United Stales
Environmental Prottv'.on
Agency
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Ldborstory
Rfsen'1 h Tn.inyip Pdrk NC 27711
EPA 600 7-78 201
October 1978
IERL-RTP
Procedures Manual:
Level 1 Environmental
Assessment
(Second Edition)
Interagency
Energy/Environment
R&D Program Report
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the/INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-2Q1
October 1978
IERL-RTP Procedures Manual:
Level 1 Environmental Assessment
(Second Edition)
by
D.E. Lentzen, D.E. Wagoner, E.D. Estes, and W.F. Gutknecht
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2156
T.D. No. 21300
Program Element No. INE624
EPA Project Officer: LD. Johnson
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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PREFACE
The Process Measurements Branch, IERL/RTP, has developed and recom-
mended the implementation of a three-phased sampling and analytical strategy
for environmental assessment programs. The first phase, Level 1, has as its
goal the class identification and semiquantitation of mass emissions within
a factor of 3 for inorganic and organic compounds. The goal of Level 2 is
the quantitation and identification of specific compounds present, and the
goal of the third phase, Level 3, is the continuous monitoring, under various
process conditions, of indicator compounds.
IERL/RTP contractors or grantees are required to use the system described
in this document for environmental assessment programs in accordance with a
guideline issued by IERL/RTP on April 8, 1977. It is anticipated that
non-IERL-RTP organizations that are active in the environmental assessment
field will also utilize this manual.
Although this guidelines manual does define Level 1 environmental
assessment measurements, it is impossible to specify the exact sampling and
analysis procedure for unusual circumstances. More detail and answers to
specific questions may be obtained from the EPA Process Measurements Branch,
IERL-RTP, Research Triangle Park. When situations arise where alternative
Level 1 sampling and analysis procedures are necessary or desired, the
contractor is directed to submit his alternate plan to his project officer
and the Process Measurements Branch for approval before actual work is
initiated.
Universal implementation of this document will result in the generation
of sets of comparable data from which prioritization of the environmental
insults associated with differing processes can be made.
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ABSTRACT
This manual presents revised Level I procedures and supersedes the
manual published in June 1976 (EPA-600/2-76-160a). The manual is intended
for personnel experienced in collecting and analyzing samples from indus-
trial and energy-producing processes. The phased environmental assessment
strategy provides a framework for determining industrial process and stream
priorities on the basis of a staged sampling and analysis technique. Level 1
is a screening phase that characterizes the pollutant potential of process
influent and effluent streams.
The manual is divided into two major sections according to the procedure
used. Chapters 3 through 7 discuss sampling procedures for gases, fugitive
emissions, liquids (including slurries), and solids. The remainder of the
manual is divided into four chapters on procedures for inorganic, organic,
bioassay, and particle analyses.
m
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LEVEL 1 PROCEDURAL MODIFICATIONS
Following is a list of changes that have been introduced into this
latest edition of the Level 1 Environmental Assessment Procedures Manual
Item
SASS train
passivation
SASS filter
material
XAD-2 cleaning
sequence
SASS train
SASS train
leak check
Cyclone vortex
breakers
Cleaning
impingers
Cyclone gaskets
Impinger solutions
First impinger
solution
Fourth impinger
solution
Rinsing the back
half of the SASS train
Changes in Sampling
Procedure
First Edition
50/50 nitric
acid used
Not specified
Water, methanol,
ether, pentane
No isolation
valve
0.0014 nrVmin
at 508 mmHg
Use in all
cyclones
Rinse with
1:1 isopropanol/H20
Teflon
750 mL each
6 M H202
Drierite
Methanol/methylene
chloride
This Draft
15% nitric acid
used (pp. 67-69)
Reeve Angel 934 AH (p.67)
Water, methanol,
methylene chloride
(Appendix B)
Check valve in
cyclone section (p.63)
Front at 0.0014 irrVmin
at 127 mmHg; back at
0.0014 mVmin at 508 mmHg
(p.71)
Use only in cyclone for
trapping I- to 3-p:m ~
particles (p. 72)
Rinse with
deionized water methanol
(p. 70)
Teflon or Viton A
(p. 71)
500 mL each
(p. 74)
30% H202
(P- 74)
Silica gel
(p. 74)
Methylene chloride
(pp. 75-76)
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Liquid sample
volume
Gas volume
(reactive gases:
N and S species, organic
species with bp <100° C)
Gas volume
(fixed gases:
C02s and CO)
I, N;
Volume of
fugitive emissions
particulate sample
Volume of
fugitive vapor
with or without
particulate
Sampling device
for fugitive
emissions in air
10 L
Volume not
specified
Volume not
specified
Volume not
specified
Volume not
specified
Modified hi-volume
sampler
20-200 L
(p. 93)
2 L
(pp. 48-50)
10-30 L
(p. 53)
2,496 m3 (p. 86)
67.2 m3 (p. 86)
FAST system or modified
hi-volume sampler
(pp. 84-86)
Item
NO measurement
NH3 and HCN
measurement
C02, CO, 02, and
N2 measurement
S02 and H2S
measurement at >25 ppm
H2S, S02) COS, CH3SH,
• • • C6H13SH measure-
ment at >1 ppb to
25 ppm
Changes in Analytical
Procedure
First Edition
Single grab sample
and measurement
using chemilumi-
nescence
GC using Porapak
Q for 1-100 ppm
detection
GC using a single
column and Mole-
cular Sieve 5A
GC using Molecular
Sieve 5A
GC using 3%
OV-1 Chromosorb
This Edition
Series of grab samples
and measurement using
EPA Method 7 (p. 57)
GC for >100 ppm
(p. 54)
GC using dual columns
containing Chromosorb
102 and 13X Molecular
Sieve (p. 55)
GC using Porapak N
(P- 55)
GC using Teflon
column with 12% polyphenyl
ether and 0.5% H3P04 on
40/60 Chromosorb T (p. 55)
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Measurement of volatile
hydrocarbons
Measurement of volatile
hydrocarbons
Measurement of nonvola-
tile hydrocarbons
Extraction of aqueous
solutions
XAD-2 extraction
Liquid chromatography
(LC)
LC
LC
LC
Infrared analysis
Water analysis
For Cj-Ce, GC using
Porapak Q and iso-
thermal
For C7-C12, GC using
1.5% 0V 101 and
temperature program
50° C - 150° C
For >C13, use
gravimetric analysis
Extract at neutral
PH
Use pentane
Dry packed column
No dehydration
of mixture to be
separated
Column temperature
not controlled
8-fraction separation
Use single KBr
pellet to mount
sample
Use Hach or similar
kits for measurement
of select ions
For organics bp range
-160° C to +30° C, GC using
Porapak Q and tempera-
ture program 60°-110° C
(p. 55)
For organics bp range
+30° C to 100° C, GC
using 20% 0V 101 or
Chromosorb W-HP
and isothermal at
30° C (p. 56)
For organics bp >100° C,
measure as Total Chroma-
tographable Organics (TCO)
(pp. 140-142)
Extract first at
acid pH and then
at alkaline pH (p. 136)
Use methylene chloride
(p. 139)
Slurry packed column
(p- 145)
Dehydrate mixture to be
separated using
sodium sulfate at
head of column
(p. 145)
Column temperature
controlled
(p. 144)
7-fraction separation
(pp. 146-148)
Use double NaCl plate
(preferred) or make
KBr pellet to hold
sample (p. 150)
Ion chromatography
preferred for measurement
of these ions though
Hach or similar kits
still acceptable
(p. 102)
VI
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Gaseous effluent
opacity measurement
Detection limits
for inorganic species
Ringelmann technique
to be used
Specified goal
of 1 ppm
Measurement of anionic
species (F~, Cl", NOa,
NOa, SOs, $04, PO^, etc.)
Parr bomb combustion
and aqua regia
digestion procedures
Use wet chemical or
ion-selective elec-
trode methods
Limited descriptions
Measurement of As and Sb Wet chemistry
in APS impinger solutions
Measurement of As and
Sb in all other samples
Wet chemistry
Instrumental resolution
of the spark source mass
spectrometer
Quantification of SSMS
data
Not specified
Extracts of the cyclone
and filter catches
Use the "just-
disappearing- 1 ine"
technique for minor
components. Major
components not
specified.
Analyze for
C7-C12
Previously certified
observer to estimate
degree of opacity (p. 81)
Goals set according
to matrix: 0.1-1 ug/m3
for particulate
matter; 0.5-10 nig/kg
for noncornbustible
solids; 0.5-10 (jg/L
for liquids; and ~1
mg/m3 for gases
(1 ug/m3 for sulfur
compounds)
(p. 20)
Ion chromatography
is preferred though
previously used methods
remain acceptable
(pp. 125,127,128)
Complete descriptions
of procedures provided
in appendixes
(Appendix C)
Hydride evolution and
atomic absorption
spectrophotometry
(p. 120)
Measurement, along with
other elements using
spark source mass
spectrometry
(p. 115)
M/AM specified as
3,000 (with 50%
valley between peaks)
(p. 115)
Quantify all components
of sample to 10 percent
(p. 118)
Not to be analyzed
for TCO (p. 140)
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Biological testing
Morphological measure-
ments
Plan for allocation of
material from SASS train
for chemical and biological
testing
General outline
presented
Not defined
None presented
Specific tests now
summarized (pp. 167-173)
Analysis now defined
(pp. A-45, A-46)
Plan now presented
(p. 80)
Item
Pretest planning
Quality control/quality
assurance
Miscellaneous Changes
First Edition
This Edition
Not discussed in detail Discussed in moderate
detail (pp. 8-14)
Not discussed in detail A chapter is dedi-
cated to this topic
(pp. 23-45)
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CONTENTS
Page
Preface •}-,•
Abstract j-ji
Level 1 Procedural Modifications iv
Figures xiii
Tables ' xiv
Acknowledgments xv
1. Introduction 1
1.1 Environmental Assessment Program Overview 1
1.1.1 Program Definition and General Goals 1
1.1.2 Source Assessment Strategies 1
1.1.3 The Phased Approach 2
1.2 Level 1 Overview 3
1.2.1 Level 1 in a Phased Approach 3
1.2.2 Level 1 Analytical Scheme 4
1.2.3 Level 1 Quantitative Goals 4
1.3 Level 1 Assessment Protocol 8
1.3.1 Pretest Planning 8
1.3.2 Pretest Site Survey 9
1.3.3 Sampling 13
1.3.4 Level I Analysis 18
1.4 Summary and Conclusions 22
2. Quality Control/Quality Assurance 23
2.1 Introduction 23
2.2 Suitable Laboratory Techniques 24
2.2.1 Material and Equipment Procurement Controls .... 24
2.2.2 Cleanliness Controls 26
2.2.3 Reagent Formulation 27
2.2.4 Metrology and Standardization 27
2.2.5 Sampling 30
2.2.6 Procedures 33
2.2,7 Subtraction of "Blank" Background Values 39
2.2.8 Limits of Detection 41
2.2.9 Data Computation and Reporting 42
2.3 Quality Control 43
2.4 Quality Assurance 44
2.5 Conclusions 45
3. Sampling and Analysis of Non-Particulate-Laden Gases 46
3.1 Introduction 46
3.2 Sampling Methodology 46
3.2.1 Gaseous Process Streams 47
3.2.2 Gaseous Process Vents 47
3.2.3 Gaseous Process Effluents 47
3.3 Sampling Guidelines 47
ix
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CONTENTS (continued)
Page
3.3.1 Process Streams, Flues, and Ducts 47
3.3.2 Vents 48
3.4 Gas Sampling Techniques 4S
3.4.1 Grab Gas Sampling 50
3.4.2 Integrated Gas Sampling 52
3.5 Field Measurements 53
3.6 Analysis Methodology 54
3.6.1 Sampling and Analysis of Total Oxides
of Nitrogen 57
3.6.2 Onsite GC Analysis for CO, C02, 02, and N2 57
3.6.3 Analysis of Sulfur Compounds 59
3.6.4 Organic Species (bp <100° C) Analytical
Methodology 59
Sampling of Particulate and Vapor Streams 62
4.1 Introduction 62
4.2 Equipment and Personnel Requirements 64
4.3 Equipment Preparation for Sample Collection 68
4.3.1 Precleaning Procedures for the SASS Train
and Sample Containers 68
4.3.2 Apparatus Checkout 71
4.4 SASS Train Sampling Procedure 72
4.5 Sample Handling and Shipment 75
4.6 SASS Sample Analysis 76
4.7 Plume Opacity Tests 81
Fugitive Emissions Sampling 82
5.1 Introduction 82
5.2 Fugitive Emission Categories 82
5.3 Sampling Techniques and Equipment 83
5.3.1 Airborne Fugitive Emissions 84
5.3.2 Waterborne Fugitive Emissions 88
5.4 Sampling Program Planning and Performance 89
5.5 Data Reduction 91
Liquid and Slurry Sampling and Chemical Analysis 92
6.1 Introduction 92
6.2 Preparing for Sample Collection 92
6.2.1 Personnel Requirements 92
6.2.2 Dipper Sampling 93
6.2.3 Automatic Sampling 93
6.2.4 Heat Exchange Sampling Systems for
High Temperature Lines 93
6.2.5 Tap Sampling 94
6.3 Liquid Sample Handling and Shipment 96
6.4 Liquid Analysis 102
Solid Sampling 10.4
7.1 Introduction 104
7.2 Solids Sampling Procedures 104
7.2.1 Shovel Grab Sampling 105
7.2.2 Boring Techniques 105
7.3 Sample Collection and Storage 107
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CONTENTS (continued)
Page
8. Level 1 Inorganic Analysis Techniques 109
8.1 Introduction 109
8.2 Sample Preparation 110
8.2.1 Gases 110
8.2.2 Bulk Liquids 110
8.2.3 Bulk Solids 113
8.2.4 SASS Train Samples 113
8.3 Analytical Methods 115
8.3.1 Elemental Analysis By Spark Source Mass
Spectrometry 115
8.3.2 Atomic Absorption Spectrometry 120
8.4 Ion Chromatography 125
8.4.1 Sample Analysis 127
8.4.2 Sample Calculations and Report Forms 127
9. Level 1 Organic Analysis Techniques 130
9.1 Introduction 130
9.2 Level 1 Organic Analysis Methodology 130
9.3 Preparation of Sample Extracts 136
9.3.1 Aqueous Solutions 136
9.3.2 Solids, Particulate Matter, and Ash 137
9.3.3 Slurries and Sludges 137
9.3.4 SASS Train Rinses 138
9.3.5 Sorbent Trap 139
9.4 Analysis of Samples for Organics 139
9.4.1 Total Chromatographable Organics
(TCO) Analysis 140
9.4.2 Gravimetric (GRAV) Analysis 142
9.4.3 Concentration of Extracts and •
Solvent Exchange Procedure 142
9.4.4 Liquid Chromatographic (LC) Separation 144
9.4.5 Infrared Analysis 148
9.4.6 Low Resolution Mass Spectrometry 152
9.5 Organic Analysis Summary Tables 155
9.6 Quality Control in Level 1 Organic Analysis 161
10. Particulate Morphology and Classification 164
10.1 Introduction 164
10.2 Handling Particulates for Microscopic Examination 164
10.3 Equipment Specifications 165
10.4 Mounting of Sample Materials 165
10.5 Sample Viewing 166
10.6 Graphic Illustrations 166
11. Biological Assessment 167
11.1 Introduction 167
11.2 Sampling 168
11.3 Health Effects Tests 168
11.3.1 Salmonella/Microsome Mutagenesis Assay (Ames) . . . 168
11.3.2 Clonal Toxicity Assay 170
11.3.3 Cytotoxicity Assays 170
11.3.4 Acute In Vivo Test in Rodents 171
XI
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CONTENTS (continued)
11.4 Aquatic Ecological Effects Test 171
11.4.1 Freshwater Algal Assay Procedure: Bottle Test ... 171
11.4.2 Bioassay with Unicellular Marine Algae 171
11.4.3 Acute Static Bioassays with Freshwater
Fish and Daphnia 172
11.4.4 Static Bioassays with Marine Animals 172
11.5 Terrestrial Ecology Tests 172
11.5.1 Stress Ethylene/Foliar Injury Plant Response .... 173
11.5.2 Seed Germination/Seedling Growth Test 173
11.5.3 Soil Respiration/Nitrogen Fixation Text 173
11.5.4 Insect Bioassays 173
References 174
Appendixes
A. Data Summary Collection Forms A-l
B. Preparation of XAD-2 Sorbent Resin B-l
C. Parr Bomb Combustion Procedure C-l
D. Aqua Regia Digestion Procedure D-l
E. Procedure for Leaching of Bulk Solids E-l
F. Atomic Absorption Spectrometric Procedures for Hg, Sb,
and As F-l
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FIGURES
Number
1 Basic Level 1 sampling and analytical scheme for
solids, slurries, and liquids 5
2 Basic Level 1 sampling and analytical scheme for
particulates and gases 6
3 Multimedia sampling strategy overview 15
4 Multimedia analysis overview 21
5 Examples of baseline, test signal, true blank signal, and
interference + test signal 41
6 Grab sampling apparatus 49
7 Integrated gas-sampling train 51
8 Source assessment sampling train schematic 63
9 Flue gas sampling flow diagram 65
10 Flue gas analysis requirements 66
11 SASS cleaning procedures 69
12 Sample handling and transfer—nozzle, probe,
cyclones, and filter 77
13 Sample handling and transfer--XAD-2 module 78
14 Sample handling and transfer—impingers 79
15 Fugitive Air Sampling Train components 85
16 Diagrammatic presentation of connections for
sorbent cartridge to high-volume sampler 87
17 Stormwater runoff sampling plug collector 88
18 Sampling apparatus for high pressure high temperature lines . . 95
19 Sample handling summary 97
20 Level 1 inorganic laboratory analysis plan
for solid samples Ill
21 Level 1 inorganic laboratory analysis plan
for liquid samples 114
22 Sample preparation for SSMS elemental analysis 116
23 SSMS analysis sheet 121
24 SSMS report—standardization results 122
25 SSMS report—test sample results 123
26 AAS analysis sheet 126
27 1C analysis sheet 128
28 1C report—standardization and test sample results 129
29 Multimedia organic analysis overview 132
30 Organic analysis methodology 134
31 Sample LC report 149
32 Sample IR report 151
33 Sample LRMS report 156
34 Organic extract summary table 158
35 Sample calculations of concentration estimates from
LRMS data 159
36 Biological analysis overview 169
B-l XAD-2 cleanup extraction apparatus B-4
B-2 XAD-2 fluidized-bed drying apparatus B-5
xi i i
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TABLES
Number
1 Basic Level 1 Analyses 7
2 Requirements for Level 1 Stream Sampling 18
3 List of Calibration Standards 29
4 A Suggested Format for Sample Coding and Identification 32
5 Methodology Calibration Check 35
6 Checklist for Analysis for Hg Using AAS 43
7 Recommended Analysis of Gas Species 55
8 Level 1 Boiling Point Ranges 61
9 Apparatus and Reagents for a SASS Run 67
10 SASS Train Impinger System Reagents 74
11 Suggested SASS Sample Distribution Based on Total Sample
Available 80
12 Recommendation for Sampling and Preservation
of Samples According to Measurement 98
13 Level 1 Methods for Solid Sampling 106
14 Summary of Results for Organic Extracts for SASS
Train Sample 131
15 Summary of Expected Data From Level 1 Organic Analysis 133
16 Liquid Chromatography Elution Sequence 147
17 Categories for Reporting LRMS Data 154
Estimation of Fraction Composition From
18 IR and LC Data Only 162
xiv
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ACKNOWLEDGMENTS
The revision of this document was conducted under the direction of
Dr. L. D. Johnson, EPA Task Order Manager, Industrial Environmental Research
Laboratory, Research Triangle Park, North Carolina. The Applied Chemistry
Department of the Chemistry and Materials Laboratory, Applied Technology
Division, TRW Systems and Energy, Redondo Beach, California, was responsible
for the original document (EPA-600/2-76-160a, June 1976).
