysis by either HPLC or GC/MS.
The HPLC method was developed for use with reversed-phase Cis columns
since reversed-phase columns are less apt than normal-phase columns to
sorb organic analytes irreversibly. The UV-VIS detector was selected
as the detection system for the generalized HPLC method. Since this
detector can measure absorbances over a broad range (190 or 600 nm),
this detection system offers selectivity and versatility in determining
a variety of compound types.
Two reversed-phase columns were used with an acetonitrile/water eluent:
• Perkin-Elmer HC-ODS-Sil-X-1, 10-um particle size, 25 cm x
2.6 ram I.D.; and
• Waters Associates' uBondapack Cis, 10-ym particle size,
30 cm x 3.9 mm I.D.
(The Waters column was employed only after it was found that the
chromatography of certain compounds on the Perkin-Elmer column was not
optimal.)
Rather than establish a single set of HPLC operating conditions, various
procedural options have been developed that will allow determination of
a broad range of compound types. Several isocratic and gradient elution
programs with an acetonitrile/water mobile phase were investigated.
In the determination of several POHCs, the eluent was acidified. The
wavelength of UV-VIS detection was also varied as required to optimize
sensitivity.
Six procedural options were developed. Three were formulated for a
Perkin-Elmer reversed-phase Cis column, and three for a Waters reversed-
phase Cia column. The options for both columns were either variations
of the isocratic composition of the mobile phase or variations of the
solvent program. The various procedures for the Perkin-Elmer column
are as follows:
• Option 1A
Solvent A: Distilled, deionized water
Solvent B: Acetonitrile
Solvent program: 10% B, 5 min; 10 to 100% B in 35 min;
100% B, 10 min
Solvent flow rate: 1 mL/min
119
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• Option IB
Solvent A: 1% (v/v) acetic acid in distilled, deionized
water
Solvent B: Acetonitrile
Solvent program: 20% B, 10 min; 20 to 50% B in 10 min;
50% B, 5 min
Solvent flow rate: 2 mL/min
• Option 1C
Solvent A: 1% (v/v) acetic acid in distilled, deionized
water
Solvent B: Acetonitrile
Solvent program: 10% B, 2 min; 10 to 100% B in 18 min
Solvent flow rate: 2 mL/min
The various procedures for the Waters column are as follows:
• Option 2A
Solvent A: Distilled, deionized water
Solvent B: Acetonitrile
Solvent program: 2% B, isocratic
Solvent flow rate: 1 mL/min
• Option 2B
Solvent A: Distilled, deionized water
Solvent B: Acetonitrile
Solvent program: 10% B, isocratic
Solvent flow rate: 1 mL/min
• Option 2C
Solvent A: Distilled, deionized water
Solvent B: Acetonitrile
Solvent program: 20 to 100% B in 20 min; 100% B, 10 min
Solvent flow rate: 1 mL/min
Table 20 summarizes the data of the HPLC/UV determinations for the
constituents listed in Appendix VIII. The appropriate procedural
option, approximate retention time, and optimum wavelength of detection
are listed for each compound.
d. Aldehydes and Acids (Methods A132, A133)
Aldehydes and acids were grouped together because of their chemical
similarity.
120
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TABLE 20
SUMMARY OF DETERMINATIONS OF POHCs BY THE GENERALIZED HPLC ANALYSIS METHOD
Compound
Streptozotocin
6-Amino-l,la,2,8,8a,8b-hexahydro-
8-(hydroxymethyl)-8a-methoxy-5-
methylcarbamate azirino[2',3':3,4]
pyrrolo [1,1a] indole-4,7-dione
(ester) (Mitomycin C)
Phenol
4-Nitrophenol
2-Chlorophenol
Melphalan
5-Nitro-o-toluidine
Thiuram
Chloro-m-cresol
2,4-Dichlorophenol
Procedural
Option3
1A
1A
1A
1A
1A
1A
1A
1A
1A
1A
Retention
Time (min)
1.4
5.0
5.4
9.5
12.4
14.0
14.3
16.3
16.8
17.6
On-Column
Detection
Limit^ (ng)
17
78
54
6
72
6
10
1
77
4
100
2
Wavelength of
Detection (nm)
254
230C
254
254
280°
254
280C
254
280°
254
254
253C
254
280C
254
280C
254
280C
-------
TABLE 20 (Continued)
SUMMARY OF DETERMINATIONS
OF POHCs BY
THE GENERALIZED
HPLC ANALYSIS
METHOD
Procedural
Retention
On-Column
Detection
Wavelengtl
Compound
Option3
Time (min)
Limit'3 (ng)
Detection
3-(alpha-Acetonylbenzyl)-4-
hydroxycoumarin and salts
[Warfarin]
1A
19.8
2
254
280'
2,4,6-Trichlorophenol
1A
20.0
53
7
254
280*
2,3,4,6-Tetrachlorophenol
1A
21.5
19
17
254
280'
Reserpine
1A
22.7
28
254
267'
Chlorambucil
1A
23.9
1
254
258'
2,4-Dichlorophenoxyacetic acid
IB
7.6
69
254
284'
d
Daunomycin
IB
8.0
75
254
2,4,5-Trichlorophenoxyacetic acid
IB
14.2
55
254
287'
2,4,5-Trichlorophenoxypropionic
acid
IB
16.5
38
254
287
2,4-Dinitro-o-cresol (and salts)
1C
7.6
20
378
Azaserine^
2A
4.0
2
254
N-Nitroso-N-methylurea
2A
8.4
10
254
234'
-------
TABLE 20 (Continued)
SUMMARY OF DETERMINATION OF POHCs BY THE GENERALIZED
HPLC ANALYSIS
METHOD
Compound
Saccharine and salts
Trypan blue**
Epinephrine^
Thiosemicarbazide^
d
Thiourea
Thioacetamide^
Ethylene thiourea**
Crotonaldehyde^
Diethylstilbestrol
Procedural
Option3
2B
2C
2C
2C
2C
2C
2C
2C
2C
Retention
Time (min)
3.2
3.0
3.0
3.0
s3.0°
s4.0C
s4.0C
5.0
14.0
On-Column
Detection
Limitb (ng)
20
60
5
6
2
8
1
4
Wavelength of
Detection (nm)
254
224°
315
279
254
254
254
254
230
240
See text for description of options.
^Quantity injected that is required to yield a response twice the magnitude of background signal,
c
This wavelength was selected from the reference UV spectrum as the optimum wavelength for analysis.
^Potential candidates for analysis by HPLC/UV.
Source: Reference 20.
-------
Aldehydes are sufficiently polar that they exhibit poor chromatography
unless they are first subjected to a derivatization procedure. This is
reflected in the sampling procedure for aldehydes which uses a derivatizing
reagent (2,4,-dinitrophenylhydrazine) for trapping the aldehydes. This
reagent produces a colored product which can be identified by HPLC
techniques with UV detection. This is the preferred method for analysis
of aldehydes. An alternative method which uses pentafluorobenzylhydrazine,
forms a derivative of the aldehyde which can then be analyzed by gas
chromatography with MS or ECD detection.
The carboxylic acid POHCs are prepared for analysis by esterification
with diazomethane to form the methyl ester, or with bis(trimethylsilyl)-
acetamide to form the trimethylsilyl ester of the acid POHC. Following
esterification, these compounds may be analyzed with GC/MS methods.
e. Alcohols (Method A134)
The alcohol POHCs may be analyzed with GC methods if the chromatographic
phase is sufficiently polar. Columns coated with polyethyleneglycol
phases have been used for these analyses. The most promising GC column
packing material for alcohols is a Carbopack C coated with 0.8% tetra-
hydroxyethyleneamine. If a capillary GC column is used, a Carbowax 20M
column is sufficiently polar to allow analysis of alcohols. If the
sample contains significant quantities"of water, then a SE-52 capillary
column should be used. Either MS or FID techniques may be used for
detection of these compounds.
f. Inorganic-containing POHCs
In this edition of the manual, the analytical methods for the inorganic-
containing organic materials are based on measurement of the inorganic
species. However, analytical methods for the determination of organometallic
constituents are currently under development.
g. Others
The analytical methods for the analysis of several POHCs cannot be
classified under any of the preceding groups. The analysis methods for
these constituents tend to be single-compound methods. The compounds
found in this category generally represent fairly difficult analytical
problems and, as such, require specialized analysis procedures. The
individual methods are found at the end of this chapter. A cross-reference
to the method appropriate for each POHC is found in Appendix C.
Although the number of compounds in the "other" category is moderately
high, analyses for these species need to be conducted only in those
rare instances when professional judgment (or survey analysis) suggests
their probable presence in the waste to be incinerated.
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2. Inorganic Constituents (Appendix VIII)
The inorganic constituents which may be analyzed during a directed analysis
are categorized as metal or metal-containing, anion-containing, or gases.
This designation is referenced to the portion of the POHC which is of
primary environmental concern. Thus, a series of organometallic constituents
all of which contain mercury, or a series of thallium salts, or a series of
cyanide-containing salts are analyzed for mercury, thallium, and total
cyanides, respectively. This approach permits a minimum number of analysis
methods to encompass the range of inorganic constituents and thus,
minimizes the analysis method costs. This approach, also, since it focuses
on the environmentally active components of the waste, yields the most
accurate assessment of the inorganic emissions of the incineration facility.
a. Metals (Methods A221-A235)
The metal-containing constituents from Appendix VIII are analyzed by atomic
absorption spectroscopy (AAS), or inductively coupled plasma emission
spectroscopy (ICAP) techniques. Two modes of analysis are used for these
species; direct analysis from solution, or cold vapor/hydride evolution.
The choice of the analysis mode depends upon the specific metal of interest
in the directed analysis. The specific analytical methods are well
documented in SW-846 (4) and elsewhere. The following discussion summarizes
the general details concerning the AAS and ICAP analyses of these samples.
Specific details for each element can be found in the method summaries
and the included references (Methods A221 to A235).
The samples containing inorganic compounds are prepared for directed
analysis by one of the digestion procedures discussed in the previous
chapter. These procedures convert the metal-containing compounds into
the inorganic form for analysis. For all of the metals, except arsenic,
selenium, and mercury, the solution resulting from the digestion procedure
may be aspirated directly into the flame for flame AAS, or into the plasma
for ICAP, or injected directly into the furnace for flameless AAS analysis.
Within the flame, plasma, or furnace, the inorganic compounds are reduced
to their atomic state from which either absorption (AAS) or emission (ICAP)
occurs at a wavelength which is specific for the element under investigation.
The spectrometer is adjusted so that only the specific wavelength(s)
of interest are detected at the photomultiplier detector. The amount of
absorption or emission which occurs during the AAS or ICAP experiment
may be directly related to the concentration of the metals present.
For selenium and arsenic, the solution resulting from the digestion of
the sample is treated with stannous chloride to form the trivalent ion.
The solution is then treated with zinc metal which converts the trivalent
compound to the volatile hydride. The hydride is then detected by the
AAS method.
125
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For mercury, the solution resulting from digestion of the sample is
treated with stannous sulfate which reduces the ionic mercury in the
sample to the atomic species. The volatile atomic mercury is swept from
the sample in a closed system through an absorption cell to a scrubber
trap. The level of mercury in the sample is obtained from the integrated
AAS signal formed during its evolution from the sample.
Table 21 summarizes the analytical wavelengths for each of the metals
from the Appendix VIII list of hazardous constituents which are analyzed
by AAS and ICAP procedures. Quantification of the levels of the metals
listed in Table 21 must be done with direct methods (i.e., either by
comparison to an external calibration curve, or by the method of standard
additions). Both of these methods are well known, and have been described
in numerous references (4).
An external calibration curve is prepared by plotting the absorbance
(AAS) or transmittance (ICAP) versus concentration for a series of
standards which span the linear working range of the analytical instrument.
If the measured absorbance, or transmittance, of the sample analyzed
under the same conditions as the standards is compared to the calibration
curve, the concentration of the material in the sample can be interpolated.
For many of the samples which will be collected at hazardous waste
incineratorsj the level of potential interferences will be high enough
that the method of standard additions must be used for quantification.
With this method, aliquots of the digested sample are spiked with known
amounts of the standard reference material and the ab9orbance for the
spiked and unspiked samples measured. The concentration in the original
sample is obtained by extrapolation of the calibration curve for the
spiked and unspiked samples to zero absorbance.
b. Anions (Methods A251, A252, A253)
A number of the inorganic species listed in 40 C.F.R.' Part 261, Appendix VIII
are hazardous primarily because of the anionic portion of the compound.
These compounds, which contain either cyanide or phosphide, are analyzed
by a single method for that anion. A general procedure for the determination
of anions in solution employs ion chromatography as an analytical technique (21) .
The general procedure for the determination of inorganic cyanides is to
acid-treat the sample, which causes the evolution of gaseous hydrocyanic
acid (HCN). The HCN formed is trapped in a scrubber containing sodium
hydroxide. The scrubber solution is then analyzed for total cyanide by
titration with silver (for concentrations exceeding 1 mg/L of cyanide)
or by a colorimetric procedure for lower concentrations. Because of
the toxicity of HCN, the sample preparation steps for total cyanide
measurement must be performed in a closed system placed in a well ventilated
hood.
126
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TABLE 21
CHARACTERISTIC DATA FOR METALS LISTED IN APPENDIX VIII
Wavelength (nm)
Metal (Element Symbol)
AAS
ICAP
Sample Form
Antimony (Sb)
217.6
206.8,
187.1
Solution
Arsenic (As)
193.7
189.0,
197.2
Hydride
Barium (Ba)
553.6
455.4,
233.5
Solution
Beryllium (Be)
234.9
313.0,
234.9
Solution
Cadmium (Cd)
228.8
226.5,
214.4
Solution
Chromium (Cr)
357.9
267.7,
294.9
Solution
Lead (Pb)
217.0
220.3,
217.0
Solution
Mercury (Hg)
253.7
194.2,
187.1
Cold Vapor
Nickel (Ni)
232.0
231.6,
227.0
Solution
Osmium (Os)
290.8
225.6,
189.8
Solution
Selenium (Se)
196.0
196.1,
204.0
Hydride
Silver (Ag)
328.1
328.1,
224.6
Solution
Strontium (Sr)
460.7
407.8,
346.4
Solution
Thallium (Tl)
276.8
190.9,
351.9
Solution
Vanadium (V)
318.5
309.3,
214.0
Solution
127
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The phosphide-containing inorganic species may be analyzed by the
reaction of the sample with either acid or water to form phosphine. For
the directed analysis of phosphide, the sample is placed in a sealed
volumetric gas flask which has been flushed with high-purity N2;
dilute mineral acid (0.01N HNO3) is added to the flask and mixed.
A second calibrated gas volumetric flask is prepared by placing three
to eight quartz glass chips into the flask and flushing with high
purity N2• After the sample equilibrates, an amount of N2 is removed
from the second flask and the same amount of phosphine-containing gas
transferred into it. The transfer syringe is pumped several times before
removal and the flask swirled to ensure adequate mixing. This gaseous
mixture is then analyzed by gas chromatography with a flame photometric
detector.
c. Gases
The gaseous inorganic species, for the most part, have standard methods
available to define the operational conditions for their analysis. These
methods are all based on GC with either selective detectors such as an
alkali flame ionization detector (AFID), a flame photometric detector
(FPD), an electron capture detector (ECD) or a nonspecific detector, such
as the thermal conductivity detector (TCD). An advantage in using TCD
detection is that its characteristics are completely compatible with
the requirements for field work and hence, may be used to measure
gaseous inorganic species in the field. For a particular sampling and
analysis program, field analysis of these gaseous species may be highly
advantageous, since the gas samples obtained for these compounds would
not need to be transported from the field to the laboratory.
Other GC detectors are frequently utilized because of their selectivity.
As the selectivity of the detector increases, the separation requirements
of the GC and the preliminary cleanup procedures required for sample
analysis are reduced. The characteristics of the selective detectors
for those species may be summarized as follows: AFID is best for nitrogen-
containing compounds, FPD is best for sulfur- and phosphorus-containing
compounds, and ECD is best for halogen-containing compounds.
3. Directed Organic Analysis Criteria
The methods for the qualitative and quantitative analysis of POHCs in
hazardous waste incinerator streams are similar or identical to those
described in SW-846 (4) or Federal Register Methods 624 and 625 (19).
The preferred analysis methods for organics involve the detection of
chromatographic eluents, either GC or HPLC. The retention time for
each POHC serves as one portion of the qualitative identification
criteria, while the detector response integrated over the elution of
the POHC of interest serves as the primary quantitative measurement. The
following discussion describes the criteria for qualitative identification
and quantitative measurement of POHC compounds.
128
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a. Instrumental Operating Parameters
The primary analytical tool for the measurement of hazardous waste
incinerator process streams is the GC/MS using fused silica capillary GC
columns. The second most important analytical tool for measurement of
these streams is HPLC with a variety of detection systems depending upon
the compounds of interest. The general details for these methods are
described below.
The mass spectrometer is operated in a full mass range scanning mode
for most of the analyses of hazardous waste incinerator process streams.
The range for which data are acquired in a GC/MS run is sufficiently
broad to encompass the major ions, as listed in Appendix E of this
report, for each of the potential POHCs in a waste characterization
analysis, or for each of the designated POHCs in a trial burn incinerator
effluent analysis.
For most purposes, electron impact (EI) spectra are collected since a
majority of the POHCs listed give reasonable EI spectra. Also, EI
spectra are compatible with the NBS Library of Mass Spectra and other
mass spectral references, which aid in the identification process for
other components in the incinerator process streams.
To clarify some identifications, chemical ionization (CI) spectra using
either positive ions or negative ions may be used to elucidate molecular
weight information and simplify the fragmentation patterns of some
compounds. In no case, however, should CI spectra alone be used for
compound identification.
Although the permitting process specifies the high priority POHCs which
must be measured at any hazardous waste incineration facility, incomplete
characterization of the incinerator influents may result in unexpected
occurrence of additional species in the effluent streams which need to
be dealt with. Hence, the more general EI mode of ionization is preferred.
In general, the cycle time between collections of complete mass spectra
needs to be selected to be compatible with elution of the components in
the sample. For capillary column GC separations, the cycle time should
be on the order of one second. Longer cycle times may lead to distortion
of the spectra. To characterize a GC peak adequately, at least five
spectra should be collected across the peak. For low level components in
the extract, the elution peak may be less than 3 seconds wide and,
consequently it might not be possible to collect enough scans to
characterize the GC peak if the scan repetition rate were greater than
1 second.
To ensure consistency with sources of mass spectra, the GC instrumentation
must be tuned to meet the spectra criteria for decafluorotriphenylphosphine
(when using analysis Methods AOlla, Alll, A121 or other fused silica glass
capillary column methods), or bromofluorobenzene (when using analysis
129
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Method A101 or other analyses of highly volatile organic species). The
criteria for meeting the tuning requirements for these analyses are found
in EPA Federal Register Methods 624 and 625 (19) and summarized in
Tables 22 and 23, respectively.
When a method specifies analysis by HPLC, the HPLC system consists of
several components: reservoir(s) for the elution solvent(s) which may
or may not include a gradient device; pumps; injection port; columns;
detection and readout devices; and thermostats for the column and detector.
These components are commercially available as individual modules, or
incorporated into complete HPLC systems. The general operating conditions
for HPLC analyses are thoroughly specified in the analytical method
description for the various POHCs. The most common HPLC detectors utilize
either ultraviolet absorption or fluorescence emission at a single
wavelength. In general, these detectors are nonspecific and, consequently,
multiple analyses are required to provide accurate identity assignments.
b. Qualitative Identification
The identification of organic POHCs is based on both the chromatographic
elution of those compounds and on the specificity of the detection system
(i.e., MS for GC/MS and ultraviolet, fluorescence, MS, refractive index
or electrochemical for HPLC). The relative retention time of a POHC
compared to an appropriate internal standard (discussed in the following
section) is generally constant to within about ± 0.2 percent, depending
upon the compound. For GC/MS, a match in both the relative retention
time for the POHCs and the simultaneous elution of multiple analytical
ions specific to that POHC will serve to establish the qualitative
identification of the components of the sample. For HPLC with nonspecific
detectors (e.g., UV, fluorescence, RI), the qualitative identification
is confirmed by a match of the relative retention times on multiple columns
between the suspect POHC and a corresponding analytical standard.
MS detection may be used in either a directed or a survey mode. The
directed analysis mode is intended to track those POHCs designated in
the permitting process for determination of compliance with the DRE
performance criterion. The survey analysis mode is intended to identify
those and other hazardous constituents which may be present due to unexpected
reactions, incomplete combustion, and the like. For the most part,
features of the directed mode are also present in the survey mode.
For directed analyses, where specific POHCs are to be measured in the
sample, the identification criteria to confirm the presence of a POHC
by MS are that 1) the GC retention time for the suspect peak relative to
some standard match that for the corresponding POHC, and 2) that the
characteristic ions of the suspected POHC are present in the unknown
sample at approximately the same ratio as is present in the standard and
that those ions coelute. For those POHCs which may be analyzed with MS
detection, Appendix E lists the characteristic ions for use with electron
impact ionization.
130
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TABLE 22
TUNE CRITERIA FOR DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
Mass Ion Abundance Criteria
51 30 to 60
68 < 2% of mass 69
70 < 2% of mass 69
127 40 to 60
197 < 1
198 100 (base peak)
199 5 to 9
275 10 to 30
365 > 1
441 Present, but less than mass 443
442 >40
443 17% to 23% of mass 442
All values in percent abundance relative to mass 198, unless other-
wise stated.
131
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TABLE 23
TUNE CRITERIA FOR BROMOFLUOROBENZENE
*
Mass Ion Abundance Criteria
50 20 to 40
75 50 to 70
95 100 (base peak)
96 5 to 9
173 < 1
174 70 to 90
175 5 to 9
176 70 to 90
177 5 to 9
*
All values in percent abundance relative to mass 95, unless otherwise
stated.
•k-k
Abundance at mass 176 should be about 98% of that at mass 174.
132
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For survey analyses, the qualitative identification of POHCs in a sample
is based on the individual mass spectrum of the compound of interest.
These identifications are performed primarily by comparison with
libraries of mass spectra, using both computerized and, if necessary,
manual data base search routines. These tentative identifications may
be supplemented by chromatographic retention time data, as appropriate.
The following discussion explains the use of computer searches for POHC
identification.
A key factor in the use of computerized mass spectra search systems is
the data base. Ideally, the data base would include spectra of all
potential compounds of interest and the data would have been obtained
under the same conditions as used in the analysis of the incinerator
process samples. As a practical alternative, the NBS data base is used
and supplemented with spectra for those POHC compounds which are not
in the library, preferably obtained on the instrument to be used for the
sample analysis.
A second key factor in the use of computerized mass spectral search
systems is the assessment of the confidence to be placed in the qualitative
compound identification or "match" with the reference spectrum in the
library. The computerized search system typically generates one or more
numerical indicators of the "goodness of fit." In the Finnigan 4000/
INCOS data system, for example, goodness of fit is indicated by three
values:
• the fit - how well each library entry is represented
in the sample spectrum;
• the reverse fit - how well the sample spectrum is represented
in each library entry; and
• the purity - how well both the fit and the reverse fit
match the sample spectrum and the library
entry.
Of these terms, the purity is the most powerful since a high purity value
indicates that both the library entry and the sample spectrum match each
other closely and either spectrum accounts for virtually all of the other
spectrum. When using a Finnigan 4000/INCOS GC/MS/DS system for survey
analysis, it is appropriate to base qualitative compound identifications
of POHCs on the purity value. For purity values in excess of 900 on a
0 to 1000 scale, the computer search could be regarded as having
identified a single component in the GC peak. A list of the top 5 to 9
choices should also be retrieved as output from the search system. If
several compounds with purity values that are close to one another are
identified, the analyst should retrieve and examine the library spectra
and use the elution order data to ascertain the best candidate for the
identity of the GC peak of interest. Similarly, if the purity value has
decreased below the 900 value threshold, the analyst should retrieve and
examine the library spectra, the sample spectrum, and any retention time
data to determine the identification of the sample compound.
133
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The algorithms for calculated "goodness of fit" parameters and the
numerical values that are associated with specific levels of confidence
in the identification vary, depending on the particular software in
the GC/MS system employed for analysis. For this reason, and also because
the professional judgment of the mass spectrometrist is an essential
element in the qualitative compound identification process, it is not
appropriate to specify in this document numerical goodness of fit criteria
to be applied to all POHC analyses.
It is essential, however, that all compound identifications be reported
with an indication of the goodness of fit criteria that were used in
making the assignment. These may include numerical values of parameters
from the computerized search system and/or the analyst's professional
judgment (e.g., "strong," "probable," "tentative"). (See Table 17 for
a suggested format.) Of course, both elution order and accordance with
the correct or reference spectrum must be utilized to assure correct
identification of any and all POHCs in wastes and in samples from
hazardous waste incinerators.
For nonspecific detectors such as most of those with HPLC, POHC identifi-
cation must be made using multiple LC columns whose relative retention
behavior is significantly different. The sample is analyzed on two
columns and the retention of the suspect peak, compared to that of a
reference standard. If the retention on both columns match between the
suspect peak and the reference peak, then the suspect peak has been
tentatively identified. Isolation of the suspect peak and subsequent
analysis by MS and IR, as appropriate, serves to confirm the
multicolumn identification.
c. Quantitative Measurement
Following the qualitative identification of POHCs in either the influent
or effluent streams of a hazardous waste incineration facility, the levels
of the identified species need to be measured. Two purposes are served
with these measurements. For those POHCs which were designated during
the trial burn permitting process, the quantitative measurements of the
influents and effluents are used to check that the DRE value is in
excess of 99.99 percent for each of the designated POHCs. For other
species which are identified in the samples, the measurement can be
used, if necessary, to identify any unexpected environmental hazards.
Measurements will be based either on direct calibration using authentic
standards or on indirect methods.
External calibration methods, using either the raw response of a standard
or the relative response of the standard versus an internal standard as
a function of the amount of standard, are widely used in analytical
chemistry for quantification. For these methods, a series of calibration
standards are prepared from reagent material of the compound(s) of
interest which span the linear working range of the analytical instrumenta-
tion being used. Each of these standards is analyzed using the same
134
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conditions as would be used for the actual samples. The response-
concentration data pairs are combined into a calibration curve by
regression methods. The level of the compound in the sample is determined
by interpolation within the calibration curve. This method is routinely
used for GC/MS and HPLC analysis.
For samples analyzed by GC/MS, stable labeled isotope spikes may be used
for quantification. The use of stable labeled isotope spikes has a
number of advantages. A stable labeled isotope compound which is added
to the sample prior to any cleanup steps exhibits essentially the same
characteristics as the nonlabeled compound when taken through the various
processing steps involved in the sample workup and analysis. As in other
calibration methods, it is necessary to prepare a series of standard
solutions to establish the linearity of response over the desired
concentration range.
Direct quantification procedures are recommended for any species which
are identified in the hazardous waste incinerator samples. However,
this may not be possible due to a shortage of reference standards, for
example, and indirect methods may be necessary in some cases. The most
common of the indirect methods is to use the response characteristics of
a chemically similar compound to estimate the level of the target
constituent of interest (4). Thus, if for example, benzofluoranthenes
were unexpectedly found in a sample, but no standard were available, then
the level of benzofluoranthenes present in the sample might be estimated
from the response curve of benzo(a)pyrene, benzo(e)pyrene, or perylene.
Chemical similarity includes similar functionalities, isomeric structures,
and homologous series of compounds. The quantitative estimates by this
method are of increasing accuracy as the chemical structure of the
reference compound approaches that of the compound of interest. This
method assumes that the compound which is being measured has the same
response characteristics as the reference compound. In some cases, it
may be appropriate to correct for predictable differences in MS response
characteristics (22, 23). This approach does not compensate for possible
differences in chromatographic behavior between the target constituent
and the reference compound. It should be noted that direct quantification
using an authentic standard of the POHC of concern is always preferable
to indirect quantification.
F. ANALYSIS METHOD SUMMARIES
The analysis methods (designated with an A) appropriate to each hazardous
constituent from Appendix VIII (40 C.F.R. Part 261) are summarized in
tabular form on the following pages. Also included are summaries of the
methods for the test procedures used in determining the characteristics
of the waste (designated with a C).
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Method Number:
Method Name:
Basic Method:
Matrices:
C001
Ignitability
Flash Point Determination
Aqueous Liquids
Organic Liquids
Sludges
Solids
Apparatus: Pensky-Martens Closed Cup Tester
Procedure: ASTM D-93-79 (1979)
Setaflash Closed Cup Tester
Procedure: ASTM D-3278-78 (1978)
Analysis Method Parameters:
The flash point of a liquid will be determined according to
either of the ASTM procedures referenced above, or
• the waste will be identified as a compressed gas, as
defined in 49 C.F.R. 173.300, or
• the waste will be identified as an oxidizer, as defined
in 49 C.F.R. 173.151.
Reference: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980), Section 4.
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Method Number:
C002
Method Name:
Corrosivity
Basic Method:
pH Determination
Corrosivity Toward Steel
Matrices:
Aqueous Liquids
Organic Liquids
Sludges
Solids
Apparatus:
pH Meter - pH Determination
SAE Type 1020 Steel - Corrosivity Toward
Steel
Analysis Method Parameters:
pH Determination - The pH of the sample will be determined
electronically using either a glass electrode in combination
with a reference potential or a combination electrode, as
specified in SW-846.
Corrosivity toward steel - The weight loss of a circular coupon
of SAE type 1020 steel will be determined after a designated time
period (200-2000 hours). The waste must be agitated and maintained
at 55°C throughout the duration of exposure. The coupon must be
carefully cleansed prior to each weighing.
Reference: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980), Section 5.
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Method Number:
Method Name:
Basic Method:
Matrices:
Analysis Method Parameters:
C003
Reactivity
Professional Judgment
Aqueous Liquids
Organic Liquids
Sludges
Solids
A solid waste will be considered to exhibit the characteristic
of reactivity if it shows any of the following properties:
it readily undergoes violent chemical changes;
• it reacts violently or forms potentially explosive mixtures
with water;
• it generates toxic fumes when mixed with water or, in the
case of cyanide or sulfide bearing wastes, when exposed to
mildly acidic or basic conditions;'
• it explodes when subjected to a strong initiating force;
• it explodes at normal temperatures and pressures;
• it fits within the Department of Transportation's forbidden
explosives, Class A explosives, or Class B explosives
classification.
Reactivity will be determined by applying best professional
judgment to the available data. There are no explicit experimental
test procedures for the determination of this characteristic.
Reference: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980), Section 6.
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Method Number:
Method Name:
Basic Method:
Matrices:
Apparatus:
C004
Extraction Procedure Toxicity
Extraction of a sample followed by analysis
of the extract by GC/ECD, ICAP, and AAS
Sludges
Solids
Filtration Apparatus
Structural Integrity Tester
Extraction Apparatus - Stirrer or Tumbler
GC/ECD
ICAP Spectrophotometer
AAS Spectrophotometer
Analysis Method Parameters:
The solid waste sample will be extracted for 24h with aqueous
acetic acid at pH = 5.
The extract will then be analyzed for pesticides and herbicides
in the leachate by GC/ECD on Supelcoport 100/200 Mesh, coated
with 3% OV-1, 180 cm x 4 mm I.D. glass column with 5% methane/
95% argon carrier gas at 60 mL/min. The column temperature will
be maintained at 200°C.
Analysis of metals in leachate by either AAS or ICAP as specified
in the following method numbers:
Metal
Method
Method Number
Arsenic
AAS
A222 '
Barium
ICAP
or
AAS
A223
Cadmium
ICAP
or
AAS
A225
Chromium
ICAP
or
AAS
A226
Lead
AAS
A227
Mercury
AAS
A228
Selenium
AAS
A231
Silver
ICAP
or
AAS
A232
Reference: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980), Section 7.
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Method Number:
AOOla.b
Method Name:
Moisture, Solid and Ash Content - Macroscale
Technique
Basic Method:
Sample Drying and Ignition
Matrices:
Aqueous Liquids
Organic Liquids
Sludges
Solids
Apparatus:
Balance
Hot Plate
Muffle Furnace
Analysis Method Parameters:
An aliquot of the waste sample will be transferred to a prepared
evaporating dish and weighed. Any liquid will be removed by
drying the liquid at 103°C without boiling. Then, the sample
will be cooled, weighed with repeated drying and weighing of
the sample to constant weight (difference of less than 4% in
weight).
An aliquot of the dried sample will then be ignited for 30 min
at 600°C, and the ash weighed to constant weight.
Detection Limit: 1-10 ppm
References: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Method
D-1888-78, Part 31 (1979).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
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Method Number: A002
Method Name: Moisture, Solid and Ash Content -
Microscale Technique
Basic Method: Thermogravimetric Analysis (TGA)
Matrices: Organic Liquids
Sludges
Solids
Apparatus: TGA
Analysis Method Parameters:
An aliquot of the sample (<50 mg) will be placed in the sample boat
of the TGA and heated in air atmosphere by either of two methods:
• at a programmed rate of 10°C/min to 500°C, or
• two isothermal measurements at 125°C and 500°C, allowing
two min equilibration at each isothermal temperature.
' Data can be reported by:
• a plot of weight (mg) vs. temperature, °C, or
• a plot of percent lost vs. temperature, °C.
Detection Limit: 1-10 ppm
Reference: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Method D-1888-78,
Part 31 (1979).
141
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Method Number:
A003
Method Name:
Basic Method:
Matrices:
Apparatus:
Analysis Method Parameters:
Reference
Elemental Composition - Organic
Elemental Analysis
Aqueous Liquids
Organic Liquids
Sludges
Solids
Varied
Carbon
Nitrogen
Oxygen
Phosphorus
Sulfur
Chlorine
Detection Limit:
ASTM D-3178-73 (1979)
ASTM D-3179-73 (1979)
E-258-67 (1977)
ASTM D-3176-74 (1979)
ASTM D-2795 (1965)
ASTM D-3177 (1975) ,
D-129-64 (1978)
ASTM D-2361-66 (1978),
D-808-63 (1976)
100 ppm
Measurement
CO2 & H2O on combustion
N2 by Kjeldahl
Difference method
Spectroscopic method
Sulfate titration
Halide titration
Reference: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Methods for
each element, as specified above.
142
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Method Number:
Method Name:
Basic Method:
Matrix:
Apparatus:
Analysis Method Parameters:
A004
Total Organic Carbon (TOC)
Total Organic Halogen (TOX)
Combustion
Aqueous Liquids
TOC Analyzer
TOX Analyzer
Carbon: An aliquot of the sample will be analyzed using a TOC
analyzer by measuring the CO2 and CHi^ which is evolved.
Halogen: The sample will be combusted and the hydrogen halides
collected. The collected halides will be titrated and
their concentration compared to the total halogen
concentration as determined by potentiometric titration.
Detection Limit: 100 ppm
Reference: Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS.No. PB297686/AS.
143
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Method Number:
A005
Method Name:
Basic Method:
Matrices:
Apparatus:
Analysis Method Parameters:
Viscosity
Flow Measurement
Aqueous Liquids
Organic Liquids
Kinematic Viscometer
Thermometer
The time will be measured for the flow of a fixed volume of
sample through the viscometer.
Detection Limit:
0.002 to 3,000 Stokes (A series of
viscometers is needed to cover this range.)
Reference: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Methods," Method D-445
(1979).
144
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Method Number:
A006
Method Name:
Heating Value of Waste
Basic Method:
Combustion/Calorimetry
Matrices:
Aqueous Liquids
Organic Liquids
Sludges
Solids
Apparatus:
Calibrated isothermal jacket bomb calorimeter
under controlled conditions (ASTM D-2015), or
adiabatic bomb calorimeter under controlled
conditions (ASTM D-3286)
Analysis Method Parameters:
Calorific value will be computed from temperature observations
made before, during, and after combustion of a weighed sample.
Proper allowance must be made for heat contributed by other
processes.
Reference: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Method
D-2015-77 (1978) and Method D-3286-77 (1977).
145
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Method Number:
Method Name:
Basic Method:
Matrices:
A101
Volatiles
GC/MS - Purge and Trap
Aqueous Liquids
Organic Liquids (neat or diluted)
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Acetonitrile
Acrolein
Acrylamide
Acrylonitrile
Benzene
Bromoacetone
Bromomethane
Carbon disulfide
Carbon oxyfluoride
Chlorinated benzenes, N.O.S.
Chlorinated ethane, N.O.S.
Chlorinated fluorocarbons, N.O.S.
Chloroalkyl ethers, N.O.S.
Chlorobenzene
1-Chloro-2,3-epoxypropane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloromethyl methyl ether
1,2-Dibromo-3-chloropro.pane
1,2-Dibromoethane
Dibromomethane
Dichlorobenzene (meta, ortho, and para isomers)
Dichlorobenzene, N.O.S.
l,4-Dichloro-2-butene
Dichlorodifluoromethane
1.1-Dichloroethane
1.2-Dichloroethane
trans-1,2-Dichloroethene
Dichloroethylene, N.O.S.
1,2-Dichloroethylene
Dichloromethane
Dichloropropane, N.O.S.
1.2-Dichloropropane
Dichloropropene, N.O.S.
1.3-Dichloropropene
146
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1,4-Dioxane
Formic acid
Halomethane, N.O.S.
Hexachloroethane
Hexachloropropene
Hydraz ine
Iodomethane
Isocyanic acid, methyl ester
Methanethiol
Methyl ethyl ketone (MEK)
Methyl hydrazine
Tetrachloroethane, N.O.S.
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Tetrachloromethane
Tetranitromethane
Toluene
Tribromomethane
1.1.1-Trichloroethane
1.1.2-Trichloroethane
Trichloroethene
Trichlorotnonof luorome thane
Trichloropropane, N.O.S.
1.2.3-Trichloropropane
Vinyl chloride
Apparatus: Finnigan 4000 GC/MS/DS or equivalent
Purge and Trap Device (Tekmar LSC-1 or
equivalent)
Analysis Method Parameters:
Purge and Trap: A 25 cm trap will be prepared which contains
1/3 activated charcoal, 1/3 silica gel, and 1/3
Tenax. A 5 mL sample will be purged onto the trap
(Methods AlOla, AlOlb, or AlOlc) at 40 mL/min
with helium or nitrogen for 12 min, and desorbed
with backflushing at 180°C with 40 mL inert gas
into GC for 4 min.
