United States
Environmental Protection ,
Agency
Office of Water and
» Waste Management
Washington DC 20460
February 1982
SEPA Sampling and Analysis
Methods for
Hazardous Waste
Incineration
(First Edition)
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tosr«^
A %
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
L PftO^
OFFICE OF
SOLID WASTE AND EMERGENCY RESPONSE
July 26, 1982
Ms. Diane McCreary
USEPA Region III
Curtis Building
Philadelphia, PA
Dear Ms. McCreary:
Enclosed is a copy of the first edition of EPA's Sampling and
Analysis Manual for Hazardous Waste Incineration which you re-
quested during our telephone conversation. Please note that
this document is a draft, as it has not yet completed internal
Agency peer review. The document is actually an appendix
to EPA's Test Methods for Evaluating Solid Wastes (SW-846),
available through Ms. Debra Villari: (202)382-4487. Addition-
ally, please bear in mind that EPA will be updating the Manual
as improved methods for stack gas sampling and analysis evolve.
Questions regarding the use of the Manual may be addressed to
either Dr. Ed Martin or Mr. Gene Crumpler: (2 0 2)7 55-9200.
Sincerely
Environmental Scientist
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SAMPLING AND ANALYSIS METHODS
FOR
Replnn 111 Ubrary
HAZARDOUS WASTE INCINERATION ^ Protection Agency
(First Edition)
Prepared by
Judith C. Harris, Deborah J. Larsen
Carl E. Rechsteiner, Kathleen E. Thrun
Arthur D. Little, Inc.
Acorn Park
Cambridge, Massachusetts 02140
A Guidelines Document for
Hazardous Waste Incineration
Under
EPA Contract No. 68-02-3111
Technical Directive No. 124
Arthur D. Little, Inc., Case No. 82480-54
EPA Project Officer: Larry D. Johnson
Technical Support Staff
Environmental Protection Agency
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
February 1982
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DISCLAIMER
This is a contractor's final report, which has been
reviewed by technical staff within EPA's Office of
Environmental Engineering and Technology and Office
of Solid Waste and by external peer reviewers. The
contents do not necessarily reflect the views and
policies of the U. S. Environmental Protection Agency,
nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.
ii
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TABLE OF CONTENTS
PAGE
List of Figures ix
List of Tables xi
Glossary xiii
ACKNOWLEDGEMENT xix
I. ABSTRACT 1
II. INTRODUCTION 3
A. Purpose 3
B. Scope of Manual 4
C. Use of Manual 5
III. SAMPLING AND ANALYSIS STRATEGY TO MEET
REGULATORY REQUIREMENTS 7
A. Introduction 7
1. General Facility Standards 7
2. Interim Status Standards for Incinerators 7
3. Performance Standards for Incinerators 8
4. Hazardous Waste Permit Program 9
B. Waste Characterization Strategy 10
1. Sampling 10
2. Analysis 10
a. Characteristics 11
b. Composition - Proximate Analysis 11
c. Composition - Survey Analysis 13
d. Composition - Directed Analysis 13
e. Selection of POHCs 14
C. Stack Gas Effluent Characterization Strategy 15
D. Additional Effluent Characterization Strategy 16
E. Selection of Specific Sampling and Analysis Methods 16
iii
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TABLE OF CONTENTS (continued)
PAGE
1. Scenario 18
2. Strategy 18
a. Sampling Strategy 19
b. Analysis Strategy 19
3. Tactics and Methods 20
a. Selection of POHCs 20
b. Selection of Sampling Methods 20
c. Selection of Analysis Methods 24
4. Results and Calculations 24
a. Calculation of Win (lb/hr) 24
b. Calculation of Wout (lb/hr) 26
c. Calculation of DRE 27
d. Calculation of HC1 Emissions (lb/hr) 27
e. Calculation of Particulate Loading (mg/m3) 28
f. Summary 28
IV. SPECIFIC SAMPLING PROCEDURES 31
A. Overview of Sampling Methods 31
B. Sampling Methods for Influent Streams 31
1. Sampling Methods for Liquid Wastes 34
a. Coliwasa 34
b. Dipper (Pond Sampler) 34
c. Weighted Bottle 35
d. Tap 35
2. Sampling Methods for Solid Wastes 35
a. Thief (Grain Sampler) 36
b. Trier (Sample Corer/Waste P!.le Sampler) 36
c. Trowel (Scoop) 36
3. Sampling Methods for Slurries and Sludge Samples 37
4. Sampling Methods for Scrubber Water 37
C. Sampling Methods for Effluent Streams 37
1. Sampling Methods for Stack Gas 37
a. Modified Method 5 Train 38
b. Source Assessment Sampling System (SASS) 40
iv
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TABLE OF CONTENTS (continued)
PAGE
c. Gas Bulb and Gas Bag Sampling Systems 43
d. Specific Sorbent/Reagent Methods 44
e. Monitoring of Gaseous Combustion Products 48
2. Sampling Methods for Solid and Liquid Effluents 49
D. Health and Safety Precautions 49
E. Collection of' Representative Samples 51
1. Gases 51
2. Liquids 51
3. Solids 51
4. Slurries 51
5. Sample Handling 52
F. Identification of Samples 52
1. Sample Labels 52
2. Field Log Book 52
3. Field Observations 53
G. Sampling Method Summaries 53
V. SPECIFIC PREPARATION PROCEDURES 65
A. Overview 65
B. Representative Aliquots from Field Samples 65
(Methods P001-P003)
C. Recovery Measurements (Methods P011-P014) 67
D. Solvent Extraction of Organic Compounds 67
(Methods P021-P024)
1. Aqueous Liquids (Method P021) 70
a. Semivolatiles (Method P021a) 70
b. Volatiles (Method P021b) 70
2. Sludges (Method P022) 70
a. Semivolatiles (Method P022a) 71
b. Volatiles (Method P022b) 71
3. Organic Liquids (Method P023) 72
4. Solids (Method P024) 72
a. Semivolatiles (Method P024a,b) 72
b. Volatiles (Method P024c) 73
v
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TABLE OF CONTENTS (continued)
PAGE
E. Drying and Concentrating of Solvent Extracts 74
(Method P031)
F. Digestion (Method P032) 74
G. Sample Clean Up Procedures (Methods P041-P045) 75
H. Preparation Method Summaries 75
VI. SPECIFIC 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 101
(Methods A001-A002)
a. Macro-Scale Technique (Method A001) 101
b. Micro-Scale Technique (Method A002) 103
2. Elemental Composition (Method A003) 104
3. Total Organic Carbon and Total Organic 104
Halogens (Method A004)
4. Viscosity (Method A005) 104
5. Heating Value of Waste (Method A006) 105
D. Survey Analysis 105
1. Survey Analysis for Organics 106
a. Organic Content by TCO (Method A011) 106
b. Organic Content by GRAV (Method A012) 108
c. Organic Content - Volatiles (Method A013) 109
d. Compound Class Type by Infrared Analysis 109
(Method A014)
e. Mass Spectrometric Analysis (Method A015) 112
f. Specific Major Components by GC/MS 115
(Method A016)
g. Specific Major Components by HPLC/IR or HPLC/LRMS 115
(Method A017)
vi
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TABLE OF CONTENTS (continued)
2. Survey Analysis of Metals (Method A021)
E. Directed Analysis
1. Organic Appendix VIII Constituents
a. Volatiles (Method A101)
b. Extractable Species (Method A121)
c. Specific Compounds by HPLC
(Methods A122, A123)
d. Aldehydes and Acids (Methods A132, A133)
e. Alcohols (Method A134)
f. Inorganic-Containing POHCs
g. Others
2. Inorganic Appendix VIII Constituents
a. Metals (Methods A221 - A235)
b. Anions (Methods A251, A252, A253)
c. Gases
3. Directed Organic Analysis Criteria
a. Instrumental Operating Procedures
b. Qualitative Identification
c. Quantitative Measurement
F. Analysis Method Summaries 137
VI. QUALITY ASSURANCE AND QUALITY CONTROL PROCEDURES 217
A. Overview 217
B. Title Page and Table of Contents 218
C. Project Description 218
D. Project Organization and Responsibility 218
1. Personnel Responsibilities 218
E. Quality Assurance objectives 222
1. Accuracy 222
2. Precision 224
3. Completeness 225
4. Representativeness 225
5. Comparability 225
F. Sampling Procedures 225
G. Sample Custody 225
vii
PAGE
115
118
120
120
120
121
122
125
125
125
126
126
127
129
130
130
131
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TABLE OF CONTENTS (continued)
PAGE
H. Data Maintenance and Chain-of-Custody 227
I. Calibration Procedures and Frequency 227
1. Sampling 227
2. Analysis 227
J. Analytical Procedures 234
K. Data Reduction, Validation and Reporting 234
1. Data Reduction 234
2. Data Validation 236
3. Reporting 237
L. Internal Quality Control Checks 237
1. Blank Samples 232
2. Analytical Replicates 237
3. Spiked Samples 238
M. Performance and System Audits 238
N. Preventive Maintenance 238
0. Specific Routine Procedures Used to Assess Data 238
Precision, Accuracy and Completeness
1. Calculation of Mean Values and Estimates 238
of Precision
2. Assessment of Accuracy 239
3. Assessment of Causes of Variance 240
P. Corrective Action 240
Q. Quality Assurance Reports 242
VIII. REFERENCES 243
APPENDIX A: HAZARDOUS CONSTITUENTS - Physical/Chemical Data 247
APPENDIX B: HAZARDOUS CONSTITUENTS - Stack Gas Sampling Methods 323
APPENDIX C: HAZARDOUS CONSTITUENTS - Analysis Methods 349
APPENDIX D: SUMMARY OF METHOD NUMBERS 375
APPENDIX E: MS-ANALYTICAL IONS 383
viii
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Page
12
17
39
41
42
45
46
202
221
226
228
229
230
241
LIST OF FIGURES
Overview of the Analytical Approach
for Waste Characterization
Overview of an Analysis Scheme for Stack
Gas Samples from a Comprehensive Sampling
Train
Modified Method 5 Train
Adsorbent Sampling System
SASS Schematic
Evacuated Grab Sampling Apparatus
(for subatmospheric pressures)
Integrated Gas-Sampling Train
Apparatus for Flameless Mercury Determination
Example of Project Organization and
Responsibility
Samples of Waste Feed and Stack Emissions
are Taken as Composites over Four-hour Long
Periods. Three Destruction and Removal
Efficiences (DRE) are Calculated from the
Ratios, E^/F^, E2/F2,
Field Sampling Chain-of-Custody Form
Chain-of-Custody Record
Example of Record of Analysis Report
Form with Acceptable Documentation
Diagram of a Sampling and Analysis Procedure
Which Uses Replicate Samples to Provide
Information on Sources of Variance
ix
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LIST OF TABLES
Table No. Page
1. Available Information on Composition of 21
Hypothetical Waste
2. Candidate POHCs for Hypothetical Waste 22
3. Recommended Stack Sampling Methods for 23
Candidate POHCs in Hypothetical Trial
Burn Example
4. Recommended Analysis Methods for Candidate 25
POHCs in Hypothetical Trial Burn Example
5. Choice of Samplers 32
6. Sampling Points for Most Waste Containers 33
7. Sorbents and Special Reagents for Specific 47
POHCs
8. Summary of Procedures for Compositing of 66
Samples
9. Estimated Quantities of Sample Required for 68
Analysis
10. Potential Compounds for Use as Surrogates 69
11. Threshold Levels of Contaminants in the 100
Extraction Procedure Toxicity Test
12. Proximate Analysis Reporting Form 102
13. Summary of Results for Organic 107
Extracts of a SASS Train Sample
14. IR Analysis Report Form 111
15. Categories for Reporting LRMS Data 113
16. LRMS Analysis Report Form 114
17. GC/MS Survey Report Form 116
18. HPLC/IR or HPLC/LRMS Survey Report Form 117
19. Metals Sought in Survey Analysis of Waste 119
xi
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LIST OF TABLES (continued)
Table No.
20. Summary of Determinations of POHCs by
the Generalized HPLC Analysis Method
21. Characteristic Data for Metals Listed in
Appendix VIII
22. Tune Criteria for Decafluorotriphenyl-
phosphine (DFTPP)
23. Tune Criteria for Bromofluorobenzene
24. Essential Elements of a QA Project Plan
According to QAMS-005/80
25. Precision Goals for Analysis
26. Activity Matrix for Calibration of
Equipment
27. Activity Matrix for Calibration of
Apparatus
xii
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GLOSSARY
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.
AFID Alkali Flame Ionization Detector
amu Atomic Mass Unit
Appendix VIII Hazardous Constituent List (AO CFR Part 261)
ASTM American Society for Testing and Materials
atm Atmosphere (760 Torr)
Btu/lb British Thermal Unit per Pound
C Corrosivity Test—RCRA Measurement
CFR Code of Federal Regulations
CI Chemical Ionization Mode (Mass Spectrometry)
_2
cm Centimeter (10 meter)
CO Carbon Monoxide
Coliwasa Composite Liquid Waste Sampler
CV Coefficient of Variation
2,4-D 2,4-Dichlorophenoxyacetic acid
DDD Dichlorodiphenyldichloroethane
DDE Dichlorodiphenyldichloroethylene
DDT Dichlorodiphenyltrichloroethane
D.E.S. Diethylstilbestrol
DFTPP Decafluorotriphenylphosphine
Directed Analysis 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 pro-
fessional judgement and/or the results of pro-
ximate and survey analyses.
xiii
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DNPH Dinitrophenylhydrazine
DRE 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 waste.
DSCF Dry Standard Cubic Foot
3
dsm Dry Standard Cubic Meter
E Extraction Protocol Toxicity Test-RCRA Measurement
ECD Electron Capture Detector
EI Electron Impact Ionization Mode (Mass Spectrometry)
EP Extraction Protocol
EPA U.S. Environmental Protection Agency
ESP Electrostatic Precipitator
eV Electron Volt
FPD Flame Photometric Detector
ft Foot
FT-IR Fourier Transform-Infrared Spectrometry
g Gram
gal Gallon
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
xiv
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GRAV Gravimetric Analysis
HC1 Hydrochloric Acid
HPLC High Pressure Liquid Chromatography
HPLC/UV High Pressure Liquid Chromatography/Ultraviolet
Spectroscopy
I Ignitability Test—RCRA Measurement
ICAP Inductively Coupled Argon Plasma Atomic
Emission Spectroscopy
ID Internal Diameter
in Inch
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 undis-
turbed gas stream at the sample point.
K-D Kuderna-Danish Evaporative Concentrator
3
kg Kilogram (10 grams)
L Liter
LC Liquid Chromatography
LC/EC Liquid Chromatography/Electrochemical Detector
LOD Loss on Drying
LOI Loss on Ignition
LRMS Low Resolution Mass Spectrometry
—6
lag Microgram (10 gram)
yL Microliter (10 ^ liter)
yM Micrometer (10 ^ meter)
m Meter ,
-3
mg Milligram (10 gram)
xv
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Minute
Milliliter (10 liter)
-3
Millimeter (10 meter)
Modified Method 5 Sampling Train
Mass Spectrometry
Millivolt
MW Molecular Weight
NDIR Non-Dispersive Infrared Analyzer
-9
ng Nanogram (10 gram)
-9
nm Nanometer (10 meter)
N0x Nitrogen Oxides (NO, NO2, etc.)
N.O.S. Not Otherwise Specified
OD Outer Diameter
Opacity Measurement of the optical density of stack
gas emissions of an incinerator.
PCB(s) Polychlorinated Biphenyl(s)
POHC(s) Principal Organic Hazardous Constituent(s)
ppb Part Per Billion
9
one part in 10 . For gaseous mixtures, a
volume:volume brtsis is typically used and
1 ppb is on the order of 1 yg/m^:
3 RT
yg/m = ppb x —
where RT = 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 yg/L (% 1 yg/Kg.for liqjuids with density
^ 1). For solid materials, a weight:weight
basis is most commonly used and 1 ppb
1 yg/Kg.
min
mL
mm
MM5
MS
mV
xvi
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PPm
Part Per Million
One part in 10 (see ppb).
1 ppm ^ 1 mg/m^ 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 determintions. The
relative standard deviation expressed as a
percentage of the mean is a common measure of
precision.
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
QA/QC Quality Assurance/Quality Control
R Reactivity Test—RCRA Measurement
RCRA Resource Conservation and Recovery Act
RI Refractive Index Detector
rpm Revolutions Per Minute
SASS Source Assessment Sampling System
sec Second
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 100°C
or higher, molecular weights of 100-400, seven
to twenty carbon atoms per molecule.
Sulfur Oxides (SO , SO )
2 3
Removal of the volatile constituents of a sample
by bubbling an inert gas stream through the
sample.
Surrogate Addition of a known compound 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.
xvii
SO
x
Sparging
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Survey Analysis
T
2,4,5-T
TCD
TCDD(s)
TCO
TGA
THEED
TLC
TOC
TOX
2,4,5-TP
TSDF
UV
V
VOA
Volatiles
Provides an overall description of the sample in
terms of the major organic compounds and major in-
organic 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
xviii
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ACKNOWLEDGEMENT
The authors wish to acknowledge the assistance of several people whose
efforts led to the successful production of this document. The authors
especially wish to acknowledge the authorship of Ms. Debi J. Sorlln and
Mrs. Virginia Grady on previous drafts of this manual. The assistance
of Dr. Afaf Wensky of Battelle Columbus Laboratories and Ms. 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.
In addition to Dr. Wenksy and Ms. James, the following people provided
valuable comments as external peer reviewers of previous versions of
this manual: Dr. Bruce N. Colby of Systems, Science and Software, Dr.
Alvia Gaskill of Research Triangle Institute, Mr. Paul Gorman of Midwest
Research Institute, and Dr. Herbert C. Miller of Southern Research
Institute. We are also grateful for constructive criticism received
from EPA reviewers, Ms. Jan Jablonski and Dr. Edward Martin of the
Office of Solid Waste, Mr. Charles Rogers of the Hazardous Waste
Incineration Branch, IERL in Cincinnati, Ohio, and most especially, Dr.
Larry Johnson of the Technical Support Staff, IERL in Research Triangle
Park, North Carolina.
Many individuals at Arthur D. Little, Inc. contributed to this manual.
In particular, the authors wish to thank Ms. Katherine Norwood and
Mr. Anthony DeMarco for their technical contributions to the associated
appendices, and Dr. Philip Levins for his review comments. The authors
are also grateful to Ms. Christine McGrail, Mrs. Marie Kerr and Mrs.
Joanne Piandes for their heroic efforts in the preparation of this
manuscript.
xix
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I. ABSTRACT
As part of the Resource Conservation and Recovery Act, the United States
Environmental Protection Agency has proposed regulations for the owners/
operators of facilities which treat hazardous wastes by incineration to
ensure that these incinerators are operated in an environmentally re-
sponsible manner. In support of these regulations, this document has
been prepared as a reference document which describes the sampling and
analysis methodologies appropriate to the measurement of the principal
organic hazardous constituents in both influent and effluent streams at
these facilities. The sampling and analysis methods for these principal
organic hazardous constitutents (POHCs) are described in the text.. Also
included are concise summary sheets for all of the recommended methods,
stating the method name and number, the types of samples and specific
analytes to which the method applies, a brief description of the method,
instrument and operating conditions, and a reference to a more detailed
description of the procedure. Technician-level protocols are thus in-
corporated by reference rather than reproduced in this document. In
addition to specific methods for the sampling and analysis activities
at these facilities, information concerning general strategies and guide-
lines for reporting and documentation are discussed.
Appendix A provides basic information (structure, CAS Registry Number,
molecular weight, melting point, boiling point and heat of combustion,
when available) for all compounds listed in Appendix VIII of the May
20, 1981 Federal Register. Additional appendices list specific Appendix
VIII compounds with the appropriate sampling and analysis methods. Mass
spectral analytical ions for compounds analyzed by GC/MS are tabulated
in Appendix E.
1
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II. INTRODUCTION
A. PURPOSE
As part of the Resource Conservation and Recovery Act (RCRA), the United
States Environmental Protection Agency (EPA) has promulgated interim,
final and proposed regulations for the owners/operators of facilities
which treat hazardous wastes by incineration to ensure that these in-
cinerators are operated in an environmentally responsible manner. The
regulations cover a range of activities including operational perfor-
mance standards, waste analysis, trial burns, monitoring and inspections,
record keeping and reporting, emission control criteria, fugitive emis-
sions control, and lastly, closure of the facility. The specific details
for each incinerator facility are authorized via facility permits.
In the permitting process, the permitting officials are obligated to use
best professional judgment to determine the performance parameters which
must be followed for each facility. The permit writer has available
technical advisory information contained in the documents, "Guidance
Manual for Evaluating Permit Applications for the Operation of Hazardous
Waste Incineration Units" (1) and "Engineering Handbook for Hazardous
Waste Incineration" (2). Those documents provide engineering information
in terms of waste and effluent characterization, incinerator design, con-
trol 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
the specific points which are raised during the permitting process.
This guidance manual is another supporting document. The primary
criterion upon which all operational specifications are based is the
destruction and removal efficiency (DRE) of the incinerators. This
value, which is defined in terms of waste input levels and stack out-
put levels of the principal organic hazardous constituents (POHCs) de-
signated in the trial burn permitting process must be equal to or great-
er than 99.99% according to the permitting standards for hazardous waste
incineration. This report addresses the specific sampling and analysis
methods to be used when measuring the levels of POHCs in the various
streams of an incinerator facility: inlet waste, stack gas, process
water, fly ash, bottom ash, etc. This compilation of sampling and
analysis methods expands upon and augments the information contained in
the "Guidance Manual for Evaluating Permit Applications for Hazardous
Waste Incineration Units" (1).
This report is 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 document is an initial attempt, the
information on sampling techniques and analytical procedures should be
considered guidance rather than prescriptions. These protocols lack
3
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definitive data on accuracy and precision due to limited use within the
context of Hazardous Waste Incineration. As new data are developed over
time, the precision and accuracy data will be made available through up-
dated versions of this manual or other sources. It is important that
users of these protocols provide information on verified techniques, new
procedures and other relevant matters to the Agency (EPA) so that updates
can be made available.
B. SCOPE OF MANUAL
This document describes the sampling and analysis methods which are
appropriate to the measurement of POHCs in hazardous waste incineration
facility streams. The material in this document is divided into sections
which address different aspects of the sampling and analysis approach for
hazardous waste incinerators.
The regulatory requirements for such 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 POIICs which are expected to be present in the
effluents. Also during trial burns, the waste samples are characterized
to establish limits on the waste compositions which may be incinerated.
During routine facility operation, the incoming wastes are examined peri-
odically to ascertain whether the composition of the waste has changed.
Some gaseous species, such as carbon monoxide, are monitored contin-
uously 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 criterion and general incinerator performance.
Section III of this document deals with the strategies involved in pre-
paring sampling and analysis plans to meet the 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 document contains a separate section for specific sampling metho-
dologies (Section IV), specific preparation methodologies (Section V)
and specific analysis methodologies (Section VI), addressed in terms
of the various types of streams and sample media which will be encoun-
tered. As an auxiliary to these sections, Section VII describes general
methods which will aid in the collection of high quality sampling and
analysis data. This section also discusses the reporting and documen-
tation concerns for the sampling and analysis of incinerators. Other
aspects of these requirements are fully discussed in the permit writers
guidance document (1).
4
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C. USE OF MANUAL
The specific procedures described are primarily in the form of brief
descriptions with reference to other documents which contain highly
detailed method descriptions. Existing collections of sampling and
analysis methods such as "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods" S'..,-846 (3) or "Samplers and Sampling Proce-
dures for Hazardous Waste Streams" (4) have not been directly incor-
porated into this document but are incorporated by reference.
The structure of this manual is intended to permit quick access for
the user. A number of tables have been prepared which cross reference
the locations of specific methods to individual POHCs. Appendices B and
C reference each POHC by sampling and analysis method number and method
title. All of the sampling, preparation and analysis methid descriptions
are grouped together at the ends of their respective sections.
5
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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 United States Environmental Protection
Agency (EPA) to promulgate such performance standards for owners and op-
erators 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 are also 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 inciner-
ation are incorporated in the Code of Federal Regulations, Title 40 (40
CFR), Parts 122, 264 and 265. Under Part 122, EPA Administered Permit
Programs, Subpart A presents definitions and general program requirements,
while Subpart B specifies the additional requirements for hazardous waste
permitting programs under RCRA. Under both Parts 264 (Performance Stan-
dards) and 265 (Interim Status Standards), Subpart A presents general
facility standards, including general waste characterization requirements,
and Subpart 0 relates specifically to incinerators.
1^ General Facility Standards
The General Facility Standards as they relate to sampling and analysis
of hazardous waste are identical in the interim status (§ 265.13) and
permitting (§ 264.13) standards. The General Waste Analyis requirement
is that the owner or operator must obtain a detailed chemical and physi-
cal analysis of a representative sample of waste. At a minimum, the
analysis must generate all of the information that must be known to
treat, store or dispose of the 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 "in-
spect" 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 Subpart B permit application.
2^ Interim Status Standards for Incinerators
The Part 265 Subpart 0 Incinerator standards require, in addition to the
general waste analysis, that the owner/operator sufficiently analyze any
waste that he has not previously burned in his incinerator to enable him
to establish normal operating conditions and to determine the type of
pollutants that might be emitted.
7
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The interim status standards for incinerators incorporate no explicit
requirements for sampling and analysis of stack gases or other incinera-
tor effluents.
3^ Performance 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 of the Part 264 regulations
are cross referenced to the Part 122 Hazardous Waste Permit Program regu-
lations and include analysis to determine: heating value of the waste,
viscosity or physical form, and detailed chemical analysis to identify
the principal organic hazardous constituents (POHCs) of the waste.
The Part 264 performance standards relate to:
• Destruction and Removal Efficiency (DRE) for each POHC desig-
nated in the permit. The DRE, defined in terms of the mass
emission rate of a POHC in the stack gas vs. the mass feed
rate of the sample POHC in the waste, must be 99.99%. The
DRE performance standard implicitly requires sampling and
analysis to quantify the POHC(s) in the waste and in the stack
gas during a trial burn.
• Limitation on hydrochloric acid emissions from the stack of
incinerators. This performance standard implicitly requires
sampling and analysis, in some cases, to quantify hydrochloric
acid in the stack gas and/or to determine the efficiency of air
pollution control devices.
« Limitation on stack emissions of particulate material to
_< 180 mg/m3 (< 0.08 gr/DSCF), corrected to a standard excess
air level. This performance standard implies measurement of
particulate emission rates.
The sampling and analysis requirements of the Part 264 regulation perfor-
mance 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/in-
spection 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 Part 264 regulations. 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 on an annual or other periodic schedule.
8
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A_. Hazardous Waste Permit Program
The Part 122, Subpart B requirements for hazardous waste incineration
permit programs under RCRA require that the owner/operator of an in-
cineration facility must either:
• submit results of a trial burn demonstrating facility operating
conditions under which the waste can be incinerated in accor-
dance with the Part 264 performance standards, or
• submit data based on waste analysis and on other trial or opera-
tional burns sufficient to specify operating conditions under
which the waste can be incinerated in accordance with the Part
264 performance standards.
(An exemption to these requirements may be sought in the case of incin-
eration of waste that is hazardous only because it has the characteristic
of Ignitability, Corrosivity, or Reactivity (in some cases) under Part 261,
Subpart C of the RCRA regulations and that contains insignificant con-
centrations 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 also known or suspected to be present in the waste,
• quantification of those hazardous constituents that may be
designated as Principal Organic Hazardous Constituents (POHCs)
for purposes of demonstrating compliance with DRE performance
standards.
Sampling and analysis requirements for incinerator effluent characteri-
zation in the event that a trial burn is conducted include:
• quantitative analysis of the stack exhaust gas for concentra-
tion (mass emissions) of designated POHCs,
• continuous monitoring of carbon monoxide in the stack exhaust
gas,
s determination of the excess air level (oxygen/carbon dioxide
measurement),
9
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e quantitative analysis (in some cases) of the stack exhaust
gas for hydrochloric acid for purposes of calculating a re-
moval efficiency and/or emission rate.
It is important to emphasize that most of the sampling and analysis pro-
cedures described in this manual relate to trial burns. It is further
important to note that only a small fraction of the procedures speci-
fically selected to address individual POHCs will generally be applied
in any single trial burn.
For operating burns, the only explicit sampling and analysis requirement
is the determination of carbon monoxide in the stack gas. Although the
permit writer or the state/local authorities may impose additional moni-
toring requirements in some instances, it is not anticipated that compre-
hensive 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 equipment and tactics for collection
of the subsamples, as specified in "Test Methods for Evaluating Solid
Waste — Physical/Chemical Methods," SW-846 (3) 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 compo-
site sample, the sampling strategy requires collection of a minimum of
three subsamples which provide 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 is primarily a precaution against breakage or loss of sample, but
also provides the potential for a check on the homogeneity of the compo-
site sample.
To ensure that sampling and analysis results will withstand scrutiny,
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 can be divided into three sec-
tions :
10
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« Proximate Analysis
® Survey Analysis
• Directed Analysis
Figure 1 provides an overview of this analytical approach. The discus-
sion 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)
will be determined according to the procedures and guidelines presented
in Subpart C of Part 261, 40 CFR and in SW-846 (3). These tests will
be 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
it affects procedures for safely storing, handling and disposing of the
waste at the facility. The data are also relevant to possible exclu-
sion from the trial burn requirements of Part 122. The I, C, R, and E
test data for each hazardous waste to which the tests are applicable
will generally be available from the waste generator and manifest or
shipping papers received by the incinerator facility owner/operator.
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, solid and ash content,
• elemental composition (carbon, nitrogen, sulfur, phosphorus,
fluorine, chlorine, bromine, iodine to 0.1% level),
• heating value of the waste,
• viscosity.
This information meets the waste analysis requirements of the Part 264,
Subpart 0 regulations, as well as being 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 (N0X, S0X> P2O5, hydrogen halides and halogens). These data
also facilitate an informed selection of the Appendix VIII hazardous
constituents that might be present in the waste, by indicating whether
the overall waste composition, and hence the types of components present,
11
-------
NJ
Approximate Mass Balance:
Moisture Content
Solid Content
Ash Content
Elemental Analysis
Heating Value of
the Waste
Viscosity
Estimated Quantities
of Major Components:
Specific Most Abundant
Organics
Identification and Quanti-
fication of Hazardous
Constituents Selected from
the Appendix VIII List
Organic Compound Classes
Metals
FIGURE 1:
Overview of the Analytical Approach for Waste Characterization
-------
are consistent with 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% by weight, the list of compounds
sought by directed analysis should be expanded to include the organobro-
mines. It may 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 (a) the major types of organic compounds and (b) the
inorganic elements (metals) that are present. The survey analysis pack-
age includes determination of:
e organic content by chromatographic and gravimetric procedures,
s organic compound class types present by infrared and probe
mass spectrometric procedures,
e specific major organic compounds by gas chromatographic/mass
spectrometric or high performance liquid chromatographic/in-
frared or high performance liquid chromatographic/mass spectro-
metric procedures,
• specific metals by inductively coupled argon plasma emission
spectroscopic and atomic absorption spectroscopic 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 Appendix VIII hazardous constituents
may be present in the waste and may lead to the selection of alternative,
previously unsuspected POHCs. Knowledge of the major components of the
sample will also be 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
13
-------
are actually present.
For the organic directed analyses, a high resolution separation technique -
fused silica capillary gas chromatography - and a high specificity detec-
tion technique - mass spectrometry - is 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 has a high initial capital cost, it is widely available
in contractor laboratories, routine analytical service laboratories, and
EPA laboratories. The combination of high specificity and reliable com-
pound identification, high sensitivity, and good quantitative capability,
and 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 chromatog-
raphy 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 and
inductively coupled argon plasma emission spectroscopy (metals) and ion
chromatography (anions) are the primary analytical procedures.
The results of the directed analysis will establish that the waste con-
tains the suspected pollutant and demonstrate the concentration range
at which the pollutant may be expected to be found. Directed analysis
will also be 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 selection of POHCs and pre-
diction of hazardous by-products of combustion.
e. Selection of POHCs
The criteria for selection of POHCs (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.
It is anticipated that the designation of POHCs 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 Ap-
pendix VIII compounds present in the waste will be designated as POHCs
for trial burn purposes. The intent is to select a few specific com-
pounds as indicators of satisfactory incinerator performance when burning
a particular waste. It is necessary that the compounds selected pro-
vide a sufficiently stringent test of the incinerator performance in
terms of DRE to ensure that incineration of the waste can be carried out
14
-------
in an environmentally sound fashion. This criterion mandates selection
of the more thermally stable constituents as POHCs. At the same time,
however, it is also necessary that the designated POHCs 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
.01% 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 POHCs
in the exhaust gas. Although the burning of auxiliary fuel might not
affect the mass emission rate of POHCs, it would lead to an increased
volumetric flow of stack gas and thus to a decreased concentration of
POHC at the stack. This lower concentration directly affects the detec-
tion limit achievable for a given stack gas sample size (e.g., 5 m3 or
30 m3).
It is recommended that, whenever possible, the permit writer select
POHCs 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 ap-
plication must include calculations and supporting data to indicate
that 0.01% of the mass feed rate of that component in the waste could
in fact be detected in the stack effluent. A waste concentration of
100 ppm probably represents a practical lower level below which deter-
mination of 99.99% 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 CFR
Part 261 Subpart D), the constituents which caused the Administrator to
list the waste as toxic (tabulated in Appendix VII of 40 CFR Part 261)
would be logical candidates for designation as POHCs 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 defini-
tion, 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 Part 264 performance stan-
dards is to collect replicate 3-6 hour, 5-30 m3 samples of stack gas
using a comprehensive sampling train, such as a modified EPA Method (5)
train or the EPA/IERL-RTP Source Assessment Sampling System (SASS) (6).
Either of these trains provides a sample sufficient for determination
of: particulate mass loading; concentrations of particulate and vapor
phase organics; and concentrations of particulate and volatile metals.
Directed analyses for POHCs is performed on these samples. For burns
of wastes that could also produce significant emissions of HC1, a Method
5 type train is used to collect and quantify HC1 in the stack gas.
15
-------
Figure 2 shows an overview of the analysis scheme for stack gas samples.
The same sample (cyclone and particulate catch) can be used for deter-
mination of particulate mass loading and subsequent extraction of non-
volatile organic components. Volatile organic components of the stack
gas that might be lost on drying will be collected in the sorbent trap/
condensate portion of the Modified Method 5 or SASS train, and analysis
of the volatile content performed prior to extraction of the sample.
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 deter-
mined, at least three samples should be analyzed in order to compute an
error bound for the measured values. The incremental cost of the repli-
cate sampling and analysis is warranted by the increased confidence in
the resulting data; quantitative results from a single sampling and anal-
ysis run should not generally be considered as an acceptable indicator
of performance.
The survey analysis, which is a qualitative screen of the collected
material to ensure that potentially hazardous but unexpected emissions
do not go overlooked, need be performed on no more than one stack
gas sample. During a trial burn, the oxygen/carbon dioxide levels in
the stack gas must be measured using an Orsat analyzer as detailed in
40 CFR Part 60, Appendix A, Method 3 (5) 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 carbon
monoxide levels in the incinerator effluent.
D. ADDITIONAL EFFLUENT CHARACTERIZATION STRATEGY
The basic strategy for sampling scrubber water, ash and other residue (if
any) is to prepare composite samples from grab subsamples, collected using
the same types of sampling devices and tactics used for waste characteri-
zation. This sampling is required only during trial burns in accordance
with Part 122.27 40 CFR. These additional effluent samples are analyzed
for POHCs to determine appropriate disposal or subsequent treatment methods
and to ensure that significant discharges of POHCs in other media do not
go undetected. A target detection limit of 0.01-0.5% of the mass feed
rate of the POHC in the waste should be achievable with a reasonable
sample size.
E. SELECTION OF SPECIFIC SAMPLING AND ANALYSIS METHODS
The preceeding discussion has briefly described the RCRA regulations that
define sampling and analysis requirements for hazardous waste incinera-
tion and presented an overview of the strategic sampling and analysis ap-
proaches that have been developed to meet these requirements. Subsequent
sections of this document will present descriptions of the specific
sampling, sample preparation, and analysis methods that are recommended
for implementation of this strategy. This portion of Section III will
16
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Probe
Wash
Concentrate
to
Dryness
Weigh
Particulate
Catch
w
Dry
Sorbent
Trap
Soxhlet
Extraction
Weigh
Combine extracts
r
Metals by
ICAP (if
any metals
in waste)
Aliquot(^10%)
Condensate
Liquid/
Liquid
Extraction
Combine extracts
Soxhlet
Extraction
Concentrate*
Impingers
I
Chloride Analysis
Metal analysis
by ICAP (if any
metals present
in waste)
Concentrate*
Survey
Analysis
Directed
Analysis
Survey
Analysis
Directed
Analysis
FIGURE 2: Overview of an Analysis Scheme for Stack Gas Samples from a Comprehensive Sampling Train
* As an alternative, the extracts from particulate and vapor portions of the train may be
combined prior to analysis.
-------
illustrate, by means of a hypothetical example, the transition from
strategy, as described above, to tactics and methods as described in the
following chapters. The example is somewhat oversimplified in the inter-
ests of clarity, but should serve for demonstration of how to use this
document in development and evaluation of a hazardous waste incineration
trial burn plan. The discussion will deal with sampling and analysis
considerations only and will not address adequacy of 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.
The facility is a liquid injection incinerator with a capacity of 10 x 10^
Btu/hr; 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 sec. with 150% excess
air.
The waste is a still bottom from the production of perchloroethylene.