Special acknowledgment is given to the many helpful discussions with
J. A. Dorsey, F. E. Briden, W. B. Kuykendal, and R. G. Merrill, Jr., IERL-RTP,
and Dr. C. H. Lochmuller, Duke University, during the course of this task
order.
Input from the following PMB/IERL-RTP contractors is also appreciated:
Arthur D. Little, Inc., sampling and analysis of organic materials, Drs. J.
Harris and P. L. Levins; Research Triangle Institute, development of environ-
mental assessment quality assurance programs, Mr. F. Smith; Aerotherm/Acurex
Corporation, sampling of particulate and vapor streams, Mr. D. Smith, Mr. D.
Blake, and Mr. F. E. Moreno; Southern Research Institute, particulate sampling
support, Dr. W. B. Smith; TRC, Inc., The Research Corporation of New England,
fugitive emissions methodology, Dr. H. J. Kolnsberg; and TRW Systems and
Energy, sampling and analysis of inorganic materials, Dr. R. F. Maddelone.
The many helpful suggestions on sampling and application of spark source
mass spectrometry provided by personnel of the GCA Corporation are also
gratefully acknowledged.
xv
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CHAPTER 1
INTRODUCTION
1.1 ENVIRONMENTAL ASSESSMENT PROGRAM OVERVIEW
1.1.1 Program Definition and General Goals
A sampling and analytical program has been developed for conducting
environmental source assessments of the feed, product, and waste streams
associated with industrial and energy processes. As described in this
document and supporting references, an environmental source assessment
involves: (a) a systematic evaluation of the physical, chemical, and bio-
logical characteristics of selected streams associated with a process;
(b) predictions of the probable effects of those streams on the environment;
(c) prioritization of those streams relative to their individual hazard
potential; and (d) identification of any necessary control technology pro-
grams. An environmental source assessment program addresses, to the maximum
extent possible, the identification of all potential air, water, and ter-
restrial pollution problems, both for pollutants for which specific stand-
ards have been set and for pollutants that are suspected to have deleterious
effects on the environment and therefore may be subject to future regula-
tion. The ultimate goal of an environmental source assessment is to insure
that the materials evolving from a given processing scheme are environmen-
tally acceptable, or that adequate control technology exists or can be
developed to reduce their pollution potential.
1.1.2 Source Assessment Strategies
Two clearly distinct strategies of approach to an environmental sampling
and analysis program that satisfy the requirements for producing compre-
hensive information are the direct approach and the phased approach. In a
direct approach, all streams would be carefully sampled and the samples
subjected to complete, detailed analysis for all detectable components at an
-------
overall accuracy of ±50 percent for the mass emission rates. In a phased
approach, all streams would first be surveyed using simplified, generalized
sampling and analytical methods that would permit their being ranked on a
priority basis. Subsequent phases would then involve more extensive and
detailed sampling, analysis, and long-term study of those streams determined
to be of high priority. This latter or phased approach focuses available
resources (both manpower and dollars) on emissions that have a high poten-
tial for causing measurable health or ecological effects, and provides
comprehensive chemical and biological information on all sources of indus-
trial emissions. Discussions of this philosophy, the information-cost
benefits, and a summary of the application of the phased approach to sam-
pling and analysis follow.
1.1.3 The Phased Approach
The phased approach, as developed by the Process Measurements Branch
(PMB) of the Environmental Protection Agency, requires three separate levels
of sampling and analytical effort. The first level, Level 1, utilizes
quantitative sampling and analysis procedures that yield final analytical
results accurate to within a factor of 3 of the sample. (See Section 1.2.3
for more discussion of this error limit.) Level 1 is designed to (a) pro-
vide preliminary environmental assessment data, (b) identify problem areas,
and (c) formulate the data needed for the prioritization of energy and
industrial processes, streams within a process, components within a stream,
and classes of materials for further consideration in the overall assess-
ment. The second sampling and analysis effort, Level 2, is directed by
Level 1 results and is designed to provide additional information that will
confirm and expand the information gathered in Level 1. This information
will be used to define control technology needs, and may, in some cases,
give the probable or exact cause of a given problem. The third phase, Level
3, involves monitoring the specific problems identified in Level 2 so that
the critical components in a stream can be determined exactly as a function
of time and process variation for control device development.
The three sampling and analysis levels are closely linked in the overall
environmental assessment effort. Level 1 identifies the questions that must
be answered by Level 2, and Level 3 monitors the problems identified in
-------
Level 2 to provide information for control device design and development.
For example, if a Level 1 test indicated that polycyclic organic material
(POM) might be present in significant amounts and also gave a positive
mutagenicity test, Level 2 sampling and analysis would be designed to de-
termine the exact quantities of organic constituents, the percentage of POM,
and the identity of as many specific POM compounds present as is economically
possible. In addition, using the Level 1 data and any available Level 2
results, the sample would be retested for cytotoxicity and mutagenicity in
order to confirm and expand the total bioassay information. A test for
carcinogenicity would also be run if the results of these tests were posi-
tive.
The phased approach offers potential benefits in terms of the quality
of information that is obtained for a given level of effort and in terms of
the costs per unit of information. This approach has been investigated and
compared to the more traditional approaches (ref. 1) and has been found to
offer the possibility of substantial savings in both time and funds required
for assessment.
1.2 LEVEL 1 OVERVIEW
1.2.1 Level 1 in a Phased Approach
The Level 1 sampling and analysis program is designed to produce a
comprehensive survey of emissions from any industry or energy-generating
facility that might be of environmental consequence. This survey shows,
within broad general limits, the absence or presence, the approximate con-
centrations, and the emission rates of inorganic elements, selected anions,
and classes of organic compounds in gaseous, liquid, and solid samples. Any
particulate matter suspended in the effluent gases is analyzed separately
for chemical composition, for size, and for other physical parameters that
can be determined by microscopic examination. Selective biotesting is
performed on samples to obtain information indicative of the possible human
health and ecological effects of the material. If it can be proven that
equivalent Level 1 data exist for all streams of interest, then a Level 1
effort need not be conducted. If only partial data exist, then a complete
complement of Level 1 tests must be performed on all streams.
-------
The Level 1 methods of sampling and analysis are chosen on the basis of
their information outputs, their cost effectiveness, their availability,
their reliability, and their ease of application. Whenever possible, stand-
ard EPA-recognized methods are employed; however, due to the comprehensive
nature of the information requirements of Level 1 assessment, new and some-
times developmental methods are used to fill these needs. The efforts of
competent samplers, biologists, microscopists, engineers, analytical inor-
ganic chemists, and organic chemists will be required to produce quality
information from these environmental assessment endeavors.
It is anticipated that many process streams tested by these techniques
will contain only nonhazardous substances, or hazardous substances in non-
hazardous concentrations. This would mean that more extensive testing of
the source and application of additional control devices would be unwarranted
at this time. When Level 1 results identify possible hazardous emissions,
those specific streams will be priority-ranked and scheduled for the inten-
sive investigation of Level 2 efforts. Level 1 findings will continue to
provide useful information in Level 2 tests by the delineation of specific
sampling, analysis, and decisionmaking problem areas. These outputs also
help direct subsequent planning and the preliminary choice of methodology
for the Level 2 effort so that the additional information needs will be
satisfied effectively.
1.2.2 Level 1 Analytical Scheme
As indicated above, the Level 1 philosophy involves a multimedia ap-
proach. Solids and liquids are to be analyzed according to the scheme shown
in Figure 1. Flue gases and particulates are to be collected by means of a
Source Assessment Sampling System (SASS) train (see Chapter 4) and are to be
analyzed according to the scheme shown in Figure 2. The techniques to be
used in the analysis scheme are listed in Table 1.
1.2.3 Level 1 Quantitative Goals
The goal of Level 1 assessment is to identify the pollution potential
of a source in a quantitative manner, with a target accuracy factor of 3.
That is, the final analytical result obtained should be between 1/3 and 3
times the "true" value. Those familiar with environmental problems will
4
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LEACHABLE
MATERIALS
BIO ASSAY
INORGANIC
SPECIES
ORGANIC
SPECIES
SUSPENDED
SOLIDS
(See Figure 19)
BIOASSAY
INORGANIC
SPECIES
SELECTED
WATER
TESTS
(AQUEOUS)
ORGANIC
SPECIES
INORGANIC
SPECIES
See Chapter 11
Elements
(See Chapter 8)
Extraction/solubilization
and physical separation
into fractions with
chemical classification
(See Chapter 9)
INORGANIC
SPECIES
ORGANIC
SPECIES
See Chapter 11
Elements and
selected anions
(See Chapter 8)
(See Chapter 8)
ORGANIC
EXTRACTION
OR DIRECT
ANALYSIS
Physical separation
into fractions and
chemical classification
(See Chapter 9)
Elements and
selected anions
(See Chapter 8)
Elements
(See Chapter 8)
Physical separation
into fractions and
chemical classification
(See Chapter 9)
Physical separation
into fractions and
chemical classification
(See Chapter 9)
Figure 1. Basic Level 1 sampling and analytical scheme for solids,
slurries, and liquids.
-------
(See Chapter 8)
INORGANIC
SPECIES
ORGANIC
MATERIALS
bp>100°C
Eler
(See
nents
Chapter 8)
XAD-Z
ADSORBER
ANDCH2CI2
EXTRACTION
Physical separation
BIOASSAY
ORGANIC
SPECIES
ORGANIC
ASH IF
NEEDED
CH2CI2
EXTRACTION
PARTICIPATE
MORPHOLOGY
BIOASSAY
(See Chapter 10)
(See Chapter 11)
NOX EPA METHOD 7
Onsitegas
chramatography or
approved alternative
Onsita gas
chromatography
SPECIES
Elements
(See Chapter 8)
(See Chapter 11)
TCO,
GRAV.IR
(See Chapter 9)
Physical separation
into fractions and
chemical characterization
(See Chapter 9)
Physical separation
into fractions and
chemical characterization
(See Chapter 9)
ASH IF
NEEDED
CH2CI2
EXTRACTION
PARTICIPATE
MORPHOLOGY
BIOASSAY
—
INORGANIC
SPECIES
ORGANIC
SPECIES
(See Chapter 10)
(See Chapter 11)
Elements
(See Chapter 8)
Physical separation
into fractions and
chemical characterization
(See Chapter 9)
"WEIGH INDIVIDUAL CATCHES
Figure 2. Basic Level 1 sampling and analytical scheme for participates and gases.
-------
TABLE 1. BASIC LEVEL 1 ANALYSES
Physical: Cyclone particle size
Optical microscopy
Chemical: Spark source mass spectrometry (SSMS)
Atomic absorption spectroscopy (AAS)
Wet chemical (selected anions)
Gas chromatography (GC)
Elution chromatography (LC)
Ion chromatography (1C)
Infrared spectrometry (IR)
Low resolution mass spectrometry (LRMS)
Total chromatographable organic (TCO)
Biological: Rodent acute toxicity
Microbial mutagenesis
Cytotoxicity
Fish acute toxicity
Algal bioassay
Soil microcosm
Plant stress ethylene
recognize that this accuracy factor is not as liberal as it might seem.
Real sample procurement problems and matrix effects may contribute unknown
errors to an overall analytical scheme that utilizes quite accurate measure-
ment techniques (AAS, for example). To minimize the effects of these possible
difficulties, care must be exercised in each step of the Level 1 procedures.
This is well -demonstrated by the variance relationship between the standard
deviations (s) for a total procedure and the parts of that procedure. That
is, for a typical procedure,
c - f<;2 + c2 + S2 -I ^
total " sampling sample measurement '
treatment
If each step has a relative standard deviation of ±20 percent, the total
relative standard deviation would be approximately ±35 percent. Allowing
each step to have a relative standard deviation of ±50 percent would lead to
a s. . of ±87 percent, which is beyond the -70 percent (1/3 of true value)
goal of the Level 1 program. Again, reasonable care must be exercised in
all of the Level 1 sampling and analytical techniques.
-------
1.3 LEVEL 1 ASSESSMENT PROTOCOL
Level 1 assessment can be divided into the following formal steps:
Pretest Planning, Pretest Site Survey, Sampling, and Analysis. Each is
important to the performance of a high-quality assessment.
1.3.1. Pretest Planning
The final decision to test a particular plant will be the result of the
prioritization studies and of the preliminary selection process based on the
site selection criteria of a given program and on the data requirements of
the overall program or general EPA objective.
Before the actual sampling and analysis effort is initiated, the data
requirements must be established and used to help identify test requirements
as well as any anticipated problems. The following paragraphs present a
general summary of these requirements and planning functions; they must be
applied or expanded to meet the needs of the individual tests to be per-
formed. Specific recommendations concerning data requirements associated
with each of the process streams are discussed in the appropriate chapters
of this manual.
Before traveling to a plant for a pretest site survey, it is necessary
to become familiar with the processes used at the site. This involves under-
standing the chemistry and operational characteristics of the various unit
operations as well as any pollution control devices or processes. It is
particularly important to know that detailed relevant process data are
necessary for the sampling and analysis effort as well as for the overall
environmental assessment for the following reasons.
a. From a knowledge of the process and the composition of input
materials and products, conclusions about pollutants likely to be
found in waste streams can be drawn. This should not, however,
result in the deletion of portions of Level 1 activities.
b. One must know where to look for waste streams, including fugitive
emissions.
c. One must know how plant operating conditions are likely to affect
waste stream flow rates and compositions.
8
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d. Thorough familiarity with the process permits design of proper
sampling programs.
e. Thorough knowledge of the interrelationships among process vari-
ables permits extrapolation to conditions in other systems (larger
or smaller) being assessed.
f. Detailed process data are the basis from which control technology
development programs proceed, should environmental assessments
indicate such need.
Familiarization with the process is also necessary so that a checklist of
the requisite data can be developed, including temperatures, pressures, flow
rates, and variations of conditions with time for the pretest site survey.
For any given sampling and analysis task, the data collected must be
consistent with the overall Level 1 objectives. Thus, the minimum amount of
data for a given stream is flow rate per unit time at a given temperature
and pressure. It is expected that professional sampling and analysis personnel,
in conjunction with the EPA Project Officer and the Process Measurements
Branch, Industrial Environmental Research Laboratory (PMB-IERL), will select
the appropriate data requirements for a given industry.
1.3.2 Pretest Site Survey (ref. 2)
1.3.2.1 General-
After establishing the necessary process data needs and selecting a
tentative set of sampling points, a pretest site survey should be performed.
At the test site, the survey team should meet with the plant engineer to
verify the accuracy of the existing information and arrange for the addition
of any missing data. Using this information and detailed, accurate process
flow diagrams, the survey team will then proceed to select the actual sam-
pling sites with the following criteria in mind:
a. The sampling points should provide an adequate base of data for
characterizing the effluent stream of the source within a factor
of 3.
b. When possible, each sampling point should provide a representative
sample of the effluent streams.
-------
c. The sampling site must have a reasonably favorable working environ"
ment. The survey personnel must consider what the temperature and
noise levels are in the sampling areas, if protection from rain or
strong winds exists, and whether scaffolding, ladders, pulleys,
etc., are safe.
The identification of support facilities and services is an essential
aspect of the site survey. In an effort to minimize the requests made upon
the operators and to minimize scheduling problems for these support services,
it is desirable that the onsite laboratory operate completely independently
of external support facilities.
The results of the pretest site survey must be sufficiently detailed so
that the field test problem of sampling the correct process stream at the
proper sampling location and using the appropriate methodology will be
completely defined prior to arrival of the field test team at the source
site.
1.3.2.2 Sampling for Gaseous Components—
A pretest Level 1 site survey of process streams and vents involves
the following steps:
a. Tracing the process flow to establish gaseous outputs. Using the
process flow diagrams as a guide, a physical inspection of the
system must be conducted to uncover any undocumented output sources
or unrecorded equipment modifications.
b. Locating and itemizing process vents.
c. Locating and itemizing stacks and flares.
d. Recording the physical parameters of the stream in as much detail
as possible.
Aside from these general considerations, there are two specific require-
ments for gas and vapor sampling:
a. All process streams and vent systems recirculated into process
streams will require in-line valves for sampling.
b. All vents to the atmosphere require a means of access as well as
suitable working space for personnel involved in the sampling
process.
10
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1.3.2.3 Sampling for Particulates—
In performing the pretest site survey, the crew should provide for
the following requirements of the Source Assessment Sampling System:
a. The sampling port: To accommodate the sampling probe, the port
must have an opening of at least 2-1/2 in. A 3-in. nipple welded
to the stack is usually the best way to obtain access. The port
must be centered and at least 13 in. above the platform to comply
with the oven clearance requirements.
b. The test platform: The size of the test platform, which supports
the sampling equipment and test personnel, depends on the length
of the probe to be used. For the standard 5-ft probe, an ideal
platform would be 13 ft long and 8 ft wide. If such large plat-
forms are not available, compromises must be made prior to sam-
pling.
c. Electrical power: Power is required for the probe and oven heaters,
for the organic sorbent module water circulation pump, and for the
two vacuum pumps. To operate the entire system, a total of two
30-A circuits or four 15-A circuits are required.
d. Ice for cooling the impinger train: A source of large quantities
of ice should be located near the sampling location. At normal
temperatures (205° C at the oven and 20° C at the sorbent cartridge
inlet), 15 to 50 Ib of ice will be required per hour of testing.
1.3.2.4 Fugitive Emissions--
Fugitive emission sampling will be performed whenever there is a like-
lihood of there being a significant amount of this material generated at a
given site. Planning Level 1 fugitive emissions sampling requires knowledge
of the probable sources of emissions, the processes and materials involved,
the operating schedules of sources and processes, the physical arrangement
of the site, and general meteorological and topographical characteristics.
Most of the required information can be gathered during the pretest survey
of the site: the physical aspects through personal observation, and the
remaining aspects from historical data provided by the site operators and
local weather stations.