GC: Column - 6 ft 0.2% Carbowax 1500 on Carbopack C 60/80
mesh
Carrier Gas - He at 50 mL/min
Injector - 160°C
Temperature Program - 30°C for 7 min isothermal
(beginning at start of purge); then, 30-160°C
at 8°C/min; and 160°C for 15 min isothermal.
147
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MS:
Mass Range - 20-260 amu
Scan Rate - 2 s/scan
Ionization - EI, 70 eV
Detection Limit: 10-100 ug/L of each compound on-colunvn.
References: U.S. Environmental Protection Agency, Federal Register,
44, 69464-69575 (December 3, 1979).
U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
148
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Method Number:
AlOla
Method Name:
Volatiles
Basic Method:
Purge and Trap
Matrix:
Aqueous Liquids
Purging Method Parameters:
An aliquot (5 mL) of the aqueous sample will be transferred into
the purging device; and purged with helium for 12 min at 40 mL/min.
Reference: U.S. Environmental Protection Agency, Federal Register,
44, 69464-69575 (December 3, 1979).
149
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Method Number:
AlOlb
Method Name:
Volatiles
Basic Method:
Purge and Trap
Matrix:
Sludges (including gels and slurries)
Purging Method Parameters:
An aliquot of a sludge sample will be diluted to 0.5% solids with
reagent grade water. A 5-mL portion of this diluted mixture will
then be transferred to the purging device and purged for 12 min
with helium at 40 mL/min. If the sludge sample is not readily
dispersible, polyethylene glycol (MW 400) will be used to dilute
the sample.
Reference: Miller, H.C., R.H. James and W.R. Dickson, "Evaluated
Methodology for the Analysis of Residual Wastes," Report
prepared for U.S. Environmental Protection Agency/Effluent
Guidelines Division, Washington, D.C., by Southern Research
Institute, Birmingham, Alabama under Contract No. 68-02-2685
(December 1980).
150
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Method Number:
AlOlc
Method Name:
Volatiles
Basic Method:
Purge and Trap
Matrix:
Solids
Purging Method Parameters:
An aliquot of the solid sample will be diluted to 2% solids with
reagent grade water. A 5-mL portion of this diluted mixture will
be transferred to the purging device and purged for 12 min with
helium at 40 mL/minute. If the solid sample is not readily
dispersible in water, polyethylene glycol (MW 400) will be used
to dilute the sample.
Reference: Miller, H.C., R.H. James and W.R. Dickson, "Evaluated
Methodology for the Analysis of Residual Wastes," Report
prepared for U.S. Environmental Protection Agency/Effluent
Guidelines Division, Washington, D.C., by Southern Research
Institute, Birmingham, Alabama under Contract No. 68-02-2685
(December 1980).
151
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Method Number: A121
Method Name: Extractables
Basic Method: GC/MS
Matrices: Sample Extracts
Organic Liquids (neat or diluted)
Constituents from Appendix VIII to which method may be applied:
*Acetophenone
2-Acetylaminofluorene
Aldrin
*4-Aminobiphenyl
*5-(Aminomethyl)-3-isoxazolol
*Amitrole
*Aniline
*Aramite
*Auramine
*Benz(c)acridine
Benz(a)anthracene
*Benzene, dichloromethyl-
*Benzenethiol
Benzidine
Benzo(b)fluoranthene
Benzo(j)fluoranthene
Benzo(a)pyrene
*p-Benzoquinone
Benzotrichloride
Benzyl chloride
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl)ether
*N,N-Bis(2-chloroethyl)-2-naphthylamine
Bis(2-chloroisopropyl)ether
*Bis(chloromethyl)ether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
*2-Butanone peroxide
Butyl benzyl phthalate
*2-sec-Butyl-4,6-dinitrophenol (DNBP)
Chlordane (alpha and gamma isomers)
Chlorinated benzene, N.O.S.
Chlorinated naphthalene, N.O.S.
Chlorinated phenol, N.O.S.
p-Chloroaniline
*Chlorobenzilate
+*p-Chloro-m-cresol
2-Chloronaphthalene
t*2-Chlorophenol
*3-Chloropropionitrile
152
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Chrysene
*Coal Tars
Creosote
+*Cresols
*2-Cyclohexyl-4 ,6-dinitropheriol
DDD
DDE
DDT
*Diallate
*Dibenz(a.h)acridine
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
*7H-Dibenzo(c,g)carbazole
*Dibenzo(a,e)pyrene
*Dibenzo(a,h)pyrene
*Dibenzo(a,i)pyrene
Di-n-butyl phthalate
Dichlorobenzene (meta, ortho, and para isomers)
Dichlorobenzene, N.O.S.
3,3'-Dichlorobenz idine
*2,4-Dichlorophenol
2,6-Dichlorophenol
Dichloropropanol, N.O.S.
Dieldrin
*1,2:3,4-Diepoxybutane
*N,N-Diethylhydrazine
.*0,0-Diethyl S-methyl ester of phosphorodithioic
acid
*0,0-Diethylphosphoric acid, O-p-nitrophenyl
ester
Diethyl phthalate
*0,0-Diethyl 0-2-pyrazinyl phosphorothioate
*Dihydrosafrole
*Diisopropylfluorophosphate
*Dimethoate
*3,3'-Dimethoxybenzidine
*p-Dimethylaminoazobenzene
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine
*•1,1-Dimethylhydrazine
•1,2-Dimethylhydrazine
*alpha,alpha-Dimethylphenethylamine
*2,4-Dimethylphenol
Dimethyl phthalate
Dimethyl sulfate
Dinitrobenzene, N.O.S.
*4,6-Dinitro-o-cresol and salts
*2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Diphenylamine
153
-------
1,2-Diphenylhydrazine
*Di-n-propylnitrosamine
*Disulfoton
*2,4-Dithiobiuret
tEndosulfan
Endrin and metabolites
*Ethyl carbamate
*Ethyleneimine
*Ethyl methacrylate
tEthyl methanesulfonate
Fluoranthene
*Fluoroacetic acid, sodium salt
Formic Acid
Heptachlor
Heptachlor epoxide (alpha, beta, and
gamma isomers)
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclohexane (all isomers)
Hexachlorocyclopentadiene
Hexachloroethane
*1,2,3,4,10,10-Hexachloro-l,4,4a,5,8,8a-
hexahydro-1,4:5,8-endo,endo-
dimethanonaphthalene
*Hexachlorophene
*Hexaethyl tetraphosphate
•^Hydrazine
Indeno(1,2,3-cd)pyrene
*Isosafrole
*Kepone
Maleic anhydride
*Maleic hydrazide
Malononitrile
*Methacrylonitrile
*Methapyrilene
*Methoxychlor
*2-Methylaziridine
3-Methylcholanthrene
*4,4'-Methylenebis(2-chloroaniline)
*Methyl ethyl ketone
•Methyl hydrazine
*2-Methyllactonitrile
*Methyl methacrylate
*N-Methyl-N'-nitro-N-nitrosoguanidine
*Methyl parathion
*Methylthiouracil
Naphthalene
1,4-Naphthoquinone
tl-Naphthylamine
*2-Naphthylamine
tNicotine and salts
154
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p-Nitroaniline
Nitrobenzene
*Nitroglycerine
+4-Nitrophenol
*Nitrosam±ne, N.O.S.
N-Nitrosodi-n-butylamine
*N-Nitrosodiethanolaniine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
*N-Nitroso-N-ethylurea
N-Nitrosomethylethylamine
t*N-Nitroso-N-methylurea
N-Nitroso-N-methylurethane
*N-Nitrosomethylviny1 amine
*N-Nitrosomorpholine
*N-Nitrosonornicotine
*N-Nitrosopiperidine
N-Nitrosopyrrolidine
*N-Nitrososarcosine
*Octamethylpyrophosphoramide
Parathion
Pentachlorobenzene
P ent achloroe thane
*Pentachloronitrobenzene (PCNB)
*Pentachlorophenol
*Phenol
*Phenylenediamine
*Phosphorodithioic acid, 0,0-diethyl
S-((ethylthio)methyl)ester [Phorate]
*Phosphorothioic acid, 0,0-dimethyl
0-(p-((dimethylamino)sulfonyl)
phenyl)ester [Famphur]
*Phthalic acid esters, N.O.S.
Phthalic anhydride
+2-Picoline
Polychlorinated biphenyl, N.O.S.
*Pronamide
*l,3-Propane sulfone
*n-Propylamine
*Propylthiouracil
*Pyridine
*Saccharin and salts
tSafrole
1,2,4,5-Tetrachlorobenzene
**2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)
+*2,3,4,6-Tet rachloropheno1
*Tetraethyldithiopyrophosphate
*Tetraethylpyrophosphate
Toluenediamine
Tolylene diisocyanate
Toxaphene
155
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Apparatus:
Analysis Method Parameters:
GC:
tl,2,4-Trichlorobenzene
*Trichloromethanethiol
+2,4,5-Trichlorophenol
*+2,4,6-Trichlorophenol
*0,0,O-Triethyl phosphorothioate
*sym-Trinitrobenzene
*Tris(2,3-dibromopropyl) phosphate
Finnigan 4000 GC/MS/DS or equivalent
Column - Fused-silica capillary, 25m,
0.31 mm, wall-coated with SE-54
Carrier Gas - He = 2 mL/min
Temperature Program - 40° to 280QC at 10°C min;
280°C, 15 min isothermal
Injector Temperature - 250°C
Injector Type - Splitless
Mass Range - 41 to 450 amu
Scan Rate - <_ 1 s/scan
Ionization -EI, 70 eV
5 -20 ng of each compound injected on-column
(50 ng for mixtures like PCBs)
1 - 4 um/m3 in a 5 m3 stack gas sample
0.25- 1 yg/g in 20g sludge/solid sample
5 -20 yg/L in a 1L aqueous sample
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
U.S. Environmental Protection Agency, Federal Register,
44, 69464-69575 (December 3, 1979).
MS:
Detection Limit:
*The compounds marked (*) are not referenced in EPA Method 625 (19), but
are additional compounds from Appendix VIII to which this method is
expected to apply.
+The compounds marked (t) may also be analyzed by the HPLC techniques
outlined in Methods A122 and A123.
•The compounds marked (•) are volatile enough to be partially swept
from the splitless injector of the GC/MS system along with the
solvent. It is likely that these compounds can be determined, with
some loss of sensitivity, by GC/MS with split injection techniques.
**Special sample preparation and selected ion monitoring (rather than
full mass range scanning) would be necessary for adequate detection
of TCDD.
156
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Method Number:
Method Name:
Basic Method;
Matrix:
Apparatus:
A122
HPLC/UV Generalized Procedure (three options)
HPLC/UV
Sample Extracts
(aqueous or acetonitrile)
HPLC/UV
Constituents from Appendix VIII to which method (Option 1A) may be
applied:
3-(alpha-Acetonylben2yl)-4-hydroxycoumarin
and salts [Warfarin]
6-Amino-l,la,2,8,8a,8b-hexahydro-8-
(tiy dr oicymethy 1) - 8a-roe thoxy- 5-
methylcarbamate azirino[21,3';3,4]
pyrrolo [l,2-a]indole-4,7-dione(ester)
(Mitomycin C)
Chlorambucil
+p-Chloro-m--cresol
+2-Chlorophenol
t2,4-Dichlorophenol
t*2,6-Dichlorophenol
+*2,4-Dinitrophenol
Melphalan
*Methomyl
t4-Nitrophenol
5-Nitro-o-toluidine
Phenol
Reserpine
Streptozotocin
t2,3,4,6-Tetrachlorophenol
Thiuram
t*2,4,5-Trichlorophenol
+2,4,6-Trichlorophenol
Analysis Method Parameters (Option 1A):
HPLC: Column - Perkin-Elmer HC-ODS-Sil-X-1
or equivalent reversed-phase column,
10-vm particle size,
25 cm x 2.6 mm I.D.
Column Temperature - 30°C
Solvent A - Distilled, deionized water
Solvent B - Acetonitrile
157
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Solvent Program - 10% B, 5 min isocratic;
10 to 100% B in 35 min; 100% B, 10 min
isocratic
Solvent Flow Rate - 1 mL/min
UV: At 254 nm (greater sensitivity can be
achieved if compound-specific maximum
wavelengths are used - see Table 20)
Constituents from Appendix VIII to which method (Option IB) may be
applied:
Daunomycin
2,4-Dichlorophenoxyacetic acid
2,4,5-Trichlorophenoxyacetic acid
2,4,5-Trichlorophenoxypropionic acid
Analysis Method Parameters (Option IB):
HPLC: Column - Perkin Elmer HC-ODS-Sil-X-1
or equivalent reversed-phase column,
10-ym particle size,
25 cm x 2.6 mm I.D.
Column Temperature - 30°C
Solvent A - 1% (v/v) acetic acid in
distilled, deionized water
Solvent B - Acetonitrile
Solvent Program - 20% B, 10 min isocratic;
20 to 50% B in 10 min; 50% B, 5 min
isocratic
Solvent Flow Rate - 2 mL/min
UV: At 254 nm (greater sensitivity can be
achieved if compound-specific maximum
wavelengths are used - see Table 20)
Constituent from Appendix VIII to which method (Option 10) may be
applied:
4,6-Dinitro-o-cresol (and salts)
Analysis Method Parameters (Option 1C):
HPLC: Column - Perkin Elmer HC-ODS-Sil-X-1
or equivalent reversed-phase column,
10-ym particle size,
25 cm x 2. 6 mm I.D.
158
-------
Column Temperature - 30°C
Solvent A - 1% (v/v) acetic acid in
distilled, deionized water
Solvent B - Acetonitrile
Solvent Program - 1OX B, 2 min isocratic;
10 to 100% B in 18 min
Solvent Flow Rate - 2 mL/min
UV: At 254 nm (greater sensitivity can be
achieved if compound-specific maximum
wavelengths are used - see Table 20)
Reference: Dillon, H.K., R.H. James, H.C. Miller and A.K. Wensky
(Battelle Columbus Laboratories, Columbus, Ohio),
"POHC Sampling and Analysis Methods," Report prepared for
U.S. Environmental Protection Agency/Industrial Environ-
mental Research Laboratory, Research Triangle Park,
North Carolina by Southern Research Institute, Birmingham,
Alabama under Contract No. 68-02-2685 (December 1981).
*The compounds marked (*) are additional constituents from Appendix VIII
to which this method is expected to apply.
+The compounds marked (t) can also be determined by the GC/MS techniques
in Method A121.
159
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Method Number: A123
Method Name: HPLC/UV Generalized Procedure (three options)
Basic Method: HPLC/UV
Matrix: Sample Extracts
(aqueous or acetonitrile)
Apparatus: HPLC/UV
Constituents from Appendix VIII to which method (Option 2A) may be
applied:
*Azaserine
N-Nitroso-N-methylurea
Analysis Method Parameters (Option 2A):
HPLC: Column - Waters Associates yBondpack-Cjg
or equivalent reversed-phase column,
10-pm particle size,
30 cm x 3.9 mm I.D.
Column Temperature - 30°C
Solvent A - Distilled, deionized water
Solvent B - Acetonitrile
Solvent Program - 2% B, isocratic
Solvent Flow Rate - 1 mL/min
UV: At 254 nm (greater sensitivity can be
achieved if compound-specific maximum
wavelengths are used - see Table 20)
Constituent from Appendix VIII to which method (Option 2B) may be
applied:
Saccharin (and salts)
Analysis Method Parameters (Option 2B):
HPLC: Column - Waters Associates yBondpack-Cjg
or equivalent reversed-phase column,
10-pm particle size,
30 cm x 3.9 mm I.D.
Column Temperature - 30°C
Solvent A - Distilled, deionized water
160
-------
Solvent B - Acetonitrile
Solvent Program - 10% B, isocratic
Solvent Flow Rate - 1 mL/min
UV: At 254 nm (greater sensitivity can be
achieved if compound-specific maximum
wavelengths are used - see Table 20)
Constituents from Appendix VIII to which method (Option 2C) may be
applied:
*l-Acetyl-2-thiourea
*1-(o-Chlorophenyl)thiourea
Cro t ona1dehyde
Diethylstilbestrol (D.E.S.)
3,4-Dihydroxy-alpha-(methylamine)methyl
benzyl alcohol (Epinephrine)
Ethylenethiourea
*l-Naphthyl-2-thiourea
*N-Phenylthiourea
Thioacetamide
Thiosemicarbazide
Thiourea
Trypan blue
Analysis Method Parameters (Option 2C):
HPLC: Column - Waters Associates uBondpack-Cie
or equivalent reversed-phase column
10-um particle size,
30 cm x 3.9 mm I.D.
Solvent A - Distilled, deionized water.
Solvent B - Acetonitrile
Solvent Program - 20 to 100% B in 20 min;
100% B, 10 mia isocratic
Solvent Flow Rate - 1 mL/min
Injection Size - 10 pL
UV: At 254 nm (greater sensitivity can be
achieved if compound-specific maximum
wavelengths are used - see Table 20)
161
-------
Reference: Dillon, H.K., R.H. James, H.C. Miller and A.K. Wensky
(Battelle Columbus Laboratories, Columbus, Ohio), "POHC
Sampling and Analysis Methods," Report prepared for
U.S. Environmental Protection Agency/Industrial Environ-
mental Research Laboratory, Research Triangle Park,
North Carolina by Southern Research Institute, Birmingham,
Alabama under Contract No. 68-02-2685 (December 1981).
*Compounds marked (*) are additional compounds from Appendix VIII to
which this method is expected to apply.
162
-------
Method Number:
Method Name:
Basic Method:
Matrices:
A131
Aldehydes - Derivatization Procedure
Derivatization (DNPH), extraction, and
analysis by either the GC/MS procedures
described in Method A121 or by the HPLC
procedures described in Method A132
Aqueous Liquids (including DNPH Impinger
Reagents)
Sample Extracts
Constituents from Appendix VIII to which method may be applied:
Chloral
Chloroacetaldehyde
Crotonaldehyde
Fo rmaldehyde
Glycidylaldehyde
Paraldehyde
Extraction and Derivatization Method Parameters:
A sample aliquot (20-200 mL) will be taken for derivatization/
extraction. If the matrix is a DNPH impinger reagent which has
been used for collection of aldehydes, it will immediately be
extracted with methylene chloride (100 mL) and n-pentane (100 mL).
If the sample is an aqueous liquid such as a scrubber water or an
extract prepared from a waste stream or comprehensive stack
sampling train, it will be treated by mixing with DNPH reagent
(2,4-Dinitrophenylhydrazine in 2N HC1) for 10 min prior to
extract ion.
After extraction, the combined methylene chloride/pentane layers
will be washed with 2N HC1 and then distilled water. The extracts
will then be evaporated to dryness and the residue dissolved in
2 mL acetonitrile.
These solutions will be analyzed as the DNPH derivatives of the
aldehydes by the GC/MS procedures described in Method A121, or
by the HPLC procedures described in Method A132.
Reference: Kuwata, K., M. Uebori and Y. Yamasaki, "Determination of
Aliphatic and Aromatic Aldehydes in Polluted Airs as
their 2,4-Dinitrophenylhydrazones by High Performance
Liquid Chromatography," J. Chromatogr. Sci., 1J, 26A-268
(1979).
163
-------
Method Number:
A132
Method Name:
Basic Method;
Matrix:
Aldehydes - HPLC Analysis
HPLC/UV
Sample Extracts (after derivatization)
Constituents from Appendix VIII to which method may be applied:
Chloral
Chloroacetaldehyde
Crotonaldehyde
Formaldehyde
Glycidylaldehyde
Paraldehyde
Apparatus:
Analysis Method Parameters:
HPLC:
HPLC/UV
Detection Limit:
Reference:
Column - Zorbax-ODS (250 x 4.6 mm I.D.)
Solvent - 75% CH3OH/25% H20
Detector - At 254 nm or 370 nm
5 -20 ng of each compound injected on-column
1 - 4 vig/m3 in a 5 m3 stack gas sample
5 -20 yg/L in a 1L aqueous sample
0.25- 1 Ug/g in a 20g sludge/solid sample
Kuwata, K. , M Uebori and Y. Yamasaki, "Determination of
Aliphatic and Aromatic Aldehydes in Polluted Airs as
their 2,4-Dinitrophenylhydrazones by High Performance
Liquid Chromatography," J. Chromatogr. Sci.. 17, 264-268
(1979).
164
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Method Number:
A133
Method Name: Carboxylic Acids
Basic Method: Derivatization (followed by GC/MS analysis
using Method A121)
Matrices: Sample Extracts
Organic Liquids (neat or diluted)
Constituents from Appendix VIII to which method may be applied:
2,4-Dichlorophenoxyacetic acid (2,4-D)
Formic acid
7-0xabicyclo[2.2.l]heptane-2,3-dicarboxylic
acid
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4,5-Trichlorophenoxypropionic acid
(2,4,5-TP) (Silvex)
Derivatization Techniques:
Hydrolysis
Distilled water (15 mL) and 75% (w/v) aqueous potassium hydroxide
(2 mL) will be added to a Kuderna-Danish (K-D) flask containing
the waste sample extract. The extract will be heated on a hot
water bath for a total of 60 min. The concentrate will be
transferred to a 60-mL separatory funnel, acidified with cold
(4°C) 25% H2SO4 (2 mL), and extracted once with diethyl ether
(10 mL).
The extract will then be transferred to a 125-mL erlenmeyer flask
containing sodium sulfate and be allowed to stand for approximately
two hours.
Esterification
The ether extract will be transferred through a funnel plugged
with glass wool into a (K-D) flask equipped with a 10-mL graduated
receiver, with liberal washings of ether. Any caked sodium sulfate
will be crushed with a glass rod. The acids in the extract will
be esterified using either diazomethane or boron trifluoride.
Diazomethane: The extract will be evaporated to 4 mL. An aliquot
(2 mL) of diazomethane will be added to the extract. The mixture
will stand for 10 min with occasional swirling and subsequently
rinsed with diethyl ether.
165
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Boron Trifluoride: An aliquot (0.5 mL) of benzene will be added to
the ether extract. The extract and benzene will be evaporated to
0.5 mL. The ampule will be removed and further concentrated to
0.4 mL using a two-ball microSnyder column. After cooling, boron
trifluoride methanol reagent (0.5 mL) will be added to the benzene
solution. This mixture will be held at 50°C for 30 min on the
steam bath. After cooling, neutral, 5% sodium sulfate (4.5 mL)
will be added, and the flask stoppered, shaken, and allowed to
stand for three min for phase separation. The solvent layer
will be transferred to a small column packed with 2.0 cm sodium
sulfate over 1.5 cm florisil adsorbent and eluted with benzene.
The final eluent volume will be adjusted to 5 mL with benzene.
The extracts will be analyzed as the methyl esters of the carboxylic
acids using the GC/MS procedures described in Method A121.
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Smith, A.E., "Use of Acetonitrile for the Extractions of
Herbicide Residues from Soils," J. of Chrom.. 129, 309-
314 (1976).
166
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Method Number:
MeChod Name:
Basic Method:
Matrices:
A134
Alcohols
GC/FID, GC/MS
Aqueous Liquids
Organic Liquids (neat or diluted)
Constituents from Appendix VIII to which method may be applied:
Allyl alcohol
Isobutyl alcohol
2-Propyn-l-ol
Resorcinol
Apparatus:
GC:
GC/MS/DS CFinnigan 4000 or equivalent)
Column - Carbopack C + 0.8% THEED
(tetrahydroxyethylenediamine) packed in
55 cm x 0.2 cm I.D. glass column
Carrier Gas - He
Temperature Program - 115°C isothermal
-or-
Column - Fused silica capillary, 30 m x 0.25 mm,
wall coated with Carbowax 20M or SE-54
Carrier Gas - He
Mass Range - 42-450 amu
Scan Rate - 1-1.5 s/sca'n
Ionization - EI, 70 eV
5 -20 ng of each compound, injected on-column
1 - 4 ug/m3 of each compound (in a 5 m3 stack
gas sample)
5 -20 ug/L of each compound (in a 1L aqueous
sample)
0.25- 1 ug/g of each compound (in a 20g sludge/
solid sample)
Reference: DiCorcia, A. and R. Samperi, "Gas Chromatographic Determination
of Glycols at the Parts-Per-Million Level in Water by
Graphitized Carbon Black," Anal. Chem., 51 776-778 (1979).
MS:
Detection Limit:
167
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Method Number:
A136
Method Name: Phosphine
Basic Method: GC/FPD
Matrix: Gas
Constituent from Appendix VIII to which method may be applied:
Phosphine
Apparatus: GC/FPD
Analysis Method Parameters:
Column - 3% Carbowax 20M, 100/120 Gas Chrom Q
Flame Photometric Detector
Detection Limit: 1 pg/mL
Reference: Berck, B., W.E. Westlake and F.A. Gunter, "Microdetermination
of Phosphine by Gas-Liquid Chromatography with Microcoulometric,
Thermionic and Flame Photometric Detection," J. Agric. Food
Chem., 18, 143-147 (1970).
168
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Method Number:
A137
Method Name:
Fluorine
Matrix:
Gas
It has riot been possible to obtain an analysis method for the
specific determination of free fluorine (Fj) that can be
recommended with confidence. Total fluorides may be determined
by the procedures outlined in EPA Method 13 (40 C.F.R. Part 60,
Appendix A).
A proposed method (Engineering Report No. G115B, Matheson Gas
Products) for the sampling and analysis of fluorine involves
pre-scrubbing the air stream to remove HF, and then collecting
fluorine in dilute base contained in a bubbler. Hydrolysis of the
fluorine in the scrubber would result in a solution containing
fluoride (as F ) which could be measured by the ion chromatographic
technique, outlined in Method A251.
169
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Method Number: A138
Method Name: Gases - Cyanogens and Phosgene
Basic Method: GC/TGD, GC/ECD (for CI),
GC/AFID (for N)
Matrix: Gas
Constituents from Appendix VIII to which method may be applied:
Cyanogen
Cyanogen Bromide
Cyanogen Chloride
Phosgene
Apparatus: GC/TCD, GC/ECD, GC/FPD equipped with a
gas sampling loop for sample introduction
Analysis Method Parameters:
Column - Kel-F 40, Nickel Tubing
(10 ft x 1/4 in)
Detection Limit: 10 ug/L
Reference: Heftman, E. (ed.)> Chromatography - A Laboratory Handbook
of Chromatographic and Electrophoretic Methods, 3rd ed.,
Van Nostrand Reinhold Company, New York (1975).
170
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Method Number: A.139
Method Name: Gases - Mustards
Basic Method: GC/FPD
Matrix: Gas
Constituents from Appendix VIII to which method may be applied:
Mustard Gas
Nitrogen Mustard (and hydrochloride salt)
Nitrogen Mustard N-Oxide (and hydrochloride
salt)
Apparatus: GC/Flatne Photometric Detector in Sulfur
Mode
Bubblers to collect air samples
Analysis Method Parameters:
GC: Column - 10% QF-1 on 80/100 Chromosorb W-HP
Detection Limit: 0.2 yg/mL
Reference: Hudson, R., "U.S. Army Toxic and Hazardous Materials
Agency Report," Aberdeen Proving Ground, Maryland,
Report No. 7509. (December 1975).
171
-------
Method Number: A141
Method Name: Gases
Basic Method: GC/TCD, GC/AFID(N)
GC/FPD(S)
Matrix: Gas
Constituents from Appendix VIII to which method may be applied:
Carbon disulfide
Hydrazine
Hydrocyanic acid
Hydrogen sulfide
Nitric oxide
Nitrogen dioxide
Apparatus: GC/TCD, GC/AFID(N), GC/FPD(S)
Analysis Method Parameters:
GC: Column - Porapak Q
Detection Limit: 10 pg/L
Reference: Waters Associates, Framingham, Massachusetts, "Porapak
Resin."
172
-------
Method Number:
A144
Method Name:
Acid Chlorides
Matrix:
Gas
Constituents from Appendix VIII to which method may be applied:
It has not been possible to obtain an analysis method that can
be recommended with confidence for acid chlorides. A reference
to a colorimetric analysis method is provided. However, farther
research would be needed to validate this method within the
context of the matrices which are involved.
It seems unlikely that acetyl chloride, or dimethylcarbamoyl
chloride would survive within stack gas effluent streams because
of the high concentration of water in these streams.
Reference: Kostyukovskii, Y.L., "Rapid Method for Determining Vapors
of Organic Acid Halides in Air," Zh. Anal. Khim, 25
2228-2230 (1970).
Acetyl chloride
Dimethylcarbamoyl chloride
173
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Method Number:
A145
Method Name: Aflatoxins
Basic Method: HPLC/Fluorescence
Matrices: Sample Extracts
Organic Liquids (neat or diluted)
Constituents from Appendix VIII to which method may be applied:
Aflatoxins
Apparatus: HPLC
Analysis Method Parameters:
LC: Column - Sperisorb ODS
Solvent - H2O or acetonitrile/methanol (3:2)
Fluorimeter: A 365 nm
excitation
A . . - 400 nm
emmision
Detection Limit: <0.5 ppb (detected in dairy products)
References: Beebe, R.M. and D.M. Takahashi, "Determination of Aflatoxin
Mi by High-Pressure Liquid Chromatography Using Fluorescence
Detection," J. Agric. Food Chem., 28, 481-482 (1980).
Gregory, J.F. Ill and D. Manley, "High Performance Liquid
Chromatographic Determination of Aflatoxins in Animal
Tissues and Products," J. Assoc. Off. Anal. Chem., 64
144-151 (1981).
174
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Method Number:
Method Name:
Basic Method:
Matrices:
A148
Brucine
GC/FID
Sample Extracts
Organic. Liquids (neat or diluted)
Constituent from Appendix VIII to which method may be applied:
Brucine
GC/FID
Apparatus:
Analysis Method Parameters:
GC:
Column - Fused-silica capillary, 30 m x 0.25 mm
I.D., wall-coated with SE-52
Carrier Gas - He at 2 inL/min
Temperature Program - 102° to 300°C at 8°C/min;
300°C, 32 min isothermal
FID:
Detection Limit:
Injector Temperature
Detector Temperature
5-20 ng
300 °C
300° C
Reference: Wensky, A.K., Battelle Columbus Laboratories, Columbus,
Ohio, personal communication (January 21, 1982).
175
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Method Number:
A149
Method Name:
Basic Method:
Matrices:
Citrus Red No. 2
HPLC
Sample Extracts
Organic Liquids (neat or diluted)
Constituent from Appendix VIII to which method may be applied:
Citrus Red No. 2
Apparatus: HPLC/UV
Analysis Method Parameters:
HPLC: Column - OXS-1025 ODS-2
Solvent - Methanol/Water gradient
(Tetrabutylammonium phosphate as a
counter ion)
At 254 nm
(It is possible that Citrus Red No. 2
could be analyzed by one of the options
described in Method A122 or Method A123.)
UV:
Reference:
Gloor, R. and E.L. Johnson, "Practical Aspects of Reverse-
Phase Ion Pair Chromatography," J. Chromatog. Sci. , 15
413-432 (1977).
176
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Method Number:
A150
Method Name:
Cycasin
Matrices:
Sample Extracts
Organic Liquids (neat or diluted)
It has not been possible to obtain an analysis method that can
be recommended with confidence for Cycasin within the sample
matrices involved. A reference is provided below, however further
research would be needed to either validate this method or develop
a new method.
(It is possible that Cycasin could be determined by one of the
options for HPLC in either Method A122 or Method A123.)
Reference: "Simultaneous Detection of Cycasin, Methylazoxymethanol
and Formaldehyde by HPLC," Agric. Biol. Chem., 44,
1423-1425 (1980).
177
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Method Number: A156
Method Name: Ethylene Oxide
Basic Method: GC/FID
Matrix: Gas
Constituent from Appendix VIII to which method may be applied:
Ethylene oxide
Apparatus: GC/FID
Analysis Method Parameters:
GC: Column - 5% Carbowax 20M
Detection Limit: 0.1 mg
References: Greve, P.A. and E.A. Hogendoorn, "Determination of Fumigant
Residues in Grain," Meded. Fac. Landbouwwet., Rijksuniv.
Gent, 44, 877-884 (1979).
Bicchi, C. and S. Mina, "An Improved Method for the Deter-
mination of Low Amounts of Ethylene Oxide in Surgical
Plastics," Farmaco, Ed. Prat., 35, 632-641 (1980).
178
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Method Number:
Method Name:
Basic Method:
Matrices:
A157
2-Fluoroacetamide
GC/FID
Sample Extracts
Organic Liquids (neat or diluted)
Constituent from Appendix VIII to which method may be applied:
2-Fluoroacetamide
Apparatus: GC/FID
Analysis Method Parameters:
GC: Column - Chromosorb 101 (100/120 mesh)
1.8 m x 2 mm I.D.
Carrier Gas - He at 30 mL/min
Temperature Program - 155°C, isothermal
^ 20 ng
Detection Limit:
Reference: Warner, J.S. and M.C. Landes, Internal Communication,
Battelle Columbus Laboratories, Columbus, Ohio,
(November 10, 1981).
179
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Method Number:
A160
Method Name:
Lasiocarpine
Matrices:
Sample Extracts
Organic Liquids (neat or diluted)
It has not been possible to obtain an analysis method that can be
recommended with confidence. References to a colorimetric
analysis method are provided. However, further research would
be needed to validate the method within the context of the sample
matrices involved or to develop a new method.
References: Mattocks, A.R., "Spectrophotometric Determination of
Pyrrolizidine Alkaloids - Some Improvements," Anal.
Chem., 40, 1749-1750 (1968).
Mattocks, A.R., "Spectrophotometric Determination of
Unsaturated Pyrrolizidine Alkaloids," Anal. Chem., 39
443-447 (1967).
180
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Method Number:
AI74
Method Name:
Basic Method:
Matrices:
Phenacetin
HPLC/UV
Sample Extracts
Organic Liquids (neat or diluted)
Constituent from Appendix VIII to which method may be applied:
Phenacetin
Apparatus: HPLC/UV
Analysis Method Parameters:
HPLC: Column - LiChrosorb KP-18
Solvent - Acetonitrile/O.IN acetate buffer
0.1 ug
Detection Limit:
Reference: Ohamoto, M. , F. Yanada, M. Ishiguro and A. Umemura, "Liquid
Chromatographic Method for Determination of Phenacetin in
Serum by HPLC," Gifu-Kien Eisei Keukyusho Ho, 25, 38-40
(1980).
181
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Method Number:
A180
Method Name: Strychnine
Basic Method: HPLC
Matrices: Sample Extracts
Organic Liquids (neat or diluted)
Constituent from Appendix VIII to which method may be applied:
Strychnine (and salts)
Apparatus: HPLC/UV
Analysis Method Parameters:
HPLC: Column - n-Propyl sulfonic acid modified
silica
Solvent - Methanol/2M NHi+NC^ (27:2)
References: Wheals, B.B., "Isocratic Multi-Column High-Performance
Liquid Chromatography as a Technique for Qualitative
Analysis and its Application to the Characteristics of
Basic Drugs Using an Aqueous Methanol Solvent,"
J. Chromatogr., 187, 65-85 (1980).
Lurie, I.S. and S.M. Demchuk, "Optimization of a Reverse
Phase Ion-Pair Chromatographic Separation for Drugs of
Forensic Interest. Part I. Variables Effecting
Capacity Factors," J. Liq. Chromatogr., _4, 337-355 (1981).
182
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Method Number: A183
Method Name: Oximes
Basic Method: GC/FPD
Matrices: Sample Extracts
Organic Liquids (neat or diluted)
Constituents from Appendix VIII to which method may be applied:
3,3-Dimethyl-l(methylthio)-2-butanone-0-
(methylamino carbonyl)oxime [Thiofanox]
2-Methyl-2-(methylthio)propionaldehyde-0-
(methylcarbonyl)oxime
Apparatus: GC/FPD
Analysis Method Parameters:
The sample will be derivatized with Trimethylphenylammonium
hydroxide prior to analysis.
GC: Column - 1.5% OV-17/1.95% OV-210 or
6% DC-200
Carrier Gas - 80 mL/min
Temperature Program - 185°C isothermal
-or-
Column - 0.5% Carbowax-20M/5% SE-30
Carrier Gas - 60 mL/min
Temperature Program - 210°C isothermal
References: DeMey, W., W.J. Pauwels and D.E. Stallard, "Determination of
Thiofanox Residues in Sugar Beet Roots and Tops Over a
Three-Year Period in Eight European Countries," Meded. Fac.
Landbouwwet Rijksuniv. Gent. 42, 1763-1778 (1977).
Chin, W.T., W.C. Duane, M.B. Szalkowski and D.E. Stallard,
"Gas Chromatographic Determination of Thiofanox Residues
in Soil, Plants, and Water," J. Agric. Food Chem., 23,
963-966 (1975).
t
Bromilow, R.H. and K.A. Lord, "Analysis of Sulfur-Containing
Carbamates by Formation of Derivatives in the Gas-Liquid
Chromatograph Using Trimethylphenylammonium Hydroxide,"
J. Chromatogr.. 125. 495-502 (1976).
183
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Method Number: A190
Method Name: Tris(l-aziridinyl)phosphine sulfide
Basic Method: GC/FPD
Matrix: Gas
Constituent from Appendix VIII to which method may be applied:
Tris(1-aziridinyl)phosphine sulfide
Analysis Method Parameters:
GC: Column - 3% Dexsil 410
Carrier Gas - He at 20 mL/min
Temperature Program - 140°C isothermal
FPD: At 526 nm, phosphorus mode
Reference: Carlson, D.A. and D.L. Bailey, "Determination of Mosquito
Chemosterilant Recovered from Air During Real and Simulated
Use," J. Agric. Food Chem., 29, 78-82 (1981).
184
-------
Method Number:
A221
Method Name:
Basic Method:
Matrices:
Antimony
ICAP Spectroscopy
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituent from Appendix VIII to which method may be applied:
Antimony and compounds, N.O.S.