Based on engineering analysis it is expected to be a non-viscous organic
liquid with a heating value <5000 Btu/lb. The major components of the
waste are expected to be highly chlorinated species such as hexachloro-
benzene, hexachlorobutadiene, etc.
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 to comply with the Part 264 performance
criteria when burning this type of waste. Therefore, a trial burn 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. Therefore,
additional analysis of the waste will not be necessary to support the
trial burn permit application. The POHCs for which destruction and re-
moval efficiences are to be demonstrated in the trial burn must be des-
ignated, based on review of existing information and/or additional anal-
ysis 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 (3) replicate tests
under that set of operating conditions.
The trial burn sampling and analysis strategy must address:
18
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• The waste analysis requirements of 40 CFR Part 122
e The performance standards of 40 CFR Part 264 Subpart 0
• The monitoring requirements of 40 CFR Part 264 Subpart 0
a. Sampling Strategy
During each of the three (3) replicate tests the following samples must
be obtained:
• one composite sample of the waste actually treated
® one time-averaged (3-4 hour) sample of stack gas
• one composite sample of spent scrubber water
No bottom ash or fly ash streams (other than the stack particulate emis-
sions) are expected to be generated as effluents from this facility.
_b. Analysis Strategy
The waste must be analyzed to determine:
- quantity of designated trial burn POHCs
- heating value of the waste*
- viscosity or physical form*
- quantity of organically-bound chlorine* (this analysis is not
mandatory, however the data obtained may be helpful in deter-
mining a potential for HC1 emissions)
- identity and approximate quantity of known or suspected Appendix
VIII constituents*
The stack gas must be analyzed to determine:
- quantity of designated trial burn POHCs
- quantity of particulate matter emissions
- quantity of hydrochloric acid emissions
- carbon monoxide level
- excess air level (oxygen/carbon dioxide level determination).
The scrubber water must be analyzed to determine:
- quantities of designated trial burn POHCs.
*It has been hypothesized for this example that this information was avail
able from the waste generator. Some or all of these determinations may
be repeated on the actual composite waste sample.
19
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3. Tactics and Methods
a . Selection of POHCs
Table 1 summarizes the information that is hypothetically available from
the generator of the waste in this example. The major organic components
that would appear to be candidates for selection as POHCs are listed in
Table 2, along with relevant physical/chemical properties (from Appendix
A).
It is hypothesized that the permit writer has designated hexachlorobuta-
diene, hexachlorobenzene and hexachloroethane as POHCs. All three species
are present in significant concentrations 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, 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) or tap sampling (Method S004)
would be appropriate for collection of discrete subsamples of waste feed
and of spent scrubber water at regular time intervals over the duration
of each trial burn. These would then be 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 or other target species affects the
choice of a sampling method. Appendix B of this document lists recom-
mended sampling methods for each candidate POHC. Table 3 summarizes
these recommendations for the candidate POHCs in this hypothetical example.
Note that designation of tetrachloroethylene as a POHC in this instance
would add a special sampling requirement, while the Modified Method 5/
SASS approach would collect all of the other candidate POHCs. The MM5
train would also suffice to determine compliance with the two other per-
formance standards of 40 CFR Part 264. The particulate matter emission
rate can be 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'can be determined
by using caustic scrubbing solution in the impinger portion of the MM5
train and determining the hydrochloric acid level as chloride.
In addition to the procedures chosen for the collection of POHCs, it
would be necessary to specify procedures to accomplish the required
monitoring for carbon monoxide and excess air (oxygen/carbon dioxide) levels
in the stack gas.
20
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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 had a pungent odor and fumed slightly
when the cap was removed.
Loss on Ignition: Ignition at 900°C resulted in a 99.8% loss of mass.
Higher Heating Value: The waste would not burn in a bomb calorimeter;
Its higher heating value is estimated at ^2000 Btu/lb.
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 showed no -C00H, -OH, -NH, or C=0 functionality.
Most of the spectral peaks could be attributed to hexachlorobutadiene.
Hexachlorobenzene peaks were also identified.
LRMS: The major components identified were mass 258, 6 Cl's, or
hexachlorocyclobutadiene and, less abundant, mass 282, 6 Cl's, CgClg or
hexachlorobenzene.
GC/MS: This analysis confirmed that hexachlorobutadiene is the major
component and hexachlorobenzene is present at about 10% of the C^Clg
concentration. Other peaks in the chromatogram corresponded to hexa-
chloroethethane, (^4%), tetrachloroethanes (^3%), tetrachloroethylene
(^.1%) plus four others at about 0.5% concentration of the C4CI6 con-
centration.
Summary: All of the available evidence suggests that this waste contains
essentially no perchloroethylene, 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.
21
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TABLE 2
CANDIDATE POHCs FOR HYPOTHETICAL WASTE
Compound
Approximate
Concentration in Waste
B.P.
°C
AH*
Kcal/mole
MW
g/mole
Hexachlorobutadiene
65%
215
N/A
260.76
Hexachlorobenzene
6%
323
567.7
284.8
Hexachloroethane
2%
186.8
173.8
236.74
Tetrachloroe thane
1,1.1,2- I
1,1,2,2- (
1.5%
130.5
146.2
230
233
167.84
167.84
Tetrachloroethylene
.1%
121.0
197
165.85
*Standard Enthalpy of Combustion
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TABLE 3
RECOMMENDED STACK SAMPLING METHODS FOR CANDIDATE
POHCs IN HYPOTHETICAL TRIAL BURN EXAMPLE
Candidate POHC
Number
Stack Sampling Method
Description
Hexachlorobutadiene
S008*
MM5 - Sorbent
Hexachlorobenzene
S008*
MM5 - Particulate and Sorbent
Hexachloroethane
S008*
MM5 - Sorbent
Tetrachloroethane(s)
S008*
MM5 - Sorbent
Tetrachloroethylene
S010
Glass Bulb Grab Sample
* Method S009, SASS, could also be selected. A specially fabricated
glass-lined SASS train might be necessary to withstand the hydro-
chloric acid expected in the stack.
23
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c. Selection of Analysis Methods
The analytical procedures used for qualitative identification and quanti-
tative determination of POHCs and other target species are determined pri-
marily by the nature (volatility, polarity) of the species sought.
Appendix C of this document lists recommended analysis methods for each
candidate POHC after the appropriate sample preparation steps as des-
cribed in Section IV have been performed. Table 4 summarized the recom-
mendation for analysis of the candidate POHCs in this hypothetical ex-
ample. 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 tetrachloroethylene.
4. Results and Calculations
Chapter IV includes formats for reporting the results of specific analysis
and Chapter VII deals with overall reporting and documentation procedures.
This section of Chapter; III will supplement those discussions and those
available in other resources (1-4), by showing the calculations of DRE,
corrected particulate loading, and HC1 emissions for the hypothetical
example described above. Again, this example has been somewhat over-
simplified for purposes of illustration.
According to 40 CFR Part 264, the DRE for each POHC is calculated as:
W
DRE =
in
- W
out
x 100%
W.
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
exhaust emissions.
Calculations of W. (lb/hr)
in
W
in
C x FR
w w
100
Where:
w
FR =
w
Concentration one POHC in the waste, %
Mass Feed Rate of waste to the incinerator, lb/hr.
24
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TABLE 4
RECOMMENDED ANALYSIS METHODS FOR CANDIDATE
POHCs IN HYPOTHETICAL TRIAL BURN EXAMPLE
Candidate POHC
Analysis Method
Number
Description
Hexachlorobutadiene
A121
GC/MS Extractables
Hexachlorobenzene
A121
GC/MS Extractables
Hexachloroethane
A121
GC/MS Extractables
Tetrachloroethane(s)
A101
GC/MS Volatiles
Tetrachloroethylene
A101
GC/MS Volatiles
25
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Assume that quantitative analysis of a representative aliquot drawn from
the composite waste sample from test #1 gave the following concentrations:
hexachlorobutadiene: 63%
hexachlorobenzene: 9.4%
hexachloroethane: 1.1%
Further, assume that the 10 x 10& Btu/hr 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. The
total mass feed rate to the incinerator was therefore 600 lb/hr of which
540 lb/hr was auxiliary fuel (waste oil) and 60 lb/hr was chlorinated
waste.
The Win values for the three POHCs are therefore:
POHC Win
hexachlorobutadiene (.63 x 60 lb/hr) 38 lb/hr
hexachlorobenzene (.094 x 60 lb/hr) 5.6 lb/hr
Hexachloroethane (.011 x 60 lb/hr) 0.66 lb/hr
b. Calculation of Wout (lb/hr)
W = C x ER x 1.32 x 10"4
out s s
Where: C = concentration of one POHC in the stack gas effluent
S (mg/m3)
ERg= volumetric flow rate of stack gas in m^/min
1.32 x 10 4 = conversion factor from mg/min to lb/hr
Assume that quantitative analysis of the extract prepared from the time-
integrated comprehensive sampling train sample from test #1 gave the
following concentrations in the sampled gas:
3
hexachlorobutadiene: 0.080 mg/m
3
hexachlorobenzene: 0.020 mg/m
3
hexachloroethane: <^ 0.004 mg/m
Further, assume that the average measured volumetric flow of stack gas
during test #1 was 3200 SCFM or 90 m3/min.
The W values for the three POHCs are therefore:
out
POHC Wout
-4 -4
hexachlorobutadiene: 0.080x90x1.32x10 9.5 x 10 lb/hr
—A —4
hexachlorobenzene: 0.020x90x1.32x10 2-4 x 10 lb/hr
-4 -4
hexachloroethane: <0.004x90x1.32x10 <.48 x 10 lb/hr
26
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c. Calculation of DRE
DRE =
Win Wl x 1Q0
Win
POHC DRE
hexachlorobutadiene 99.997
hexachlorobenzene 99.996
hexachloroethane >99.993
Note that compliance with a 4-nines 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 wasterfuel blend fed
to the incinerator) unless the detection limit for that component in the
stack gas were < 4 yg/m^.
In this hypothetical example compliance with the 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 HC1 Emissions
An incinerator burning highly chlorinated hazardous waste capable of
producing significant stack gas emissions of hydrogen chloride (HC1)
must monitor and/or control HCi emissions.
The hypothetical waste in this example contains approximately 75% chlo-
rine by weight (Table 1). At the proposed 60 lb/hr feed rate of waste
(blended 1:10 with auxiliary fuel for a total feed of 600 lb/hr or
9.8 x 106 Btu/hr), the maximum HCI emission rate would be 45 lb/hr of
(chlorine basis) or 46 lb/hr as HCI. This is sufficiently high to war-
rant concern for potential HCI emissions and to indicate the necessity
for stack measurement of HCI.
The stack emission rate of HCI can be calculated from:
HCI = C, x ER x 1.32 x 10~4
out in s
Where: C^n = concentration of HCI (as CI ) in the stack gas effluent
and collected in the impingers
3
ER = volumetric flow rate of the stack gas in m /min.
s
1.32 x 10 4 = conversion factor from mg/min to lb/hr.
27
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Assume that quantitative analysis of the impinger/condensate solution
from the time-integrated comprehensive sampling train from test #1 gave
34 mg/m3 HC1 in the stack effluent.
The stack emission rate of HC1 is calculated by:
HClQut = 34 mg/m^ (90 m^/min) (1.32 x 10
=0.40 lb/hr HC1
This emission level is < 1% of the 46 lb/hr of HC1 potentially generated
from the waste, indicating that the removal efficiency of the wet scrubber
was > 99%.
e^ Calculation of Particulate Loading (mg/m3)
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 in the stack gas.
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 sample train) were dried
and weighed.
The hypothetical particulate loading from these measurements was calcu-
lated to be
3
80 mg/m
at the actual excess air level of the stack. The excess air level was
determined to be 150% based on hypothetical measured values of
oxygen 12.8%
carbon dioxide 6.7%
Correction to standard excess air level as specified in the Part 264
regulations, leads to a particulate loading of
140 mg/m^ (0.06 gr/SCF).
This total particulate emission level is in compliance with the Part
264 performance standard that specifies 180 mg/m3 (<^ 0.08 gr/SCF).
f. Summary
It is apparent that this sample from the hypothetial waste when burned
under these conditions complies with the Part 264 Subpart Q Incinerator
Standards as they relate to:
• Destruction and Removal Efficiency -
All three POHCs showed compliance with the 99.99% DRE
performance standard.
28
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e
Limitation on HC1 Emissions -
The HC1 emission rate of 0.40 lb/hr shows compliance
with a 99% removal standard for HC1.
e Limitation on Stack Emissions of Particulate Material -
The corrected particulate loading of 140 mg/m3 shows
compliance with the 180 mg/m3 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. SPECIFIC SAMPLING PROCEDURES
A. OVERVIEW OF SAMPLING METHODS
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 in the form of a solid, liquid, slurry, or
sludge. Following combustion, POHCs may be found in solids (e.g., bot-
tom ash, fly ash/ESP catches) in liquids (scrubber water), or in the
stack gas with its entrained particulate material. In this discussion,
the sampling methods appropriate to each of the influent and effluent
streams of a hazardous waste incinerator are discussed. Each of the
sampling methods is described in the form of an outline which also in-
dicates 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 sampling methods and gaseous sampling methods are likely to be
the most important methods for both routine monitoring and trial burn
monitoring. It is expected that a majority of the 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 sam-
pling with a Coliwasa (composite liquid waste sampler). During trial
burn situations, the calculation of the Destruction and Removal Effi-
ciency (DRE) value for the designated POHCs requires the measurement
of those POHCs in the stack gas following all emission control devices.
The required DRE value, 99.99% minimum, for POHCs places severe con-
straints on the sampling system for stack gases. It should be remem-
bered that it is only during the trial burn that specific POHC sampling
activity occurs. During routine incinerator operation, sampling re-
quirements 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.). In this section, a summary description of the
general methods which are to be used for the sampling of the influent
streams to a hazardous waste incinerator are presented. Table 5 sum-
marizes the sampling devices appropriate for hazardous waste sampling.
Table 6 summarizes the typical sampling points for most waste containers.
31
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TABLE 5
CHOICE OF SAMPLERS
Waste Type
Liquids, sludges
and slurries in
drums, vacuum
trucks, barrels,
and similar con-
tainers
Sampler
Liquids and
sludges in
ponds, pits or
lagoons
Wastes in
storage tanks
Powdered or
granular solids
in bags, drums,
containers
Dry wastes in
shallow con-
tainers and
surface soil
Coliwasa
a) Plastic
b) Glass
a) Pond
Sampler
b) Weighted
Bottle
Sampler
Weighted
Bottle
Sampler
a) Grain
Sampler
(thief)
b) Sample
Corer
(trier)
Trowel
or Scoop
Limitations/Comments
Not for containers >1.5 m
deep
Not for wastes containing
ketones, nitrobenzene,
dimethylformamide, mesityl
oxide, or tetrahydrofuran (4).
Not for wastes containing
hydrofluoric acid and
concentrated alkali
solutions.
Cannot be used to collect
samples beyound 3.5 m.
Dip and retrieve sampler
slowly to avoid bending
the tubular aluminum
handle.
May be difficult to use on
very viscous liquids.
Device lowered to proper depth
and the bottle uncapped to
allow filling. The bottle may
also be used as the sample
container.
May be difficult to use on
very viscous liquids. Device
lowered to proper depth
and the bottle uncapped to
allow filling. The bottle may
also be used as the sample
container.
Limited applications for sampling
moist and sticky solids and
when the diameter of the solids
is greater than 0.6 cm.
May incur difficulty in retaining
core sample of very dry granular
materials during sampling.
Not applicable to sampling deeper
than 8 cm. Difficult to obtain
a reproducible mass of samples.
Waste piles
Waste Pile Not applicable to sampling solid
Sampler wastes with dimensions greater
than 1/2 the diameter of the
sampling tube.
Source - References 1, 3, and 4.
32
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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, 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.
Withdraw samples through fill openings of
bags and sacks. Withdraw samples 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.
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 samples through at least
three different points near the top of pile
to points diagonally opposite the point of
entry.
Sample from the top through the sampling hole.
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 1, 3, and 4.
33
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The basic strategy for the sampling of the influent waste streams to a
hazardous waste incinerator during a trial burn is the compositing of
individual grab samples of the influent waste. In order to obtain a
representative sample of the waste, the number and frequency of grab
samples collected 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 S001)
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 discarded
after a single use if the parts cannot be easily cleaned.
The fabrication of the Coliwasa has been throughly documented (4), 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 sampler
is slowly lowered into the waste container, and a liquid sample removed
from the waste and transferred to the 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
can not exceed 1.5 m. However, it is expected that a majority of the
liquid hazardous wastes which will be sent to incinerator facilities
will be contained in drums, barrels, and tanks where this limitation
will not be very important.
b. Dipper (Pond Sampler) (Method S002)
The pond sampler or dipper permits collection of liquid samples in ponds,
pits, lagoons, and tanks with open tops. The sampler consists of an ad-
justable clamp attached to the end of a multiple-piece telescoping alu-
minum tube; the clamp is used to secure a sampling beaker or bucket.
This device is 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 the 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. Tap sampling will be appropriate for
use whenever liquid wastes in pipes or ducts must be sampled.
34
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A sample is collected by inverting the beaker and slowly lowering the
beaker into the liquid to be sampled. At the appropriate depth, a rapid
push-pull motion will rotate the beaker opening towards the surface and
allow sample to be collected. This device may be used to obtain samples
as far as 3.5 m from the edge of the tank and at different depths.
c. Weighted Bottle (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 open the bottle at the appropriate
sampling depth. Descriptions of this device are found in ASTM Methods
D-270 (7) and E-300 (8). These methods use a metallic bottle basket
which also serves as a weight sinker. These devices may be either fab-
ricated or purchased.
The use of these devices to sample liquids contained in storage tanks,
wells, sumps, or other containers which can not be adequately sampled
with the other liquid sampling devices, involves lowering the bottle to
the appropriate depth, uncapping the bottle, and after completely filling
the bottle, withdrawing the sampler. Once out of the waste, the bottle
may be capped, rinsed off, and used as the sample storage container. The
sampler can not be used to collect liquids that are incompatible with or
chemically react with the weight sinker or the control lines.
d. Tap (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, will allow 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 de-
scribed fully in ASTM Method D-270 (7).
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 hazardous waste sam-
pling are the grain sampler (thief), the sampler corer (trier), and the
trowel (scoop). The use of each sampler is described in detail in
SW-846 (3).
35
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a. Thief (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.
b. Trier (Sample Corer/Waste Pile Sampler) (Method S006)
A typical sampling corer or trier is a long tube with a slot that extends
almost the entire length of the tube. The waste pile sampler is essen-
tially a large sample corer. While not commercially available, these
samplers can be easily fabricated from sheet metal or plastic 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 1 m. 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 of the diameter of
the tube.
c. Trowel (Scoop) (Method S007)
A trowel looks like a small shovel. A laboratory scoop is similar to the
trowel except that the blade 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 choice
because it is usually made of materials less subject to corrosion or
chemical reactions, thus lessening the probability of sample contami-
nation.
36
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3. Sampling Methods for Slurries 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.,
nonfree-flowing, the solid waste samplers used for moist samples (such
as corers and trowels) are appropriate.
4. Sampling Methods for Scrubber Water
Scrubber water and other liquid hazardous waste influents to a hazardous
waste incinerator may be sampled by a dipper or tap sampling method.
C. SAMPLING METHODS FOR EFFLUENT STREAMS
Sampling of the effluent streams of a hazardous waste incinerator serves
several purposes. During test 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
need 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:
(1) an extractive probe which must be resistant to physical and chemical
reactions with the gas being sampled, (2) 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 volatile constituents) and (3) 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 sampling trains for Hazardous Waste
Incinerator emissions measurements should parallel the procedures speci-
fied in EPA Methods 1-5 (5) for particulate emissions testing. Criteria
selection of sampling port locations, 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 the specified EPA Methods and in "Air Pollution (Volume
III)" (9).
37
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a. Modified Method 5 Train (Method S008)
The Modified Method 5 (MM5) sampling train is one of the two comprehen-
sive sampling systems which will be used for the sampling of stack gas
effluents. This system is based upon the design of units which normally
are employed for sampling under EPA Method 5. The modified system con-
sists of a probe, an optional cyclone, a high efficiency glass or quartz
fiber filter stage, a sorbent module, four impingers, and some control
hardware. 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. The first impinger is empty and
is used to collect the condensate which percolates through the sorbent
resin module. A diagram of this system is shown in Figure 3. Physical
construction details and assembly details of this system have been de-
scribed by Martin (10) and maintenance procedures have been described by
Rom (ll), This system may be used for either stack gas sampling or com-
bustion zone sampling with differences due only to the type of probe
being utilized.
For stack gas sampling, either medium wall Pyrex glass tubing (for probes
less than 2.1 m or 7 ft in length) or 1.6 cm OD Incology 825 tubing (for
probes greater than 7 ft long) are wrapped with heating wire and a stain-
less 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 (12). A stain-
less steel jacket surrounds the quartz probe liner, and the water cooling
decreases the exiting gas temperature to about 205°C (400°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
to 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 thermo-
statically maintained at a temperature of [120°C ± 12°C (250°F±25°F)]
which is sufficient to prevent water condensation in this portion of the
train.
Dowstream 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 _> 100°C (200°F) (13,14,15,16).
38
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TEMPERATURE
SENSOR
v PROB
REVERSE-TYPE
PITOT TUBE
CHECK
VALVE
PITOT MANOMETER
RECIRCULATION PUMP
THERMOMETERS
IMPINGERS IICE BATH"
' VACUUM LINE
PASS VALVE
r^H—t&-2-
MAIN
VALVE
DRY GAS METER AIR-TIGHT
PUMP
*First impinger which serves as condensate trap has a very short
stem that does not extend into the condensate; it may be oversized.
FIGURE 3: Modified Method 5 Train
39
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A diagram of one suitable sorbent module is shown in Figure 4. Alter-
native 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 is 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 be-
come 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.
At the downstream side of the sorbent module are four impingers 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 this impinger collects the condensate which passes through the sor-
bent module for subsequent organic analysis. The second impinger is of
a modified Greenberg-Smith design; this impinger is initially 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 acid gases such as IIC1. (The sodium acetate may be
used to prevent depletion of scrubbing reagent by carbon dioxide). For
collection of 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 tip
and also filled with the appropriate scrubbing solution. The fourth
impinger is typically filled with silica gel to adsorb 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 dry standard
cubic meter (dsm3) sample over a sampling time of three to five hours.
A near isokinetic sampling rate is maintained throughout the sample
collection.
b. Source Assessment Sampling System (SASS) (Method S0Q9)
The Source Assessment Sampling System (SASS train) is an alternative in-
tegrated stack gas sampling system. In many respects, the SASS train is
about a five-fold scale-up of the MM5 train and collects larger samples,
typically 30 dsm^ over a three-hour sampling period. This sampling train
is appropriate whenever a large sample of stack gas (greater than 10 dsm^)
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
40
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FLOW DIRECTION
RETAINING SPRING -
8 mm GLASS
COOLING COIL
28/12 BALL JOINT
GLASS WATER JACKET
GLASS WOOL PLUG J
FRITTED STAINLESS STEEL DISC
15 mm SOLV-SEAL JOINT
(OR 28/12 SOCKET JOINT)
FIGURE 4 Adsorbent Sampling System
-------
HEAT
CONTROLLER
STACK T.C.
CONVECTION OVEN
ISOLATION
BALL VALVE
FILTER
t
©
3m
GAS COOLER
CAS
TEMPERATURE yf \
T.C.
I <=3f=>
I jlL j
SORBENT
CARTRIDGE
OVEN T. C.
CONDENSATE
COLLECTOR
IMP/COOLER
TRACE ELEMENT
COLLECTOR
DRY GAS METER/ORIFICE METER
CENTRALIZED TEMPERATURE
AND PRESSURE READOUT
CONTROL MODULE
TWO 10-ft /min VACUUM PUMPS
FIGURE 5 SASS Schematic
-------
in series to provide large collection capacities for particulate matter
nominally size-classified into three ranges: (a) >10 vim, (b) 3 ym to
10 ym, and (c) 1 pm to 3 ym. By means of a standard 142 mm or 230 mm
filter, a fourth cut, <1 ym, is also 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 car-
tridge 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 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. The last impinger in the series
contains silica gel for moisture removal. Trapping of some inorganic
species also may occur in the sorbent module.
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 (9).
The appropriately sized nozzle is attached to the probe for the subse-
quent sampling effort.
c. Gas Bulb and Gas Bag Sampling Systems (Methods S010, SOU)
In addition to the sample collected with the comprehensive sampling sys-
tem, other gas phase stack samples may need to be collected during some
particular trial burns if volatile organic species are among the desig-
nated trial POHCs for purposes of calculating the DRE performance. The
sample is required because the sorbent module and filter units contained
within the comprehensive sampling system are not efficient for the col-
lection of organic material with boiling points much below 100°C (200°F).
Organic materials with high volatility, therefore, may be passed through
the comprehensive sampling system without being collected quantitatively.
In order to collect volatile POHC species, gas bulb sample of the stack
gas stream should be obtained during each trial burn when constituents of
high volatility are designated as POHCs. The gas bulb may be either
directly coupled to a point that is downstream of the sorbent module in
a MM5 or SASS sampling train or to a separate sampling line that is be-
ing taken from the stack. The latter alternative is preferred because it
does not disturb the flow in the comprehensive sampling system.
43
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For gas bulb sampling, the bulb is evacuated prior to connection to the
sample line and is then allowed to fill with stack gas effluent (or com-
bustion zone effluent if desired). Once the bulb is filled, the sample
valve is closed and firmly seated. 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.
The amount of sample which needs to be collected is a function of the
limit of detection requirements for the POHCs which are being monitored.
An alternative approach is to use bag sampling with a gas sampling train,
such as that shown in Figure 7. The gas bag collects a 10 to 30 L gas
sample which can be integrated over a reasonably long sampling time
(e.g., three hours). .
For gas bag sampling, a nonreactive probe is inserted into the stack and
the gas sample is 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 com-
patible 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.
d. Specific Sorbent/Reagent Methods
Specific sorbents and reagents are used to collect those POHCs which are
subject to reaction or loss when collected with the previous approaches.
The use of these sample collection methods will require devices similar
to that shown previously for integrated gas bag samples. A nonreactive
probe will be inserted into the gas stream and gas collected at a con-
trolled rate. A gas cooler is located before the sorbent or reagent
collector to reduce the temperature of the gas stream to levels com-
patible 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.
The special purpose sorbents/reagents may be incorporated into the
Modified Method 5 or SASS train modules if the substitution for stan-
dard train components does not adversely affect collection of other
POHCs. Alternatively, a separate train to collect the compound types
listed in Table 7 may be used.
44
-------
PYREX
WOOL PLUG
Ui
STYROFOAM
PROTECTOR
FIGURE 6
Evacuated Grab Sampling Apparatus (for Subatmospheric Pressures)
-------
FIGURE 7 Integrated Gas-Sampling Train
-------
TABLE 7
SORBENTS AND SPECIAL REAGENTS FOR SPECIFIC POHCs
Compound Type
General purpose - organics
General purpose - organics
General purpose - chlorinated
organics
General purpose - nonpolar
General purpose, better
for polar organics than
XAD-2 resin
General purpose - polar
organics
Sorbents
XAD-2 resin
Tenax GC
Florisil
Ambersorb XE-340
XAD-8 resin
Ambersorb XE-347
Compound Type
Acidic compounds
Basic compounds
Volatile metals
Aldehydes
Special Reagent
Dilute caustic (such as 1% NaOH)
Dilute acid (such as 1% HC1)
Oxidizing reagents (such as
ammonium persulfate)
Dinitrophenylhydrazine in 2N HC1
(or 2,3,4,5,6-Pentachlorobenzylhydrazine)
47
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e. 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) is the level of carbon monoxide (CO) in the stack effluent. This
measurement is needed during trial burns as well as during routine in-
cinerator operation. Plume color and plume opacity may also be measured
frequently for control purposes, although routine documentation is not
required.
In addition, oxygen and/or carbon dioxide levels in the incinerator
effluent must be measured to allow correction of the measured particu-
late 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. purposes of calculating a removal efficiency.
Sample Conditioner
A portion of any on-line, continuous monitoring instrumentation set-up
for incinerator use is a sample delivery system which provides a properly
conditioned representative sample to the instrumentation for measurement.
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 to remove particulate, cool, dilute and/or dehumidify
the effluent is generally required prior to continuous analysis by instru-
ments 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 (5)). Selection of this
instrument is consistent with the need to continuously monitor combustion
efficiency by monitoring CO. Many commrrcial CO analyzers (NDIR) are
available, however, selection should be based on the EPA specifications
described in EPA Method 10 (5). Such specifications are required to pro-
vide 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 is best measured by EPA
Method 9 (5). 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.
48
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Oxygen/Carbon Dioxide Measurement
The oxygen and/or carbon dioxide levels in the incienrator effluent must
be measured to allow correction of the measured particulate loading to a
standard excess air level. EPA Method 3 (5). invlves 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 hydro-
gen halides in stack gas effluents. These methods generally involve the
collection of the hydrogen halides in impingers containing water or dilute
alkali (0.1 N NaOH). A filter is utilized upstream of the impingers to
remove particulates. Considering potential interferences, a specific
ion electrode method is the preferred analysis method.
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 incinerator testing. Both
techniques will permit analysis of effluent concentrations as low as about
1 ppm.
2. Sampling Methods for Solid and Liquid Effluents
The solid and liquid effluents from a hazardous waste incinerator, in-
cluding bottom ash or fly ash/ESP catches, may be sampled by the methods
discussed previously for the influent streams. Solid effluents will be
sampled using scoops, corers, etc., as appropriate. Detailed information
concerning the selection of solid sampling locations are presented later.
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 necessay in deciding the extent of sampling safety precautions
to be observed and in the choice of protective equipment' to be used.
49
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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 oil-and-acid proof apron (4).
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 safety re-
gulations.
The following precautions should be employed by all field crew members:
• Steel-toed safety shoes or boots should be worn.
• 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 loca-
tions, this probably means that there should be at least two field
crew members.
e 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.
0 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. These will include fire departments, rescue squads,
poison information center, and hospital emergency facilities. Home
telephones of all team members will also be recorded by the team
leader in case of need for emergency notification of relatives.
50
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E. COLLECTION OF REPRESENTATIVE SAMPLES
1. Gases
The representativeness of all gas samples is insured by the integrated
sampling approaches presented previously. Stack gas samples collected
by MM5 or SASS methods represent collections obtained over a several-
hour period collected at or near the isokinetic sampling point. Hence,
MM5 and SASS samples contain the average composition of the stack gas
during the period sampled. Bag samples are also collected over a several
hour time span and thus integrate any fluctuations in the levels of speci-
fic components to yield an average composition sample.
2. Liquids
Every collected sample should be prepared in strict accordance with a
specified procedure. When sampling nonvolatile liquid products, the
sampling apparatus shall be filled and allowed to drain before drawing
the actual sample. If the actual sample is to be transferred to an-
other container, the sample container shall 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 must allow for some element or randomness
in the selection of subsamples since there is a possible variation in the
quality of the material. Generally, where segregation is known to exist
and random variation of quality is not possible, the sampling should be
designed to allow for this. 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 uni-
form subsamples given in EPA manuals (3,4) should be used to ensure
adequately representative samples.
4. Slurries
The sampling of slurries with any degree of accuracy is quite difficult.
This is particularly true when sampling a normally static system such as
a storage tank or vat. Arrangements must 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 there, it is difficult to obtain an accurate
sample because slurries subjected to shearing will tend to change in
composition due to the loss of liquid.
51
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If only a portion of any slurry sample can be used for analysis, the
sample should be shaken and a portion more than adequate for analysis
should be dumped out. Attempts to pour out a predetermined volume of
a heterogeneous sample for analysis are unsatisfactory because the solids
have time to separate during the pouring. The more frequently
subsamples are taken, the more accurately will the sample represent the
total stream.
5. Sample Handling
After a sample is 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
air.
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 chemicallv
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 onlv be kept open as briefly as possible.
F. IDENTIFICATION OF SAMPLES
Each sample must be labelled 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 re-
corded in a log book. This must be a bound book, with pages numbered
consecutively. Entries in the log book should include the following:
52
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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 (if known) producing waste
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 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 re-
construct the sampling situation without reliance on the sample collector's
memory.
G. SAMPLING METHOD SUMMARIES
The sampling methods described in the previous portions of this section
are presented in a summary form here. 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 litera-
ture 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.
53
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Method Number: S001
Method Name: Coliwasa
Basic Method: Liquid grab sample
Matrix: Contained liquids
Sampling Hardware Parameters:
Hardware: Coliwasa sampler as described in SW-846.
Use: Insert sampler in closed position into liquid
sample. Open sampler to fill, cap and then
remove.
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.
54
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Method Number:
S002
Method Name: Dipper (Pond Sampler)
Basic Method: Liquid grab sample
Matrix: Static liquids
Sampling Method Parameters:
Hardware: Beaker attached to telescoping pole as described in
SW-846.
Use: Insert beaker into liquid with opening downward
until desired depth is reached. Turn beaker
right side up to fill. Raise dipper and transfer
to storage vessel. Collect 2-4 L of 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).
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:
S003
Method Name:
Weighted bottle
Basic Method:
Liquid grab sample
Matrix:
Liquids
Sampling Method Parameters:
Hardware:
Weighted bottle constructed as described in
ASTM D-270 and ASTM E-300.
Use:
Lower stoppered bottle to directed depth and
remove stopper. Raise sampler after bottle
is filled, cap, and wipe 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).
56
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Method Number:
S004
Method Name:
Tap
Basic Method:
Liquid grab sample
Matrix:
Moving streams
Sampling Method Parameters:
Hardware
Valves for tap, sample line (washed Teflon),
collection bottles.
Insert sample line into collection vessel. Rinse
sample line and bottle thoroughly with liquid waste
prior to isolating sample. Collect a minimum of 2 L
of sample with a sampling time which exceeds five
minutes.
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. PB 293795/AS
American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Method
D-270 (1975).
57
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Method Number:
S005
Method Name: Thief (Grain Sampler)
Basic Method: Solid grab sample
Matrix: Free-flowing solids
Sampling Method Parameters:
Hardware: Thief - available from laboratory supply houses.
Use: Insert thief into solid, rotate inner tube, wiggle
it to encourage flow into thief. Close and with-
draw.
Reference: U.S. Environmental Protection Agency / Office of Solid Waste,
Washington, D.C., "Test Methods for t/valuating Solid Waste -
Physical/Chemical Methods," SW-846 (1980).
58
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Method Number: S006
Method Name: Trier (Sample Corer/Waste Pile Sampler)
Basic Method: Solid grab sample
Matrix: Sludges and moist powders
Sampling Method Parameters:
Hardware: Sample corer (trier) as in SW-846. The waste pile
sampler is a larger scaled version. Both samplers
are fabricated from PVC pipe or sheet metal.
Use: Insert sampler into solid material at an angle of
0-45°, rotate to cut a core of the waste, and re-
move with concave side up.
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; S007
Method Name; Trowel (Scoop)
Basic Method: Solid grab sample
Matrix: Solids
Sampling Method Parameters:
Hardware: Stainless steel or polypropylene laboratory scoop,
7 x 15 cm.
Use: Remove top \ inch prior to sample collection. Collect
Kg-sized sample by combining samples 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). NTIS No.
PB80-153353.
60
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Method Number: S008
Method Name: Modified Method 5 (MM5) Train
Basic Method: Comprehensive sampling train (filter-sorbent-impinger)
Matrix: Stack gas (particulate plus vapor phase material)
Sampling Method Parameters:
Hardware: RAC or equivalent sampling train modified to
include sorbent module as shown in Figure 4.
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 ).
Use: Traverse stack and samples isokinetically as specified,
in EPA Methods 1-5.
3
Collect 5 m sample at a sampling rate of approximately
0.75 ft^/min.
Recovery Check:
Spike filter/sorbent and/or impingers before or immediately after
sampling with a known quantity of the deuterated or fluorinated
analog(s) of target compound(s).
References: Title 40, Code of Federal Regulations, Part 60, Appendix A,
Method 5 (1980).
Martin, R.M., "Construction Details for Isokinetic Source
Sampling Equipment," EPA-APTD-0581 (1971). NTIS No.
PB 203060.
Rom, J.J., "Maintenance, Calibration and Operation of
Isokinetic Source Sampling Equipment," EPA-APTD-0576
(1972). NTIS No. PB 209022.
61
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Method Number: S009
Method Name: SASS
Basic Method: Comprehensive sampling train (filter-cyclone-
sorbent-impinger)
Matrix: Stack gas (particulate plus vapor phase material)
Sampling Method Parameters:
Hardware: 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 ym, 1 ym.
Use: Traverse stack to determine point of average velocity
and sample isokinetically as specified in EPA methods
1-5.
3 3
Collect 30 m sample at approximately 4 ft /min with
a sampling rate near isokinetic conditions.
Recovery Check:
Spike filter/sorbent and/or impingers before or immediately after
sampling with a known quantity of a deuterated or fluorinated ana-
log of target compound(s).
Reference: Lentzen, D.E., D.E. Wagoner, E.D. Estes and W.F. Gutknecht,
"EPA/IERL-RTP Procedures Manual: Level 1 Environmental Assess-
ment," EPA-600/7-78-201 (October 1978). NTIS No. PB 293795/AS.
62
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Method Number:
S010
Method Name:
Basic Method:
Matrix:
Sampling Method
Gas bulb
Gas grab sample
Stack gas
Parameters:
- reactive gases
Hardware: 2-L glass bulb in styrofoam package.
Glass wool for particulate removal.