11
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In performing a pretest site survey, the program planner should obtain
the following information:
a. Site description: A general plan of the site with sufficient
detail to indicate the processes of concern, the location of
emission sources, important topographical features, etc.
b. Prevailing wind data: Typically, a local wind rose to indicate
the most probable wind direction and speed ranges.
c. Fugitive emissions sources: A physical description of the sources
to be measured, the processes involved, and their location in the
site plan.
d. Fugitive emissions to be measured: Classification as particu-
lates, gases, etc.; categorization per definitions; estimations of
magnitude (cloud or plume size and distribution); concentration
(visibility of cloud or plume); and frequency (continuous or
cyclic).
e. Sampler requirements: Number and type of samplers.
f. Sampler locations: Approximate for prevalent and alternative
conditions.
g. Sampling schedule: Approximate number and duration of samplings
to be performed.
Sampler locations can only be suggested in the planning of the assess-
ment program since it is impossible to predict what meteorological and
process conditions will exist during the actual assessment. A good plan
will suggest primary sampler locations based on the most likely conditions
and alternate locations for secondary conditions.
1.3.2.5 Liquid and Slurry Sampling—
The same criteria for locating a gas sampling point can be applied to
locating sampling sites for liquid samples. A review of those criteria and
procedures is contained in Section 1.3.2.1 of this chapter.
While the site selection criteria for gas and liquid sampling are
generally the same, the test personnel must be aware of the problems associ-
ated with the sampling of liquids and how these factors affect the choice of
a sampling site. Two factors will affect the selection of a sampling site
for liquid/slurry streams:
12
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a. Stream homogeneity: This is the most important problem that must
be addressed by the site survey crew. Unlike gas streams, which
mix fairly evenly, liquid streams tend to be more stratified
because of lower thermal agitation and higher fluid viscosities.
b. Stream flow rate: Large, slow-moving streams will offer more of a
chance for stratification to occur. This factor is especially
important in large pipes or open sluices and ditches.
1.3.2.6 Solid Sampling--
Solid input and output streams in most process operations consist of
fuels, primary reaction components, treatment or maintenance chemicals, and
marketable output products or output refuse products. These solids range
from very fine powders to very coarse lumps. This variation in sample
consistency influences the sampling technique to be used, which must be
established in the pretest site survey. For the purpose of the pretest site
survey, therefore, the following questions must be answered:
a. Can the material be sampled as it enters or leaves the process, or
must it be sampled in its storage or pile form?
b. If the material can be sampled as it enters or leaves the process,
what is the nature of the conveyor system (belt, worm screw, duct)
and what is the closest available sampling location to process
entry and farthest available sampling location from process exit?
c. What is the consistency of the material (powder, coarse grain,
lump) and what is the apparent variance within this consistency?
d. What is the approximate size of the storage reserve and what is
the method of access to said reserve?
1.3.2.7 Pretest Site Survey Forms--
The information to be obtained during a pretest site survey has been
discussed in detail. To assist the reader in developing an overview of this
survey, copies of pretest site survey forms to be used on an actual survey
are included in Appendix A of this manual.
1.3.3 Sampling
Level 1 sampling stresses the concept of completeness by presuming that
any and all streams leaving the process will be sampled unless data equiva-
13
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lent to Level 1 programmatic output already exist. Further, Level 1 samp-
ling is not predicated on a priori judgments as to stream composition. The
techniques utilized presume that whatever a priori knowledge is available
is, at best, incomplete. Predictive and extrapolative techniques employed
during source assessments serve as a check on the empirical data and not as
a replacement for them. Level 1 sampling systems are therefore designed to
permit collection of all substances in the stream at a reasonably high level
of efficiency. They do not necessarily produce information as to specific
substances or their chemical form. Further, Level I sampling programs are
designed to make maximum use of existing stream access sites. While care
must be exercised to insure that the samples are not biased, the commonly
applied concepts of multiple point, isokinetic, or flow proportional samp-
ling are not rigidly adhered to.
The Level 1 procedures described in this manual can be utilized to
acquire process samples, effluent samples, and feed stock samples. The
Level 1 environmental assessment program must, at a minimum, acquire a
sample from each process feed stock stream and from each process effluent
stream. Samples of fugitive air/water emissions are obtained only when
circumstances indicate the need. The data obtained from the feed streams
are necessary to establish a baseline for comparison. The effluent stream
sampling program is required to estimate the mass emissions rate and the
environmental impact that will result. Sampling and analytical procedures
that are required to support a comprehensive environmental source assessment
must be multimedia in nature.
1.3.3.1 Classification of Streams for Sampling Purposes--
The basic multimedia sampling strategy (shown in overview form in
Figure 3) has been organized around the five general types of sampling found
in industrial and energy-producing processes rather than around the analyt-
ical procedures that are required on the collected samples. This facilitates
the complex and difficult task of organizing the manpower and equipment
necessary for successful field sampling and establishing meaningful units of
cost.
The five sample types are:
14
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MULTIMEDIA SAMPLING
APPROACH OVERVIEW
cn
GENERAL
BOUNDARY
ASSESSMENTS
COAL PILE AND/OR
RAW MATERIALS
Figure 3. Multimedia sampling strategy overview.
-------
a. Gas/vapor: These are samples for light hydrocarbon and inorganic
gas analysis. They include samples from input and output process
streams, process vents, and ambient air.
b. Liquid/slurry streams: Liquid streams are defined as those con-
taining less than 5 percent solids. Slurries are defined as those
containing greater than 5 percent solids. Nonflowing pastes are
considered solids.
c. Solids: These include a broad range of material sizes from large
lumps to powders and dusts as well as nonflowing wet pastes.
Because the distinction between solids and slurries can become
blurred, the reader should consult both Chapters 6 and 7 of this
manual when in doubt.
d. Particulates or aerosols: These emissions are found in contained
streams such as ducts or stacks.
e. Fugitive emissions: These are gaseous and/or particulate emis-
sions from the overall plant or various process units.
1.3.3.2 Phased Approach Sampling Point Selection Criteria—
The selection of sampling points in processes where phased-level sam-
pling techniques are employed is based on the concept previously stated:
that Level 1 sampling is oriented toward obtaining quantitative data with
relaxed accuracy requirements for determination of the pollution potential
of a source, whereas Level 2 sampling is intended to acquire the more accu-
rate data necessary for a definitive environmental assessment on prioritized
streams. Stream parameters such as flow rates, temperature, pressure, and
other physical characteristics will be obtained on both levels within the
accuracy requirements of a given level of sampling. For example, a Level 1
particulate matter sample is obtained at a single point under pseudoisoki-
netic conditions. This means that the sample is acquired at the point of
average velocity, which has been determined by a velocity traverse taken at
typical points in the stream. The sample is withdrawn at an appropriate
rate through the SASS train cyclones (see Chapter 4) by using a probe nozzle
that is specifically selected for isokinetic conditions; however, this flow
rate must not be allowed to change since a change in flow rate will alter
the particle cutoff efficiency of the cyclone system. In Level 2, however,
16
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where quantitative data requirements may be more stringent, isokinetic
samples must be withdrawn using a full traverse with a port in specific
locations away from ducting bends and other obstructions in order to insure
a sample representative of the actual effluent. The recommendations in this
manual are restricted to Level 1 sampling and analysis criteria only.
Similar considerations apply to site selection for sampling liquids and
solids. In Level 1, liquid samples can be taken from tanks' or other con-
tainers without extensive depth integration using a multiported probe.
Pipes may be accessed with a simple tap sampler. In slurry streams, an
effort should be made to sample a turbulent or well-mixed area.
In the case of solids sampling, the standard procedures used in sampl-
ing piles and stationary containers are relaxed on Level 1 both by taking
fewer increments to make a composite and by relaxing the requirements for
depth-integrated sampling. For moving solid streams, a simplified sample is
obtained by reducing the number of increments required for the time-averaging
aspect of the sampling procedure.
In most cases, Level 1 sampling methods generally encompass approved
standard EPA, American Society for Testing and Materials (ASTM), and American
Petroleum Institute (API) techniques. Modifications are then made to these
techniques to adapt them to the time and cost constraints consistent with
the Level 1 sampling philosophy. These modifications include: (a) reducing
port selection criteria; (b) eliminating the requirements for traversing,
continuous isokinetic sampling, and replicate sampling in the collection of
particulate matter; and (c) use of grab samples for some gaseous, liquid,
and solid samples.
1.3.3.3 Sampling Requirements—
Guidelines indicating amounts of sample to be collected in order to
carry out meaningful analyses have been developed. These amounts are pre-
sented in Table 2. Further details regarding sampling are provided in later
chapters of this manual.
17
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TABLE 2. REQUIREMENTS FOR LEVEL 1 STREAM SAMPLING
Stream
Vapors with
or without
parti cul ate
Sample size Location
30 m3 Ducts, stacks
Sample procedure
SASS train
Liquid
Solids
Gas (reactive)
organic material
with bp <100° C;
N and S
species
Gas (fixed)
02, N2, C02, and
CO
20 L* Lines or tanks
Open free-flowing
streams
1 kg Storage piles
Conveyors
2 L Ducts, stacks,
pipelines, vents
10-30 L Ducts, stacks,
pipelines, vents
Fugitive emission 2,496 m3 Ambient atmosphere
Tap or valve sampling
Dipper method or
composite sampler
Coring
Full stream cut
Grab sample
(glass bulb)
Integrated bag sample
FAST or modified
hi-vol
*May need additional sample volume depending on the nature of the biotesting
employed.
1.3.4 Level 1 Analysis
During an environmental source assessment, the analytical methods
applied will vary from relatively simple manual wet chemistry to relatively
complex instrumental techniques. Analyses proceed from general, broadly
applicable survey methods to more specialized techniques tailored to spe-
cific component measurements. This broad range requirement has been struc-
tured to adhere to the same phased concept described for the sampling pro-
gram. At each level of the analytical program, the depth and sophistication
of the techniques are designed to be commensurate with the quality of the
samples taken and the information required. Hence, expenditure of analytical
18
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resources on screening samples from streams of unknown pollution potential
is minimized.
1.3.4.1 Analytical Methodologies--
Chapters 8 through 11 specify analysis schemes and procedures that will
provide data relatable to all existing EPA standards and those additional
data requirements specified above for Level 1 environmental assessment.
There are seven categories of analysis:
a. Organic analysis: Survey techniques are used to identify compound
classes by functional group.
b. Inorganic element analysis: Based on spark source mass spectros-
copy (SSMS), which can perform a general survey of all effluent
streams for possible inorganic elements. Atomic absorption spec-
trophotometry is to be used for analysis of mercury. Antimony and
arsenic quantisations will also be made using atomic absorption
spectrophotometry on the impinger solutions.
c. Particulate morphology: Includes microscopic examination of
shape, size distribution, surface features, for possible source
assignment.
d. Water analysis: Ion chromatography and reagent test kits will be
used as a supplement for those analyses not covered by SSMS or
organic analysis.
e. Gas chromatographic analysis: Consists of onsite analysis of
gaseous and/or low boiling organic and inorganic species.
f. Opacity: Consists of onsite evaluation of smoke plume light
transmittance.
g. Bioassay testing: Includes selected health and ecological testing
on all solid and liquid samples, and is designed to measure the
environmental and health effects potential of a given source
stream in a broad and general manner.
The three major categories, though, are organic analysis, inorganic analysis,
and bioassay testing.
The Level I organic analysis achieves a semiquantitative estimate of
the predominant classes of organic compounds present in samples taken from
process streams. The Level 1 strategy is to isolate well-defined fractions
by conventional liquid chromatography rather than to isolate specific classes.
19
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Level I inorganic analysis utilizes the spark source mass spectroscopic
technique to achieve qualitative and semiquantitative elemental analyses on
all solids, particulates, filterable solids from liquid streams, and evap-
orated residues of liquid samples. This technique is used because of its
general multielement capability, acceptable detection limits, speed, and
cost. Atomic absorption spectrometry is to be used for those elements
and/or samples for which SSMS is not suitable or appropriate; for example,
mercury. An overview of the scheme for analysis of organic and inorganic
species is presented in Figure 4.
Biological tests included in the Level 1 analysis scheme are intended
to indicate potential biohazards independently of chemical analysis. While
chemical analysis provides quantisation for known dangerous compounds,
bioassay provides complementary information on the unclassified compounds
and their mixtures. The biological test matrix presently being applied
allows for the individual design of testing employed relative to a partic-
ular sample.' Only the appropriate tests are selected from the representa-
tive health and environmental effects indicators.
1.3.4.2 Level 1 Detection Limit-
On the basis of environmental concern and/or potential health effects,
the nature of the analytical techniques to be used, and the amount of sample
that can be practically collected, acceptable and attainable detection
limits have been identified. These attainable detection limits for inorganic
species will vary with the element and the sample matrix but should be
within the limits of 0.002-0.2 ug/m3 with particulate matter, 0.02-2 mg/kg
with noncombustible solids, 0.2-2 ug/L with liquids and ~1 mg/m3 with gases
(1 ug/m3 for sulfur compounds). See Section 8.3.4 and Table 14 for further
discussion.
A realistic detection limit of the TCO organic analysis procedure with
environmental assessment samples is 100 ng/injected sample while that of the
gravimetric analysis is 1 mg/column aliquot. The resultant sample detection
limits will be variable according to the concentration factor applicable to
that particular analysis. See Section 9.4.4.4 for further details.
20
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LEVEL 1 SAMPLE
GASES
LIQUIDS
SOLIDS
INORGANIC
GC-S02,H2S. COS. CO.
C02, 02, NH3, HCN.
(CN)2
NOX-METHOD 7
IMPINGERS
- SSMS
- ATOMIC ABSORPTION
ORGANIC
GCFORbp<100°C
ORGANIC SORBENT
EXTRACT
- GCFORhp>100°C
- IR
- LC/IR/LRMS
INORGANIC
ELEMENTS
- SSMS
- ATOMIC ABSORPTION
LEACHABLE MATERIAL
- ION CHROMATOGRAPHY
- REAGENT TEST KIT
ORGANIC EXTRACTS
• GCFORbp>100°C
• IR
• LC/IR/LRMS
INORGANIC
ELEMENTS
- SSMS
- ATOMIC ABSORPTION
SELECTED ANIONS
AQUEOUS
- SELECTED TESTS
- ION CHROMATOGRAPHY
ORGANIC
EXTRACT AQUEOUS
SAMPLES WITH CH2CI2
GCFORbp>100°C
IR
LC/IR/LRMS
Figure 4. Multimedia analysis overview.
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1.4 SUMMARY AND CONCLUSIONS
The three-phased approach to source assessment is reasonable from both
scientific and economic points of view. The first phase of this three-phased
program is designed to be comprehensive in terms of detection of all efflu-
ents above some minimum levels, though exacting quantification is not re-
quired. Nevertheless, this first phase, Level 1, will provide useful infor-
mation and give direction to the second sampling and analysis effort, Level
2.
The following chapters provide detailed information about the various
aspects of the Level 1 program including multimedia sampling techniques, the
analytical methodologies to be used, and guidelines for quality control and
quality assurance throughout the program.
22
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CHAPTER 2
QUALITY CONTROL/QUALITY ASSURANCE*
2.1 INTRODUCTION
As discussed in Chapter I, the goal of the Level 1 program is to acquire
environmental assessment data having an accuracy factor of 3. Since virtu-
ally nothing is known a priori about the composition of a given sample, the
analyst cannot count on being able to recognize a spurious result or artifact
except by comparison with concurrently analyzed controls. Furthermore, the
analyst is not able to predict, on the basis of past experience, what pre-
cautions are necessary and sufficient to maintain the integrity of the
(unknown) sample components. Finally, because Level 1 environmental assess-
ment (EA) samples are not taken in duplicate and because in most instances
the sample cannot be split into aliquots without changing the effective
limits of detection, the analyst has, basically, only one opportunity to
treat each sample correctly.
Conventional statistical parameters are based on the concepts of repli-
cate analyses (precision) and independently verified true values (accuracy).
Since each Level 1 EA sample is unique and presumed to be totally unknown,
these concepts do not rigorously apply to the EA samples themselves. Cali-
bration standards can and will be used in all analyses. It can be assumed
that values obtained for samples are no better, in terms of precision and
accuracy, than those obtained for standards; they may be considerably worse
if the sample matrix introduces substantial interferences.
Given these Level 1 objectives and constraints, and given also the fact
that the Level 1 sampling procedures are not designed to provide a rigorously
representative sample in all cases, it is clearly not cost-effective to con-
centrate a large amount of resources to attempt to achieve very high precision
*For a more detailed discussion see Guidelines for Environmental Assess-
ment Data Quality Programs (ref. 3).
23
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in the analytical laboratory. It is suggested, therefore, that the analyst
aim for a precision, expressed as a coefficient of variation (relative
standard deviation), for within-laboratory analyses of about 10 percent in
each quantitative operation involved in Level 1 analyses. Thus, calibration
data should be rejected if replicate determinations on standards indicate
that the precision criterion is not being satisfied. Similarly, the phrase
"quantitatively transfer" should be taken to mean that at least 90 percent
of the sample is transferred. Although the 10 percent guideline may not be
rigorously related to the overall "factor of 3" criterion, it would seem to
provide the analyst with a working criterion that is consistent with the
objectives of the Level 1 environmental assessment.
A program of suitable laboratory techniques (SLT), quality control
(QC), and quality assurance (QA) is necessary to assure that this desired
accuracy goal is attained. In the area of chemical analysis, the analyst is
responsible for putting into effect both good laboratory practices and
quality control. This is different from an industrial situation where, for
example, one group is involved in manufacture and another in quality control.
With this difference in mind, this chapter has been divided into three
parts. Good laboratory practices and some quality control procedures will
be discussed first, followed by a discussion of quality control and then a
discussion of quality assurance.
2.2 SUITABLE LABORATORY TECHNIQUES
A program of suitable laboratory techniques can be divided into the
following areas of concern:
a. Material and equipment procurement,
b. Cleanliness,
c. Metrology and standardization,
d. Sampling,
e. Analysis procedures, and
f. Data computation and reporting.
2.2.1 Material and Equipment Procurement Controls
In the Level 1 program, this factor would relate to sampling apparatus
analytical instrumentation, and chemical reagents. Sampling apparatus
24
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whether purchased or constructed in-house, should be constructed of corrosion-
resistant materials, should be designed to be safe to use and relatively
easy to clean, and should allow for only minimum carryover from sample to
sample. As a matter of quality control, the volumes of the various contain-
ment apparatuses should be checked upon their delivery (see Section 2.2.3).
The analytical instrumentation should provide the desired levels of
repeatability (precision) and detectability (the appropriate signal-to-noise
ratio at a particular sample level) and should also be designed to result in
the minimum amount of carryover from sample to sample. Finally, the instru-
ment should be relatively easy to clean and maintain. As a matter of quality
control, the instrument should undergo a thorough evaluation upon receipt,
including running it through an electronic checkout procedure (normally
provided in the manual) and "running" a standard curve using well-character-
ized samples.