Apparatus:
Analysis Method Parameters:
ICAP:
AA:
ICAP Spectrophotometer
AA Spectrophotometer
Hydride generator
Graphite furnace
Sample input via direct aspiration of
solution
Analytical Wavelengths - 206.8 and 187.1 nm
Analytical Wavelength - 217.6 nm
206.8 nm (or
231.1 nm if Pb is
present at high
concentration)
Furnace Parameters - Dry @ 125°C for 30s
Ash @ 800°C for 30s
Atomize @ 2700°C for 10s
Argon purge
Background correction
Flame Conditions - Air/acetylene
Fuel lean
Detection Limit (Typical Working Range):
ICAP:
Furnace AA:
Flame AA:
0.1 mg/L (0.5-300 mg/L and less if hydride
generator is used)
3 yg/L (20-300 yg/L)
0.2 mg/L (1-40 mg/L)
185
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References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
186
-------
Method Number:
A222
Method Name:
Basic Method:
Matrices:
Arsenic
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Arsenic and compounds, N.O.S.
Arsenic acid
Arsenic pentoxide
Arsenic trioxide
Benzenearsonic acid
Dichlorophenylarsine
Diethylarsine
Hydroxydimethylarsine oxide
Apparatus:
Analysis Method Parameters:
Hydride Generation:
AA:
AA spectrophotometer
Hydride generator
Graphite furnace
In the generator SnCl2 will be added to
form trivalent arsenic, and then zinc
added to form the hydride. (NaBH^ can
also be used to generate the hydride.)
Analytical Wavelength - 193.7 nm
Furnace Parameters - Dry @ 125°C for 30s
Ash @ 1100°C for 30s
(if nickel has been
added to prevent
atomization of arsenic)
Atomize @ 2700°C for 10s
Argon purge
Background correction
Flame Conditions - Argon/hydrogen
Detection Limit (Typical Working Range):
Hydride AA: >1 yg/L (2- 20 yg/L)
Furnace AA: 1 ug/L (5-100 yg/L)
187
-------
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
188
-------
Method Number:
A223
Method Name:
Basic Method:
Matrices:
Barium
ICAP Spectroscopy
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Barium and compounds, N.O.S.
Barium cyanide
Apparatus: ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Analysis Method Parameters:
ICAP:
AA:
Sample input via direct aspiration of
solution
Analytical Wavelengths - 455.4 and 233.5 nm
Analytical Wavelength - 553.6 nm
Furnace Parameters - Dry @ 125°C for 30s
Ash 0 1200°C for 30s
Atomize @ 2800°C for 10s
Argon purge
Background correction
(Tungsten Iodide lamp)
Flame Conditions - Nitrous oxide/acetylene
Fuel rich
Detection Limit (Typical Working Range):
ICAP: 2 ug/L (0.01-10 mg/L)
Furnace AA: 2 Ug/L (10-200 yg/L)
Flame AA: 0.1 mg/L (1-20 mg/L)
189
-------
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
190
-------
Method Number: A224
Method Name: Beryllium
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Beryllium and compounds, N.O.S.
Apparatus: ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Analysis Method Parameters:
ICAP: Sample input via direct aspiration of
solution
Analytical Wavelengths - 313.0 and 234.9 nm
AA: Analytical Wavelength - 234.9 nm
Furnace Parameters - Dry @ 125°C for 30s
Ash @ 1000°C for 30s
Atomize @ 2800°C for 10s
Argon purge
Background correction
Flame Conditions - Nitrous oxide/acetylene
Fuel rich
Detection Limit (Typical Working Range):
ICAP: 0.5 ug/L (0.005- 5 mg/L)
Furnace AA: 0.2 ug/L (1 - 30 ug/L)
Flame AA: 5 yg/L (0.05 - 2 mg/L)
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis of
Water and Wastes," EPA-600/4-79-020 (March 1979).
NT1S No. PB297686/AS.
191
-------
Method Number:
Method Name:
Basic Method:
Matrices:
A225
Cadmium
ICAP Spectroscopy
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Cadmium and compounds, N.O.S.
Apparatus:
Analysis Method Parameters:
ICAP:
AA:
ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Sample input via direct aspiration of
solution
Analytical Wavelengths - 226.5 and 214.4 nm
Analytical Wavelength - 228.8 nm
Furnace Parameters - Dry @ 125°C for 30s
Ash @ 500°C for 30s
Atomize @ 1900°C for 10s
Argon purge
Flame Conditions - Air/acetylene
Fuel rich
Detection Limit (Typical Working Range):
ICAP: 0.05 mg/L (0.2- 50 mg/L)
Furnace AA: 1 Mg/L (5 -100 Pg/L)
Flame AA: 0.05 mg/L (0.5- 10 mg/L)
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste ¦
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
192
-------
Method Number:
A226
Method Name:
Basic Method:
Matrices:
Chromium
ICAP Spectroscopy
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Chromium and compounds, N.0.S.
Calcium chromate
Apparatus:
Analysis Method Parameters;
ICAP:
M:
ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Sample input via direct aspiration of
solution
Analytical Wavelengths - 267.7 and 294.9 nm
Analytical Wavelength - 35 7.9 nm
Furnace Parameters - Dry @ 125°C for 30s
Ash @ 1000°C for 30s
Atomize @ 2 700°C for 10s
Argon purge
Flame Conditions - Nitrous oxide/acetylene
Fuel rich
Detection Limit (Typical Working Range):
ICAP: 0.05 mg/L (0.2- 50 mg/L)
Furnace AA: 1 yg/L (5 -100 yg/L)
Flame AA: 0.5 mg/L (0.5- 10 mg/L)
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis of
Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
193
-------
Method Number:
A22 7
Method Name:
Basic Method:
Matrices:
Lead
Atomic Absorption Spectroscopy
ICAP Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Lead and compounds, N.O.S.
Lead acetate
Lead phosphate
Lead subacetate
Tetraethyl lead
Apparatus:
Analysis Method Parameters:
ICAP:
AA:
ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Sample input via direct aspiration of
solution
Analytical Wavelengths - 220.3 and 217.0 nm
Analytical Wavelength - 217.0 nm
Furnace Parameters - Dry @ 125°C for 30s
Ash 0 500°C for 30s
Atomize @ 2700°C for 10s
Argon purge
Background correction
Flame Conditions - Acetylene/air
Oxidizing
Detection Limit (Typical Working Range):
ICAP: 0.1 mg/L (1-100 mg/L)
Furnace AA: 1 yg/L (5-100 Ug/L)
Flame AA: 0.1 mg/L (1- 20 mg/L)
194
-------
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
195
-------
Method Number:
A228
Method Name:
Mercury
Basic Method:
Cold Vapor/Atomic Absorption Spectroscopy
Matrices:
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Mercury fulminate
Mercury and compounds, N.O.S.
Phenylmercury acetate
Apparatus:
AA spectrophotometer
Cold vapor apparatus (Figure 9)
Analysis Method Parameters:
AA:
Analytical Wavelength - 25 3 nm
In a closed system, the sample will be pretreated at 95°C in a
water bath with HaSO^, HN03-potassium permanganate solution and
potassium persulfate to digest the sample. Excess permanganate
will be removed with sodium chloride-hydroxylamine sulfate. SnCl2
will be added to the cooled solution and mercury signal measured
while air is recirculating at 1 L/min.
Detection Limit (Typical Working Range):
Cold Vapor/AA: 0.2 yg/L (0.2-40 Ug/L)
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis of
Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
196
-------
o
AIR PUMP
DESICCANT
~
r"—"1
BUBBLER
ABSORPTION
CELL
SAMPLE SOLUTION
IN BOD BOTTLE
XI
~
SCRUBBER
CONTAINING
A MERCURY
ABSORBING
MEDIA
FIGURE 9 APPARATUS FOR FLAMELESS MERCURY DETERMINATION
197
-------
Method Number:
Method Name:
Basic Method:
Matrices:
A229
Nickel
ICAP Spectroscopy
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Nickel and compounds, N.O.S.
Nickel carbonyl
Nickel cyanide
Apparatus: ICAP spectrophotometer
AA spectrophotometer with burner
Graphite furnace
Analysis Method Parameters:
ICAP:
AA:
Sample input via direct aspiration of
solution
Analytical Wavelengths - 231.6 and 227.0 nm
Analytical Wavelength - 232.0 nm
Furnace Parameters
Dry @ 125°C for 30s
Ash @ 900°C for 30s
Atomize @ 2700°C for 10s
Argon purge
Background correction
Flame Conditions - Air/acetylene
Oxidizing
Detection Limit (Typical Working Range):
ICAP: 0.04 mg/L (0.1- 50 mg/L)
Furnace AA: 1 Pg/L (5 -100 Mg/L)
Flame AA: 0.04 mg/L (0.3- 5 mg/L)
198
-------
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis of
Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
199
-------
Method Number: A230
Method Name: Osmium
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituent from Appendix VIII to which method may be applied:
Osmium tetroxide
Apparatus: ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Analysis Method Parameters:
ICAP: Sample input via direct aspiration of
sample solution
Analytical Wavelengths - 225.6 and 189.8 nm
AA: Analytical Wavelength - 290.9 nm
Furnace Parameters - Dry @ 105°C for 30s
Ash @ <140°C* for 30s
Atomize @ 2700°C for 10s
Argon purge
Flame Conditions - Nitrous oxide/acetylene
Fuel rich
Detection Limit (Typical Working Range):
ICAP: 5 ug/L ( 0.010- 10 mg/L)
Furnace AA: 20 pg/L (50 -500 pg/L)
Flame AA: 0.3 mg/L ( 2 -100 mg/L)
^OsO^ vaporizes at ca. 150°C.
200
-------
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis of
Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
201
-------
Method Number:
A231
Method Name:
Basic Method:
Matrices:
Selenium
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Selenious acid
Selenium and compounds, N.O.S.
Selenium sulfide
Selenourea
Apparatus:
Analysis Method Parameters:
Hydride Generation:
AA:
AA spectrophotometer
Hydride generator
Graphite furnace
In generator SnCl2 will be added to form
trivalent arsenic, and then zinc added to
form the hydride. (NaBH^ can also be used
to generate the hydride.)
Analytical Wavelength - 196.0 nm
Furnace Parameters - Dry @ 125°C for 30s
Ash @ 1200°C for 30s
Atomize @ 2700°C for 10s
Argon purge
Background correction
Flame Conditions - Argon/hydrogen
Detection Limit (Typical Working Range):
Hydride AA: >1 Pg/L (2- 20 ug/L)
Furnace AA: 2 pg/L (5-100 pg/L)
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
202
-------
Method Number: A232
Method Name: Silver
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied
Potassium silver cyanide
Silver and compounds, N.O.S.
Silver cyanide
Apparatus: ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Analysis Method Parameters:
ICAP: Sample input via direct aspiration of
solution
Analytical Wavelengths - 328.1 and 224.6 nm
AA: Analytical Wavelength - 328.1 nm
Furnace Parameters - Dry @ 125"C for 30s
Ash @ 400°C for 30s
Atomize 0 2700°C for 10s
Argon purge
Background correction
Flame Conditions - Acetylene/air
Oxidizing
Detection Limit (Typical Working Range):
ICAP: 0.01 mg/L (0.1 -50 mg/L)
Furnace AA: 0.2 ug/L (1 -25 ug/L)
Flame AA: 0.01 mg/L (0.14- 4 mg/L)
203
-------
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
204
-------
Method Number:
Method Name:
Basic Method:
Matrices:
A233
Strontium
ICAP Spectroscopy
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituent from Appendix VIII to which method may be applied:
Strontium sulfide
Apparatus:
Analysis Method Parameters;
ICAP:
AA:
ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Sample input via direct aspiration of
solution
Analytical Wavelengths - 407.8 and 346.4 nm
Analytical Wavelength - 460.7 nm
Furnace Parameters - Dry (? 125 °C for 30s
Ash
-------
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
206
-------
Method Number:
Method Name:
Basic Method:
Matrices:
A234
Thallium
ICAP Spectroscopy
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Thallium and compounds, N.O.S.
Thallic oxide
Thallium(I)acetate
Thallium(I)carb onat e
Thallium(I)chloride
Thallium(I)nitrate
Thallium selenite
Thallium(I)sulfate
Apparatus:
Analysis Method Parameters:
ICAP:
AA:
ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Sample input via direct aspiration of
solution
Analytical Wavelengths - 190.9 and 351.9 nm
Analytical Wavelength - 276.8 nm
Furnace Parameters - Dry @ 125°C for 30s
Ash @ 400°C for 30s
Atomize @ 2400°C for 10s
Argon purge
Background correction
Flame Conditions - Air/acetylene
Oxidizing
Detection Limit (Typical Working Range):
ICAP: 0.1 mg/L (1-100 mg/L)
Furnace AA: 1 pg/L (5-100 pg/L)
Flame AA: 0.1 mg/L (1- 20 mg/L)
207
-------
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
208
-------
Method Number:
A235
Method Name:
Basic Method:
Matrices:
Vanadium
ICAP Spectroscopy
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Vanadic acid, ammonium salt
Vanadium pentoxide
Apparatus:
Analysis Method Parameters:
ICAP:
AA:
ICAP spectrophotometer
AA spectrophotometer
Graphite furnace
Sample input via direct aspiration of
solution
Analytical Wavelengths - 309.3 and 214.0 nm
Analytical Wavelength - 318.4 nm
Furnace Parameters - Dry @ 125°C for 30s
Ash
-------
Method Number:
A251
Method Name:
Anions
Basic Method:
Ion Chromatography
Matrices:
Aqueous Liquids
Sludges
Sample Extracts
Constituents from Appendix VIII to which method may be applied:
Hydrocyanic acid
Hydrofluoric acid
Apparatus:
Ion chromatograph
Electrochemical detector
Analysis Method Parameters:
There are many methods which involve ion chromatography for the
analysis of anions available in the literature.
One method involves eluting anions from a 500 mm anion separator
column and an anion suppressor with a 0.003M NaHCOj/O.0024M Na2C0 3
solution. This suppressor column must be regenerated every 20 hours
of operation with a IN aqueous ^SO^ solution.
Reference: Small, H., T.S. Stevens and W.C. Baumar, "Novel Ion
Exchange Chromatographic Method Using Conductimetric
Detection," Anal. Chem., 47, 1801-1809 (1975).
210
-------
Method Number:
Method Name:
Basic Method:
Matrices:
A252
Total Cyanides
Titration
Colorimetry
Aqueous Liquids
Organic Liquids
Sludges
Solids
Constituents from Appendix VIII to which method may be applied:
Apparatus:
Analysis Method Parameters:
Barium cyanide
Calcium cyanide
Copper cyanide
Cyanides, N.O.S.
Ethyl cyanide
Nickel cyanide
Potassium cyanide
Potassium silver cyanide
Silver cyanide
Sodium cyanide
Zinc cyanide
Spectrophotometer
Microburet
Cyanide distillation apparatus
Sample Preparation: Oxidizing agents (indicated by Kl-starch
test paper) will be removed with ascorbic
acid.
Sulfides (indicated by lead acetate test
paper) will be removed with cadmium
carbonate.
Fatty acids will be removed in a single
extraction with hexane at pH 6 to 7.
Following the extraction, the pH of the
solution will be raised above 12.
211
-------
HCN Collection: A vacuum will be adjusted to draw ca.
1 bubble/s through flask, gas will be
collected continuously from prior
to adding acid to 15 min after removal
of heat.
The total cyanide concentration may be determined by either of the
following methods:
Titration
The solution will be titrated with standard silver nitrate in the
presence of benzalrhodamine indicator to first color change from
yellow to brownish pink.
Colorimetry
To solution, Chloramine T will be added and the solution mixed
thoroughly. After 1-2 min, pyridine-barbituric acid solution
will be added, the adsorbance read at 578 nm after start of color
development (8-15 min).
Or after 1-2 min, pyridine-pyrazolone solution can be added and
the absorbance read at 620 nm after 40 min.
Detection Limit (Typical Working Range):
Titration: 0.3 mg/L (>1 mg/L)
Colorimetry: 0.01 mg/L(0.02-l mg/L)
References: U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979).
NTIS No. PB297686/AS.
212
-------
Method Number:
A253
Method Name:
Basic Method:
Matrix;
Phosphides
GC/FPD
Solids
Constituents from Appendix VIII to which method may be applied:
Apparatus:
Analysis Method Parameters:
Sample Preparation:
GC:
Detection Limit:
Aluminum phosphide
Zinc phosphate
Gas Chromatograph/Flame Photometric Detector
One-liter calibrated gas flasks
A sample will be placed into a calibrated
gas flask, flushed with 99-99% % and dilute
acid (0.01N HNOj) added. A measured amount
of N2 from a second calibrated gas flask
will then be replaced with equilibrated
phosphine-containing gas.
Column - 3% Carbowax 20M on Gas Chrom Q.
10 yg/L
Reference: Berck, B., W.E. Westlake and 1J.A. Gunter, "Microdetermination
of Phosphine by Gas-Liquid Chromatography with Microcoulometric,
Thermionic, and Flame Photometric Detection," J. Agric. Food
Chem. , 18, 143-14 7 (1970).
213
-------
It has been impossible to find an analysis method which can be
recommended with confidence for the following constituents
from Appendix VIII:
Cyclophosphamide
Ethylenebisdithlocarbamic acid (salts and
esters)
Iron dextran
Methyl chlorocarbonate
4-Nitroquinoline-l-oxide
o-Toluidine hydrochloride
Uracil mustard
214
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VII. QUALITY ASSURANCE AND QUALITY CONTROL PROCEDURES
A. OVERVIEW
A vital part of any sampling and analysis program is the provision for
procedures which maintain the quality of the data obtained throughout
the sampling and analysis exercise. These procedures, termed quality
assurance and quality control (QA/QC), serve to (1) document the quality
(i.e., accuracy and precision) of the generated data; (2) maintain the
quality of the data within predetermined tolerance limits for specific
sampling and analysis procedures; and (3) provide guidelines for corrective
actions if the QC data indicate that a particular procedure is out of
control. It should be noted that, at this stage in the development of the
hazardous waste incineration program, predetermined tolerance limits for
the overall precision and accuracy of the recommended sampling and analysis
procedures have not been established. Tolerance limits may be established
as experience with trial burns accumulates and a data base is generated.
In this section, specific QA/QC procedures are described. For any
individual sampling and analysis program, these procedures and others may
be selected to reach the goal of obtaining high-quality data. At a
minimum, the procedures which are selected must be consistent with the
standard operating procedures and/or good laboratory practices of the
sampling crew and analytical laboratory involved.
The fcollowing definitions, which represent interdependent activities,
serve to differentiate between the complementary activities of QA and QC.
• Quality Assurance (QA) activities address delegation of program
responsibilities to individuals, documentation, data review,
and audits. The objective of QA procedures is to permit an
assessment of the reliability of the data.
• Quality Control (QC) activities address the maintenance of
facilities, equipment, personnel training, sample integrity,
chemical analysis methods, and production and review of QC
data. QC procedures are used continuously during a sampling
and analysis program to maintain the quality of data within
predetermined limits. QC data are immediately evaluated by
the analysts and if the QC data fall outside of their pre-
determined (tolerance) limits, corrective actions specified
in the work plan are taken.
The following discussion of QA/QC procedures is based upon a guidelines
document (24) issued by the Office of Monitoring Systems and Quality
Assurance of the EPA Office of Research and Development. That document,
QAMS-005/80, entitled "Interim Guidelines and Specifications for Pre-
paring Quality Assurance Project Plans," and the references cited
215
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therein provide an extensive resource for the permit applicant and the
permit writer in selecting the appropriate QA/QC procedures for the
sampling and analysis effort in a particular trial burn and/or operating
burn.
This section of the report presents a brief description of the essential
elements of a QA project plan. The guidelines presented here are intended
to be sufficient to allow the permit writer to select the features that
must be treated in detail for any particular trial burn. It should be
noted that these guidelines are necessarily general and would not, in
themselves, suffice as a QA plan for a specific project. In each case,
it would be necessary to develop a specific plan that addresses the
specific POHCs, necessary detection limits for the 99.99 percent DRE,
waste feed sampling frequency, and the like.
The QAMS-005/80 document has identified sixteen essential elements of a
QA project plan. These are listed in Table 24. Although every trial
burn plan need not have a QA project plan organized in strict accordance
with this list, each of these elements should be explicitly addressed
somewhere in the trial burn plan. Each element is therefore discussed
briefly in this section.
B. TITLE PAGE AND TABLE OF CONTENTS
These elements are self-explanatory. It may be noted, however, that the
title page should indicate the cognizant individuals with QA responsibility
for the project both at the applicant (and/or sampling and analysis
contractor) institution and at the EPA. If the organization of the QA
plan as outlined in the table of contents, does not follow the list of
16 QAMS-005/80 QA elements, a supplementary table which cross-references
the plan to the QAMS-005/80 list should be provided.
C. PROJECT DESCRIPTION
The project description is typically presented in some detail elsewhere
in a hazardous waste incineration permit application. In the QA project
plan, it is sufficient to present a brief summary of the project,
including a list of the wastes to be treated, the POHCs for which DREs
are to be determined, and the target stack gas detection limits that
correspond to 99.99 percent DRE.
D. PROJECT ORGANIZATION AND RESPONSIBILITY
Individuals should be designated who will have responsibility for the
following functions in specifying the QA/QC program, as part of the
program work plan, and in carrying out all elements of the QA/QC plan:
The trial burn project manager has overall responsibility for management
of the project. The project manager must ensure that proper materials,
instruments, and qualified personnel are available, and he must designate
individuals to assist in discharging the QA/QC responsibilities.
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TABLE 24
ESSENTIAL ELEMENTS OF A QA PROJECT PLAN
1. Title Page
2. Table of Contents
3. Project Description
4. Project Organization and Responsibility
5. QA Objectives
6. Sampling Procedures
7. Sample Custody
8. Calibration Procedures and Frequency
9. Analytical Procedures
10. Data Reduction, Validation, and Reporting
11. Internal Quality Control Checks
12. Performance and System Audits
13. Preventive Maintenance
14. Specific Routine Procedures Used to Assess Data Precision,
Accuracy, and Completeness
15. Corrective Action
16. Quality Assurance Reports to Management
Source: Reference 24.
217
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The quality assurance coordinator is responsible for reviewing and advising
on all aspects of QA/QC. His responsibilities include:
• assisting the project manager in specifying the QA/QC procedures
to be used during the program,
• making on-site evaluations and submitting audit samples to
assist in reviewing QA/QC procedures, and
• if problems are detected, making recommendations to the
project manager and upper corporate/institutional management
to ensure that appropriate corrective actions are taken.
The quality assurance coordinator must be autonomous, i.e., not reporting
to the project manager. The QA coordinator is responsible to upper
management independently of project management. An example of a management
structure that meets this requirement for independence is shown in
Figure 10.
The analysis coordinator is responsible for laboratory activities. These
include:
• training and qualifying personnel in specified laboratory QC
and analytical procedures, prior to receiving samples,
• receiving samples from the field and verifying that incoming
samples correspond to the packing list or chain-of-custody
sheet, and
a verifying that laboratory QC and analytical procedures are
being followed as specified in the work plan and reviewing
sample and QC data during the course of analyses. If questionable
data exist, the analysis coordinator determines which repeat
samples or analyses are needed.
The sampling coordinator is responsible for field activities. These
include:
• determining (with the analysis coordinator) appropriate
sampling equipment and sample containers to minimize
contamination,
• ensuring that samples are collected, preserved and
transported, as specified in the work plan, and
• checking that all sample documentation (labels, field note-
books, chain-of-custody records, packing lists) are correct
and transmitting that information, along with the samples, to
the analytical laboratory.
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Analysis Coordinator
Sampling Coordinator
CORPORATE QUALITY
ASSURANCE OFFICER
QUALITY ASSURANCE
COORDINATOR
PROGRAM MANACER
SECTION MANACER
PROFESSIONAL OPERATIONS
OFFICER
Quality Control
and
Data Manager
PERMUTING OFFICIAL
FIGURE 10
EXAMPLE OF PROJECT ORGANIZATION AND RESPONSIBILITY
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The quality control and data manager is responsible for QC activities
and data management. These include:
• maintaining records of all incoming samples, tracking those
samples through subsequent processing and analysis and ultimately
appropriately disposing of those samples at the conclusion of the
program,
• preparing quality control samples for analysis prior to and during
the program,
• preparing QC and sample data for review by the analysis
coordinator and the program manager, and
• preparing QC and sample data for transmission and entry into
a computer data base, if appropriate.
E. QUALITY ASSURANCE OBJECTIVES
The overall measurement objective is to determine, for each of the waste
feed materials selected for testing, the effectiveness of the incineration
facility in achieving thermal destruction of the principal organic hazardous
constituents (POHCs) of the waste, according to criteria established in
AO C.F.R. Part 264. At the present time, the EPA has not established
quantitative guidelines as to the precision, accuracy, completeness,
representativeness and/or comparability criteria that must be met by data
generated in a trial burn. However, numerical QA objectives for accuracy
and precision of the sampling system calibration, sample preparation,
and analysis procedures have been developed. These guidelines are based
on previous experience in applying comparable procedures to a variety of
complex sample matrices. In the event that the QA objectives given in
this section are not achievable (due to the fact that sample matrices are
highly variable as well as complex), revised objectives must be formulated
in consultation with the trial burn permitting official(s).
1. Accuracy
Accuracy is defined in QAMS-005/80 as the degree of agreement of a
measurement, or average of measurements, with an accepted reference or true
value. In general, appropriate accuracy goals would include using refer-
ence materials of highest, known purity for calibrations and spiking so
that (a) the determinate errors due to instrument response and incomplete
preparation recoveries can be corrected, and (b) the primary uncertainties
in the analytical data due to random errors do not exceed those specified
in Table 25. The QA objectives for accuracy may be expressed in terms of
the following parameters:
220
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TABLE 25
PRECISION GOALS FOR ANALYSIS
Analysis Procedure
Matrix
Precision
RSD* (%)
N>
fO
Proximate
Moisture, Solid, and Ash Content
Elemental Analysis
Viscosity
Survey
GRAV
TCO
IR
LRMS
Directed
GC/MS
HPLC
GC
ICAP/AAS
IC
Waste Feed
Waste Feed
Waste Feed
Waste Feed
Stack Gas Samples
Waste Feed
Stack Gas Samples
Scrubber Water
Bottom Ash
<10
<10
<10
<10
<30
Factor of 3
Factor of 3
<30
<30
<30
<30
<30
RSD = Relative Standard Deviation
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Reference materials: All reference materials used as calibration
standards or surrogate compounds should be of the highest purity
commercially available, usually >98%. Mass spectra of surrogates
POHCs and other organic Appendix VIII compounds used as reference
materials must be obtained on each new lot of material to confirm
qualitative identification;
Instrument performance: Each instrument used in a project must
be checked each day samples are analyzed to demonstrate perfor-
mance. One of the QA objectives should be that the absolute
instrument response (e.g., area counts/ng injected for the
internal standard(s) or surrogates in a GC/MS analysis) be
within a stated percentage of comparable measurements made
subsequent to the most recent calibration of the instrument;
Recovery of surrogates: The recovery of a surrogate compound(S)
added to a sample is defined as follows:
D yg S found in sample 1An
Recovery (%) = -fi—-—, . . tL— x 100
yg S added to sample
This equation assumes that the surrogate is not present in
the sample. The mean and standard deviation of the recovery
data should be compiled on a cumulative basis for each surrogate
compound in each type of sample matrix. The objectives for
recovery of surrogates are:
Mean Standard Deviation
Aqueous liquids £70% £30%
Organic liquids
Stack gas samples £50% £40%
Recovery of POHCs or other Appendix VIII Compounds: The recovery
of a POHC, or other Appendix VIII compound (P), can be defined
as follows:
Bo,™™ (ja = Ug P found in spiked sample - P in native samcle
y K } yg P added to sample x 100
It may not be appropriate to specify numerical targets for
recovery of POHCs or Appendix VIII compounds from the waste
sample. It is expected that recoveries of the target compounds
will approximate the recoveries given for surrogates. This
type of recovery data is generated only in those cases for which
the sample shows detectable levels of the POHC or Appendix VIII
compound, and the spiked level is high enough to be measurable
above the native level in the sample. If recovery data are
generated, they should be reported with the sample data.
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2. Precision
Precision is defined in QAMS-005/80 as a measure of mutual agreement
among individual measurements of the sample property. The QA objectives
for precision might be expressed in terms of the following parameters:
• Analysis of standards: One of the QA objectives should be
that the correlation coefficient for each calibration curve,
including all data points for standards analyzed subsequent
to the most recent recalibration of the instrument, be greater
than some specified value (e.g., 0.9, 0.99);
• Analysis of surrogates: Another QA objective for a trial burn
project should be that the relative standard deviation for
analysis of surrogate compounds in replicate samples from a
given waste stream be within the limits specified in Table 25;
• Analysis of replicate samples: A final QA objective should be
that results of directed analysis of laboratory replicate samples
(i.e., replicate samples drawn from the same field composite
sample) be within the limits specified in Table 25, when at
least three replicate samples are analyzed. At least 10 percent
of all analyses performed should be triplicate QC checks.
3. Completeness
The QA objective for completeness during a trial burn project is to
obtain analytical results for at least 95 percent (or other specified
percentage) of the samples collected during that project.
4. Representativeness
The following factors, which must be addressed to ensure, as much as
possible, a representative sample, are discussed in Section IV and V
of this report: sampling sites, process cycles, catch flow rates
(sampling frequency), sample preservation, sampling procedures,
sampling equipment, and sample preparation procedures.
5. Comparability
All data are reported in mg, yg, or ng of analyte per kilogram, liter,
or cubic meter of orginal sample. When precise recovery values for a
given component are known, the recovery information and the corrected
concentration data should also be provided.
223
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F. SAMPLING PROCEDURES
The sampling procedures to be used for hazardous waste incineration are
described in Section IV of this report. This element of the trial burn
QA plan specifies which of the Methods S001-S012 should be applied to
each of the streams to be sampled. Any method modifications that are
anticipated must be described in detail. The plan should indicate the
frequency with which waste, stack gas, and other effluent samples should
be taken to ensure that feed and emission measurement for DRE calculations
correspond to comparable test periods. Figure 11 illustrates a possible
approach to this aspect of the sampling methodology.
The number of replicate tests to be run (triplicate determinations are
specified as a minimum in Section IV of this report), and the provisions
for generation of sufficiently large samples to allow a specified number
of split and spiked QC samples to be prepared must be explicitly addressed.
G. SAMPLE CUSTODY
Since trial burn data are part of the regulatory permitting process, it
is essential that adequate chain-of-custody procedures be established for
each project. This section provides a brief description of the appropriate
procedures. A complete and detailed chain-of-custody protocol that will
satisfy EPA enforcement requirements for litigation is provided in
reference 25.
H. DATA MAINTENANCE AND CHAIN-OF-CUSTODY
Guidelines for the maintenance of records for the engineering data and
the routine operating parameters of the incinerator are described in
detail in the engineering guidelines manual (3) and are not repeated
here. For any sampling and analysis test of an incinerator facility, the
collected data must be documented and maintained for as long as there may
be questions concerning the results of the test. Typically, this may
mean storage of the collected data for. a minimum of one to two years
following the sampling and analysis effort. The data may be kept in any
one of several forms, such as laboratory notebooks, reports, raw data on
magnetic tape and/or disk media. For routine data and calibration
information, laboratory notebooks are appropriate. To answer identification
questions and to confirm the identities of additional POHCs at a later
date, storage of the raw data as computer data files is a more practical
method of archiving the data. Specific guidelines for data maintenance
should be incorporated into the QA/QC plan for each test; representative
information is found in documents, such as SW-846 (4).
Chain-of-custody procedures cover both field sampling and laboratory
analysis. For field work, the protocols described in Chapter II of
SW-846 (4) should be observed. These procedures include detailed
labeling of each sample, permanent recording of information pertinent to
the sample collection, and any field observations made at the same time
the sample was collected. A copy of all such materials must accompany
224
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fo
ho
L/l
Emission
Samples
Time L
(hrs) 0
8
12
Feed
Samples
Source: J.E. Picker and B.N. Colby, S-Cubed (26).
FIGURE 11
SAMPLES OF WASTE FEED AND STACK EMISSIONS ARE TAKEN AS COMPOSITES OVER
FOUR-HOUR LONG PERIODS.THREE DESTRUCTION AND REMOVAL EFFICIENCIES (DRE) ARE
CALCULATED FROM THE RATIOS El/F1 , E2/F2, Ej/Fj
-------
each sample returning from the field. In the laboratory, similar paperwork
tracks the samples completely through the analysis procedure. A typical
example of a chain-of-custody record is illustrated by Figures 12 through 14.
I. CALIBRATION PROCEDURES AND FREQUENCY
1. Sampling
Calibration of stack sampling equipment is performed within two weeks
prior to the initiation of field sampling activity. The calibration
procedures should conform to the specifications of the EPA document,
"Quality Assurance Handbook for Air Pollution Measurement Systems,
Volume III, Stationary Source Specific Methods" (27). Dry gas meters,
nozzles, orifices and pitot tubes are included in the calibration.
Tables 26 and 27 summarize the methods to be used for calibration.
The other types of sampling equipment described in Section IV (Coliwasa,
dipper, scoop, etc.) require no calibration.
2. Analysis
Instrument calibration procedures have been described in Section VI.
The QA plan for each project specifies the materials and concentration
ranges of standards for calibration of each instrument to be used in the
project.
J. ANALYTICAL PROCEDURES
The analytical procedures used in trial burns are detailed in Section VI.
The majority of these methods have not yet been validated for application
to hazardous wastes or to effluent samples associated with trial burns,
although considerable experience has been accumulated from their use in
other contexts.
Extensive method validation may be beyond the scope of most trial burn
projects. The QC data on analysis of surrogates, duplicates, and spiked
samples serve as indicators of the performance of the sample preparation
and analytical methods.
K. DATA REDUCTION, VALIDATION, AND REPORTING
1. Data Reduction
The QA project plan includes explicit procedures for data reduction,
showing all equations and conversion factors. An example data reduction
procedure for GC/MS analysis, which is expected to be the most commonly
used technique for trial burn POHC analysis, is given here.
226
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Field Sampling Chain-of-Custody Form
Leader
Name of Survey or Activity
Date of Collection
Sheet
Description of Shipment
Total Number Sample Containers
Type of Sample
Contents of Shi
Field
Sample No.
No. of Containers/Field No.
Analyses Required — Check Where Appropriate
Plastic
Glass
VOA
Cyanide
Phenols
Asbestos
Pesticides
Metals
V OA
Semi-
Personnel Custody Record
Relinquished by (Sampler)
Sealed Unsealed I
Relinquished by
Received by
| Sealed
Unsealed I
Date
Time
Reason
Received by
~ate
Time
Reason
FIGURE 12 FIELD SAMPLING CHAIN-OF-CUSTODY FORM
227
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Collector's Sample No.
CHAIN-OF-CUSTODY RECORD
Location of Sampling: Producer Hauler Disposal Site
Other _
Sample
Shipper's Name:
Address:
number street city state zip
Collector's Name __
signature
Date Sampled Time Sampled Hours-
Type of Process Producing Waste .
Field Information —
Sample Receiver:
name and address of organization receiving sample
2.
3. ———
Chain of Possession:
1.
signature title inclusive dates
2.
signature title inclusive dates
3.
signature title inclusive dates
FIGURE 13 CHAIN-OF-CUSTODY RECORD
228
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TO:
SAMPLE NO.:
SAMPLE DESCRIPTION:
ANALYSIS PERFORMED: TYPE
ON (date)
BY (name)
(organi-
zation)
METHOD USED:
(ref)
VARIATIONS IN CONDITIONS/PROCEDURES (if any)
SAMPLE SIZE TAKEN FOR ANALYSIS:
CALIBRATION METHOD USED: (reference
material used)
(# and name
of cal. stds.)
DETECTION LIMIT
PRECISION OF DETERMINATION:
ANALYSIS LOG NO. (or other
reference to raw data)
SIGNATURE OF ANALYST
FIGURE 14 RECORD OF ANALYSIS REPORT FORM WITH ACCEPTABLE DOCUMENTATION
229
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TABLE 26
ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Wet test meter
Dry gas meter
Thermometers
Probe heating
system
Barometer
Probe nozzle
Analytical
balance
Acceptance Limits
Capacity j>3.4 m3/h
(120 ft3/h); accuracy
within ±1.0%.
Y. = Y ± 0.02Y.
Impinger thermometer
± 1°C (2°F); dry gas
meter thermometer
+ 3°C (5.4°F) over
range; stack tempera-
ture sensor ± 1.5% of
absolute temperature.
Capable of maintaining
120° ± 14°C (248° ±
25°F) at a flow rate of
21 L/min (0.71 ft3/min).
± 2.5 mm (0.1 in) Hg of
mercury-in-glass barom-
eter.
Average of three I.D.
measurements of nozzle;
difference between high
and low _<0.1 mm
(0.004 in).
i 1 nig of Class-S
weights.
Frequency and Method
of Measurement
Calibrate initially, and then
yearly by liquid displacement.
Calibrate vs. wet test meter
initially, and when post-test
check exceeds Y + 0.05Y.
Calibrate each initially as a
separate component against a
mercury-in-glass thermometer;
then before each field trip
compare each as part of the
train with the mercury-in-glass
thermometer.
Calibrate component initially
by APTD-0576 (12), if con-
structed by APTD-0581 (11),
or use published calibration
curves.
Calibrate initially vs.
mercury-in-glass barometer;
check before and after each
field test.
Use a micrometer to measure
to nearest 0.025 mm (0.001 in).
Check with Class-S weights
upon receipt.
Action if Requirements
Are Not Met
Adjust until specifi-
cations are met, or
return to manufacturer.
Repair, or replace;
recalibrate.
Adjust; determine a
constant correction
factor, or reject.
Repair, or replace;
reverify the calibration
Adjust to agree with a
certified barometer.
Recalibrate, reshape,
and sharpen when nozzle
becomes nicked, dented,
corroded.
Adjust or repair.
Source: EPA-600/4-77-027b (27).