Side bleed gas control mounted perpendicular to
duct.
Use: Purge bulb with 20 L gas sample at ^ 0.5 L/min
prior to isolating sample. Re-evacuate the gas bulb.
Open valve and collect a 2 L gas sample, close valve.
References: Lentzen, D.E., D.E. Wagoner, E.D. Estes and W.H. Gutknecht,
EPA/IERL-RTP Procedures Manual: Level I Environmental Assess-
ment" EPA-600/7-78-201 (October 1978) NTIS No. PB 293795/AS.
Title 40, Code of Federal Regulations, Part 60, Appendix A,
Method 7 (1980).
63
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Method Number:
S011
Method Name:
Gas bag
Basic Method:
Gas grab sample - unreactive gases
Matrix:
Stack gas
Sampling Method Parameters:
Hardware: Integrated gas sampling train including probe with
filter, condenser, flow controllers, meters and
pumps.
Polymer sandwiched aluminized bag or equivalent.
Use:
Insert probe into the center of a duct, and collect
30 L of sample at rate of 0.5 L/min.
References: Lentzen, D.E., D.E. Wagoner, E.D.Estes and W.H. Gutknecht,
"EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment," EPA-600/7-78-201 (October, 1978). NTIS No.
PB 29375/AS.
Title 40, Code of Federal Regulations, Part 60, Appendix A
Method 3, (1980).
64
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V. SPECIFIC 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, needs to be converted into a matrix which is
compatible with the final analysis methods needed for measurement of the
designated POHCs. The sample preparation scheme may require extraction
of the sample, concentration of an extract and clean up of the extract
to remove potential interferences. Digestion of a sample will be needed
for the analysis of inorganic constitutents. Surrogate and standard
addition methods are required for better precision in the assessment of
POHC levels by determining recoveries for the POHC species of interest.
In this section, the sample preparation steps appropriate for the haz-
ardous constituents identified in Appendix VIII of the May 20, 1981
Federal Register are described. The sample preparation methods were
chosen to be as widely applicable as possible. Preparation methods,
such as extraction and concentration for organics, or digestion for
inorganic species, are not necessarily optimized for each specific POHC,
but rather have been generalized to encompass a large number of compounds.
Method description outlines are compiled at the end of this chapter.
The types of samples expected from the evaluation of a hazardous waste
incinerator include:
ft Gases - Permanent (reactive and nonreactive) and stack gas
samples in the form of comprehensive sampling train components—
particulate catch, sorbent, impinger reagents.
e Liquids - Aqueous liquids (including process waters, scrubber
waters, etc.) and organic liquids.
• Sludges - Including suspensions, slurries and gels.
• Solids - Including particulates, solid residues, sorbents, etc.
1. REPRESENTATIVE ALIQUOTS FROM FIELD SAMPLES (Methods P001-- P003)
Combination and preparation of representative aliquots (i.e., composites)
of the collected samples is appropriate for all solid and liquid grab
samples. Samples of gases collected with the bag sampling approach and
stack gas samples collected via either the MM5 or SASS train represent
time-averaged sample collections. In effect, the sampling approach has
composited the gas sample on a time-averaged basis. Other grab samples
(liquids and solids) will be homogenized prior to withdrawal of aliquots
for analysis. The individual aliquots will then be composited to form
a single sample for subsequent preparation and analysis procedures. The
procedures appropriate for aliquoting and compositing samples are sum-
merized in Table 8.
65
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Method #
P001
TABLE 8
SUMMARY OF PROCEDURES FOR COMPOSITING OF SAMPLES
Physical Form of Sample Proportioning Method
Liquids Homogenize; pour aliquot
Compositing Method
Combine aliquots in
container; shake
P002
Sludges
Homogenize; use dipper
to take three portions
Combine aliquots in
container; mix
ov
P003
Solids
Grind, if necessary to
reduce particle size (20
mesh screen) using agate
or alumina equipment;
riffle through steel or
aluminum riffler
Combine aliquots;
cone-blend three
times; roll-blend;
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,
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).
-------
The aliquot sizes that will be taken from each type of field sample for
each of the 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 in
waste based on professional judgment.
All sample aliquots removed for organic analysis will be stored in glass
containers with Teflon-lined screw caps and the sample aliquots for
volatile organic analysis stored such that there is no headspace above
the sample. Sample aliquots for inorganic analysis will be stored in
high-density linear polyethylene containers.
C. RECOVERY MEASUREMENTS (Methods P011 - P014)
It is important to monitor the recovery of POHC materials during sample
preparation to obtain an estimate of the accuracy of the analytical
measurement and to assess the overall efficiency of the analytical
procedures. Two methods will be used for these purposes, the addition
of surrogate compounds which are chemically similar to the POHCs of
interest and the addition of POHCs themselves in stable isotopically-
labelled forms. These compounds will be added to the various samples
immediately after return to the analytical laboratory. Table 10 is a
list of some potential compounds for use as surrogates*. For stack
gas samples, injection of the surrogate compounds directly into the
bulb/bag for bag samples or onto the filter or sorbent for MM5 or SASS
samples is appropriate.
The spiking levels used in each instance will be selected after consider-
ation of: (1) target detection limits for potential hazardous waste com-
ponents and (2) expected concentrations of organic waste components based
on professional judgment. It is expected that concentrations for surrogate
standards 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 limit required to measure
99.99% DRE of the POHCs.
D. SOLVENT EXTRACTION OF ORGANIC COMPOUNDS (Methods P021 - P024)
Solid and liquid samples will be extracted at acidic and basic conditions
(except for extractions using a Soxhlet apparatus). The extracts will
generally be combined prior to analysis, unless the information from the
engineering study suggests that species from the acid and base/neutral
fractions will react, in which case the acidic and basic extracts will
be analyzed separately.
*To avoid interferences with conventional detectors, it is important that
the deuterated and 13c_surrogates are only added to those samples that are
to be taken for mass spectrometric analysis.
67
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TABLE 9
ESTIMATED QUANTITIES OF SAMPLE REQUIRED FOR ANALYSIS*
Analysis/Sample Type
PROXIMATE ANALYSIS
Aqueous Liquids
Sludges
Organic Liquids
Solids
00
Moisture, Solid and
Ash Content
Macroscale
Technique
Microscale
Technique
Elemental Composition
TOC, TOX
SURVEY ANALYSIS
Metals
Organics
DIRECTED ANALYSIS
Organics
Inorganics
100 mL
N/A
50-300 mg
(solid content)
<100 mL
50-300 mg
(solid content)
1L
1L
1L
25 g
50 mg
50-300 mg
(solid content)
20 mL
50-300 mg
(solid content)
100 mL
100 mL
100 g
2 mL
50 mg
50-300 mg
(solid content)
N/A
50-300 mg
(solid content)
1 mL
1 mL
100 mL
10 g
50 mg
50-300 mg
(solid content)
N/A
50-300 mg
(solid content)
20 g
50 g
100 g
*Minimum quantity for a single analysis.
N/A = Not Analyzed
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TABLE 10
POTENTIAL COMPOUNDS FOR USE AS SURROGATES
Volatile Organics (Method P011)
Chloroform-13C
Diethylether-dig
1,2-Dichloroethane-d^
Benzene-dg
Bromoform-13C
Bromomethane-d3
Ethylbenzene-d j g
Basic Extractable Organics (Method P012)
m-Fluoroaniline
Acridirie-dg
Acidic Extractable Organics (Method P013)
2-Chlorophenol-3,4,5,6-d4
Pentachlorophenol-13C0,
Phenol-d5
Bromophenol
2,4,-Dinitrophenol-3,5,6-d3
Benzoic acid-ds
Benzoic acid-13C
Neutral Extractable Organics (Method P014)
Hexachlorobutadiene-1-13C
Octafluorobiphenyl
Naphthalene-d8
1-Fluoroanaphthalene
2,6-Dinitrotoluene-a-a-a-d3
1,2-Dichlorobenzene-d^
Di-n-butylphthalate-3,4,5,6-d^
Hexachlorobenzene-13Cg
Benz(a)anthracene-dj 2
9-Phenylanthracene
69
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1. Aqueous Liquids (Method PQ21)
These procedures apply to spent scrubber liquor or other wastewater from
the incineration facility, to incinerator influent waste streams that are
highly aqueous, and to aqueous condensate collected from the stack gas
effluent using the Modified Method 5 or SASS trains.
a. Semivolatiles (Method P021a)
Reference: U.S. Environmental Protection Agency, Federal Register, 44.
69464-69575 (December 3, 1979).
AIL 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 H2SO4 and the sample again extracted with
three 60 mL portions of methylene chloride. If the aqueous aliquot is
initially acidic, the sample will be extracted first at pH £ 2 and sub-
sequently adjusted to pH _> 11 for the second extraction. All extracts
(ca. 360 mL) will be combined in a labelled amber glass bottle. If for
each individual extract, less than 51 mL (85%) of the methylene chloride
organic phase is recovered, the aqueous phase will be centrifuged at 3000
rpm for 15 min and the recovered organic phase added to the combined ex-
tracts in the bottle.
b. Volatiles (Method P021b)
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 Guidelines Division, Washington, D.C. by
Battelle Columbus Laboratories, Columbus, Ohio under Contract
No. 68-03-2552 (January 1981).
A 20 mL aliquot of an aqueous liquid sample will be placed in a 125 mL
separatory funnel with 2 mL of carbon disulfide and 20 yL of methanol
containing 200 ug of 1,2-dichloropropene internal standard. The contents
will be shaken for 2 minutes and the layers allowed to settle. The sam-
ple extract will be transferred to a labelled container (the transfer need
not be quantitative).
2. Sludges (Method P022)
These 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.
70
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a. Semivolatiles (Method P022a)
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 Guidelines Division, Washington, D.C. by
Battelle Columbus Laboratories, Columbus, Ohio under Con-
tract No. 68-03-2552 (January 1981).
A 100 mL aliquot will be taken for liquid/liquid extraction using homo-
geniza!tion. 100 mL of methylene chloride will be added to the waste
sample in a glass container. If the sludge is known or expected to con-
tain > 1% by weight of extractable organics, 200 mL of methylene chloride
will be used for each extraction. The mixture will be homogenized using
a blender or impeller for 45 to 60 seconds (maximum). The homogenized
mixture will be transferred with a 100 mL pipette to a labelled amber
glass bottle. The extraction/homogenization/centrifugation will be
repeated two additional times.
For sludge/slurry samples suspected to contain > 80% water (based on
professional judgment) the pH will be adjusted to H with 6N NaOH
prior to extraction. (Note: if precipitation is observed when NaOH is
added, the sample will be made slightly acidic with 6N and CO2
evolution will be allowed to cease before adjusting the pH to _> 11).
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.
After extraction with three 100 mL volumes of methylene chloride, the pH
will be adjusted to 2 with 6N H2SO4 and the extraction repeated with 3
additional 100 mL portions of methylene chloride. All extracts will be
combined in a labelled amber glass bottle.
b. Volatiles (Method P022b)
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 Guidelines Division, Washington, D.C. by
Battelle Columbus Laboratories, Columbus, Ohio under Con-
tract No. 68-03-2552 (January 1981).
A 2 gram (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
sludge is known or expected to contain > 20 mg/gram by weight of extract-
able organics, the sample will be placed in a 100 mL centrifuge tube and
71
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the volumes of carbon disulfide will be increased to 20 mL (or more).
The tube will be capped and the contents agitated for 1 minute using
a vortex mixer. The mixture will then be centrifuged at 3000 rpm for
15 minutes and the extract transferred to a labelled container.
3. Organic Liquids (Method P023)
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 Guidelines Division, Washington, D.C. by
Battelle Columbus Laboratories, Columbus, Ohio under Con-
tract No. 68-03-2552 (January 1981).
This procedure applies to incinerator influent waste streams that are
organic liquids. A 1 mL aliquot will be diluted to 100 mL with methy-
lene chloride. If it is apparent that a portion of the sample is in-
soluble in methylene chloride, a separate 100 mL aliquot will be taken
and treated as a sludge sample.
4. Solids (Method P024)
These procedures apply to incinerator waste influent streams that are
solid, to ash collected from flue gas cleaning systems, or from the in-
cinerator itself, and to particulate material and solid sorbent samples
collected from stack gas sampling using the MM5 or SASS trains.
a. Semivolatiles (Method P024a,b)
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).
Two procedures will be used for extraction of solid samples. Homogeniza-
tion (for non-abrasive materials) will be used for most wastes. Extrac-
tion using a Soxhlet apparatus will be 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 40 gram aliquot will be weighed into a 250 mL centrifuge tube. 40 mL
of 10% sodium chloride in reagent water (deionized, distilled water with
organics removed by carbon adsorption) will be added and the pH adjusted
to 2 11. Methylene chloride (60 mL) will be added and a probe device
(SDT tissue mixer) will be used to disperse the sample for a total of
72
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one minute. Then the mixture will be centrifuged for 15 minutes at 1,400
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 portion of methylene chloride will be
used for the extraction. The extraction and dispersion will be repeated
a total of three times, using 60 mL methylene chloride each time.
The pH of the aqueous/solid mixture will then be adjusted _< 2 with 6N
H2SO4 (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 labelled sample container.
® Semivolatiles by Soxhlet Extraction (Method P024b)
The MM5/SASS particulate materials or solid adsorbent (XAD-2), or a 20
gram aliquot of a solid waste sample combined with 20 grams anhydrous
sodium sulfate will be placed in a glass or ceramic extraction thimble.
(If high levels of water are present in the waste sample and the tempera-
ture of the sample rises when sodium sulfate is added, the sample will be
suspended in methylene chloride prior to adding the sodium sulfate).
Sorbent or particulate samples on filters will be placed directly in the
thimble after weighing. A pre-extracted glass wool plug will be placed
on top of the sample. A 200 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 hours (3-4 turnovers per hour). The extract will be transferred to
a labelled amber glass bottle.
b. Volatiles (Method P024c)
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 Guidelines Division, Washington, D.C., by
Battelle Columbus Laboratories, Columbus, Ohio under Con-
tract No. 68-03-2552 (January 1981).
A 2 g (wet weight) aliquot of solid waste sample 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/
gram 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 minute using a vortex mixer. The mixture will then be centrifuged
at 3000 rpm for 15 minutes and the extract transferred to a labelled
container. (This procedure does not apply to MM5/SASS particulate or
sorbent).
73
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E. DRYING AND CONCENTRATING OF SOLVENT EXTRACTS (Method P031)
Reference: U.S. Environmental Protection Agency, Federal Register, 44.
69464-69575 (December 3, 1979).
Aliquots of all methylene chloride sample extracts will be taken for TCO
analysis (Method A011) 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 receiving
tube containing a Teflon boiling chip.
The extract will be evaporated rapidly to 5 to 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 two-ball microSnyder 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% 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 will
include a digestion step. The purpose of the digestion step is to
convert all of the metal-containing species into an inorganic form
for subsequent metals analysis. There are numerous digestion pro-
cedures which may be applied to different types of samples in order
to convert metals in organic and bound compounds to a readily analyzable
inorganic form. Nitric acid digestion will be outlined as the typical
digestion method for purposes of illustration.
An aliquot from well mixed field samples, such as an aqueous liquid,
a sludge or solid will be 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
on cooling. The beaker is covered and heated with additions of nitric
acid until the material is light in color. This completes the digestion
of the sample. The sample mav the be transferred quantitatively to volu-
metric glassware for analysis of the metal of interest.
74
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G. SAMPLE CLEAN UP PROCEDURES (Methods P041-Q045)
For some samples, the level of interfering compounds will be sufficiently
high to preclude successful analysis for the POHCs of interest. For such
samples, one or more clean up steps need to be included in the sample
preparation procedures. Due to the wide variation in the physical and
chemical properties of the listed POHCs, no single sample clean up
method has been demonstrated to be appropriate for all of the listed
POHCs. A number of different clean up methods, such as size exclusion
chromatography, liquid column chromatography using columns filled with
silica gel, Florisil, activated alumina, etc., solvent partitioning,
filtration, and others, may be used alone or in combination to clean
up waste samples for analysis.
Florisil column chromatography will generally be the method of choice
for preparing a sample that requires clean up prior to analysis Add-
itional clean up 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 will elute first from the column and subsequently lower
molecular weight compounds will be eluted. If necessary, this clean
up procedure will be 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 will be employed. These sorbents will
allow fractionation of the sample constituents based upon their mole-
cular activity (polarity, function groups) which allows the less ac-
tive constituents to elute first and the more active constituents to
be retained and eluted in a later fraction. Again, these clean up
methods will be 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 additional modes of sample preparation.
H. 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.
75
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Method Number:
Method Name:
P001-P003
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) usine agate or alumina equipment. The
sample will then be riffled through a steel or aluminum riffler.
Appropriate aliquots will be combined, cone-blended three times,
roll-blended and subsequently coned and quartered.
References: 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, 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).
76
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Method Numbers:
P011-P014
Surrogate Addition to Sample Aliquots for
Organic Analysis
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 labelled surrogates only be added to those
samples that are taken for mass spectrometric analysis. The sur-
rogate compounds will include but not necessarily be limited to the
following:
Volatile Organics (Method P011)
Chloroform-^C
Diethylether-d^g
1,2-Dichloroethane-d.
4
Bromoethane-d^
Benzene-d,
o
Ethylbenzene-d n
13
Bromoform- C
Basic Extractable Organics (Method P012)
m-Fluoroaniline
Acridine-dg
Acidic Extractable Organics (Method P013)
2-Chlorophenol-3,4,5,6-d^
Benzoic Acid-d,.
Phenol-d,
6
2,4-Dinitrophenol-3,5,6-d^
Bromophenol
13
Benzoic Acid- C
Method Name:
Matrices:
77
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Neutral Extractable Organics (Method P014)
13
Hexachlorobutadiene-1- C
Octafluorobiphenyl
Naphthalene-dg
1-Fluoronap hthalene
2,6-Dinltrotoluene-2,2,2-d^
Di-n-butylphthalate-3,4,5,6-d^
Benz (a) anthracene-d^
9-Phenylanthracene
The spiking levels used in each instance will be selected after consider-
ation of: (1) target detection limits for potential hazardous waste com-
ponents and (2) expected concentrations of organic waste components based
on professional judgment. It is expected that surrogate concentrations
on the order of 50 - 1000 ppm will be used, depending on the total organic
content of the waste.
78
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Method Number: P021a
Method Name: Semivolatiles
Basic Method: Liquid/Liquid Extraction
Matrix: Aqueous Liquids
Method Parameters:
AIL aliquot will be taken for liquid/liquid extraction. If the
aqueous aliquot is initially neutral or basic, the pH will be ad-
justed 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 l^SO^
and the sample again extracted with three 60 mL portions of methy-
lene chloride. All extracts (ca. 360 mL total) will be combined
in a labelled 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).
79
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Method Number
P021b
Method Name:
Volatiles
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 2 mL of carbon disulfide and 20 pL
of methanol containing 200 ug of 1,2-dichloropropene internal
standard. The contents will be shaken for 2 minutes and the
layers allowed to settle. The sample extract will be trans-
ferred to a labelled container (the transfer need not be quan-
titative) .
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 Guidelines Division, Washington, D.C. by
Battelle Columbus Laboratories, Columbus, Ohio under Con-
tract No. 68-03-2552 (January 1981).
80
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Method Number: P022a
Method Name: Semivolatiles
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 ex-
traction. The mixture will be homogenized using a blender or impel-
ler for 45 to 60 seconds (maximum). The homogenized mixture will
be centrifuged for 30 minutes at 3000 rpm. The organic phase will
be transferred with a 100 mL pipette to a labelled 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 _>.ll with 6N
NaOH prior to extraction. (Note if precipitation is observed when
NaOH is added,' the sample will be made slightly acidic with 6N H2SO4
and COo evolution will be 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 6 N H2SO4 and the extraction repeated with
3 additional 100 mL portions of solvent. All extracts will be
combined in a labelled 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 Guidelines Division, Washington, D.C. by
Battelle Columbus Laboratories, Columbus, Ohio under Con-
tract No. 68-03-2552 (January 1981).
81
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Method Number: P022b
Method Name: Volatiles
Basic Method: Liquid/Liquid Extraction
Matrix: Sludges (including gels and slurries)
Method Parameters:
A 2 gram (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 ug of 1,2 dichloropropene internal standard will be
added. If the sludge is known or expected to contain >20 mg/gram
by weight of extractable organics, the sample will be placed in a
100 mL centrifuge tube and the volume of carbon disulfide will be
increased to 20 mL (or more). The tube will be capped and the
contents agitated for 1 minute using a vortex mixer. The mixture
will then be centrifuged at 3000 rpm for 15 minutes and the extract
transferred to a labelled 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 Guidelines Division, Washington, D.C., by
Battelle Columbus Laboratories, Columbus, Ohio under Con-
tract No. 68-03-2552 (January 1981).
82
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Method Number:
Method Name:
Basic Method:
Matrix:
P023
Semivolatiles
Solvent Dilution
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 in-
soluble in methylene chloride, a separate 100 mL aliquot will be
taken and treated as a sludge sample (Method P022a).
Reference: MclCown, 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 Guidelines Division, Washington, D.C., by
Battelle Columbus Laboratories, Columbus, Ohio under Con-
tract No. 68-03-2552 (January 1981).
83
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Method Number:
P024a
Method Name:
Semivolatiles
Basic Method: Liquid/Solid Extraction
Homogenization
Matrix:
Solids (non-abrasive materials)
Method Parameters:
A 40 gram 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) will
be used to disperse the sample for a total of one minute. Then
the mixture will be centrifuged for 15 minutes at 1,400 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 portion of methylene
chloride aliquot will be used for the extraction. The extraction
and dispersion will be repeated a total of three times, using 60
mL methylene chloride each time.
The pH of the aqueous/solid mixture will then be adjusted to pH < 2
with 6N H2SO4 (add 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 labelled sample
container.
Sample extracts will be passed through a short column of anhydrous
sodium sulfate and concentrated to 1 mL (if possible) using a
Kuderna Danish apparatus fitted with a macroSnyder column and
then a microSnyder column.
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).
84
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Method Number: P024b
Method Name: Semivolatiles
Basic Method: Liquid/Solid Extraction
Soxhlet Apparatus
Matrix: Solids (abrasive materials)
Method Parameters:
A 20 gram aliquot of the solid sample will be combined with 20 grams
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 niL round bottom flask
containing a teflon boiling chip. The flask will be attached to
the extractor and the solids extracted for 16 hours (3-4 turnovers
per hour). The extract will be transferred to a labelled 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).
85
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Method Number:
P024c
Method Name: Volatiles
Basic Method: Liquid/Liquid Extraction
Matrix: Solids
Method Parameters:
A 2 g (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/gram by weight of
extractable organics, the sample will be placed in a 100 mL centri-
fuge tube, and the volume of carbon disulfide increased to 20 mL
(or more). The tuba will be capped and the contents agitated for
1 minute using a vortex mixer. The mixture will then be centri-
fuged at 3000 rpm for 15 minutes and the extract transferred to
a labelled 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 Guidelines Division, Washington, D.C., by
Battelle Columbus Laboratories, Columbus, Ohio under Con-
tract No. 68-03-2552 (January 1981).
86
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Method Number:
P031
Method 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 cali-
brated receiver tube containing a teflon boiling chip.
The extract will be evaporated rapidly to 5 to 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 two-ball microSnyder 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% or 2%
total extractable organics as determined by the TCO analysis
(Method A001).
Reference: U.S. Environmental Protection Agency, Federal Register, 44,
69464-69575 (December 3, 1979).
87
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Method Number:
P032
Method Name:
Basic Method:
Matrices:
Digestion Procedures for Metals
Acid Digestion
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 (lOOg or 100 mL or 5-10 g if sample is primarily solid) from
well mixed field samples (Methods P001-P003), aqueous and organic,
liquids, sludges and solids) will be used for the analysis of metals.
Most samples will be prepared for analysis by general HNO^ 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 HNO^-
H2S2 for As, Se, and Sb. 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 digest-
ing 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 BaSO.,
PbSO^, or AgCl precipitate.
*These elements are not included in the SW-846 reference, it is believed
that this digestion procedure would also apply to them.
88
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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).
89
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Method Number;
P041
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 will be determined. The amount
of Florisil to be used for each column will be calculated by the
formula:
100 t lauric acid value x 20 grams Florisil per column
This amount of Florisil will be weighed out and each preweighed
portion will be heated for more than five hours 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.
Reference: U.S. Environmental Protection Agency, Federal Register, 44,
69464-69575 (December 3, 1979).
90
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Method Number
P042
Method Name:
BioBeads SX-3
Matrix:
Sample Extracts
Method Parameters:
An aliquot of the sample extract (P021-P030) will be used for this
procedure. Twenty to twenty-five grams 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 ID chromatographic
column, with a glass wool plug at the bottom of the column, and
rinsed with methylene chloride. A glass wool plug followed by a
layer of glass beads will be placed on top of the BioBeads. The
column will be pre-eluted with 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. The column
will be eluted with 200 mL methylene chloride. Ten mL fractions will
be collected. Aliquots of these fractions will be analyzed for
bis(2-ethylhexyl)phthalate and pentachlorophenol by GC/FID on a
1% 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 concen-
tration 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]
Typical Calibration:
The first 60 mL (85% corn oil) will be discarded and the
next 110 mL retained for sample analysis.
91
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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),
92
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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 clean up procedure
to other preparation techniques such as derivatization. The
procedure described below is the Level 1 approach. Other procedures
are described in the Federal Register, also referenced below.
Silica gel (Davison, 60-200 mesh, Grade 950) which has been activ-
ated at 130°C for >5 hours will be stored in a dessicator until
used. ; A 10 mm ID chromatographic column will be slurry packed
with 6.0 grams of activated silica gel in n-pentane.: Approxi-
mately 3 ± 0.2 grams of 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. Two mL of sample in cyclopentane will be pipetted onto the
column. The following solvents will be used to elute the con-
stituents 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 chloride (10 mL),
References: Lentzen, D.E., D.E. Wagoner, E.D. Este and W.F. Gutknecht,
"EPA/IERL-RTP Procedures Manual. Level I Environmental
Assessment (Second Edition)," EPA-600/4-78-201 (October 1978).
NTIS No. PB 293795/AS.
U.S. Environmental Protection Agency, Federal Register, 44 »
69464-69575 (December 3, 1979).
93
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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 ex-
traction 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,
LA., or equivalent, deactivated to 3% water) to a liquid chroma-
tography 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).
94
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Method Number: P045
Method Name: Liquid/Liquid Extraction
Matrix: Sample Extracts
Method Parameters:
A 10 gram 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, will be added to the solvent. This sample solvent mixture
will be shaken in a 125 mL separatory funnel for one minute. The
phases will be allowed to settle for ten minutes and the aqueous
phase removed. The organic solvent layer will be extracted two
more 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).
95
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VI. SPECIFIC ANALYSIS PROCEDURES
A. OVERVIEW
The overall strategy for the analysis of the wastes includes both test
procedures to determine the characteristics of the waste and also analy-
sis procedures to determine the composition of the waste. In this sec-
tion, the test procedures for determining the characteristics of the
waste are summarized. Also, the particular analysis methods appropriate
to the various POHCs of interest during a trial burn are described. Both
the preparation and analysis methods have been chosen to be as widely
applicable as possible. The specific analytical procedures and the sur-
vey analytical procedures have been selected to be appropriate to a
large number of compounds, and are not necessarily optimized for each
specific POHC. The primary rationale for this approach is to minimize
the cost for providing assessments of the levels of POHCs while meeting
the constraints of the permitting process.
The test procedures for determining 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 preceeding 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), Corrosivity (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), will be used to
determine whether the wastes exhibit the characteristics of a hazardous
waste as defined by Section 3001 of RCRA.
1^ Ignitability (Method C001)
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.
The objective of the ignitability characteristic is to identify wastes
which present fire hazards due to being ignitable under routine storage,
disposal, and transportation and also wastes capable of severely ex-
acerbating a fire once it is started.
97
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A solid waste is considered to exhibit the characteristic of ignitability
if a representative sample of the waste has any of the following prop-
erties:
• It is a liquid, other than an aqueous solution containing less
than 24 percent alcohol by volume, and has a flash point less
than 60°C.
• It is not a liquid and 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.
• It is an oxidizer.
2. Corrosivity (Method C002)
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.
The characteristic of corrosivity as defined in 40 CFR 261.22, is de-
signed to identify wastes which might pose a hazard to human health or
the environment due to their ability to mobilize toxic metals if dis-
charged into a landfill environment. In addition, wastes that would re-
quire handling, storage, transportation and management equipment to be
fabricated of specially selected materials of construction, will be iden-
tified. Also, corrosivity tests will identify waste that might destroy
human or animal tissue in the event of inadvertant 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 less than or equal to 2 or greater
than or equal to 12.5.
• It is liquid and corrodes steel at a rate greater than 6.35 mm
per year at a test temperature of 55°C.
jL Reactivity (Method C003)
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.
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, pose a problem at all stages of the waste manage-
ment process. The definition is to a large extent a paraphrase of the
narrative definition employed by the National Fire Protection Association.
98
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A solid waste is considered to exhibit the characteristic of reactivity
if it shows any of the following properties:
e It readily undergoes violent chemical changes.
• It reacts violently or forms potentially explosive mixtures
with water.
o 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.
9 It explodes when subjected to a strong initiating force.
• It fits within the Department of Transportation's forbidden
explosives, Class A explosives, or Class B explosives clas-
sification.
Reactivity will be 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)
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.
The Extraction Procedure Toxicity Test (E) is designed to simulate the
leaching a waste will undergo if disposed of 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 pH
5 with acetic acid. The extract obtained, the "EP Extract," is then
analyzed to determine if any of the thresholds established for 8 elements
(i.e., arsenic, barium, cadmium, chromium, lead, mercury, selenium,
silver), four pesticides (i.e. Endrin, Lindane, Methoxychlor, Toxa-
phene), and two herbicides (i.e., 2,4,5-Trichlorophenoxypropionic
acid (2,4,5-T), 2,4-Dichlorophenoxyacetic acid (2,4-D) have been exceeded.
A solid waste is considered "EP Toxic" if the following threshold levels,
(Table 11) designated in 40 CFR 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.
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
Methoxychlor 10.0
Toxaphene 0.5
Herbicides
2,4-D 10.0
2,4,5-T 1.0
100
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The type of data to be generated by the proximate analysis is indicated
on the Proximate Analysis Reporting Form, Table 12.
1. Moisture, Solid and Ash Content (Methods A001-A002)
Reference: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Method D-
1888-78, Part 3 (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.
PB 297686/AS
a. Macro-scale Technique (Method A001)
Loss on Drying - LOP (Method AOOla)
An aliquot (Table 9) of a well mixed sample will be transferred to a
tared porcelain, platinum, or Vycor evaporating dish, previously ignited
at 600°C for one hour and cooled in a desiccator. The sample and dish
will be weighed, and then heated on a hotplate to evaporate the sample,
without boiling, to near dryness. The sample and dish will be transferred
to a 103°C oven to complete the evaporation. Periodically (at intervals
usually greater than or equal to one hour), the sample will be removed
from the oven, cooled in a desiccator and weighed. The drying will be
considered complete when the loss of weight in a given interval is less
than 4% of the previous weight.
The % solids will be calculated as follows:
Final Weight - Tare
% Solids - x 100
Initial Weight - Tare
The % moisture will be calculated as follows:
% Moisture = 100 - % Solids
It should be noted here that the % moisture determination involves heating
a waste 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. This would also be applicable to the-micro^scale % moisture deter-
mination.
Loss on Ignition LOI (Method AOOlb)
After removal of an aliquot (< 10% of the solid residue) for elemental
analysis, the weighed solids in the evaporation dish will be ignited
for 30 minutes at approximately 600°C. The ash will then be cooled in
101
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TABLE 12
PROXIMATE ANALYSIS REPORTING FORM
Sample
Analyst and/or
Moisture, Solid and Ash Content Laboratory
% Moisture
% Solids
% Ash
Elemental Composition
% Carbon
% Nitrogen
% Sulfur
% Phosphorus
% Fluorine
% Chlorine
% Bromine
% Iodine
Total Organic Carbon
Total Organic Halogens
Heating Value of Waste
Viscosity
-------
a desiccator and weighed.
The ash content will be calculated as follows:
Weight of Solid After Ignition
% Ash = : ¦ x 100
Weight of Sample Before Drying
If ash content is less than 0.1% the result will be reported as ppm ash:
4
ppm Ash =10 x % Ash
b. Micro-scale Technique (Method A002)
Thermogravimetric analysis (TGA) may also be used for micro-scale deter-
mination of % moisture, % solid and ash content on 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) will be placed in the sample boat of the TGA
instrument and heated at the rate of 10°C per minute, in air to 500°C.
The results of the TGA analysis will be reported as a plot of weight,
(mg) versus temperature (°C). The moisture, solid and ash content will
be estimated from the curve as follows.
Weight at 125°C
. % Solids = -— — :— x 100
Initial Weight
% Moisture = 100 - % solids
Final Weight at 500°C
% Ash = 1— x 100
Initial Weight
If the thermal instrument is capable of presenting weight loss directly
in percent, this would be preferable. Determine values directly from
the curve as follows:
% Moisture (% Volatiles) = value at 125°C
% Solids = 100 - value at 125°C
% Ash = 100 - value at 500°C
A faster method involves two isothermal measurements, at 125°C and 500°C.
Instrument recording may be by either of the two methods above. Allow
two minutes equilibration at each isothermal temperature.
103
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2. Elemental Composition (Method A003)
Reference: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards, "Methods as
specified:
Carbon, Hydrogen
Nitrogen
Oxygen
Sulfur
Chlorine
Phosphorus
D-3178-73 (1979)
D-3179-73 (1979); E-258-67 (1977)
D-3176-74 (1979)
D-3177 (1975); D-129-64 (1978)
D-2361-66 (1978); D-808-63 (1976)
D-2745 (1969)
Aliquots of organic liquid wastes or solid wastes, or of the dried solid
(from the LOD determination) portion of aqueous wastes or sludges will
be analyzed to determine the following elements: carbon, nitrogen,
phosphorus, sulfur and halogens, i.e., iodine, chlorine, fluorine, bro-
mine. A number of service laboratories perform these analyses on a
routine basis.
3. Total Organic Carbon and Total Organic Halogens (Method A0Q4)
Reference: Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA-600/4-79-020 (March 1979). NT1S
No. PB 297686/AS.
The levels of total organic carbon and total organic halogen are measured
in much the same way as carbon and halogens were measured in Method A003.
The total organic carbon is measured by combustion of the sample to form
CO2 (with or without subsequent conversion to CH4) and measuring the C02
and CH4 formed during combustion. For organic halogens the sample is
combusted to form the halide which is trapped in solution. Potentio-
metric titration against silver will determine a total halogen concen-
tration (except for the concentration of fluorine).
This method for determination of the Total Organic Carbon and Total Or-
ganic Halogens is more useful than the elemental composition determination
where the waste sample is primarily an aqueous liquid.
4 . Viscosity (Method A005)
Reference: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Method D-445
(1979).
The viscosity of liquid wastes affects the feasibility of destroying
those wastes at a particular incineration facility. This arises in part
from 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
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
104
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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 incinera-
tion processes, is obtained by multiplication of the measured kinematic
viscosity by the density of the liquid waste.
5. Heating Value of the Waste (Method A006)
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).
The heating value of a waste corresponds to the quantity of heat released
when the waste is burned (commonly expressed in Btu/lb). Since combus-
tion 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 incoming waste up 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 destablilize molecular bonds and create reactive inter-
mediates so that the exothermic reaction with oxygen will then proceed.
The experimental determination of heating value for the waste influents
is measured by calorimetry.
D. SURVEY ANALYSIS
The survey analysis methods are designed to provide an overall descrip-
tion of the chemistry of the sample during a trial burn in terms of
(a) the major types of organic compounds and (b) 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 identifica:,tion of high priority POHCs in the wastes or in the
effluents which may be unexpected and supplements the chemical informa-
tion obtained during the directed analysis of those POHCs specified in
the facility permit.
A survey analysis approach which is compatible with the sample procedures
presented earlier and is consistent with the environmental goals des-
cribed previously is an adaptation of the Level 1 Environmental Assess-
ment procedures (6) developed by the Process Measurements Branch of the
U.S. Environmental Protection Agency as part of a phased approach to
environmental assessments. For POHCs the survey analysis methods in-
clude determination of:
« organic content by chromatographic (TCO) and gravimetric
(GRAV) procedures;
105
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• organic compound class type by infrared and probe mass
spectrometrie procedures;
o specific major organic components by gas chromatography/
mass spectrometric 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 Organics
The survey analysis methods for organic POHCs provide information for
identifying the major classes of organic compounds present in the waste,
in the facility process streams and in the stack gas. There is also
sufficient information for estimating the concentrations of those
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)
Reference: Lentzen, D.E., D.E. Wagoner, E.O. Estes and W.F. Gutknecht,
"EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment," EPA-600/7-78-201 (October 1978), NTIS No.
PB 293795/AS.
The chromatographable organics (TCO) value provides a quantitative
measure of the amount of organic material in the sample which has a
boiling point betweem 100°C and 300°C. This method is based on gas
chromatography.
A 2-5 yL aliquot of the organic extract prepared according to the pro-
cedures in methods P021 to P030 of this manual will be taken for gas
chromatographic TCO analysis. The analysis will be done using the
Level 1 GC conditions (10% OV-101 on 100/120 mesh support; 30°C (6 min)-»-
@20°C/min->-250oC (hold); FID). Normal hydrocarbons will be used for
qualitative retention time and for quantitative detector response cali-
bration. The TCO results will be reported as mg of TCO range organics
(b.p. 100-300°C) per mL of extract and also per L (kg) of waste sample
extracts. The chromatograms, which contain "fingerprint" data beyond
the TCO values will be retained.