Care must be exercised in the purchase of chemical reagents. Reagent-
grade chemicals often contain significant levels (ppm) of trace metals and
other impurities. In certain cases, specially purified reagents may be
required. Once delivered, reagents should be checked for purity by preparing
control or blank samples and analyzing in the normal manner. This quality
control procedure should be done prior to any actual analyses (at which time
blanks would be prepared and analyzed again). Such preliminary checking of
reagent quality will allow time for reagent replacement or purification.
Each lot of organic solvent (i.e., each new batch number) must be
checked for contamination. A volume of solvent equivalent to that used in
sample extraction should be evaporated to dryness. The residue should be
weighed; it should also be analyzed by gas chromatography. If any signif-
icant quantity of organic contamination is found, the solvent batch must be
redistilled or rejected entirely. Solvents used should be Burdick and
Jackson "distilled in glass" or equivalent quality. Note that use of chem-
icals of the specified grade does not eliminate the necessity of performing
checks on the quality of each new batch of material used. However, use of
high quality reagents is important to minimize the probability of acquiring
unsatisfactory lots of material, which would require repurification or
replacement. Sodium sulfate and silica gel used in the liquid chromatography
(1C) separation will frequently require cleanup by extraction with organic
solvent prior to use, as described in Section 9.4.4.
25
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2.2.2 Cleanliness Controls
Cleanliness must be an integral part of analytical methodology if
quality data are to be acquired.
The containers in which samples are held for inorganic analysis must be
made of high-density linear polyethylene. They must be cleaned in the
following manner:
a. Wash with Alconox detergent,
I '>
b. Rinse liberally with tap water,— t^'iti-aH1^.
c. Rinse with 1:1 concentrated sulfuric acid and nitric acid mix, and
d. Rinse liberally with distilled water.
Samples for organic analysis, including CH2C12 extractions, must be
shipped in amber glass bottles that have been cleaned by the above-described
method adding the following steps:
e. Rinse with methanol,
f. Rinse with methylene chloride, and
g. Dry in a filtered, clean, hot air stream from an oilless compressor
or place in an oven at 40° C (104° F).
Caps for containers holding organic analysis materials shall be lined
with Teflon. Perform preliminary testing on appropriate aqueous and methylene
chloride control samples held in a manner simulating shipment to insure that
no contamination arises from this procedure. Do not use Teflon tape to seal
these containers because this product contains potential contaminants.
Except for the SASS train components, all portions of the sampling
apparatus that come into contact with the sampled stream should be cleaned
using the same procedure that was used in cleaning the container for that
sample. Such cleaning is to be performed both before the sampling apparatus
is used for the first time and after a sample is acquired.
After the apparatus has been cleaned and dried, it should be stored in
boxes to prevent spurious contamination. As a matter of quality control a
control sample (e.g., some test reagent) should periodically be taken into
the sampling apparatus and then analyzed for contamination.
Of special concern during the sampling process itself is the accidental
acquisition of substances at the sampling site that are not representative
of the sample. Examples of such substances would include corrosion products
26
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particulate matter adhering to a sampling port, or a scum floating on some
liquid to be sampled. All members of the sampling team must be alert to
avoid these situations.
2.2.3 Reagent Formulation
Once purchased, chemical compounds must be maintained at the desired
level of purity. Chemicals and reagents prepared from these compounds
should be mixed and stored only in vessels that have been thoroughly cleaned
following the procedures described in Section 2.2.2. The vessels should not
lead to contamination of the sample through vessel decomposition (especially
caps), leaching, or permeation of contaminants through the vessel walls.
Care should be taken not to contaminate reagents. Also, deterioration may
result from oxidation, deliquescence, or light-induced decomposition. A
suitable quality control procedure to guard against reagent contamination is
to note any significant changes in the blanks or standards prepared with
these reagents.
The procedures for cleaning the XAD-2 resin prior to use are specified
in Appendix B.* The quality control checks described in the appendix should
be applied to each batch of resin before it is used in a field study. These
controls and blanks should permit the analyst to identify the source of any
background contaminant and to make corrections to the results of sample
analyses. If contamination is excessive (more than 10 percent of the sample
level), the source should be traced and the contamination eliminated, if
possible. Note that silicones (from lubricants/sealants) and phthalates
(from plastics) are major potential interferences and use of these materials
must be avoided entirely in collection, storage, and handling of samples for
organic analysis.
2.2.4 Metrology and Standardization
Metrology is the study of devices used for measurement and their proper
operation and application, while standardization is a methodology for deter-
mining the response of some particular instrument to a well-characterized
sample. Metrology is of principal concern to instrument manufacturers,
*Resin not utilized within 2 months should be retested. Resin not
meeting the specified criteria must be recleaned to meet these requirements
before its use.
27
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though analysts should be alert to deficiencies and/or problems. Examples
of such deficiencies would include: nonlinearity with changes in instrument
sensitivity settings, meters that are difficult to read, and electronically
"noisy" phototubes or photomultipliers. Standardization is fully the respon-
sibility of the analyst and will be the principal focus for this section of
the chapter.
Little in the way of standardization is available for sampling. Cali-
bration of sampling apparatus volumes should be done as a part of procure-
ment quality control. Calibration of flow meters on sampling devices should
be carried out regularly as a part of procedural quality control and quality
assurance (see Sections 2.3 and 2.4).
A very important part of standardization is choosing and/or preparing
reagents to serve as standards. Reagents for standardization, such as
certain gaseous samples, may be purchased ready to use. Other reagents are
either not available as standards, or may be too expensive to use on a
regular basis. In these latter cases, standards must be prepared and sub-
sequently verified by some appropriate means. One way to verify laboratory-
prepared standards is to analyze them against primary standards such as
those available from the National Bureau of Standards (NBS) or the American
Industrial Hygiene Association (AIHA). Table 3 contains a list of various
suitable standards. If primary standards are not available, laboratory-
prepared standards may possibly be verified by analyzing the standards by
several different means. Once verified, the standards should be reverified
on a regular basis as they may become contaminated and/or degrade. Such
reverification may be considered a quality control procedure.
The standard inorganic gases can be purchased from the NBS, as indi-
cated in Table 3. Commercially available permeation tubes can provide a
good primary standard for gas liquid chromatography (GLC) analysis if the
devices are gravimetrically calibrated using NBS or ASTM traceable certified
weights as a reference. The availability of certified gaseous organic
standards (bp <100° C) is more limited. NBS methane and propane standards
are available. Others will have to be prepared and verified by other means
e.g., quantitative or elemental analysis. In using gaseous standards, one
must take care that unwanted dilution does not occur, or that if mixtures
28
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TABLE 3. LIST OF CALIBRATION STANDARDS
Available NBS-SRM
S02/N2
C3H8/air
CH4/air
C02/N2
CO/N2
NO/N2
02/N2
cylinder
cylinder
cylinder
cylinder
cylinder
cylinder
cylinder
Trace metals in coal
Trace metal in fly ash
Trace metal in fuel oil
Hg/H20
Trace metals/orchard leaves
Trace metals/bovine liver
NO2 Permeation Tube
Commercially Available Permeation Tubes
Bromine
Ethylene oxide
Acetaldehyde
Chlorine
Hydrogen fluoride
Cyclohexane
Hexane
Benzene
Toluene
Ammonia
Sulfur dioxide
Hydrogen sulfide
Methyl mercaptan
Dimethyl disulfide
Propane
Propylene
n-Butane
Carbon tetrachloride
Freon — 11
Freon - 12
Carbonyl sulfide
Dibutyl sulfide
Diethyl sulfide
Dipropyl sulfide
Wastewater Standards*
'Available from:
Minerals
Calcium
Magnesium
Sodium
Potassium
Alkalinity
Sulfate
Chloride
Fluoride
Total dissolved solids
Total hardness
pH i
Conductance
U.S. Environmental Protection Agency
Environmental Monitoring and Support Laboratory
Quality Assurance Branch
Cincinnati, Ohio 45268
Nutrients
Ammonia — N
Nitrate - N
Orthophosphate — P
Total Kjeldahl
Total - P
Demand
B.O.D.
C.O.D.
T.O.C.
Trace metals
Aluminum
Arsenic
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Mercury
Manganese
Nickel
Lead
Selenium
Vanadium
Zinc
29
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are being prepared, diluted mixtures are verified. Also, the purity of
individual components used to prepare a mixture must be documented. Certain
elemental and anion standards are available from either the NBS or EPA (see
Table 3). Such standards are not difficult to prepare in the laboratory due
to the commercial availability of relatively pure metals and salts. In
preparing mixtures of standards, one must be careful of interactions that
'might lead to preferential loss; for example, some metal sulfate mixed with
a barium salt. In preparing mixtures of standards, one must be wary of
components added in large amounts having levels of contamination that could
interfere with other components of the mixture introduced at low concentra-
tion. Standards below 10 ppm must be prepared fresh daily. They should be
stored in dark, clean containers. Sub-ppm standards should always be pre-
pared and stored in vessels reserved for this use. These vessels should
have received pure water rinses and rinses with the standard solution before
use.
2.2.5 Sampling
Level 1 sampling techniques have been selected to provide a good
approximation of the true levels of the gases, liquids, or solids sampled.
They are being employed here in a survey application and not in a protracted,
intensive study of the source. Information gained from the Level 1 survey
approach will be used as an indicator of the total source emissions. As
such, poor sampling technique could easily lead to an immediate error factor
of 2 to 10, which, when combined with the error factor of the measurement
procedure, means that the Level 1 assessment goal will most likely not be
achieved for the source.
Gases should be acquired in clean, calibrated sampling devices. If
possible, the sample holding device should be evacuated prior to sample
acquisition, or, at the very least, purged with several volumes of the
gaseous sample before a final sample is acquired. Another concern is the
homogeneity of the process stream, flue, or enclosed atmosphere from which
the sample is taken. Stratification of gases does occur readily and every
effort should be made to sample from a point where mixing is maximized, such
as turbulent regions after restrictions. In acquiring samples, care should
be taken that debris at or around the sampling point does not accidentally
enter the sample vessel.
30
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The SASS train and the Fugitive Assessment Sampling Train (FAST) pre-
sent special sampling techniques because they are complex and are used to
acquire both gaseous and solid samples. An extremely important considera-
tion in using these devices is that they be thoroughly cleaned before use.
While using the devices, one must be wary of clogging of any part of their
complex "plumbing." Also, flow rates must be carefully monitored and con-
trolled during a sampling run. Samples from the SASS and FAST trains must
be removed carefully under clean conditions. Containers for sample storage
and shipping should be thoroughly cleaned and properly sealed after loading.
Appropriate containers for SASS samples are listed in Table 4.
Liquids in process and waste streams may not mix well, making repre-
sentative sampling difficult. Every effort should be made to sample where
the liquid is most homogeneous or to take samples from several points and
combine them. Sample containers must be clean and nonreactive (See Table 12,
Chapter 6). The sampling device should be rinsed with several portions of
the liquid of interest before an actual sample is acquired.
Solids tend to be even more heterogeneous than liquids. Thus, great
care must go into selecting a sample. If some bulk solid, such as a waste
pile, shows major heterogeneity, then a composite sample is necessary. (A
composite sample is always preferred.)
Sample handling is a general concern no matter what the sample type.
Once the sample is collected, care should be taken that it does not chemi-
cally or physically change other than by approved procedures (see Table 12,
Chapter 6), that it does not become contaminated, that no portion of the
sample is lost, and that the sample does not become diluted. Reactive
samples such as the sulfur and reduced gases should be protected from light,
kept warm (without condensation), and analyzed as soon as possible (within
h h). Containers for shipment of aqueous metal ion samples should be acid-
rinsed prior to use so as to prevent loss of trace metal ions to the con-
tainer wall. Stabilization of liquid and slurry samples (as described in
Chapter 6) is necessary and should be carried out consistently. One type of
solid especially difficult to handle is particulate material on filters.
Loss is to be avoided by using shipping containers that seal in such a way
that loose particulate material will not pass through the seal or become
lodged in the seal joint. One suggested method is to roll the filters up
31
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TABLE 4. A SUGGESTED FORMAT FOR SAMPLE CODING AND IDENTIFICATION
Sample code
1C
3C
IOC
PF-a
PR
MR
XR
XRB
CD-0
CD-LE
CD-AE
HM
HMB
HI
HIB
AI-1B
MCB
MMB
FF
CF
FA
BA
Container
Amber glass
Amber glass
Amber glass
Tight- seal ing
glass tube
Amber glass
Amber glass
Amber glass
Amber glass
HDLP*
Glass
HDLP
HDLP
HDLP
HDLP
HDLP
HDLP
Amber glass
Amber glass
HDLP
HDLP
HDLP
HDLP
Size
100 mL - WM
100 mL - WM
100 mL - WM
250 x 24 mm
500 mL
500 mL
500 mL
500 mL
500-1000 mL
500 mL
1000 mL
500 mL
250 mL
2 L (+ 1 L)
1 L
500 mL
500 mL
500 mL
500 mL
1 gal
1 gal - WM
1 gal - WM
Sample description
l-3|j cyclone catch
3-10u cyclone catch
> 10|j cyclone catch
Participate filter(s)
CH2Cl2/Methanol probe and
cyclone rinse
CH2C12 organic module
rinse
XAD-2 resin
XAD-2 resin blank
Neat condensate
CH2C12 extract of condensate
Acidified, extracted
condensate
HN03 module rinse
HN03 blank
First (H202) impinger--
Special handling
First (H202) impinger blank--
Special handling
2nd (First APS) impinger
blank
CH2C12 blank
CH2Cl2/Methanol blank
Liquid (oil) fuel feed
Solid (coal) fuel feed
Fly ash
Bottom ash
*HDLP = high density linear polyethylene.
32
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and place them in a long test tube that can be tightly capped with a glass
or Teflon plug.
A major problem in sample acquisition, handling, and analysis is sample
identification. To minimize sample mixup and to make data treatment more
efficient, it is suggested that a comprehensive sample coding system be
adopted. The format code suggested would include the following:
a. Site code (e.g., Acme Power Station would be APS);
b. Contractor code (e.g., John Doe Engineering would be JDE);
c. Sample code (from presite survey; see Table 4);
d. Date of sample acquisition; and
e. General sample number.
An example identification number would thus be:
APS-JDE-1C-6/8/78-22130.
This same code number should be used from sample acquisition through final
data tabulation.
2.2.6 Procedures
Suitable laboratory techniques are an essential part of sample preparation.
Digestions, extractions, or combustions should be carried out in a vapor-
free laboratory. Any reagents (e.g., HN03, HC1, acetic acid, benzoic acid)
or solvents to be used in these processes should be checked for purity
before use. These reagents may need to be purified using such techniques as
distillation, zone refining, and recrystallization. Concentration through
solvent evaporation must be performed without contamination of the sample.
The grinding apparatus for solids must not contribute to the sample.
For example, carbide rather than steel blades should be used in any blender-
type device. Of course, significant effort must be made to assure that
there is no sample carryover from one grinding operation to the next.
Personnel should be thoroughly trained in the basics of the analytical
procedure(s) they are to use. This training should include imparting a
thorough knowledge of the operation of any instrumentation to be used.
Quality control procedures will measure the success of this training. More
difficult to instill is an alertness to procedures not working as they
should. To develop such alertness, dialogue on ways to improve all aspects
of the procedures should be encouraged.
33
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Cleanliness must also be of concern when using instrumentation. In-
strumentation must not be exposed to corrosive materials that could cause
instrument degradation and/or failure. Instrument-associated sample con-
tainers must be kept clean and sample carryover avoided. For example,
syringes and cuvettes should be rinsed several times with the sample to be
analyzed. In general, the equipment and the place of analysis must be
maintained in a clean and orderly manner. The laboratory temperature and
humidity should be kept reasonably constant.
An essential aspect of Level 1 techniques is the analysis of control
samples. The control sample and its handling throughout the laboratory
sequence should be identical to the real sample and its handling. For
instance, an unexposed XAD-2 cartridge must be dumped, homogenized, and a
5-g aliquot reserved for the Parr bomb ashing and trace element assays. The
remainder must be Soxhlet extracted and the extract subjected to the entire
organics analysis sequence. Similarly, for every type of analysis performed
there should be a control sample analysis performed periodically.
Another good laboratory practice is that of testing for matrix effects,
those interactions between the species of interest and some other component(s)
of the sample that lead to high or low analytical results. The presence of
matrix effects leading to low analytical results can be easily ascertained
by the method of multiple standard additions. This procedure should be
carried out with several test samples every time a new type of sample matrix
is encountered. If no matrix effects are detected, the analysis can proceed
using a standard curve. If significant matrix effects are detected, all
analyses must be carried out using the method of standard additions. Matrix
effects leading to high results are more difficult to identify. One way of
doing so is to analyze the sample by two or more methods, each of which is
based upon a different physical and/or chemical property of the substance of
interest. High background, resulting from a component of the sample and not
the reagents added to it, may also lead to high analytical results. The
availability or development of a true blank is one way to identify and deal
with this problem; multiple method analysis is another. A false high result
will not be as serious in a Level 1 assessment as a false low result because
a false high result will trigger a call for a Level 2 assessment wherein
34
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TABLE 5. METHODOLOGY CALIBRATION CHECK
Check rate
Methodology
1C
Test kits
AAS
GC
Multipoint
Weekly
V
V .
Each analysis
session
V
v
Three points — center
and bracketing points
Each analysis
session
v
V
more accurate analytical methodologies should lead to its discovery. The
conclusion is that false low results due to matrix effects must be tested
for and dealt with; testing for false high results due to matrix effects or
high backgrounds should receive only a moderate amount of attention.
A fourth general concern is calibration, or development of a standard
curve. Once an instrumental system is functioning properly, a multipoint
standard curve should be acquired. The accuracy of this curve should be
checked using NBS, ASTM, or EPA standards. The frequency of checking the
standard curve (single point or multipoint check) depends upon the method-
ology, as some are more susceptible to drift than others. Table 5 indicates
the minimum time interval between checks for each methodology.
For SSMS, a single control sample should be prepared and analyzed
during each analysis session. Accurate results will indicate that the
instrument is operating in a stable manner.
Good laboratory procedures associated with the specific analytical
techniques used in the Level 1 program are discussed below.
2.2.6.1 Spark Source Mass Spectrometry—
It is apparent that the accuracy and precision of spark source mass
spectrometry (SSMS) will be limited by the exposure factor used in the "just
disappearing line" quantification procedure (see Chapter 8). The other
major sources of variation are electrode preparation, the sparking process,
35
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and photoplate development. Uniform electrodes can be obtained with thorough
mixing of finely ground solid samples and graphite. Liquid samples are
mixed with graphite and taken to dryness, then slurried and dried again
before finally milling them thoroughly in dry form and forming an electrode.