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TABLE 27
Apparatus
Type S pitot
tube and/or
probe
assembly
Stack gas
temperature
measurement
system
Barometer
Differential
pressure
gauge (does
not include
inclined
manometer)
ACTIVITY MATRIX FOR CALIBRATION OF APPARATUS
Acceptance Limits
All dimension speci-
fications met.
Capable of measuring
within 1.5% of minimum
stack temperature
(absolute)
Agrees within 2.5 mm
(0.1 in) Hg of mercury-
in-glass barometer.
Agree within ± 5% of
inclined nanometers.
Frequency and Method
of Measurement
Calibrate initially and
visually inspect after each
field test.
Calibrate initially and
after each field test.
Initially and after every
field use, compare to a
liquid-in-glass barometer.
Calibrate initially and
after each field use.
Action if Requirements
Are Not Met
Do not use pitot tubes
that do not meet face
opening specifications;
repair or replace as
required.
Adjust to agree with Hg
bulb thermometer, or con-
struct a calibration curve
to correct the readings.
Adjust, repair, or discard.
Reject test results, or
consult administrator if
post-test calibration is
out of specification.
Source: EPA-600/4-77-027b (27).
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Raw daCa for the quantitative GC/MS analysis procedure consist of peak
areas for the surrogate species and analytes of concern. Raw data are
converted to concentrations by use of a calibration curve that relates
peak area to the quantity of analyte introduced into the instrument. A
calibration curve for each analyte and analytical method can be constructed
by fitting a linear regression equation to the results of the analyses
of calibration standard solutions which contain the analyte at five
different concentration levels.
The raw data are converted to concentration of analyte in a sample by
automated data processing routines or by the analyst. Peak areas for
the series of known calibration standards are first entered and a
regression line computed. A plot of the calibration curve with the
actual calibration data superimposed should be generated for visual
examination of deviations from linearity or of outlying data points.
Peak areas from the analyses of the unknown samples are then entered,
corresponding quantities of analyte are computed from the regression
line, and a summary of the raw and converted data printed. The original
copy of the data summary should be included in the analyst's notebook
and copies forwarded to the analysis coordinator and the project
manager.
An internal standard (such as d10-anthracene) is added to each standard
solution or concentrated sample extract immediately prior to analysis.
The quantity added is sufficient to give the same concentration (ng/uL)
of internal standard in all solutions/extracts analyzed.
A calibration curve and regression equation are then created, using the
relative area, A', where:
, _ Raw area for peak corresponding to analyte (POHC)
Raw area for peak corresponding to internal standard
Blank corrections are made by subtracting A' for the method blank from
A' for the standard. The calibration curve consists of a plot of A'
vs. ng of analyte (POHC) injected.
The concentration of analyte or surrogate in an unknown sample, C, is
calculated as follows:
Quantity injected, Q (ng)
Q is calculated from the regression equation of the calibration curve:
A' = m x Q + b
where:
A' = the relative area corrected by subtracting A' for the
blank from A' for the sample,
232
I
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Q = the quantity of analyte injected (ng),
m = the slope of the regression line, and
b = the intercept of the regression line (which will not be force-
fit to zero).
Thus:
Concentration in Extract, C (ng/pL)
C is calculated from Q and the injection volume, V_^ (pL) . Thus:
C (ng/pL) =
i
Concentration in Sample, C (mg/L, mg/kg, or mg/dscm)
*
C is calculated from C , the volume of the concentrated sample extract,
V , and the initial quantity of sample extracted, Vg.
For aqueous liquids, organic liquids and slurries:
*
C x V
C (mg/L) - - . 1000
s
where:
C = concentration in extract (ng/pL = pg/mL),
= volume of concentrated extract (mL), and
Vg = volume of sample taken for extraction (L).
For solids and sludges:
*
C x V
C (mg/kg) - — t 1000
s
where:
C * concentration in extract (ng/pL = pg/mL),
Vx = volume of concentrated extract (mL), and
Wg = weight of sample taken for extraction (kg).
233
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For stack gas samples:
•k
C x V
C (mg/dscm) = — — * 1000
8
where:
A
C » concentration in extract (ng/uL = ug/mL),
= volume of concentrated extract (mL), and
= volume of stack gas sampled (dscm).
2. Data Validation
The principal criteria that are used to validate the data integrity
during collection and reporting of data include:
• frequent verification by the QC and data manager that all
raw data generated in the preceding week have been stored
on magnetic tape and/or in hard copy, and that storage
locations have been documented in the laboratory chain-of-
custody records;
• examination of at least 5 percent of the raw data (e.g.,
chromatograms, AAS recorder outputs) on a frequent basis by
the analysis coordinator to verify adequacy of documentation,
confirm peak shape and resolution, assure that the automatic
integrator was sensing peaks appropriately, and so forth;
• confirmation that raw areas for internal standards and calibration
standards and raw and relative areas for surrogate compounds
are within 50 percent of the expected value;
• reporting of all associated blank, standard, and QC data along
with results for analyses of each batch of samples; and
• reporting of all analytical data for samples with no values
rejected as outliers, because of the small number of replicate
samples for analysis.
3. Data Reporting
Results of directed, survey, and proximate analyses are reported in the
formats, or equivalent, presented in Section VI.
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L. INTERNAL QUALITY CONTROL CHECKS
This section presents guidelines for the number and frequency of replicate
and spiked QC samples and calibration standards to be used, including
concentration of surrogate or spike compounds to be added to designated
QC samples.
Quality control samples are analyzed in the same way as field samples
and interspersed with the field samples for analysis. The results of
analyzing the QC samples are used to document the validity of data and to
control the quality of data within predetermined tolerance limits. QC
samples include blank samples, analytical replicates, and spiked samples.
1. Blank Samples
These samples are analyzed to assess possible contamination from the field
and/or laboratory, so that corrective measures may be taken, if necessary.
Blank samples include:
• Field Blanks—These blank samples are exposed to field and
sampling conditions and analyzed to assess possible contamination
from the field (one for each type of sample preparation).
• Method Blanks—These blank samples are prepared in the laboratory
and are analyzed to assess possible laboratory contamination
(one for each lot of samples analyzed).
• Reagent and Solvent Blanks—These blanks are prepared In the
laboratory and analyzed to determine the background of each of
the reagents or solvents used in an analysis (one for each new
lot number of solvent or reagent used).
2. Analytical Replicates
Replicate analysis of specific samples may be undertaken by the analyst
to check on the validity of certain anomalous samples. For example, if
the internal standard response for a specific sample changes drastically
from its prior value, a problem could be present in the instrument or in
the sample workup. Repeat analyses of the sample in question and a pre-
vious "normal" sample serve to indicate which of the possible problems
is, In fact, present.
3. Spiked Samples
All samples are spiked with one or more selected surrogate compounds prior
to extraction and analysis. The data on surrogate concentration are used
to calculate the recovery of the surrogate compounds as one measure of the
accuracy of the sample preparation and analysis procedures.
235
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For directed analysis of POHCs, one sample from each set of three replicates
should be spiked with each analyte at a concentration corresponding to
two times the expected POHC concentration for waste feed samples and
corresponding to two times the target detection limit (based on 99.99
percent) DRE for stack gas samples. Scrubber water or ash samples should
be spiked with analyte at a concentration of 10-100 ppm if no specific
target detection level has been established in the trial burn permit.
M. PERFORMANCE AND SYSTEM AUDIT
A system audit by the project manager and quality assurance officer is
made prior to the implementation of any new experimental procedures.
Systems audits for trial burn projects include frequent review by the
QC and data manager and project manager of all recent data to ensure that
all required QC checks are made and evaluation criteria followed.
The quality assurance officer participates in these reviews on a
regular basis. Because of the anticipated difficulty in obtaining
reference samples with matrices similar to the hazardous waste incinerator
samples, performance audits must rely heavily on the replicate analyses
of real samples, spiked and unspiked. However, standard reference
materials should also be employed as a means of auditing performance.
At the discretion of the EPA, the preliminary systems audit may include
analysis of a simple performance evaluation standard and/or analysis of
spiked resin traps, feed samples, or other materials supplied by the EPA.
N. PREVENTIVE MAINTENANCE
The QA project plan for a trial burn should itemize the procedures for
preventive maintenance that are relevant to the analyses required in
the project.
0. SPECIFIC ROUTINE PROCEDURES USED TO ASSESS DATA PRECISION, ACCURACY
AND COMPLETENESS " ~
1. Calculation of Mean Values and Estimates of Precision
The mean, C, of a series of replicate measurements of concentration, C ,
for a given surrogate compound or analyte is calculated as:
— 1 n
C = ~ E C.
n . , l
236
-------
where:
n = number of replicate measurements, and
= concentration in the sample (mg/L, mg/kg, or mg/dscm).
The estimate of precision of a series of replicate measurements is
expressed as the relative standard deviation (RSD):
RSD (%) = ^ x 100
C
where
SD = standard deviation
C = mean of the concentration for the sample set.
Alternatively, for data sets with a small number of points (e.g.,
concentration of POHC in triplicate samples of one waste stream), the
estimate of precision may be expressed as a range percent, R:
Ci - C2
R (%) = x 100
c
where:
Ci = highest concentration value measured in data set, and
C2 = lowest concentration value measured in data set.
The standard deviations calculated should be compared on a frequent
basis with the respective goals identified in Table 25.
2. Assessment of Accuracy
Accuracy is evaluated by comparing the mean recovery of surrogate
compounds on a weekly basis. The recovery of a surrogate compound is
defined as:
C x V (or W )
Recovery (%) » — ^ — x 100
s
237
-------
where:
C = measured concentration of surrogate compound in sample
(mg/L or mg/kg),
V (W ) = total volume (or weight) of sample to which surrogate
was added (L or kg), and
Qg = quantity of surrogate compound added to sample (mg).
3. Assessment of Causes of Variance
If the calculated destruction and removal efficiencies have very small
variance, the three composite four-hour samples are all that would be
necessary to provide quality assurance. If variances in the calculated
DREs are large, however, it would be useful to identify the cause of the
large variance. A sample preparation and analysis protocol similar to
the one pictured in Figure 15 is helpful in identifying some of the causes
of variances. When the rule of additivity of variance is used, the
precision (expressed as total variance for a particular sampling and
analysis scheme) is expressed as the sum of the variances for the
separate activities of sampling, sample preparation and measurement.
This is expressed as follows:
s2 ^ g2 g2
Total Sampling Preparation Measurement.
It is possible to subdivide the variances into more detailed steps in
the sampling scheme, if necessary. To determine sampling variance (S2)
the variance obtained from analyzing E_ , E_, , and E.C1, is subtracted
3a 3b 3
from that obtained for E^, E^, and E^. Similarly, sample preparation
precision (S2) is determined by subtracting the variance obtained from
triplicate measurements (s£, variance of E3C1, E^, and E 3) from
the variance o f E3a' E3b' and E3C1- This type of variance analysis would
also be applied to the sampling and analysis of waste feed in the same
way it is applied to the stack emissions. Ideally, variance analysis is
done for each of the POHCs identified for evaluation in a trial burn.
These data are extremely useful in identifying the sources of imprecision
and subsequently in directing adjustments in sampling and analysis
methodology.
P. CORRECTIVE ACTION
For each analytical method employed in a trial burn project, it is
appropriate to compute the standard deviation or range of results of
replicate analyses. Periodic determinations of recovery of the surrogates
and POHCs should also be made. The mean recovery and the standard
deviation data for replicate sets are accumulated for each kind of sample
2 38
-------
Sampling
Preparation
Analysis
NJ
U>
vO
ci
e2
> E
> E
3a
^ E3b
E3C
~\
> Ei
> E2
3a
^ E3b
E
~\
3C1
#> E
s?+ s2+s2
s2+ s2
D m
3C2 *
^ E3C3.
m
m
Source: J.E. Picker and B.N. Colby, S-Cubed (26).
FIGURE 15 DIAGRAM OF A SAMPLING AND ANALYSIS PROCEDURE WHICH USES REPLICATE
SAMPLES TO PROVIDE INFORMATION ON SOURCES OF VARIANCE
-------
matrix analyzed (e.g., solid, stack gas, aqueous liquid, and ash) and
updated from lot to lot as additional analyses are performed and more
experience is gained. When either the relative standard deviation of
replicate samples or the surrogate recoveries exceed the performance
goals established for that trial burn project (Part E of this section),
corrective action should be taken to improve performance prior to
analysis of the next lot. If weaknesses or problems are uncovered during
system or performance audits, corrective action should be initiated
immediately.
Corrective action includes, but is not necessarily limited to:
recalibration of instruments using freshly prepared calibration standards;
replacement of lots of solvent or other reagents that give unacceptable
blank values; additional training of laboratory personnel in correct
implementation of sample preparation and analysis methods; and reassignment
of personnel, if necessary, to improve the overlap between operator
skills and method requirements.
Whenever a long-term corrective action (28) is necessary to eliminate the
cause of nonconformance, the following closed-loop corrective action
system should be used. As appropriate, the sample coordinator, analysis
coordinator or the program manager, ensures that each of these steps
is followed:
1. The problem is defined.
2. Responsibility for investigating the problem is assigned.
3. The cause of the problem is investigated and determined.
4. A corrective action to eliminate the problem is determined.
5. Responsibility for implementing the corrective action is
assigned and accepted.
6 The effectiveness of the corrective action is established and
the correction implemented.
7. The fact that the corrective action has eliminated the
problem is verified.
Q. QUALITT ASSURANCE REPORTS
On a regular basis, the quality assurance officer meets with the project
manager and key staff responsible for sampling, analysis, QC and data
management to review QC data summaries, documentation, and other aspects
of the project quality assurance performance. The QC officer's assessment
of the adequacy of project quality control/quality assurance performance
is summarized in a memorandum which would be distributed to upper corporate/
institutional management, as well as to the project manager and hia/her
240
-------
immediate superior in the line management. The memorandum must identify
any areas that appear to require remedial action and present the remedies
that have been proposed. The results of any earlier remedial action must
be described as well. The permit writer would receive documented copies
of all QA reports along with the trial burn sampling and analysis results
241
-------
VIII. REFERENCES
1. Resource Conservation and Recovery Act, Subtitle C §§3001-3013,
42 U.S.C. §§6921-6934 (1976) and Supplement IV (1980).
2. U.S. Environmental Protection Agency/Office of Solid Waste
(U.S. EPA/OSW), Washington, D.C. "Guidance Manual for Hazardous
Waste Incinerator Permits," Report prepared by U.S. EPA/OSW,
Washington, D.C. and the MITRE Corporation, McLean, Virginia
(September 1982). This draft is a revision of a draft report
entitled, "Guidance Manual for Evaluating Permit Applications
for the Operation of Hazardous Waste Incinerator Units," (April 1981).
3. U.S. Environmental Protection Agency/Industrial Environmental
Research Laboratory, Office of Environmental Engineering and
Technology, Cincinnati, Ohio, "Engineering Handbook for Hazardous
Waste Incineration," SW-889 (September 1981).
4. U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980), SW-846 Revision A
(August 8, 1980), and SW-846 Revision B (July 1981).
5. deVera, E.R., B.P. Simmons, R.D. Stephens and D.L. Strom,
"Samplers and Sampling Procedures for Hazardous Waste Streams,"
EPA-600/2-80-018 (January 1980). NTIS No. PB80-135-353.
6. Title 40, Code of Federal Regulations, Part 60, Appendix A (1980).
7. Lentzen, D.E., D.E. Wagoner, E.D. Estes and W.F. Gutknecht, "EPA/
IERL-RTP Procedures Manual: Level 1 Environmental Assessment
(Second Edition)," EPA-600/7-78-201 (October 1978). NTIS No.
PB293795/AS.
8. American Society for Testing and Materials, Philadelphia, Pennsylvania
"Annual Book of ASTM Standards," Method D-270 (1975). '
9. American Society for Testing and Materials, Philadelphia, Pennsylvania
"Annual Book of ASTM Standards," Method E-300 (1973). '
10. Stern, A.C. (ed.), Air Pollution: Third Edition, Academic Press,
New York, Vol. Ill (1976).
11. Martin, R.M., "Construction Details for Isokinetic Source Sampling
Equipment," EPA-APTD-0581 (1972). NTIS No. PB-209060.
12. Rom, J.J., "Maintenance, Calibration and Operation of Isokinetic
Source Sampling Equipment," EPA-APTD-0576 (1972). NTIS No. PB-209022.
242
-------
13. Adams, J.W., N.J. Cunningham, E.H. Dohnert, J.C. Harris, P.L.
Levins, J.L. Stauffer, K.E. Thrun, L.R. Woodland, D.G. Akerman,
J.F. Clausen, A. Grant, R.J. Johnson, C.C. Shih, R.F. Tobias
and C.A. Zee, "Destroying Chemical Wastes in Commercial Scale
Incinerators," (May 1978). NTIS No. PB278-816/3WP.
14. Adams, J.W., K.T. Menzies and P.L. Levins, "Selection and Evaluation
of Sorbent Resins for Collection of Organic Compounds," EPA-600/7-
77-044 (April 1977). NTIS No. PB268559.
15. Gallant, R.F., J.W. King, P.L. Levins and J.F. Piecewicz,
"Characterization of Sorbent Resins for Use in Environmental
Sampling," EPA-600/7-78-054 (March 1978). NTIS No. PB284347.
16. Piecewicz, J.F., J.C. Harris and P.L. Levins, "Further Characteri-
zation of Sorbents for Environmental Sampling," EPA-600/7-79-216
(September 1979). NTIS No. PB80-118763.
17. Harris, J.C., M.J. Hayes, P.L. Levins and D.B. Lindsay, "EPA/IERL-
RTP Procedures for Level 2 Sampling and Analysis of Organic Materials,"
EPA-600/7-79-033 (February 1979). NTIS No. PB293800.
18. Stauffer, J.L., "Interpretation of Low Resolution Mass Spectra for
Level 1 Analysis of Environmental Mixtures," EPA-600/7-82-033
(May 1982).
19. (J.S. Environmental Protection Agency, Federal Register, 44,
69464-69575 (December 3, 1979).
20. Dillon, H.K., R.H. James, H.C. Miller and A.K. Wensky (Battelle
Columbus Laboratories, Columbus, Ohio), "POHC Sampling and Analysis
Methods," Report prepared for U.S. Environmental Protection Agency/
Industrial Environmental Research Laboratory, Research Triangle Park,
North Carolina by Southern Research Institute, Birmingham, Alabama
under Contract No. 68-02-2685 (December 1981).
21. Small, H., T.S. Stevens and W.C, Baumer, "Novel Ion Exchange
Chromatographic Method Using Conductimetric Detection," Anal. Chem.,
47, 1801-1809 (1975).
22. Otvos, J.W. and D.P. Stevenson, "Cross-Sections of Molecules for
Ionization by Electrons," £. Am. Chem. Soc., 78, 546-551 (1956).
23. Hood, A., "Standardization of Mass Spectra by Means of Total Ion
Intensity," Anal. Chem., 30, 1218-1220 (1958).
24. U.S. Environmental Protection Agency/Office of Monitoring Systems
and Quality Assurance, Office of Research and Development,
Washington, D.C., "Interim Guidelines and Specifications for
Preparing Quality Assurance Project Plans," QAMS-005/80 (December
29, 1980).
243
-------
25. U.S. Environmental Protection Agency/Office of Enforcement,
"NEIC Policies and Procedures Manual," Report prepared by U.S.
Environmental Protection Agency/National Enforcement Investigations
Center, Denver, Colorado, EPA-300/9-78-001-R (October 1979).
26. Picker, J.E. and B.N. Colby, "Quality Assurance Review of 'Sampling
and Analysis Methods for Hazardous Waste Incineration,'" (August 1981).
27. U.S. Environmental Protection Agency/Environmental Monitoring and
Support Laboratory, Research Triangle Park, North Carolina, "Quality
Assurance Handbook for Air Pollution Measurement Systems, Volume III,
Stationary Source Specific Methods," EPA-600/4-77-027b (January 1980).
28. vonLehmden, D.J. and C. Nelson, "Quality Assurance Handbook for
Air Pollution Measurement Systems, Volume I, Principles," EPA-600/9-
76-005 (January 1976). NTIS No. PB254658.
Note: References with assigned NTIS Numbers are available from the
National Technical Information Service, Springfield, Virginia 22161.
244
-------
APPENDIX A
Hazardous Constituents - Physical/Chemical Data
Appendix A catalogs the Hazardous Constituents
listed in 40 C.F.R. Part 261, Appendix VIII
(May 20, 1981) with the following chemical and
physical data for each compound (when available):
CAS Registry Number
Formula
Boiling Point (°C)
Melting Point (°C)
AH Combustion (kcal/mol) (kcal/gram)
Molecular Weight
Structure
245
-------
KAHE
CAS
REGISTRY NO.
FORMULA
BOIL1NC
POINT *C
AceLonitrile 75-05-8 ^2^3** 81.6
Acctophenone 96-86-2 C^llgO 2QJ.6
3-taLp2ia-AceCunyl 81-83-2
benzyl >~£»-hydroxy
couiuri.1 and salts
(Warfarin]
2-AcecylaBinofluaren^ 53-96-5 *"15**13^
Acetyl chloride
75-36-5
c,n3cio
*0.9
iiK
GOKBUSTHXi
MELTING licai/mol
POINT "C (Jccal/jratj) KOLECULAR WEIGHT
302
(7.37)
CUj- CN
76 5C
0
1
C-H' C'Cl
-------
CAS BOILING MELTING
HAHE REGISTRY NO. FORMULA POINT 'C POINT *C
l-Acecyl-2-rhiourea 591-08-2 C^H,NnOS 165
3 o i
Acrolein 207-O2-S C„H,0 52.5-53.5 -Ml.. 9
3 H
ro
js
Acrylanide 79-06-1 C^KcN0 12»(al 2*»iyu) 84.5
Acrylonitrile 107-13-1 C3H3N 77.5-77.9 -83.'55
Aflacoxins
1402-68-2
ca. 237-299(1
6H
COMBUSTION
kcal/nol
(kcal/gran) MOLECULAR UEICHT STRUCTURL
538
(4.55*)
I
390
(6.95)
409
(5.57*)
421
(7.93)
tu-CH-L-HM..
+ similar stiucturo
-------
CAS BOILING MELTING
MAKE REGISTRY NO. FORMULA POINT 'C POINT aC
Aldrin 3Q9-00-2 104-104.
It o t>
Allyl alcci.ul IC7-18-6 CJi.O 97.0 -l'V 0
3d
N>
00
AluminuiB phosphide 20859-73-8 AIP
4-Aalnobiphenyl 92-67-1 Cl2HllH 302.0 53.0
fc-Ami*jo-ltla,2,&, 30-07-7 C H -N,0 >360
8a,8b-hexahydro-8- D 18 45
(hydroxy«ethyI)-8a-
»ethoxy-5-»ethyl -
carbamate arirlao(2',
3*:3,4Jpyrrolo[1,
2-a]inaole-4,7-dione,
(ester) (Mitomycin C)
4H
COtifiUSTION
kcal/ool
(kcal/eram)
MOLECULAR WEIGHT
1370*
(3.7!>*)
P
4b0
(7-75)
5 7.96
oo
-------
MAKE
CAS
RECISTRY MO.
FORMULA
BOILING
POINT *C
5-(Aainoraethyl)- 276 3-96-4 ^4^6^2^2
3-isojtazolol
Ataltcole 61-82-5
N>
¦P-
vO
Aniline 62-53-3 C6H?N 184
AnCi»ony 7440-36-0 Sb 1750
and compounds,
N.O.S.
(as Ancinony)
Araalce
140-57-8
195»(at 2 tan)
AH
COMBUSTION
HELTINC kcal/aol
POINT *C (kcal/gram) MOLECULAR WEIGHT
175d 545 114.12
(4-78)
337*
(4.01*)
-6(solidifles) 813 93.12
(8.73)
:o
IT""
-------
KAK£
CAS
REGISTRY MO.
FORMULA
BOILING
POINT *C
Arsenic 7440-38-2 As 613 subl.
and compounds
N.O.S. (as Arsenic)
Arsenic acid 7770-39-4 H,AsO,.l/2 H„0
3 4 2
Arsenic pencoxide 1303-28-2
Arsenic trloxlde 1327-53-3 A*2°3 457.Z
Auraaloe
492-60-6
MELTING
POINT *C
fiH
COMBUSTION
kcal/nol
(kcal/gran)
MOLECULAR UEICHT
817(at 3.0 x 10 on)
WO-Ri-OH o
- O -
o» «* - 0-*»*0
2060*
(7.69*)
-------
IWffi
CAS
KgCISTSY HO.
FORMULA
BOILINC
POINT 'C
K5
Ul
ilarium
and compounds,
N.O.S. (as fiariua)
Bariua cyanide
Bern (c)acridioe 225-51-4 ^17KHN
Bene(a)anthracene 56-55-3
435 subl.
MELTINC
POINT °C
4H
COMBUSTION
kcal/aol
(kcal/zram)
MOLECULAR WEIGHT
dec in air
556*
(3.21*)
N'N'Ol-t-O-CH^tW-COH
NHi
2040«
(8.92*)
a
214 0
(9.39)
-------
C*5 SOILING HELTINC
B£CISTEY NO. FORMULA POIHT 'C POIHT 'C
temene 71-43-2 C,H, 80.1 5 5
it 0
Benxeoeftrsoolc acid 98-05-5 C^HyiflO 158-162d
N>
Ul
ro
Beaseoe, dichleroneehyl- 98-87-3 C-H..C1- 205.2 -16.4
7 6 2
Beazeaetklol 1QB-98-5 C6M6S 168-7
leuidine
92-87-S
400 (ac 7A0w) 12&
AH
COffiUSTIOW
kcal/aol
(kcal/graa) MOLECULAR WEIGHT
783 78. U
(10.03)
687*
<3.AO*)
820*
(5.09*)
929
(8.43)
1&9L
(9.18)
O!
0-
o-
-------
CAS BOILING
Nrtim REGISTRY NO. FOKNUiA POINT aC
Uouzo(b) f luoranchcne 205-99-2 ^"»oH12
Bo»zo(j)fluoranthene 205-82-3 ^20^12
N3
Ln
h»!i>zo(a)|)yrpiif 50-32-8 ''20^12 3l0-3l2(«t lOmn)
j»-lk nzuquinoiiti 106-51-4 subl.
o k I
Kear.otii ttlilori do
98-07-7
220.8
MELTING
POINT *C
£U
roimusfioN
kt-.il/nrfji
(Lcal/orau)
Muut&ULAK Ul.ldiT
SiUUCTUKl
2330
(9.25)
252.32
2330
(9.25)
252.32
CT
170-177
2330
(9.25)
115.7
656
(6.07)
lOB.oy
-5.0
762
(3.90*)
1**5.47
-------
CAS
BOILING
REGISTRY NO. FORMULA POINT *C
Benzyl chloride
BerylHun «od 7440-41-7 Be 2970(at 5n.) 1278+5
compounds, N.O.S. ~
fO (as Berylli.ua)
U1
Bls(2-chloroetboxy)
aechue
Bis(2-chloroethyl) 111-44-4
ether
-24.5
HiN-fci»(2-chloro- 494-03-1
ethyl)-2-
uphthylaKine
2l0(at 5«)
54-56
AH
CONSUSTIOM
kcal/nol
(kcal/graml MOLECULAR WEIGHT STRUCTURE
782
(6.18)
CV'v
9.0122
796*
(4.60*)
C» C.H - C* -a-Crt -6-Ct»
483*
(3.38*)
- fi-CN'U, Cl
1780*
(6.64*)
268.20
CO"
-------
CAS BOILING MELTING
"ME BEC1STEY NO. FORMULA POINT 'C POINT 'C
Bls(2-chIorolsopropyl) 106-60-1 C,H,,C1,0 187
ether 6 " 2
flis(chloroaethy1) 542-88-1 C_H,C1,0 104 -41.5
etiier 2 4 2
ro
Ui
Ln
01 s (2-echyihexyl > U1-91-?
phthalace 2i* M 4
ftrowcacetone 598-31-2 C^H^&rO 136.5(at 72ta») -36.5
Broaoaecbanc
74-83-9
3.56
-93.6
AH
COMBUSTION
kcal/nol
ikcal/arag) MOLECULAR WEIGHT
943*
(4.93*)
226*
(1.97*)
3290*
(8.42*)
H C- 0<-0-CH-<
at* -a-cw^ci
364*
(2.66*)
ta "C - C*
161*
(1.70*)
94.94
-------
BOILXHC HELTINC
POINT 'C POINT *C
4-Broaophenyl 101-55-3 ci?MQBr0 310.14 18.72
phenyl ether '
Brucine 357-57-3 C23H26N2°4 178
to
Ui
2-Butanone peroxide 1336-23-4 C-H,,0
B 16 4
Butyl benxyl 85-68-7
phthalate 19 20 4
CAS
REGISTRY NO.
2-sec-Butyl-4,6 88-85-7 C _H. DO.
dinlcrophenol 10 12 1 3
(DNBP)
AH
COMBUSTION
kcal/aol
(kcal/gram) MOLECULAR WEIGHT STRUCTURE
1450*
(5.84*)
688
(7.42)
2930*
(6.96*)
o°o*
CM.CN-t-iH -o-o-CM -C-C« cn
' i a v * j
-------
HAHE
CAS
REGISTRY HO.
FORMULA
BOILING
POINT *C
Cadnlua and 7440-43-9 Cd 765
confounds, W.O.S.
(as Cadmiua)
Calclun chromate 6012*75-7
fsj
Ui
"vj
C«lclua cyanide 592-01-8 C^CaN^
Carbon disulfide 75-15-0 CS2 46.3
Carboa oxyfluoride 353-50-4
-83
AH
COHNJSIICtf
MELTING kcal/Mol
POINT *C (kc»l/ftra») MOLECULAR WEIGHT
Ca Cr 0+ ¦ 2 Ht0
MC-Ca-CN
5 = C =5
0
II
F- C -F
-------
CAS
REGISTRY MO.
BOILING MELTING
POINT *C POINT *C
Chloral
(as hydrate)
96.3d(at 764jr.a) -57
Chlorambucil
64-66
to
U1
00
Chlordane
(alpha and ganaa
lsoaers)
Chlorinated
benzenes, N.O.S.
Chlorinated
eth&ae, N.O.S.
AH
COMBUSTION
kcal/ IBOl CTBIirTllHK
(kcal/grao) HOLECULAK WEICHT MKUiiUM.
132*
(0.80*)
1800*
(5. 93s*)
104.23
-1 - cV ,L
1110*
(2.71*)
409.80
X
-------
CAS BOILING MELTING
REGISTRY NO, FOSMOLA POIWT *C P03WT *C
Chlorinated
fluo rocarbon®,
Chlorinated ^in^A ^
naphthalene, N.O.S. x x
fO
Ui
v©
Chlorinated phenol, C,H, CI 0
v * 6 6-x x
Chloroacetaldehyde 107-20-0 C^CIO 85-85.5(at K8»>
Chloroalkyl echera, N.O.S.
AH
COMBUSTION
kcal/aol
MOLECULAR WEIGHT STRUCTURE
-------
CAS
REGISTRY MO.
p-Chloroaailine 106-47-8
Chlorobe&teoe
108-90-7
N5
o
Chlorobeazil&te 510-15-^
p*£hloro-*-crea«l 59-50-7
l-Chloro-2,3-
epoxypropaae
FORMULA
BOILING
POIWT *C
MELTING
POINT "C
c3"5u
&H
COMBUSTION
kcal/*ol
(kcal/gran) MOLECULAR WEIGHT
783*
(6.14*)
743
(6.60)
1790*
(5.50*)
0
o
a-
o
c - © «-•» x
-oio
724*
(5.08*)
TO"
Ago*
(5.19*)
92.53
0
/ \
CtiM-
-------
CAS BOILING MELTING
REGISTRY MO. FORMULA POINT *C POINT *C
2-Chloro«thyl 110-75-8 C.H.CIO 108
vinyl ether
Chloroform 67-66-3 CHCl^ 61.7 -6i.5
NJ
O*
J—1
ChloroM Chine 74-67-3 CH}C1 -24.2 -97.73
Chloroaethyl 107-30-2 C.H.C10 59.15 -103.5
¦ethyl ether 1 *
2-Chlorooephthaieae 91-58-7 CJ0M7C1 256 61
AH
COMBUSTION
kcel/aol
(kcaL/araw)
MOLECULAR WEIGHT
553*
(5.19*)
MjC-CH-O-CHiCH^a
89.5
(0.75)
hccu
m
<3.25)
50.49
HxCQ
2 SO*
(3.40*)
ClCHrO"CHj
1199
(7.37)
-------
HAME
CAS
REC1STM WO.
FORMULA
BOILING
POtKT *C
2-Chlorophenol 95-57-8 C,H.C10
o >
l-(o-Chleropheoyl) C?H?C1N2S
thiourea
ro
o\
N)
3-€bloropropio- 542-76-7 C-H.C1N
Qitrlle J k
Chroaiua «o4 7440-47-3 Cr
coapounds, H.O.S.
(a* Chroalua)
175-176
Chrysene
216-01-9
44B
MELTING
POINT *C
M
COHBUSTIGN
kcal/nol
(kcal/graa)
MOLECULAR UEICHT
886
(6.89)
128.56
989*
(5.30*)
S-c-««*
0'
403*
(4.50*)
Cl
2140
(9.37)
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT *C
Citrus Red No. 2 6356-53-8 C18M16N2°3
Coal Tars 8007-45-2
N>
a*
Lo
Copper cyanide 544-92-3 CCuN
Creosote 8001-56-9 ca.203
Cresola
1319-77-3
191-202.2
MELTING
POINT *C
AH
COMBUSTION
kcal/*ol
(Ucal/graa)
MOLECULAR WEIGHT
884
(8.18)
U-CN
mixture of phenols
-------
BOILING HELTINC
REGISTRY NO. FORWLA POINT *C POINT *C
Crotoo-
aldehyde
Cyanides (soluble salts
hO and complexes), N.O.S.
ON
4S
Cyanogen
Cyanogen broaide 506-66-3 CftrN 61-62 52
Cyanoien 506-77-4 CC1N 12.66 -6
chloride
AH
COMBUSTION
kcal/mol
(kcal/graa) MOLECULAR WEIGHT STRUCTURE
542
(7.73)
ch5ch«chch
353
(6.79)
52.04
NC- CN
85.8*
(0.81*)
fcr-CN
79.3*
(1.29*)
61.47
Ci - CM
-------
CAS BOILING MELTING
KAHE REGISTRY MO. FORMULA POIHT *C POINT *C
Cycasin 14901-08-7 C8H16M2°7
2-£yclohejcyl-4.6- 131-39-5 C12H14H2°5 106 5-107
dloitropheool
Cyclophosphamide 50-18-0 C7H15C*2N2^2P
Daunoaycln 20830-81-3 C27H29M010
DOD
72-54-8
109-110
CaUUSTlON
kcal/Mol
(fccal/gcan)
MOLECULAR WEIGHT
989*
(3.92*)
1530*
(5.74*)
0°
"Oj.
1040*
(3.97*)
r°
3010*
(5.70*)
1640*
(5.14*)
L 'v»
N-44
-------
CAS
REGISTRY NO.
BOILING
POIWI *C
MELTING
POIHT *C
50-29-3
C10H17C12NOS 150
Dlbeaz(a,h)
•cridiae
W
Dibeu(i,J)
acrldlne
224-42-0
216
AH
COMBUSTION
kcal/aol
(Wcal/gran) MOLECULAR UEICHT
1610*
(5.05*)
1600*
(4.51*)
C Ci,
»oro
I* ? r
1520* 270.24 i-<.* -c »c
(5.62*) 4
2660*
(953*)
2660*
(9.53*)
-------
CAS BOILING MELT1NC
"*HE lECISTH MO. FOBMHA POIKI *C POIKT *C
DlbeniU.t) 53-70-3 C,,H , »ukl. 269-270
anthracene " "
Ta-Dibeulo(c.g) 194-59-2 C„H .* 158
crkuol. 20 15
NJ
O
VJ
DlbenxoU.e) 192-65-4 233-234
pyrcac « 14
DlkcoxoU.b) 189-64-0 281.5-282
pjr.ae 24 14
Dlbenzo(a»i)
pyrene
189-55-9
353-355
AH
COMBUSTION
kcal/aol
(kcal/gra») MOLECULAR WEIGHT
2620*
(9.40*)
2380*
(8.90*)
2820*
<9.33*)
2820*
(9.33*)
2820*
(9-33*)
-------
CAS BOILING MELTING
REGISTRY NO. FORMULA POINT *C POINT *C
to
ON
00
1.2-Dibroao-3- 96-12-8
cbloropropaae
1,2-Dibroaoethane 106-93-4
DlbroMonechane 74-95-3
Dl-fl-butyl
pbthalace
Dlchlorobeueoc 25321-22-6
(¦eta, orcho tad
para leoaers)
Dlchlorobeazene,N.0.S.
Ml
COMBUSTION
kcal/nol
(kcal/graa) MQLECUXJUt WEIGHT STRUCTURE
350*
(1.48*)
269*
(1.43*)
86.9*
(0.50*)
2040*
(7.34*)
672
(4.57)
BrCHi-CHBr-CHaCJ
BrCHj-CH], Br
»"i J
c-o t««a- tHj-
-------
CAS
REGISTRY NO.
BOILING
POINT *C
MELTING
POINT *C
3,3'-Dlchloro-
bauldiM
91-94-1
1,4-Dicbloro-2-
butCM
764-41-0
152.5(at 758mm)
to
as
534*
(4.27*)
ClCNiCH- CHCHiO
26.6*
(0.22*)
120.92
297
(3.00)
CHjCHQ^
297
(3.00)
98.96
CJHiC-CHiGI
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT *C
trans-1,2- 156-60-5
Dichloroetheoc
Dichloro*thyl«oe, 25323-30-2
H.O.S.
ro
O
1,1-Oichloroethyleoe 75"35-4
Dlchioro— th ine 75-09-2
2,«-&lc.hl0rophenol 12Q-S3-2
C2H2C12 *7,5
C2«2Ci2 37-61
CH2C12 40
C6H4Cl2° 210
MELTING
POIHT *C
&U
COMBUSTION
kcal/nol
(kcal/fcraa)
MOLECULAR WEIGHT
290
(3.00)
tJ H
\ / '
c = c
' V«
H Cl
-50-(-122)
262
(2.70)
262
(2.70)
0tC»CHk
144
(1.70)
ch2 az
621*
(3.81*)
-------
CAS
REGISTRY MO.