106
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TABLE 13
SUMMARY OF RESULTS FOR ORGANIC EXTRACTS OF A SASS TRAIN SAMPLE
(mg/m3)
Particulate module
Categories
Rinses*
Aliphatic hydrocarbons
Aromatic hydrocarbons—
benzenes
Fused Aromatics, MW <216
Fused aromatics, MW >216
>3 ym
<0.06
0.25
0.25
<3 nm
0.04
0.15
0.15
Sorbent module
Resin
0.3
6.3
4.2
Rinse
0.8
22
21
Condensatet
Total*
1.1
0.6
29.
26.
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
2
2
0.1
20.
2.4
2.2
0.2
0.5
Carboxylic acids
Sulfur
Inorganics
Unclassified
Silicones
<0.6
<0.04
0.06
0.06
<0.04
0.04
0.3
0.1
0.2
0.3
0.2
0.6
0.2
0.1
0.3
0.1
*Rinses corresponded to 0.03 mg/m3 of organics and were not subjected to LC-IR-LRMS analysis.
+No condensate was collected for this sample
+Rounded results
(Source: Reference 6)
-------
Data from this analysis will be reported as:
Sample Number
TCO in Extract
mg/mL
TCO in Waste
mg/L or mg/kg
I
b_. Organic Content by GRAY: (Method A012 )
Reference: Lentzen, D.E., D.E. Wagoner, E.D. Estes and W.F. Gutknecht,
"EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment," EPA-600/7-78-201 (October 1978) NTIS No.
PB 293795/AS.
The gravimetric (GRAV) value provides a quantitative measure of the
amount of organic material in the sample which has boiling point in
excess of about 300°C.
An aliquot corresponding to one-tenth of the concentrated sample extract
will be taken for gravimetric analysis. The aliquot will be transferred
to a clean, tared aluminum weighing dish and evaporated in a dessicator
at room temperature to constant weight (+ 0.1 mg). The GRAV results
will be reported as mg of GRAV range organics (b.p. > 300°C) per mL
of extract and also per L (kg) of waste sample extracted.
108
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Data from this analysis will be reported as:
Sample Number
GRAV in Extract
mg/mL
GRAV in Waste
mg/mL or mg/kg
£. Organic Content - Volatiles: (Method A013^
Reference: Lentzen, D.E., D.E. Wagoner, E.D. Estes and W.F. Gutknecht,
"EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment," EPA-600/7-78-201 (October 1978) NTIS No.
PB 293759/AS.
This method provides an estimate of the level of volatile materials pre-
sent in the sample with bbiling points below about 100°C.
A 0.5, iiL aliquot of the carbon disulfide extract prepared according to
Methods P021b, P022b or P024c, or of the waste itself if it is an
organic liquid, will be taken for survey analysis of volatile organics
by gas chromatography with flame ionization detection. A packed column,
0.2% Carbowax 1500/Carbopack C 60/80 mesh, will be used with a tempera-
ture program of 47°C (3 min)-H3 8°C/min-*-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 will be taken for GC/MS analysis according to the procedures
presented in Method A016 below. The total FID intensity will be: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 will be reported as:
estimated volatile organic content < 10 ppm (for liquids)
and <100.ppm (for solids)
d. Compounds Class Type by Infrared Analysis (Method A014)
Reference: Lentzen, D.E. D.E. Wagoner, E.D. Estes and W.F. Gutkneckt,
"EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment," EPA-600/7-78-201 (October 1978). NTIS No.
PB 293795/AS.
109
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The infrared analysis provides information on the functional groups pre-
sent in the samples. The identified functional groups provide a description
of the chemistry of the sample.
An aliquot corresponding to 2-5 mg of total organic content of the sample
extract (Methods A011, P021-PO3O)or neat organic liquid waste will be analyzed
by infrared (IR) spectrometry. IR spectra will be obtained on samples held
between two NaCl plates or on KBr pellets. Sample size will be adjusted so
that the signal of the strongest sample peak is less than 1.0 absorbance
unit. IR instrument conditions which will be used for most samples are
given below; variations, if necessary, will be documented.
Dispersive instrument;
1. Resolution: The spectral split width should not exceed 4 cm thtough
at least 80 percent of the wave number range.
2. Wave number accuracy: ±4cm ^ below 2,000 cm ^ and ± 15 cm ^ above
2,000 cm"1.
3. Noise level: No more than 2 percent peak to peak.
4. Baseline flatness: the I. or 100% line must be flat to within
5 percent across the recorded spectrum.
5. Energy: The instrument should be purged with dry gas or evacuated so
that atmosphere water bands do not exceed the allowable noise level
(2 percent) when the instrument is used in a double beam mode.
6. Spectral range: Spectra should be recorded, without gaps,.over the
spectral range 3,800-600 cm~l.
7. False radiation: Not to exceed 2 percent.
Fourier Transform Instrument:
The instrument conditions will be generally designed to meet the criteria
stated above for dispersive instruments. FT-IR analysis will accumulate
64 scans average or the number necessary to achieve a signal-to-noise
ratio on the order of 0.5% T average. All spectra in a related sample
set will be acquired using the same apodization function to allow spectral
subtraction. FT-IR spectra will be 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. This
data is combined with the mass spectral data (Methods A015 and A016) to
characterize the sample in terms of the major chemical classes present.
110
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Contractor
Sample ID Number_
Sample Description^
TABLE 14
1R ANALYSIS REPORT FORM
Analyst Responsible _Date Analyzed Time
Instrument_ ¦ Sample Cell Type_
Observations
Results
Frequencies on which
Major Functional Groups Assignments are Based
111
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e_. Mass Sepctrometric Analysis (Method A015)
Reference: Lentzen, D.E., D.E. Wagoner, E.D. Estes and W.F. Gutknecht,
"EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment," EPA-600/7-78-201 (October 1978) NTIS No.
PB 293795/AS.
The low resolution mass spectrometric (LEMS) analysis provides specific
compound identifications (non-isomer specific) which may be integrated
with other survey analysis information to identify the chemical classes
which are present in terms of the major chemical classes present.
A 100 yL sample of the organic extract (Method P021 to P030) or neat
waste sample will be dried down to room temperature on the direct in-
sertion probe of the mass spectrometer. Spectra will be acquired over
a probe temperature range of 50°C to 400°C.
The ionization mode used for the direct LRMS analysis will be 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 ioni-
zation (17). In the EI mode, an ionization voltage of 70 eV will be
used to obtain spectra for comparison with standard reference spectra
ionization. Voltages of 8-20 eV will be used to obtain spectra with
reduced fragmentation. A mass spectrometer capable of attaining a true
resolution of 1 part in 600 minimum will be used to ensure that it is
possible to identify heteroelement compositions.
Spectra will be interpreted according to the procedures described by
Stauffer (18). The results will be 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 neces-
sary to incorporate multifunctional organics and other specific categories
of interest. For each category, the molecular weight range will be
specified. The relative abundance of each category will be indicated
on a three point logarithmic scale.
100 = major component
10 = minor component
1 = trace component
Specific notation will be made of any compound categories which make
their first appearance at elevated probe temperature (> 200°C) since
these low volatility materials are less likely to be detected in the
complementary GC/MS analysis. An estimate will be 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.
112
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CATEGORIES
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)
TABLE 15
FOR REPORTING 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
-------
TABLE 16
LRMS ANALYSIS REPORT FORM
Contractor ,
Sample ID Number . •
Sample Description __ i__
Analyst Responsible Date Analyzed Time
Ins t rument '
Observations ¦
Results
Major Categories, Subcategories, Specific Compounds:
Intensity
Category
MV Range
114
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fj Specific Major Components by GC/MS (Method A016)
In addition to being the primary analytical tool for the directed analy-
sis 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 (from Method P031) with or without
additional clean up procedures (Method P041 to P045) of the semivolatile
fraction of the sample is spiked with a retention time standard such as
dlO-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% 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 would be reported as a list of specific
compounds identified, the relative retention time (vs. 10-phenanthrene)
and relative intensity of the peak, and an indication of the goodness
of fit. The latter will be 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=tenta-
tive for a manual identification or confirmation. Table 17 shows an
example report form.
_g. 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 2 20:1) and/or to
contain organic compound categories not amenable to gas chromatography
will be analyzed by HPLC in a survey mode. A reverse phase Cig HPLC
column will be used with an acetonitrile/water or methanol/water system.
Fractions of the eluent corresponding to the ten most intense peaks as
recorded by a 254 nm UV detector will be collected and analyzed by IR
(Method A014) or probe LRMS (Method A015) after evaporation of solvent.
The results of this analysis will be reported as a list of specific com-
pounds, functional groups and/or compound classes identified in the
HPLC fractions. An indication of the confidence of the assignment(s)
will be provided by the designations "M=strong" or "M=tentative" for
manual identification or confirmation. Table 18 shows an example report
form.
2. Survey Analysis of Metals (Method A021)
Reference: U.S. Environmental Protection Agency, Federal Register,
44, 69559-69564 (December 3, 1979).
115
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TABLE 17
GC/MS SURVEY REPORT FORM
Contractor
Sample ID Number
Sample Description
Analyst Responsible Date Analyzed Time_
Ins trument ;
Co lumn '
GC Temperature Program
Observations
Results:
Compound
Identified
Peak
RRT, Rel Intensity
min %
Goodness of
Fit Criterion
116
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TABLE 18
HPLC/IR OR HPLC/LRMS SURVEY REPORT FORM
Contractor
Sample ID Number
Sample Description
Analyst Responsible Date Analyzed Time
HPLC Column Detector Sensitivity
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
117
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A survey analysis will be conducted to determine the possible presence
in the waste of ppm levels of the metals listed in Table 19. The list
given in Table 19 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;
the others will be 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) will be taken for survey analysis
by ICAP. Separate portions will be taken for the AAS determinations of
antimony, arsenic, lead, mercury, and selenium. Samples will be digested,
using the procedures indicated in Method P032, prior to analysis. The
AAS analyses of disgested samples will be performed as described in
Methods A221 to A235 of this manual.
The results of the survey analysis for metals will be 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 will be on the order
of 10-100 ppm in the waste for this survey analysis. Accuracy, precision
and recovery data will not generally be 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 Section 261 of
RCRA have been sorted into groups, whose members share a common analy-
tical 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 POHC compounds in this way, the costs incurred
during the directed analysis activities may be minimized.
Whenever possible 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 the generally
good quantification ability of these systems. For those instances where
GC/MS is not appropriate, HPLC methods have been designated whenever
possible.
Appendix C provides cross reference information for each listed POHC
and its method number.
118
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TABLE 19
METALS
SOUGHT IN SURVEY
ANALYSIS
OF WASTE
Metal
Drinking
Water
Standard
Priority
Pollutant
Method
Name Number
Alternative Metl
Name Number
Aluminum
ICAP
A021
Antimony
V
AAS
A221
Arsenic
/
/
AAS
A222
Barium
/
ICAP
A021
AAS
A223
Beryllium
~
ICAP
A021
AAS
A224
Boron
ICAP
A021
Cadmium
~
~
ICAP
A021
AAS
A225
Calcium
ICAP
A021
Cobalt
ICAP
A021
Chromium
/
/
ICAP
A021
AAS
A226
Copper
/(2°)
/
ICAP
A021
Iron
/ (2°)
ICAP
A021
Lead
/
/
ICAP
A021
AAS
A227
Magnesium
ICAP
A021
Manganese
/ (2°)
ICAP
A021
Mercury
/
/
AAS
A228
Molybdenum
ICAP
A021
Nickel
/
ICAP
A021
AAS
A229
Osmium
ICAP
AO 21
AAS
A230
Phosphorus
ICAP
A021
Potassium
ICAP
A021
Selenium
/
/
AAS
A231
Silicon
ICAP
A021
Silver
/
/
ICAP
A021
AAS
A232
Sodium
ICAP
A021
Strontium
ICAP
A021
AAS
A233
Thallium
/
ICAP
A021
AAS
A234
Thorium
ICAP
A021
Titanium
ICAP
A021
Vanadium
ICAP
A021
AAS
A235
Zinc
~ (2°)
/
ICAP
A021
Zirconium
ICAP
A021
119
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1. Organic Appendix VIII Constituents
a . Volatiles (Method A101)
The analysis method for volatile organic POHCs is that specified in SW-846
(3) and EPA Method 624 (18). This method utilizes a purge-and-trap pro-
cedure to remove the volatile organics from the sample matrix and col-
lect the volatiles on a sorbent cartridge for subsequent work. The
collected sample is then thermally desorbed from this 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 and an analysis like that for purge-and-trap follows. The analy-
tical finish specified in this method is also suitable for direct appli-
cation 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 (3) or EPA Method 625 (18) 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 capillary GC column.
The method for this set of POHC compound is outlined as follows:
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 hy-
drogen (preferred) or helium as the carrier gas. Electron impact ioniza-
tion at 70eV is utilized to produce mass spectra. Alternatively, CI
conditions may be used to produce mass spectra, although the significant
ions for POHC identification are different than for EI ionization. The
qualitative and quantitative criteria for identifying and measuring the
POHCs in this category are found later in this chapter. The ions and
their abundance ratios for qualitative purposes are found in Appendix E.
120
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c. Specific Compounds by HPLC (Mthods A122, A123)
HPLC analysis procedures (19) were developed by Southern Research Insti-
tute for several organic compounds listed in Appendix VIII (40 CFR Part
261) that could not be determined by gas chromatography with mass spectro-
metry (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 Ci8 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 ym particle size, 25 cm x
2.6 mm ID.
« Waters Associates pBondapack Cl8, 10 vim particle size, 30
cm x 3.9 mm ID.
(The Waters column was employed only after it was- found that certain
compounds did not chromatograph well on the Perkin Elmer column.)
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. Severalisocratic and gradient elution
programs with an acetonitrile/water mobile phase have been 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 have been developed. Three were formulated for a
Perkin-Elmer reversed-phase Cig column, and three for a Waters reversed-
phase Ci8 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:
a 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
121
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• Option IB
Solvent A: 1% (v/v) acetic acid in distilled, deionized
water
Solvent B: Acetonitrile
Solvent program: 20% B, lOmin; 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
is listed for each compound.
d. Aldehydes and Acids (Methods A132, A133)
Aldehydes and acids have been grouped together due to their chemical
similarity.
122
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TABLE 20
SUMMARY OF DETERMINATIONS OF POHCs
BY THE GENERALIZED HPLC ANALYSIS METHOD
On-Column Wavelength
Procedural Retention Detection of Detection,
Compound Option3 Time, Min. Limit,^ ng nm
Streptozotociji 1A 1.4 2 254
230C
6-Amino-l,la,2,8,8a,8b-
hexahydro-8-(hydroxy-
methyl)-8a-methoxy-5-
methylcarbamate azirino[2', 1A 5 17 254
3',:3,4] pyrrolo [1,1-a]
indole-4,7-dione (ester)
(Mitomycin C)
Phenol 1A 5.4 78 254
- 280°
4-Nitrophenol 1A 9.5 54 254
6 280C
2-Chlorophenol 1A 12.4 72 254
6 280°
Melphalan 1A 14 10 254
5-Nitro-o-toluidine 1A 14.3 1 254
253°
Thiuram 1A 16.3 1 254
- 280C
Chloro-m-crespl 1A 16.8 77 254
4 280C
2,4-Dichlorophenol 1A 17.6 100 254
2 280°
3-(alpha-Acetonylbenzyl)- 1A 19.8 2 254
4-hydroxycoumarin and - 280°
salts [Warfarin]
2,4,6-Trichlorophenol 1A 20.0 53 254
7 280°
2,3,4,6-Tetrachlorophenol 1A 21.5 19 254
17 280
Reserpine 1A 22.7 28 254
267°
!23
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TABLE 20 (Continued)
SUMMARY OF DETERMINATION OF POHCs
BY THE GENERALIZED HPLC ANALYSIS METHOD
Procedural
Compound Option'
Chlorambucil 1A
2,4-Dichlorophenoxy- IB
acetic acid
Daunomycin^ IB
2,4,5-Trichlorophenoxy- IB
acetic acid
2,4,5-Trichlorophenoxy- IB
propionic acid
4,6-Dinitro-£-cresol and salts 1C
Azaserine^ 2A
N-Nitroso-N-methylurea 2A
Saccharin and salts 2B
Trypan blue^ 2C
Epinephrine 2C
Thiosemicarbazide^ 2C
Thiourea*1 2C
Thioacetamide^ 2C
Ethylene thiourea*1 2C
Crotonaldehyde^ 2C
Diethylstilbestrol^ 2C
a
Retention
Time, Min.
23.9
7.6
8
14.2
16.5
7.6
4
8.4
3.2
3
3
3
=3C
-4C
=4C
5
14
On-Column
Detection
Limit,^ ng
1
69
75
55
38
20
2
10
Wavelength
of Detection,
nm
20
60
5
6
2
8
1
4
254
25 8C
254
284C
254
254
287c
254
287C
378°
254
254
234C
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.
cThis wavelength was selected from the reference UV spectrum as the optimum
wavelength for analysis.
^Potential candidates for analysis by HPLC/UV.
Source: Reference 19.
124
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Aldehydes are sufficiently polar that they exhibit poor chromatography
unless they are first derivatized. This is reflected in the sampling
procedure for aldehydes which uses a derivatizing reagent (2,4-dinitro-
phenylhydrazine) 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 chromatog-
raphy 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 used is polar. Packed columns coated with polyethyleneglycol
phases have been used for these analyses. The most promising GC column
packing material for alcohols is a Carbopak C coated with 0.8% tetra-
hydroxyethyleneamine. If capillary GC is used, a Carbowax 20M column
is sufficiently polar to allow analysis of alcohols. If, however, the
sample contains significant quantities of water then a SE-52 capillary
column should be used. Either MS or FID detection may be used for these
compounds.
_f. Inorganic-containing POHCs
In this manual, the analytical methods for the inorganic^containing
organic materials aire 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 preceeding groups. . The analysis methods
for these constituents tend to be single compound methods. The com-
pounds 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 methods 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 needs to be conducted only in those
rare instances when professional judgment suggests their probable
presence in the waste to be incinerated.
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2. Inorganic Appendix VIII Constituents
The inorganic constituents which may be analyzed during a directed analysis
may be 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 organometallics
which all contain mercury, or a series of thallium salts or a series of
cyanide containing salts will be 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, since it
focuses on the environmentally active components of the waste, will yield '
the most accurate assessment of the inorganic emissions of the incinera-
tor facility.
a. Metals (Methods A221-A235)
All the Appendix VIII metals will be analyzed by either atomic absorp-
tion 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 analysis mode depends upon the specific metal of interest in
the directed analysis. The specific analytical methods are well docu-
mented in SW-846 (3), and elsewhere. The following discussion summarizes
the general details concerning the AAS and ICAP analyses of these samples.
Specific details for each element are found in the method descriptors
and their included references (Methods A221 to A235).
All of the inorganic containing samples are prepared for directed analy-
sis by one of the digestion procedures discussed in the previous chapter.
These procedures convert all of the metal containing compounds into an
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 analy-
sis. Within either 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 triva-
lent compound to the volatile hydride. The hydride is then detected by
AAS methods.
126
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For mercury, the solution resulting from the 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 Hazardous Constituents list 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 described in numerous
references (e.g., SW-846).
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 instru-
ment. 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 in-
cinerators, 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 absorbance 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 Appendix VIII of Subpart C
or RCRA are hazardous due primarily to the anionic portion of the com-
pound. These compounds, which contain either cyanide or phosphide, will
be analyzed by a single method for that anion. A general procedure for
the determination of anions in solution emplpys ion chromatography as an
analytical technique (20).
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 analyzed for total cyanide by
titration with silver (for concentrations exceeding 1 mg/L of cyanide)
or by a colorimetric procedure for lower levels of cyanide. Due to
the toxicity of HCN, all of the sample preparation steps for total cyanide
measurement need to be performed in a closed system placed in a well
ventilated hood.
127
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TABLE 21
CHARACTERISTIC DATA FOR METALS LISTED IN APPENDIX VIII
Wavelength (nm)
Metal (Element Symbol)
AA
I CAP
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
128
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The phosphide-containing inorganic species may be analyzed by the re-
action of the sample with either acid or water to form phosphine. For
the directed analysis of phosphide, the sample will be placed in a
sealed volumetric gas flask which has been flushed with high purity
N?; dilute mineral acid (.01N HNCL) 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.N„. After the sample equilibrates, an amount of ^ 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 have, for the most part, standard methods
available to define the operational conditions for their analysis. These
standard methods are all based on GC with either selective detectors such
as the alkali flame ionization detector (AFID), the flame photometric
detector (FPD), or the electron capture detector (ECD) or a nonspecific
detector such as the thermal conductivity detector (TCD). An advantage
to the use of 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 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 due to their selectivity. As
the selectivity of the detector increases, the separation requirements
of the GC and the preliminary clean up 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.
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3j 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 (3) or Federal Register Methods 624 and 625 (18).
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 identifica-
tion and quantitative measurement of POHC compounds.
a. Instrumental Operating Parameters
The primary analytical tool for the measurement of hazardous waste
incinerator process streams is 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 will be 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 will be
sufficiently broad to encompass the major ions, as listed in Appendix
E of this document, for each of the potential POHCs in a waste character-
ization analysis or each of the designated POHCs in a trial burn incin-
erator effluent analysis.
For most purposes, electron impact (EI) spectra will be 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 will be used to elucidate molecular
weight information and simplify the fragmentation patterns of some com-
pounds. In no case, however, should CI spectra alone be used for com-
pound identification.
Although the permitting process specifies the high priority POHCs which
must be measured at any hazardous waste incinerator facility, incomplete
characterization of the incinerator influents may result in unexpected
occurance of additional species in the effluent streams which need to be
dealt with. Hence, the more general EI mode of ionization is to be
preferred.
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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 will be
on the order of one second." Longer cycle times may lead to distortion
of the spectra. To adequately characterize a GC peak, at least five
spectra will be collected across the peak. For low level components in
the extract, the elution peak may be less than 3 sec wide and it might
not be possible to collect enough scans to characterize the GC peak, if
the scan repetition rate were greater than 1 sec.
To insure consistency with sources of mass spectra, the GC instrumentation
will be tuned to meet the spectral criteria for decafluorotriphenylphosphine
(when using analysis methods AOlla, Alll, A121 or other fused silica glass
capillary column methods) or bromofluorobenzene (when using analysis 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 and summarized in Table 22 and 23.
When a method specifies analysis by HPLC, the HPLC system will consist of
several components; reservoir(s) for the elution solvent(s) which may or
may not include a gradient device, pumps, injection port, columns, de-
tection and readout devices and thermostats for both the column and
detector being used. 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 fluores-
cence emission at a single wavelength. These detectors are, in general,
nonspecific and consequently, multiple analyses are required to provide
accurate identity assignments.
bj Qualitative Identification
The identification of organic POHCs is based both on the chromatographic
elution of those compounds and on the specificity of the detection system
i.e., MS for GC/MS, 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%, 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.
131
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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
f All values in percent abundance relative to mass 198, unless
otherwise stated.
132
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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 of mass 174
176 70 to 90**
177 5 to 9
All values in percent abundance relative to mass 95 unless otherwise stated.
Abundance at mass 176 should be about 98% of that at mass 174.
133
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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 POHCs which may be present due to unexpected reactions,
incomplete combustion, etc. 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 the GC retention time for the suspect peak relative to
some standard match that for the corresponding POHC and that the charac-
teristic 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 either electron
impact or chemical ionization.
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 will be performed primarily by comparison with
libraries of mass spectra, using both computerized and, if necessary,
manual data base search routines. These tentative identifications will
be supplemented by chromatographic retention data as appropriate. The
following discusses the use of computer searches for POHC identification.
A key factor in the use of computerized mass spectral search systems is
the data base. Ideally, the data base would Include spectra of all of
the potential compounds of interest and would have been obtained under
the same conditions for the GC and the MS as for the incinerator process
samples. As a practical alternative, the NBS data base will be 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 a qualita-
tive 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.
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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 would be appropriate to base qualitative compound identifi-
cations of POHCs on the purity value. For purity values in excess of 900
on the 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 are identified with purity values that are close to one
another, the analyst should retrieve and examine the library spectra and
use the elution order data to ascertain the best candidate for the identi-
ty of the GC peak of interest. Similarly, if the purity value has de-
creased 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.
The algorithms for calculating "goodness of fit" parameters and the numeri-
cal values that are associated with specific levels of confidence in the
identification will 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 ap-
plied 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 for use with HPLC, POHC
identification must be made using multiple LC columns whose relative
retention behavior is significantly different. The sample is analyzed
on the two columns and the retention of the suspect peak is compared to
that of the 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, will serve to confirm
the multicolumn identification.
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£. Quantitative Measurement
Following the qualitative identification of POHCs in either the influent
or effluent streams from a hazardous waste incinerator 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% for each of the priority POHCs. For other species
which are identified in the samples, the measurement can be used, if
necessary, to identify any unexpected environmental hazards. Measure-
ments will be based either on direct calibration using authentic stan-
dards 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 inter-
est which span the linear working range of the analytical instrumenta-
tion being used. Each of these standards is analyzed using the same
conditions as would be used for the actual samples. The response-concen-
tration data pairs are combined into a calibration curve by regression
methods. The level of the compound in the sample is determined by inter-
polation within the calibration curve. This method is routinely used
for GC/MS and HPLC analysis.
For samples analyzed by GC/MS, stable labelled isotope spikes may be
used for quantification. The use of stable labelled isotope spikes
has a number of advantages. A stable labelled isotope compound which
is added to the sample prior to any clean up steps will exhibit essen-
tially the same characteristics as the nonlabelled compound when taken
through the various processing steps involved in the sample work up
and analysis. As in other calibration methods it is necessary to pre-
pare 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, etc.,
and indirect methods may be necessary in some cases. The most common of
the indirect methods is to use the response characteristics of a chemical-
ly similar compound to estimate the level of the target constituent of
interest (3). 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 will be of increasing accuracy as the chemical structure of the
reference compound approaches that of the compound of interest. This
136
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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 difference in MS response
characteristics (21, 22). 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 CFR 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).
137
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Method Number:
C001
Method Name:
Ignitability
Basic Method:
Flash Point Determination
Matrices:
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 CFR 173.300, or
The waste will be identified as an oxidizer as defined in
49 CFR 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.
138
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Method Number: C002
Corrosivity
pH Determination
Corrosivity towards steel
Aqueous Liquids
Organic Liquids
Sludges
Solids
pH Determination - pH Meter
Corrosivity toward steel - SAE Type 1020 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 the proper time
frame (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.
Method Name:
Basic Method:
Matrices:
Apparatus::
139
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Method Number:
C003
Method Name:
Reactivity
Basic Method:
Professional judgment
Matrices:
Aqueous Liquids
Organic Liquids
Sludges
Solids
Analysis Method Parameters:
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 mildy
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 classi-
fication.
Reactivity will be determined by applying best professional judgment
to the available data. There are no explicit experimental test pro-
cedures for determining 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.
140
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Method Number: C004
Method Name: Extraction Procedure Toxicity
Basic Method: Extraction followed by analysis of the extract by
GC/ECD, ICAP, AAS
Matrices:
Apparatus:
Solids
Liquids (aqueous and organic)
Sludges
Filtration Apparatus
Structural Integrity Tester
Extraction Apparatus - Stirrer or Tumbler
GC/ECD - organic analysis
ICAP Spectrophotometer - inorganic analysis
AAS Spectrophotometer - inorganic analysis
Analysis Method Parameters:
The solid waste sample will be extracted for 24 hr with aqueous
acetic acid at pH = 5
The extract will then be analyzed for pesticides and herbicides
in the leachate by GC/ECD on Suplecoport 100/200 Mesh, coated
with 3% OV-1, 180 cm x 4 mm ID 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:
Compound
Method
Method
Arsenic
AAS
A222
Barium
ICAP/AAS
A223
Cadmium
ICAP/AAS
A225
Chromium
ICAP/AAS
A226
Lead
AAS
A227
Mercury
AAS
A228
Selenium
AAS
A231
Silver
ICAP/AAS
A232
141
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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.
142
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Method Number:
A001a,b
Method Name:
Moisture, Solid and Ash Content - Macroscale Technique
Sample Drying & Ignition
Basic Method:
Matrices:
Liquids (aqueous and organic)
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.
Detection Limits:
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.
PB 297686/AS.
143
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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:
A sample of _< 50 mg is placed in the sample boat of the TGA and
heated in air atmosphere by either of two methods: 1) at a pro-
grammed rate of 10°C/minute to 500°C or 2) two isothermal measure-
ments at 125°C and 500°C, allowing two minutes equilibration at
each isothermal temperature. Data can be reported by 1) a plot
of weight (mg.) vs. temperature, °C or 2) a plot of percent lost
vs temperature, 5C~.
Detection Limits:
1-10 ppm
References: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Method
D-1888-78, Part 31 (1979).
144
-------
Method Number:
Method Name:
Basic Method:
Matrices:
Apparatus:
A003
Elemental Composition - Organic
Elemental Analysis
Aqueous Liquids
Organic Liquids
Sludges
Solids
Varied
Analysis Method Parameters:
Reference
Measurement
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)
CO2 & H^O on combustion
Carbon
Nitrogen
Oxygen
Phosphorus
Sulfur
Chlorine
Detection Limit:
0.1% by weight
Reference: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Standards," Methods
as specified above.
N^ by Kjeldahl
Difference method
Spectroscopic method
Sulfate titration
Halide titration
145
-------
Method Number:
A004
Total Organic Carbon
Total Organic Halogen
Combustion
Aqueous Liquids
TOC analyzer, TOX Analyzer
Analysis Method Parameters:
Carbon: An aliquot of the sample will be analyzed by a TOC
analyzer by measuring the CO^ and CH^ 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:
0.1%
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. PB 297686/AS.
Method Name:
Basic Method:
Matrices:
Apparatus:
146
-------
Method Number:
A005
Method Name:
Viscosity
Basic Method
Flow Measurement
Matrices
Aqueous Liquids
Organic Liquids
Apparatus:
Kinematic Viscometer; Thermometer
Analysis Method Parameters:
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 (series of viscometers needed to cover
this range).
Reference: American Society for Testing and Materials, Philadelphia,
Pennsylvania, "Annual Book of ASTM Methods," Method
D-445 (1979).
147
-------
Method Number:
A006
Method Name:
Heating Value of Waste
Basic Method:
Combustion
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 condi-
tions (ASTM D-3286)
Analysis Method Parameters:
Calorific value is computed from temperature observations made
before, during, and after combustion of a weighed sample. Proper
allowance is made for heat contributed by other processes.
References: American Society for Testing and Materials, Philadelphia,
Pennsylvania. "Annual Book of ASTM Standards," Method
D-2015t77 (1978) and Method D-3286-77 (1977).
148
-------
Method Number:
A101
Volatiles
GC/MS - Purge and Trap
Aqueous Liquids
Organic Liquids (neat or diluted)
Sludges
Solids
Specific POHC 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-chloropropane
1,2-Dibromoethane
Dibromomethane
Dichlorobenzene (meta, ortho and para isomers)
Dichlorobenzene, N.O.S.
1,4-Dichloro-2-butene
Dichlorodifluoromethane
1.1-Dichloroethane
1.2-Dichloroethane
trans-1,2-Dichloroethene
Dichloroethylene, N.O.S.
1.1-Dichloroethylene
Dichloromethane
Dichloropropane, N.O.S.
1.2-Dichloropropane
Dichloropropene, N.O.S.
1.3-Dichloropropene
Method Name:
Basic Method:
Matrices:
149
-------
1,4-Dioxane
Formic acid
Halomethane, N.O.S.
Hexachloroethane
Hexachloropropene
Hydrazine
Iodomethane
Isocvanic acid, methvl 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 i
Tribromomethane
1.1.1-Tr ichloroe thane
1.1.2-Trichloroethane
Trichloroethene
Tr ichloromono fluor ome 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: 25 cm Trap containing 1/3 activated charcoal,
1/3 silica gel and 1/3 Tenax
Purge a 5 iL sample at 40 mL/min with helium or
nitrogen for 12 min
Desorb with backflushing at 180°C with 40 mL inert
gas onto GC for 4 min then start the GC/MS analysis.
GC: Column - 6 ft 0.2% Carbowax 1500 or Carbopack C 60/80
mesh
Carrier Gas - Helium at 50 mL/min
Injector at 160°C
Temperature Program - 30°C for 7 min isothermal
(starting at start of purge) After 7 min, 30-160°
at 8°C/min, 160°C for 15 min isothermal.
150
-------
MS:
Mass Range - 20-260 amu
Scan Rate - 2 sec/scan
Ionizaton - EI, 70 eV
Detection Limits:
10-100 pg/L
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).
151
-------
Method Number: AlOla
Method Name:
Volatiles
Basic Method
Purge and Trap
Matrix:
Aqueous Liquids
Purging Method Parameters:
Transfer a 5 mL portion of the aqueous sample into the purging
device and purge with helium for 12 minutes at 40 mL/mlnute.
Reference: U.S. Environmental Protection Agency, Federal Register, 44.
69464-69575 (December 3, 1979).
152
-------
Method Number:
AlOlb
Method Name:
Volatiles
Basic Method:
Purge and Trap
Matrix:
Sludges (including gelsi and slurries)
Purging Method Parameters:
Dilute an aliquot of a sludge sample to 0.5% solids with reagent
grade water. A 5 mL portion of this diluted mixture will then be
transferred to this purging device and purged for 12 minutes with
helium at 40 mL/min. If the sludge sample is not readily dis-
persible,'"polyethylene glycol (MW 400) will be used to dilute the
sample.
References: Miller, H.C., R.H. James and W.R. Dickson, "Evaluated
Methodology for the Analysis of Residual Wastes," Report
priepared 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).
153
-------
Method Number
AlOlc
Method Name
Volatiles
Basic Method
Purge and Trap
Matrix
Solids
Purging Method Parameters:
Dilute an aliquot of the solid sample 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 minutes with
helium at 40 mL/minute. If the solid sample is not readily dis-
persible in water, polyethylene glycol (MS 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).
154
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Method Number:
A121
Method Name: Extractables
Basic Method: GC/MS
Matrices: Sample extracts
Organic Liquids (neat or diluted)
Specific POHC 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 benzenes, 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
155
-------
Chyrsene
*Coal Tars
Creosote
t*Cresols
*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
Di-n-butyl phthalate
Dichlorobenzene (meta, ortho and para isomers)
Dichlorobenzene, N.O.S.
3,3'-Dichlorobenzidine
*2,4-Dichlorophenol
2,6-Dichlorop henol
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-Dime thylphene thylamine
*2,4-Dimethylphenol
Dimethyl phthalate
Dimethyl sulfate
Dinitrobenzene, N.O.S.
*4,6-Dinitrc-o-cresol and salts
*2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Diphenylamine
1,2-Diphenylhydrazine
*Di-n-propylnitrosamine
156
-------
*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
Hexachlorobutadietie
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
*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
Methyl isobutyl ketone
*2-Methyllactonitrile
*Methyl methacrylate
*Methyl methanesulfonate
*N-Methyl-N'-nitro-N-ni trosoguanidine
*Methyl parathion
*Methylthiouracil
Naphthalene
1,4-Naphthoquinone
tl-Naphthylamine
*2-Naphthylamine
tNicotine and salts
p-Nitroaniline
Nitrobenzene
157
-------
*Nitroglycerine
t4-Nitrophenol
*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-Ni troso-N-me thylurethane
*N-Ni tro some thylvinylamine
*N-Nitrosomorpholine
*N-Nitrosonornicotine
*N-N itrosopiperidine
N-Nitrosopyrrolidine
*N-Nitrososarcosine
*Octamethylpyrophosphoramide
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-((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)
t*2,3,4,6-Tetrachlorophenol
*Tetraethyldithiopyrophosphate
*Tetraethylpyrophosphate
Toluenediamine
Toluene diisocyanate
Toxaphene
+1,2,4-Trichlorobenzene
*Trichloromethanethiol
+2,4,5-Trichlorophenol
*t2,4,6-Trichlorophenol
158
-------
*0,0,0-Triethyl phosphorothioate
*sym-Trinitrobenzene
*Tris(2,3-dibromopropyl) phosphate
Apparatus: Finnigan 4000 GC/MS/DS or.equivalent
Analysis Method Parameters:
GC: Column - Fused-silica capillary, 25 m
0.31 mm, wall-coated with SE-£4
Carrier gas - He, - 2 mL/min
Temperature program - 40 to 280°C at 10°C/min;
280°C, 15 min isothermal
Injector temperature - 250°C
Injector type - Splitless
MS: Mass Range - 41 to 450 amu
Scan Rate - _<1 s/scan
Ionization - EI, 70 eV
Detection Limits:
5-20 ng of each compound injected on column (50 ng for mixtures
like PCBs)
or
3 3
1-4 yg/m in a 5 m stack gas sample
0.25-1 yg/g in 20 g 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).
*The compounds marked (*) are not referenced in EPA Method 625 (18), but
are additional compounds from Appendix VIII to which this method is ex-
pected to apply.
159
-------
tThe 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 sol-
vent. 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.