Good techniques in photoplate development, including using fresh reagents
and controlling development bath temperatures, are also necessary. Internal
standards are always included in these samples. One has to assume that the
internal standard will behave similarly to the unknowns; that is, it will
distribute like the unknowns on and among the graphite particles and ionize
with an efficiency equal to that of the unknowns. Checks of the internal
standard should be run at least once a month against the mass and molar
response of another standard sample, i.e., elements in an NBS-defined sample.
Any gross changes in this response will indicate that something is wrong
either with the instrument or with the internal standard.
2.2.6.2 Ion Chromatography—
This is a relatively straightforward technique, the number of experi-
mental variables being minimal. The principal analytical concern while per-
forming ion Chromatography (1C) is the introduction of contamination. To
avoid contamination, columns must be thoroughly cleaned before use and then
equilibrated with very pure eluting solutions. Appropriate controls and a
standard concentration series should be included in the daily runs as standard
operating procedures.
2.2.6.3 Water Test Kits-
Water samples may be analyzed in the field using commercial test kits.
Little can go wrong with the mechanics of these test kit procedures; how-
ever, interferences are a real possibility in that the test kits are usually
rather simple chemical systems. Standard addition tests should be performed
if interferences are at all suspected. False low results at this stage of
the phased approach for environmental assessments are much more serious than
false high results.
2.2.6.4 Atomic Absorption Spectrometry—
The cold vapor and hydride complex techniques are used to generate the
gaseous forms of Hg, Sb, and As for measurement by atomic absorption spec-
trometry (AAS). Great care must be taken to see that the gas-generating
36
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systems do not become contaminated and that there is no retention of pre-
viously generated gases. Control samples should be measured after every
five or ten field samples. Care must be exercised to see that none of the
generated gaseous sample escapes before entering the AA system. Newer
atomic absorption spectrometers are quite stable electronically, and measur-
ing an absorption signal due to cold Hg vapor is done with minimum difficulty.
The analysis procedures used for As and Sb are characterized by more signifi-
cant sources of variation and error. As a matter of good laboratory practice,
a multipoint standard curve should be acquired along with each set of unknowns
analyzed. Also, it is good practice to run a single point standard after
five to ten unknowns have been analyzed to assure that instrument drift or
sample input blockage has not occurred.
2.2.6.5 Colorimetric Method for NOV Analysis (Method 7) (refs. 4, 5)--
/\
Method 7 consists of three primary steps. First the NO gases are
J\
collected and reacted in an acidic, oxidizing medium to produce a nitrate
ion. The nitrate ion is then reacted with phenoldisulfonic acid to produce
6-nitrophenol-2,4-disulfonic acid. Finally, the free base form of this
latter acid is measured colorimetrically. Special care must be exercised at
several points in this multistep procedure. First, condensation of water in
the gas collection system must be avoided. The introduction of particulate
matter into the sample flask must also be avoided as such particulate matter
might contain nitrates, which would result in erroneously high NO valves.
X
A sufficient quantity of oxygen is necessary for conversion of NO to
N02. If this is not present in the original sample, it must be introduced.*
In so doing, care must be exercised so that sample is not lost nor inter-
ferences introduced. Great care must be exercised in measuring the sample
flask pressure before and after reaction of the NO gases with the acidic,
/S
oxidizing media. Of course, system gas leakage rates must be controlled.
Overheating during the evaporation step or the nitration step can lead
to low results; heating with steam is required. Also the pH of the test and
standard solutions used in the spectrophotometric step must be within 1 pH
unit of one another. Finally, the wavelength setting of the spectrophotom-
eter used must be checked for proper calibration on a regular basis.
37
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2.2.6.6 Gas Chromatography--
Gas chromatography (GC) is to be used for both inorganic and organic
analyses. One good practice is to regularly monitor the GC parameters such
as column, injection port, and detector temperatures; current and/or voltage
setting on detectors; and gas flow rates. Attenuation controls on the gas
chromatograph should be checked as a part of instrument procurement quality
control. The columns to be used are specified; hence, analytical error due
to sample degradation in the column, column bleed, etc., should be minimal.
All column connections should be leak-checked regularly, and the carrier gas
freed of residual oxygen. Water vapor should be filtered from the air
delivered to the flame ionization detector. Good injection technique is
always important. A fixed volume gas injection loop should be used to
facilitate gas sample injection. The septum should be replaced after every
20 to 50 injections of liquid samples.
2.2.6.7 Liquid Chromatography—
Liquid chromatography (LC) demands great care in column packing. The
packing should be homogeneous with no cracks or bubbles present. The pack-
ing material itself must first be thoroughly cleaned with organic and aque-
ous solvents, and then rinsed in contaminant-free pentane and methanol prior
to activation. Careful placement of the sample in the column is critical.
The sample should enter the column as a uniform "plug" of minimum thickness.
Eluting solvent should be added to the column without agitation of the
sample plug. Reagents used to prepare eluting solvents must be of high
purity. This solvent purity must be checked by the appropriate blank deter-
mination techniques prior to use. See Section 9.4.4.1 for more detail on
column preparation.
2.2.6.8 Infrared Spectroscopy--
This qualitative tool is used to determine the predominant classes of
organic compounds present. The major error sources of this technique are
associated with sample handling. Salt plates and cells must be kept free of
contamination, including moisture and sample carryover. Infrared (IR) work
should be done in a low humidity, dust- and fume-free environment. As a
control, empty cells and plates should be analyzed with each sample series.
One further concern is wavelength calibration; a standard polyethylene film
should be analyzed daily as a calibration check.
38
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2.2.6.9 Low Resolution Mass Spectroscopy—
Low resolution mass spectroscopy (LRMS) is to be used to indicate the
presence of different types or classes of compounds, and, if possible, the
presence of particular compounds. A skilled operator is necessary in order
to maintain an LRMS system; also, a mass spectroscopist will be needed to
interpret the data since such interpretation may be a matter of pattern
recognition and analysis. Good laboratory practice dictates that the mass
calibration should be checked at least once a week.
2.2.6.10 Morphology—
This technique is used for characterizing particulate sample collected
as part of a Level 1 assessment. In the area of particle morphology, good
laboratory practice begins with sample acquisition. There should be a
minimum of handling and manipulation of materials during the sample^taking
steps, since increases or decreases in size or aggregation may result. Care
must be exercised in protecting samples from introduction of extraneous
materials. It is preferable to view sample material as soon after acquisi-
tion as possible, if only to obtain an initial photograph and observation.
This evidence will serve as a reference to change with passage of time. The
microscopist should make frequent references to standard known materials
when making judgmental determinations on matters such as crystal systems,
surface characteristics, refractive indices, etc. At least every tenth
sample should be analyzed by another microscopist as a quality control
check.
2.2.6.11 Biotests—
These tests can be categorized into two general types: (a) those
attempting quantification of test sample ecological effects, and (b) those
giving indication of possible health effects. The list of good laboratory
practices to be used in biotesting is long and complex. A discussion of all
these practices is beyond the scope of this chapter. For more detailed
information refer to Guidelines for Environmental Assessment Data Quality
Programs (ref. 3, pp. 59-65).
2.2.7 Subtraction of "Blank" Background Values
It has been determined that there is no single, accepted definition
39
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among IERL/EPA contractors for the term "blank." To some, "blank" refers to
the signal due to the total amount of species of interest found in reagents,
glassware, and instrumentation used to analyze an actual test sample. To
others it refers to the general background signal that could arise from
species of interest, other chemical interferences, or instrumental compo-
nents, as for example, stray light. In this manual, we will adopt the more
restrictive definition, as it allows a more precise explanation of the
sources of measurement difficulties.
A measurable "blank" then is a signal (above some nominal baseline) due
to the actual presence of some amount of the species of interest. An "inter-
ference," on the other hand, is a signal above the baseline due to a species
other than the one of interest; by definition, it overlaps the signal from
the species of interest. The "baseline" itself is the third type of back-
ground. This nonzero signal is usually not discrete or "peaked," but is
generally horizontal; it is usually due to instrumental parameters such as
unbalanced amplifiers, electronic drift, stray light, etc.
During the analysis of an actual test sample, these three sources of
background are dealt with in different ways. The "baseline" signal is to be
subtracted from the test sample signal prior to calculation of test sample
concentration. The "blank" signal value is used to calculate a concentra-
tion or mass that is subtracted from the test sample concentration or mass.
An interference, on the other hand, is usually difficult to deal with.
Numerical resolution of the signal due to the interference and that due to
the species of interest is a possibility, though it is not very probable
with the types of sample matrixes found in Level 1 work. If the species
interfered with is of environmental concern, it may be necessary to use
another technique for the analysis. In the case of an unresolved inter-
ference, the final analytical result should be designated "I".
Examples of a baseline, a test signal, a true blank signal, and an
interference and test signal combined are given in Figure 5. The baseline-
corrected blank and test signals are simply I. - I. and I. - I ' resoec-
t DS bl bs '
tively. If we assume that the relation between signal and concentration is
simply C. = kl., then the true test concentration is given as
Ct,corrected = k(It - W>~
40
-------
CO
1X1
I-
C9
35
BASELINE
0.0
TEST SIGNAL
TRUE BLANK SIGNAL
INTERFERENCE
+ TEST SIGNAL
'bl
Figure 5. Examples of baseline, test signal, true blank signal,
and interference + test signal.
For some analytical determinations made under certain matrix condi-
tions, there may be an interference that is strongly negative, and the test
sample signal will thus fall below the blank and/or normal baseline signal.
In this case, the final analytical result should be designed "NG" (for
negative).
2.2.8 Limits of Detection
The limit of detection is calculated from the uncertainty, indetermin-
ate error, or "noise" in either the "blank" signal value, or the "baseline"
signal value measured at maximum instrumental or procedural sensitivity. A
positive or negative interference prohibits the calculation of a meaningful
limit of detection value.
The uncertainty or noise value can be determined in three ways. First,
several replicate blank or baseline signals can be measured and their stand-
ard deviation calculated. A second approach is to determine the standard
deviation of the intercept of a calibration curve by means of linear regres-
sion analysis; that is, to calculate ab for y = mx + b. Finally, one can
estimate visually the noise level of a signal. There is some disagreement
41
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as to the relationships between the uncertainty of the blank or baseline
signal and the lower limit of detection. Generally accepted, though, is the
definition of lower limit of detection being that concentration or mass that
would give rise to a signal two times the standard deviation of the blank or
baseline signal. For those cases where a of the background cannot be calcu-
lated, the limit of detection is defined as that concentration or mass that
will give rise to a signal equal to the peak-to-peak noise of the baseline
or blank. This is the concentration or mass that gives a signal-to-noise
ratio of 2.
2.2.9 Data Computation and Reporting
Suitable laboratory techniques in this area involve avoiding data
interpretation errors, calculation errors, and errors in recording calcula-
tion results.
Data interpretation error, in this case, refers to using the wrong
model for a calculation. For example, one might assume a linear response at
the high or low end of a particular concentration range when, in fact, this
is not true. As another example, one might assume that a particular multiple
standard addition curve is linear when, in fact, it is not. This kind of
error is especially dangerous when microcomputers and minicomputers are used
to produce the end result and the raw data are seldom seen. It is impera-
tive that response (standard) curves be periodically plotted and studied to
be sure that the correct calculation model is being used.
Calculation errors can be controlled by good laboratory practice and
good quality control; that is, a calculation should be carried through using
data that have already been analyzed and for which the correct results are
known.
Recording errors are not uncommon. The best way to control these is
through conscientious verification of each number or other result recorded
regarding its accuracy and where it is recorded. Having available well-
designed calculation and tabulation sheets (examples are presented through-
out this manual and in Appendix A) will help to minimize math and recording
errors. All results that are reported in a study should be independently
checked for their correctness before release of the data.
42
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2.3 QUALITY CONTROL
As noted in the previous section, good laboratory practices and quality
control are often inseparable. There are, however, several QC procedures
that involve management and that allow management to judge the SLT and QC
procedures performed by the analytical staff.
The first of these procedures involves management and staff working
together to plan the SLT/QC/QA program. Such a plan would cover all aspects
of acquiring quality data, including:
a. Development of checklists of SLT/QC procedures to be
followed in each aspect of sampling and analysis (see
Table 6 for sample checklist).
b. Delegation of responsibility for implementing SLT/QC
procedures.
c. Designation of lines of communication between management
and analytical staff for reporting concerns about weak-
nesses (or excesses) in certain SLT/QC procedures.
d. Delegation of responsibility for in-house review of data
and calculations.
e. Formalization of procedures for continued review and
improvement of the SLT/QC program.
TABLE 6. CHECKLIST FOR ANALYSIS FOR Hg USING AAS
1. Excess H202 decomposed.
2. Hg° generation system clear of old
sample.
3. Proper wavelength and lamp current
selected.
4. Blank obtained.
5. Multipoint calibration performed.
6. Check performed for volatile organic
materials absorbing at 253.7 mm
7. Standard and sample absorbances verified
43
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Another QC procedure to be employed by management alone is periodic
onsite inspection. The inspection would be for purposes of verifying that
those SLT and QC procedures listed on the checklists are being performed and
are sufficient.
A third procedure would be for management periodically to collect
running reports of instrument readings for blanks and select calibration
and/or control standards. That is, each time an analysis session is held,
the instrument readings obtained with blanks and select calibration or
control standards should be recorded on a graph or such values plotted
against analysis session number (Shewhart quality control chart or equiva-
lent). This running plot should be submitted on a weekly basis to manage-
ment for review. Any abrupt or even gradual changes in these values that
cannot be explained by some change in procedure is grounds for suspicion of
changes in data quality, and, accordingly, should trigger an investigation.
One final procedure is for management to periodically submit (e.g.,
once a month) select, blind test samples for analysis. Such samples might
be NBS, ASTM, or EPA standards. These blind test samples might also take
the form of replicates of a single sample, the analyses of which would
provide a measure of precision. An alternate approach to that of using
blind samples is to submit portions of samples to other laboratories for
analysis. This yields a measure of precision (between laboratories). There
is no guarantee, however, that the other laboratories will do work that is
any more accurate than that done in the home laboratory.
2.4 QUALITY ASSURANCE
The analytical staff is to monitor the quality of its work through
various SLT and QC procedures. Management is to further monitor quality
through QC procedures carried out in cooperation with the analytical staff.
Quality assurance (QA) is an independent monitor of the quality of work per-
formed, but, in this case, the procedures are carried out by an independent
group in cooperation with both management and the analytical staff.
There are several procedures that the QA group will perform. The first
of these is to review the SLT/QC plan as conceived by management and the
analytical staff. This should be a critical review through which weaknesses
and excesses will be noted.
44
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Another activity will involve the performance of onsite inspections to
observe the implementation of analytical methodology and the SLT and QC
procedures. The same checklists utilized by management are to be used here.
The value in having two groups, management and QA personnel, check for
performance of desired procedures is that one group may note weaknesses
missed by the other. In addition, the independent QA personnel will most
likely be more objective in their judgments.
A third QA procedure is for QA personnel to analyze portions of the
samples collected by the analytical staff. The QA personnel should have
equipment and expertise available to perform state-of-the-art analyses that
should lead to analytical accuracy well within the bounds imposed by the
Level 1 Assessment Program. Comparisons of results obtained by analytical
staff and QA personnel should indicate effectiveness of SLT and QC pro-
cedures.
As an alternative to the third QA procedure, QA personnel can provide
the analytical staff with select, blind test samples. Again, these may be
NBS-, ASTM-, or EPA-certified standards, or well-character!" zed standards
prepared by QA personnel.
2.5 CONCLUSIONS
Suitable laboratory techniques, quality control, and quality assurance,
then, are the three programs that should lead to data quality meeting the
goals of the Level 1 Assessment Program. Strict adherence to these programs
will maximize the accuracy and suitability of study data. Indeterminate
errors in sampling; unknown and uncharacterized sample matrix effects; and
unknown, indeterminate errors in analytical techniques offer an ever-present
possibility of poor quality data despite the above precautions. For these
reasons, SLT, QC, and QA procedures must be continually evaluated and im-
proved, and this evaluation and improvement must be concurrent with evalua-
tion and improvement of analytical methodologies.
45
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CHAPTER 3
SAMPLING AND ANALYSIS OF NON-PARTICULATE-LADEN GASES
3.1 INTRODUCTION (refs. 6-12)
This chapter covers the general sampling methodology and measurement
techniques to be used in the field for determination of the organic (bp
<100° C) and inorganic gaseous samples. The methods are as detailed as
possible, but it should be realized that not every detail for every source
can be covered. It is important, therefore, that the personnel involved in
the field effort be well trained and experienced. Moreover, obtaining a
representative sample from a simple gaseous stream can be complicated by
stratification from incomplete mixing or by variations in stream components
over a period of time. Generally, gaseous samples are obtained from the
process vents and effluent streams either by a grab sample technique or by
an integrated sampling train, but for the purpose of Level 1 assessment, a
single 1- to 2-h integrated sample is sufficient. Careful planning is also
necessary to insure that sample acquisition is made at a reasonably repre-
sentative point (position and time) in the stream or process cycle.
The details of the sampling guidelines and sampling techniques are
briefly discussed in Sections 3.3 and 3.4, respectively. The details of the
onsite analysis of inorganic gases (NO , CO, C02, 02, N2, and sulfur gases)
/\
and organics (bp <100° C) are presented in Sections 3.5, 3.6, and 3.7. Data
report forms for sampling and measurements in the field are presented in
Appendix A.
3.2 SAMPLING METHODOLOGY
This chapter briefly discusses the sampling methodology for gases
emitted from the following stream types:
a. Process streams,
b. Vents, and
c. Effluents.
46
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3.2.1 Gaseous Process Streams
Gaseous process streams refer to contained, non-particulate-laden gases
being transported from one area to another. These streams exist under
conditions that range from a slightly negative pressure to highly pressurized
pipeline systems. Also, the contents of gaseous process streams range from
corrosive and toxic process effluents to complex organic mixtures. For the
purposes of source assessment, only those streams that are either influents
to (input water, gas, fuel, etc.) or effluents from the process are consid-
ered for sample acquisition. Consequently, internal process streams are
seldom of concern since they do not constitute influents or effluents in
contact with the environment. Exceptions to this rule involve such streams
existing prior to control devices or being held for interim periods prior to
discharge, such as holding or surge systems situated in-line prior to flare
discharge. Fugitive leaks of gaseous materials are discussed in Chapter 5.
3.2.2 Gaseous Process Vents
Gaseous process vents are generally found in tank farm areas or in
various system operations requiring pressure surge variability.
3.2.3 Gaseous Process Effluents
Gaseous process effluents refer to those gases exhausted into the
atmosphere from ducts or flues. For the purposes of this chapter, gaseous
organic species with boiling points less than 100° C and inorganic gaseous
effluents from these units are considered. The particulate matter content
along with higher molecular weight organics are obtained via the Source
Assessment Sampling System, which is discussed in detail in Chapter 4.