BOILING
POINT *C
NJ
-vl
2,6-Dichloropheool 87-65-0
2,4-Dlchloropheooxy 94-75-7
ACfttiC ACid
Dlcbloropheayl- 696-28-6
•rtlne
Dlchloropropaoe,
11,0.S
26638-19-7
1,2-Dichloropropaoe 78-87-5
96.37
LU
COMBUSTION
MELTING kcal/aol
POINT *C fkcal/era») MOLECULAR WEIGHT
621* 163.00 \ /~6H
(3.ax*) ^
jT\ '
800* 221.OA
(3.62*) \ /
520*
(2.31*)
o
A»cit
ca. -99-<-100)
447
(3.99)
CV
-100.44
451
(3.99)
112.99
CH3-CHCI - CHtCJ
-------
CAS
HAME REGISTRY NO.
Dlchloropropanol,
N.O.S.
Dichloropropene,
N.O.S.
ro
*-J
ro
1,3-Dlchloropropene 542-75-6
Dteidrin 60-57-1
BOILING MELTING
FORMULA POINT *C POINT *C
C3B6C12° ca' 146"176
C3H4C12 76-112
C3H4C12 104-112
C12Vlb° 17S-1 ?fa
1,2:3,4-Diepozybut*ne 1464-53-5
144,
-16-4
AH
COMBUSTION
kcal/aol
(kcal/graw) MOLECULAR WEIGHT STRUCTURE
366
(2.84)
128.99
382*
(3.44*)
382*
(3.44*)
2120*
(5.56*)
acHi.-c-H = chCi
° P
cj "0
494
(5-74)
86.10
-------
CAS BOILING MELT IMC
KECISTKY MO. FORMULA POINT *C POINT *C
Diethylamide 692-42-2 c4Hii** 103
U.N~Metbylbydr»xii* 1615-80-1 C«H12*2 ®5~*6
(O
l«<>
O,0-Dl«thyl S- 3288-58-2 c*Mit°5ps?
¦ethyl ester of * J
phocphorodlthlolc
icid
0,0-Dlethylphoephorlc 311-45-5 ciaHi4ii°Ap 169-170UC l«j
acid, O-p-nltroptaeayl
ester
Diethyl phthalate 84-66-2
298
AH
COMBUSTION
kcal/aol
(keel/area> MOLECULAR WEICUT
704* 134.05 (CH, CHj ) A* H
(5.25*) ^ IL
«5* 88.18
(6<68*) 3 *
(cHjCHjO^ P-S-CHs
(cwjr5-
¦O"
1420
(6.39)
222.26
a;
-------
CAS BOILING MELTING
REGISTRY MQ. FOtHULA POINT *C POIHT *C
0,0-Diethyl 0- 297-97-2 C8H13H2°3PS 80 ~1'7
2-pyrasiayl
phosphorothloate
N5
•C-
Diethylstllbeetrol
Dihydrouf role
3,4-Dihydroxy-
«lpba>(Mthyl*
*aiao)aethyl
benzyl alcohol
Dilsopropyl
f1uorophoephace
(DFP)
SS-91-4 C6H14F03P 183 -82
AH
COMBUSTION
kcal/aol
(Real/gram) MOLECULAR UEIGHT STRUCTURE
j^j
268.38 HO
Ot)
~\
1260*
(7.66*)
1110* 183.23 uo,
(6,05*) H0"
"7~\^
184.17
O
(O^Vc^-O-P-O-O*
S'l I
f
-------
CAS BOILING HELTINC
MAME REGISTRY MO. FORMULA POINT *C POIHT *C
Dlaeeho«C« 60-51-5 C5H12M°3PS2 52-52.5
3,3'-Diacthoxyb*axldla* 119-90-4 C1AH16N2°2 137-138
hO
Ul
p-UwthylnlDoua- 40-11-7
beauw
7,12-DiMtby lbcns (•)
Anthracene
3,3'-Dlaethyl-
bensidine
119-93-7
129-131
&H
CCKBUSTIOM
kc*l/»ol
(kcal/graa)
HOLECUUUt WEIGHT
922
{4.02)
« °
(cHj^P-J-CJji-t-NH C.H3
1800*
(7.16*)
VB-
WjCO
1570*
<6.97*)
2660
(9.61)
1470*
(8.81*)
nj»- ^ J
mOO"'
-------
CAS
REGISTRY NO.
BOILING
POUtt *C
MELTING
POINT *C
Dlaethylcarbaaoyl
chloride
1,1-Dlaethyl-
hydraziae
63(at 752m)
1,2-Dlaethyl-
hydrazlne
8l(ac 753m)
3,3-Di»ethyl-l-
(aechylthio)-
2-butaoone , 0-
((Methyluioo)
carbony1) oxlac
[Thiofanox]
alpha, alpha- 122-09-8
Dlaethylpheiicthyl-
AH
CdfflUSTION
kcal/aol
(kcal/graa) MOLECULAR WEIGHT STRUCTURE
H,<\ I
54'* 107.55 M- C - CI
(5.08*) t
„ CM.
473 60.12 H.N-N
(7.87) VtH
3
473 60.12 HjCNH- NH C-H»
(7.87)
1270*
(5.82*)
O-Miou)
I r
M
1420*
(9.54*)
149.26
HJCv /=\
)
-------
CAS BOILING MELTING
MAME tECISTBY MO. FORMULA POIHT *C POINT *C
2,4-Dlaethylpbenol 105-67-9 C8H10° 211'5 27~28
Dlaethyl pbctuUc* 131-11-3 C10H10°4 283.8 0-2
ro
-vJ
Dlaechyl sulfate 77-78-1 C2H6°4S C-< 188d "21
Dinltrobanaene, 25154-54-5 C.H.N,0. 291-319 89-174
N.O.S. 6424
4,6-Dlnlcto-o- 534-52-1
cretol (and sales)
86.5
&H
CCHAUSTIOM
kcal/aol
(kcal/graa)
MOLECULAR WEIGHT
1040
(8.51)
1110
(5.74)
C«t
cm,
o
o
1-6tH,
C-OtHx
9 *
0
361
(2.86)
OOb
I
Om£_ (JCXj
D
698
(4.15)
MO,
•NO,
804*
(4.06*)
OH
"0*
MO,
-------
CAS
REGISTRY NO.
2,4-Dinitrophenol
51-28-5
NJ
00
2,4-Dloltrotolu*ne
2,6-Dlnltrotoluene
W-«-octyl
phthalAt*
FORMULA
BOILING
POINT *C
MELTING
POINT *C
Wl0J
subl.
115-116
1, 4-DIoxim
123-91-1
101 (at 750m) 11.8
&E
COMBUSTION
kcal/aol
(kcal/era«)
MOLECULAR WEIGHT
648
(3.52)
832
(4.68)
OH
rHli
Oit
rNO,
852
(4.68)
MO*
2600*
(6.67*)
565
(6.41)
88.10
0
-------
CAS BOILINC KELT IMC
IECISTRT MO. FORMULA POIKT *C POIKT *C
Dlpheaylaalo* 122-39-4 C12H11N 302 53-55
1,2-Diptwayl 122-*6-J C12H12N2 131
hydrazine
to
•vj
-------
CAS
REGISTRY NO.
BOILING
POINT *C
MELTING
POINT *C
Eodrin 72-20-6
(and metabolites )
NJ
CO
o
Ethyl carbamate 51-79-6
182-IC4
Echyl cyanide 107-12-0
79(ac 775—) < -66
Ethylenebls- 142-59-6
dithlocarbaalc acid
(salts and esters)
Mi
COMBUSTION
kcal/aol
(kcal/graa)
MOLECULAR WEIGHT
948*
(2.33*)
>-
1320*
(3.46*)
421*
(4.73*)
H1N-C-OCH1CH3
252 55.09 C.H, CM. C.KI
(4.57) 3 1
&
1460* 256.34 I
(5.70*) c.h^nh-c-5-Mi*
-------
CAS BOILING HELTIMG
REGISTRY MO- FORMULA POIMT *C POINT »C
Ethyleneleloe 151-56-4 CzV 56-57
Ethylmm 75-21-® C^O
oxld*
Ethylua-
ChlOUTM
Ethyl Mthacrylatft 97-63-2 117
Ethyl 62-50-0
¦ethuMftulfooAte
ca. 85-86 (at LObb)
&H
COaUSTION
kc«l/w>l
(kcal/gTM) MOLECULAR WEIGHT STRUCTURE
339*
(7-86*)
302
(6.86)
611*
(5.98*)
/\
CH,
A
V ut,
Cf
' MM
030*
(7.27*)
0
CHl=C-C-OCHiCHj
en.
CM,
o
a
-s
a
o
OCHiCHj
-------
CAS
KlftlSm NO.
POLLING
POINT °C
!¦ 1 loraitt iw
C16»10
ca. 373
776w-4i-4
IS3
00
N)
2-I I uoruaceLauiidc
640-19-7
Kluortvacetjc
acid, sodium &all
62-74-B
FoiTMldeltyde
50-00-0
-19.5
All
CLNliUSTJON
MIXI INt^ Ucal/mol
LPJNJl (kcal/firato) HOLIXULAK WKlCliX
1890 ?0?. i(i
(9.35)
T I
250 /? .0? CH F -C-N J
(3.2U)
NaT (Ch.F - t O)
-92
13^
(i-47)
3a. Oi
-------
CAS
REGISTRY MO.
Ni
00
U)
Ponlc acid
Glxcld/ltldchydt
lUlOMthMC,
M.O.S.
HtpCtcblor
UeptAchlor
epoxide
(alplu, bet* and
gaai leoaers)
1024-57-3
BOILING
POINT *C
MELTING
POINT *C
100.5
CH^X
»S-96
an
COMBUSTION
kcal/aol
(teal/gram) MOLECULAR WEIGHT STRUCTURE
60.8
(1.32)
O
H
CH-OH
414
(5.74)
72.07
V7
CM * O
CH#-X
o d
1100*
(2.96*)
1060*
(2.71*)
373.30
O
a a
-------
CAS
REGISTRY WO.
BOILING
POINT *C
MELTING
POINT *C
Hexechloro-
benzene
323-326
Hexachloro-
butedlene
N)
00
4>-
Hexechloro-
cyclohmne
(ell Itoaers)
608-73-1
Hexachloro-
cyclopentedlene
239(at 753m)
Bexechloroethene
67-72-1
186.8
subl.
Ail
COMBUSTION
kcal/aol
(kcal/gran)
MOLECULAR WEIGHT
510
(1.79)
a
Ci
553*
(2.12*)
326*
(1.12*)
C.
t itomtrj
573*
(2.10*)
-8
cj
109
(0.46)
236.72
-------
CAS
aECIST&Y HO.
BOILING
POIHT *C
MELTING
POIHT *C
NJ
00
Ui
1,2,3,4,10,10-
HezJchloro-1,4,
4a,5,8,8«-
hexAliydro-l., 4:5, B~
dteethaooaaphchaleae
HtxiehldropheM 70-30-4
Ueuchloroprop«u
c«. 209-210
HaxMthyl
tftriphoaphitt
>150d
Hydr*xlaa
302-01-2
113.5
2.0
AH
CCMBUST10M
kcal/aol
(kcal/gr—1 MOLECULAR WEIGHT
1230*
(3.39*i
1550* 406.69
<3.»2*)
174*
CI
a
a
OH OH
'OXj
CLC- C-CCI,
(0.70*) J ^
506. W
t-,-
^ V'
J i-
eV
, -c^-« *e
142*
(4.44*)
32.06
H2«* - N
-------
NAME
CAS
RECISTKY MO.
FOBHULA
BOILING
POINT *C
Hydrocyanic acid 74-90-8
Hydrofluoric acid 7664-39-3
K>
00
ON
Hydrogen sulfide 7783-06-4 H,S -60.33
Hydroxydlaecbylartlne 75-60-5 C_H_As0,
oxide 21 2
Indeoo (1,2,3-c.d) 193-39-5
pyreae
MELTING
POIWT *C
AH
CGKBUST10H
kcal/aol
(kcal/gran)
MOLECULAR WEIGHT
HF
HiS
2350*
(8.52*)
-------
CAS BOILING MELTING
mm KECISTET WO. FOgHULA POIMT *C POIKT *C
lodoaathane 74-86-4 CU^K 42.4 -66.5
Iron dtKtra 9004-66-4
(coaplex)
ro
00
Isocyaalc acid, 624-85-4 C_H_tt) 59.6 -45
¦ethyl «*c«r
Iaobutyl Alcohol 76-63*1 C,H,_0 106 -104
4 10
IsoMfrole 120-56-1 C1DH10°2 253 8*2
AB
COMBUSTION
kcal/mo2
(kcal/eraa> HOLECULA& WEIGHT
190
(1.34)
CH.I
^180,000
268*
(4.69*)
O- C -N-CH,
-------
C*5 BOILING MELTING
REGISTRY MO. FORMULA POIKT *c POIKT *c
Itepooe 143-50-0 C10C110°
Laslocarplne 303-34-4
N>
00
00
Lead aad 7439-92-1
compounds, N.O.S.
(*• Lead)
Lead acetate
Lead phosphate
7446-27-7
1014
AU
COMBUSTION
kcal/aol
(kcal/graal MOLECULAR WEIGHT STRUCTURE
1050*
490.60
(2.15*)
a.
.2
\
1 1 ' 1
207.19
(CMj-C
811.59
h'')}">/)z
-------
CAS BOILING MELTING
KAHE 1ECISTKY MO. FOKHULA POINT *C FOIKT *C
L«ad aubaceut* 1335-32-6
Mal*lc 108-31-6 C,H,0_ 20Z.0 52.8
•ohydrlda
N?
00
\D
Maltlc fayd»sl4* 123-33-1 26Od >300
Miloooftltrll* 109-77*3 C3H2*2 219-219 12
Mftlphal«tt
146-82-3
1B2-I83d
Alt
COtBUSTtOH
kcAl/aol
(kcal/«ra») HOLECUUB WEIGHT
333
(3.40)
1590*
(S.21*)
•07.71 Pt»*(tH^C-CT )2 Z
H
°V'Mv
460* 112.10 I 'J*'
(4.10*)
u
CN
395 66.07 CH
(5.98) Kfjt
¦c" - r
-------
CAS 80ILINC MELTING
REGISTRY HQ. FORMULA POINT *C POINT *C
Mercury fulminate 628-86-4 CflHinH*°^S explodes
Mercury and 7439-97-6 Hg 336. 72 -36.87
compounds
N.O.S.
(as Mercury)
Methacryloaltrlle 126-98-7 C^N 90.3 -35.8
Methane thiol
Methapyrllene
91-80-5
173-175(at 3»)
Ml
COMBUSTION
kcal/aol
(kcal/graa) MOLECULAR WEIGHT STRUCTURE
H^CCNO^
200.59
574* 67.10 CH.»C-CN
(8.55*)
284*
(5.91*)
2070*
(7.93*)
-------
CAS
IECISW MO.
Metholayl
Hetboxycblor
N>
v£>
2-NechylMlrldiM 75-55-8
3-ffethylcbolinthrene 36-49-5
BOILING
POINT *C
MELTING
POIMT *C
w
78-79
78-78.2
66-86
280(ftt 80*) 179-180
HethjlchiorocarboaaCe 79-22-1
C2H3C1°2
71
AH
COHBUSTIOM
kcal/mol
(kcal/itr—) HQLECULAK WEIGHT STRUCTURE
844*
(5.20*)
CH -c»w
i-cw-
O-C -NH-C.H
19)0*
<5.59*1
519*
(9.09*)
2570*
(9.57*)
0*0-
n
A.
-------
"s BOILING MELT INC
REGISTRY NO. FORMULA POINT 'C point 'c
4,4'-Methyleoe-
bis(2-chloro-
aniline)
101-14-4
Methyl ethyl
ketone (MEK)
78-93-3
ro
10
ro
Methyl
hydrazine
2-Methyllacto-
nltrlle
C^NO
Methyl
¦ethacrylate
100-101
AH
COMBUSTION
kcal/aol
(kcal/grai)
MOLECULAR UEIGHT
1290*
(4.84*)
;cra
582
(B.07)
312*
(6.78*)
46.09
54 7
(6.43)
CN-C-CH,
\ 3
Oh
653*
(6.52*)
-------
CAS BOILING MELT1HG
KECI8TRY MO. FORMULA P01KT *C POINT *C
Ifechyl
aethaoMulfoMt* 66-27-3 C,Ht0 S 203 (at 753m)
2-*tethyl-2-(«tbylthlo) 116-06-3 C-H. .R.0.S
P rop loaAldchydc
-0- (at thy lcftrbeoy 1)
oxlaft
H-Mctbyl-N'- 70-25-7
Dltnrlh
nlcrosofuAiildiQ*
Matbyl 298-00-0
pacichloa
Nechyl
Chiouracll
56-04-2
326-33U
&H
COHBUSTICH
kcal/aol
(kot/grw.)
MOUCULAB WEIGHT
412
(3 74)
C^-S-CHj
0
1020*
(5.34*)
?S
597*
(4.06*)
HN^C-NH-NC^
1050*
(4.00*)
3 >-o
681*
(4.79*)
H
vrr
VMH
-------
CAS BOILING MELTING
NAME REGISTRY no. FORMULA POINT *C POINT *C
Mustard ga» 505-60-2 C^CljS 215-217 13-14
Itepfathalne 91-20-3 217.9 80.2
NJ
vO
4^
l,4-N*pbthoquinoM 130-15-4 C10H6°2 subl. 126
1-N*phtbylaalnc 134-32-7 ciOH911 301 50
2-tUphtbTUmlne 91-59-8
306
111-113
Ml
COMBUSTION
kcal/aol
(k-c»l/gra»)
H0LECUU& WEIGHT
646*
(4.06*)
1230
(9.62)
126.18
1100
(6.97)
1220
(8.54)
NH,
1220
(8.54)
MH,
-------
CAS
KECXSTtt HO.
lHhpbthyl
-2-Chlouraa
K>
v£>
Ln
N.O.S.
(as iickal)
Nlck«l carbooyl 13463-39-3
Nlck*l cyanide
557-19-7
•OILING
POINT *C
MELTIMC
POIWT *C
Wl
Nicotine (and
salts)
54-11-5
247 (at 745mb)
AH
COMBUSTION
kcal/nol
(kcal/graa) MOLECULAR UEICttT
1520* 202.29
(7.50*)
5a. 7i
170.75
110.7
1450* 162.26
(8.92*)
STRUCTURE
Ni4(CO")^.
Ni**(c»r\
-------
CAS
HAKE RECISTKY WO.
tllcrlc o*idc 10102-43-9
p-MitroaoiUne 100-01-6
Mltrobcuta* 98-95-3
tttcrogca dloxld* 10102-44-O
FOILING MELTIMC
FOKMUU POINT *C P01MT *C
MO -151.7 -163.6
C6U5»2 210-211 6
21.15 -9-3
Nitrogen Miaurd
(sad
hydrochloride Mlc)
51-75-2
87
AH
COMBUSTION
kcal/aol
(kcal/graa) MOLECULAR WEIGHT STRUCTURE
N • O
760
(5.50)
677
(5 50)
o
o
0-W=0
CH,-CH Cl
r;„> 156.o7 ch3-NccHj.CMjC1
-------
CAS
BOILINC MELTIHC
EECISTKY MO. FORMULA POINT *C FOIHT *C
Nitrogen austard 126-85-2 CJL CI »(-BCl)
M-Oxldc Und 302-70-5 -CI (• HC1) 311 ^
hydrochloride ult)
NltroglycerlA* 55-63-0 C3U5M3°9 50-60 d 2.8
VO
4-Nltrophenol 100-02-7 279d 113-114
4-Nltroqulaollne 56-57-5 CflH.N_0, 154
, . , y o i J
-1-oxlde
Mltros«aia«,
N.O.S.
&H
COMBUSTIOM
kc*l/wol
(tc«l/gr»») HOLECULAK WEIGHT
613 172.07 CICH-CMt-N-CH3
(J.56) 208.53 ( HC1) CH, CH,CI
c ^ - o - NO,
«61 227.11 tH,-0-NO„
CH -O-Not
689
(4.95)
MO-^^-NOi
1060
(5.59)
190.17
M0t
CO
-------
CAS SOILING MELTING
RECISTIY MO. FORMULA POINT *C POINT *C
N-Nlcrosodi- S24-16-3 CAXO
Q-butylaaioe
M-Mitrosodi- 1116-54-3 C-tL-M-O.
echanolamlne 4^° 2 3
N-Mlcrosodl- 55-18-5 C4lLnM-0 175-177
cthylaalae 4 *° 2
N-Nleroso4i- 62-75-9 C?H&H3° 151-153
aethylaaioc £
H-Nitroao-W- 759-73-9 C-H-H-O.
ethylur** 3 1 3 i
CCMBUSTIOH
kcal/aol
-------
CAS BOILING MELTING
MAKE areigraT up, FOBHULA POIKT mC POIHT *C
N-NltroMMChyl-
•thylselne
M-Nitroao-N-
¦ethyiutu
6S4-9J-5
WA
123-I24d
K3
SO
V0
K-MlCroso-lh
iBthylurathftni
615-53-2
63(ac 13n)
«-Mitro*o- 4549-40-0 ciH*M
Mthjflvlojrluiu
N-Nitroso-
¦orfholinc
59-69-2
AH
CQHKUSTIOH
kctl/mol
(kol/Br»») H0LECUL4K UEIGBT
N*0
I
5*0* 88.13 CW-N-CH-CH,
(6.13») 1 * 3
2M* 103.10 CH.-N-C-NH.
(2.69*) 1 S. 2
"2« 1J2.H CH.-N-C-0-CH-CH
N = 0
-c-
«
0
H*0
681* 86.11 CH-N-CH-CH
(7.91*) # *
60«*
(5.22*)
116.14
-------
BOILING MELTING
REGISTRY MO. FORMULA POINT *C POIKT *C
H-Nltroao- 16543-55-8 (LB HO
nornlcotine
N-Nitroao- 100-75-4 C.H..N.0 217(at 721m)
piperidlne >wz
U>
o
o
H-Nitioso- 930-55-2 CzH«M ca. 214
pyrrolidine
M-NlCroso-
UtCMlM
5-Nltro-o-toluldine 99-55-8
C7V2°2
107-108
AH
C0HEUST10M
kcal/aol
(kcal/graa)
MOLECULAR WEIGHT
1250*
(7.07*)
Ot5
804*
(7.04*)
644*
(6.43*)
377*
(3.19*)
H'O °
i a
CH-N-CH- C-OH
910
(5.98)
152.17
.,0*
-------
CAS BOILtNC MELTING
KECIST1Y M. FQtMOLA POIHT *C POINT *C
Octaaethylpjrxophos- 152-14-9 CJL.H.O,*. 154 (at 2.0m)
pbor*al4* 8 M 4 3 2
Oaaiu* C«troxl
O
?-Oublcy«lo[2.2.1)
hept»ne-2,3-dl-
carboxyUc acid
Panldchydt 123-63-7 C6HI2°3
Parathlon
56-38-2
6
&H
caausiiw
kcal/aol
-------
CAS
NAME REGISTRY HQ,
Peatftchlorobenxeae 608-93-5
Pentachloroechane 76-01-7
LO
O
NJ)
Pent*chloroaitro- 62-66-6
beAseoe (PCUB)
Pt&Uchlorophutol 87-86-5
BOILING MELTING
FOBMULA PQIHT *C POINT *C
C6HCX5 277 86
C2BC15 161-162 -29
C6C15»02 328d 144
C&HC1 0 309~310d 190-191
Phenecetln
62-44-2
134-135
AH
CCMBUSTIOM
kcal/aol
(kcal/fcraa) MOLECULAR WEIGHT STRUCTURE
a
513*
(2.05*)
ci
a
107^> 202.28 CI^CH CCIj
MO,
478* 295.32
a-62,> oLAo
a
557
(2.09)
a o
a
1290
(7.17)
-------
CAS BOILING MELTING
KECism wo, rowla eoitrr *c point *c
Phenol
Phnyl«Dft41Mint a 106-45-2 C.H.M. ¦ 214-247 ¦ 62-63
q 95-54-5 0 B 1 o 256-25B o 103-104
p 106-50-3 p 267 p 145-147
U>
O
LJ
Phenylaercury 62-36-4 CgB.ttf0j 149
•ceuca
M-fb«nylthiourea
Phoagane
75-44-5
8.2
-118
m
COMMOTION
kc*l/mol
(kc*l/er»») HOLECMJUt WEIGHT STRUCTURE
732
<7.78)
845 106.16
(7.81)
o*
0
(5
»»• J34.75 / V-rfoE-
(2.71*) f
a-
10S0*
(6.93*)
-O
98.91
C^C = O
-------
0X3 BOILINC MELTING
REGISTRY WO. FOfcMULA POINT *C POINT *C
Phosphlne 7803-51-2 H-P -87.7
Phosphorodlthiolc 298-02-2 C-H.-O.PS. 125-127(at 2.0m)
acid, 0,0-diethyl i if 2 3
S-((ethylthio)acchyl)
MCei(Phortte]
Phosphorothioic acid, 52-85-7
O.Q—dimethyl 0-(p-
((dlaethylaaino)sulfonyl)
phenyl)ester(Faaphur)
52.5-53.S
Phthalic Acid
esters, M.O.S.
Phthalic anhydride 85-44-9
w
128-129
AH
CCHBUST10H
kcal/w>l
(kcal/graa) MOLECULAR UE1GHT
784
(5.29)
ph3
(cH3CH2°)r P-5cH£5-CHiCH3
i
c-o - ^
a
812
(8.72)
93.14
o
-------
CAS BOILING HELTtNC
MAKE KECISTW MO, FOPfllLA POIMT *C PQ1HT *C
Polychlorinattd 1336-36-3 C,,H,A CI
biphanyl, B.O.S. 12 lft_x *
Potatclua cyanide 151-50-8 CKN 634
LO
O
in
PotMilu* 506-61-6 C24tKjf2
silver cyinldi
Proaaalda 239SO-58-5 Ci2HijC12N0
1,3-PropaM sulfonc 1120-71-4
ca. 180Uc 30m) ca. 30-33
AH
COMBUSTION
kcal/w>l
tkcal/eraa) H0LECU1JUI WEIGHT
1470*
<5-72*)
* XX
fK>
% X«- M ,Cl
K*(CN~)
U
448*
(3.6?*)
r
-------
CAS
MAKE REGISTRY MO.
Q-Propylaaioe 107-10-6
Propylthiouracil 51-52-5
U)
O
ON
2-Propyn-l-ol 107-19-7
Pyridine 110-86-1
BOILING MELTING
FOmUlA POINT *C POINT *C
C3H9N 48-49 -83
C7H10N2OS 219-221
CjH^O 114-115 -48-(-52)
CjHjH 115-116 -42
Reserplne
50-55-5
264-265d
AH
COMBUSTION
kcal/aol
(kcal/graa)
MOLECULAR WEIGHT
566
(9.58)
1070*
(6.28*)
417*
(7.43*)
HCSC-C-OH
619
(7.83)
4080*
(6.70*)
Up
-------
CAS SOILING MELTING
EECISTKY MO. FORMULA POIKT 'C POINT *C
tesoxclaol 106-46-1 C6B6°2 280 109-111
Saccharin
(and sales)
U>
O
Safrole 94-59-7 C10H10°2 232-234 11
S«l*nloufl acid 7 783-00-8 H^S*
Salitalus and co^oudi, 7792-49-2
i.0.S.
(•» Selenium)
685
AH
COMBUSTION
kctl/Bol
(fccal/w—)
MOLECULE WEIGHT
682
(6.19)
ON
OH
823*
(4.49*)
1250
(7.66)
r
G*< -•
128.90
0»Se
.aw
76.96
-------
CAS BOILING
RECISTRY MO. FORMULA POIHT *C
Selenlu* sulfide 7446-34-6 SSe
Seleoourea 630-10-4 CH^N^Se
LO
O
00
Silver and co^otrads, 7440-22-4 Ag ca. 2000
H.O.S.
(as Silver)
Silver cyanide 306-64-9 CAgN 320d
Sodlua cyanide
143-33-9
CM Ha
AH
COMBUSTION
MELTING kcal/aol
POINT *C (kcal/graa) MOLECULAR WEICtiT
960. 5
S* Sc
A9*(CM")
563
49.01
Nfc (CN~)
-------
CAS
MAKE EEGISTKY MO.
StnptuotoclB
ScroaCiiM sulfide 1314-96-1
U>
O
V0
Strychnia* (and talta) 57-24-9
1.2,4,5-Tctrachlcro- 95-94-3
b«ax«ac
BOILING MELTING
FOKMUU POIWT *C POIHT *C
Vu-3tt7
SSr
C2AA°2 270(aC 5m) 268-290
C6H2C14 243-246 139.5-140.5
2,3,7,8-T«ttichlorodl- 1746-01-6
benso-p-dloxin (TCDD)
> 700d
305
AH
COMBUSTION
fecal/sol
(kc*l/gra»)
HOLECULAt WEIGHT
CM.4N
ft
m MM - W - M *
S- Sr
2690
(8.03)
563*
(2.61*)
1100*
(3.43*)
-------
CAS
REGISTRY NO.
Tetrachloroeth&o*,
H.O.S.
1*1,1,2-Tetr«chloro-
ethane
630-20-6
U>
1
o
1,1,2»2-Tetrachloro-
cthane
Te trachloroe thene
W1«
BOILING
POINT *C
MELTING
POINT *C
121
Tetrachloroaethaoe 56-23-5
76.7
-23
AH
C0KBUSTI0N
kcal/*ol
(kcal/graa) HOLECULAR WEIGHT STRUCTURE
233
(1.39)
233 147.84
(1.39)
233
(139)
197
(1-19)
34.9
(0.24)
-------
CAS BOILING HELTIHC
RECISTO WO. FQBHULA POINT *C POINT "C
2,3»4,6~T«£rjchloro- 53-90-2 C6H2Cl4° 150 15™#) 70
phenol
Tetraethyl- 3689-24-5 COJ.S. 136-134 <*t 2m)
dlthiopyrophosphate *
Tecraethyl le*d 78-00-2
Tctraethylpyro- 107-49-3 C8H20®7P2 I55(*t 5wm) l70-213d
phoaphae*
TttraoltroMtHtM 509-U-S
126
11.8
AH
CCKBUSIlOtl
kcal/aol
(fccal/graa) H0LCCU1AK WEIGHT STRUCTURE
^ •)
C M -6H.-Q * -
322.34 * * vP-0PT 4 *
1310* 323.47 CH-CH -Pk-CH.-CH.
(4.04*) ' * *
6V<
CH,-o'
,0-CHj-OH
"0-CM,-CM
80.4*
(0.41*)
196.OS
c
-------
MAKE
CAS
fcECISTRY WO.
FORMULA
BOILING
POIWT *C
Thallium and compounds 7440-28-0 T1
H.O.S.
(as Thalllu*)
Thalllc
H4
N>
Thalllua(I)acetaee 563-68-8 C^HjO^Tl
Thalliua(I)carbonate 6533-73-9 CAjTlj
Thallt«(I)chloxide 7791-12-0
C1T1
AH
COMBUSTION
MELTING kcal/«ol
POIWT 'C (kcal/gra») MOLECULAK WEIGHT
0 « T l~ O * T» *0
(K-
-------
CAS SOILING HELTIHC
fcEGlSTWt HO. FORMULA POIWT 'C POINT 'C
ThallluB(I)nitr«tc 10102-45-1 JWjTJt 450d 206
U>
M
U>
Ttulliiw ttleoita
IhlMCtCUltfl
TbloiC«lc«riMfld< 79-19-6
182-184
AH
COMBUSTION
kcal/ftol
3
415
<*-55)
91.15
S
H^N-C - MH NHj
-------
CAS BOILING MELTING
MAHE REGISTRY HO. FOWUtA POIMT *C POIHT *C
Thiourea 62-56-6 CH^S 176-178
Thlur« 137-26-8 1S5-156
o 12 2 *
U>
h-»
4^
Toluene 100-63-3 CyH$ 110.6 -95
Toluenediaaioe 25376-45-8 C7H10M2 255-292 < 0-106
0-Toluidlae 636-21-5 C-1L Cltf 242.2 215
hydrochloride
AH
COMNJSTIOU
kcal/aol
(kcal/graa) MOLECULAR HEIGHT STRUCTURE
346
(4.55)
1410*
(5.85*)
934
(10.14)
1010*
(8.24*)
952*
(6.63*)
s
II
H k|-C-UH„
(ch^-n-c-s-s-c-n-Cch^
-------
CAS BOILING
NA.ML RECtSTRY NO. FORMULA POINT cC
Tolylene dilsocvannte 584-84-9 251
y w 1 i
To^ipUeno 8001-35-2 °10H10CI8
lor i»lxcure)
^ Trlbrunamcchane 75-25-2 CHRij 140—15(»
I ,2,4-frlclilovo- 120-82-1 213
benzene
1,1,1 —T r I chloroel luiiiit
71-55-6
V\. 1
Ail
COfUlUSTION
HK.LTJ NO ki:al/nol
POINT °C (kcal/gram) M01.ErUj.AK WliHJ»T
1.9.5 -21 - ri 1030* 174.15
(5.92*)
»*; C - o
'--"Kr"'
1030* 413.60 'I „ f"!
(2.50*) 2{,
32.9 252 - 75 HCBk.
(0.13) "
617* 181.64
(3.40*)
r
Ci
-32.5
265
(1-99)
1 13.40
-------
CAS
RECXSTKY MO,
BOILING
POIMT *C
MELTING
POIHT *C
1,1,2-Trlchloroethane 79-OO-S
113-114
U>
ON
Trlchloroethene 79-01-6
Trlchloroaethaoethlol 75-70-7
TricUonaM»fluocoMth«M 75-69-4
2,4,5-Trlchlorophen0l 95-95-4 C,H,C1.0 253 67
o ] 3
ta
COMBUSTION
kcal/eol
(kcaL/graa)
MOLECULAR UlilCHT
265
(1.99)
CC\_ H - C VI CI
229
(1.74)
CCla* CCltt
127*
(0.84*)
C Cl3-SH
15.1*
(0.11*)
F - C - CI
569*
(2.88*)
-------
CAS BOILING MELTING
MCtSTtT HO. FOKMtflA POIOT *C POINT *C
2,4,6-TrichloEopbenol 88-06-2
2,4,5-Tridiloropbaioxy- 93-76*5
acetic acid (2,4,5-T)
UJ
2,4, S-TrlchlorophenoJiy- 9J- 72-1
propionic acid (2,4,5-Tf)
(Silvan)
Tclehloropropaaa.
H.O.S.
1,2,3-Trichloropropao«
96-18-4
156-85
-14. 7
AH
COMBUSTION
kcal/aol
(kcalZ&TAe) MOLECULAR tfEltMT
569* 197.44
(2.88*)
733*
(2.67*)
1500* 269.51
0.58M
414
(2.an
OH
•0'
D
H
0-CHtC-»M
.0"
0
-O
Ci
Ci
414
(2.61)
147.43
CH^CI-CHC I - CH^CI
-------
CAS BOILING MELTING
RECISTRY NO. FORMULA POINT *C POINt "C
0,0,0-Trlethyl 126-68-1 C6H15°3PS
phosphorothioate
U)
00
sy*-TrInitrobenzene
TrlsCl-uridinyl)
phosphlne sulfide
Tris(2,3-dlbroaopropyl)
phosphate
Trypan blue
72-57-1
AH
COMBUSTION
fecal/sol
Qccal/gran)
MOLECULAR WEIGHT
656
(3.06)
CW^.0.CH
O"
NOj
l
Nf P a-S
k 3
pf 0CH1tH6r CMjiBr-^
3690*
(3.B4*)
-------
CAS SOILING MELTING
kbcistw »a. roauu ponri *c ?om *c
Uracil auacard 64-75-1
OJ
ViMdii* p«8(oxl4e 1314-62-1
VUyi chloride ?5-01-« C,M,C1 -I*
Use cytold* SS7-21-1
Zloc pboaphid*
1314-84-7
1100
420
tu
COMBUSTION
kcal/aol
(kcal/fr*m) HOLECUUIB WEIGHT
10l0«
(4.0G*)
H vJ
r y
(v°3>n;)
o
n»* isi.b# \-o-v*
(4.45*) 0* "°
CI HC .
(2-;'i iw\
<"J'X
-------
APPENDIX B
Hazardous Constituents - Stack Gas Sampling Methods
Appendix B catalogs the Hazardous Constituents listed
in 40 C.F.R. Part 261, Appendix VIII (May 20, 1981)
with a description of their most probable location
in the stack gas effluent sampling scheme.
320
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS
Compound
Description
Acetonitrile
Ace tophenone
3-(alpha-Acetonylbenzyl)-4-hydi,oxycoumarin and salts (Warfarin)
2-Acetylaminofluorene
Acetyl chloride
1-Acety1-2-thiourea
Acrolein
Acrylamide
Acrylonitrile
Aflatoxins
Aldrin
Ally! alcohol
Aluminum phosphide
4-Aminobipheny1
6-Amino-l,1a,2,8,8a,8b-hexahydro-8-(hydroxymethyl)-Sa-
me thoxy-5-me thy lcarbamate azirino[2',3':3,h]pyrrolo
[l,2-a]indole-4,7-dione(ester) (Mitomycin C)
Gas Bulb
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Gas Bulb
Sorbent
Gas Bulb
Sorbent
Gas Bulb
Particulate/Sorbent
Particulate/Sorbent
Gas Bulb
Particulate
Particulate/Sorbent
Particulate/Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound Description
5-(Aminomethyl)-3-isoxazolol Sorbent
Amitrole Sorbent
Aniline Sorbent
Antimony and compounds, N.O.S. Particulate/Impingers
Aramite Particulate/Sorbent
Arsenic and compounds, N.O.S. Particulate/Impingers
Arsenic acid Particulate/Impingers
Arsenic pentoxide Particulate/Impingers
Arsenic trioxide Particulate/Impingers
Au'ramine Particulate/Sorbent
Azaserine Sorbent
Barium and compounds, N.O.S. Particulate
Barium cyanide Particulate(metal)/lmpingers(CN)
Benz(c)acridine Sorbent
Benz (a)anthracene Particulate/Sorbent
Benzene Gas Bulb
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound Description
Benzenearsonic acid
Particulate/Impingers
Benzene, dichloromethyl-
Sorbent
Benzenethiol
Sorbent
Benzidine
Particulate/Sorbent
Benzo(b)fluoranthene
Particulate/Sorbent
Benzo(j)fluoranthene
Particulate/Sorbent
Benzo(a)pyrene
Particulate/Sorbent
p-Benzoquinone
Sorbent
Benzotrichloride
Sorbent
Benzyl chloride
Sorbent
Beryllium and compounds, N.O.S.