160
-------
Method Number:
A122
Method Namei HPLC/UV Generalized Procedure (three options)
Basic Method: HPLC/UV
Matrix: Aqueous or acetonitrile sample extracts
Apparatus: HPLC/UV
Specific POHC to which method (Option 1A) may be applied:
3-(alpha-Acetonylbenzyl)-4-hydroxycoumarin and salts
[Warfarin]
6-Amino-l,la,2,8,8a,8b-hexahydro-8-(hydroxymethyl)-8a-
methoxy-5-methylcarbamate azirino[2',3':3,4]pyrrolo
[l,l-a]indole-4,7-dione(ester) (Mitomycin C)
Chloroambucil
tp-Chloro-m-cresol
+2-Chlorophenol
+2,4-Dichlorophenol
t*2,6-Dichlorophenol
t*2,4-Dinitrophenol
Melphalan
*Methomyl
+4-Nitrophenol
5-Nitro-o-toluidine
Phenol
Reserpine
Streptozotocin
t2,3,4,6-Tetrachlorophenol
Thiuram
t*2,4,5-Trichlorophenol
t2,4,6-Trichlorophenol
Analysis Method Procedure (Option 1A):
HPLC Column - Perkin Elmer HC-ODS-Sil-X-1 or equivalent).
Reverse Phase column, 10-ym particle size, 25 cm x
2.6 mm ID
Column temperature - 30°C
Solvent A - Distilled, deionized water
Solvent B - Acetonitrile
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
161
-------
UV: At 254 nm (greater sensitivity can be achieved if
compound-specific maximum wavelengths are used**
Table 20).
Specific POHC to which method (Option 2A) may be applied:
Daunomycin
2,4-Dichlorophenoxyacetic acid
2,4,5-Trichlorophenoxyacetic acid
?., 4,5-Trichlorophenoxypropionic acid
Analysis Method Procedure (Option 2A):
HPLC Column - (Perkin Elmer HC-ODS-Sil-X-1 or equivalent).
Reverse Phase column, 10-ym particle size, 25 cm x
2.6 mm ID
Column Temperature - 30°C
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
UV: At 254 nm (greater sensitivity can be achieved if
compound-specific maximum wavelengths are used-
Table 20).
Specific POHC to which method (Option 3A) may be applied:
4,6-Dinitro-jo-cresol and salts
Analysis Method Procedure (Option 3A):
HPLC: Column - (Perkin Elmer HC-ODS-Sil-X-1 or equivalent).
Reverse Phase column, 10-ym particle size, 25 cm x
2.6 mm ID
Column temperature - 30°C
Solvent A - 1% (v/v) acetic acid in distilled, de-
ionized water
Solvent B - Acetonitrile
Solvent Program: 10% B, 2 min; 10 to 100% B in 18 min
162
-------
Solvent Flow Rate: 2 mL/min
UV At 254 nm (greater sensitivity can be achieved if
compound-specific maximum wavelengths are used-
Table 20).
Reference: Dillon, H.K., R.H. James, H.C. Miller and A.K. Wensky (Battelle
Columbus Laboratories, Columbus, 0hio),"P0HC Sampling and
Analysis Methods," Report prepared by Southern Research
Institute, Birmingham, Alabama for U.S. Environmental Pro-
tection Agency/Industrial Environmental Research Laboratory,
Research Triangle Park, North Carolina under Contract No.
68-02-2685 (December 1981).
*The compounds marked (*) are additiona constituents from Appendix VIII
to which this method is expected to apply.
+The compound marked (t) can also be determined by the GC/MS techniques
in Method A121.
163
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Method Number: A123
Method Name: HPLC/UV Generalized Procedure (three options)
Basic Method: HPLC/UV
Matrix: Aqueous or acetonitrile sample extracts
Apparatus: HPLC/UV
Specific POHC to which method (Option 2A) may be applied:
*Azaserine
N-Nitroso-N-methylurea
Analysis Method Procedure (Otpion 2A):
HPLC: Column - yBondpak C^g (Waters Associates)
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
Table 20).
Specific POHC to which method (Option 2B) may be applied:
Saccharin and salts
Analysis Method Procedure (Option 2B)
HPLC: Column - (Waters Associates yBondpak C^g or
equivalent). Reverse Phase column, 10 ym particle
size, 30 cm x 3.9 mm ID
Column temperature - 30°C
Solvent A - Distilled, deionized water
Solvent B - Acetonitrile
Solvent Program: 10% B, isocratic
164
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Solvent Flow Rate: 1 mL/min
UVj At 254 nm (greater sensitivity can be achieved if
compound-specific maximum wavelengths are used-
Table 20).
Specific P0HC to which method (Option 2C) may be applied:
*l-Acetyl-2-thiourea
*1"(o-Chlorophenyl)thiourea
Crotonaldehyde
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 Procedure (Option 2C);
HPLC; Column yBondpak C^g (Waters Associates)
Solvent Program; 20% acetonitrile in water to 100%
acetonitrile in 20 min; hold at 100% for 10 min;
re-equilibrate for 15 min.
Solvent Flow Rate; 1 mL/min
Injection Size; 10 yL
UY; At 254 nm (greater sensitivity can be achieved if
compound-specific maximum wavelengths are used-
Table 20).
Reference; Dillon, H.K, R.H. James, H.C. Miller and A.K. Wensky (Battelle
Columbus Laboratories, Columbus, Ohio) "P0HC Sampling and
Analysis Methods," Report prepared by Southern Research
Institute, Birmingham, Alabama for U.S. Environmental Pro-
tection Agency/Industrial Environmental Research Laboratory,
Research Triangle Park, North Carolina under Contract No.
68-02-2685 (December 1981).
*Compounds marked (*) are additional compounds from Appendix VIII to which
this method is expected to apply.
165
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Method Number: A131
Method Name: Aldehydes - Derivatization Procedure
Basic Method: Derivatization (DNPH) and extraction, (followed by
the GC/MS analysis described in Method A121 or by
the HPLC analysis described in Method A132)
Matrices: Aqueous Liquids (including DNPH Impinger Reagents)
Sample Extracts
Specific POHC to which method may be applied:
Chloral
Chloroacetaldehyde
Crotonaldehyde
Formaldehyde
Glycidyladehyde
Paraldehyde
Extraction and Derivatization Method Parameters:
A 20-200 mL sample size is taken for derivatization/extraction
If the matrix is a DNPH Impinger Reagent that has been used for
collection of aldehydes, it is Immediately extracted with methy-
lene chloride (100 mL) and n-pentane (100 mL). If the sample
is an aqueous liquid such as a scrubber water or an extract pre-
pared from a waste stream or comprehensive stack sampling train,
it is treated by mixing with DNPH reagent(2,4-Dinitrophenylhy-
drazine in 2N HC1) for 10 min prior to extraction.
After extraction, the combined methylene chloride/pentane layers
are washed with 2N HC1 and then with distilled water. The extracts
are then 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., 17, 264-268 (1979).
166
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Method Number:
A132
Method Name : Aldehydes - HPLC Analysis
Basic Method: HPLC/UV
Matrix: Extract of derivative
Specific POHC to which method may be applied:
Chloral
Chloroacetaldehyde
Crotonaldehyde
Formaldehyde
Glycidyladehyde
Paraldehyde
Apparatus: HPLC/UV (254 nm or 370. nm)
Analysis Method Parameters:
HPLC Column - Zorbax-ODS (250 x 4.6 mm ID, 75% CH3OH/25% ^0)
Detector - UV at 254 nm or 370 nm
Detection Limits:
5-20 ng of each compound, injected on column
or 1-4 yg/m3 of each compound (in a 5 m3 stack gas sample)
5-20 yg/L of each compound (in a 1L aqueous sample)
0.25-1 yg/g of each compound (in a 20 g sludge/solid sample)
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., 17, 264-268 (1979).
167
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Method Number:
A133
Carboxylic acids
Derivatization (followed by GC/MS analysis using
Method A121)
Sample Extracts
Organic Liquids (neat or diluted)
which method may be applied:
2,4-Dichlorophenoxyacetic acid (2,4-D)
Formic acid
7-0xabicyclo[2.2.1]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
15 mL of distilled water and 2 mL 37% (w/v) aqueous potassium hydroxide
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 minutes. The concentrate will be transferred to a 60 mL separatory
funnel, acidified with 2 mL of cold (4°C) 25 percent HjSO^, and extracted
once with 20 mL of diethyl ether and twice with 10 mL of ether.
The extract will then be transferred to a 125 mL erlenmeyer flask con-
taining sodium sulfate and be allowed to stand for approximately two
hours.
Esterfication
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. A 2 mL portion
of diazomethane will be added to the extract. The mixture will stand
for 10 minutes with occasional swirling and subsequently rinsed with
diethyl ether.
Method Name:
Basic Method:
Matrices:
Specific POHC to
168
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Boron Trifluoride: A 0.5 mL portion 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, 0.5 mL of boron trifluo-
ride methanol reagent will be added to the benzene solution. This mixture
will be held at 50°C for 30 minutes on the steam bath. After cooling,
4.5 mL neutral, 5 percent aqueous sodium sulfate will be added, and the
flask will be stoppered, shaken and allowed to stand for three minutes
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.
These 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).
169
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Method Number: A134
Method Name:
Alcohols
Basic Method:
GC/FID, GC/MS
Matrices:
Aqueous Liquids
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
Allyl alcohol
Isobutyl alcohol
2-Propyn-l-ol
Resorcinol
Apparatus:
GC/MS/DS (Finnigan 4000 or equivalent)
GC: Column - Carbopak C + 0.8 THEED (tetrahydroxyethylenediamine)
packed in 55 cm x 0.2 cm ID glass column
Carrier Gas - He
Temperature Program - 115 °C (isothermal)
Column - Fused silica capillary, 30 m x 0.25 mm,
wall coated with Carbowax 20M or SE-54.
Carrier Gas - He
MS; Mass Range - 42-450 amu
Scan Rate - 1-1.5 sec/scan
Ionization - EI, 70 eV
Detection Limits:
5-20 ng of each compound; injected on column
1-4 lig/m^ of each compound (in a 5 stack gas sample)
50-20 yg/L of each compound (in a 1 L aqueous sample)
0.25-1 yg/g of each compound (in a 20 g sludge/solid sample)
Reference: DiCorcia, A. and R. Samperi, "Gas Chromatographic Deter-
mination of Glycols at the Parts-Per-Million Level in
Water by Graphitized Carbon Black," Anal. Chem., 51
776-778 (1979).
-or-
170
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Method Number:
A136
Method Name: Phosphine
Basic Method: GC/FPD
Matrix: Gas
Specific POHC 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 Limits:
1 yg/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).
171
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Method Number
A137
Method Name:
Fluorine
Matrix:
Gas
It has not been possible to obtain an analysis method for the specific
determination of free fluorine (F2) that can be recommended with
confidence. Total Fluorides may be determined by the procedures outlined
in EPA Method 13 (40 CFR, 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.
172
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Method Number: A138
Method Name: Gases - Cyanogens and Phosgene
Basic Method: GC/TCD, GC/ECD (for CI),
GC/AFID (for N)
Matrix: Gas
Specific POHC 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 Limits:
^ 10 yg/L
Reference: Heftman, E. (ed.)> Chromatography - A Laboratory Handbook
of Chromatographic and Electrophoretic Methods, 3rd ed.,
Van Nostrand Reinhold Company, New York (1975).
173
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Method Number; A139
Method Name: Gases <- Mustards
Basic Method: GC/FPD
Matrix; Gas
Specific POHC to which method may be applied:
Mustard Gas
Nitrogen Mustard and hydrochloride salt
Nitrogen Mustard N^-Oxide and hydrochloride salt
Apparatus: GC/Flame 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 Limits:
0.2 ug/mL
Reference; Hudson, R., "U.S. Army Toxic and Hazardous Materials
Agency Report", Aberdeen Proving Ground, Maryland,
Report No. 7509. (December 1975).
174
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Method Number:
A141
Method Name: Gases
Basic Method: GC/TCD, GC/AFID(N)
GC/FPD(S)
Matrix: Gas
Specific POHC 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 Limits:
10 yg/L
Reference: Waters Associates, Framingham, MA., "Porapak Resin"
175
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Method Number:
A144
Method Name:
Acid chlorides
Matrix:
Gas
Specific POHC to which method may be applied:
Acetyl chloride
Dimethylcarbamoyl chloride
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, further re-
search 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 due
to 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).
176
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Method Number;
Method Name:
Basic Method:
Matrices:
A145
Aflatoxins
HPLC/fluorescence
Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied;
Aflatoxins
Apparatus: HPLC with fluorescence detection
Analysis Method Parameters:
LC: Column - Spherisorb ODS
Detection - Fluorescence excitation 365 nm, detection 400 nm
Solvent - ^0 or acetonitrile/methanol (3:2)
Detection Limits: <0.5 ppb (detected in dairy products)
References: Beebe, R.M. and D.M. Takahashi, "Determination of Aflatoxin
M. 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).
177
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Method Number:
A148
Method Name: Brucine
Basic Method: GC/FID
Matrix: Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
Brucine
Apparatus: GC/FID
Analysis Method Parameters:
GC: Column - Fused-silica capillary, 30 m 0.25 mm ID, wall-coated
with SE-52
Carrier Gas - He at 2 mL/min
Temperature Program - 120° to 300°C at 8°C/min
300°C, 32 min isothermal
Injector Temperature- 300°C
FID: Detector Temperature - 300°C
Detection Limit:
5-20 ng
Reference: Wensky, A.K., Battelle Columbus Laboratories, Columbus,
Ohio, personal communication (January 21, 1982).
178
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Method Number;
A149
Method Name:
Citrus Red #2
Basic Method:
HPLC
Matrices:
Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
Citrus Red #2
Apparatus:
HPLC/UV
Analysis Method Parameters:
LC: Column - PXS-1025 ODS-2
Detector - UV at 254 nm
Solvent - Methanol/Water gradient
(Tetrabutylammonium phosphate as a counter ion)
(It is possible that Citrus Red #2 could be analyzed by one
of the options described in Method A122 or Method A123.)
Reference: Gloor, R. and E.L. Johnson, "Practical Aspects of Reverse-
Phase Ion Pair Chromatography", J. Chromatog. Sci., 15
413-432 (1977).
179
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Method Number: A150
Method Name: Cycasin
Matrices: Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
Cycasin
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).
180
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Method Number:
A156
Method Name:
Ethylene oxide
Basic Method
GC/FID
Matrix:
Gas
Specific POHC to which method may be applied:
Ethylene oxide
Apparatus
GC/FID
Analysis Method Parameters:
GC: Column — 5% Carbowax 20M
Detection Limits:
0.1 mg
References: Greye, 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).
181
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Method Number; A157
Method Name: 2-Fluoroacetamide
Basic Method: GC/FID
Matrices: Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
2-Fluoroacetamide
Apparatus: GC/FID
Analysis Method Parameters:
GC: Column - Chromosorb 101 (100/120 m6sh) 1.8 m x 2 mm ID
Carrier Gas - He at 30 mL/min
Temperature Program - Isothermal at 155 °C
Detection Limits
^ 20 ng
Reference: Warner, J.S. and M.C. Landes, Internal Communication,
Battelle Columbus Laboratories, Columbus, Ohio,
(November 10, 1981).
182
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Method Number:
A160
Method Name:
Lasiocarpine
Matrices:
Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
Lasiocarpine
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 in-
volved 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).
183
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Method Number:
A174
Method Name:
Phenacetin
Basic Method:
HPLC/UV
Matrices:
Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
Analysis Method Parameters:
LC: Column - LiChrosorb RP-18
Detection - UV
Solvent - Acetonitrile/0.1 acetate buffer
Detection Limits:
Reference: Ohamoto, M., F. Yanada, M. Ishiguro and A. Umemura, "Liquid
Chromatographic Method for Determination of Phenacetin in
Serum by HPLC," Gifu-Kien Eisel Keukyusho Ho, 25, 38-40
(1980).
Phenacetin
Apparatus:
HPLC/UV
0.1 yg
184
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Method Number:
A175
Method Name: Pronamide
Basic Method: GC/ECD
Matrices: Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
Pronamide
Apparatus: GC/ECD
Analysis Method Parameters:
GC: Column - QF-1
Carrier Gas - Nitrogen
Temperature Program - Isothermal at 160°C
or
Column - DC-200
Carrier Gas - Nitrogen
Temperature Program - Isothermal at 160°C
Detection Limits:
0.005^-0.01 mg/kg
References: Gnusowski, B., "A Method for the Determination of Pyopyzamide
Residue in Medicinal and Spice Herb Raw Materials and in the
Soil," Bromatol. Chem. Toksykol.» 13, 23-26 (1980).
Nolting, H.G. and W.D. Weinmann, "Analytical Methods for
the Determination of Residues of Propyzamide in Various
Food Crops, Water, and Soil," Nachrichtenbl. Dtsch.
Pflanzenschutzdienstes, 30, 137-140 (1978).
185
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Method Number:
A180
Method Name:
Strychnine
Basic Method;
HPLC
Matrices:
Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
Strychnine and salts
Apparatus:
HPLC/UV
Analysis Method Parameters:
LC: Column - n-Propyl sulfonic acid modified silica
Detector - UV
Solvent - Methanol/2M NH^NC^ (27:2:1)
References: Wheals, B.B., "Isocratic Multi-Column High-Performance
Liquid Chromatography as a Techtiique for Qualitative
Analysis and its Application to the Characteristics of
Basic Drugs Using an Aqueous Methanol Solvent,"
J. Chromatogr., 187, 65-85 (1980).
I
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)
186
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Method Number:
A183
Method Name:
Oximes
Basic Method:
GC/FPD
Matrices:
Sample Extracts
Organic Liquids (neat or diluted)
Specific POHC to which method may be applied:
3,3-Dimethyl-l-(methylthio)-2-butanone-0-(methylamino
carbonyl)oxime [Thiofanox]
2-Methyl-2-(methylthio)propionaldehyde-O-(methyl-
carbonyl)oxime
Analysis Method Parameters:
Derivatize sample with Trimethylphenylammonium hydroxide
GC: Column - 1.5% OV-17/1.95% OV-210 or 6% DC-200
Carrier Gas - 80 mL/min
Temperature Program - isothermal at 185°C
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 Ri.lksuniv. 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).
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).
Apparatus:
GC/FPD
or
Column - 0.5% Carbowax 20M/5% SE-30
Carrier Gas - 60 mL/min
Temperature Program - isothermal at 210°C
187
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Method Number;
A190
Method Name: Tris(_l-aziridinyl)phosphine sulfide
Basic Method: GC/FPD
Matrix: Gas
Specific POHC to which method may be applied:
Tris(l-aziridinyl)phosphine sulfide
Apparatus: GC/FPD
Analysis Method Parameters:
GC: Column - 3% Dexsil 410
Carrier Gas - Helium at 20 mL/min
Temperature Program - isothermal at 140°C
Detector - Flame photometric detector in Phosphorus mode
at 526 nm
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).
188
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Method Number:
A221
Method Name: Antimony
Basic Method: Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Antimony and compounds N.O.S.
Apparatus: ICAP Spectrophotometer
AA Spectrophotometer with burner and graphite furnace
Hydride generator
Analysis Method Parameters:
ICAP: Sample input via direct aspiration of solution
Analytical Wavelengths - 206.8 and 187.1 nm
AA: 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 30 sec
Ash @ 800°C for 30 sec
Atomize @ 2700°C for 10 sec
Argon gas purge
Background correction
Flame Conditions - Air / acetylene
Fuel lean
Detection Limits and Typical Working Range:
ICAP: 0.1 mg/L; 0.5-100 mg/L and less if hydride
generator is used
Furnace AA: 3 ug/L; 20-300 ug/L
Flame AA: 0.2 mg/L; 1-40 mg/L
189
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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. PB 297686/AS
190
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Method Number:
A222
Method Name: Arsenic
Basic Method: Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species 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: AA spectrophotometer
Hydride generator
Graphite furnace
Analysis Method Parameters:
Hydride Generation: In generator add SnC^ to form trivalent arsenic,
then add zinc metal to form hydride. NaBH^ can
also be used to generate the hydride.
AA: Analytical Wavelength - 193.7 nm
Flame Conditions - Argon/hydrogen
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 11008C for 30 sec (if nickel
has been added to prevent
atomization of arsenic)
Atomize @ 2700°C for 10 sec
Argon purge
Background correction
191
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Detection Limits and Typical Working Range:
Hydride: >1 pg/L; 2-20 pg/L
Furnace: 1 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. PB 297686/AS.
192
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Method Number:
A223
Method Name: Barium
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Barium and compounds, N.O.S.
Barium cyanide
Apparatus: ICAP spectrophotometer
AA spectrophotometer with burner and graphite furnace
Analysis Method Parameters:
ICAP: Sample input via direct aspiration of solution
Analytical Wavelength - 455.4, 233.5 nm
AA: Analytical Wavelength - 553.6 nm
Furance Parameters - Dry @ 125°C for 30 sec
Ash @ 1200°C for 30 sec
Atomize @ 2800°C for 10 sec
Argon purge gas
Background correction (Tungsten
Iodide lamp)
Flame Conditions - Nitrous oxide/acetylene
Fuel rich
Detection Limits and Typical Working Range:
ICAP: 2 yg/L; 0.010-10 mg/L
Furnace AA: 2 ug/L; 10-200 pg/L
Flame AA: 0.1 mg/L; 1-20 mg/L
193
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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. PB 297686/AS.
194
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Method Number; A224
Method Name; Beryllium
Basic Method; ICAP spectroscopy
Atomic Absorption Spectroscopy
Matrices; Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Beryllium and compounds, N.O.S.
Apparatus: ICAP spectrophotometer
AA spectrophotometer with burner and graphite furnace
Analysis Method Parameters:
ICAP: Sample input via direct aspiration of solution
Analytical Wavelengths - 313.0, 234.9 nm
AA: Analytical Wavelength - 234.9 nm
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 1000°C for 30 sec
Atomize @ 2800°C for 10 sec
Argon purge gas
Background correction
Flame Conditions - Nitrous oxide/acetylene
Fuel rich
Detection Limits and Typical Working Range:
ICAP: 0.5 yg/L; 0.005-5 mg/L
Furnace AA: 0.2 yg/L; 1-30 yg/L
Flame AA: 5 yg/L; 0.05-2 mg/L
195
-------
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.
PB 297686/AS.
196
-------
Method Number: A225
Method Name: Cadmium
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Cadmium and compounds, N.O.S.
Apparatus: ICAP Spectrophotometer
AA Spectrophotometer with burner and graphite furnace
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelengths - 226.5, 214.A nm
AA: Analytical Wavelength - 228.8 nm
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 500°C for 30 sec
Atomize @ 1900°C for 10 sec
Argon purge
Flame Conditions - Air/acetylene
Fuel rich
Detection Limits and Typical Working Range:
ICAP: 0.05 mg/L; 0.2-50 mg/L
Furnace: lyg/L; 5-100 Ug/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. PB 297686/AS.
197
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Method Number:
A226
Method Name: Chromium
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Chromium and compounds, N.O.S.
Calcium chromate
Apparatus: ICAP spectrophotometer
AA spectrophotometer with burner and graphite furnace
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelengths - 267.7, 294.9 nm
AA: Analytical Wavelength - 357.9 nm
Furnace Parmameters - Dry @ 125°C for 30 sec
Ash @ 10008C for 30 sec
Atomize @ 2700°C for 10 sec
Argon purge
Flame Conditions - Nitrous oxide/acetylene
Fuel rich
Detected Limits and Typical Working Range:
ICAP: 0.05 mg/L; 0.2-50 mg/L
Furnace: 1 pg/L; 5-100 pg/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.
PB 297686/AS.
198
-------
Method Number:
A227
Method Name:
Lead
Basic Method:
Atomic Absorption Spectroscopy
ICAP Spectroscopy
Matrices:
Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Lead and compounds N.O.S.
Lead acetate
Lead phosphate
Lead subacetate
Tetraethyl lead
AA spectrophotometer with burner and graphite furnace
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelengths - 220.3, 217.0 nm
AA: Analytical Wavelength - 217.0 nm
Furnace Parameters - Dry 0 125°C for 30 sec
Ash @ 500°C for 30 sec
Atomize @ 2700°C for 10 sec
Argon purge gas
Background correction
Flame Conditions - Acetylene/air
Oxidizing
Detection Limits and Typical Working Range:
Apparatus:
ICAP spectrophotometer
ICAP:
Furnace AA:
Flame AA:
0.1 mg/L; 1-100 mg/L
1 lig/L; 5-100 yg/L
0.1 mg/L; 1-20 mg/L
199
-------
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. PB 297686/AS.
200
-------
Method Number:
A228
Method Name: Mercury
Basic Method: Atomic Absorption Spectroscopy - cold vapor
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species 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 8)
Analysis Method Parameters:
AA: Analytical Wavelength - 253 nm
In closed system, pretreat sample with I^SO^, HNO^-potassium
permanganate solution and potassium persulfate to digest
sample at 95°C in water bath. Remove excess permanganate
with sodium chloride - hydroxylamine sulfate. Add SnCl2 to
cooled solution and measure mercury signal while recirculating
air at 1 L/min.
Detection Limits and Typical Working Range:
Cold vapor/AA: 0.2 yg/L; 0.2-40 yg/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.
PB 297686/AS.
201
-------
-o-
AIR PUMP
XX
DESICCANT
~
4h
£=!h
BUBBLER
ABSORPTION
CELL
SAMPLE SOLUTION
IN BOD BOTTLE
XX
~
SCRUBBER
CONTAINING
A MERCURY
ABSORBING
MEDIA
FIGURE 8
APPARATUS FOR FLAMELESS
MERCURY DETERMINATION
202
-------
Method Number:
A229
Nickel
ICAP Spectroscopy
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
im Appendix VIII to which method may be applied:
Nickel and compounds, N.O.S.
Nickel carbonyl
Nickel cyanide
AA Spectrophotometer with burner and graphite furnace
ICAP spectrophotometer
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelengths - 231.6, 227.0 nm
AA: Analytical Wavelength - 232.0 nm
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 900°C for 30 sec
Atomize @ 2700°C for 10 sec
Argon purge gas
Background correction
Flame Conditions - Air/acetylene
Oxidizing
Detection Limits and Typical Working Range:
ICAP: 0.04 mg/L; 0.1-50 mg/L
Furnace AA: 1 yg/L; 5-100 yg/L
Flame: 0.04 mg/L; 0.3-5 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 1980). NTIS No.
PB 297686/AS.
Method Name:
Basic Method:
Matrices:
Inorganic species
Apparatus:
203
-------
Method Number:
A230
Method Name: Osmium
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Osmium tetr.oxide
Apparatus: ICAP spectrophotometer
AA spectrophotometer with burner and graphite furnace
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelengths - 225.6, 189.8 nm
AA: Analytical Wavelength - 299.9 nm
Furnace Parameters - Dry @ 105°C for 30 sec
Ash @ <140°C* for 30 sec
Atomize @ 2700°C for 10 sec
Argon purge
Flame Conditions - Nitrous oxide/acetylene
Fuel rich
Detection Limits and Typical Working Range:
ICAP: 5 yg/L; 0.010-10 mg/L
Furnace AA: 20 yg/L; 50-500 yg/L
Flame AA: 0.3 mg/L; 2-100 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.
PB 297686/AS.
*0s0^ vaporizes at ca. 150°C.
204
-------
Method Number:
A231
Selenium
Atomic Absorption Spectroscopy
Aqueous Liquids
Organic Liquids
Sludges
Solids
from Appendix VIII to which method may be applied:
Selenious acid
Selenium and compounds, N.O.S.
Selenium sulfide
Selenourea
AA spectrophotometer with graphite furnace
Hydride generator
Analysis Method Parameters:
Hydride Generation: Reduction with SnCl2 or NaBH*
Zinc metal added to drive of? hydride
AA: Analytical Wavelensth - 196.0 nm
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 1200°C for 30 sec
Atomize @ 2700°C for 10 sec
Argon purge gas
Background correction
Flame Conditions - Argon/hydrogen
Detection Limits and Typical Working Range:
Hydride Generation: >1 yg/L; 2-20 yg/L
Furnace AA: 2 yg/L; 5-100 yg/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. PB 297686/AS
Method Name:
Basic Method:
Matrices:
Inorganic species
Apparatus:
205
-------
Method Number:
A232
Method Name: Silver
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Potassium silver cyanide
Silver and compounds, N.O.S.
Silver cyanide
Apparatus: AA spectrophotometer with graphite furnace
ICAP spectrophotometer
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelengths - 328.1, 224.6 nm
AA: Analytical Wavelength - 328.1 run
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 400°C for 30 sec
Atomize @ 2700°C for 10 sec
Argon purge
Background correction
Flame conditions - Acetylene/air
Oxidizing
Detection Limits and Typical Working Range:
ICAP: 0.01 mg/L; 0.1-50 mg/L
Furnace AA: 0.2 pg/L; 1-25 yg/L
Flame AA: 0.01 mg/L; 0.14-4 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.
PB 297686/AS.
206
-------
Method Number: A233
Method Name: Strontium
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Strontium sulfide
Apparatus: AA spectrophotometer with graphite furnace
ICAP spectrophotometer
Analysis Method Parameters:
ICAP: Analytical Wavelengths - 407.8, 346.4 nm
AA: Analytical Wavelength - 460.7 nm
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 1000°C for 30 sec
Atomize @ 2500°C for 10 sec
Argon purge gas
Background correction
Flame Conditions - Nitrous oxide/acetyle
Fuel lean
Detection Limits and Typical Working Range:
ICAP: 2 yg/L; 0.05-10 mg/L
Furnace AA: .2 yg/L; .4-20 yg/L
Flame AA: .08 mg/L; .2-5 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. PB 297686/AS.
207
-------
Method Number:
A234
Method Name: Thallium
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
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
Apparatus: AA spectrophotometer with graphite furnace
ICAP spectrophotometer
Analysis Method Parameters:
ICAP: Analytical Wavelengths - 190.9, 351.9 nm
AA: Analytical Wavelength - 276.8 nm
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 400°C for 30 sec
Atomize @ 2400°C for 10 sec
Argon purge gas
Background correction
Flame Conditions - Air/acetylene
Oxidizing
Detection Limits and Typical Working Range:
ICAP: 0.1 mg/L; 1-100 mg/L
Furnace AA: 1 yg/L; 5-100 yg/L
Flame AA: 0.1 yg/L; 1-20 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).
208
-------
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis
of Water and Wastes," EPA<-600/4<-79-020 Qlarch 1979). NT1S
No. PB 297686/AS.
209
-------
Method Number: A235
Method Name: Vanadium
Basic Method: ICAP Spectroscopy
Atomic Absorption Spectroscopy
Matrices: Aqueous Liquids
Organic Liquids
Sludges
Solids
Inorganic species from Appendix VIII to which method may be applied:
Vanadic acid, ammonium salt
Vanadium pentoxide
Apparatus: AA spectrophotometer with graphite furnace
ICAP spectrophotometer
Analysis Method Parameters:
ICAP: Analytical Wavelengths - 309.3, 214.0 nmg
AA: Analytical Wavelength - 318.4 nm
Furnace Parameters - Dry 125°C for 30 sec
Ash @ 1400°C for 30 sec
Atomize @ 2800°C for 15 sec
Argon purge gas
Background correction
Flame Conditions - Nitrous oxide/acetylene
Fuel rich
Detection Limits and Typical Working Range:
ICAP: 0.01 mg/L; 0.1-150 mg/L
Furnace AA: 4 yg/L; 10-200 iJg/L
Flame AA: 0.2 mg/L; 2-100 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. PB 297686/AS.
210
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Method Number:
A251
Method Name:
Anions
Basic Method:
Ion Chromatography
Matrices:
Aqueous Liquids
Sludges
Sample Extracts
Species 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 NaHCO^/O/0024m Na.CO,
aqueous solution.
The suppressor column must be regenerated every 20 hours of operation
with a IN aqeous ^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).
211
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Method Number:
A252
Total cyanides
Titration
Colorimetry
Aqueous Liquids
Organic Liquids
Sludges
Solids
Species from Appendix VIII to which method may be applied:
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
Apparatus: Spectrophotometer
Microburet
Cyanide distillation apparatus
Analysis Method Parameters:
• removal of oxidizing agents (indicated by Kl-starch telst paper)
with ascorbic acid;
a removal of sulfides (lead acetate test paper) with cadmium car-
bonate;
• removal of fatty acids by single extraction with hexane at pH
6 to 7. Following extraction, raise pH of solution above 12.
HCN Evolution:
Add concentrated I^SO ^ and magnesium chloride solution to flask and
reflux for one hour.
HCN Collection:
Adjust vacuum to draw ca. 1 bubble/sec through flask, collect
gas continuously prior to adding acid to 15 min. after removal
of heat.
Method Name:
Basic Method:
Matrices:
212
-------
Analytical Method:
Titration:
Titrate solution with standard silver nitrate in the presence of
benzalrhodamine indicator to first color change from yellow to
brownish pink.
Colorimetry:
To solution, add Chloramine T and mix solution. After 1-2 min.
add pryidine-barbituric acid solution and mix, read adsorbance
at 578 nm between 8 and 15 min after start of color development;
Or after 1-2 min., add pyridine-pyrazolone solution and mix.
Measure absorbance at 620 nm after 40 min.
Detection Limits and Typical Working Range:
Titration: 0.3 mg/L; > 1 mg/L
Colorimetry: 0.01 mg/L; 0.02-1 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. PB 297686/AS.
213
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Method Number: A253
Method Name: Phosphides
Basic Method: GC/FPD
Matrix: Solids
Species from Appendix VIII to which method may be applied:
Aluminum phosphide
Zinc phosphate
Apparatus: Gas Chromatograph
One-liter calibrated gas flasks
Analysis Method Parameters:
Sample Preparation:
Place sample into calibrated gas flask, flush with 99.99% N^.
Add dilute acid (0.01N HNO^) and mix.
Replace measured amount of ^ from second calibrated gas flask
with equilibrated phosphine containing gas.
GC Conditions:
Column - 3% Carbowax 20M on Gas Chrom Q
Detector - Flame Photometric
Detection Limits:
10 pg/L
Reference: Berck, B., W.E. Westlake and F.A. Gunter, "Microdetermination
of Phosphine by Gas-Liquid Chromatography with Microcolometric,
Thermionic, and Flame Photometric Detection," J. Agric. Food
Chem., 18, 143-147 (1970).
214
-------
It has been impossible to find an analysis method that can be recommended
with confidence for the following Appendix VIII constituents:
Cyclophosphamide
Ethylenebisdithiocarbamic acid, salts and esters
Iron dextran
Methyl chlorocarbonate
4-Nitroquinoline-l-oxide
o-Toluidine hydrochloride
Uracil mustard
215
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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 document the quality
(i.e., accuracy and precision) of the generated data, to maintain the
quality of the data within predetermined tolerance limits for specific
sampling and analysis procedures, and to provide guidelines for correc-
tive 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 sampling and analysis
have not been established; tolerance limits may be established as ex-
perience with trial burns accumulates and a data base is generated.
In this section, a number of specific QA/QC procedures are described.
For any specific sampling and analysis program these procedures and
others may be selected to reach the goal of obtaining high quality
data. At a minimum, those procedures which are selected must be con-
sistent with the standard operating procedures and/or the good laboratory
practices of the sampling crew and analytical laboratory invovled.
The following definitions, which represent activities which are inter-
dependent, will serve to differentiate between the complementary activi-
ties of QA and QC.
0 Quality Assurance (QA) activities address delegation of pro-
gram responsibilities to individuals, documentation, data
review and audits. The intent of QA procedures is to per-
mit the assessment of the reliability of the data.
6 Quality Control (QC) activities address maintaining facilities,
equipment, training personnel, sample integrity, chemical ana-
lysis methods, producing and reviewing 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 are outside of their predetermined (tolerance) limits,
corrective actions specified in the work plan are taken.
The following discussion of QA/QC procedures is based upon a guidelines
document (23) 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 therein
provide an extensive resource for the permit applicant and the permit
writer in selecting appropriate QA/QC procedures for a particular trial
burn and/or operating burn sampling and analysis effort.
217
-------
This section of the Sampling and Analysis Methods document 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. It will be necessary in each case to
develop a specific plan that addresses the specific POHCs, necessary
detection limits for 99.99% DRE, waste feed sampling frequency, etc.
The QAMS-005/80 document identified sixteen (16) essential elements of
a QA Project Plan. These are listed in Table 24. Although it is not
necessary that every trial burn have a QA project plan organized in
strict accordance with this list, it is important that each of these
elements be explicity addressed somewhere in the trial burn plan. Each
element is therefore discussed briefly below.
B. TITLE PAGE AND TABLE OF CONTENTS
These elements are largely 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 organiza-
tion of the QA plan as outlined in the Table of Contents does not follow
the list of 16 QAMS-005/80 QA elements, it is recommended that a supple-
mentary Table which cross-references the Plan to the QAMS-005/80 list
be provided.
C. PROJECT DESCRIPTION
The project description will typically have been presented in some detail
elsewhere in a hazardous waste incineration permit application. In the
QA Project Plan, ife will usually be sufficient to include 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% DRE.
D. PROJECT ORGANIZATION AND RESPONSIBILITY
1. Personnel Responsibilities
It is necessary to designate individuals who will have responsibility for
the following functions in specifying the QA/QC program, as part of the
program work plan, and carrying out all elements of the QA/QC plan.
« The trial burn project manager has overall responsibility for
management of the project. The manager must ensure that proper
materials, instruments and qualified personnel are available.
Further, the project manager must designate individuals to assist
in discharging the QA/QC responsibilities.
218
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TABLE 24
ESSENTIAL ELEMENTS OF A QA PROJECT PLAN ACCORDING TO QAMS-005/80
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
Source: Reference 23
Title Page
Table of Contents
Project Description
Project Organization and
Responsibility
QA Objectives
Sampling Procedures
Sample Custody
Calibration Procedures and
Frequency
Analytical Procedures
Data Reduction, Validation and
Reporting
Internal Quality Control Checks
Performance and System Audits
Preventive Maintenance
Specific Routine Procedures Used
to Assess Data Precision,
Accuracy and Completeness
Corrective Action
Quality Assurance Reports to
Management
219
-------
The quality assurance coordinator is responsible for reviewing
and advising on all aspects of QA/QC. This includes:
- Assisting the project manager in specifying 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 manage-
ment to ensure that appropriate corrective actions are taken.