3.3 SAMPLING GUIDELINES
This section briefly describes the problems and considerations involved
in sampling process streams, flues, ducts, and vents.
3.3.1 Process Streams, Flues, and Ducts
Careful planning is needed for the selection of the most representative
sampling point. Frequently, pipeline, duct, and vent systems consist of
composite streams wherein the main or primary stream is joined in one or
more places by secondary streams. When this is the case, a sampling point
47
-------
must be chosen far enough downstream of the joint to insure component homo-
geneity. An optimum choice for sample withdrawal in a gaseous system is at
a point downstream from a bend in the pipe or duct, since a bend induces
turbulence and therefore homogeneity.
In-line valves or sampling ports must also be assessed for their com-
patibility with available apparatus. For example, the process port or valve
entrance will in many cases be larger than the probe diameter. To solve
this problem, a series of one-hole stoppers of various size increments or
gland-type valves may be used to fit over the probe and seal the port en-
trance.
3.3.2 Vents
Vent systems generally consist of relief tubes or exit ducts regulated
by in-line pressure release valves. Vents are found in holding tanks and
storage tanks and usually discharge into the air when the tank pressure
exceeds the pressure setting of the in-line valve. The velocity of the
gases being emitted from vent systems as well as the time duration of the
vent cycle are directly proportional to the diameter of the vent tube, the
headspace volume of the system being vented, and the pressure setting of the
in-line relief valve.
Units or tanks with pressure vent releases to ambient air are sampled
with a grab gas sampling train (Figure 6). The important considerations in
obtaining vent gas samples are:
a. The sample must be taken while the vent cycle is in progress.
(Cycle periods for individual processes should be known as a
result of the pretest survey.)
b. The probe should be situated so that a representative sample of
the vent effluent is obtained without dilution by ambient air.
3.4 GAS SAMPLING TECHNIQUES
All except fixed gas samples must be taken in glass bulbs. The reac-
tive sulfur and nitrogen gas samples should be collected quickly and analyzed
immediately. Fixed gas samples may be collected by using an integrated gas
sampling train (see Section 3.4.2). These two methods are discussed in this
section.
48
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PYREX
WOOL
PLUG
STYROFOAM
PROTECTOR
Figure 6. Grab sampling apparatus.
-------
3.4.1 Grab Gas Sampling (refs. 13-20)
Gaseous grab samples may be taken in one of three ways, depending on
the pressure of the stream in question: high pressure line, slight positive
pressure grab, or negative pressure grab samples. The basic sampling bulb
is illustrated in Figure 6.
3.4.1.1 High Pressure Line Grab Samples--
The apparatus illustrated in Figure 6 is used when the pressure is high
enough in the stream to require a side-split-bleed to provide a sufficient
pressure reduction for effective bulb purge. The sampling bulb is the dual
valve, positive displacement type and is 2 L in volume. The bulb must be
purged with approximately ten volumes of the stream gas before the sample is
isolated.
A small glass wool plug is inserted in-line prior to sampling to pre-
vent the influx of particulate matter into the bulb during the purge and
sample collection periods.
3.4.1.2 Slight Positive Pressure Grab Sampling--
The positive displacement, dual valve glass sampling bulb described
above may also be used in ducts, pipes, or vent systems where line pressure
is slight. Because the pressure is slight, a side-bleed may not be required
for pressure reduction. The pressure bleed valve is adjusted accordingly or
may be totally closed. A small glass wool plug is inserted in-line before
sampling is begun, and approximately ten volumes of sample gas must be
purged through the bulb prior to isolation of the sample.
3.4.1.3 Negative Pressure Evacuated Bulb Sampling--
An evacuated flask or a gas sampling train, as shown in Figure 7, is
used for sampling negative pressure systems or open effluent lines such as
vent systems or point fugitive emissions (the latter are discussed in Chap-
ter 5). The number of bulbs required for a given sampling effort will be
known as a result of the pretest site survey (Section 3.2). The bulbs are
evacuated in the field using a small vacuum pump and are then taken to their
respective sites for sample acquisition. They should be checked for vacuum
with a gauge immediately before sampling.
50
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AIR-COOLED
CONDENSER
FILTER
(GLASS
WOOL)
QUICK
DISCONNECT
RIGID CONTAINER
Figure 7. Integrated gas-sampling train.
-------
The entrance nozzle of the bulb must be fashioned so that a probe may
be attached. Supported pyrex glass, quartz, or ceramic tubing of greater
than 0.6 cm (k in.) diameter and at least 30 cm (12 in.) in length are
acceptable materials for the probe intake section. Other connecting tubing
to the collection vessel must be of a similarly nonreactive material. At
the time of sampling, attach the probe to the evacuated bulb, and then
insert it into the vent or negative pressure duct for sample withdrawal.
3.4.1.4 General Considerations--
For safety reasons, all of the above-described sampling bulbs must be
encased in a protective jacket of styrofoam. The new and used containers
should be thoroughly cleaned following procedures outlined in Chapter 2,
filled with nitrogen, and stored for further use. Teflon valves should be
used in the sampling system. Stopcock grease should never be used.
3.4.2 Integrated Gas Sampling
The nonreactive fixed gas samples shall be taken using an integrated
gas sampling train (see Figure 7). The gas sample is bled or drawn through
a nonreactive probe and passed through an air-cooled condenser by means of
negative pressure from a small diaphragm pump. The air-cooled condenser, or
equivalent, removes excess moisture in the gas stream and also cools the hot
gases. A flow rate meter is used to measure flow into the bag. The collec-
ted gas sample is then analyzed by gas chromatography or by wet methods of
analysis.
3.4.2.1 Apparatus--
a. Probe: Borosilicate glass or other nonreactive material equipped
with a filter (either in-stack or out-stack) to remove particulate
matter.
b. Condenser: Air-cooled condenser or equivalent.
c. Valve: Needle valve, to adjust sample gas flow rate.
d. Pump: Leak-free, diaphragm type, or equivalent, to transport
sample gas. Install a small surge tank between the pump and rate
meter to eliminate pulsation effect of diaphragm pump on the
rotameter.
52
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e. Flow rate meter: Rotameter capable of measuring a flow range from
0 to 1.0 L/min.
f. Vacuum gauge: At least 305 mm H20 (12 in. H20) gauge to be used
for the sampling train leak check.
g. For fixed gases only (CO, C02, 02 and N2): Polymer sandwiched
aluminized bag, or equivalent, with a capacity in the range of 10
to 30 L (0.3-1 ft3). Bags may be reused if they are clean.
3.4.2.2 Reagents—
None.
3.4.2.3 Sampling Procedure--
Prior to field use, all bags are to be leak-checked. In the field,
prior to the sampling operation, the train is also leak-checked. This is
done by plugging the probe inlet and drawing a 250 mm H20 (10 in. H20)
vacuum on the system minus the bag. The vacumm should remain stable for at
least 1 minute.
The sampling point in the duct should be approximately at the centroid
of the cross section at a point preferably no closer to the walls than 1 m
(3.28 ft). This is only a general rule, however, which may vary considera-
bly depending on duct diameter. A sample is taken as follows:
a. Place the probe in the stack at the sampling point and then purge
the sampling line up to the bag.
b. Connect the bag and make sure that all connections are tight and
leak-free.
c. Pass the sample gas stream through an air-cooled condenser.
d. Sample at a rate to fill the bag in about 3 hours.
e. At the conclusion of the sampling interval, disconnect the bag and
analyze as quickly as possible.
3.5 FIELD MEASUREMENTS (refs. 21-24)
Gaseous samples to be analyzed will come from various sources including
stacks, vents, process input streams, process product streams, and ambient
air.
These samples must be analyzed for inorganic species over a short span
of concentrations ranging from sub-ppm levels for sulfur compounds to sev-
53
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eral percent for C02 and water in stack gas effluents. Because many of the
samples that are taken, especially those that contain H2S and other sulfur
species, are unstable due to wall adsorption or possible chemical reaction,
it is specified that the analysis be performed onsite immediately. This
also eliminates the shipping of a potentially large number of bulky sample
containers and permits additional sample taking if a problem area is identi-
fied.
Because no single unit is suitable for all the gaseous species, a
recommended set of measurement techniques and conditions is shown in Table
7. It is not expected that the proposed set of conditions will be suitable
for all mixtures and all possible concentration ranges. If a unique situa-
tion should arise, an alternative set of analysis conditions should be
selected and submitted to the Project Officer and PMB-IERL-EPA for approval.
The actual onsite sampling will be accomplished by using the methods
described in the previous sections. The sample will then be returned to the
mobile laboratory and attached to the gas chromatograph or the appropriate
instrument via a sampling valve. The sampling vessel can then be stored for
further analysis at the laboratory or purged, cleaned, and evacuated for
further use in the field. The actual onsite measurement techniques for
inorganic and organic (bp <100° C) gaseous species are discussed below.
3.6 ANALYSIS METHODOLOGY
The concentration of total oxides of nitrogen (NO ) in an emission
A
stream for Level 1 is determined using EPA Method 7 (phenoldisulfonic acid
method). Analysis of gas samples for inorganic components (CO, C02> 02, N2,
and sulfur species) will be performed in the field by gas chromatography.
The columns and appropriate conditions are shown in Table 7. The samples
should be analyzed the same day they are taken and as soon after acquisition
as possible. The instrument is set up with the column and conditions appro-
priate for the specific analysis to be performed. Retention time and quanti-
tation calibrations are made with the proper standard gas mixture. Ammonia,
hydrogen cyanide, and cyanogens are analyzed by using GC methods. Wet
chemical methods are satisfactory if lower detection limits are essential.
The sulfur compounds are especially prone to degradation and must be analyzed
immediately after taking the grab sample in the field by the gas chromatography/
flame photometric detector (GC/FPD) procedure described in Table 7.
54
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TABLE 7. RECOMMENDED ANALYSIS OF GAS SPECIES
Species of interest Sensitivity Column
Temperature and conditions Detector
C02, CO, 02, and N2 >25 ppm
en
tn
H2S*, SQ2*
H2S, S02s COS
mercaptans and
thiophene
>25 ppm
ppbt
NH3, HCN, cyanogen >100 ppm
NO, N02, NO
1 ppm
Volatile organics 1 ppm
(bp range -160° C to
+30°C)
a) 5 ft x 1/8 in., SS
with Chromosorb 102
b) 8 ft x 1/8 in., SS
13 x Molecular Sieve
c) 5 ft x 1/8 in, SS
no packing
6' x 1/8" Teflon
Porapak N
36' x 1/8" Teflon
column with 12%
polyphenyl ether
and 0.5% H3P04 on
40/60 Chromosorb T
6' x 1/8" glass
Porapak Q
6' x 1/8" stainless
steel or glass,
Porapak Q
Dual thermal
conductivity
Isothermal at 40° C.
When the C02 peak has
eluted in the Chromosorb
102 column, switch to
the Molecular Sieve
column and obtain the
remaining peaks
Isothermal at 80° C
Isothermal at 50° C
for 5 min then in-
crease at 10°/min
to 100° C. Hold for
10 min.
Isothermal at 40° C.
Helium carrier gas
EPA Method 7 or in-line
chemiluminescent analyzer
Helium carrier at 20 mL/ Flame ionization
min. Detector temperatures
200° C. Isothermal at 60°
for 4 min, increased 20° C/
min to 110° C; hold at
110°. Bake-out at 170° C
as necessary between
injections.
Thermal conductivity
Flame photometric
detector
Thermal conductivity
See footnotes at end of table.
-------
TABLE 7 (continued)
Species of interest Sensitivity Column
Temperature and conditions Detector
Volatile organics
(bp range 30° C to
inn0 n
1 ppm
100° C)
6' x 1/8" glass, 20%
OV-101 or 100/120
mesh Chromosorb-W-HP
Helium carrier at 20 ml/ Flame ionization
min. Injector and detector
temperatures: 200° C.
Isothermal at 30° C.
^Concentrations greater than 25 ppm only. For survey work and lower concentrations, the flame photometric
detector system must be used.
tl. Exit end of column should be fitted directly into the base of the detector and any metal transfer
lines should be eliminated.
2. The FPD response tends to saturate at concentrations greater than 2 ppm for a 10-mL injection
volume. Injections should be repeated with smaller (1 or 0.1 ml) sample size if apparent con-
centration exceeds 2 ppm.
3. Detector temperatures above 130° C are reported to result in losses of sulfur species.
NOTE: SS = stainless steel.
o>
-------
3.6.1 Sampling and Analysis of Total Oxides of Nitrogen
As stated above, the concentration of total oxides of nitrogen (NO ) is
to be determined using EPA Method 7. This procedure involves conversion of
NOX to nitrate, reaction of that nitrate with phenoldisulfonic acid to
produce 6-nitro-2,4-phenoldisulfonic acid, and colorimetric measurement of
the anion form of the nitro product. Sampling consists of taking six evacu-
ated grab samples at a point of average velocity every 30 min for a total
time period of 3 h. This procedure provides a pseudointegrated NO value.
The method is suitable for the detection of NO in the range of 2 to
f\
400 mg/dsm3 and the sensitivity is approximately 1 mg/dsm3. It should be
noted that this method does not supply a nitric oxide value but does supply
a total NOX value that is reported as N02. If NO concentration is of special
interest, a grab sample must be taken and immediately analyzed by some other
suitable method.
Data from an in-line chemiluminescence NO analyzer are acceptable by
/\
Level 1 specifications.
3.6.2 Onsite GC Analysis for CO, CQ2> 02, and N2
During instrument setup at each new site, the gas chromatographs will
be fully calibrated as follows: Connect the inorganic standard gas bottle
to the gas sampling valve containing dual (matched ±1 percent) sample loops
(1-, 3-, and 5-mL loop sizes should be available). Flow the gas through the
valve at a constant and reproducible flow rate of 20 stdmL/min, measured at
the sample valve outlet with a soap bubble flow meter. When the valve is
sufficiently purged, actuate the valve and inject the contents of the first
sample loop into the chromatograph. Simultaneously start the integrator.
When the C02 peak has eluted in the Chromosorb 102 column, switch to the
second loop connected to the Molecular Sieve 13X column and obtain the
remaining peaks. The retention times and peak areas of replicate standards
must agree to within 5 percent relative standard deviation. The inorganic
standard gas mixture will be injected and analyzed at the beginning and end
of each day. The retention times and responses of each component must agree
with the initial site calibration data to within ±10 percent.
The analysis of an actual sample proceeds as follows:
57
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a. Set up chromatograph, recorder, and integrator according to manu-
facturers' manuals, calibrate, and confirm operating parameters
(list these on each chromatogram).
b. Conditions
Carrier flow rate: 30 ±2 mL/min nitrogen
Bridge current: 100 mA
Detector temperature: 100° C
Oven temperature: 45° C
Attenuator: as required
Recorder: 1 mV full scale, 1 in./min
Integrator: as required
c. Label the recorder chart with sample number, date, and operating
parameters.
d. Connect the gas sampling container to the gas sampling valve.
Purge the sample loops with the sample. Inject the sample.
e. Simultaneously start the integrator and recorder.
f. When the analysis is finished, give the chromatogram and integra-
tor output to the data analyst.
The required data for these analyses are on the data sheet. Data
reduction is effected as follows:
a. Components (CO, C02, 02, N2) are identified by retention time
comparison with the standard chromatograms (flow rate reproduci-
bility is critical).
b. Divide the areas found in the sample chromatogram by the appropri-
ate slope and obtain the concentration of each component in mg/m3.
Periodically, the gas sampling valve should be checked to determine if
it is contributing contamination to the analysis of samples. Pass dried and
filtered reactor grade helium carrier through the sample loops; then inject
their contents and analyze as if it were a sample. If significant peaks are
noted, the valve should be cleaned per the manufacturer's instructions.
Calibration of the gas chromatograph is performed as follows:
a. Calculate the average and standard deviation of the retention
times and responses from the chromatograms of the standard gas
mixtures.
58
-------
b. Plot responses (MV-sec) as ordinates versus component concentra-
tions (mg/m3) as abscissa. Draw in the curves. Perform least
squares linear regressions for each component, and obtain the
slopes (uV'sec'nrVing).
3.6.3 Analysis of Sulfur Compounds
In the field, sulfur compounds are analyzed by gas chromatography
using flame photometric or thermal conductivity detectors. The procedure
and conditions of operation are listed in Table 7 for a dual flame FPD and a
thermal conductivity detector. Use the manufacturer's recommended condi-
tions for air, hydrogen flow rates, and thermal conductivity filament current.
It is important to note that in the analysis of sulfur compounds, the sample
must not come in contact with anything but Teflon or glass until it reaches
the detectors.
If the sample contains high concentrations of hydrogen sulfide (>200 ppm),
then the sample should be analyzed by gas chromatography with a thermal
conductivity detector. At concentration levels of about 100 ppm and lower,
a flame photometric detector with a 394-nm filter is very suitable for
sulfur compounds analysis because of its specificity and sensitivity.
The procedure for the analysis of sulfur compounds is as follows: The
GC injection-system including the Teflon loop is evacuated to 1 mmHg using
the pump. A small amount of sample from the containers is then introduced
and the system reevacuated for adequate flushing. A known amount of stand-
ard sulfur gases is introduced into the sample loop and injected onto the GC
columns specified for the respective gases in Table 7. The areas of the
eluting peaks are printed by the digital integrator or calculated manually
and calibration plots of area versus concentrations for each individual gas
should be drawn. The unknown sample is then injected, the eluting peaks are
identified by their retention times, and the respective concentrations are
noted from the calibration plots.
3.6.4 Organic Species (bp <1QO° C) Analytical Methodology
Materials with boiling points below 100° C require an onsite gas chromat-
ographic analysis of a collected sample. Two separate GC procedures are
required in order to allow resolution of the very volatile organics while
59
-------
eluting the higher boiling gases in a reasonable period of time. The GC
systems will primarily be separating materials on the basis of boiling point
ranges, although the separations will also be influenced by polarity in some
cases. A gas chromatograph with a flame ionization detector is needed.
The conditions recommended for these analyses are specified in Table 7.
Slight modifications in temperature and duration of the isothermal hold
periods and/or rate of temperature increase may be necessary to accommodate
variations in individual column performance.
The GC system should be calibrated for quantitative analysis with a
normal hydrocarbon mixture. The sample analysis procedure is to connect the
glass gas containers to the sampling valve and draw the gas through the
valve and loop. When the sample valve is sufficiently purged, actuate the
valve and inject the contents of the sample loop into the chromatograph.
Simultaneously start the integrator and temperature programmer. Obtain the
chromatograms and the integrator output. Retention times and responses
shall agree to within 5 percent relative standard deviation. Assumption of
uniform flame ionization detector (FID) response for varying compound classes
is acceptable in Level 1 analysis.
The Ci-C7 standard gas mixture should be used to calibrate the field GC
procedures and should be analyzed at the start of each day. A retention
time vs. boiling point calibration curve is prepared for each compound in
the standard manner. The Level 1 boiling point ranges and the hydrocarbons
falling in each range are given in Table 8.