Particulate
Bis(2-chloroethoxy)methane
Sorbent
Bis(2-chloroethyl) ether
Sorbent
N,N-Bis(2-chloroethyl)-2~naphthylamine
Particulate/Sorbent
Bis(2-chloroisopropyl) ether
Sorbent
Bis(chloromethyl) ether
Gas Bulb/Sorbent
Bis(2-ethylhexyl) phthalate
Particulate/Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound
Description
Bromoacetone
Bromomethane
4-Bromophenyl phenyl ether
Brucine
2-Butanone peroxide
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol (DNBP)
Cadmium and compounds, N.O.S.
Calcium chromate
Calcium cyanide
Carbon disulfide
Carbon oxyfluoride
Chloral
Chlorambucil
Chlordane (alpha and gamma isomers)
Chlorinated benzenes, N.O.S.
Chlorinated ethane, N.O.S.
Sorbent
Gas Bulb
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate
Particulate
Particulate(metal)/impingers(CN)
Gas Bulb
Gas Bulb
Special Reagent
Particulate/Sorbent
Sorbent
Sorbent
Gas Bulb/Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound Description
Chlorinated fluorocarbons, N.O.S.
Gas Bulb/Sorbent
Chlorinated naphthalene, N.O.S.
Sorbent
Chlorinated phenol, N.O.S.
Sorbent
Chloroacetaldehyde
Special Reagent
Chloroalkyl ethers, N.O.S.
Gas Bulb/Sorbent
p-Chloroaniline
Sorbent
Chlorobenzene
Sorbent
Chlorobenz ilate
Particulate/Sorbent
p-Chloro-m-cresol
Sorbent
l-Chloro-2,3-epoxypropane
Sorbent
2-Chloroethyl vinyl ether
Gas Bulb/Sorbent
Chloroform
Gas Bulb
Chloromethane
Gas Bulb
Chloromethyl methyl ether
Gas Bulb
2-Chloronaphthalene
Sorbent
2-Chlorophenol
Sorbent
1-(o-Chlorophenyl)thiourea
Sorbent
-------
HAZARDOUS CONSTITUENTS
• Compound
3-Chloropropionitrile
Chromium and compounds, N.O.S.
Chrysene
Citrus red No. 2
Coal Tars
Copper cyanide
Creosote
Cresols
Crotonaldehyde
Cyanides (soluble salts and complexes), N.O.S.
Cyanogen
Cyanogen bromide
Cyanogen chloride
Cycasin
2-Cyclohexyl-4,6-dinitrophenol
Cyclophosphamide
Daunomycin
STACK GAS SAMPLING METHODS (Continued)
Description
Sorbent
Particulate
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate(metal)/impingers(CN)
Sorbent
Sorbent
Special Reagent
Impingers (CN)
Gas Bulb
Gas Bulb
Gas Bulb
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Part iculate/Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound Description
DDD
Particulate/Sorbent
DDE
Particulate/Sorbent
DDT
Particulate/Sorbent
Diallate
Sorbent
Dibenz(a,h)acridine
Particulate/Sorbent
Dibenz(a,j)acridine
Particulate/Sorbent
Dibenz(a,h)anthracene
Particulate/Sorbent
7H-Dibenzo(c,g)carbazole
Particulate/Sorbent
Dibenzo(a,e)pyrene
Particulate/Sorbent
Dibenzo(a,h)pyrene
Particulate/Sorbent
Dibenzo(a,i)pyrene
Particulate/Sorbent
1,2-Dibromo-3-chloropropane
Sorbent
1,2-Dibromoethane
Sorbent
Dibroraomethane
Gas Bulb/Sorbent
Di-n-butyl phthalate
Particulate/Sorbent
Dichlorobenzene(meta, ortho and para isomers)
Sorbent
Dichlorobenzene, N.O.S.
Sorbent
3,3'-Dichlorobenzidine
Particulate/Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound Description
1,4-Dichloro-2-butene
Sorbent
Dichlorodifluoromethane
Gas Bulb
1,1,-Dichloroethane
Gas Bulb
1,2-Dichloroethane
Gas Bulb
trans-1,2-Dichloroethene
Gas Bulb
Dichloroethylene, N.O.S.
Gas Bulb
1,1-Dichloroethylene
Gas Bulb
Dichloromethane
Gas Bulb
2,4-Dichlorophenol
Sorbent
2,6-Dichlorophenol
Sorbent
2,4-Dichlorophenoxyacetic acid (2,4-D)
Particulate/Sorbent
Dichlorophenylarsine
Particulate/Impingers
Dichloropropane, N.O.S.
Gas Bulb/Sorbent
1,2-Dichloropropane
Gas Bulb/Sorbent
Dichloropropanol, N.O.S.
Sorbent
Dichloropropene, N.O.S.
Gas Bulb/Sorbent
1,3-Dichloropropene
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS
Compound
Dieldrin
1,2:3,4-Diepoxybutane
Diethylarsine
N,N-Diethylhydrazine
0,0-Diethyl S-methyl ester of phosphorodithioic acid
0,0-Diethylphosphoric acid, O-p-nitrophenyl ester
Diethyl phthalate
0,0-Diethyl 0-2-pyrazinyl phosphorothioate
Diethylstilbestrol (D.E.S.)
Dihydrosafrole
3,4-Dihydroxy-alpha-(raethylamino)methyl benzyl alcohol
Diisopropylfluoroohosphate (DFP)
Dlmethoate
3,3Dimethoxybenzidine
p-Dimethylaminoazobenzene
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine
METHODS (Continued)
Description
Particulate/Sorbent
Sorbent
Gas Bulb/Sorbent/Impingers
Gas Bulb
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Gas Bulb
Particulate/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS
(Continued)
Compound
Descripi
Dimethylcarbamoyl chloride
Sorbent
1,1-Dimethylhydrazine
Gas Bulb
1,2-Dimethylhydrazine
Gas Bulb
3,3-Dimethyl-l-(methylthio)-2-butanone,0-((methylamino)
carbonyl)oxirae [Thiofanox]
Particulate/Sorbent
alpha,alpha-Dimethylphenethylamine
Sorbent
2,4-Dimethylphenol
Sorbent
Dimethyl phthalate
Sorbent
Dimethyl sulfate
Sorbent
Dinitrobenzene, N.O.S.
Particulate/Sorbent
4,6-Dinitro-o-cresol (and salts)
Particulate/Sorbent
2,4-Dinitrophenol
Sorbent
2,4-Dinitrotoluene
Sorbent
2,6-Dinitrotoluene
Sorbent
Di-n-octyl phthalate
Particulate/Sorbent
1,4-Dioxane
Sorbent
Diphenylaraine
Particulate/Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound Description
1,2-Diphenylhydrazine
Sorbent
Di-n-propylnitrosamine
Sorbent
Disulfoton
Particulate/Sorbent
2,4-Dithiobiuret
Sorbent
Endosulfan
Particulate/Sorbent
Endrin (and metabolites)
Particulate/Sorbent
Ethyl carbamate
Sorbent
Ethyl cyanide
Gas Bulb/Impingers (CN)
Ethylenebisdithiocarbamic acid (salts and esters)
Particulate/Sorbent
Ethyleneimine
Gas Bulb
Ethylene oxide
Gas Bulb
Ethylenethiourea
Sorbent
Ethyl methacrylate
Sorbent
Ethyl methanesulfonate
Gas Bulb
Fluoranthene
Particulate/Sorbent
Fluorine
Special Reagent
2-Fluoroacetamide
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound
Fluoroacetic acid, sodium salt
Formaldehyde
Formic acid
Glycidylaldehyde
Halomethane, N.O.S.
Heptachlor
Heptachlor epoxide (alpha, beta, and gamma isomers)
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclohexane (all isomers)
Hexachlorocyclopentadiene
Hexachloroethane
1,2,3,4,10,10-Hexachloro-l,4,4 a,5,8,8a-hexahydro-1,4:5,8
endo,endo-dimethanonaphthalene
Hexachlorophene
Hexachloropropene
Hexaethyl tetraphosphate
Hydrazine
Hydrocyanic acid
Description
Sorbent
Special Reagent
Gas Bulb/Sorbent
Special Reagent
Gas Bulb
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Gas Bulb/Sorbent
Gas Bulb/Impingers (CN)
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound Description
Hydrofluoric acid
Gas Bulb/Special Reagent
Hydrogen sulfide
Gas Bulb/Special Reagent
Hydroxydimethylarsine oxide
Particulate/Impingers
Indeno(1,2,3-c,d)pyrene
Particulate/Sorbent
Iodoraethane
Gas Bulb
Iron dextran
Particulate
Isocyanic acid, methyl ester
Gas Bulb
Isobutyl alcohol
Sorbent
Isosafrole
Sorbent
Kepone
Particulate/Sorbent
Lasiocarpine
Particulate/Sorbent
Lead and compounds, N.O.S.
Particulate/Impingers
Lead acetate
Particulate/Impingers
Lead phosphate
Particulate/Impingers
Lead subacetate
Particulate/Impingers
Maleic anhydride
Sorbent
Maleic hydrazide
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound
Description
Malononitrile
Melphalan
Mercury fulminate
Mercury and compounds, N.O.S.
Methacrylonitrile
Methanethiol
Methapyrilene
Metholmyl
Methoxychlor
2-Methylaziridine
3-Methylcholanthrene
Methylchlorocarbonate
4,4'-Methylenebis(2-chloroaniline)
Methyl ethyl ketone (MEK)
Methyl hydrazine
2-Methyllactonitrile
Methyl methacrylate
Sorbent
Particulate/Sorbent
Particulate/lmpingers
Particulate/Impingers
Particulate/Sorbent
Gas Bulb
Sorbent
Sorbent
Particulate/Sorbent
Gas Bulb
Particulate/Sorbent
Gas Bulb
Particulate/Sorbent
Gas Bulb
Gas Bulb
Gas Bulb
Gas Bulb/Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound.
Methyl methanesulfonate
2-Methyl-2-(methylthio)propionaldehyde-o-(methylcarbonyl)
oxitne
N-Methyl-N'-nitro-N-nitrosoguanidine
Methyl parathion
Methylthiouracil
Mustard gas
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
1-Naphthy1-2-thiourea
Nickel and compounds, N.O.S.
Nickel carbonyl
Nickel cyanide
Nicotine (and salts)
Nitric oxide
Description
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate
Particulate
Particulate(metal)/Impingers(CN)
Sorbent
Gas Bulb
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound
p-Nitroaniline
Nitrobenzene
Nitrogen dioxide
Nitrogen mustard (and hydrochloride salt)
Nitrogen mustard N-Oxide (and hydrochloride salt)
Nitroglycerine
4-Nitrophenol
4-Nitroquinoline-l-oxide
Nitrosamine, N.O.S.
N-Nitrosodi-n-butylamine
N-Nitrosodiethanolamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitroso-N-ethylurea
N-Nitrosomethylethylamine
N-Nitroso-N-methylurea
N-Nitroso-N-methylurethane
Description
Particulate/Sorbent
Sorbent
Gas Bulb
Gas Bulb
Sorbent
Gas Bulb/Sorbent
Sorbent
Sorbent
Gas Bulb/Sorbent/Particulate
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING
Compound
N-Nitrosomethylvinylamine
N-Nitrosomorpholine
N-Nitrosonornicotine
N-Nitrosopiperidine
N-Nitrosopyrrolidine
N-Nitrososarcosine
5-Nitro-o-toluidine
Octamethylpyrophosphoramide
Osmium tetroxide
7-Oxabicyclo[2.2.l]heptane-2,3-dicarboxylic acid
Paraldehyde
Parathion
Pentachlorobenzene
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenacetin
(Continued)
Description
Gas Bulb/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Particulate
Sorbent
Special Reagent
Particulate/Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound
Phenol
Phenylenediamine
Phenylmercury acetate
N-Phenylthiourea
Phosgene
Phosphine
Phosphorodithioic acid, 0,0-diethyl S-((ethylthio)methyl)
ester[Phorate]
Phosphorothioic acid, 0,0-dimethyl 0-(p-((dimethylamino)sulfonyl)
phenyl)ester [Famphur]
Phthalic acid esters, N.O.S.
Phthalic anhydride
2-Picoline
Polychlorinated biphenyl, N.O.S.
Potassium cyanide
Potassium silver cyanide
Pronamide
Description
Sorbent
Sorbent
Particulate/Impingers
Sorbent
Gas Bulb
Gas Bulb
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Particulate/Sorbent
Particulate(metal)/impingers(CN)
Particulate(metal)/Impingers(CN)
Particulate/Sorbent
-------
HAZARDOUS CONSTITUENTS
Compound
1,3-Propane sulfone
n-Propylamine
Propylthiouracil
2-Propyn-l-ol
Pyridine
Reserpine
Resorcinol
Saccharin (and salts)
Safrole
Selenious acid
Selenium and compounds, N.O.S.
Selenium sulfide
Selenourea
Silver and compounds, N.O.S.
Silver cyanide
Sodium cyanide
Streptozotocin
Strontium sulfide
STACK GAS SAMPLING METHODS (Continued)
Description
Sorbent
Gas Bulb
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Particulate/lmpingers
Particulate/Impingers
Particulate/lmpingers
Particulate/lmpingers
Particulate
Particulate(metal)/Impingers(CN)
Particulate(metal)/Impingers(CN)
Particulate/Sorbent
Part iculate
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound
Strychnine (and salts)
1.2.4.5-Te trachlorobenzene
2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)
Tetrachloroethane, N.O.S.
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Tetrachloromethane
2.3.4.6-Te trachlorophenol
Tetraethyldithiopyrophosphate
Tetraethyl lead
Tetraethylpyrophosphate
Tetranitromethane
Thallium and compounds, N.O.S.
Thallic oxide
Thallium(I)acetate
Thallium{I)carbonate
Description
Particulate/Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent/Impingers
Particulate/Sorbent
Sorbent
Particulate
Particulate
Particulate
Particulate
-------
HAZARDOUS CONSTITUENTS
Compound
Thallium(I)chloride
Thallium(I)nitrate
Thallium selenite
Thallium(I)sulfate
Thioacetamide
Thiosemicarbazide
Thiourea
Thiuram
Toluene
Toluened iamine
o-Toluidine hydrochloride
Tolylene diisocyanate
Toxaphene
Tribromomethane
1,2,4-Trichlorobenzene
1.1.1-Trichloroethane
1.1.2-Trichloroethane
STACK GAS SAMPLING METHODS (Continued)
Description
Particulate
Particulate
Particulate
Particulate
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Gas Bulb
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound _ Description
Trichloroethene
Gas Bulb
Trichloromethanethiol
Sorbent
Trichloromonofluoromethane
Gas Bulb
2,4,5-Trichlorophenol
Sorbent
2,4,6-Trichlorophenol
Sorbent
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
Particulate/Sorbent
2 > 4,5- Trichlorophenoxypropionic acid (2,4.5-TP)(Silvex)
Particulate/Sorbent
Trichloropropane, N.O.S.
Sorbent
1,2,3-Trichloropropane
Sorbent
0,0,0-Triethyl phosphorothioate
Particulate/Sorbent
sym-Trinitrobenzene
Sorbent
Tris(1-azridinyl) phosphine sulfide
Sorbent
Tris(2,3,-dibromopropyl)phosphate
Particulare/Sorbent
Trypan blue
Particulate/Sorbent
Uracil mustard
Particulate/Sorbent
Vanadic acid, ammonium salt
Particulate
Vanadium pentoxide
Particulate
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (Continued)
Compound
Description
Vinyl chloride
Zinc cyanide
Zinc phosphide
Gas Bulb
Particulate(metal)/Impingers(CN)
Particulate
N.O.S. = Not Otherwise Specified.
u>
u>
-------
APPENDIX C
Hazardous Constituents - Analysis Methods
Appendix C catalogs the Hazardous Constituents
listed in 40 C.F.R. Part 261, Appendix VIII
(May 20, 1981) with their corresponding
Analysis Method Numbers, as recommended in
Section VI.
344
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
Method Number
Description
Acetonitrile
A101
Volatiles
Acetophenone
A121
Extractables
3-(alpha-Acetonylbenzyl)-4-hydroxycoumarin and salts (Warfarin)
A122
HPLC
2-Acetylaminofluorene
A121
Extractables
Acetyl chloride
A144
Acid chlorid*
l-Acetyl-2-thiourea
A123
HPLC
Acrolein
A101
Volatiles
Acrylamide
A101
Volatiles
Acrylonitrile
A101
Volatiles
Aflatoxins
A145
—
Aldrin
A121
Extractables
Allyl alcohol
A134
Alcohols
Aluminum phosphide
A253
Phosphides
4-Aminobiphenyl
A121
Extractables
6-Ami no-1,la,2,8,8a,8b-hexahydro-8-(hyd roxymethy1)-8a-
A122
HPLC
methoxy-5-raethylcarbamate azirino[2',3':3,4]pyrrolo
[l,2-a]indole-4,7-dione(ester) (Mitomycin C)
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
5-(Aminomethyl)-3-isoxazolol
Amitrole
Aniline
Antimony and compounds, N.O.S.
Aramite
Arsenic and compounds, N.O.S.
Arsenic acid
Arsenic pentoxide
Arsenic trioxide
Auramine
Azaserine
Barium and compounds, N.O.S.
Barium cyanide
Benz(e)acridine
Benz(a)anthracene
Benz ene
(Continued)
Method Number
Descrip tion
A121 Extractables
A121 Extractables
A121 Extractables
A221 Antimony
A121 Extractables
A222 Arsenic
A222 Arsenic
A222 Arsenic
A222 Arsenic
A121 Extractables
A123 1IPLC
A223 Barium
A223 Barium
A252 Cyanides
A121 Extractables
A121 Extractables
A101 Volatiles
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
Method Number
Description
Benzenearsonic acid
A222
Arsenic
Benzene, dichloromethyl-
A121
Extractables
Benzenethiol
A121
Extractables
Benzidine
A121
Extractables
Benzo(b)fluoranthene
A121
Extractables
Benzo(j)fluoranthene
A121
Extractables
Benzo(a)pyrene
A121
Extractables
p-Benzoquinone
A121
Extractables
Benzotrichloride
A121
Extractables
Benzyl chloride
A121
Extractables
Beryllium and compounds, N.O.S.
A224
Beryllium
Bis(2-chloroethoxy)methane
A121
Extractables
Bis(2-chloroethyl) ether
A121
Extractables
N,N-Bis(2-chloroethyl)-2-naphthylamine
A121
Extractables
Bis(2-chloroisopropyl) ether
A121
Extractables
Bis(chloromethyl) ether
A121
Extrac tables
Bis(2-ethylhexyl) phthalate
A121
Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
Bromoacetone
Broraomethane
4-Bromophenyl phenyl ether
Brucine
2-Butanone peroxide
Butyl benzyl phthalate
2-sec-Buty1-4,6-dinitrophenol (DNBP)
Cadmium and compounds, N.O.S.
Calcium chromate
Calcium cyanide
Carbon disulfide
Carbon oxyfluoride
Chloral (as hydrate)
Chlorambucil
Chlordane (alpha and gamma isomers)
Chlorinated benzenes, N.O.S.
Chlorinated ethane, N.O.S.
A101 Volatiles
A101 Volatiles
A121 Extractables
A148
A121 Extractables
A121 Extractables
A121 Extractables
A225 Cadmium
A226 Chromium
A252 Cyanides
A101 Volatiles
A141 Gases
A101 Volatiles
A131 Aldehydes
A122 HPLC
A121 Extractables
A101 Volatiles
A121 Extractables
A101 Volatiles
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
Chlorinated fluorocarbons, N.O.S.
Chlorinated naphthalene, N.O.S.
Chlorinated phenol, N.O.S.
Chloroacetaldehyde
Chloroalkyl ethers, N.O.S.
p-Chloroaniline
Chlorobenzene
Chlorobenzilate
p-Chloro-m-cresol
1-Chloro-2,3-epoxypropane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloromethyl methyl ether
2-Chloronaphthalene
2-Chlorophenol
(Continued)
Method Number
A101
A121
A121
A131
A101
A121
A101
A121
A121
A122
A101
A101
A101
A101
A101
A121
A121
A122
Descrip tion
Volatiles
Extractables
Extractables
Aldehydes
Volatiles
Extractables
Volatiles
Extractables
Extractables
HPLC
Volatiles
Volatiles
Volatiles
Volatiles
Volatiles
Extractables
Extractables
HPLC
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
1-(o-Chlorophenyl)thiourea
3-Chloropropionitrile
Chromium and compounds, N.O.S.
Chrysene
Citrus Red No. 2
Coal tars
Copper cyanide
Creosote
Cresols
Crotonaldehyde
Cyanides (soluble salts and complexes), N.O.S.
Cyanogen
Cyanogen bromide
Cyanogen chloride
Cycasin
2-Cyclohexyl-4,6-dini trophenol
A123 HPLC
A121 Extractables
A226 Chromium
A121 Extractables
A149
A121 Extractables
A252 Cyanides
A121 Extractables
A121 Extractables
A123 HPLC
A131 Aldehydes
A252 Cyanides
A138 Gases
A138 Gases
A138 Gases
A150
A121 Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
Cyclophosphamide
Daunomyc in
DDD
DDE
DDT
Diallate
Dibenz(a,h)acridine
Dlbenz(a,j)acrIdine
Di benz(a,h)an th racene
7H-Dibenzo(c,g)carbazole
Dlbenzo(a,e)pyrene
Dlbenzo(a,h)pyrene
Dlbenzo(a,i)pyrene
1,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
Di-n-butyl phthalate
(Continued)
Method Number
Description
A122 HPLC
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A101 Volatiles
A101 Volatiles
A101 Volatiles
A121 Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
Dichlorobenzene(meta, ortho and para isomers)
Dichlorobenzene, N.O.S,
3,3'-Dichlorobenzidine
1,4-Dichloro-2-butene
Dichlorodifluoromethane
1,1-Dichloroethane
oj 1,2-Dichloroethane
Ln
N5
trans-l,2-Dichloroethene
Dichloroethylene, N.O.S.
1,1-Dichloroethylene
Dichloromethane
2,4-Dichlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
Dichlorophenylarsine
Dichloropropane, N.O.S.
Method Number
A101
A121
A101
A121
A121
A101
A101
A101
A10I
A101
A101
A101
A101
A121
A122
A121
A122
A122
A133
A222
A101
Description
Volatiles
Extractables
Volatiles
Extractables
Extractables
Volatiles
Volatiles
Volatiles
Volatiles
Volatiles
Volatiles
Volatiles
Volatiles
Extractables
HPLC
Extractables
HPLC
HPLC
Carboxylic acids
Arsenic
Volatiles
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
UJ
gj
1.2-Dichloropropane A101
Dichloropropanol, N.O.S. A121
Dichloropropene, N.O.S. A101
1.3-Dichloropropene A101
Dieldrin A121
l,2:3,4-Diepoxybutane A121
Diethylarsine A222
N,N-Diethylhydrazine A121
0,0-Diethyl S-methyl ester of phosphorodithioic acid A121
0,0-Diethylphosphoric acid, O-p-nitrophenyl ester A121
Diethyl phthalate A121
0,0-Diethyl O-2-pyrazinyl phosphorothioate A121
Diethylstilbestrol A123
Dihydrosafrole A121
3.4-Dihydroxy-alpha-(methyIajnino)methyl benzyl alcohol (Epinephrine) A123
Diisopropylfluorophosphate (DFP) A121
Dimethoate A]21
3,3'-Dimethoxybenzidine A121
Description
Volatiles
Extractables
Volatiles
Volatiles
Extractables
Extractables
Arsenic
Extractables
Extractables
Extractables
Extractables
Extractables
HPLC
Extractables
HPLC
Extractables
Ext ractables
Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS
Compound
p-Dimethylaminoazobenzene
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine
Dimethylcarbamoyl chloride
1.1-Dimethylhydrazine
1.2-Dimethylhydrazine
3.3-Dimethyl-l-(methylthio)-2-butanone,0-((methylamino)
carbonyl)oxime[Thiofanox]
alpha, alpha-Dimethylphenethylamine
2.4-Dimethylphenol
Dimethyl phthalate
Dimethyl sulfate
Dinitrobenzene, N.O.S.
4,6-Dinitro-o-cresol (and salts)
2,4,-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
10DS (Continued)
Method Number
A121
A121
A121
A144
A121
A121
A183
Description
Extractables
Extractables
Extractables
Acid chlorides
Extractables
Extractables
Oximes
A121
A121
A121
A121
A121
A121
A122
A121
A122
A121
A121
A121
Extractables
Extractables
Extractables
Extractables
Extractables
Extractables
HPLC
Extractables
HPLC
Extractables
Extractables
Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
1,4-Dioxane
Diphenylamine
1,2-Diphenylhydrazine
Dl-n-propylnitrosamine
Disulfoton
2,4-Dithiobiuret
Endosulfan
Endrin (and metabolites)
Ethyl carbamate
Ethyl cyanide
Ethylenebisdlthlocarbamic acid (salts and esters)
Ethyleneimine
Ethylene oxide
Ethylenethiourea
Ethyl methacrylate
Ethyl methanesulfonate
Fluoranthene
Method Number
A101
A121
A121
A121
A121
A121
A121
A121
A121
A252
A121
A156
A123
A121
A121
A121
Description
Volatiles
Extractables
Extractables
Extractables
Extractables
Extractables
Extractables
Extractables
Extractables
Cyanides
Extractables
HPLC
Extractables
Extractables
Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
Fluorine
2-Fluoroacetamide
Fluoroacetic acid, sodium salt
Formaldehyde
Formic acid
Glycidylaldehyde
Halomethane, N.O.S.
w
Ln
ON
Heptachlor
Heptachlor epoxide (alpha, beta, and gamma isomers)
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclohexane (all isomers)
Hexachlorocyclopentadiene
Hexachloroethane
1,2,3,4,10,10-Hexachloro-l,4,4a,5,8,8a-hexahydro-l,4:5,8
endo,endo-dimethanonaphthalene
A137
A157
A121 Extractables
A131 Aldehydes
A101 Volatiles
A121 Extractables
A133 Carboxylic acids
A131 Aldehydes
A101 Volatiles
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A101 Volatiles
A121 Extractables
A121 Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
Hexachlorophene
Hexachloropropene
Hexaethyl tetraphosphate
Hydrazine
Hydrocyanic acid
Hydrofluoric acid
Hydrogen sulfide
Hydroxydimethylarsine oxide
Indeno(1,2,3-c,d)pyrene
Iodomethane
Iron dextran (complex)
Isocyanic acid, methyl ester
Isobutyl alcohol
Isosafrole
Kepone
Lasiocarpine
(Continued)
Method Number
Description
A121 Extractables
A101 Volatiles
A121 Extractables
A101 Volatiles
A141 Gases
A141 Gases
A251 Anions
A251 Anions
A141 Gases
A222 Arsenic
A121 Extractables
A101 Volatiles
A101 Volatiles
A134 Alcohols
A121 Extractables
A121 Extractables
A160
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
Lead and compounds, N.O.S.
Lead acetate
Lead phosphate
Lead subacetate
Maleic anhydride
Maleic hydrazide
Malononitrile
Melphalan
Mercury fulminate
Mercury and compounds, N.O.S.
Methacrylonitrile
Me thanethiol
Methapyriline
Metholmyl
Methoxychlor
2-Methylaziridine
3-Methylcholanthrene
(Continued)
Method Number
A227
A227
A227
A227
A121
A121
A121
A122
A228
A228
A121
A101
A121
A122
A121
A121
A121
Description
Lead
Lead
Lead
Lead
Extractables
Extrac tables
Extractables
HPLC
Mercury
Mercury
Extractables
Volatiles
Extractables
HPLC
Extractables
Extractables
Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
Me thylchlorocarbona te
4,4'-Methylenebis(2-chloroaniline)
Methyl ethyl ketone (MEK)
Methyl hydrazine
2-Methyllactonitrile
Methyl methacrylate
Methyl methanesulfonate
2-Methyl-2-(methylthio)propionaldehyde-0-(methylcarbonyl)
oxime
N-Methyl-N'-nitro-N-nitrosoguanidine
Methyl parathion
Methylthiouracil
Mustard gas
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthy1amine
1-Naphthy1-2-thiourea
A121 Extractables
A101 Volatiles
A121 Extractables
A101 Volatiles
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A183 Oximes
A121 Extractables
A121 Extractables
A121 Extractables
A139 Mustards
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A]2J IfPf.C
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
Nickel and compounds, N.O.S.
Nickel carbonyl
Nickel cyanide
Nicotine (and salts)
Nitric oxide
p-Ni troaniline
Nitrobenzene
Nitrogen dioxide
Nigrogen mustard (and hydrochloride salt)
Nitrogen mustard N-Oxide (and hydrochloride salt)
Nitroglycerine
4-Nitrophenol
4-Nitroquinoline-l-oxide
Nitrosamine, N.O.S.
N-Ni trosodi-n-butylamine
N-Ni trosodiethanolamine
A229 Nickel
A229 Nickel
A229 Nickel
A252 Cyanides
A121 Extractables
A141 Gases
A121 Extractables
A121 Extractables
A141 Gases
A139 Mustards
A139 Mustards
A121 Extractables
A121 Extractables
A122 HPLC
A121 Extractables
A121 Extractables
A121 Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Ni troso-N-e thy1urea
N-Ni trosomethyle thylamine
N-Nitroso-N-methylurea
N-Nitroso-N-methylurethane
N-Nitrosomethylvinylamine
N-Ni trosomorpholine
N-Nitrosonornicotine
N-Ni trosop iperid i ne
N-Nitrosopyrrolidine
N-Nitrososarcosine
5-Nitro-o-toluidine
Octamethylpyrophosphoramide
Osmium tetroxide
7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A122 HPLC
A121 Extractables
A230 Osmium
A133 Carboxylic acid
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
Paraldehyde
Parathion
Pentachlorobenzene
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenacetin
Phenol
Phenylenediamine
Phenylmercury acetate
N-Phenylthiourea
Phosgene
Phosphine
Phosphorodithioic acid, 0,0-diethyl S-((ethylthio)methyl)
ester [Phorate]
Phosphorothioic acid, 0,0-dimethyl 0-(p-((dimethylamino)sulfonyl)
phenyl)ester [Famphur]
Phthalic acid esters, N.O.S.
(Continued)
Method Number
Description
A131 Aldehydes
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A174
A121 Extractables
A122 HPLC
A121 Extractables
A228 Mercury
A123 HPLC
A138 Gases
A136
A121 Extractables
A121 Extractables
A121 Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
Phthalic anhydride
2-Picoline
Polychlorinated blphenyl, N.O.S.
Potassium cyanide
Potassium silver cyanide
Pronamide
1,3-Propane sulfone
n-Propylamine
Propylthiouracil
2-Propyn-l-ol
Pyridine
Reserpine
Resorcinol
Saccharin (and salts)
Safrole
Selenious acid
(Continued)
Method Number
Description
A121 Extractables
A121 Extractables
A121 Extractables
A252 Cyanides
A232 Silver
A252 Cyanides
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A134 Alcohols
A121 Extractables
A122 HPLC
A134 Alcohols
A121 Extractables
A123 HPLC
A121 Extractables
A231 Selenium
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
Selenium and compounds, N.O.S.
Selenium sulfide
Selenourea
Silver and compounds, N.O.S.
Silver cyanide
Sodium cyanide
Streptozotocin
Strontium sulfide
Strychnine (and salts)
1,2,4,5-Tetrachlorobenzene
2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)
Tetrachloroethane, N.O.S.
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Tetrachlorome thane
A231 Selenium
A231 Selenium
A231 Selenium
A232 Silver
A232 Silver
A252 Cyanides
A252 Cyanides
A122 HPLC
A233 Strontium
A180
A121 Extractables
A121 Extractables
A101 Volatiles
A101 Volatiles
A101 Volatiles
A101 Volatiles
A101 Volatiles
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHOD (Continued)
Compound
2,3,4,6-Te trachlorophenol
Tetraethyldithiopyrophosphate
Tetraethyl lead
Tetraethylpyrophosphate
Tetranitromethane
Thallium and compounds, N.O.S.
Thallic oxide
Thallium(I)acetate
Thallium(I)carbonate
Thallium(I)chloride
Thallium(I)nitrate
Thallium selenite
Thallium(I)sulfate
Thioacetamide
Thiosemicarbazide
Thiourea
Thiuram
Method Number
A121
A122
A121
A227
A121
A101
A234
A234
A234
A234
A234
A234
A234
A234
A123
A123
A123
A122
Description
Extractables
HPLC
Extractables
Lead
Extractables
Volatiles
Thallium
Thallium
Thallium
Thallium
Thallium
Thallium
Thallium
Thallium
HPLC
HPLC
HPLC
HPLC
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Toluene
Toluenediamine
o-Toluidine hydrochloride
Tolylene diisocyanate
Toxaphene
Tribromomethane
1.2.4-Trichlorobenzene
1.1.1-Trichloroethane
1.1.2-Trichloroethane
Trichloroethene
Trichloromethanethiol
Tichloromonofluoromethane
2.4.5-Trichlorophenol
2.4.6-Trichlorophenol
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4,5-Trichlorophenoxypropionic acid (2,4,5-TP) (Silvex)
A101
A121
A121
A121
A101
A121
A101
A101
A101
A121
A101
A121
A122
A121
A122
A122
A133
A122
A133
Description
Volatiles
Extractables
Extractables
Extrac tables
Volatiles
Extractables
Volatiles
Volatiles
Volatiles
Extractables
Volatiles
Extractables
HPLC
Extractables
HPLC
HPLC
Carboxylic acid
HPLC
Carboxylic acid
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
Trichloropropane, N.O.S.
1,2,3-Trichloropropane
0,0,0-Triethyl phosphorothioate
sym-Trini trobenzene
Tris-(l-azridinyl)phosphine sulfide
Tris(2,3-dibromopropyl) phosphate
Trypan blue
Uracil mustard
Vanadic acid, ammonium salt
Vanadium pentoxide
Vinyl chloride
Zinc cyanide
Zinc phosphide
Method Number
A101
A101
A121
A121
A190
A121
A123
A235
A235
A101
A252
A253
Description
Volatiles
Volatiles
Extractables
Extractables
Extractables
HPLC
Vanadium
Vanadium
Volatiles
Cyanides
Phosphides
N.O.S. = Not Otherwise Specified.
-------
APPENDIX D
Summary of Method Numbers
Appendix D cross-references each sampling and analysis
method to its corresponding Method Number and the page
where the method may be found within the text.
368
-------
METHOD NUMBER
SUMMARY OF METHOD NUMBERS
METHOD NAME
PAGE NO.
OJ
vo
5001
5002
5003
5004
5005
5006
5007
5008
5009
5010
SOU
S012
P001-P003
P001
P002
POO 3
P011-P014
POll
P012
P013
P014
Sampling Methods
Coliwasa
Dipper (Pond Sampler)
Weighted Bottle
Tap
Thief (Grain Sampler)
Trier (Sample Corer/Waste Pile Sampler)
Trowel (Scoop)
MM5 Train
SASS Train
Gas Bulb
Gas Bag
VOST
Sample Preparation Methods
Representative Aliquots from Field Samples
Liquids (aqueous and organic)
Sludges
Solids
Surrogate Addition to Sample Aliquots for
Organic Analysis
Volatile Organics
Basic Extractable Organics
Acidic Extractable Organics
Neutral Extractable Organics
55
56
57
58
59
60
61
62
63
64
65
66
77
77
77
78
78
78
79
-------
SUMMARY OF METHOD NUMBERS (Continued)
METHOD NUMBER
METHOD NAME
PAGE NO.
uj
o
P021-P024
P021
P021a
P021b
P022
P022a
P022b
P02 3
P024
P024a
P024b
P024c
P031
P032
P041-P045
P041
P042
P043
P044
P045
Extraction of Organic Compounds
Aqueous Liquids
Semivolatiles
Volatiles
Sludges (including gels and slurries)
Semivolat iles
Volatiles
Organic Liquids
Solids
Semivolatiles by Homogenization
Semivolatiles by Soxhlet Extraction
Volatiles
Drying and Concentrating Solvent Extracts
Digestion Procedures for Metals
Sample Cleanup Procedures
Florisil Column Chromatography
BioBeads SX-3
Silica Gel Chromatography
Alumina Column Chromatography
Liquid/Liquid Extraction
80
81
82
83
84
85
86
87
88
89
91
92
94
95
96
-------
SUMMARY OF METHOD NUMBERS (Continued)
METHOD NUMBER
METHOD NAME
PAGE NO.
GJ
-«J
C001-C004
C001
C002
COO 3
C004
A001-A006
A001-A002
A001
AOOla
AOOlb
A002
A003
A004
A005
A006
A011-A021
A011
A012
A013
AO 14
Analysis Methods
Characteristics
Ignitability
Corrosivity
Reactivity
Extraction Procedure Toxicity
Proximate Analysis
Moisture, Solid and Ash Content
Macroscale Technique
Loss on Drying
Loss on Ignition
Microscale Technique
Elemental Composition - Organic
Total Organic Carbon (TOC)/Total Organic
Organic Halogen (TOX)
Viscosity
Heating Value of Waste
Survey Analysis
Organic Content by TCO
Organic Content by GRAV
Organic Content - Volatiles
Compound Class Type by Infrared Analysis
136
137
138
139
140
140
140
141
142
143
144
145
105
107
107
108
-------
SUMMARY OF METHOD NUMBERS (Continued)
METHOD NUMBER
METHOD NAME
PAGE NO.