- It is important to note that the quality assurance coordinator
must be autonomous from the project manager. The QA coordi-
nator should be responsible to upper management independently
of project management. An example of a management structure
that meets this requirement for independence is shown in
Figure 9.
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;
- 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 ques-
tionable 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;
Checking that all sample documentation (labels, field note-
books, chain-of-custody records, packing lists) are correct
and transmitting that information with the samples to the
analytical laboratory.
220
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FIGURE 9 Example of Project Organization and Responsibility
-------
• The quality control and data manager is responsible for QC
activities and data management. This includes:
- Maintaining records of all incoming samples, tracking those
samples through subsequent processing and analysis and ulti-
mately the appropriate disposal of those samples at the con-
clusion 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;
- 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 Hazard-
ous Constituents (POHCs) of the waste, according to criteria established
under the Resource Conservation and Recorvery Act (RCRA; 40 CFR Part 264,
Subpart 0). At the present time, the Agency has not established quanti-
tative guidelines as to the precision, accuracy, completeness, representa-
tiveness and/or comparability criteria that must be met by data generated:
in a trial burn of hazardous waste. However, some specific numerical QA
objectives for accuracy and precision of the sampling system calibration,
sample preparation and analysis procedures used in the analytical labora-
tory have been developed. These guidelines are based on previous exper-
ience 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 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.
Thus, determinate errors due to instrument response and incomplete prepara-
tion recoveries can be corrected for and the primary uncertainties in the
analytical data are due to random errors not exceeding those in Table 25.
The QA objectives for accuracy may be expressed in terms of the following
parameters:
i. Reference materials: All reference materials used as calibration
standards or surrogate compounds should be the highest purity commer-
cially 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.
222
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TABLE 25
PRECISION GOALS FOR ANALYSIS
TECHNIQUE OR PARAMETER
COMPOSITION
Proximate
Solids, Ash, Elemental Content
Survey
GRAV
TCO
IR
LRMS
Directed
GC/MS
HPLC
GC
ICAP/AAS
IC
MATRIX
PRECISION
REL. STD. DEV.
Waste Feed
Waste Feed
Stack Gas Samples
Waste Feed
Stack Gas Samples
Scrubber Water
Bottom Ash
< 10%
< 10%
< 30%
Factor of 3
< 30%
< 30%
< 30%
< 30%
< 30%
-------
ii. Instrument Performance; Each instrument used in a project must be
checked on each day that samples are analyzed to demonstrate perfor-
mance. Once of the QA objectives should be that the absolute instru-
ment response (e.g., area counts/ng injected for the internal stan-
dard (s) or surrogates in a GC/MS analysis) be within a stated per-
centage of comparable measurements made subsequent to the most re-
cent calibration of the instrument.
iii. Recovery of Surrogates: The recovery of a surrogate compound(s),
added to a sample can be defined as follows:
Recovery, 7. - "8 g f°T? ln * 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 complied
on a cumulative basis for each surrogate compound in each type of sample
matrix. The objectives for recovery of surrogates are:
MEAN STD Deviation
aqueous liquids 70% 30%
organic liquids 50% 40%
stack gas samples
iv. Recovery of POHCs or other Appendix VIII Compounds: The recovery
of a POHG, or other Appendix VIII Compound, P can be defined as
follows:
Recovery %= Mg P found in spiked sample - yg P in native sample ^ 10Q
y' * yg P added to sample
It may not be appropriate to specify numerical targets for recovery of
POHCs or Appendix VIII compounds from the waste sample. It should be
expected that recoveries will approximate the recoveries given for sur-
rogates. This type of recovery data can be generated only in those cases
for which the sample showed detectable levels of the POHC or Appendix VIII
Compound and the spiked level was high enough to be measurable above the
native level in the sample. If recovery data are generated they should
be reported along with the sample data.
2. Precision is defined in QAMS-005-80 as a measure of mutual agree-
ment among individual measurements of the sample property. The QA objec-
tives for precision might be expressed in terms of the following
parameters:
i. 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 should be greater than some specified
value (e.g., 0.9, 0.99).
224
-------
ii. Analysis of Surrogates; Another QA objective for a trial burn pro^
ject should be that the standard deviation for analysis of surrogate
compounds in replicate samples from a given waste stream be within
the limits specified in Table 25.
iii. 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 re-
plicate samples are analyzed. At least 10% of all analyses per-
formed should be triplicate QC checks.
3. Completeness. The QA objective for a trial burn project should be
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
in order to ensure as much as possible a representative sample, are dis-
cussed in Sections III and IV of this document: sampling sites, process
cycles, catch flow rates (sampling frequency), sample preservation,
sampling procedures and sampling equipment.
5. Comparability. All data should be reported in mg, pg, or ng of
analyte per kilogram, liter, or cubic meter of original sample. When
precise recovery values for a given component are known, the recovery
information and the corrected concentration data should also be provided.
F. SAMPLING PROCEDURES
The sampling procedures to be used for hazardous waste incineration are
described in Section IV of this sampling and analysis methods document.
This element of the trial burn QA plan should specify which of the Methods
S001-S011 will 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 will be taken to ensure that feed and emission
measurements for DRE calculations correspond to comparable test periods,
for example, Figure 10 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 document), 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
Because trial burn data form part of a 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
-------
ho
ro
ON
Emission
Samples
Time L-
(hrs) 0
Feed
Samples p
j
r
~v r
J
8
12
_X.
^ r
_A»
000 000 000
FIGURE 10: 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 E^/F^, ^2/^ 2*^2^ 3'
Source: J. E. Picker and B. N. Colby, Systems Science and Software
-------
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 de-
tail in the engineering guidelines manual and will not be repeated here.
For any sampling and analysis test of an incinerator facility the col-
lected 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 archived
in one of several forms, such as laboratory notebooks, reports, raw
data on magnetic tape and/or disk media, etc. For routine data and
calibration information, laboratory notebooks are appropriate. To
answer identification questions and to confirm the identities of addi-
tional 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 (3).
Chain-of-custody procedures must cover both field sampling and laboratory
analysis. For field work, the protocols described in Chapter II of SW-846
(3) should be adhered to. These procedures include detailed labelling of
each sample, permanent recording of information pertinent to the sample
collection and any field observations made at the same time as the sample
was collected. A copy of all such materials must accompany 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 11 through 13.
I. CALIBRATION PROCEDURES AND FREQUENCY
1. Sampling
Calibration of stack sampling equipment should be performed within two
weeks previous to initiation of field sampling. The procedures should
conform to the specifications of the EPA document, "Quality Assurance
Handbook for Air Pollution Measurement Systems," Volume III, Stationary
Source Specific Methods (25). Dry gas meters, nozzles, orifices and
pitot tubes will be covered in the calibration. Tables 26 and 27 sum-
marize 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 of
this document. The QA Plan for each project should specify the materials
and concentration ranges of standards for calibration of each instrument
to be used in that project.
227
-------
FIELD SAMPLING CHAIN OF CUSTODY FORM
LEATJEK
NAME OF SURVEY OR ACTIVITY
DATE OF COLLECTION
! SHEET
Molvin
Priority Pollutant Survey 523.10
9/12/84
!i of i
DESCRIPTION OF SHIPMENT
TYPE OF SAMPLE Water Samples
TOTAL NUMBER SAMPLE CONTAINERS lu
CONTENTS OF SHIPMENT
FIELD
NO. OF CONTAINERS/
FIELD NO
. I ANALYSES REQUIRED -
CHECK WHERE
APPROPRIATE
SAMPLE NO.
PLASTIC
GLASS'
VOA
CYANIDE
PHENOLS
ASBESTOS
PESTICIDES
METALS
VOA
SF.MI-
067t'
]
08->5>
;
/
199.:
1
/
3862
1
~
3812
3
/
6413
i
/
V
68o3
j
/
PERSONNEL CUSTODY RECORD
RELINQUISHED BY (SAMPLER)
RECEIVED BY
DATE
TIME
REASON
H. Melvin
Harpy Airlines
10/1/84
1600
Delivery to lab
SEALED UNSEALED I
X|SEALED UNSEALED i
RELINQUISHED BY
RECEIVED BY
DATE
TIME
REASON
Airline
Vendor
10/3/84
900
FIGURE 11 Field Sampling Chain-of-Custody Form
228
-------
Collector's Sample No.
CHAIN OF CUSTODY RECORD
Location of Sampling: Producer Hauler Disposal Site
Other:
Sample
Shipper Name:
Address:
number street city state zip
Collector's Name Telephone: ( _)
signature
Date Sampled Time Sampled hours
Type of Process Producing Waste
Field Information
Sample Receiver:
1.
name and address of organization receiving sample
2. __
3.
Chain of Possession:
1.
signature
2 .
signat ure
3.
signature title inclusive dates
FIGURE 12 Chain-of-Custody Record
229
title inclusive dates
title inclusive dates
-------
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 13 Example of Record of Analysis Report Form with Acceptable
Documentation
230
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TABLE 26
ACTIVITY MATRIX FOR CALIBRATION OF EQUIPMENT
Apparatus
Wet test meter
Acceptance Limits
3
Capacity > 3,4 m /h
(120 ft3/hr); accuracy
with ±1.0%
Frequency and Method
of Measurements
Calibrate initially,
and then yearly
by liquid dis-
placement
Action if
Requirements
Are not Met
Adjust until
specifications
are met, or
return to manu-
facturer
Dry gas meter
Y± = Y ±0.02Y
Calibrate vs. wet
test meter initially,
and when post-test
check exceeds
Y±0.05 Y
Repair, or re-
place and then
recalibrate
Thermometers
Probe heating
system
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
21L/min (0.71 ft^/min)
Adjust; de-
termine a con-
stant correc-
tion factor;
or reject
Calibrate each ini-
tially 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 Repair, or re-
initially by place and then
APTD-0576(11), if con- reverify the
structed by APTD- calibration
0581(10) or use
published calibra-
tion curves
Barometer ±2.5 mm (0.1 in.) Hg of
mercury-in-glass barom-
eter
Calibrate initially
vs. mercury-in-glass
barometer; check
before and after
each field test
Adjust to
agree with a
certified
barometer
Probe nozzle
Average of three ID
measurements of nozzle;
difference between high
and low ^0.1 mm
(0.004 in.)
Use a micrometer to
measure to near-
est 0.025 mm (0.001
in)
Recalibrate,
reshape, and
sharpen when
nozzle becomes
nicked,dented
or corroded
231
-------
TABLE 26 (Continued)
Apparatus
Analytical
balance
Acceptance Limits
±1 mg of Class-S
weights
Frequency and Method
of Measurement
Check with Class-S
weights upon receipt
Action if
Requirements
Are not Met
Adjust or
repair
Source: EPA-600/4-77-027b (25)
232
-------
TABLE 27
ACTIVITY MATRIX FOR CALIBRATION OF APPARATUS
Apparatus
Type S pitot
tube and/or
probe
assembly
Stack gas tem-
perature
measurement
system
Barometer
Differential
pressure
gauge (does
not include
inclined
manometers)
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 manometers
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
Initially and after
each field use
Action if
Requirements
Are not Met
Do not use
pitot tubes
that do not
meet face
opening
specifica-
tions; re-
pair or re-
place as re-
quired
Adjust to
agree with Hg
bulb thermom-
eter, or con-
struct a cal-
ibration
curve to cor-
rect the
readings
Adjust, re-
pair or
discard
Reject test
results, or
consult
administra-
tor if post-
test calibra-
tion is out
of specifi-
cation
233
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J. ANALYTICAL PROCEDURES
The analytical procedures to be used for trial burn purposes are given
in Section VI of this document. 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 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 will serve as indicators of the performance of the sample pre-
paration and analytical methods.
K. DATA REDUCTION, VALIDATION, AND REPORTING
1. Data Reduction
The QA Project Plan must include 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.
Raw data 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/analytical method can be constructed
by fitting a linear regression equation to the results of the analyses
of calibration standard solutions containing the analyte at five different
concentration levels.
The raw data are converted to concentration of analyte in the sample by
automated data processing routines or by the analyst. Peak areas for
the series of known calibration standards are first entered and a re-
gression line is computed. A plot of the calibration curve with the
actual calibration data superimposed on it should be generated for ex-
amination for indications of deviations from linearity or of outlying
data points. Peak areas from the analyses of unknowns are then entered,
corresponding quantities of analyte are computed from the regression
line, and a summary of the raw and converted data is printed. The ori-
ginal copy of the data summary should be included in the analyst's note-
book and copies forwarded to the Analysis Coordinator and the Project
Manager.
An internal standard (such as d-^-anthracene) is added to each standard
solution or concentrated sample extract immediately prior to analysis.
The quality added is sufficient to give the same concentration (yg/mL)
of internal standard in all solutions/extracts analyzed.
234
-------
The calibration curve and regression equation can be based upon the re-
lative area, A1, where:
_ Raw area for peak corresponding to analyte
Raw area for peak corresponding to internal standard
Blank corrections are made by subtracting A1 for the method blank from
A' for the standard. The calibration curve consists of a plot of A'
vs. ng of analyte injected.
The concentration of analyte or surrogate in an unknown sample will be
calculated as follows:
Quantity injected, Q (ng)
Q is calculated from the regression equation of the calibration curve:
A1 = m • Q + b
where A' is the relative area corrected by subtracting A' for the blank
from A' for the sample.
Q is the quantity in ng of analyte injected
m is the slope of the regression line
b is the intercept of the regression line (which will not be force-
fit to zero)
Thus,
Q = A' - b
m
Concentration in Extract C* (ng/yL)
C* is calculated from Q and the injection volume, V^, in yL.
C* (ng/yL) = ^
i
Concentration in Sample, C (mg/L or mg/kg)
C is calculated from C*; the volume of the concentrated sample extract,
Vx; and the initial quantity of sample extracted.
For aqueous liquids, organic liquids, slurries:
C (mg/L) - C*y' V* * 1000
s
235
-------
For solids, sludges;
C (mg/kg) = C w* Vx * 1000
where C* = concentration in extract, ng/yL e ug/mL
V = volume of concentrated extract, mL
x 3
Vg = volume of sample taken for extraction, L
Wg = Weight of sample taken for extraction, kg
For Stack Gas
C (mg/m3) = C*v'V* t 1000
g
where C* = concentration in extract, ng/yL = pg/mL
V = volume of concentrated extract, mL
x
3
V = volume of stack gas sampled, dry standard m
§
2. Data Validation
The principal criteria that should be used to validate the data integrity
during collection and reporting of data include:
1. Verification on a frequent basis 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 docu-
mented in the laboratory chain-of-custody records.
2. Examination of at least 5% of the raw data (e.g., chromatograms,
AAS recorder outputs) on a frequent basis by the analysis coordin-
ator to verify adequacy of documentation, confirm peak shape and
resolution, assure that the automatic integrator was sensing peaks
appropriately, etc.
3. Confirmation that raw areas for internal standards and calibration
standards and raw and relative area's for surrogate compounds are
within 50% of the expected value.
4. Reporting of all associated blank, jstandard, and QC data along with
results for analyses of each batch jof samples.
5. Reporting of all analytical data for samples with no values re-
jected as outliers, because of the jsmall number of replicate samples
for analysis.
236
-------
3. Reporting
Results of directed analysis, survey analysis and proximate analysis
should be reported in the formats presented in Section VI.
L. INTERNAL QUALITY CONTROL CHECKS
This section presents guidelines for 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 must be analyzed in the same way as field samples
and interspersed with the field samples. The results of analyzing these
samples are used to document the validity of data and to control the
quality of data within predetermined tolerance limits. QC samples are:
1. Blank Samples
These samples are analyzed in order 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 in order to assess possible
contamination from the field (one for each type of sample
preparation).
e Method Blanks - These blank samples are prepared in the lab-
oratory and are analyzed in order to assess possible laboratory
contamination. (One for each lot of samples analyzed).
e Reagent and Solvent Blanks - These blanks are prepared in the
laboratory and analyzed in order 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 analogous 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.
237
-------
3. Spiked Samples
All samples should be 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.
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 corres-
ponding to two times the target detection limit (based on 99.99%) 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 should
be made prior to the implementation of any new experimental procedures.
Systems audits for trial burn projects should include frequent review by
the QC Data Manager and Project Manager of all recent data to insure that
all required QC checks are being made and evaluation criteria followed.
The Quality Assurance Officer should participate in these reviews on a
regular basis. Because of the anticipated difficulty in obtaining ref-
erence 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 EPA's discretion, the preliminary systems audit may include analysis
of a simple performance evaluation standard and/or analysis of spiked
XAD resins traps, feed samples, or other materials supplied by EPA.
N. PREVENTIVE MAINTENANCE
The QA Project Plan for a trial burn should itemize the procedures 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 can be calculated as:
C
i
1=1
238
-------
where n = number of replicate measurements; C, are both in mg/L or
mg/kg.
The estimate of precision of a series of replicate measurements can be
expressed as the relative standard deviation, RSD:
RSD =
SD
x 100%
where SD = Standard deviation
z
(q - c)2
sd = - ' 1 = 1
(n-l)
Alternatively, for data sets with a small number of points (e.g., con-
centration of POHC in triplicate samples of one waste stream), the
estimate of precision may be expressed as a range percent, R:
„ C1 " C2 x 100%
K —
where = highest concentration value measured in data set
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 can be evaluated by comparing the mean recovery of surrogate
compounds on a weekly basis. The recovery of a surrogate compound can
be defined as:
C • V (or W )
„ a, s s s x 100
Recovery, % = -
s
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)
Qg = Quantity of surrogate compound added to sample, mg.
239
-------
3. Assessment of Causes of Variance
If the calculated destruction removal efficiences had a very small variance,
the three composite four-hour samples are all that would be necessary to
provide quality assurance. If variances in the calculated DRE's were
large, it could be useful to identify the cause of the large variance.
This would be done by following a sample preparation and analysis proto-
col similar to the one pictured in Figure 14. Using the rule of additivity
of variance, the precision, expressed as total variance for a particular
sampling and analysis scheme, can be expressed as the sum of the variances
for the separate activities of sampling, sample preparation and measurement.
This is shown by equation 1:
2 2 2 2
S = S + S + S
Total Sampling Preparation Measurement (1)
It is possible to subdivide the variances into more detailed steps in the
sampling scheme if necessary. To determine sampling variance (S^), the
variance obtained from analyzing and E3ci, would be subtracted
from that obtained for E-^, E2 and E3a. Similarly sample preparation pre-
cision (Sp) can be determined by subtracting the variance obtained from
triplicate measurements (S^ obtained from E3C^, E^^ and £3^) from the
variance of E3a, E3b and E3cj. This type of variance analysis could also
be applied to the sampling and analysis of waste feed in the same way
as it is applied to the emission gases in the stack. Ideally variance
analysis would be done for each of the POHC's identified for evaluation
in a trail burn. These data would be extremely useful in identifying
the source 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 appro-
priate 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 devia-
tion data for replicate sets can be accumulated for each kind of sample
matrix analyzed, e.g., solid,stack gas sample, aqueous liquid, 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 recoveries exceeds the performance goals
established for that trial burn project (Part D of this Section
corrective action should be taken to improve performance prior to analyses
of the next lot.
If weaknesses or problems are uncovered during system or performance
audits corrective action should be initiated immediately.
240
-------
Preparation
Analysis
=> E,
5> E2 =
> E
3a
^ ^3b
3C
> E
> E2
> E
3a
^ E3b
s|+ sl+s*
s p m
E
#> E
3C1
3C2
d m
j
#> E
3C3
m
j
FIGURE 14: Diagram of a Sampling and Analysis Procedure Which Uses
Replicate Samples to Provide Information on Sources of Variance
Source: J.E. Picker and B. N. Colby, System, Science and Software
-------
Corrective action might include, but not necessarily be limtied to: re-
calibration 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 reassign-
ment of personnel, if necessary, to improve the overlap between operator
skills and method requirements.
Whenever a long-term corrective action (27) is necessary to eliminate the
cause of nonconformance, the following closed-loop corrective action sys-
tem should be used. As appropriate, the sample coordinator, analysis
coordinator or the program manager, ensures that each of these steps are
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
must be verified.
Q. QUALITY ASSURANCE REPORTS
On a regular basis, the Quality Assurance Officer should meet with the
Project Manager, and key staff responsibile 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 should be summarized in a memorandum which is dis-
tributed to upper corporate/institutional management, as well as to the
Project Manager and his/her 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 should receive documented copies of all QA reports along with the
trial burn sampling and analysis results.
242
-------
VIII. REFERENCES
1. Vogel, G., K. Brooks, J. Cross, I. Frenkel, S. Huas and W. Jacobsen,
"Guidance Manual for Evaluating Permit Applications for the Operation
of Hazardous Waste Incinerator Units," Report prepared for U. S.
Environmental Protection Agency/Industrial Environmental Research
Laboratory, Research Triangle Park, North Carolina by The MITRE
Corporation, McLean, Virginia under Contract No. 68-01-6092
(April 1981).
2. U. S. Environmental Protection Agency/Industrial Environmental Re-
search Laboratory, Office of Environmental Engineering and Technol-
ogy, Cincinnati, Ohio, "Engineering Handbook for Hazardous Waste
Incineration," SW-889 (September 1981).
3. U. S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste - Physical/
Chemical Methods," SW-846 (1980), SE-846, Revision A (August 8, 1980)
and SW-846, Revision B (July 1981).
4. 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.
5. Title 40, Code of Federal Regulations, Part 60, Appendix A (1980).
6. Lentzen, D.D., D. E. Wagoner, E. D. Estes and W. F. Gutknecht, "EPA/
IERL-RTP Procedures Manual: Level 1 Environmental Assessment," EPA-
600/7-78-201 (October 1978). NTIS No. PB 293795/AS.
7. American Society for Testing and Materials, Philadelphia, Pennsylvania,
"Annual Book of ASTM Standards," Method D-270 (1975).
8. American Society for Testing and Materials, Philadelphia, Pennsylvania,
"Annual Book of ASTM Standards," Method E-300 (1973).
9. Stern, A. C. (ed.)» Air Pollution: Third Edition. Academic Press,
New York, Vol. III. (1976).
10. Martin, R. M. "Construction Details for Isokinetic Source Sampling
Equipment," EPA-APTD-0581 (1972). NTIS No. PB-209060.
11. Rom, J. J., "Maintenance, Calibration and Operation of Isokinetic
Source Sampling Equipment," EPA-APTD-0576 (1972). NTIS No. PB-209022.
12. 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," NTIS No. PB 278-816/3WP (May 1978).
243
-------
13. Adams, J.W.,K. 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. PB-268559.
14. Gallant, R. F., J. W. King, P. L. Levins and J. F. Piecewicz,
"Characterization of Sorbent Resins for Use in Environmental Monitor-
ing," EPA-600/7-78-054 (March 1979). NTIS No. PB-284347.
15. 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.
16. 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. PB-293800.
17. Stauffer, J. L., "Interpretation of Low Resolution Mass Spectra for
Level 1 Analysis of Environmental Mixtures," Report prepared for
U. S. Environmental Protection Agency/Industrial Environmental
Research Laboratory, Research Triangle Park, North Carolina by
Arthur D. Little, Inc., Cambridge, Massachusetts under Contract No.
68-02-3111 (September 1980).
18. U. S. Environmental Protection Agency, Federal Register, 44, 69464 -
69575 (December 3, 1979).
19. 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).
20. Small, H., T. S. Stevens, and W. C. Baumer, "Novel Ion Exchange
Chromatographic Method Using Conductimetrie Detection," Anal. Chem.,
47, 1801-1809 (1975).
21. Otvos, J. W. and D. P. Stevenson, "Cross-Sections of Molecules for
Ionization by Electrons," J^. Am. Chem. Soc., 78, 546-551 (1956).
22. Hood, A., "Standardization of Mass Spectra by Means of Total Ion
Intensity," Anal. Chem., 30, 1218-1220 (1958).
23. 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).
24. U. S. Environmental Protection Agency/Office of Enforcement, "NEIC
Policies and Procedures Manual," Report prepared by U. S. Environ-
mental Protection Agency/National Enforcement Investigations Center,
Denver, Colorado, EPA-300/9-78-001-R (October 1979).
244
-------
25. 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).
26. Picker, J. E. and B. N. Colby, "Quality Assurance Review of 'Sampling
and Analysis Methods for Hazardous Waste Incineration,1" personal
communication (August 1981).
27. 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. PB-254658.
Note: References with assigned NTIS Numbers are available from the
National Technical Information Service, Springfield, VA 22161.
245
-------
APPENDIX A
Hazardous Constituents «- Physical/Chemical Data
Appendix A is a list of the Appendix VIII Hazard-
ous Constituents (according to the May 20, 1981
Federal Register) with the following chemical/
physical data for each compound (when available):
CAS Registry Number
Formula
Boiling Point (°C)
Melting Point (°C)
AH Combustion (KCAL/mol)
Molecular Weight
Structure
247
-------
CAS BOILING
REGISTRY MO. FORMULA POINT *C
Acotonitrilo
75-05-8
w
175-180
Acc-to[)licnone 98-86-2 (' H„0 202
o o
ho
3-(nlph.i-AcctonyL .129-06- 6 C .B ,0,
bcn«yl)-4-hydroxy 19 16 1
(•otimarla and salts
I Warfarin)
2-Acctylaminofluor<'.nc 19361-41-2 CjjHjjNO
Ac.til-yl chloride
75-36-5
c2h3cio
51-52
AH
MELTING COMBUSTION
POINT °C KCAL/mol MOLECULAR WEIGHT
63.0
302.4
41.06
20.5
992
120.15
161
338.33
194
282.6
223.26
-112
217.44
78.50
STRUCTURE
CH -CN
O5-
flY t
"0
axr'
o
K
ch-c-ci
-------
CAS BOILING
NAMK REGISTRY NO. FORMULA POINT °C
l-Acetyl-2-thloure.i 591-08-2 C H^N^OS
Acrolein- 107-02-8 C„H,0 52.5-53.5
3 4
to
Ln
° Any],amide 79-06-1 CjH NO 125 (at 25mm)
Acrylonitrlle 107-13-1 C3HJN 77.5-77.9
Af latoxins
1402-68-2
AH
MELTING COMBUSTION
POINT °C KCAL/raol MOI.KCU1.AR WEIGHT STRUCTURE
167
537.67
118.17
-87.7 389.68 56.07 CM-C«-jjM
84.0-85.0 408.71 71.08
e
-82.0 421 53.07
ca. 237-289
+ similar structures
-------
NAME
CAS
REGISTRY MO.
FORMULA
BOILING
POINT *C
Aldrln 309-00-2 C12H8C16
Allyl alcohol
107-18-6
C3H6°
97.0
ro
en
Aluminum phosphide
1302-76-7
A1P
4-Aminobiphenyl
92-67-1
C12H11N 302,0
6-Amlno-l,la,2,8,
8a,8b-hexahydro-8-
(hydroxymethyl)-8a-
methoxy-5-methyl -
carbamate azlrlnol2',
3*:3#4]pyrrololl,
2-aJlndole*-4,7-dione,
(ester) (Mitomycin C)
4055-39-4
C15W5
MELTING
POINT *C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
104-104.5
364.90
-129.0
450.19
58.09
CM- tH-C<1000 57.96
53.0 1524 169.24
O-O
>360
344.37
1
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
5-(Aminomethyl)- 2763-96-
3-isoxazolol
C4H6N2°2
Amitrole
61-82-5
N>
Ui
^ Aniline
62-53-3
C6H?N 184-186
Antimony 7440-36-0 Sb 1380
and compounds,
N.O.S.
(as Antimony)
Aramite 140-57-8 C.-H--C10.S 195
15 23 4
AH
MELTING COMBUSTION
POINT "C KCAL/mol MOLECULAR WEIGHT amuLimui
175d 545.49 114.12
a.
159 343 84.10
-6(solidifies) 812 93.12
cr
O*
630.5 121.75
-37.1
334.86
i*y \ .*
cvt-c-f X-o-Mjtu-o-i-ouijajfi
—/ tMi
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Arsenic
and compounds
N.O.S. (as Arsenic)
7440-38-2
Arsenic acid
7778-39-4
As
613 subl.
HjAsO^.1/2 H20
-v
at 160
IS3
Ln
U>
Arsenic pentoxlde
1303-28-2
As2°5
Arsenic trloxide
1327-53-3
ta2°3
457.2
Auramine
492-80-8
c17h2iN3
MELTING
POINT °C
&H
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
817(at 3.0 * 104mm) 74.92
35.5 141.93 WO-tJm-OM JiMjO
<*»
315d 229.84 fts - O -
o o
275 197.84 o-n»-o-A,.o
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Azascrine 115-02-6 C_H_N_0.
5 7 3 4
Barium 1304-28-5 Ba 1140
iind compounds,
N.O.S. (an Barium)
Barium cyanide 542-62-1 C^BaNj
Benz(c.)ncrldlne 63040-05-1 ^17^11^
Bens (a)antliraccne 56-55-3
435(at 760mm)
subl.
MELTING
POINT °C
AH
COMBUSTION
KCAL/nol
MOLECULAR WEIGHT
STRUCTURE
725
dec in air
173.15
* i
137.34
189.38
229.29
162
2144
228.30
-------
NAME
CAS
RECISTRY NO.
FORMULA
BOILING
POINT *C
Benzene
71-43-2
C6H6
80.1
Benzenearsonlc acid 98-05-5
ho
Ln
Ul
Benzene, dichloromcthyl- 98-87-3
l:7H6C12 205
Benzenetlilol
108-98-5
CfiHgS 168.7
Benzidine
92-87-5
ca. 400
AH
MELTING COMBUSTION
POINT °C KCAL/mol MOLECULAR WEIGHT STRUCTURE
5.5 781 78.11
158-162d 202.05
-14.8 928 110.18
Olr
-17(solidlfics) 161.03 O""1"*
o
ca. 115-128 1558 184.24
oo
-------
NAME
CAS
REGISTRY HO,
FORMULA
BOILING
POINT °C
Benzo(b)fluoranthcnG 205-99-2 C20^12
Bcnzo(j)fluoroanthene 205-82-3 C20H12
ro
Ui Benzo(o)pyrene 50-32-8 C.ft H.,., 310-312
ON 20 1Z
p-Benzoquinone 106-51-4 C,H.0« subl.
6 4 2
Benzotrlchlorlde 8-07-7
C7«5C13
220.8(at 760mm)
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE^
217
ca. 2340
252.32
165
ca. 2340
252.32
179-179.3 ca. 2340
252.32
115.7
-5.0
108.09
195.47
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT "C
Benzyl chloride 100-44-7
Beryllium and 7440-41-7
compounds, N.O.S.
(as Beryllium)
Bls(2-chloroethoxy) 111-91-1
methane
Bio(2-chloroethyl) 111-44-4
ether
N,N-Bis(2-chloro- 494-03-1
ethyl)-2-
naphthy limine
C7H?C1 179.3
Be 2970
CAHgCl20 178(at 760mm)
C14H15C12N 210(at 5mm)
MELTING
POINT "C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-39.0 886.4
1278+5
-24.5
173.05
143.02
-CH^Cl
54-56
268.20
00—
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
His (2-chloroisopropyt) 108-60-1
ether
Bis(chloromethyl) 542-88-1
ether
Bis(2-ethylhexyl)
phthalate
117-81-7
Bromoacetone 598-31-2
Bromomcthane 74-83-9
C6H12C12°
187(at 760mm)
C2H4C12°
104(at 760mm)
C24H38°4
ca. 384
C3H5Br°
136.5
3.56
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
171.07 H.C.-C.-0-C-CH.
i I I »
CM CI
-41.5
114.96
ca. -50
3290
390.62
9
c- O-Cdj-C*1 •yx,
O M-W,
-36.5
136.98
-93.6
328.4
94.94
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
4-Bromophenyl
phenyl ether
101-55-3 '
C12H9Bt°
310.14
Brucine
357-57-3
JO
Ui
V0 2-Butanonc peroxide 1338-23-4
C8H16°4
Butyl benzyl 85-68-7
phthalate
C19H20°4
2-sec-Butyl-4,6 88-85-7 C|nH.,N 0
dlnitxophenol lu " ' 1
(DNBP)
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Cadmium and 7440-43-9 Cd 765
compound 8, N. 0. S.
(as Cadmium)
Calcium chromate 8012-75-7 CaCrO^^^O
Calcium cyanide 592-01-8 C^CaN^
Carbon disulfide 75-15-0 CS2 46.3
Carbon oxyfluoride
353-50-4
-83 (at 760mni)
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
320.9
. ~2H20 at 200
>350 d
-110.8
-114
112.40
192.09
c*,c.v oif ¦ an^o
92.12
403
76.14
S c c -s
66.01
o
0
-c-r
-------
CAS BOILING
NAME REGISTRY NO. FORMULA POINT °C
Chloral CjHCljO 97.8
(as hydrate)
Chlorambucil 305-03-3 ^14^19^2^2
to
ON
Chlordane 57-74-9 C^HjClg 175
(alpha' and gamma
Isomers)
Chlorinated C,R,_ CI
benzenes, N.O.S.
Chlorinated C_H, CI
ethane, N.O.S.
MELTING
POINT "C
AH
COMBUSTION
KCAL/raol
MOLECULAR WEIGHT
STRUCTURE
-57.5
147.40
64-66
304.23
m o- 2 y*^yyi),
104-106
409.80
c,»
-------
CAS BOILING MELTING
NAME REGISTRY NO. FORMULA POINT °C POINT °C
Chlorinated
fluorocarbons, N.O.S*
Chlorinated __ C1QH_ CI
naphthalene, N.O.S.
Ni
Chlorinated phenol, C.H CI 0
N.O.S.
Chloroacetaldehyde 107-20-0 C2H3C10 85-85.5(at 748mm)
Chloroalkyl ethers, N.O.S.
AH
COMBUSTION
KCAL/mol MOLECULAR WEIGHT STRUCTURE
-------
CAS BOILING
NAME REGISTRY HO. FORMULA POINT"C
p-Chlaroaniline 106-6 7-8
C6H6C1H
232 (st 760ran)
Chlorobenzene
108-90-7
w1
132
NJ
ON
w Chlorobenzilate 510-15-6
C16HWC12°3
p-Ch]oro-m-creBol 59-50-7
c7h7cio
235 (at 760mn)
l-Chloro-2,3-
epoxypropane
106-89-8
c3h3cio
116.5
H£LTING
POINT *C
&n
COMBUSTION
KCAT./mol
MOLECULAR WEIGHT
STRUCTURE
72.5 127.58
0
-45.6 744 112.56 / \
O
325.20 a
66-68
142.59
-48
423
92.53
/ \
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
2-Chloroethyl
vinyl ether
110-75-8
Chloroform
67-66-3
C,H,C10
4 7
108(at 760mn>)
CHC1,
61.7
Chloromethane 74-87-3 CII.C1 -23.7
N> 3
ON
Chloromethyl 107-30-2 C.IUC10 59.15
methyl ether
2-Chloronaphthalene 91-58-7 C^^H^Cl 256
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR HEIGHT
STRUCTURE
106.55
-63.5
119.38
-97.73
50.49
-103.5
80.52
=-»*ac-o-c>»3
61
1199
162.62
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT *C
2-Chlorophenol 95-57-8 CjHjCIO 174.9
l-(o-Chlorophenyl) C^H^ClNjS
thiourea
ro
Ln
3-Chloroproplo- 542-76-7 C,H.C1N 175-176
nit rile J *
Chromium and 7440-47-3 Cr 2672
compounds, N.O.S.
(as Chromium)
Chrysene
218-01-9
C18»12
448
MELTING
POINT *C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
9.0
ca. 695
128.56
202.67
-51 89.53
1857+20 51.996
6"
¦» 5
i 1
H-C -
Or
Cl tH
255-256
2139.1
228.30
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Citrus Red No. 2 6358-53-8 C ftH fiN.O,
Coal Tars 8007-45-2
to
ON
ON
Copper cyanide 544-92-3 CCuN d
Creosote 8001-58-9 ca 203
Cresoli
1319-7 -3
195-205
AH
MELTING COMBUSTION
POINT °C KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
473
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Croton- 123-73-9 caha° 104-105
aldehyde 4 •
Cyanides (soluble salts
and complexes), N.O.S.
N>
as
Cyanogen 460-19-5 CjN -21.17
Cyanogen bromide 506-68-3 CBrN 61-62
Cyanogen
chloride
506-77-4
CC1N
12.66
AH
MELTING COMBUSTION
POINT *C KCAL/mol MOLECULAR WEIGHT STRUCTURE
-74 546.71 70.09
-27.9 261 52.04 h
52 105.93
6v-Ch
-6
61.47
C»-C H
-------
CAS BOILING
NAME REGISTRY NO. FORMULA POINT °C
Cyc.asin 1490J.-08-7 CgH^N^
2-Cyclohexyl-4,6- 131-89-502 C..N^O.
dinitrophenol
hO
ON
Cyclophosphamide 50-18-0 C^H^C^^OjP
Daunomycln 20830-81-3 ^27^29^10
DDI) 72-54-8 C^.H^Cl,
14 10 4
MELTING
POINT *C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
154 d
252.22
«N|6H
/l M •« '
106.5-107.5
266.25
V.
41-45
261.10
•v
188-190d
109-1.L0
527.51
320.05
oei». ©
L 4^"
-------
NAME
CAS
REGISTRY HO.