Since the chromatogram peaks for Level 1 samples will usually represent
mixtures of materials present in a certain boiling range rather than pure
individual compounds, it is recommended that the chromatographic data be
reported on the Organic Compounds form shown in Appendix A.
It is important to recognize that in many, if not most, cases, the
species present will not be identical to those used for calibration of the
onsite procedure. The required data for sampling, calibration, and analysis
are summarized in the data sheets. Any subsequent data interpretations must
use sensitive criteria (MATE value of the worst case compound unless that
compound is ruled out, in which case the next lowest MATE value would be
assumed, etc.) in that boiling range; not the normal hydrocarbon MATE value.
60
-------
TABLE 8. LEVEL 1 BOILING POINT RANGES
Level 1 bp range bp
designation (°C) Hydrocarbon (°C)
GC1 -160 to -100 Methane, Cx -161
GC2 -100 to - 50 Ethane, C2 - 88
GC3 - 50 to 0 Propane, C3 - 42
GC4 0 to 30 Butane, C4 0
GC5 30 to 60 Pentane, C5 36
GC6 60 to 90 Hexane, C6 69
GC7 90 to 100 Heptane, C7 96
61
-------
CHAPTER 4
SAMPLING OF PARTICULATE AND VAPOR STREAMS
4.1 INTRODUCTION
Stationary source participate matter sampling and analysis have been
restricted to streams of high mass loading until recently because the flow
rates through sampling equipment had not been high enough to collect an
adequate amount of material in a reasonable length of time (refs. 7, 25,
26). Because of this restriction, the development and application of con-
trol technology, which requires effluent information on four particulate
size ranges, has been hampered. It has also limited health effects studies,
which require information on the distribution and composition of respirable
and nonrespirable particulate size classes, the presence of volatile organic
compounds, and the presence of trace elements to be complete. To correct
this situation, EPA (IERL-RTP) has developed and specified the use of the
Source Assessment Sampling System (SASS)* for the collection of particulate
samples and volatile matter from ducted emissions (Figure 8).
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 (see Figure 8). Size fractionation is accomplished in
the cyclone portion of the SASS train, which incorporates the three cyclones
in series to provide large collection capacities for particulate matter
nominally size-classified into three ranges: (a) >10 urn, (b) 3 |jm to 10 pm,
and (c) 1 urn to 3 pm. By means of a standard 142-mm or 230-mm filter, a
fourth cut, <1 urn, 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 cartridge or "trap" containing a
*Manufactured by Aerotherm Corporation, 485 Clyde Avenue, Mountain
View, CA 94042, (415)964-3200.
62
-------
01
CO
STACK T.C.
-------
sorbent, which is designated to be XAD-2, a microreticular resin with the
capability of adsorbing a broad range of organic species. Volatile inorgan-
ic 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. The pumping capacity is supplied by two 10-ft3/min, high-
volume vacuum pumps, while required pressure, temperature, power, and flow
conditions are regulated through a main controller. At least 60 A of power
at 110 V is needed for operating the sampling equipment.
The gross volume of sample needed in order to perform the required
analyses as presented in Chapter 1 (Table 2) is 30 dsm3. This sample must
be taken with a flow rate of 0.184 snrVmin (6.5 sftVmin) at the cyclones,
which will result in a flow rate of about 0.113 dsmVmin (4 dsft3/min) at
the dry gas meter. The PMB has developed an additional series of sampling
guidelines criteria for acquiring the required quantity of sample during
each run. These criteria are:
a. At least one full process cycle and 30 dsm3 (1,060 dsft3) of the
process effluent are to be sampled during each run.
b. In the event that the process is not cyclic in nature, the 30 dsm3
figure must still be satisfied over a period of time conducive to
obtaining a sample representative of process conditions. A sample
duration of 5 h has satisfied this requirement in the past.
Schematics outlining flue gas sampling and analysis are shown in Fig-
ures 9 and 10. Details of the sample handling and transfer procedures are
presented in a later section of this chapter.
4.2 EQUIPMENT AND PERSONNEL REQUIREMENTS
The apparatus and reagents required to perform a source assessment
sampling are shown in Table 9. The personnel requirements are related to
the magnitude of the sampling task, with three as the minimum number of
people per SASS system. A relatively linear correlation may be made between
time requirements and number of SASS teams deployed in a given sampling task
(refs. 6, 25, 27, 28).
64
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cn
OPACITY
XAD-2
INORGANIC
GASES
1
XAD-2
MODULE
I
SORBENT
AAnnui p
i
1st
IMPINGER
I
r
2nd AND
3rd
IMPINGER
INORGANIC
COMBINE
RINSE
-*• ORGANIC
BIOASSAY
COMBINE
ORGANIC
INORGANIC
•Analysis when >10 percent of the total paniculate catch.
Figure 9. Flue gas sampling flow diagram.
-------
SAMPLE
inif PYPI nmc
o . . r v P 1 ft M F
1 r i TVPI OMF
SORBENT CARTRIDGE
AQUEOUS CONDENSATE
FIRST IMPINGFR
UJ
V)
go
_" tt°0
U UJ 0
I i\/
y o Q.
1 ca5
1- WO
y cc z
1 s<
2 3§
SPLIT \
5 GRAMS
ft
\
Z
O
0
cc
> 5
I 8 H
= £ 5
* o =i
1 I I
.. . .A A
"\I A^" SPLIT
A^ ^^
•L # jX'
^- 9^ SPLIT
^^r ^^S^_
• -1 —^"^ 001 IT
*
^ 0
_/
AQUEOUS PORTION
ORGANIC EXTRACT
2
O
&
u
a
" Q
a y
_i <
< O T CC S
CC (j U < U>
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•. A
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, A
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/ '
5
<
m
£
£ «?
SECOND AND THIRD
IMPINGERS COMBINED
TOTALS
6 1
* If required, sample should be set aside for biological analysis at this point.
This step is required to define the total mass of particulate catch. If the sample exceeds 10% of the total cyclone and
filter sample weight, proceed to analysis. If the sample is less than 10% of the catch, hold in reserve.
Figure 10. Flue gas analysis requirements.
66
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TABLE 9. APPARATUS AND REAGENTS FOR A SASS RUN
Item
Apparatus quantity
4-liter glass or high density
polyethylene containers to be used
in cleaning operations
Nylon brushes
150 x 25 mm diameter glass test tubes
with caps
Linear high density polyethylene wide-
mouth containers for particulate
Amber glass containers for organic
solutions, 500-mL capacity
Linear high density polyethylene
containers for impinger solutions,
1-L capacity
Linear high density polyethylene
containers, 0.5-L capacity
Reagents
Aqueous nitric acid (15%)
Distilled water
Methylene chloride
(distilled in glass)
Silica gel (desiccant)
Hydrogen peroxide
Silver nitrate
Ammonium persulfate
Methanol (distilled in glass)
Miscellaneous
XAD-2 resin (special instructions
for cleaning the XAD-2 resin are
provided in Appendix B)
Reeve Angel 934 AH filter
Assume 5 per SASS run
Assume 5 per SASS run
Assume 3 per SASS run
Assume 10 per SASS run
Assume 5 per SASS run
Assume 5 per SASS run
Assume 2 per SASS run
Item
ACS REAGENT GRADE
OR BETTER QUALITY
UNLESS SPECIFIED
Item
Assume 150 g per SASS run
Assume 3 per SASS run
67
-------
The acquisition of a Level 1 sample using a SASS train generally re-
quires two and, in some cases, three persons for equipment assembly and
disassembly. After assembly, the train requires one full-time and one
half-time person for operation. The remaining manpower is then available
for other onsite efforts. Each SASS train run will consist of approximately
a 5-h period (specific sample acquisition criteria are described later in
this chapter). The number of required personnel for this function will not
increase regardless of the number of sample sites, provided that a sufficient
time allotment exists within the sampling task to allow for consecutive
sampling. Manpower projections can thus be determined by considering the
number of SASS particulate samples required to characterize the location in
question, the time required for the acquisition of each sample, and the
number of personnel and/or samplers available for the task.
4.3 EQUIPMENT PREPARATION FOR SAMPLE COLLECTION
The following sections discuss the equipment preparation required for
the SASS train, including procedures for cleaning the train components and
sample containers. For further information on the device see the Operating
and Service Manual Source Assessment Sampling System (ref. 29). The SASS
train schematic and other parts of the train are shown in Figure 8.
4.3.1 Precleaning Procedures for the SASS Train and Sample Containers
(refs. 7, 8, 25, 30, 31)
Since the SASS train is the most complex sampling unit discussed in
this manual, a generalized cleaning procedure is presented in Figure 11.
Two primary cleaning methodologies are required. The first methodology,
described in this section, concerns the technique involved in producing
biologically inert surfaces throughout the SASS train. The second methodol-
ogy, described in Section 4.5, Sample Handling and Shipment, presents the
techniques required for cleaning or removing sample from various parts of
the train after the run.
The first stage in preparing a new sampling train and new sample con-
tainers for sample collection is prepassivation with a nitric acid solution.
All metal and glass surfaces in the sampling train that come in contact with
68
-------
ID
REPEAT SEQUENCE
INITIAL
CLEANING
PROCEDURES
*
SASS TRAIN PARTS
AND ALL SAMPLE
RECEPTACLES
»
CLEAN ALL WORK AREAS WITH
A METHYL ALCOHOL WIPE
IMPINGERS
* »
PASSIVATION BY 1/2
HOUR QTAMniWR PHMTAPT
WITH 15% HN03
PERIODIC REPEAT
OF PASSIVATION*
PASSIVATION BY 1/2
HOUR STANDING CONTACT
WITH 15%HN03
* r »
YES
NO •*
DISTILLED WATER
RINSE
*
METHYL ALCOHOL,
RINSE
*
METHYLENi CHLORIDE
RINSE
*
DRY WITH A FILTERED
STREAM OF AIR
(NITROGEN PERMISSIBLE)
^,,._m.,. DISASSEMBLE - — ••*
*
INSPECT VISUALLY
FOR CONTAMINATION
REASSEMBLE AND
CAP OFF ORIFICES
UTILIZATION
OF TRAIN
/
DISTILLED WATER
RINSE
*
METHYL ALCOHOL
RINSE
»
DRY WITH A FILTERED
STREAM OF AIR OK
DRY NITROGEN
*
INSPECT VISUALLY
FOR CONTAMINATION
REASSEMBLE AND
CAP OFF ORIFICES
REPEAT SEQUENC!
YES
.«*. t\ir\
* Refer to text for passivation time schedule.
Figure 11. SASS cleaning procedures.
-------
the sample will be prepassivated by a 30-min standing contact with 15 percent
(v/v) aqueous nitric acid. Use a stiff nylon brush or hard Teflon scraper
to aid in cleaning encrusted materials from the surfaces if necessary-
Agitate the parts initially to remove trapped air bubbles. Rinse in a
second solution of 15 percent (v/v) HN03 then rinse with distilled water.
>
Next, rerinse by spraying thoroughly with alcohol (taking care to cover all
surfaces) or dip in alcohol and agitate for 10 s. Finally, dry with puri-
fied air or nitrogen. If the impingers are to be used immediately after
cleaning, they should be thoroughly dried or rerinsed with distilled water
to prevent foaming when the peroxide is added.
Passivation should be carried out initially (as stated above) and then
every 6 mo when the frequency of tests is one per month or less, every 3 mo
when the frequency of tests is between one per week and one per month, and
monthly for testing in excess of one per week. If the tests are more fre-
quent or of longer duration, passivation should be conducted more frequently.
If corrosion has occurred, the corrosion should be removed and the passiva-
tion repeated. The passivation and rinse solutions should be replaced after
every fourth use or should be discarded weekly.
Two separate approaches are used for subsequent cleanings of SASS train
components and organic sample receptacles and for bottles holding impinger
solutions. The components and receptacles are cleaned in three successive
stages using a different solvent in each stage. The solvents used are
distilled water, methanol, and methylene chloride, in the order listed.
This procedure removes all extraneous particulate matter and produces a
clean, dry surface. As each part is treated with the final solvent (meth-
yl ene chloride), it is purged dry in a filtered stream of air or dry nitro-
gen and inspected thoroughly for any sign of contaminating residue, scale,
rust, etc. A contaminated train component may not be used in a sampling
run. All equipment treated in the above fashion must be placed in a clean
area to await the next test. The bottles holding the impinger solutions are
cleaned with distilled water.
The field area in which these cleaning operations are performed must be
as clean as possible under existing field conditions. An enclosed space is
required in which reasonable precaution has been taken to remove spurious
70
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dust, dirt, or participate contaminants. Reasonable precaution is intended
to mean that the area has been swept clean, doors or significant draft-
inducing sources have been closed, and all work bench areas have been wiped
down with methanol.
4.3.2 Apparatus Checkout
The following tasks should be performed in the home base laboratory
prior to shipment:
a. Assemble all components required for the complete system.
b. Clean components in accordance with the procedures described in
Section 4.3.1.
c. Obtain a sufficient quantity of solvents to maintain adequate
reserves during the elapsed time in the field.
d. Obtain a tank of purified dry nitrogen or clean compressed air.
e. Accumulate an inventory of Swagelok fittings (in triplicate) for
each SASS train.
f. Examine all SASS train parts closely for defects that might induce
down-time problems in the field.
g. Leak-check the entire system.
Besides the cleaning procedures, leak-checking the train prior to field
use is one of the most important pretest tasks to be performed. This proce-
dure can save hours of time in the field. The leak-checking procedure
involves assembling the entire train, sealing the probe tip, opening the
isolation ball valve, turning on the pumping system, and observing flow
meter gauges for the existence of any appreciable flow. Evacuate the train
to 127 mmHg (5 inHg). The allowable leak rate for the SASS train is 0.0014
mVmin (0.05 ftVmin) at this pressure. Close the isolation ball valve and
leak check the remainder of the train at 508 mmHg (20 inHg). The leak rate
should again be less than 0.0014 mVmin (0.05 ftVmin). If this criterion
is not easily achievable using Teflon gaskets in the system, Viton A gasket
substitution may facilitate meeting this standard. The instructions accom-
panying the train will present in detail the steps involved in leak-checking
the system.
71
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4.4 SASS TRAIN SAMPLING PROCEDURE (refs. 8, 17, 32-34)
A Level 1 SASS sample is acquired at a point of average velocity near
the center of the duct (the average velocity being determined by a velocity
traverse). The sample is withdrawn at a constant flow rate using a nozzle
that is specifically selected for near isokinetic conditions when the test
is initiated.
The steps involved in using the train to acquire this sample are described
in detail in the manuals provided with the SASS train. An outline of the
procedure follows:
I. Test Site
A. Prepare sampling port on duct, flue, or stack.
B. Secure electrical power.
II. SASS Train Assembly
A. Attach probe to oven.
B. Assemble the three cyclones. (Note that to achieve the
proper size fractionation, the vortex breakers for the ">10
urn" and for the "10- to 3-um" cyclones should not be used.
The vortex breaker for the "3- to 1-um" cyclone should,
however, be included in the train assembly.) Fit the filter
into the filter holder and place the combined components in
the oven.
C. Connect large cyclone to probe.
D. Assemble impinger train.
1. Place heat exchanger tubing in impinger case.
2. Fill impinger bottles with the reagents listed in Table
10.
3. Place bottles in tray in impinger case, cap bottles, and
make appropriate connections.
4. Connect recirculation pump (for cooling gas) and fill
impinger case with ice and water.
E. Connect oven outlet (i.e., filter housing outlet) to gas
cooler/gas adsorbent/condensate reservoir assembly.
F. Connect gas cooler/gas adsorbent/condensate reservoir assembly
to first impinger bottle.
G. Connect gas cooling systems.
72
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H. Connect gas condensate collector bottle to gas cooler/gas
adsorbent/condensate reservoir assembly.
I. Connect vacuum pumps in parallel to fourth impinger outlet.
J. Connect all temperature sensors and power lines to control
unit.
III. Checkout and Inspection
A. Run gas flow leak check.
B. Check temperature indicators with all thermocouples at ambient
temperature.
C. Activate gas cooling systems. IT IS EXTREMELY IMPORTANT THAT
THE XAD-2 RESIN NEVER BE ALLOWED TO RISE IN TEMPERATURE ABOVE
50° C, AS DECOMPOSITION WILL OCCUR. This decomposition will
result in high TCO blanks.
D. Heat oven and probe to 204° C (400° F).
E. Note operation of vacuum pumps and gas meter.
F. Inspect pi tot tube; also, compare results of volume measured
with orifice meter and dry gas meter. Calibrate each as
necessary.
IV. Operation
A. Measure stack temperature, moisture content, and velocity
profile.
B. Calculate size of probe nozzle needed for isokinetic sampling
and select and attach appropriate size nozzle. The effluent
water vapor content must be considered when choosing the
proper nozzle size.
C. Calculate train gauge reading to achieve train flow rate of
0.113 smVmin (4.0 sftVmin). (This flow rate is necessary
for proper operation of the cyclones.)
D. Install probe in stream at point of average stream velocity
and turn on vacuum pumps; adjust train flow rate to 0.113
smVmin.
E. Collect sample. Monitor all temperatures and flow rates, and
adjust as necessary.
F. Regularly drain condensate from condensate reservoir.
73
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V. Shutdown
A. Close valves at pumps.
B. Let vacuum return to zero.
C. Turn off pumps.
D. Switch off main power.
For the accuracy requirements of Level 1, the duct flow rate is allowed
to vary from -30 to +50 percent of the specified isokinetic rate. Conditions
existing outside of the above-specified margin must result in SASS train
shutdown for an inspection and correction; for example, changing the probe
nozzle. The cause of the deviation from isokinetic conditions frequently
may be traced to a continuous high grain-loading density, an increase or
decrease in gas velocity, or a buildup of particulates leading to failure of
the pump to pull at the rate required to meet particulate matter collection
requirements.
Three possible situations occurring within the SASS train will manifest
pressure variations outside of the acceptable margin. They are clogging of
the probe nozzle, clogging of the filter, and saturation of the silica gel.
The solution in these cases requires SASS train shutdown and probe nozzle
cleaning or filter or silica gel replacement.
TABLE 10. SASS TRAIN IMPINGER SYSTEM REAGENTS
Impinger
#1
Reagents
30% H202
Quantity Purpose
500 mL Trap reducing gases such as
S02 to prevent depletion of
oxidative capacity of trace
element collecting impingers
2 and 3.
#2 0.2 M (NH4)2S2Og 500 mL Collection of volatile trace
+0.02 M AgN03 elements by oxidative
dissolution.
#3 0.2 M (NH4)2 S208 500 mL Collection of volatile trace
+0.02 M AgN03 elements by oxidative
dissolution.
#4 Silica gel 750 g Prevent moisture from reaching
pumps.