N)
A015
A016
A017
A021
A101-A190
A101
AlOla
AlOlb
AlOlc
A121
A122
A123
A131
A132
A133
A134
A136
A137
A138
A139
A141
Mass Spectrometric Analysis 109
Specific Major Components by GC/MS 112
Specific Major Components by HPLC/IR or HPLC/LRMS 112
Inorganic Content 116
Directed Analysis: Organics
Volatiles 146
Purging Procedure for the Analysis of
Aqueous Liquids 149
Purging Procedure for the Analysis of
Sludges 150
Purging Procedure for the Analysis of
Solids 151
Extractables 152
HPLC/UV Generalized Procedure 157
HPLC/UV Generalized Procedure 160
Aldehydes - Derivatization Procedures 163
Aldehydes - HPLC Analysis 164
Carboxylic Acids 165
Alcohols 167
Phosphine 168
Fluorine 169
Gases - Cyanogens and Phosgene 170
Gases - Mustards 171
Gases 172
-------
SUMMARY OF METHOD NUMBERS (Continued)
METHOD NUMBER
METHOD NAME
PAGE NO.
A144
Acid Chlorides
173
A145
Aflatoxins
174
A148
Brucine
175
A149
Citrus Red No. 2
176
A150
Cycasin
177
A156
Ethylene Oxide
178
A157
2-Fluoroacet amide
179
A160
Lasiocarpine
180
A174
Phenacetin
181
A180
Strychnine
182
A183
Oximes
183
A190
Tris(1-aziridinyl)phosphine sul£ide
184
A221-253
Directed Analysis: Inorganics
A221
Ant imony
185
A222
Arsenic
187
A223
Barium
189
A224
Beryllium
191
A225
Cadmium
192
A226
Chromium
193
A227
Lead
194
A228
Mercury
196
A229
Nickel
198
A230
Osmium
200
-------
SUMMARY OF METHOD NUMBERS (Continued)
METHOD NUMBER
METHOD NAME
PAGE NO
A231
Selenium
202
A232
Silver
203
A233
Strontium
205
A234
Thallium
207
A235
Vanadium
209
A251
Anions
210
A252
Total Cyanides
211
A253
Phosphides
213
-------
APPENDIX E
MS - Analytical Ions
Appendix E catalogs the Hazardous Constituents
listed in 40 C.F.R. Part 261, Appendix VIII
(May 20, 1981) for which GC/MS analysis
procedures have been recommended with their
appropriate MS analytical ions and corresponding
intensities (when available).
375
-------
Compound
Acetonitrile
Acetophenone
2-Acetylaminofluorene
Acrolein
Acrylamide
Acrylonitrile
Aldrin
u> Allyl alcohol
CT\
4-Aminobiphenyl
5-(Aminomethyl)-3-isoxazolol
Amitrole
Aniline
Aramite
Auramine
Benz(c)acridine
ANALYTICAL IONS
Ions (Intensities)
41(100), 40(50), 39(17), 38(5)
105(100), 77(83), 51(31), 120(25)
181(100), 180(82), 223(62), 152(37)
56(72), 27(100), 26(54), 55(51)
27(100), 44(89), 71(72), 55(58)
53(100), 26(93), 52(79), 51(30)
66(100), 263(73), 220(11)
57(100), 29(39), 31(32), 58(26)
169(100), 170(14), 168(11), 84.5(9)
98(100), 41(66), 39(49), 67(23)
28(100), 84(66), 57(28), 29(23)
93(100), 66(33), 65(18), 39(18)
229(100), 228(19), 230(19), 201(10)
-------
MS - ANALYTICAL
Compound
Benz(a)anthracene
Benzene
Benzene, dichloromethyl-
Benzenethiol
Benzidine
Benzo(b)fluoran thene
Benzo(j)fluoranthene
Benzo(a)pyrene
p-Benzoquinone
Benzotrichloride
Benzyl chloride
Bis(2-chloroethoxy) methane
Bis(2-chloroethyl) ether
N,N-Bis(2-chloroethyl)-2-naphthylamine
Bis(2-chloroisopropyl) ether
Bis(chloromethyl) ether
Bis(2-ethylhexyl) phthalate
IONS (Continued)
Ions (Intensities)
228(100), 229(19), 226(19), 114(18)
78(100), 77(19), 52(16), 51(15)
110(100), 66(38), 39(28), 109(25)
184(100), 185(15), 183(11), 92(8)
252(100), 250(25), 253(25), 126(25)
252(100), 250(25), 253(25), 126(25)
252(100), 250(25), 253(23), 125(21)
108(100), 54(99), 82(37), 53(32)
159(100), 161(64), 89(14), 163(11)
91(100), 126(28), 65(9), 92(8)
93(100), 63(65), 95(32), 27(22)
93(100), 63(98), 27(75), 95(32)
45(100), 43(36), 41(34), 77(19)
79(100), 49(47), 81(33), 51(16)
149(100), 57(54), 169(33), 71(27)
-------
MS
Compound
Bromoacetone
Bromomethane
4-Bromopheny1 phenyl ether
Brucine
2-Butanone peroxide
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol (DNBP)
u> Carbon disulfide
•-4
00
Carbon oxyfluoride
Chloral (as hydrate)
Chlordane (alpha and gamma isomers)
Chlorinated benzenes, N.O.S.
Chlorinated ethane, N.O.S.
Chlorinated fluorocarbons, N.O.S.
Chlorinated naphthalene, N.O.S.
Chlorinated phenol, N.O.S.
Chloroacetaldehyde
IONS (Continued)
Ions (Intensities)
43(100), 15(84), 14(19), 79(13)
94(100), 96(94), 15(47), 93(21)
248(100), 250(99), 141(45), 77(32)
149(100), 91(50), 206(18), 104(12)
76,(100), 32(22), 44(17), 78(9)
47(100), 66(55), 28(14), 31(4)
•k
373(19), 375(17), 377(10)
112(100), 77(45), 114(33), 51(12)
64(100), 28(91), 29(84)
**
162(100), 164(33), 127(30)
128(100), 130(33), 65(24)
-------
MS - ANALYTICAL
Compound
Chloroalkyl ethers, N.O.S.
p-Chloroaniline
Chlorobenzene
Chlorobenzilate
p-Chloro-m-cresol
1-Chloro-2,3,-epoxypropane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloromethyl methyl ether
2-Chloronaphthalene
2-Chlorophenol
3-Chloroproplonitrile
Chrysene
Coal tars
Creosote
Cresols
IONS (Continued)
Ions (Intensities)
**
127(100), 65(34), 129(31), 92(20)
112(100), 77(45), 114(33), 51(12)
142(100), 107(80), 144(32), 77(24)
63(100), 27(62), 43(42), 44(38)
83(100), 85(64), 47(37), 35(20)
50(100), 52(32), 15(21), 49(9)
45(100), 29(25), 15(22), 49(17)
162(100), 164(33), 127(33), 128(17)
128(100), 130(33), 65(24), 64(12)
49(100), 54(77), 51(39), 53(26)
228(100), 226(26), 229(21), 114(13)
**
**
-------
MS
Compound
Crotonaldehyde
2-Cyclohexyl-4,6-dinitrophenol
DDD
DDE
DDT
Diallate
Dibenz(a,h)acridine
Dibenz(a,j)acridine
Dibenz(a.h)anthracene
7H-Dibenzo(c,g)carbazole
Dibenzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo(a,i)pyrene
1,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
Di-n-butyl phthalate
IONS (Continued)
Ions (Intensities)
*
235(100),
246(100),
235(100),
279(100),
279(100),
278(100),
302(100)
302(100)
302(100)
157(100),
107(100),
174(100),
149(100),
237(66),
318(83),
237(72),
280(25),
280(25),
139(24),
165(38),
316(66),
165(59),
75(21)
248(58)
75(22)
139.5(23), 278(14)
139.5(23), 278(14)
279(16), 276(16)
155(78), 75(46), 159(25)
109(95), 27(54), 28(11)
93(72), 95(62), 172(52)
41(28), 29(25), 28(22)
-------
MS - ANALYTICAL IONS (Continued)
Compound Ions (Intensities)
Dichlorobenzene (meta, ortho, and para isomers)
Dichlorobenzene, N.O.S.
3,3'-Dichlorobenzidine
1,4-Dichloro-2-butene
Dichlorodifluoromethane
1.1-Dichloroethane
1.2-Dichloroethane
trans-l,2-Dichloroethene
Dichloroethylene, N.O.S.
1,1-DicHloroethylene
Dichloromethane
2,4-Dichlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
Dichloropropane, N.O.S.
1,2-Dichloropropane
Dichloropropanol, N.O.S.
146(100), 148(62), 111(39), 75(23)
146(100), 148(62), 111(39), 75(23)
252(100), 254(67), 256(10), 126(12)
75(100), 89(48), 53(36), 77(33)
63(100), 27(72), 65(33), 83(12)
*
62(100), 64(33), 27(70)
61(100), 96(80), 98(51), 63(29)
146(100), 148(62), 111(38), 113(13)
61(100), 96(80), 98(52), 63(33)
49(100), 84(72), 86(44), 51(31)
162(100), 164(65), 63(65), 98(40)
162(100), 164(64), 63(29), 126(20)
162(100), 220(78), 164(64), 222(49)
63(100), 62(74), 27(41), 41(34)
79(100), 81(38), 43(27), 49(20)
-------
MS - ANALYTICAL
Compound
Dichloropropene, N.O.S.
1,3-Dichloropropene
Dieldrin
1,2:3,4-Diepoxybutane
N,N-Diethylhydrazine
0,0-Diethyl S-methyl ester of phosphorodithioic acid
0,0-Diethylphosphoric acid, O-p-nitrophenyl ester
Diethyl phthalate
0,0-Diethyl 0-2-pyrazinyl phosphorothioate
Dihydrosafrole
Diisopropylfluorophosphate
Dimethoate
3,3'-Dimethoxybenzidine
p-Dimethylaminoazobenzene
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine
1,1-Dimethylhydrazine
(Continued)
Ions (Intensities)
75(100), 77(33), 110(25), 112(15)
75(100), 39(55), 77(32), 49(26)
79(100), 108(19), 263(18), 277(18)
55(100), 44(91), 43(73), 29(65)
149(100), 177(28),
163(100), 164(25),
244(100), 184(61),
120(100), 225(73),
256(100), 241(70),
150(13), 176(9)
77(19), 51(12)
201(38), 229(21)
77(58), 42(38)
257(48), 240(46)
60(100), 42(51), 59(45), 45(42)
-------
Compound
1,2-Dimethylhydrazine
alpha,alpha-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
Dimethyl sulfate
Dinitrobenzene, N.O.S.
4,6-Dinitro-o-cresol (and salts)
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
1,4-Dioxane
Diphenylamine
1,2-Diphenylhydrazine
Di-n-propylnitrosamine
Disulfoton
2,4,-Dithiobiuret
IONS (Continued)
Ions (Intensities)
60(100), 42(98), 28(53), 45(52)
58(100), 91(7), 59(5), 134(3)
122(100), 107(90), 121(55), 91(20)
163(100), 77(19), 164(10), 194(6)
15(100), 29(71), 95(66), 31(66)
30(100), 75(75), 168(70), 76(52)
165(100), 89(65), 90(26), 63(35)
165(100), 89(52), 90(35), 148(22)
149(100), 57(39), 167(32), 279(2)
28(100), 29(32), 59(24), 88(22)
77(100), 182(29), 105(23), 93(15)
70(100), 42(99), 117(79), 43(65)
-------
MS - ANALYTICAL IONS (Continued)
Compound
Endosulfan
Endrin (and metabolites)
Ethyl carbamate
Ethyleneimine
Ethyl methacrylate
Ethyl methansulfonate
Fluoranthene
Fluoroacetic acid, sodium salt
Formaldehyde
Formic acid
Glycidylaldehyde
Halomethane, N.O.S.
Heptachlor
Heptachlor epoxide (alpha, beta, and gamma isomers)
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclohexane (all isomers)
Ions (Intensities)
201(100), 283(48), 278(30)
81(100), 263(70), 82(61)
42(100), 43(62), 28(59), 15(22)
79(100), 109(78), 97(26), 80(19)
202(100), 200(20), 203(18), 101(13)
*
•k •&
100(100),
355(100),
284(100),
225(100),
181(100),
272(60),
353(79),
286(80),
227(65),
183(99),
274(46)
351(60)
282(53),
223(63),
109(80),
142(29)
260(38)
217(78)
-------
MS - ANALYTICAL IONS (Continued)
Compound
Ions (Intensities)
Hexachlorocyclopentadiene
Hexachloroethane
117(100), 119(95), 199(50), 201(85)
1,2,3,4,10,10-Hexachloro-l,4,4a,5,8,8a-hexahydro-
1,4:5,8-endo, endo-dimethanonaphthalene
Hexachlorophene
Hexachloropropene
Hexaethyl tetraphosphate
Hydrazine
32(100), 31(47), 29(40), 30(31)
Indeno(1,2,3-c,d)pyrene
276(100), 138(38), 277(26), 274(21)
Iodomethane
142(100), 127(38), 141(14), 15(13)
Isocyanic acid, methyl ester
Isobutyl alcohol
Isosafrole
162(100), 104(42), 131(30), 103(28)
Kepone
Maleic anhydride
26(100), 54(62), 25(61), 28(36)
Maleic hydrazide
Malononitrile
66(100), 38(34), 39(34), 28(31)
Methacrylonit rile
-------
MS
Compound
Methanethiol
Methapyrilene
Methoxychlor
2-Me thy1az i r id ine
3-Methylcholanthrene
4,4'-Methylenebis(2-chloroaniline)
Methyl ethyl ketone (MEK)
Methyl hydrazine
2-Methyllactonitrile
Methyl methacrylate
Methyl methanesulfate
N-Methyl-N'-nitro-N-nitrosoguanidine
Methyl parathion
Methylthiouracil
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
ANALYTICAL IONS (Continued)
Ions (Intensities)
58(100), 97(71), 72(22), 71(19)
28(100), 56(80), 57(54), 30(37)
256(100)
4 3(100), 29(24), 72(17), 27(16)
46(100), 45(61), 28(58), 31(41)
41(100), 69(83), 100(51), 39(36)
128(100),
158(100),
143(100),
127(20),
104(39),
115(45),
129(18), 64(7)
76(34), 102(31)
116(25), 144(14)
-------
MS
Compound
2-Naphthylamine
Nicotine (and salts)
p-Nitroaniline
Nitrobenzene
Nitroglycerine
4-Nitrophenol
Nitrosamine, N.O.S.
w N-Nitrosodi-n-butylamine
N-Nitrosodiethanolamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitroso-N-ethylurea
N-Nitrosomethylethylamine
N-Nitroso-N-methylurea
N-Nitroso-N-methylurethane
N-Nitrosomethylvinylamine
N-Nitrosomorpholine
ANALYTICAL IONS (Continued)
Ions (Intensities)
143(100), 115(38), 144(14), 116(13)
84(100), 133(27), 42(20), 162(19)
138(100), 92(50), 108(33), 65(30)
77(100), 128(55), 51(55), 65(25)
46(100), 30(24), 29(15), 76(9)
65(100), 139(90), 109(72), 81(33)
**
84(100), 57(79), 29(53), 41(52)
43(100), 42(68), 44(60), 56(56)
74(100), 42(75), 43(40), 44(10)
88(100), 42(93), 43(46), 56(24)
43(100), 96(76), 66(28), 79(20)
56(100), 116(55), 86(37), 28(13)
-------
MS - ANALYTICAL
Compound
N-Nitrosonornicotine
N-Nitrosopiperidine
N-Nitrosopyrrolidine
N-Nitrososarcosine
Octamethylpyrophosphormide
7-0xabicyclo[2.2.1]heptane-2,3-dicarboxylic acid
Paraldehyde
Parathion
Pentachlorobenzene
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenol
Phenylenediamine
Phosphorodithioic acid, 0,0-diethyl S-((ethylthio)
methyl) ester [Phorate]
Phosphorothioic acid, 0,0-dimethyl 0-(p-((dimethyl-
amino)sulfonyl)phenyl) ester [Famphur]
IONS (Continued)
Ions (Intensities)
42(100), 114(91), 55(56), 56(24)
100(100), 41(61), 42(58), 68(16)
250(100), 252(62), 248(62), 108(41)
117(100), 119(96), 167(95), 95(93)
266(100), 264(62), 268(63), 165(54)
94(100), 66(19), 65(17)
-------
MS - ANALYTICAL
Compound
Phthalic acid esters, N.O.S.
Phthalic anhydride
2-Picoline
Polychlorinated biphenyl, N.O.S.
Pronamide
1,3-Propane sulfone
n-Propylamine
Propylthiouracil
2-Propyn-l-ol
Pyridine
Resorcinol
Saccharin (and salts)
Safrole
1,2,4,5-Tetrachlorobenzene
2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)
Tetrachloroethane, N.O.S.
1,1,1,2-Tetrachloroethane
IONS (Continued)
Ions (Intensities)
104(100), 76(84), 50(40), 148(39)
55(100), 39(8), 28(6), 29(5)
79(100), 52(71), 51(36), 50(26)
183(100), 76(99), 50(72), 120(40)
162(100), 131(38), 104(31), 135(26)
216(100), 214(79), 218(49), 179(15)
322( ), 320( )
83(100), 85(66), 131(7), 133(7)
-------
MS - ANALYTICAL
Compound
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Tetrachloromethane
2,3,A,6-Tetrachlorophenol
Tetraethyldithiopyrophosphate
Tetraethylpyropbosphate
Tetranitromethane
Toluene
Toluenediamine
Toluene diisocyanate
Toxaphene
Tribromomethane
1,2,4-Trichlorobenzene
1.1.1-Trichloroethane
1.1.2-Trichloroethane
Trichloroethene
Trichloromethanethiol
IONS (Continued)
Ions (Intensities)
131( ), 13 3( ), 117( ), 119( )
166(100), 164(78), 129(64), 131(62)
92(65), 91(100), 65(12), 51(6)
121(100), 122(93), 94(17), 105(13)
174(100), 145(40), 28(39), 27(38)
231( ), 233( ), 235( )
173(100), 171(50), 175(49), 93(22)
180(100), 182(95), 184(30), 145(30)
97(100), 99(66), 117(17), 119(16)
97(100), 83(95), 99(66), 85(60)
95(100), 130(90), 132(85), 97(66)
-------
MS - ANALYTICAL IONS (Continued)
Compound Ions (Intensities)
Trichloromonofluoromethane
2.4.5-Trichlorophenol
2.4.6-Trichlorophenol
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4,5-Trichlorophenoxypropionic acid (2,4,5-TP)
(Silvex)
Trichloropropane, N.O.S.
1,2,3,-Trichloropropane
0,0,0-Triethyl phosphorothioate
sym-Trinitrobenzene
Tris(2,3-dibromopropyl) phosphate
Vinyl chloride
196(100), 198(97), 200(31), 97(20)
196(100), 198(96), 200(31), 132(28)
75(100), 39(58), 49(42), 110(37)
62(100), 27(64), 64(33), 26(18)
N.O.S. » Not Otherwise Specified.
*Mass spectrum for aldehydes depends upon derivatization method
**Mass spectrum depends on specific compound
-------
APPENDIX F
Volatile Organic Sampling Train
Appendix F contains a paper which
describes a laboratory evaluation
by Midwest Research Institute
(Kansas City, Missouri) of a
Volatile Organic Sampling Train
(VOST).
392
-------
Presented at Ninth Annual Research
Symposium Land Disposal, Incineratii
and Treatment of Hazardous Waste,
Ft. Mitchell, KY, May 2-4, 1983
DEVELOPMENT OF A VOLATILE ORGANIC
SAMPLING TRAIN (VOST)
Gregory A. Jungclaus, Paul G. Gorman, George Vaughn,
George W. Scheil, and Fred J. Bergman
Midwest Research Institute
Kansas City, Missouri 64110
Larry 0. Johnson
Industrial Environmental Research Laboratory
USEPA, Research Triangle Park, NC 27711
David Friedman
Office of Solid Waste
USEPA, Washington, DC 20460
ABSTRACT
The hazardous waste incineration regulations include the requiiysment that, for se-
lected principal organic hazardous constituents (POHCs), a destruction/removal efficiency
(DRE) of £ 99.99% must be achieved. In order to calculate meaningful DRE values, reliable
sampling and analysis methods oust be available. This paper reports on the development
and evaluation of a volatile organic sampling train (VOST) for the collection of volatile
POHCs from stack gas. The VOST is a method designed by the USEPA as an alternative to the
use of integrated gas bulbs and bags. The paper includes data concerning the collection
and analysis of four volatile POHCs during the laboratory evaluation, descriptions of the
equipment, a description of a field version of the VOST, procedures followed to minimize
sample contamination in the field, and conclusions and recommendations from the study.
1.0 INTRODUCTION
The results of previous hazardous
waste incineration trial burns have sug-
gested that volatile principal organic
hazardous constituents (POHCs) and vola-
tile products of incomplete combustion
(PICs) may be important components in the
incineration effluents. The sampling
technique described in a recent sampling
and analysis document (1) for volatile or-
ganic compounds involves the collection
and analysis of integrated gas bulb and
bag samples. However, the authors of that
report recognized that the gas bag tech-
nique suffers several drawbacks, including
the need to position the gas bag in a bulky
evacuated sampling box, bag leakage pro-
blems, adsorption losses of sample compo-
nents, contamination problems, and low
sensitivity when the bulb or bag is
analyzed using a gastight syringe sampling
technique.
To address the need to develop a bet-
ter sampling and analysis technique for
volatile POHCs, personnel from the En-
vironmental Protection Agency (EPA) dis-
cussed concepts for a volatile organic sam-
pling train (VOST) with several contracted
laboratories. One concept was adopted for
development to provide a method to collect
a sufficient quantity of volatile POHCs to
enable calculation of destruction/removal
efficiencies (DREs) as high as 99.999% for
incinerators whose waste feed contains as
little as 100 ppm of a P0HC.
MRI was selected by EPA to carry out
a laboratory study to develop and evaluate
the sampling train concenpt. Following
the laboratory evaluation of the VOST (2),
393
-------
a field version of the VOST was designed
and built by MRI, and is currently being
evaluated under field sampling conditions.
This paper describes how the labora-
tory evaluation was performed, presents
the results of the evaluation, describes
the field version of the VOST, and presents
conclusions and recommendations based on
the results to date.
2.0 VOST CONCEPT
The VOST concept to be evaluated bas-
ically consisted of a system designed to
draw sample gas at a flow rate of 1 liter/
min through two traps in series. The first
trap contained Tenax and was preceded by a
gas cooler/ condenser and followed by an
impinger for condensate collection. A sec-
ond trap containing a section of Tenax and
a section of charcoal was located after
the the impinger. The purpose of the sec-
ond trap was to collect very volatile POHCs
(e.g., vinyl chloride), which have low
breakthrough volumes and may break through
the Tenax trap. In addition, the concept
involved replacing both pairs of traps with
fresh traps at selected intervals (i.e.,
every 20 min or 20 liters of sample) over
a 2-h sampling period. There were two
basic reasons for changing the traps at
selected intervals:
At sample volumes of greater than
20 liters, some of the very vola-
tile POHCs may break through both
the front and backup adsorbent
traps.
* The changing of the traps allows
an initial analysis of one pair of
traps. Analysis of a single pair
of traps lowers the possibility of
collecting too much sample and
overloading the GC/MS system. How-
ever, if the POHCs are not detected
or are present at low levels in
the single pair, the option exists
of combining the contents of the
remaining pairs of traps onto one
pair of traps with a concomitant
increase in sensitivity. The ad-
vantage of the seond option for
samples with low POHC concentra-
tions is given below.
If a hazardous waste incineration fa-
cility is achieving a DRE of 99.999% for a
POHC that is present in the waste at a con-
centration as low as 100 ppm, the resulting
concentration of that POHC in the flue gas
will be approximately 0.1 Mg/m3 or 0.1 ng/
liter. Sampling 20 liters of that gas will
collect only 2 ng of the POHC on a single
pair of traps. Since 2 ng may not be de-
tectable by GC/MS analysis, the concept
required collection of several (e.g., five)
additional pairs of traps and the desorp-
tion of their contents onto another pair
of traps, thereby providing a total of
10 ng for GC/MS analysis.
It was anticipated that, when the
VOST system is used in the field, one will
not know whether pairs of traps should be
analyzed individually or if the contents
of several pairs should be desorbed onto
one pair. That is, if the concentration
of a selected volatile POHC in the efflu-
ent is low (e.g., 0.1 to 1.0 ng/liter),
several pairs may need to be desorbed onto
one pair to achieve sufficient analytical
sensitivity. However, if the concentration
is high, the paif of traps should be an-
alyzed individually, since desorption of
the contents of several pairs of traps onto
one pair of traps would make the quantity
even larger and saturate the GC/MS de-
tector. Therefore, the intent was to use
the VOST to collect six pairs of sample
traps, but with one pair being analyzed
first, individually, to determine the
amount of selected POHCs present. Then,
if warranted, the contents of some or all
of the remaining pairs could be desorbed
onto one pair for analysis, or other pairs
of traps could be analyzed individually to
check the variability in the stack gas com-
position with time.
The selection of a Tenax front trap
and Tenax/charcoal backup trap was based
on several factors including the authors'
previous experience with adsorbents and
information in the literature, primarily
from work done at Research Triangle Insti-
tute (3). Tenax alone is not a very good
adsorber for very volatile organic com-
pounds such as chloromethane and vinyl
chloride. Charcoal is a good adsorber for
the very volatile organics, but compounds
that are less volatile are not easily de-
sorbed from charcoal. Thus the dual trap
configuration was considered the most ver-
satile for providing efficient sample col-
lection and recovery of all volatile or-
ganics .
394
-------
The plan was developed to evaluate
the VOST concept that consisted of the fol-
lowing:
Set up an experimental system to
generate a wet gas stream prepared
with four volatile POHCs at each
of four different concentration
levels as described in Section 3.1.
• Construct three identical VOSTs
that would simultaneously draw gas
from the synthetic gas stream.
Set up equipment for conditioning
traps and for thermally desorbing
the contents of several pairs of
traps onto one pair.
Set up equipment for analyzing
traps by GC/MS.
After the above equipment had been
set up and made operational, the plan con'
sisted of carrying out a series of 10
tests. The test runs included: tests at
each of four concentration levels, repli-
cate tests at one level, blanks, and a test
(also at the replicate level) where the
gas contained HC1. The purpose of this
last test was to determine if HC1, which
is present in many incinerator «ffluents,
had any effect on the analysis results.
The order of the tests was randomized to
prevent bias from affecting the results.
The sequence of the tests in this plan was:
Level
(concentration of
Test
POHCs in gas)
Comment
1
III (10 ng/£)
Exploratory run
to check system
2
0
Blank run
3
III (10 ng/2)
4
I (0.1 ng/J>)
5
II (1.0 ng/£)
6
IV (100 ng/£)
7
0
Blank run
8
II (1.0 ng/A)
Duplicate of
Run S
9
II-HC1 (1.0 ng/£)
Duplicate of
Run 5 with HC1
in gas
10
0
Blank run
The equipment used in carrying out the
tests is described in the next section.
395
3.0 LABORATORY EVALUATION OF THE VOST
This section contains descriptions of
the equipment and procedures used in the
laboratory evaluation of the VOST includ-
ing:
3.1
Sample Gas Generator System.
3.2
Sampling Train Design.
3.3
Trap Conditioning Equipment.
3.4
Analytical Procedures.
3.5
Results.
3.6
Summary and Interpretation of
Results.
3.1 Gas
Generation System
As shown in Figure 1, the gas gen-
eration system consisted of 1/2-in. (1.27
cm) stainless steel tubing to carry vapor-
ous N2 from a liquid N2 tank through a
heater, where the N2 was heated to about
300°F (149°C). At that point, the was
rendered "wet" by vaporizing deionized/
charcoal-filtered water fed through a
quartz tube heater. Also near that point,
the liquid containing the four POHCs was
pumped by a syringe pump (5 ml/h) into the
hot N2 stream where the liquid immediately
vaporized to a gas.
The liquid injected by the syringe
pump was a solution of the four POHCs,
vinyl chloride, carbon tetrachloride, tri-
chloroethylene, and chlorobenzene in meth-
anol.
The concentrations of each of the four
POHCs tested are listed in Table 1.
The solution with the highest con-
centration (Level IV) was prepared first,
then aliquots were serially diluted with
methanol to prepare the three lower con-
centration solutions. These same solu-
tions were used as calibration standards
for the subsequent analyses.
Following the steam and POHC solution
injection point, the gas stream entered a
sampling manifold, with a perforated dis-
persing plate at the inlet. Gases were
drawn from this manifold into the three
sampling trains. After the manifold, the
hot gas (11 to 12 liters/min) passed
through a series of impingers (for water
-------
u>
VO
1 !/Min
Syringe Pump
for Injecting
Liquid Containing
Volatile POHCs
Heat Traced &
Insulated Lines
Heater
N2 Vapor
(149°C)
300° F
£
Liquid
N2
Tank
h2o
Vaporizer
Furnace
~ Sampling Train No. I
Sampling Train No. 2
-> Sampling Train No. 3
It
in^fQ=f2p:
Pump I Met t
Exhaust
Water-Removal
Impingers (3)
Gas
Meter
14 I / mi n
h2o
~5 ml/min
Figure 1. Schematic diagram of laboratory apparatus used to generate and sample
a simulated stack gas containing known concentrations of volatile POHCs.
-------
TABLE 1. POHC CONCENTRATIONS TESTED DURING LAB EVALUATION OF THE VOST
Concentration Expected conc. Expected amount
in methanol solution in gas stream on each pair
Level (ng/ml) (ng/2) of traps (ng)
I 84 0.1 2
II 840 1.0 20
III 8,400 10.0 200
IV 84,000 100.0 2,000
removal) and on through a pump and dry gas
meter.
During each of the tests, the gas gen-
eration system operated quite well, and
all readings were consistent from run to
run. The water content of the gas stream
ranged from 35 to 37 volume percent, as
measured by the impingers and gas meter.
During Rim 9, HC1 was added to the
water at a level of 1.3 g of HC1 per liter
of water to provide an" HC1 concentration
in the gas of about 0.5 g/Nm3 (normal cubic
meter). This is the HC1 concentration
estimated to occur in the effluent from an
incinerator burning a waste containing 15%
CI and equipped with a wet scrubber operat-
ing at the relatively low HC1 removal ef-
ficiency of 95%.
The gas flow rate in the gas generator
system and the POHC syringe pump injector
rate were used to compute an "expected
value" for the quantity of each POHC in
the Tenax traps. It was not feasible
within the scope and time frame of this
project to quantify the actual concentra-
tion of the POHCs in the gas produced by
the gas generator system. An independent
analysis of the spiked gas stream would
have been desirable but very difficult to
accomplish; however, the subsequent VOST
data gave little or no reason to believe
that the actual gas stream concentrations
were significantly different than the com-
puted "expected values."
3.2 Sampling Train Design
Figure 2 shows the VOST configuration
that was evaluated. The train consisted
of:
A sampling line (1/4-in., 0.64 cm,
Teflon tubing in the test system);
• First condenser;
• Tenax trap;
Impinger (for condensate removal);
Second condenser;
• Tenax/charcoal trap; and
• Other sampling components (rotom-
eter, pump, dry gas meter).
Except for the Teflon sampling line,
most of the components were made of glass,
including the traps. However, the fittings
at the inlet and outlet of each trap were
stainless steel.
When the trains were initially as-
sembled, two problems developed. First,
the 5/8-in. (1.58 cm) stainless steel
Swagelok fittings for the inlet traps were
designed to slip over the glass trap, but
some of the traps had an outside diameter
slightly larger than the inside diameter
of the Swagelok nut. Thus, all the nuts
had to be drilled out. Secondly, some of
the glass traps were out-of-round. This
meant that some traps, when inserted into
the sampling train, would not leak-check
unless the fittings were tightened with
wrenches. Several tubes broke before they
could be tightened enough to pass a leak-
check. Since checking for leaks and cor-
recting of leaks can take considerable
time, the adsorbent traps were redesigned
for field use as described in Section 4.0.
Before each run, the gas generation
system was started up and allowed to op-
erate for about 1 h. During that time,
traps were connected in the three trains
and leak-checked. All three trains were
then started and operated for 20 min »t
397
-------
LO
CO
Glass Wool
Particulate
Filter
Stack
(or Test.
System)
Teflon
Probe
Ice Water
Tenax
Trap
Vacuum
Indicator
Tenax
Trap
Charcoal Backup
Condensate
Trap Impinger
Rotometer
Empty Silica Gel
Notes Tenax & Tenax/charcoal traps were 1.6 cm in diameter
& 10 cm long
Pump
Dry Gas
Meter
Exhaust
1 l/min
Note: 3 trains as shown above
were operated each test
day.
Both traps were changed
every 20 minutes over
2 hour period.
Figure 2.. 'Volatile .organic sampling train i(VQST).
-------
about the same rate (1 liter/min).* All
three sampling trains were then shut off
and the traps removed and placed in pre-
marked container tubes. Another pair of
traps were then inserted in each train and
leak-checked before starting the next 20-
min sampling period. A run was considered
complete after six pairs of traps had been
used in each train. During each run, ice
water was circulated through the con-
densers. Thermocouples, located against
the surface of the condenser outlet tubes,
indicated that the gas temperature enter-
ing the first trap was in the range of 60
to 80°F (16 to 27°C). (The train with the
longest Teflon sampling tube yielded the
lowest temperature.)
Overall, the train configuration
caused no particular difficulty, except
for the leak-check problem described above.
However, using this train configuration to
sample a "wet" gas stream saturates the
first trap with condensate. This caused
no problems in the sampling but did re-
quire development of special procedures
for analyzing the wet traps, as discussed
in Section 3.4.
3.3 Trap Conditioning Equipment
The trap conditioning/desorption ap-
paratus, purchased from Nutech** (Model No.
322), served two purposes for the VOST
evaluation. First, it was used to condi-
tion traps prior to use, by heating them
at 250°C for 4 h with an estimated flow of
30 ml/min of purified nitrogen gas through
each trap. Second, it was used to ther-
mally desorb the contents from each of sev-
eral low-level pairs of traps onto one pair
of traps for GC/MS analysis. The purpose
of this desorption/adsorption was, in ef-
fect, to further concentrate the samples
from the sampling train.
A schematic diagram of the condition-
ing/desorption apparatus is shown in Fig-
ure 3, along with the trapping system that
was added at the outlet to re-adsorb the
contents from the desorbed pairs of traps.
* Gas flow rates in liters per minute
refer to normal conditions of 20°C,
1 atm (dry basis).
** Nutech Corporation, 2806 Cheek Road,
Durham, NC 27704.
When four traps were being desorbed
(which is the capacity of one section of
the desorption apparatus), the carrier gas
(N2) exits the desorption chamber hot, but
cools rapidly. However, when the traps
being desorbed are wet, the cooling is not
nearly so rapid because of the steam that
must be condensed. Thus, it was necessary
to use a condenser at the outlet of the
conditioning equipment, in front of the
first trap (Tenax). An impinger was also
required to remove the condensate before
the desorbed gas passed into the second
trap. As a result, the re-adsorption sys-
tem of traps at the outlet of the desorp-
tion equipment is equivalent to the sam-
pling train itself. Also, the condensed
steam again wets the first trap, so the
need to analyze a wet trap still remains.
When using the Nutech conditioning
apparatus to desorb several pairs of traps
(e.g., five pairs), the conditioner was
first heated to its normal operating tem-
perature of 250°C. Four traps were then
dropped into the chambers and allowed to
remain there for 10 min (with the total N2
carrier flow of 120 ml/min passing through
the four traps). These four traps were
then removed and four more traps inserted,
repeating the procedure until all five
pairs had been desorbed onto the one pair
at the outlet. This pair, or any pair an-
alyzed individually without first being
desorbed, was then spiked with an internal
standard and analyzed using the equipment
and procedures described in Section 3.4.
3.4 Analytical Procedures
The analytical procedures described
below include cleanup of the Tenax and
charcoal prior to packing into traps, prep-
aration of the traps, conditioning of the
traps prior to sampling, spiking of the
traps with an internal standard following
sampling, GC/MS analysis of the traps, and
data reduction.
3.4.1 Tenax and Charcoal Cleanup--
The Tenax (35/60 mesh) and SKC pe-
troleum-based charcoal (Lot No. 104) were
initially prepared by Soxhlet extraction
for 24 h with methanol and then with pen-
tane. The sorbents were then dried in a
vacuum oven at 100°C for 6 h prior to load-
ing into empty traps, each engraved with a
unique number.
399
-------
r4 rA rA ^
CO
r\
N2
100 ml/Min
'Liquid
N2
o
o
17 II I' • I I' II I* •»
r--
_ J ilIji irzii »rr5« irr5«
Water
Tenax
Trap
Trap Conditioner
& Desorfoer
Condenser
Vent
Tenax Trap
Charcoa I
Impinger
Figure 3. Schematic diagram of trap conditioner/desorption apparatus.
-------
3.4.2 Preparation of Traps—
The 10- x 1.6 cm glass traps with one
nippled end (to facilitate removal of the
traps from the desorption apparatus with
tweezers), available from the Nutech
Corporation, were used for the VOST evalu-
ation. A minimum amount of pre-extracted
and oven-dried glass wool was used in each
of the glass tubes to hold the sorbents in
the glass traps. The all-Tenax traps con-
tained about 1.6 g of Tenax, and the Tenax/
charcoal traps contained about 1 g of Tenax
and 1 g of charcoal (two-thirds Tenax by
volume).