FORMULA
BOILING
POINT °C
DDE 72-55-9 C14H8C14
DDT 50-29-3 C14H9C15 260
N>
ON
VO
Diallate 2303-16-4 C1()H17CX2NOS 150
Dlbenz(a.h) 226-36-8 C..H.-N
acrldlne
Dlbenz(a,j)
acrldlne
224-42-0
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Dibcnz(a,h) 53-70-3 C22H14 subl#
anthracene
7H-Dibenzo(c,g) 194-59-2 C.-B.N
carbazole zu AJ
N>
O Dibenzo(a.e) 192-65-4 C24H14
pyrenc
Dibenzo(a,h) 189-64-4 coahia
pyrene
Dibenzo(a,i)
pyrene
191-30-0
AH
MELTING COMBUSTION
POINT "C KCAL/mol MOLECULAR WEIGHT STRUCTURE
266 278.36
158 267.34
233-234 302.38
281.5-282 302.38
353-355 302.38
-------
NAME
CAS BOILING
RF.G]Sl'RY NO. FORMULA POINT °C
1,2-Dibrooio-3~ 96-12-8
c hlorop ropntie
C3H5Br2Cl 196
J,2-Ulbroraoethanp 106-93-4
C-H.Br, 131.36
2 4 2
ro
Dlbromomethane
74-95-3
CH2Br2
97
Dl-n-buLy.l
ptithalatc
84-74-2
C16H22°4
340
Dlchlorobenzene
(meta, ortho and
para Isomer*)
Di chlorobenzene, N. 0. S.
25321-22-6
WJ2
ca.174-181
MELTING
POIHT °C
fill
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
236.35
9.79 187.87
-52.55 173.85
en. -35 2055
278.38
o
ca. -17 -53 ca. 701-708
147.00
-------
CAS BOILING
REGISTRY NO. FOKMULA POINT °C
3,3'-l)ichluro- 91-94-1 C.-H.-Cl N.,
benzidine 12 10 2 ^
lfA-Dichloro-2- 764-41-0 C.H-C1„ 152.5(At 758mm)
buteue 462
N3
N>
Dichlorodi- 75-71-8 CCl2F2 -29.8(at 760mm)
fluoromethane
1,1-Dichloroethane 75-34-3 C2**4^2 57.28
1,2-Dichloroethane
107-06-2
c2h4ci2
83-84
HEI.TING
POINT °C
AH
COMBUSTION
KCAL/aol
MOLECULAR WEIGHT
STRUCTURE
132-133
-48
-158
-96.98
125.00
t-t CM CH * CM CH. CI
120.92
F-C-C|
298
98.96
-35.36
297
98.96
C-IHjC" th^c.1
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT *C
trans-1,2-
Dicliloroethene
15G-60-5
Dichloroethylene,
N.O.S.
c2h2ci2
47.5
C2H2C12
59.6(at 745mm)
to
^ 1,1-Dichloroethylene 75-35-4 31.7(at 760ram)
Dlchloromethane 75-09-2 CH^Cl^ 40
2,4 -Dlchlorophenol 120-83-2 C6H4CJL2° 210
AH
MELTING COMBUSTION
POINT "C KCAL/rool MOLECULAR WEIGHT STRUCTURE
CV
-49.4 262 96.94 C = C
-81.5 261-262 96.94 tiMt = CHCi
-122.1 262 96.94
-95.1 145 84.93
45
163.55
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
2,6-DtchloroplienoJ *7-65-0 C6H4(:l2° 219
2,4-Dicblorophenoxy 94-75-7 CqH^CI.O 160
acetic acid
Dichiorophenyl- 696-28-6 C6H5AsC12 252-255
arslnc
DiehIo rop ropane,
N.O.S
C31I6C12
76-122
1,2-DlcliJ.oropropane
78-87-5
C3»6C12
96.37
MELTING
POINT °C
AH
COMBUSTION
KCAL/rool
MOLECULAR WEIGHT
STRUCTURE
68-69
163.35
\
140-141
221.04
/\ 2
Vo-c^-c**
224.93
a
A»CI-
ca. -99-(-100)
111.97
CHj- CM" CM2Cj
-100.44
112.99
C" -CMC.I
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
FOINT °C
Dlcliloropropanol, C,H,C1_0
N.O.S.
Dicliloropropone, C_H, Cl_
N.O.S.
Is»
>4
^ 1,3-l)i chloropropene 542-75-6
Dleldrin 60-57-1 C12HgCl60
47-112
104-112
l,2:3,4-Dlepoxybutane 1464-53-5
138-144
HELTINC
POINT "C
AH
COMBUSTION
KCAL/rool
MOLECULAR WEIGHT
STRUCTURE
ca. 407 128.99 c»,ci-cMCi-eit oH
MnMtn-
-109-(-137)
110.97
ca.ci-ccl »c».
110.97
175-176
380.93
-19-4
86.09
/ \ /\
CK-«Ma
-------
CAS BOILING
NAME REGISTRY NO. FORMULA rOINT °C
Dietliylavslne 692-42-2 C^H^jAs 105
N,N-Diethylhydrazine 1615-80-1 C4H12N2 85-86
0,0--Diethyl S- 3288-58-2 C H 0 PS-
methyl ester of
phosphorodithioic.
. acid
0,0-DIef.hylphoGphoric 311-45-5 C J NO.P 169-170(at 1mm)
~ acid, 0-p-nitrophei»yl
ester
Diethyl phthalate 84-66-2
298
MELTING
POINT eC
AN
COMBUSTION
KCAL/moI
MOLECULAR WEIGHT
STRUCTURE
134.05
88.15
-ch -«h -*n-cw -ch,
200.25
m.-Crt . o
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
0,0-Diethyl 0- 297-97-2 C.H J 0 PS 80
2-pyrazinyl
pho sphorothioate
Diethylstilbesterol 56-53-1 CjqH2q02
ro
s|
Dihydrosafrole 94-58-6 C10H12°2
3,4-Dihydroxy- 51-43-4 -NO- d
alpha-(methyl-
amino)methyl
benzyl alcohol
Dllsopropyl 55-91-4
fluorophosphate
(DFP)
62 (at 9mni)
MELTING
POINT °C
AH
COMBUSTION
KCAL/moX
MOLECULAR WEIGHT
STRUCTURE
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Dimethoote 60-51-5 CgH^HO PSj,
3,3'-Diraethoxybenzidine 119-90-4 ^14^16^2^2
Ni
•«J
00
p-Dlmethylaminoazo- 60-11-7 C14H15N3 ^
bcuzene
7,12-Dimethylbenz(a) 57-97-6 C20HJ6
anthracene -
3,3'-Dlmethyl-
benzldine
119-93-7
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR HEIGHT
STRUCTURE
52-52.5
229.27
s o
P - 1 -CH.-C.-MH-CH
137
244.32
V
117
122-123 2462
131-132
225.32
256.36
212.32
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Dimethylcarbamoyl 79-44-7 C_tLCJ.N0
chloride 3 6
1,1-Dimethyl-
hydrazine
57-14-7
W2
63(at 752mm)
NJ
-«4
\D
1,2-Dimethyl-
hydrazlne
540-73-8
W2
81(at 753mm)
3,3-Dimethyl-l-
(tnethylthlo)-
2-buLanone, 0-
((raethylaraino)
carbony1) oxlme
[Thiofanox]
39196-18-4
C9H20N2°2S
alpha, alpha-
Dine tbylphenethyl-
amine
122-09-8
C10H1SN
MELTING
POINT *C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
107.55
«%. »
^ N - CCI
-55
473
60.12
-CH}
473
60.12
MN-CHj
218.35
O-M-c
Cfl. 1 t")
n«
II c-c-c
' I
cha-*"*s
-------
NAME
CAS
REGISTRY NO.
FORMULA
COILING
POINT °C
2, 4-Dltnethyl phenol
Dimethyl phthalate
Dimethyl sulfate
Dinitrobenzene,
N.O.S.
4,6-Dloitro-o-
cresol and salts
105-67-9
C8H10°
211.5
131-11-3
Clo"lO°4
283.8
77-78-1 C2H6°4S 188d
C.H.tl.O, 299-319
6 4 2 4
534-52-1
C7H6N2°5
MELTING
POINT °C
SH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-27(solidifies) 667.38
126.13
H.to-A-o£-K
89-174
692-734.8
168.11
86.5
198.14
on
V
-------
NAME
CAS
REGISTRY BO.
FORMULA
BOILING
POINT °C
2,4-Dlnitrophcnol 51-28-5 CgH^N^Oj
2,4-Dlnltrotoluene 121-14-2 300d
NS
00 2,6-Dloltiotoluene 606-20-2 C,H,N,0,
u / o Z 4
Dl-n-octyl 117-81-7 C,.H,Q0. 232-267
pbthalate
1,4-Dioxane
123-91-1
101(at 750nn)
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
70-71
846
182.14
66
851
182.14
ca. -50
390.54
c-o
-------
CAS BOILING MELTING
REGISTRY NO. FORMULA POINT °C POINT °C
Dlphenylamlne 122-39-4 ^J2^J.l^ 53-54
J.,2-Diphenyl 122-66-7 C12H12N2 131
hydrazine
N5
oo Di-n-propyl- 621-64-7 C-IL.N.O 205.9
nitrosamine
Dlsulfoton 298-04-4 C8"l9°2PS3 132-133(at J.Sinm)
2,4-Dlthlobluret
541-53-7
)81d
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
274.38
'V»-° l
-------
CAS BOILING
NAME REGISTRY NO. FORMULA POINT °C
Eudosulfan 115-29-7 C^Cl^S
Endrin 72-20-8 C12H8C160
and metabolites
Ethyl carbamate 51-79-6 C,H-N0_ 185(at 760mm)
(Urethan)
Ethyl cyanide 107-12-0 CjHjN 79(at 775mm)
Ethylenebls- 142-59-6
dithlocarbamlc acid,
salts and esters
WW2"*
AH
MELTING COMBUSTION
POINT *C KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
106
406.95
->o
245 d
380.93
J.5-50
397
89.11
MgN-l-OUIgtMj
< -66
55.08
256.34
t .
CHj-WI-C-5 I
1 1
-------
CAS BOILING MELTING
NAME REGISTRY NO. FORMULA POINT "C POINT °C
Ethyleneiraine 151-56-4 C2®5" 56-57(at 760mm)
Ethylene 75-21-8 C.H.O 10.7 -111
oxide
g Ethylene- 96-45-7 C3H6N2S 200-203
thiourea
Ethyl methacrylate 97-63-2 Si^lO*^ 117 (at 760mm)
Ethyl
methanesulfonate
62-50-0
C3H8°3S
ca. 85-86 (at lOmn)
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
'381
43.07
H
A
w
302
44.05
A.
"5
102.17
CT
114.16
124.17
CM-4-0-en.cn.
1 i '
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Fluoroanthene 206-44-0
C16H10
ra. 375
Fluorine
7782-41-4
-188.14
N)
CO
Ln 2-Fluoroacetamide 640-19-7
C.H.FNO
2 4
subl.
Fluoroacetic 62-74-8 C^H^FO^'Na
acid, sodium salt
Formaldehyde 50-00-0 Cll^O -21 (at 760mn>)
MELTING
POINT °C
111
AH
COMBUSTION
KCAL/mol
1892
MOLECULAR WEIGHT
202.26
STRUCTURE
-219.62
38.00
77.06
100.03
N
-------
NAME
CAS
REGISTRY NO.
FORMULA
COILING
POINT °C
Formic acid 64-18-6 100.5
Glycidylaldehyde 765-34-4 C3U4°2 ca. 13 2-113
CHjX -78-42
Ueptachlor 76-44-8 C^H^Cl^
Hcptachlor 1024-57-3 Cinn-Cl_0
epoxide 10 5 7
(alpha, beta and
gamma isomers)
to
00
lialomethane,
N.O.S.
MELTING
POINT ftC
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
8.4
61
46.02
O
q
CH-OH
ca. -62
72.06
V
-141-1-66)
CH,-X
X-F,CI,&r,a
95-96
373.35
V «•
389.30
-------
NAME
CAS
REGISTRY NO.
FORMU1A
BOILING
POINT "C
Hexachloro-
benzene
118-74-1
C6C16
323-326
Hexachloro-
butadieae
87-68-3
C4C16
215(at 760mm)
ro
00
Hex.-ichloro-
cvclohexane
(all Isomers)
608-73-1
C6»6C16
112-315
ltexachloro-
c yc lopen t ad lene
77-47-4
C5C16
239(at 753mm)
Hexnchloroethane 67-72-1
C2C16
166.8
MELTING
POINT "C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
sublimes v/out 173.8
melting
236.74
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT *C
1,2,3,4,10,10- 465-73-6 ci2HftC1*
Hexachloro-1,4,
4a,5,8,8a-
hexahydro-1,4:5,8-
endo, endo-
dimethanonaphthalenc
Hexachlorophane 70-30-4 C^^HgC1^02
to
CO
00 Hexacliloropropene 1888-71-7 C.C1-
J b
HexaetUyl 757-58-4 C,oH,A0,,P. >150d
t _ 12 30 13 4
tetraphosphate
Hydrazine
302-01-0
113.5
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
cycuj-o^u |,o-tVc*S
ca. -40 506.26
2.0 7.21 32.05 HjN-N^
-------
NAME
CAS
REGISTRY MO.
FORMULA
BOILING
POINT °C
Hydrocyanic ncld 74-90-8 CHN 25.6
Hydrofluoric acid 7664-39-3 HF 19.51
ro
oo
v£>
Hydrogen sulfide 7783-06-4 H^S -60.33
llydroxydlmethylarslne 75-60-5 C,Il1AsO,
oxide 2 7 2
Indeno (l,2,3-c,d)
pyrene
193-39-5
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-83.55
-85.49
195-196
27.03
HC !N
20.01
HF
34.08
~V
137.99
o
H3C-f'
ON
CHJ
276.34
-------
CAS BOILING
NAME REGISTRY NO. FORMULA POINT °C
Iodometharie 74-88-4 CH^I 42.5
Iron dextran 9004-66-4
(complex)
NJ
VO
O
Isocyanic acid, 624-83-9 C,H SO 59.6
methyl ester
Isobutvl alcohol 78-83-4 C,H,„0 108
4 10
Isoaafrole
120-58-1
253
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-66.5
105.93
141.95
ch3i
^180,000
-45
12.16
57.05
O-C-N-CH,
-108
638
74.12
CH CHCH.OH
3 I 1
CH,
6. 8
1233.9
162.20
CH.CH-CH.
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT *C
Kepone 143-50-0 C10Cl10°
Lasiocarpine 303-34-4 C2IH33N07
ro
VP
Lead and 7439-92-1 Pb 1740
compounds, N.O.S.
(as Lead)
Lead acetote 301-04-2 C,H~0,Pb
4 6 4
Lead phosphate 7446-27-7 0oP<,rb,
8 2 3
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
327.502
280
490.68
z
4X1.55
9~c-c»cm
it. M
207.19
325.29
O
" v I*
1014
811.59
Pb/ (P04S")t
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT ®C
MELTING
POINT eC
Le/id subncetate 1335-32-6
VioVS
Maleic
anhydride
108-31-6
C4«2°3
202.0
52.8
N>
VO
Maleic hydrazide
C.H N,0, 260d
4 2 2
>300
Malononltrlle 109-77-3
C3HjN2 218-219 (at 760mm) 32
Melphalan
148-82-3
182-183d
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
807.71
Pb2* (CH2- C-0" )2 2 [Pba\oH-
332.10
98.06
112.09
Y WH
O
395.03 66.07 C«2
NtN
305.23 ho-c«ch-cv/
-------
CAS BOILING
NAME REGISTRY NO. FORMULA POINT °C
Mercury fulminate 628-8(i-4 CgHjgllgOjS
Mercury and 7439-97-6 llg 356.58
compounds
N.O.S.
(as Mercury)
ho
VO
w Methacrylonltrile 126-98-7 C^H^N 90.3
Methanethlol 74-93-1 CH^S 5.95
Methapyrllene
91-80-5
173-175
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
explodes
-38.87
-35.8
-123
284.63 H,CCNO)4
200.59
67.09
48.11
162
261.42
r/S'V£v"-cHia,»-"C;
0
-------
NAME
CAS
REGISTRY NO.
FORMWA
BOILING
POINT °C
MKLTING
POINT °C
Metholmyl
16752-77-5
C5H10N2°2S
78-70
Methoxychlor 72-43-5
C16H15C13°2
78-78.2
86-88
fO
VO
2-Methylaziridine 75-55-8
C3H7N
3-Methylcholanthrene 56-49-5
C21»16
280 (at 80mm) 179-180
Methylchlorocarbonate 79-22-1
C2H3Cl02
71
All
COMBUSTION
KCAL/mol MOLECULAR WEIGHT STRUCTURE
162.23 CH -C^Vl-O-C-NH-C.H,
3 I 3
S-C-Mj
H
A
c«3
9 A. 50
O
ci-£-och3
-------
CAS BOILING MELTING
NAME REGISTRY NO. FORMULA POINT °C POINT *C
4,4' -Methylene- 101-14-4 C,-11 CI N,
bis (2-chloro- " 1 '
aniline)
Methyl ethyl 78-93-3 C.H-0 79.6 -86.35
ketone (MEK) * 0
ro
VO
Cn
Methyl 60-34-4 CH,N 87.5 < -80
hydrazine
2-Methyllacto- 75-86-5 C.H7H0 95 -19
nltrile * 1
Methyl
methacrylate
80-62-6
100-101 (at 760mm) -48
fiH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
584.17
72.12
CH -CH -C-CH.
3 * it 3
O
311.95
46.09
CHj-NM- NHg
85.12
fa
CN-C-CH.
l 3
OH
100.13
o
CH.0-C-C »CH—
3 i <¦
-------
CAS B01MNG
HAME REGISTRY NO. FORMULA POINT °C
Methyl
methanesulfonate 66-27-3 C^H^O^S 203 (at 753mm)
2-Methyl-2-(ioethylthio) 116-06-3 ^7^1A^2^2^
propionaldehyde
-O-(methylcarbonyl)
oxlste
vo
ON
N-Methyl-N1- 70-25-7 C.HJ.O.
nitro-N- 2 5 J 3
nitrosoguanidine
Methyl 298-00-0 CgH^NO^S
parathion
Methyl.
thiouracil
56-04-2
c5h6n2°s
MELTING
POINT "C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
411.86
110.14
O 6
CH,- S-CH.
1 I 3
o
99-100
190.29
cm, O
i * II
H,CS-C-CH=N-0-C-NHCH,
3 i 3
c,
147.12
HN = C-NH-NO,
t z
37-38
263.22
3 vP-0
C«_. o'
HOt
299-303d
142.19
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Mustard gas 505-60-2 C^HgC^S 215-217
Naphthalene 91-20-3 C10H8 217,9
N3
SO 1^-Naphthoquinone 130-15-4 C--1L0,, sub
Vi 10 O L
1-Naphthylamine 134-32-7 C10ll9N 301
2-Naphthylamine 91-59-8 C10H9N 306
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
1-Nap!ithyl 86-68-4 CilHiON2S
-2-thiourea
Nickel and 7440-02-0 Ni 2837
- compounds,
N.O.S.
(as Nickel)
to
VO
00
Nickel carbonyl
13463-39-3
C.NiO,
43
Nickel cyanide
557-19-7
C2N2Ni-AH20
Nicotine and
salts
54-11-5
C10«14N2
247 (at 745mm)
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
198
202.29
1555
58.71
-19.3 282.1
170.75
Ni4(C0-)4.
-4HZ0 (at 200)
182.79
Ni*
-------
CAS
NAME REGISTRY NO. FORMULA
Nitric oxide 10102-43-9 NO
p-Nitroantllne 100-01-6 C,H,N_0_
0 6 2 2
N)
VO
vO
VO Nitrobenzene 98-95-3 C,H.t!0
6 j 2
Nitrogen dioxide 10102-44-0 N0j
ROILING
POINT °C
-151.7
331.73
210.8 (at 760mm)
21.15
Nitrogen Mustard
and
hydrochloride salt
51-75-2
87
MELTING
POINT *C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-163.6
30.01
N = O
148.5-149.5 761.0
138.14
o
5.7
739.2
123.12
o
-9.3
46.01
0=N=0
-60
156.07
3 NnCH2-CH2GI
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Nitrogen mustard 126-85-2 C-TL Cl-NO('HCl)
N-Oxide and 302-70-5*CI(-HC1)
hydrochloride salt
Nitroglycerine 55-63-0 ^3^5^3^9 50-256d
4-Nitrophenol 100-02-7 C.H.NO. 279d
o J J
4-Nitroquinoline 56-57-5 CQH,No0-
-1-oxide
Nitrosamine,
N.O.S.
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
2-13 368.4
114.9-115.6 688.8
O"
172.07 CICH-CH,-N+-CH,
208.53 -HC1 CHj-CH^
CH,- O-NOj
227.11 GHa - O - NO,
CHZ- O - NOj
139.12 ht-f \-l\0.
o
190.17
R-N-N-0
i
R
R a o-lK-jl gt-oup
-------
NAME
CAS
REGISTRY NO.
FORMULA
BO] I.INC
POINT "C
MELTING
POINT "C
N-Nltrosodi-
n-butylamlne
924-16-3
C8HX8N2°
N-Nltrosodl-
ethanolaminn
1116-54-7
C4H10N2°3
O
N-Nitrosodl-
ethylamine
55-18-5
VloV
176.9
N-Nltrosodi- 62-75-9 C2H6H2° 153(at 774mm)
mcthylaninfi
N-Nitroso-N-
ethylurea
759-73-9
AH
COMBUSTION
KCAL/mol MOLECULAR WEIGHT STRUCTURE
N'O
158.28 CH3-CH£CH2-CH4-N-CH2-CH2-C»^-CI^
134.16 0»N-N-fCH4CM2OH)^
N=»0
102.16 CHjCHa-N-CH,,-CH3
N'O
74.10 CHj-N-CHj
117.13
N>0
CH3~CH2"N~C-NH1
-------
CAS BOIM.NG
NAM!: REGISTRY NO. FORMULA POINT °C
N-Nitrosomethyl- 10595-95-6 ^3M8^2^
erhylamine
N-Nitroso-N- 684-93-5 C2lI5N3°2
mothylurea
O N NJtroso-N- 615-53-2 C4H8N2°3 65
-------
NAME
CAS
REGISTRY NO,
FORMULA
BOILINC
POINT °C
N-Nitroso-
nornicotlne
16543-55-8
C9HnN30
N-Nitroso-
piperldine
100-75-4
C5"lON2°
217(at 721mm)
U>
O
oj
N-Nitroso-
pyrrolldine
930-55-2
c4h8n2°
ca. 214
N-Nitroso-
sarcooine
13256-22-9
W2°3
5-Nitro-o-toluldlne 99-55-8
C7H8N2°2
MELTING
POINT "C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
177.23
114.15
ca. 104-107 910 152.17
M=v
Oq
100.14
N=0 O
134.11 CH- N-CH^ C-OH
,o
)
MMa
-------
NAME
CAS
PEG1STRYN0.
Octaructhylpyropho
phoramide
s- 152-16-9
Osmium tetroxlde 20816-12-0
U> 7-0xabicyclo[2.2.1] 345-73-3
heptanfi-2,3-di-
carboxylic acid
FORMULA
BOILING
POINT °C
MELTING
POINT *C
C8»24N403P2
Il8-I22(at 0.3mm)
0,0s
4
130
39.5
C8H10°5
Paraldehyde 123-63-7 SiH12^3 ca* ^
Parathlon 56-38-2 C H NO PS 375(at 760mm) 6.1
10 14 5
AH
COMBUSTION
KCAL/inol
MOLECULAR WEIGHT
STRUCTURE
O o
286.30
254.20
O
II
o = o» = o
II
o
810
132.16
r~r
291.28
tevv>2
P'° \ /NC^
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT_!C
Pentachlorobenzene 608-93-5
C,HC1. 277
D D
Pentachloroethane 76-01-7
C2HC15 162(at 760mm)
O
U1 Pentachloronitro- 82-68-8
benzene (PCNB)
C.Cl.NO- 3?.8d (at 760mm)
© 5 4
Fentachlorophenol 87-86-5 C-.HC1-0 309-310(at 754mm)
o 5
Phenacetin 62-44-2 C10H13N02 d
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-------
NAME
CAS
REGISTRY NO.
Phenol
108-95-2
Phenylenediaminc
in 108-45-2
o 95-54-5
p 106-50-3
FORMULA
BOILING
POINT °C
W
181.75 (at 760irau)
C6H8N2
m 284-287
o 256-258
p 267
U>
O
ON
Phenylmercury 62-38-4 CgHgHgO^
acetate
N-riienylthlourea 103-85-5 C^HgN^S
Phosgene 75-44-5 CCl^O 7.56(at 760mm)
AH
MELTING COMBUSTION
POINT °C KCAL/mol MOLECULAR WEIGHT STRUCTURE
-118
98.91
ci2c - O
-------
NAME
CAS
REGISTRY NO.
FORMULA
COILING
POINT BC
Phoaphine
7803-51-2
hjp
-87.7
Pliosphorodlthioic 298-02-2
acid, 0,0-diethyl
S-((ethylthlo)methyl)
ester[Phorate)
C7H17°2PS3
Phosphorothlolc acid, 52-85-7
0?0-diraethyl 0-(p-
((dimethylanino)sulfonyl)
phcny1)ester[Fanphur]
CXOH16N05PS2
w
5 Phtlialic acid
esters, N.O.S.
riicliallc anhydride 85-44-9 CgH^O^ 295.1
2-Picollne
109-06-8
128-129
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-133
34.00
PH.
260.40
9
(CHjCH^O ^ P-SCH^S-CH4CH3
52.5-53.5
325.36
CV>|.o.
C M-o'
-70
93.12
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT *C
Polychlorinated 1336-36-3
biphenyl, N.O.S. x x
Potassium cyanide 151-50*8 CKN
U>
O
00
Potassium 506-61-6 C^AgKNj
silver cyanide
Pronamide 23950-58-5 C^H^l^NO
1,3-Propane sulfone 1120-71-4
C3H6°3S
ca. 180(at 30mm)
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
/ < » V
X*H ,CI
634.5
65.12
K+(CN")
199.01
K + Ag+ (CM")
256.14
ca. 30-33
122.15
c
o
K
-------
NAME
CAS BOILING MELTING
REGISTRY NO. FORMULA POINT °C POINT °C
n-Propylamine 107-10-8
c3h9n
48-49
-83
Propylthiouracil 51-52-5
C7H10N2OS
219
U>
O
VO 2-Propyn-l-ol 107-19-7
W
113.6(at 760mm) -48
Pyridine 110-86-1 C^N 115.5 -42
Reserplne
50-55-5
264-265d
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
565
59.11
ch5ch2ch2nh4
170.25
H
56.07
H-C5C-C-0H
i
H
665
79.11
608.75
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT "C
Reeorcinol 108-46-3 C6H6°2 280
Saccharin 81-07-2 C7H-N0-S sub vac
and salrs
U>
M
O
Safrole 94-59-7 C10H10°2 734-5
Selenlous add 7783-00-8 R^OjSe
Selenium and compounds, 7782-49-2
N.O.S.
(as Selenium)
Se
684.8
MELTING
POINT "C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
109-111
681
110.11
288.8-289.7d
183.19
11.2
1244
162.20
-------
u>
CAS BOILING
NAME REGISTRY NO. FORMULA POINT °C
Selenium sulfide 7446-34-6
Selenourea 630-10-4 CH.N.Se
4 2
Silver and compounds, 7440-22-4 Ag 2212
N.O.S.
(as Silver)
Silver cyanide 506-64-9 CAgN
Sodium cyanide
143-33-9
CNNa
1496
MELTING
POINT °C
A H
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
118-119d
111.02
S= Sc
200d
123.03
.Se
h2n-c-nh2
961.93
107.87
320d
133.89
A'(CN')
563.7
49.01
No.* (CN~)
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Streptoaotocin L8883-6C»-4 CoH-cN.,0,
o 13 J /
Strontium sulfide 1314-96-1 SSr
1-1 Strychnine and salts 57-24-9 C,,H,,N,0, 270(at 5mm)
IO tL il I t
1,2,4,5-Tetrachloro- 95-94-3 C6H2C14 243-246
benzene
2,3,7,8-Tetrachlorodi- 1746-01-6 C H.C1.0 > 700.)
benzo-o-dioxln (TCUIJ)
MELTING
POINT "C
A H
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
113d
265.26
>2000
119.68
S •= Sr
286-288
139.5-140.5
2686
334.45
215.88
305
321.96
-------
CAS BOILING
NAME REGISTRY NO. FORMULA POINT °C
Tetrachloroethane, 130-146
N.O.S. II*
1,1,1,2-Tetrachloro-
et.liane
630-20-6
C2H2C14
130.5(at 760nan)
U)
U>
1,1,2,2-Tetrachloro-
ethane
79-34-5
C2H2C14
146.2(at 7G0mm)
Tetracliloroethenc
127-18-4
121(at 760mm)
Tptrachlorone thane 594-42-3
147-148
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-70-(-36) ca. 230 167.84
-70.2 ca. 230 J67.84 ClsC-CH,,CI
-36 233 167.84 CljHC-CHC^
-19 199 165.82 CI2C-CCla
CI
I
-23 153.84 CI - C -CI
I
CI
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
2,3,4,6-Tetrachloro- 58-90-2 e^Cl^O 150 (at 15a0n)
phenol
Tetraethyl- 3689-24-5 CfcH20°5P2S2 136-139 (at 2mm)
dithiopyrophosphate
LO
Tetraethyl lead 78-00-2 CgHjgPb 200d
Tetraethylpyro- 107-49-3 ^8^20^7P2 155 (at 5mn>)
phosphate
Tetranitromethane 509-14-8 CS^Og 126
AU
MELTING COMBUSTION
POINT °C KCAL/mol MOLECULAR WEIGHT STRUCTURE
ON
322.34
CHyCH^o^" Q ^o-ch4-c«,
-136.80
1526
323.47
9VCn3
CHj-CHj-PW-C^-CH,
ch2"chs
170-213d
290.22
cvcv°4-
eHj-CVo'
O- L°-CMa-°*s
13.8
104
196.04
C -(NO,)^
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Thnltium and compounds 7440-28-0 T1 1457+10
N.O.S.
(ns Thallium)
Thallic oxide 1314-32-5 03T12 20,875
US Thalllun(I)acetote 563-68-8 C-H,0 *T1
i 2 3 2
Ui
Th.i] lium( L)carbonate 6533-73-9 C0^-2T1
Thalllum(I)chloride 7791-12-0
Cl-Tl
720
M Ml .TING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
303.5
717+5
131
273
204.37
456.74
O « T I" O-Tl
263.42
468.75
C O,
2T \
239.82
CI" Tl*
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
Thall.lum(l)nitrate 10102-45-1 NO^Tl 430
Thallium selenlte 12039-52-0 Se-Tl
w Thallium(I)sulfate 10031-59-1 "AST12 d
ON
Thioacetami.de 62-55-5 C^H^NS
Thlosemlcarbazlde
79-19-6
CHjNjS
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
206
266.38
MO " Tl*
283.33
Sc
T |i+
632
504.80
S04 ZT\
115-116
75.14
S
CH3-C - NHt
S
183d 415 91.15 H^N-C-NH'NH^
-------
CAS BOIT.ING
NAME REGISTRY NO. FORMULA POINT °C
Thiourea 62-.S6-6 CII^N^S
Thluram 1J7-26-8 C6H12N2S4 '29(at 20mm)
W
I-*
""J Toluene 108-88-3 C?Hg 110.6(at 760mm)
Tolucnedlnmine 25376-15-8 C7H10N2 255-292
o-Tolnldlnc
hydrochloride
636-21-5
c7h9n-hci
242.2(at 7fi0mm)
AI1
MELTING COMBUSTION
rOIHT °C KCAL/mol MOLECULAR WEIGHT
182
76.13
155-156
240.43
-95
935
92.15
< 0-106
122.19
STRUCTURE
5
ii
H2N-C-MH
s
(ch3)2-n-c-s -s-c -n
-------
CAS
NAME REGISTRY NO.
FORMULA
COTLINC
POINT °<;
Tola If iK* diisooyan.'! to .r»84-84-9
S"6N2°2
251 (nl 760iron)
Toxapliene
8001-35-2
C10ll]0tl8
> l')5d
to
K-»
00
Tri brotnomo thane
73-25-2
ClIBr-
149.5(at 760mm)
1,2,4-Trlchloro-
bcnzenc
.120-82-1
C(iH3C.1.3 213.5(at 760nsn)
1,1,1-Trlcbloroothane 71-55-6
74.1(nt 760ri'm)
MF.LTJNO
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
19.5-21.5
174.17
65-90
A13.80
*Y 1 '"s
"Kpt;
wwere * * M_ C \
8.3
252.75
H C Br,
16.95
181.44
-30.41
133.40
cci3- ch3
-------
(•AS BOILING
REGISTRY NO. FORMULA POINT "C
1,.!,2-TrlchLoroothane 79-00-5 C2H3Cl3 ll3.77(nt 760mm)
Tricliloroetliene 79-01-6 C2HCi3 87(at 760mm)
OJ
h-*
^ TriclOorometlianethioI 75-70-7 CHCl^S
Tr.lchloromonof ltioromethane 75-69-4 ^^3^ 23.7
2,4,5-TrichlorophenoJ. 95-95-4
C6H3C13°
subl.
MELTING
POINT °C
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
-36.5
133.40
-73
229
131.38
151.43
-111
137.38
68-70-5
197.44
CCI..H- CH^CI
CCIa= CCIH
cc\3-sh
ci
r -c-c»
1
CI
OH
-------
NAME
CAS
REGISTRY NO.
FORMULA
BOILING
POINT °C
2,4,6-Tri chlorophenol 88-06-2
2,4,5-Trichlorophenoxy- 93-76-5
arctic acid (2,4,5-T)
N>
O
2,4,5-Trichlorophenoxy- 93-72-1
propionic acid (2,4,5-TP)
(Silvox)
Trichloropropane,
H.O.S.
], 2,3-Tricliloiopropane 96-18-4
C6H3C13° 246 (at 760inln>
c8h5ci3o3
C9H7c13°3
C3«5C13 106-157
C3H5C13 156.85 (at 760ron)
MELTING
POINT °C
AH
COMBUSTION
KCAL/idoI
MOLECULAR WEIGHT
STRUCTURE
-60-(-15)
ca, 415
147.43
-14.7
415
147.43
CH^C I - CHCI - CM^CI
-------
CAS
REGISTRY NO.
FORMULA
BOIMNC
POINT
MELTING
TOINT X
0,0,0-Trietliyl.
phosphorothioate
1.26-68-1
C6H15°3PS
c.i. 100 (at J6nim)
sym-Trinltrobonzenc
99-35-4
W3°3
sublimes or
explodes
122.5
LO
N>
TrJ s(1-uzrld Lny1)
phosphlnc sulfide
52-24-4
C6H12N3PS
51.5
Ttris (2,3-dlbroraopropy I.)
plior.ph.ite
126-72-7
C9H15Br6°4P
Trypan blue
72-57-1
AH
COMBUSTION
KCAL/mol
MOLECULAR WEIGHT
STRUCTURE
198.22
CHiCH'O «
3 a vp.0.CH CH
CHS"C
656
213.12
XT
189.24
0 - p - <]
A
697.67
BrCHjCHB." C»C °Np.0.CYt^
BrCH^CHftr-CWj;0
960.83
h
xX
-------
CAS BOILING
NAME REGISTRY NO. FORMULA rOINT *C
Uracil mustard 66-75-1 V*11C*2N3^2
Vniuidlc Acid, 7803-55-6 H/(N°3V
.•inmtonJum 3/1 It
CO
to
ro
Vanadium pentoxide 1314-62-1 1750d
Vinyl chloride 75-01-4 C2H3C1 -I3.37(at 760inro)
?Anc cyanide 557-21-1 C^N^Zn
Zinc phosphide
1314-84-7
1100
MELTING
POINT "C
AH
COMBUSTION
(KCAL/racl
MOLECULAR WEIGHT
STRUCTURE
2064
690
-153.8
800d
>420
116.99
V03-V4H4.
181.88
v-o-v
o" -o
62.50
CI HC = CH,
117.41
258.06
Ccn-)2
(p3"X
-------
APPENDIX B
Hazardous Constituents - Stack Gas Sampling Methods
This appendix lists the Appendix VIII
Hazardous Constituents (as of the May
20, 1981 Federal Register) with a de-
scription of their most probable loca-
tion in the stack gas effluent sampling
scheme.
323
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS
Compound
Acetonitrile
Acetophenone
3-(alpha-Acetonylbenzyl)-4-hydi'oxycoumarin and salts (Warfarin)
2-Acetylaminofluorene
Acetyl chloride
l-Acetyl-2-thiourea
Acrolein
Acrylamide
Acrylonitrile
Aflatoxins
Aldrin
Allyl alcohol
Aluminum phosphide
4-Aminobiphenyl
6-Amino-l,la,2,8,8a, 8b-hexahydro-8- (hydroxymethyl) -8a-
methoxy-5-methylcarbamate azirino[2',3':3,4]pyrrolo
[l,2-a]indole-4,7-dione(ester) (Mitomycin C)
Description
Sorbent
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
. _ 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(c)acridine
Benz(a)anthracene
Benzene
STACK GAS SAMPLING METHODS (continued)
Description
Sorbent
Sorbent
Sorbent
Particulate/lmpingers
Sorbent
Particulate/lmpingers
Particulate/lmpingers
Particulate/lmpingers
Particulate/Impineers
Particulate/Sorbent
Sorbent
Particulate
Particulate(metal)/Impingers(CN)
Sorbent
Particulate/Sorbent
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
Sorbent
Bis(2-chloroisopropyl) ether
Sorbent
Bis(chloromethyl) ether
Sorbent
Bis(2-ethylhexyl) phthalate
Particulate/Sorbent
-------
HAZARDOUS CONSTITUENTS
Compound
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.
STACK GAS SAMPLING METHODS (continued)
Description
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
-------
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
Chlorobenzilate
Particulate/Sorbent
p-Chloro-m-cresol
Sorbent
l-Chloro-2,3-epoxypropane
Sorbent
2-Chloroethyl vinyl ether
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
Part iculate(metal)/Impingers(CN)
Sorbent
Sorbent
Special Reagent
Impingers
Gas Bulb
Gas Bulb
Gas Bulb
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
-------
HAZARDOUS CONSTITUENTS
Compound
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
Dichlorobenzene(meta, ortho and para isomers)
Dichlorobenzene, N.O.S.
3,3'-Dichlorobenzidine
STACK GAS SAMPLING METHODS (continued)
Description
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Gas Bulb
Particulate/Sorbent
Sorbent
Sorbent
Particulate/Sorbent
-------
HAZARDOUS CONSTITUENTS
- Compound
1,4-Dichloro-2-butene
Dichlorod ifluoromethane
1,1,-Dichloroethane
1,2-Dichloroethane
trans-1,2-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.
1.2-Dichloropropane
Dichloropropanol, N.O.S.
Dichloropropene, N.O.S.
1.3-Dichloropropene
STACK GAS SAMPLING METHODS (continued)
Description
Sorbent
Gas Bulb
Gas Bulb
Gas Bulb
Gas Bulb
Gas Bulb
Gas Bulb
Gas Bulb
Sorbent
Sorbent
Sorbent
Particulate/Impingers
Gas Bulb/Sorbent
Gas Bulb
Sorbent
Gas Bulb/Sorbent
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK
Compound
Dieldrin
1,2:3,4-Diepoxybutane
Diethylarsine
N,N-Diethylhydrazine
0,0—Diethyl S-methyl ester of phosphorodlthioic acid
0,O-Diethylphosphoric acid, 0-p-nitrophenyl ester
Diethyl phthalate
0,0-Diethyl 0-2-pyrazinyl phosphorothioate
Diethylstilbestrol (D.E.S.)
Dihydrosafrole
3,4-Dihydroxy-alpha-(methylamino)methyl benzyl alcohol
Diisopropylfluorophosphate (DFP)
Dimethoate
3,3Dimethoxybenzidine
p-Dimethylarainoazobenzene
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine
GAS SAMPLING METHODS (continued)
Description
Particulate/Sorbent
Sorbent
Impingers
Gas Bulb
Sorbent
Sorbent
Particulate/Sorbent
Gas Bulb
Particulate/Sorbent
Sorbent
Sorbent
Gas Bulb
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
-------
Compound
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (continued)
Description
Dimethylcarbamoyl chloride
1.1-Dimethylhydrazine
1.2-Dimethylhydrazine
3.3-Dimethyl-l-(methylthio)-2-butanone,0-((raethylamino)
carbonyl)oxime [Thiofanox]
alpha,alpha-Dimethylphenethy1amine
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
Sorbent
Gas Bulb
Gas Bulb
Particulate/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
-------
Compound
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (continued)
Description
1,2-Diphenylhydrazine
Di-n-^propylnitrosamine
Disulfoton
2,4-Dithiobiuret
Endosulfan
Endrin and metabolites
Ethyl carbamate (Urethan)
Ethyl cyanide
Ethylenebisdithiocarbamic acid, salts and esters (EBDC)
Ethyleneimine
Ethylene oxide
Ethylenethiourea
Ethyl methacrylate
Ethyl methanesulfonate
Fluoranthene
Fluorine
2-Fluoroacetamide
Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Impingers
Particulate/Sorbent
Gas Bulb
Gas Bulb
Sorbent
Sorbent
Gas Bulb
Particulate/Sorbent
Special Reagent
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS
' 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,4,4a,5,8,8a-hexahydro-l,4:5,8-
endo,endo-dimethanonaphthalene
Hexachlorophene
Hexachloropropene
Hexaethyl tetraphosphate
Hydrazine
Hydrocyanic acid
SAMPLING METHODS (continued)
Description
Sorbent
Special Reagent
Gas Bulb/Sorbent
Special Reagent
Gas Bulb
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Part icula te/Sorben t
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Gas Bulb
-------
HAZARDOUS CONSTITUENTS
Compound
Hydrofluoric acid
Hydrogen sulfide
Hydroxydimethylarsine oxide
Indeno(1,2,3-c,d)pyrene
Iodomethane
Iron dextran
Isocyanic acid, methyl ester
Isobutyl alcohol
Isosafrole
Kepone
Lasiocarpine
Lead and compounds, N.O.S.
Lead acetate
Lead phosphate
Lead subacetate
Maleic anhydride
Maleic hydrazide
STACK GAS SAMPLING METHODS (continued)
Description
Gas Bulb
Gas Bulb
Particulate/Impingers
Particulate/Sorbent
Gas Bulb
Particulate
Gas Bulb
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Impingers
Particulate/Impingers
Particulate/Impingers
Particulate/Impingers
Sorbent
Sorbent
-------
HAZARDOUS CONSTITUENTS
Compound
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
STACK GAS SAMPLING METHODS (continued)
Description
Sorbent
Particulate/Sorbent
Particulate/Impingers
Particulate/Impingers
Gas Bulb
Gas Bulb
Sorbent
Sorbent
Particulate/Sorbent
Gas Bulb
Particulate/Sorbent
Gas Bulb
Particulate/Sorbent
Gas Bulb
Gas Bulb
Gas Bulb
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (continued)
Compound.
Methyl methanesulfonate
2-Methyl-2-(methylthio)propionaldehyde-o-(methylcarbonyl)
oxime
N-Methyl-N'-nitro-N-nitrosoguanidine
Methyl parathion
Methylthiouracil
Mustard.gas
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
l-Naphthyl-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
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
STACK GAS SAMPLING METHODS (continued)
Description
Particulate/Sorbent
Sorbent
Gas Bulb
Gas Bulb
Sorbent
Sorbent
Sorbent
Sorbent
Gas Bulb/Sorbent
Sorbent
Sorbent
Sorbent
Gas Bulb/Sorbent
Sorbent
Gas Bulb/Sorbent
Sorbent
Sorbent
-------
HAZARDOUS CONSTITUENTS
Compound
N-Nitrosomethylvinylamine
N-Nitrosomorpholine
N-Nitrosonornicotine
N-Nitrosopiperidine
N-Nitrosopyrrolidine
N-Nitrososarcosine
5-Nitro-o-toluidine
Octamethylpyrophosphoramide
Osmium tetroxide
7-0xabicyclo[2.2.1]heptane—2,3-dicarboxylic acid
Paraldehyde
Parathion
Pentachlorobenzene
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenacetin
STACK GAS SAMPLING METHODS (continued)
Description
Gas Bulb/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
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-diraethyl 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 sultone
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
Particulate/Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Sorbent
Particulate/Impingers
Particulate/Impingers
Particulate/Impingers
Particulate/Impingers
Particulate
Particulate(metal)/Impinger s(CN)
Particulate(metal)/Impingers(CN)
Particulate/Sorbent
Particulate
-------
HAZARDOUS CONSTITUENTS
Compound
Strychnine and salts
1.2.4.5-Tetrachlorobenzene
2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)
Tetrachlorofethane, N.O.S.
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Tetrachloromethane
2.3.4.6-Tetrachlorophenol
Tetraethyldithiopyrophosphate
Tetraethyl lead
Tetraethylpyrophosphate
Tetranitromethane
Thallium and compounds, N.O.S.
Thallic oxide
Thallium(l)acetate
Thallium(l)carbonate
STACK GAS SAMPLING METHODS (continued)
Description
Particulate/Sorbent
Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Par t i culate/Sorbent
Particulate/Sorbent
Particulate/ Impingers
Particulate/Sorbent
Sorbent
Particulate
Particulate
Particulate
Particulate
-------
HAZARDOUS CONSTITUENTS
Compound
Thallium(l)chloride
Thallium(l)nitrate
Thallium selenite
Thallium(l)sulfate
Thioacetamide
Thiosemicarbazide
Thiourea
Thiuram
Toluene
Toluenediamine
o-Toluidine hydrochloride
Toluene 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
Sorbent
Sorbent
Sorbent
Gas Bulb
Sorbent
-------
HAZARDOUS CONSTITUENTS - STACK GAS SAMPLING METHODS (continued)
Compound
Description
Trichloroethene
Trichloromethanethiol
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 or Silvex)
Trichloropropane, N.O.S.
1,2,3-Tr ichloropropane
0,0,0-Triethyl phosphorothioate
sym-Trinitrobenzene
Tris (1-azridinyl) phosphine sulfide
Tris(2,3,-dibromopropyl)phosphate
Trypan blue
Uracil mustard
Vanadic acid, ammonium salt
Vanadium pentoxide
Gas Bulb
Gas Bulb
Gas Bulb
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate/Sorbent
Particulate
Particulate
-------
HAZARDOUS CONSTITUENTS
Compound
Vinyl chloride
Zinc cyanide
Zinc phosphide
N.O.S. = not otherwise specified
Co
¦e-
STACK GAS SAMPLING METHODS (continued)
Description
Gas Bulb
Particulate(metal)/Impingers(CN)
Particulate
-------
APPENDIX C
Hazardous Constituents—Analysis Methods
This Appendix lists the Appendix VIII
Hazardous Constituents (according to
the May 20, 1981, Federal Register)
with their corresponding Analysis Method
Numbers, as found in Section VI. A short
descrption of the method number is also
included.
349
-------
Compound
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Method Number
OJ
1/1
Acetonitrile
Acetophenone
3-(alpha-Acetonylbenzyl)-4-hydroxycoumarin and salts (Warfarin)
2-Acetylaminofluorene
Acetyl chloride
l-Acetyl-2-thiourea
Acrolein
Acrylamide
Acrylonitrile
Aflatoxins
Aldrin
Allyl alcohol
Aluminum phosphide
4-Aminobiphenyl
6-Amino-l,la,2,8,8a,8b-hexahydro-8-(hydroxymethyl)-Sa-
me thoxy-5-methylcarbamate azirino[2',3':3,4]pyrrolo
[l,2-a]indole-4,7-dione(ester) (Mitomycin C)
A101
A121
A122
A121
A144
A123
A101
A101
A101
A145
A121
A134
A253
A121
A122
Description
Volatiles
Extractables
HPLC
Extractables
Acid chlorides
HPLC
Volatiles
Volatiles
Volatiles
Extractables
Alcohols
Phosphides
Extractables
HPLC
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
u>
Ln
to
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(c)acridine
Benz(a)anthracene
Benz ene
Method Number
A121
A121
A121
A221
A121
A222
A222
A222
A222
A121
A123
A223
A223
A252
A121
A121
A101
Description
Extractables
Extractables
Extractables
Antimony
Extractables
Arsenic
Arsenic
Arsenic
Arsenic
Extractables
HPLC
Barium
Barium
Cyanides
Extractables
Extractables
Volatiles
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
Benzenearsonic acid
Benzene, dichloromethyl-
Benzenethiol
Benzidine
Benzo(b)fluoranthene
Benzo(j)fluoranthene
Benzo(a)pyrene
p-Benzoquinone
Benzotrichloride
Benzyl chloride
Beryllium and compounds, N.O.S.
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
A222 Arsenic
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A101 Volatiles
A121 Extractables
A224 Beryllium
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
Method Number
Description
Bromoacetone
A101
Volatiles
Bromomethane
A101
Volatiles
4-Bromophenyl phenyl ether
A121
Extractables
Brucine
A148
—
2-Butanone peroxide
A121
Extractables
Butyl benzyl phthalate
A121
Extractables
2-sec-Butyl-4,6-dinitrophenol (DNBP)
A121
Extractables
Cadmium and compounds, N.O.S.
A225
Cadmium
Calcium chromate
A226
Chromium
Calcium cyanide
A252
Cyanides
Carbon disulfide
A101
Volatiles
A141
Gases
Carbon oxyfluoride
A101
Volatiles
Chloral
A131
Aldehydes
Chlorambucil
A122
HPLC
Chlordane (alpha and gamma isomers)
A121
Extractables
Chlorinated benzenes, N.O.S.
A101
Volatiles
A121
Extractables
Chlorinated ethane, N.O.S.
A101
Volatiles
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
Method Number
Description
Chlorinated fluorocarbons, N.O.S.
A101
Volatiles
Chlorinated naphthalene, N.O.S.
A121
Extractables
Chlorinated phenol, N.O.S.
A121
Extractables
Chloroacetaldehyde
A131
Aldehydes
Chloroalkyl ethers, N.O.S.
A101
Volatiles
p-Chloroaniline
A121
Extractables
Chlorobenzene
A101
Volatiles
Chlorobenzilate
A121
Extractables
p-Chloro-m-cresol
A121
A122
Extractables
HPLC
l-Chloro-2,3-epoxypropane
A101
Volatiles
2-Chloroethyl vinyl ether
A101
Volatiles
Chloroform
A101
Volatiles
Chloromethane
A101
Volatiles
Chloromethyl methyl ether
A101
Volatiles
2-Chloronaphthalene
A121
Extractables
2-Chlorophenol
A121
A122
Extractables
HPLC
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
Method Number
Description
l-(o-Chlorophenyl)thiourea
A123
HPLC
3-Chloropropionitrile
A121
Extractables
Chromium and compounds, N.O.S.
A226
Chromium
Chrysene
A121
Extractables
Citrus Red No. 2
A149
—
Coal tars
A121
Extractables
Copper cyanide
A252
Cyanides
Creosote
A121
Extractables
Cresols
A121
Extractables
Crotonaldehyde
A123
HPLC
A131
Aldehydes
Cyanides (soluble salts and complexes), N.O.S.
A252
Cyanides
Cyanogen
A138
Gases
Cyanogen bromide
A138
Gases
Cyanogen chloride
A138
Gases
Cycasin
A150
—
2-Cyclohexyl-4,6-dinitrophenol
A121
Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
(Continued)
Method Number
Description
Cyclophosphamide
—
Daunomycin
A122
HPLC
DDD
A121
Extractables
DDE
A121
Extractables
DDT
A121
Extractables
Diallate
A121
Extractables
Dibenz(a,h)acridine
A121
Extractables
Dibenz(a,j)acridine
A121
Extractables
Dibenz(a,h)anthracene
A121
Extractables
7H-Dibenzo(c,g)carbazole
A121
Extractables
Dibenzo(a,e)pyrene
A121
Extractables
Dibenzo(a,h)pyrene
A121
Extractables
Dibenzo(a,i)pyrene
A121
Extractables
1,2-Dibromo-3-chloropropane
A101
Volatiles
1,2-Dibromoethane
A101
Volatiles
Dibromomethane
A101
Volatiles
Di-n-butyl phthalate
A121
Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
Method Number
Description
Dichlorobenzene(meta, ortho and para isomers)
A121
Extractables
Dichlorobenzene, N.O.S.
A101
Volatiles
A121
Extractables
3,3'-Dichlorobenzidine
A121
Extractables
1,4-Dichloro-2-butene
A101
Volatiles
Dichlorodifluoromethane
A101
Volatiles
1 ,1-Dichloroethane
A101
Volatiles
1,2-Dichloroethane
A101
Volatiles
trans-1,2-Dichloroethene
A101
Volatiles
Dichloroethylene, N.O.S.
A101
Volatiles
1,1-Dichloroethylene
A101
Volatiles
Dichloromethane
A101
Volatiles
2,4-Dichlorophenol
A121
Extractables
A122
HPLC
2,6-Dichlorophenol
A121
Extractables
A122
HPLC
2 ,4-Dichlorophenoxyacetic acid (2,4-D)
A122
HPLC
A133
Carboxylic acids
Dichlorophenylarsine
A222
Arsenic
Dichloropropane, N.O.S.
A101
Volatiles
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
Method Number
Description
1,2-Dichloropropane
A101
Volatiles
Dichloropropanol, N.O.S.
A121
Extractables
Dichloropropene, N.O.S.
A101
Volatiles
1,3-Dichloropropene
A101
Volatiles
Dleldrin
A121
Extractables
1,2:3,4-Diepoxybutane
A121
Extractables
Diethylarsine
A222
Arsenic
N,N-Die thylhydraz ine
A121
Extractables
0,0-Diethyl S-methyl ester of phosphorodithioic acid
A121
Extractables
0,0-Diethylphosphoric acid, O-p-nitrophenyl ester
A121
Extractables
Diethyl phthalate
A121
Extractables
0,0-Diethyl 0-2-pyrazinyl phosphorothioate
A121
Extractables
Diethylstilbestrol (D.E.S.)
A123
HPLC
Dihydrosafrole
A121
Extractables
3,4-Dihydroxy-alpha-(methylamino)methyl benzyl alcohol
(Epinephrine) A123
HPLC
Diisopropylfluorophosphate (DFP)
A121
Extractables
Dimethoate
A121
Extractables
3,3'Dime thoxybenzidine
A121
Extractables
-------
HAZARDOUS CONSTITUTENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
p-Dime thylaminoazob enzene
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine
Dimethylcarbamoyl chloride
1.1-Dime thylhydrazine
1.2-Dimethylhydraz ine
3.3-Dimethyl-l-(methylthio)-2-butanone,0-((methylamino)
carbonyl)oxime[Thiofanox]
alpha,alipha-Dimethylphenethylamine
2.4-Dimethylphenol'
Dimethyl phthalate
Dimethyl sulfate
Dinitrobenzene, N.O.S.
4,6-Dinitro-o-cresol and salts
2,4,-Dinitrophenol
2,4-Dini trotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
A121 Extractables
A121 Extractables
A121 Extractables
A144 Acid chlorides
A121 Extractables
A121 Extractables
A183 Oximes
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A122 HPLC
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
-------
HAZARDOUS CONSTITUTENTS—ANALYSIS METHODS (Continued)
Compound Method Number Description
1,4-Dioxane
Diphenylamine
1,2-Diphenylhydrazine
Di-n-proplnitrosamine
Disulfoton
2,4-Dithiobiuret
Endosulfan
Endrin and metabolites
Ethyl carbamate (Urethan)
Ethyl cyanide
Ethylenebisdithiocarbamic acid, salts and esters (EBDC)
Ethyleneimine
Ethylene oxide
Ethylenethiourea
Ethyl methacrylate
Ethyl methansulfonate
Fluoranthene
A101 Volatiles
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A121 Extractables
A252 Cyanides
A121 Extractables
A156
A123 HPLC
A121 Extractables
A121 Extractables
A121 Extractables
-------
HAZARDOUS CONSTITUTENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Fluorine
2-Fluoroacetamide
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,4,4a,5,8,8a-hexahydro-l,4:5,8-
endo,endo-dimethanonaphthalene
Description
A137
A157
A121
A131
A101
A121
A131
A101
A121
A121
A121
A121
A121
A121
A101
A121
A121
Extractables
Aldehydes
Volatiles
Extractables
Aldehydes
Volatiles
Extractables
Extractables
Extractables
Extractables
Extractables
Extractables
Volatiles
Extractables
Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
Compound
Hexachlorophene
Hexachloropropene
Hexaethyl tetraphosphate
Hydrazine
Hydrocyanic acid
Hydrofluoric acid
Hydrogen sulfide
Hydroxydimethylarsine oxide
Indeno(l,2,3-c,d)pyrene
Iodomethane
Iron dextran
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
Methyapyrilene
Metholmyl
Methoxychlor
2-Methylaziridine
3-Methylcholanthrene
Method Number Description
A227 Lead
A227 Lead
A227 Lead
A227 Lead
A121 Extractables
A121 Extractables
A121 Extractables
A122 HPLC
A228 Mercury
A228 Mercury
A121 Extractables
A101 Volatiles
A121 Extractables
A122 HPLC
A121 Extractables
A121 Extractables
A121 Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
Methylchlorocarbonate
4,4'-Methylenebis(2-chloroaniline)
Methyl ethyl ketone (MEK)
Methyl hydrazine
2-Methyllactonitrile
Methyl methacrylate.
Methyl methanesulfonate
2-Methyl-2-(methylthio)proprionaldehyde-o-(methylcarbonyl)
oxime
N-Methyl-N'-nitro-N-nitrosoguanidine
Methyl parathion
Me thy1th iourac i1
Mustard gas
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naph thylamine
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-123 HPLC
-------
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-Nitroaniline
Nitrobenzene
Nitrogen dioxide
Nigrogen mustard and hydrochloride salt
Nitrogen mustard N-Oxide and hydrochloride salt
Nitroglycerine
4-Nitrophenol
4-Ni troquinoline-l-oxide
Nitrosamine, N.O.S.
N-Nitrosodi-n-butylamine
N-Nitrosodiethanolamine
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 CONSTITUTENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Description
N-Nitrosodiethylamine
Nitrosodimethylamine
N-Ni tro so-N-ethylurea
N-Nitrosomethylethylamine
N-Nitroso-N-methylurea
N-Ni troso-N-methylurethane
N-Nitrosomethylvinylamine
N-Ni t ro somorpho1ine
N-Nitrosonornicotine
N-Nitrosopiperidine
N-Nitrosopyrrolidine
N-Nitrososarcosine
5-Nitro-o-toluidine
Oc tamethylpyrophosphoramide
Osmium tetroxide
7-0xabicyclo[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 acids
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
OJ
ON
oo
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]
A131
A121
A121
A121
A121
A121
A174
A121
A122
A121
A228
A123
A138
A136
A121
A121
Description
Aldehydes
Extractables
Extractables
Extractables
Extractables
Extractables
Extractables
HPLC
Extractables
Mercury
HPLC
Gases
Extractables
Extractables
Phthalic acid esters, N.O.S.
A121
Extractables
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS
. . Compound
Phthalic anhydride
2-Picoline
Polychlorinated biphenyl, N.O.S.
Potassium cyanide
Potassium silver cyanide
Pronamide
1,3-Propane sultone
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
A175
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
Tetrachloromethane
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 CONSTITUTENTS—ANALYSIS METHODS (Continued)
Compound
Method Number
Description
2,3,4,6-Tetrachlorophenol
A121
Extractables
A122
HPLC
Tetraethyldithiopyrophosphate
A121
Extractables
Tetraethyl lead
A227
Lead
Tetraethylpyrophosphate
A121
Extractables
Te t rani trome thane
A101
Volatiles
Thallium and compounds, N.O.S.
A234
Thallium
Thallic oxide
A234
Thallium
Thallium(l)acetate
A234
Thallium
Thallium(l)carbonate
A234
Thailium
Thallium(l)chloride
A234
Thallium
Thallium(l)nitrate
A234
Thallium
Thallium selenite
A234
Thallium
Thallium(l)sulfate
A234
Thallium
Thioace tamide
A123
HPLC
Thiosemicarbazide
A123
HPLC
Thiourea
A123
HPLC
Thiuram
A122
HPLC
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound Method Number
Toluene
Toluenediamine
o-Toluidine hydrochloride
Toluene 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 or Silvex)
A101
A121
A121
A121
A101
A121
A101
A101
A101
A121
A101
A121
A122
A121
A122
A122
A133
A122
A133
Description
Volatiles
Extractables
Extractables
Extractables
Volatiles
Extractables
Volatiles
Volatiles
Volatiles
Extractables
Volatiles
Extractables
HPLC
Extractables
HPLC
HPLC
Carboxylic acids
HPLC
Carboxylic acids
-------
HAZARDOUS CONSTITUENTS—ANALYSIS METHODS (Continued)
Compound
Trichloropropane, N.O.S.
1,2,3-Trichloropropane
0,0,O-Triethyl phosphorothioate
sym-Trinitrobenzene
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 it can be
found within the text.
375
-------
Method Number
5001
5002
5003
5004
SO 05
5006
5007
5008
5009
5010
SOU
P001-P003
P001
P002
P003
P011-P014
P011
P012
P013
P014
SUMMARY OF METHOD NUMBERS
Method Name
Sampling Methods
Coliwasa
Dipper (Pond Sampler)
Weighted bottle
Tap
Thief (Grain Sampler)
Trier (Sample Corer/Waste
Pile Sampler)
Trowel (Scoop)
Modified Method 5 (MM5) Train
SASS
Gas Bulb
Gas Bag
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
Page No.
54
55
56
57
58
59
60
61
62
63
64
76
76
76
77
77
77
78
377
-------
SUMMARY OF METHOD NUMBERS (continued)
Method Name Page No.
Solvent Extraction of Organic
Compounds
Aqueous Liquids
Semivolatiles 79
Volatiles 80
Sludges (including gels and slurries)
Semivolatiles 81
Volatiles 82
Organic Liquids 83
Solids
Semivolatiles by Homogenization 84
Semivolatiles by Extraction 85
Volatiles 86
Drying and Concentrating 87
Solvent Extracts
Digestion Procedures for Metals 88
Florisil Column Chromatography 90
BioBeads SX-3 91
Silica Gel Chromatography 93
Alumina Column Chromatography 94
Liquid/Liquid Extraction 95
Sample Analysis
Characteristics
Ignitability (I) 138
Corrosivity (C) 139
Reactivity (R) 140
Extraction Procedure Toxicity (E) 141
378
-------
Method Number
A001-A006
A001-A002
A001
AO Ola
AOOlb
A002
A003
A004
A005
A006
A011-A021
AOll
A012
A013
A014
A015
A016
A017
A021
A101-A190
A101
AlOla
SUMMARY OF METHOD NUMBERS (continued)
Method Name Page No.
Proximate Analysis
Moisture, Solid and ASh Content:
Macro Scale Technique 143
Loss on Drying 143
Loss on Ignition 143
Micro Scale Technique 144
Elemental Composition - Organic 145
Total Organic Carbon and Total 146
Organic Halogens
Viscosity 147
Heating Value of Waste 148
Survey Analysis
Organic Content by TCO 106
Organic Content by GRAV 108
Organic Content - Volatiles 109
Compound Class by Infrared 109
Analysis
Mass Spectrometric Analysis 112
Specific Major Components by GC/MS 115
Specific Major Components by HPLC/IR 115
or HPLC/LRMS
Metals 115
Directed Analysis: Organics
Volatiles 149
Purging Procedure for the Analysis 152
of Aqueous Liquids
379
-------
SUMMARY OF METHOD NUMBERS (continued)
Method Numbers Method Name Page No.
AlOlb Purging Procedure for the Analysis 153
of Sludges
AlOlc Purging Procedure for the Analysis 154
of Solids
A121 Extractables 155
A122 HPLC/UV Generalized Procedure 161
A123 HPLC/UV Generalized Procedure 164
A131 Aldehydes-Extraction and Derivati- 166
zation Procedure
A132 Aldehydes - HPLC Analysis 167
A133 Carboxylic Acids 168
A134 Alcohols 170
A136 Phosphine 171
A137 Fluorine 172
A138 Gases-Cyanogens and Phosgene 173
A139 Gases-Mustards 174
A141 Gases 175
A144 Acid Chlorides 176
A145 Aflatoxins 177
A148 Brucine 178
A149 Citrus Red #2 179
A150 Cycasin 180
A156 Ethylene Oxide 181
A157 2-Fluoroacetamide 182
A160 Lasiocarpine 183
380
-------
SUMMARY OF METHOD NUMBERS (continued)
Method Number
Method Name
Page No
A174
Phenacetin
184
A175
Pronamide
185
A180
Strychnine
186
A183
Oximes
187
A190
Tris(l-aziridinyl)phosphine sulfide
188
A221-253
Directed Analysis: Inorganics
A221
Antimony
189
A222
Arsenic
191
A223
Barium
193
A224
Beryllium
195
A225
Cadmium
197
A226
Chromium
198
A227
Lead
199
A228
Mercury
201
A229
Nickel
203
A230
Osmium
204
A231
Selenium
205
A232
Silver
206
A233
Strontium
207
A234
Thallium
208
A235
Vanadium
210
A251
Anions
211
A252
Cyanides
212
A253
Phosphides
214
-------
APPENDIX E
MS - Analytical Ions
This appendix lists the Appendix VIII Hazardous
Constituents (according to the May 20, 1981
Federal Register) that are analyzed by GC/MS
procedures with the appropriate MS analytical
ions and their corresponding intensities.
383
-------
Compound
Acetonitrile
Acetophenone
2-Acetylaminofluorene
Acrolein
Acrylamide
Acrylonitrile
oo Aldrin
Ln
Allyl alcohol
4-Aminobiphenyl
5-(Aminomethyl)-3-isoxazolol
Amitrole
Aniline
Aramite
Auramine
Benz(c)acridine
ANALYTICAL IONS
Ions (Intensities)
41(100), 40(50), 39(17), 33(5)
105C100), 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)
-------
Compound
Benz(a)anthracene
Benzene
Benzene, dichloromethyt
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
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),
79(100),
149(100)
43(36),
49(47),
, 57(54),
41(34), 77(19),
81(33), 51(16)
169(33), 71(27)
-------
Compound
MS-ANALYTICAL IONS
Bromoacetone
Bromomethane
4-Bromophenyl phenyl ether
Brucine
Z-Butanone peroxide
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol (DNBP)
Carbon disulfide
Carbon oxyfluoride
Chloral
Chlordane (alpha and gamma isomers)
Chlorinated benzenes, N.O.S.
Chlorinated ethane, N.O.S.
Chlorinated fluorocarbons, N.O.S.
Chlorinated naphthelene, N.O.S.
Chlorinated phenol, N.O.S.
Chloroacetaldehyde
Chloroalkyl ethers
p-Chloroaniline
(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)
*
373(19), 375(17), 377(10)
112(100), 77(45), 114(33), 51(12)
64(100), 28(91), 29(84)
JUJ.
A /V
162(100), 164(33), 127(30)
128(100), 130(33), 65(24)
*
**
127(100), 65(34), 129(31), 92(20)
-------
MS-ANALYTICAL IONS (Continued)
Compound
Ions (Intensitites)
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-Chloropropionitrile
Chrysene
Coal Tars
Creosote
Cresols
Crotonaldehyde
2-Cyclohexyl-4,6-dinitrophenol
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)
**
**
*
-------
Compound
MS-ANALYTICAL
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-Dibromomethane
Dibromo e thane
Di-n-butyl phthalate
Dichlorobenzene (meta, ortho and para isomers)
Dichlorobenzene, N.O.S.
3,3'-Dichlorobenzidine
1,4-Dichloro-2-butene
(Continued)
Ions (Intensities)
235(100), 237(66),
246(100), 318(83),
235(100), 237(72),
279(100), 280(25),
279(100), 280(25),
278(100), 139(24),
165(38), 75(21)
316(66). 248(58)
165(59),75(22)
139.5(23), 278(14)
139.5(23), 278(14)
279(16), 276(16)
302(100)
302(100)
302(100)
157(100), 155(78), 75(46), 159(25)
107(100), 109(95), 27(54), 28(11)
174(100), 93(72), 95(62), 172(52)
149(100), 41(28), 29(25), 28(22),
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)
-------
Compound
MS-ANALYTICAL
Dichlorodifluoromethane
1.1-Dichloroethane
1.2-Dichloroethane
trans-1,2-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.
Dichloropropene, N.O.S.
1.3-Dichloropropene
Dieldrin
1,2:3,4-Diepoxybutane
N,N-Diethylhydrazine
(Continued)
Ions (Intensities)
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)
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)
-------
MS—ANALYTICAL IONS (Continued)
Compound
Ions (Intensities)
0,0-Diethyl S-methyl ester of phosphordithioic 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-Dimethylhydraz ine
1.2-Dimethylhydrazine
alpha,alpha-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
Dimethyl sulfate
149(100), 177(28), 150(13), 176(9)
163(100), 164(25), 77(19), 51(12)
244(100), 184(61), 201(38), 229(21)
120(100), 225(73), 77(58), 42(38)
256(100), 241(70), 257(48), 240(46)
60(100), 42(51), 59(45), 45(42)
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)
-------
MS-ANALYTICAL
' Compound
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-p ropyInitrosamine
Disulfoton
2,4-Dithiobiuret
Endosulfan
Endrin and metabolites
Ethyl carbamate
Ethyleneimine
Ethyl methacrylate
IONS (Continued)
Ions (Intensities)
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)
201(100), 283(48), 278(30)
81(100), 263(70), 82(61)
42(100), 43(62), 28(59), 15(22)
-------
MS-ANALYTICAL
Compound
Ethyl methansulf onate
Fluoroanthene
Fluoroacetic acid, sodium and 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,4,4a,5,8,8a-hexahydro-
1,4:5,8-endo, endo-dimethanonaphthalene
Hexachlorophene
Hexachloropropene
(Continued)
Ions (Intensities)
79(100), 109(78), 97(26), 80(19)
202(100), 200(20), 203(18), 101(13)
*
*
100(100),
272(60),
274(46)
355(100),
353(79),
351(60)
284(100),
286(80),
282(53),
142(29)
225(100),
227(65),
223(63),
260(38)
181(100),
183(99),
109(80),
217(78)
117(100),
119(95),
199(50),
201(85)
-------
MS-ANALYTICAL
Compound
Hexaethyl tetraphosphate
Hydrazine
Indeno(l,2,3-c,d)pyrene
Iodomethane
Isocyanic acid, methyl ester
Isobutyl alcohol
Isosafrole
Kepone
Maleic anhydride
Maleic hydrazide
Malononitrile
Hethyacrylonitrile
Methanethiol
Methapyrilene
Methoxychlor
2-Methylaziridine
3-Methylcholanthrene
4,4*-Methylenebis-(2-chloroaniline)
IONS (Continued)
Ions (Intensities)
32(100), 31(47), 29(40), 30(31)
276(100), 133(38), 277(26), 274(21)
142(100), 127(38), 141(14), 15(13)
162(100), 104(42), 131(30), 103(28)
26(100), 54(62), 25(61), 28(36)
66(100), 38(34), 39(34), 28(31)
58(100), 97(71), 72(22), 71(19)
28(100), 56(80), 57(54), 30(37)
256(100)
-------
MS-ANALYTICAL
Compound
Methyl ethyl ketone (MEK)
Methyl hydrazine
2-Methyllactonitrile
Methyl methacrylate
Methyl methanesulfate
N-Methyl-N'-nitro-N-nitrosoquanidine
Methyl parathion
Methylthiouracil
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
Nicotine and salts
p-Nitroaniline
Nitrobenzene
Nitroglycerine
4-Nitrophenol
(Continued)
Ions (Intensities)
43(100), 29(24), 72(17), 27(16)
46(100), 45(61), 28(58), 31(41)
41(100), 6S(83), 100(51), 39(36)
128(100), 127(20), 129(18), 64(7)
158(100), 104(39), 76(34), 102(31)
143(100), 115(45), 116(25), 144(14)
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)
-------
MS-ANALYTICAL IONS
Compound
Nitrosamine, N.O.S.
N-Nitrosodi-n-butylamine
N-Nitro sod iethanolamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitroso-N-ethylurea
N-Nitrosomethylethylamine
w N-Nitroso-N-methylurea
vo
o
N-Ni t ro s o-N-me thylurethane
N-Ni t ro some thy1viny1amine
N-Nitrosomorpholine
N-Nitrosonornicotine
N-Nitrosopiperidine
N-Nitrosopyrrolidine
N-Nitrososarcosine
5-Nitro-o-toluidine
Octamethylpyrophosphormide
(Continued)
Ions (Intensities)
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)
42(100), 114(91), 55(56), 56(24)
100(100), 41(61), 42(58), 68(16)
-------
MS-ANALYTICAL
Compound
7-0xabicyclo[2.2.l]heptane-2,3-dicarboxylic acid
Paraldehyde
Parathion
Pentachlorobenzene
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenol
P'nenylened iamine
Phosphorodithioic acid, 0,0-diethyl S-((ethylthio)
methyl)ester [Phorate]
Phosphorothioic acid, 0,0-dimethyl 0-(p-((dimethyl-
amino)sulfonyl)phenyl)ester [Famphur]
Phthalic acid esters, N.O.S.
Phthalic anhydride
2-Picoline
Polychlorinated biphenyl, N.O.S.
Pronamide
1,3-Propane sultone
ri-PropyIamine
Propylthiouracil
IONS (Continued)
Ions (Intensities)
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)
104(100), 76(84), 50(40), 148(39)
-------
MS ANALYTICAL IONS (Continued)
Compound
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
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Tetrachloromethane
2.3.4.6-Tetrachlorophenol
Tetraethyldithiopyrophosphate
Tetraethylpyrophosphate
Tetranitromethane
Toluene
Ions (Intensities)
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)
131( ), 133( ), 117( ), 119(
166(100), 164(78)» 129(64), 131(62)
92(65), 91(100), 65(12), 51(6)
-------
MS ANALYTICAL
Compound
Toluenediamine
Toluene diisocyanate
Toxaphene
Tribromomethane
1.2.4-Trichlorobenzene
1.1.1-Trichloroethane
1.1.2-Trichloroethane
Trichloroethene
Trichloromethanethiol
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 or
Silvex)
Trichloropropane, N.O.S.
1,2,3,-Trichloropropane
IONS (Continued)
Ions (Intensities)
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)
196(100), 198(97)., 200(31), 97(20)
196(100), 198(96), 200(31), 132(28)
75(100), 39(58), 49(42), 110(37)
-------
MS-ANALYTICAL IONS (Continued)
Compound
0,0,0-Triethyl phosphorothioate
sym-Trinitrobenzene
Tris(2,3-dibromopropyl)phosphate
Vinyl Chloride
Ions (Intensities)
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
------- |