3.4.3 Trap Conditioning—
The traps were thermally conditioned
prior to use, using the Nutech Model 322
thermal conditioning unit. The condition-
ing gas (nitrogen or helium) was purified
by passing through_a U-trap containing a
5-angstrom (5 x 10 8 cm) molecular sieve
with the U-trap immersed in liquid nitro-
gen. The temperature of the conditioning
unit was adjusted to 240 to 250°C, and the
flow rate of gas through each trap was
estimated to be about 30 ml/min. However,
only the sum of the flow through four of
the traps, which was set at 120 ml/min,
could actually be measured with the Nutech
conditioning unit. The traps were condi-
tioned for at least 6 h prior to their
first use in the VOST evaluation and for
at least 2 h more prior to use in sampling.
The actual flow through each trap may be
lower due to the fact that some of the con-
ditioning gas may flow around rather than
through the traps. Also residual pentane
was observed during several subsequent
analyses of the traps, suggesting that the
conditioning step was not completely ef-
fective.
Following conditioning, each trap was
transferred to a clean 25- x 150-mm screw-
cap test tube engraved with the same unique
number as engraved on the trap. The traps
were then ready for sample collection or
spiking experiments.
3.4.4 Spiking of Traps with Internal and
Calibration Standards-
Prior to GC/MS analysis, all Tenax
and Tenax/charcoal adsorbent trap samples
and standards were spiked with 25 ng of
perfluorobenzene (PFB) internal standard
using the flash vaporization technique in
which the spiking solution is vaporized
and carried onto the trap with a carrier
gas. The glass traps were attached to the
injection port (160°C) of a GC with a 5/8-
in. (1.58 cm) stainless steel Swagelok nut
containing Teflon ferrules. The Swagelok
fitting was connected to the GC column con-
nection via a reducing fitting. The helium
flow through the traps was set to about
50 ml/min. The gas flow through the trap
was turned on and off using the shutoff
valve on the side of the Varian 1400 GC.
The spiking solution was loaded and
expelled from the syringe using the solvent
flush technique to ensure that the standard
solution would be completely expelled from
the syringe. To use this technique, the
needle of a 5.0 |Jl syringe was filled with
clean methanol. The methanol was then ex-
pelled leaving methanol only in the syringe
needle. Then air was drawn into the sy-
ringe to the 1.0 pi mark followed by a 25-
ng/pl methanolic solution of the PFB to
the 2.0 |jl mark. The gas flow was turned
on through the trap and the syringe needle
inserted through the GC septum port. The
contents of the syringe were then slowly
expelled over about a 15-s period. At the
end of about 25 s, the gas flow through
the trap was shut off and the syringe re-
moved. All POHC calibration standards were
spiked using exactly the same procedure.
The total flow of gas through the traps
during spiking was thus only about 25 ml.
3.4.5 GC/MS Analysis of the Traps--
To analyze the traps, the contents of
the wet traps (dry traps in the case of
method blanks, field blanks, and calibra-
tion standards) were thermally desorbed
using a stream of carrier gas into a water
column (1 to 5 ml); this is a component of
the EPA Method 624 purge-trap-desorb GC/MS
analysis system. A schematic diagram of
the apparatus is shown in Figure 4. The
sample trap was dropped into the desorp-
tion chamber and desorbed at a flow rate
of 100 ml/min for 10 min at 180°C. The
desorbed compounds passed into the bottom
of the water column, were purged from the
water, and then were collected on an ana-
lytical adsorbent trap also containing
Tenax and charcoal. The compounds were
then desorbed from the analytical adsorbent
trap into the GC/MS system per EPA Method
624.
401
-------
CD
N'
4=£
: / \ i
Ic-Jl
k-J
iermal
Desorption
Chamber
Flow During
Flow to
GC/MS
Heated
Desorption
Flow During
[ Adsorption
©dXD©
Analytical Trap
with Heating Coi
(0.3 cm diameter
by 25 cm long)
He or N2
Vent
Purge
Column
(7) 3% SP-2100 (1 cm)
Tenax (7.7cm)
Silica Gel (7.7cm)
© Charcoal (7.7cm)
Line
Figure 4. Schematic diagram of trap desorption/analysis system.
402
-------
The normal routine for analyzing a
set of traps from each of the laboratory
VOST evaluation runs was to analyze a cal-
ibration standard on Tenax, a calibration
standard on Tenax/charcoal, and then to
intersperse calibration standards about
every fourth sample. Blank Tenax and blank
Tenax/charcoal traps (conditioned traps
spiked with internal standard) were also
analyzed when the samples from the blank
VOST train were analyzed. The same POHC
solution used to spike the wet gas in the
VOST runs was used to prepare the calibra-
tion standards for quantification of the
POHCs on the traps.
The problem of analyzing the wet sam-
ple traps was overcome by desorbing the
contents of the wet traps into an aqueous
purge and trap apparatus. Since the purge
and trap technique initially appeared to
offer minimal risk of losing or affecting
the very small amounts of each compound to
be quantified (i.e., 2 to 10 ng of POHC),
and was basically consistent with an ac-
cepted EPA method, it was used in this
evaluation. The Nutech apparatus was ini-
tially tested in the normal cryogenic trap-
ping configuration, but the desorbed water
froze and clogged the analytical system.
Other wet trap analysis techniques were
considered but not investigated because of
lack of time and possible associated pro-
blems .
3.4.6 Data Reduction--
The POHCs in the samples were quanti-
fied using the internal standard technique.
The area of the masses of m/z 62 for vinyl
chloride, m/z 117 for carbon tetrachloride,
m/z 130 for trichloroethylene, m/z 112 for
chlorobenzene, and m/z 186 for the per-
fluorobenzene internal standard were used
to calculate response factors from analy-
sis of the 8.4- and 84-ng calibration stan-
dards according to the equation*.
(A ) (CIS)
Response Factor (RF) = ^^ ^ j
IS S
where: A„ = The area of ion for the POHC.
A.- = The area of the ion for the
internal standard (m/z 186).
CT„ = The amount of internal stan-
dard (25 ng).
Cg = The amount of POHC in the
calibration standard (gen-
erally 8.4 or 84 ng).
The amounts of the POHCs in the sam-
ples were then calculated according to:
(As) (C,s)
Amount of POHC = -r-—, ,p->,
The reproducibility of the internal
standard area counts (m/z 186) was very
good with an average variation of only
about 10% for a daily batch of samples at
a given multiplier setting. There did not
appear to have been any particular dif-
ference in perfluorobenzene area counts
with the type of trap; e.g., wet traps or
Tenax/charcoal traps did not give lower
area counts than dry traps and Tenax-only
traps. This is in contrast to the POHC
vinyl chloride which gave higher response
on Tenax than on Tenax/charcoal traps dur-
ing analysis of calibration standards.
The reason for this is as yet undetermined.
There is no reason to believe that the
vinyl chloride broke through the Tenax to
the charcoal because only about 15 ml of
gas passes through the trap during spiking.
3.5 Results
It was noted in Section 2.0 that a
total of 10 runs were made during this
evaluation, involving four different con-
centration levels of the POHCs and three
blank runs. After each run, the traps from
each of the three trains were analyzed and
results reported for the traps as pairs
(i.e., Tenax trap plus Tenax/charcoal trap).
Not all pairs were analyzed, especially at
the higher concentration levels, where it
was not necessary to desorb several pairs
onto one pair. In most cases, at the lower
concentration levels, one pair of traps
from each train were analyzed individually,
while all remaining pairs from each train
were desorbed onto a single pair for analy-
sis. Several calibration standards were
analyzed along with the traps from each
run in order to be able to quantify a wide
concentration range.
Results were initially calculated
after each run based on calibration stan-
dards analyzed with the samples from each
run. After all runs and analyses had been
completed, the results were recalculated
based on the average mass spectrometric
response factor of all the appropriate cal-
ibration runs using the internal standard
technique described earlier in Section
3.4.6. These response factor data are
403
-------
shown in Table 2. The data in Table 2 also
show transfer efficiencies determined for
desorbing several pairs of traps with re-
adsorption onto a single pair. Since the
transfer efficiency for vinyl chloride was
relatively low (49%), the reported values
for vinyl chloride were corrected for this
low transfer efficiency. Also, the data
for the four POHCs were blank-corrected,
as discussed below.
Three blank runs were carried out
using the gas generation system and three
VOSTs, but without any injection of the
solution containing the POHCs into the sys-
tem. The results for these blank runs are
shown in Table 3 and include analyses of
single pairs, and several pairs combined
onto one pair. As can be seen in Table 2,
most of the blank values are relatively
low, but are still significant relative to
the run at the lowest concentration level
where the expected amount of any POHC on
each pair was only about 2 ng. In this
regard, the blank values for carbon tetra-
chloride in Runs 7 and 10 are higher than
the expected value. Thus, it was not pos-
sible to blank-correct the carbon tetra-
chloride results obtained in the lowest
level run (Run 4), which makes it difficult
to make any definitive conclusions about
using the VQST train for detecting such
low levels of carbon tetrachloride.
The problem with the high carbon
tetrachloride blanks was evident after
Run 7, and therefore another blank run was
made (Run 10), after the gas generation
system and the trains were purged with
vapor from the liquid N2 tank at room tem-
perature for 24 h. However, the blank
carbon tetrachloride values were again
found to be high in Run 10. Other blank
traps were analyzed which had not been ex-
posed to the gas generation system, but
had been exposed to room (laboratory) air,
and no POHCs were detected in these blanks
(i.e., < 0.5 ng). The absence of carbon
tetrachloride in the blanks suggested that
the high blank values for carbon tetra-
chloride resulted from within the gas gen-
eration system or the sampling trains and
was not a result of any subsequent analyt-
ical procedures or contamination from the
ambient room air.
Except for the carbon tetrachloride
data from*the lowest level run, all uncor-
rected and blank-corrected results were
tabulated, with the corrected values being
used to compute the results as a percentage
of the expected value. These tabulated
data are summarized in Table 4. The data
in Table 3 provide information on results
computed as averages but do not show the
range in results. The compounds are dis-
cussed individually below.
3.5.1 Vinyl Chloride—
Figure 5 (for vinyl chloride) shows
all results, blank-corrected and corrected
for the 49% transfer efficiency when trans-
ferring the contents of several pairs of
traps onto one pair.
The results for vinyl chloride at the
0.1 and 1.0 ng/liter gas phase concentra-
tions appear to be similar, with total re-
coveries when analyzing single pairs rang-
ing from 48 to 95% of the expected value.
When combined pairs were used the recov-
eries ranged from 48% of the expected value
up to 148%. Conversely, at the 10 ng/liter
level where only single pairs were analyzed,
all except one data point are greater than
the expected value, ranging from 100 to
180% of the expected value. Thris is a
rather wide range, but vinyl chloride is
very volatile, and it is commonly recog-
nized that analyses for this compound are
difficult.
At the highest concentration level
(Level IV, 100 ng/liter gas-phase concen-
tration, 2,000 ng/pair of vinyl chloride
expected on the traps), the results were
consistently low ("* 48% recovery). Al-
though nearly all of the other POHCs were
consistently found on the first Tenax trap
of any pair, most of the vinyl chloride
was found on the backup Tenax/charcoal
trap. The data thus suggest that break-
through or irreversible adsorption of the
vinyl chloride occurred at the highest con-
centration level. Thus in any further
testing, one should be aware that this may
occur when using the VOST method at high
concentrations of vinyl chloride.
3-5.2 Carbon Tetrachloride—
The results for carbon tetrachloride
are shown in Figure 6. These data are all
blank-corrected except for the data at the
lowest concentration level. As a conse-
quence, the data at the 0.1 ng/liter level
exhibit some very high values, which un-
doubtedly are not representative.
404
-------
TABLE 2. GC/MS RESPONSE FACTOR AND THERMAL DESORPTION COLLECTION
EFFICIENCY FOR FOUR VOLATILE POHCs
RF Desorption
Avg^ Type of following transfer
Compound RF a % RSD n trap desorption n efficiency
Vinyl chloride
0.140
± 0.042
30
15
T/C
0.069
2
49
Carbon tetrachloride
0.197
± 0.069
35
13
Te
0.143
2
73
Trichloroethylene
0.490
± 0.068
14
14
T
0.435
2
89
Chlorobenzene
0.338
± 0.065
19
14
T
0.331
2
98
Mass spectrometric response factor relative to perfluorobenzene.
k RSD = Percent relative standard deviation, which equals o r Mean x 100.
£
n - Number of determinations (includes 8.4 and 84 ng calibration standards).
^ T/C = Tenax/charcoal (~ 70:30 v/v) trap.
e T = All-Tenax trap (1.6 g).
' Contents of calibration standard thermally desorbed onto type of adsorbent
trap in previous column.
-------
TABLE 3. TABULATION OF DATA FROM BLANK RUNS
Blank
run No.
No. of
combined
pairs
Vinyl
chloride
Amount detected (ng)'
Carbon
tetrachloride
Trichloro-
ethylene
Chloro-
benzene
7
7
7
10
10
10
Single pairs data
No single pairs analyzed
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
Avg for single pairs*3
12.5
3.6
3.5
1.2
3.7
< 0.5
4.1
0.7
0.2
< 0.5
3.4
< 0.5
2.0
1.1
0.8
0.6
0.5
0.5
0.5
0.5
0.2
Combined pairs data
2
2
7
7
7
10
10
10
4
4
5
5
5
5
5
5
Average per pair
for combined pairs
5.4
4.8
4.7
1.1
Lost
< 0.5
< 0.5
< 0.5
0.5
< 0.5
< 0.5
35
49
17
53
50
54
6.8
2.3
2.5
5.0
6.6
6.3
4.8
2.2
3.0
0.9
8.0
6.4
8.1
10.0
4.0
1.8
3.6
6.2
1.3
Amounts calculated based on average response factor determined from
all standards (response factor for VC was based on analyzing stan-
dards on Tenax/charcoal traps; the other compounds were based on
analyzing standards on Tenax traps).
Less than values were assumed to be zero in order to compute an
average.
406
-------
TABLE 4. VOST DATA SUMMARY
No. of !
Expected cartridge
gas phase pairs
concentration analyzed
Run of each compound (i.e.,
Mo. (fig/liter) replicates) for analyais (ng) pairs
No. of ^
csrtridge Average
pairs expected Vinyl chloride
cos£»ioed value Single Combined
pairs
Aversge naount^found, in ng, - blank corrected,
and (X of average expected value)
Carbon tetrachloride Trlchloroethylene Chlorobenzcne
Single Coatbined Single Combined Single Combined
pairs pairs pairs pairs pairs pairs
2 0 2 4 0
7 0 3 0 0
7 0 3 5 0
10 0 3 0 0
10 0 3 S0
5.1
< 0.5
2.9
< 0.5
< 0.5
< 0.5
6.5
34
1.6
52
2.4
0.3
6.0
1.(
3.3
7.2
0.5
7.4
< 0.5
3.9
4 0.1 2 0 1.9
4 0.1 3 5 *-l
(4 U 1 »et)
1.5(791)
10.1(1111)
4.2(2211)' .
16(1761)4
1.5(791)
(((971)
•((951)
9.5(1041)
5 1.0 3 0 1*
5 1.0 3 4 77
1 1.0 3 0 20
1 1.0 3 4 ?t
9 1.0 (with MCI) 3 0 20
* 1.0 (with HC1) 3 4 77
12(431)
37(481)
17(151)
115(14(1)
19(951)
41(791)
9(471)
6((((1)
11(551)
(9(1131)
• (401)
•5(1101)
22(1161)
(3(10(1)
23(1151)
(3(1051)
19(951)
(1(1051)
29(1531)
101(1311)
21(1051)
91(1151)
l((901)
74 (961)
3 10.0 7 0 1*3
3 10.0 0
274*1421)
136(701)
210(1091)
204(1061)
4 100.0 6 0 2,020
6 100.0 0
•70(431)
2.110(10(1)
2,660(1321)
2,050(1011)
Gai voJiMe la liter* refers to dry standard conditions (20*C, I atsi).
* Cartridge pairs refers to one Teaax cartridge and an associated Tenax ~ charcoal cartridge.
c Data tor vinyl chloride include correction for 49% transfer efficiency vtien several pairs are desofbed onto one pair (per Table 1).
All valuea are blank-corrected except for carbon tetrachloride in Run 4, due to large average blank value (per Table 2).
-------
260
240
220
200
180
160
140
120
100
80
60
40
20
0
O Single Pair Data
° Combined Pairs Data
Note: Data have been
blank-corrected.
O
o
0
o
—I—
10,000
Expected Value (ng)
10
-Level I Data -
Expected value
near 2ng/pair
O
O
o
>2°
o
100
<2»
Level II Data -
Expected value
near 20ng/pair
1000
-Level III Data -
Expected value
near 200ng/pair
O
-Level IV Data —
Expected value
near 2000ng/pair
Figure 5. Vinyl chloride test results.
-------
240
220
200
180
160
140
120
100
80
60
40
20
0
o
o Single Pair Data
a Combined Pairs Data
Note; Level II, III, and IV
data have been blank-corrected.
Level I data were not blank-
corrected because correction
was large relative to measured
value and would, in several
cases, have resulted in negative
values.
a
10
Level I data was not
blank corrected.
(See Note)
~ 100
1000
%
o
oo
—e-
+
Expected Value (ng
10,000
o
o
o
o
<9
o
o
-Level I Data -
Expected value
near 2n£|/pair
-Level II Data -
Expected value
near 20ng/pair
-Level III Data -
Expected value
near 200ng/pair
-Level IV Data —
Expected value
near 2000ng/pair
Figure 6. Carbon tetrachloride teat results.
-------
Data at the 1.0 ng/liter level are
similar to that found for vinyl chloride,
in that all data for single pairs are less
than the expected value, but data for com-
bined pairs range from 60 to 170% of the
expected value. This phenomenon is not as
yet explainable, but most probably relates
to the quantity present on any trap being
analyzed and the characteristics of the
purge-trap-desorb and GC/MS analysis method
As originally conceived, the intent would
be to rely on results for combined pairs
at low levels, which does seem to be sup-
ported by the data.
At the 10 ng/liter level, data for
all the single pairs, except one, were less
than the expected value, ranging from 36
to 120%. Thus, a result for any single
pair might be quite low, but it is antici-
pated that, in any field testing, results
would be based on the average of the analy-
sis of several pairs, which in this case
would have yielded an average value of 70%
of the expected value. It is evident in
Figure 6 that, at the highest concentra-
tion level (100 ng/liter), all the single
pair results were quite close to the ex-
pected value.
In summary, the results for carbon
tetrachloride do not indicate any major
deficiency in the V0ST method, except for
the relatively high blank values and their
effect on results at the lowest concentra-
tion level. If these blank values were
due to the gas generation system, then high
blank values might not be a problem in any
field testing. However, if the high blanks
somehow resulted from the sampling trains,
further work would be needed to determine
how trains should be cleaned and prepared
prior to each test to minimize blank pro-
blems .
3.5.3 Trichloroethylene—
Results for trichloroethylene, given
in Figure 7 (blank-corrected), show a much
narrower range at all concentration levels
than did the results for vinyl chloride or
carbon tetrachloride. The extremes varied
from 70% of the expected value (at the 0.1
ng/liter level for combined pairs), up to
slightly above 140% of the expected value
(at the 100 ng/liter level for single
pairs). These results appear to be quite
good for this compound using the V0ST
method.
3.5.4 Chlorobenzene—
Results for chlorobenzene, given in
Figure 8 (blank-corrected), are not as nar-
row as for trichloroethylene, but do show
decreasing variability with increasing con-
centration levels. Again, data at the low-
est concentration level showed the greatest
deviation from the expected value, ranging
from 36% up to 173% of the expected value.
However, at the next higher concentration
level (1.0 ng/liter), data for combined
pairs ranged from 88*% to about 140% of the
expected value. At 10 ng/liter, the re-
sults for the single pairs were about the
same, ranging from 70% to about 140% of
the expected value. As is evident in Fig-
ure 8, the range at the highest level was
very narrow.
3.6 Summary and Interpretation of Results
The preceding sections have shown
that, at the two lowest concentration
levels, the results for combined pairs of
traps might range from 38 to 173% of the
expected value (excluding higher values
for carbon tetrachloride at the lowest
level, which were not blanlc-corrected).
However, the data presented earlier in
Table 4 show that if three trains (or
three runs) are used, the average for
combined pairs may range from 48% up to
146% of the expected value. At the two
highest concentration levels, the average
for several pairs analyzed individually
ranged from 70% up to 142% of the expected
value (excluding a 43% average value for
vinyl chloride at the highest concentra-
tion level where it appears that break-
through or irreversible adsorption oc-
curred) .
If one assumes, for simplicity of
number, that the average value from three
tests may span a range of 50 to 150%, it
is possible to determine the implications
on a subsequent calculation of DRE based
on that range, as explained in the two
scenarios given below.
In the first scenario, one may be try-
ing to determine DRE for an incinerator
that is actually achieving 99.999% for a
POHC present in the waste at the low con-
centration of 100 ppm. As mentioned ear-
lier, the approximate resulting true con-
centration of that POHC in the stack
effluent would be about 0.1 ng/liter. If
this gas is sampled over a 2-h period using
410
-------
260
240
220
200
180
160
140
120
100
80
60
40
20
0
O Single Pair Data
° Combined Pairs Data
Notes Data have been
blank-corrected.
10
ir
'o
o
o
oo
a
cB
a n I
n i
ft
-------
260
240
220
200
180
160
140
120
100
80
60
40
20
0
O Single Pair Data
° Combined Pairs Data
Note; Data have been
blank-corrected.
a
~
O
O
~ ~
O
o+-
100
O
o
Expected Value (ng)
8
10
CO
1000
o
10.000
o
-Level I Data —
Expected value
near 2 ng/pair
Level II Data -
Expected value
near 20 ng/pair
-Level III Data -
Expected value
near 200 ng/pair
-Level IV Data —
Expected value
near 2000 ng/pair
Figure 8. Chlorobenzene test results.
-------
five pairs of traps each time, at 20 min
each pair and a flow of 1-liter/min, the
results from combining five pairs should
be 10 ng. However, if the average for
three tests (three runs) at this low con-
centration ranged from 50 to 150%, the re-
ported value would be between 5 and 15 ng.
As a result, the computed DRE would be:
Average amount
detected
5
10
15
Computed
PRE (%)
99.9995
99.9990
99.9985
In this first scenario it is clear
that the sampling/analysis method does al-
low an accurate determination of DRE, and
minimizes the need to report a DRE value
as "greater than" 99.99% when it is actu-
ally achieving 99.999%.
As a second scenario, the situation
might be that the waste again contains 100
ppm of another volatile POHC, but the in-
cinerator is actually achieving a DRE of
99.99%. In this case, the amount of POHC
present from combining five pairs of traps
should be 100 ng. Since the average for
three tests at this level may again range
from 50 to 150% of the true value, the re-
ported value might be as low as 50 ng or
as high as 150 ng (i.e., 100 ng ± 50). As
a result, the computed DRE would be:
Average amount
detected
50
100
150
Computed
PRE (%)
99.995
99.990
99.985
From the above, it can be concluded
that:
* The sampling/analysis method does
provide assurance that the com-
puted DRE is accurate to the same
decimal place as the true DRE, even
if the true DRE is as high as
99.999%.
The computed DRE could be as low
as 99.985% for an incinerator that
is actually achieving 99.99%.
This second conclusion is vitally im-
portant since current regulations stipulate
a DRE of 99.99%. Data obtained in this
project make it appear unlikely that a
computed DRE would be below 99.985% for an
incinerator that is actually achieving
99.99%.
4.0 DEVELOPMENT OF A FIELD VERSION OF THE
VOST
Following the successful laboratory
evaluation of the VOST described above,
the VOST concept was chosen to be evalu-
ated under field sampling conditions along
with integrated gas bags. However, the
laboratory version of the VOST was not
deemed appropriate for field use for the
following reasons:
The difficulty in changing traps
under field conditions.
~ The lack of ruggedness of the sam-
pling train.
The high potential for contamina-
tion of the outside surfaces of
the traps in the hostile environ-
ment of the stack and from han-
dling the traps.
As a result of the need for a more rugged
VOST with protected traps, several pos-
sible VOST and trap designs were considered
and evaluated. This paper will only de-
scribe the final field version of the VOST
which is being used at all trial burns con-
ducted by MRI.
4.1 Trap Design
Figure 9 shows the various components
of the field adsorbent traps used in the
VOST. The following items should be noted.
The dimensions of the glass tube
remain the same except that neither
end is nippled (10-cm x 1.6-cm ID
glass tube).
The amount of Tenax and Tenax/char-
coal remains the same.
The Tenax and charcoal are held in
the tubes with a fine-mesh screen
held by a C-clip both made from
stainless steel. These supporting
materials hold the adsorbents more
uniformly inside the tubes than
the glass wool used during the lab-
oratory evaluation. This results
in a lower likelihood of channeling
413
-------
-.Mi. iJLaJhwiluuuC
Figure S. Components cf field adsorbent traps for the VOST.
/ 1 / [ Reproduced from
414 I best available copy.
-------
and lower retention of water in
the trap. The stainless steel sup-
ports were found not to cause any
degradation of volatile POHCs from
thermal desorption during analysis.
The glass tube containing the ad-
sorbents is held within a larger
diameter outside tube using Viton
0-rings. The purpose of the out-
side glass tube is to protect the
outside of the adsorbent-containing
tube from contamination.
* The glass tubes are held in a
stainless steel carrier. The glass
tubes each butt up against Viton
0-rings which are held in machined
grooves in each metal end piece.
A set of three cylindrical rods
are secured into one of the end
pieces and fasten to the other end
piece with threads and nuts, thus
sealing the glass tubes.
• The end pieces, which are fitted
with a 1-in. (2.54 cm) female nut,
are capped during transport and
storage with an end-cap which also
seals with a Viton 0-ring.
4.2 VOST Design
A photograph of the field version of
the VOST is shown in Figure 10. The upper-
most section of glass tubing attaches to
the probe which is inserted into the stack
to collect the sample. The hot wet stack
gases, which are drawn into the VOST by
the air pump in the lower right-hand part
of the photograph, are cooled in the first
spiral condenser at the upper left. The
bottom portion of the open case is filled
with ice water which is continually circu-
lated by a small water pump. The condensed
water and stack gas then pass down through
the front Tenax trap where most of the or-
ganics are adsorbed except those with very
low breakthrough volumes; e.g., vinyl
chloride. The condensed water collects in
the Erlenmeyer flask-shaped impinger and
is continually purged by the sampled gas.
Any volatile POHCs which pass through the
front Tenax adsorbent trap with the water
are then purged from the water and pass
upward through the Teflon® tube, down
through the second spiral condenser and
through the backup Tenax/charcoal trap
where they are adsorbed. The gas is then
dried in the silica gel tube and passes
into the dry gas meter for volume measure-
ment. When not in use, the VOST folds up
inside the portable case for easy trans-
port.
The field VOST is generally used as
described in the laboratory evaluation;
i.e., one pair of traps is sampled for 20
min at a flow rate of 1 liter/min. The
first trap pair is then removed and a new
pair inserted for sample collection. A
total of six pairs of traps are collected.
The changing of the trap pairs is greatly
facilitated by using the field carrier.
A "slow VOST" is also being evaluated
during which only two or three pairs of
traps are used for sample collection. The
slow VOST, which generally samples only
5-10 liters of stack gas sample over a
longer sampling period, has the following
advantages:
The lower sample volume reduces
the likelihood of breakthrough and
serves as a check on breakthrough
for the regular VOST.
• A more integrated sample is ob-
tained. This is very advantageous
in situations where the stack gas
composition changes during the in-
cineration test.
The main disadvantage of the "slow VOST"
is its decreased sensitivity.
4.3 Trap Preparation Procedures
During the development and evaluation
of the field VOST, it was discovered that
the sorbent traps were sometimes severely
contaminated with volatile organic com-
pounds. Several possible sources of con-
tamination were identified such as ambient
air, contaminated metal carriers, 0-rings,
and the adsorbents. In order to prevent
contamination, a series of stringent trap
preparation procedures were tested and
adopted which have proved very effective
in eliminating the contamination for field
sampling with the VOST. These procedures
are discussed below.
4.3.1 Preparation of Tenax and Charcoal—
New Tenax and charcoal is Soxhlet-
extracted with methanol for 16 h, and dried
in a vacuum oven at 50°C prior to packing
into tubes- The Tenax and charcoal in
415
-------
Reproduced from
best available copy.
Figure 10. Photograph of the field version of the VOST.
416
-------
packed tubes are not routinely reextracted
following sampling and analysis unless very
high concentrations (i.e., micrograms) of
sample components are collected.
4.3.2 Preparation of O-Rings—
The Viton 0-rings are thermally con-
ditioned in a vacuum oven at 200°C for 48 h
prior to use. This procedure removes vola-
tile solvents which may be present in the
0-rings and could outgas later.
4.3.3 Preparation of Metal Parts—
The metal parts (including the stain-
less steel carriers, end plugs, C-clips,
and screens) are subjected to sonification
in a warm non-ionic soap solution, rinsed
with distilled water, air-dried, and heated
in a muffle furnace at 400°C for 2 h.
4.3.4 Preparation of Glass Tubes—
The glass tubes are cut from new glass
tubing, fire-polished, and annealed.
4.3.5 Packing—
The Tenax and charcoal are packed into
the glass tubes in an organic-free labora-
tory (laboratory air filtered through char-
coal) .
4.3.6 Trap Conditioning—
The traps are conditioned as de-
scribed in Section 3.4.3. However, two
different conditioning periods are used of
at least 4 h each.
4.3.7 Trap Assembly—
The conditioned traps are assembled
into the metal field carriers in the same
organic-free room where the adsorbents are
packed into the glass tubes.
4.3.8 Leak Checking—
The assembled field traps are checked
for leaks by removing one of the end caps
and attaching the trap to a source of
organic-free nitrogen gas at 30 psi (2.1
kg/cm2). The trap is then immersed in dis-
tilled water to check for the appearance
of bubbles.
4.3.9 Trap Monitoring—
Following trap assembly and assurance
that the traps do not leak, each trap as-
sembly is attached to a manifold (capacity
of 10 traps). Organic-free nitrogen is
passed through each trap at a flow rate of
30 ml/min while the traps are heated to
190°C. The flow through each trap is se-
quentially monitored with a flame ioniza-
tion detector to check for emission of
volatile organics from the trap assembly.
Most traps show no organic emissions,
while others need to remain on the condi-
tioner for several hours until the emis-
sions from the trap are reduced to less
than a detectable level (< 2 ppb).
4.3.10 Trap Storage—
When the traps are shown to be clean
with the flame ionization detector, they
are capped and stored under ice water until
they are used for sampling. The traps are
also placed back under ice water after sam-
pling until they are analyzed by GC/MS.
The ice water serves to keep the traps cold
which slows aging of the Tenax; i.e., the
gradual transfer of compounds such as
benzene and toluene from within the poly-
meric Tenax matrix to the surface of the
Tenax where these compounds can be ther-
mally desorbed during analysis and con-
tribute to high background levels. The
water also protects the traps from vola-
tile organic compounds in the ambient at-
mosphere which could collect on the out-
side of the trap assembly and contaminate
the adsorbents during disassembly just
prior to analysis. A summary of the trap
preparation procedures is shown in Figure
11.
5.0 CONCLUSIONS AND RE COMMENDATIONS
The conclusions and recommendations
based on this evaluation of the V0ST are
presented below. Some of the conclusions
are preliminary and could change upon fur-
ther evaluation of the V0ST. We also ex-
pect that the precision and accuracy of
the method will improve during further
evaluation.
This laboratory evaluation demon-
strated that the overall concept
for the VOST is valid, and that
combining several pairs of traps
onto one pair of traps for analy-
417 sis is advantageous when the POHCs
-------
O - rings
Tenax —
Charcoal
Glass Tubes
Metal Parts—|
C - clips
Screens
Analysis
Log In
Leak Check
Sample
I90°C Oven
with N2 Flow
Culture Tubes
in VOA Lab
Store in Clean
Container
Check with
GC/FID
Assemble in
Organic-
Free Room
Store in
Organic-Free
Area
Thermally Condition
(250°C, 4 hrs) x 2
200 °C Vacuum
48 Hrs
Store Under Ice Water
Oven Dry,
Store in Closed
Container
400 °C Oven
2 hrs
Alconox
Ultrasonic
Dl Rinse
Alconox
Ultrasonic
Dl Rinse
Figure 11. VOST trap cleanup procedure.
-------
are present at low levels. The
field work thus far, however, sug-
gests that the levels of volatile
POHCs are high enough that combin-
ing the contents of several pairs
of traps onto one pair is gen-
erally not necessary.
• The VOST method does overcome the
problem of reporting a DRE value
of > 99.99% for an incinerator
which is actually achieving 99.999%.
• Results of the laboratory evalua-
tion indicate that a reported value
may be as low as 46% or as high as
146% of the expected value (based
on the average of three runs when
several pairs from each sampling
train are combined onto one pair).
• Therefore, for an incinerator that
is achieving a DRZ of 99.999% (100
ppm Concentration of the POHC in
the waste), the VOST method does
permit determination of ORE to the
third decimal place, but with re-
sults that could range from as low
as 99.9985 to as high as 99.9995.
• The VOST method does not ensure
that ORE results can always be ac-
curately computed to the third
decimal place. In fact, if an in-
cinerator is actually achieving a
DRE of 99.990%, the average re-
sults reported for three tests
could have a deviation of 99.990
± 0.005%.
• In this evaluation, results for
vinyl chloride and carbon tetra-
chloride show the most variabil-
ity, especially at lower concen-
trations.
• The presence of HC1 in the gas
being sampled did not appear to
have any serious effect on the
VOST results.
• The problem of analyzing wet traps
can be satisfactorily overcome by
desorbing the contents of the sam-
ple collection traps into a purge-
trap-desorb GC/MS analytical sys-
tem.
• Stringent trap preparation pro-
cedures are required to eliminate
the risk of contaminating the traps
prior to use.
Separate traps (blanks) should be
exposed to air in the field in
order to determine the level of
compounds on the traps due to ad-
sorption of the compounds during
handling of the traps and their
insertion into/removal from the
VOST apparatus.
6.0 ACKNOWLEDGMENTS
Much of the work discussed in this
paper was funded under contract with the
U.S. Environmental Protection Agency (EPA
Contract Mo. 68-01-5915). The work was
performed under the direction of Dave
Friedman of EPA/0SW and Larry Johnson of
EPA/IERL-RTP who provided counsel in all
phases of the work.
7.0 REFERENCES
1. Rechsteiner, C., J. C. Harris, K. E.
Thrun, D. J. Sorlin, and V. Grady.
1981. Sampling and Analysis Methods
for Hazardous Waste Incineration,
A. D. Little, Inc., in support of
Guidance Manual for Evaluating Permit
Applications for the Operations of
Hazardous Waste Incineration Units,
EPA Contract No. 68-02-3111, EPA/IERL,
Research Triangle Park, North Carolina
2. Jungclaus, G., and P. Gorman. 1982.
Draft Final Report, Evaluation of a
Volatile Organic Sampling Train, Mid-
west Research Institute, EPA Contract
No. 68-01-5915.
3. Krost, K. J., E. D. Pelli2zari, S. G.
Walburn, and S. A. Hubbard. 1982.
Collection and Analysis of Hazardous
Organic Emissions. Anal. Chem..
S(4):810-817.
4. EPA Method 624 - Purgeables. 1979.
U.S. Environmental Protection Agency,
Federal Register 44:69532-69539.
419
-------
are present at low levels. The
field work thus far, however, sug-
gests that the levels of volatile
POHCs are high enough that combin-
ing the contents of several pairs
of traps onto one pair is gen-
erally not necessary.
• The VOST method does overcome the
problem of reporting a DRE value
of > 99.99% for an incinerator
which is actually achieving 99.999%.
• Results of the laboratory evalua-
tion indicate that a reported value
may be as low as 46% or as high as
146% of the expected value (based
on the average of three runs when
several pairs from each sampling
train are combined onto one pair)
• Therefore, for an incinerator that
is achieving a DRZ of 99.999% (100
ppm Concentration of the POHC in
the waste), the VOST method does
permit determination of ORE to the
third decimal place, but with re-
sults that could range from as low
as 99.9985 to as high as 99.9995.
• The VOST method does not ensure
that ORE results can always be ac-
curately computed to the third
decimal place. In fact, if an in-
cinerator is actually achieving a
DRE of 99.990%, the average re-
sults reported for three tests
could have a deviation of 99.990
± 0.005%.
• In this evaluation, results for
vinyl chloride and carbon tetra-
chloride show the most variabil-
ity, especially at lower concen-
trations.
• The presence of HC1 in the gas
being sampled did not appear to
have any serious effect on the
VOST results.
• The problem of analyzing wet traps
can be satisfactorily overcome by
desorbing the contents of the sam-
ple collection traps into a purge-
trap-desorb GC/MS analytical sys-
tem.
• Stringent trap preparation pro-
cedures are required to eliminate
the risk of contaminating the traps
prior to use.
Separate traps (blanks) should be
exposed to air in the field in
order to determine the level of
compounds on the traps due to ad-
sorption of the compounds during
handling of the traps and their
insertion into/removal from the
VOST apparatus.
6.0 ACKNOWLEDGMENTS
Much of the work discussed in this
paper was funded under contract with the
U.S. Environmental Protection Agency (EPA
Contract Mo. 68-01-5915). The work was
performed under the direction of Dave
Friedman of EPA/0SW and Larry Johnson of
EPA/IERL-RTP who provided counsel in all
phases of the work.
7.0 REFERENCES
1. Rechsteiner, C., J. C. Harris, K. E.
Thrun, D. J. Sorlin, and V. Grady.
1981. Sampling and Analysis Methods
for Hazardous Waste Incineration,
A. D. Little, Inc., in support of
Guidance Manual for Evaluating Permit
Applications for the Operations of
Hazardous Waste Incineration Units,
EPA Contract No. 68-02-3111, EPA/IERL,
Research Triangle Park, North Carolina
2. Jungclaus, G., and P. Gorman. 1982.
Draft Final Report, Evaluation of a
Volatile Organic Sampling Train, Mid-
west Research Institute, EPA Contract
No. 68-01-5915.
3. Krost, K. J., E. D. Pelli2zari, S. G.
Walburn, and S. A. Hubbard. 1982.
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