74
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Replacement of a clogged filter is a time-consuming process that could
require as much as 2 h, depending on the sampling location and the possible
difficulties that might be encountered in removing the housing. Once removed,
the housing should be carried intact to a clean area for filter removal. A
second, preloaded filter housing should be available for use when the first
housing is removed for unloading, cleaning, and reloading. Check this
assembled replacement filter assembly for leaks before placing it in service,
then make a final check of the pressure drop of the whole SASS system when
the unit is again reassembled. The 1-um cyclone reservoir should be checked
for remaining capacity whenever the filter is replaced. Take care not to
contaminate the contents during this inspection. For a standard test,
30 dsm3 of gas must have been sampled.
4.5 SAMPLE HANDLING AND SHIPMENT (refs. 7, 8, 30, 33, 35)
The procedures used in transferring acquired sample from various por-
tions of the SASS train are complex. Therefore, a modular approach will be
used to expedite the explanation of the procedures involved in sample trans-
fer and handling. For this reason, the SASS train is considered in terms of
the following sections:
a. Nozzle and probe,
b. Cyclone system interconnect tubing,
c. Cyclones,
d. XAD-2 module, and
e. Impingers.
At the conclusion of the sampling run, the train is disassembled and
transported to the mobile lab unit or prepared work area as follows:
a. Open the cyclone oven to expedite cooling, disconnect the probe,
and cap off both ends.
b. Disconnect the line joining the cyclone oven to the gas adsorbent
assembly at the exit side of the filter and cap off (1) the en-
trance to the 10-um cyclone, (2) the filter holder exit, and (3)
the entrance to the join line, which was disconnected from the
filter holder exit point.
c. Disconnect the line joining the adsorbent module to the impinger
system at the point where it exits the adsorbent module. Cap off
75
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the exit of the adsorbent module and the entrance line to the
impinger system.
d. Disconnect the line leaving the silica gel impinger at its exit
point and cap off the impinger exit. Discard ice and water from
the impinger box to facilitate carrying.
The solvent system found to be the most effective for rinse and final
cleanout of adhered sample consists of a 1:1 mixture of methylene chloride
(CH2C12) and methanol (CH3OH) for the front half of the SASS train. Methylene
chloride alone is to be used in the gas cooler and sorbent module rinses
because methanol will interfere with the LC separation. Each step is pre-
sented in the series of flow diagrams in Figures 12, 13, and 14. It is
suggested that these diagrams be placed in an easily visible location near
the cleaning area as an aid to the sample transfer activity. Samples will
be shipped to the laboratory in the most expeditious manner possible in
order not to delay analysis unnecessarily. One special concern is the H202
solution from the first impinger. Special precautions must be taken to ship
this dangerous material. Instructions for shipment are as follows:
a. Place bottle containing sample into polyethylene bag and secure
with twist tie.
b. Line bottom of steel drum with 1-in. layer of vermiculite.
c. Place bottle in drum and pack around sides and over top with more
vermiculite.
d. Label drum "oxidizer."
e. Corrosive and/or flammable samples cannot be packed in same drum
as H202 samples.
f. Ship drum by cargo-only aircraft.
At the completion of all sample transfer activities, all SASS train
components must be completely recleaned in preparation for the sampling run.
This may be accomplished by following the steps outlined in Figure 11.
4.6 SASS SAMPLE ANALYSIS
The type and extent of analytical testing that can be performed on SASS
sample materials is determined in large part by the quantity of the sample
obtained. Table 11 presents the relative order of ranking test priorities.
Inorganic analysis will be performed first on samples of limited quantity.
Spark source mass spectrometry analyses may be performed on a one-time basis
76
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Probe and
Nozzle
IQjuCycfant
CH2CI2 : CH3OH Rinsa
(Brush as necessary)
Step 1: Tap and brush contents
cup receptacle
Sup 2: Reconnect lower cup receptacle
and rinse adhered material on wells and
vane into cup (CHjClj : CHjOH)
Step 1: Tap and brush contents from
wills into lower cup receptacle
Step 2: Reconnect lower cup receptacle
and rinse cyclone walls and interconnect-
ing tubing with CH.CU : CH,OH into
CUD
Add to 10/j Cyclone Rinse
Remove lower cup receptacle
tared LHDP container
Remove lower cup receptacle
and transfer contents using
CH2Cl2 : CH3QH
Remove lower cup receptacle
tared LHDP container
Remove lower cup receptacle
CH3OH '
Combine all
Rinses in Amber
Glass Battle for
Shipping and
Analysis
lM Cyclone
Step 1: Tap and brash content! from
walls into lower cup receptacle
Step 2: Reconnect lower cup receptacle
and rinse cyclone walls and interconnect-
ing tubing with CH2Cl2 : CH3OH into
cup
Remove lower cup receptacle
and transfer contents into a
tared LHDP container
Remove lower cup receptacle
CH2CI2 : CH3OH
v^
Step 1: Remove filter, roll, and place
in tight sealing, glass or Teflon con-
tainer
Step 2: Brush particuiate from both
housing halves into filter container and
seal
Step 3: Rinse adhering paniculate*
from 1 jim cyclone tubing and front
half of the fitter housing into the com-
bined rinse using CHZCI2:CH3OH.
NOTES: All CHjClj : CHjOH
mixtures are 1:1
All brushes must neve
nylon bristles
All containers must be
linear high density
polyethylene for inor-
ganic sample storage.
All containers must be
glass for organic sample
storage.
Figure 12. Sample handling and transfer-nozzle, probe, cyclones, and filter.
77
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INTACT SORBENT MODULE
AFTER SAMPLING RUN
RELEASE CLAMP JOINING
SORBENT CARTRIDGE SEC-
TION TO THE UPPER GAS
CONDITIONING SECTION
REMOVE CONDENSATE
RESERVOIR AND DRAIN
CONDENSATE THROUGH
VALVE INTO THE
CONDENSATE DRAIN
CONTAINER USED TO
COLLECT CONDENSATE
DURING THE SASS RUN
CLOSE CONDENSATE VALVE
AND REASSEMBLE TO MOD-
ULE TO COLLECT WASHINGS
MEASURE VOLUME AND
PH
RELEASE UPPER CLAMP
AND LIFT OUT INNER WELL
EXTRACT AT pH 2
EXTRACT AT pH 11
COMBINE CH2CI2
EXTRACTS AND
SHIP TO LAB IN
AMBER GLASS
CONTAINER
RINSE WITH TEFLON WASH
BOTTLE (CH2Cl2) ALONG
INNER WELL SURFACE
AND CONDENSER WALL
PLACE INNER WELL
ASIDE IN CLEAN AREA
MEASURE AQUEOUS
VOLUME REMAINING
MEASURE VOLUME
OF FIRST IMPINGER
RINSE ENTRANCE TUBE AND
BACK HALF OF FILTER HOUS-
ING INTO MODULE. RINSE
DOWN CONDENSER WALL
•PRESERVE AT <2 pH. MAY USE
pH PAPER FOR THIS DETERMI-
NATION.
tTHIS PROCEDURE INSURES MATING
LIPS OF EQUIPMENT ARE PROPERLY
CLEANED.
RELEASE CENTRAL CLAMP
TO SEPARATE CLEAN CON-
DENSER SECTION FROM
LOWER SECTION. RINSE LOW-
ER SECTION INTO CONDEN-
SATE CUP. RELEASE THE
BOTTOM CLAMP AND RINSE
INTO CONDENSATE CUP.
DRAIN INTO AMBER BOTTLE
VIA DRAIN VALVE*
REMOVE SORBENT CAR-
TRIDGE FROM HOLDER.
REMOVE SCREEN FROM
TOP OF CARTRIDGE.
EMPTY RES IN INTO A
WIDE-MOUTH AMBER JAR
USING CLEAN FUNNEL
RINSE SCREEN AND CAR-
TRIDGE INTO RESIN
CONTAINER WITH CHCI
REASSEMBLE MODULE
TO COLLECT WASH-
INGS
RINSE WITH
CH2CI2
LABEL RESIN
CONTAINER
AND RINSINGS
CLEAN ALL MODULE METAL
PARTS BY CLEANING PROCE-
DURE
Figure 13. Sample handling and transfer-XAD-2 module.
78
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ADD RINSE FROM CONNECTING
LINE LEADING FROM SORBENT
MODULE TO FIRST IMPINGER
IMPINGER NO. 1
MEASURE VOLUME
TRANSFER TO LINEAR HIGH DENSITY
POLYETHYLENE CONTAINER AND
MEASURE TOTAL VOLUME
RINSE WITH DISTILLED HZ0
£
Ul
C9
IMPINGER NO. 2
MEASURE VOLUME
RINSE WITH A KNOWN AMOUNT OF DISTILLED H20
IMPINGER NO. 3
MEASURE VOLUME
RINSE WITH A KNOWN AMOUNT OF DISTILLED H20
COMBINE AND
MEASURE TOTAL
VOLUME FOR
SINGLE ANALYSIS
IMPINGER NO. 4
-MVEIGH AND DISCARD OR REGENERATE
Figure 14. Sample handling and transfer-nmpingers.
79
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CO
o
TABLE 11. SUGGESTED SASS SAMPLE DISTRIBUTION BASED ON TOTAL SAMPLE AVAILABLE*
(total sample available, mg)
Analysis <50
SSMS All
Hg
Microscopy
Organic
Ames
Cytotoxicity
(RAM)
Whole Animal
Reserve
>50 >70 >80 >180 >380 >480
<70 <80 <180 <380 <480 <1,680
50 50 50 50 50 50
20 20 20 20 20
Remainder Remainder 10 10 10 10
Remainder 100-299 100-199 100-1,300
200 200
100
>1,680
<2,910
50
20-50
10
1,300
200 + 40%
to 1,000
100 + 20%
to 500
>2,910
<27,960
100
50
10
1,300-26,300
1,000
500
>27,9GO
100
50
10
1,300
1,000
500
25,000
Remainder
'Example: The quantity of material collected in the SASS cyclones may not be greater than a few hundred milligrams even when the lO-yum and 3-jum participates
are combined. The same is often true for the filter catch and 1-pm cyclone paniculate weights.
-------
with 50 mg of sample or less. Mercury analysis may be obtained with 20 mg
of material to give 1 ng/kg detection limits. Optical microscopy operations
as described in Chapter 10 can be performed on less than 10 mg of sample.
This priority is followed by organic analysis of 200 mg. Note that this
quantity is the minimum amount of material that can be extracted and assayed
in the techniques presented here. More sample material is apportioned
relative to its availability. To perform the liquid chromatography separa-
tion in an effective manner, 75 to 100 mg of extracted material are needed.
The next analysis in the priority scheme is the Ames assay, which requires
an additional 200 mg of sample. This is followed by one of the cytotoxicity
assays, which needs another 200 mg, and the soil microcosm test. The rela-
tive priority of whole animal toxicity testing is noted here although there
will rarely be an additional 25 grams from SASS train catches available for
this test. See the following chapters for more complete descriptions of the
sample handling methods and analytical procedures for each test.
4.7 PLUME OPACITY TESTS
Plume opacity determinations shall be conducted for all sources. An
acceptable test utilizes a chart that consists of a series of graduated
shades of grey, varying in five equal steps from white (0) to black (5).
The shades in between are represented by standard grids. In the field, a
comparison is made between the stack plume and grids, and the grid number
most closely resembling the plume shade is chosen and recorded. This test
must be performed by a person who has at one time been certified to read
plume opacity.
81
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CHAPTER 5
FUGITIVE EMISSIONS SAMPLING
5.1 INTRODUCTION (refs. 1, 36)
Fugitive emissions are those air and water pollutants generated by
activities at industrial sites that are transmitted into the ambient atmos-
phere or receiving water bodies without first passing through some stack,
duct, pipe, or channel designed to direct or control their flow. Their
generally diffuse nature and the absence of any restrictions to their dis-
persion preclude the use of standard stack or similar sampling methods in
the quantitation of their release to the environment. These types of emis-
sions constitute an important fraction of our total pollution problem.
Therefore, a custom-designed fugitive emission sampling program must be
enacted whenever there is a reasonable suspicion that fugitive emissions are
being emitted from a particular industry or plant site.
This chapter describes the basic strategies that can be employed for
the sampling of fugitive emissions in a Level 1 assessment effort to deter-
mine the amounts of pollutants entering the atmosphere or receiving waters.
The sampling methods described are designed to provide estimates of the
fugitive emissions within the accuracy limits discussed in Chapter 1.
5.2 FUGITIVE EMISSION CATEGORIES (refs. 1, 8, 36)
Fugitive emissions can be generated by almost any industrial operation
from a wide variety of sources. They may or may not be visible. Airborne
particulates and gases can be emitted from a number of sources in an enclo-
sure and transmitted to the atmosphere through structural openings or vents,
as with foundry casting or production-line welding operations. They can
also be generated by large-scale open or semi enclosed operations, such as
open hearth furnaces or coke oven banks, and transmitted through roof moni-
tors or partial hooding enclosures. A large proportion of airborne fugitive
emissions is generated by sources in the open and is transmitted directly
82
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into the atmosphere, as with bulk materials storage and handling operations
in coke oven operations, loading, etc..
Fugitive waterborne suspended or dissolved solids and liquids are most
frequently transported to receiving bodies by stormwater runoff. Major
sources of waterborne fugitive pollutants include materials from storage
piles, accumulated dusts and oils from impervious areas such as paved roads
or parking lots and roofs, and spills or leaks from process or handling
equipment.
For Level 1 environmental assessment purposes, airborne fugitive emis-
sions, whether particulate or gaseous, may be generally classified into two
categories with regard to their method of transmittal into the atmosphere:
a. Open origin: Any open source whose gaseous and/or particulate
emissions are transmitted directly into the atmosphere.
b. Semienclosed origin: Any enclosed or semienclosed source whose
gaseous and/or particulate emissions are transmitted into the
atmosphere through an opening other than a stack or duct.
Stormwater runoff can also be classified for Level 1 purposes into two
categories with regard to its flow:
a. Overland runoff: Flow from a source directly to a receiving body
on the ground surface.
b. Open channel runoff: Flow from a source into a natural or manmade
channel that carries it to a receiving body.
Overland runoff will usually be found in a small area near each source
where it can be isolated to estimate a specific contribution. Open channel
runoff may sometimes provide specific source isolation, but will usually be
found as a combination of at least two sources.
Under certain conditions, it may be necessary to sample the near-surface
groundwaters for the evaluation of subsurface material transport. The
project officer will make such discretionary decisions considering the
probability of contamination and hazard potential relative to the costs of
implementing this kind of task.
5.3 SAMPLING TECHNIQUES AND EQUIPMENT (refs. 18, 36-55)
Level 1 environmental assessment methodology requires the determination
of fugitive emissions source strengths whenever there is a reasonable expec-
tation that they exist at a specific site. The basic intent of the survey
83
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is the estimation of the fugitive emission potential of a site to determine
its added impact along with that of point source emissions so that a more
detailed Level 2 survey, if required, can be effectively planned and executed.
For this reason, only the most generally applicable sampling techniques need
to be utilized in a Level 1 survey. The techniques and equipment best
suited to each of the above-defined categories of emissions are described in
this section.
5.3.1 Airborne Fugitive Emissions
Open origin emissions are best sampled downwind of their source at a
location where their plume or vapor is suspected to have settled to near
ground level. Low molecular weight gaseous emissions are sampled using 10-
to 30-L containers as described in Section 3.5.2. Particulate emissions are
sampled using a high-volume sampler while vapors are collected concurrently
from a side stream that is passed through a sorbent resin.
The sampler package best meeting the requirements of a Level 1 survey
for airborne fugitive emissions is the Fugitive Ambient Sampling Train
(FAST) sampling system (Figure 15), which was developed with the support of
IERL/PMB. It is designed to provide a 500-mg particulate matter sample in
an 8-h sampling period at most industrial sources. The sampling equipment
is contained in a single portable unit that is connected by flexible ducting
to a separate unit containing the particle sampling stream blower, organic
sampling stream vacuum pump, and their electric drive motors.
The FAST system criteria include the following specifications:
a. Flow rate: Main blower capacity variable between 4.26 and 6.25
mVmin (150 and 220 ftVmin);
b. Flow control: Automated to maintain constant flow during the
sampling period;
c. Cyclic timing: Provide preset automatic start and stop to match
cyclic process emissions; and
d. Filter size: 20.3 x 25.4 cm (8 x 10 in.) Reeve Angel 934 AH
filters.
The FAST sampling system consists of a single-stage cascade impactor
that will collect about 90 percent of all particles larger than 15 pm, a
cyclone separator with about a 50 percent collection efficiency for particles
84
-------
INLET
T.C.
VV
co
Ol
IMPACTOR
STAGE
Y7
FILTER
AP
VACUUM GAUGE
0
EXHAUST
MAIN VACUUM
BLOWER
SORBENT MODULE
VACUUM GAUGE
CYCLONE
TRAP
OUTLET
T.C.
EXHAUST
FILTER
VACUUM
PUMP
Figure 15. Fugitive Air Sampling Train components.
-------
larger than 3 pm, and a glass fiber filter to collect the particles still
entrained in the sampling stream. The particle sampling stream flow rate is
5.2 mVmin (185 ftVmin). A 0.14-m3/min (5-ft3/min) side stream is taken
from the particle-free air downstream of the filter and drawn through a
sorbent bed of XAD-2 to collect organic species.
As an alternative to the FAST system, a modified conventional high-
volume sampler utilizing a high-speed vacuum-cleaner-type blower could
theoretically be constructed for this data collection (see Figure 16). This
sampler should be redesigned to approximate the performance specifications
of the FAST system. This will help insure the collection of particulate and
vapor samples of sufficient size to permit a reasonable estimation of their
classification, concentration, and probable import to biological systems.
Only the Reeve Angel 934 AH may be used as a filter for the FAST or modified
high-volume system. Sampling must be interrupted to change filters whenever
there is a 10 percent reduction in flow from the design criteria.
Semienclosed origin emissions, characterized by their definable plume,
are best sampled using the SASS train described in Chapter 4. The train
should be inserted into the plume as close to the source as possible and the
sampling performed at the maximum flow rate with the largest available
nozzle. Gaseous emissions are sampled using 10- to 30-L containers as
previously described.
Site source emissions can generally be most effectively sampled using
the upwind/downwind technique. This technique utilizes integrated sampling
for gases and high-volume packages for particulates and organics to determine
the background concentrations upwind of the site and total particulate or
organic concentrations (including the background and any point source con-
tributions) downwind of the site. The total fugitive emissions from the
site are then calculated by subtracting the measured background and point
source concentrations from the measured total pollutants. In most situa-
tions, a single upwind sampler located at the site boundary is sufficient to
determine the background concentrations of substances of interest. A net-
work of two or more samplers is usually required downwind of the site to
insure accounting for variations in downwind concentration.
Measurements of local wind speed and direction and ambient temperature
are also required at each source location during the sampling period. These
86
-------
WALL
TO 5 cfm PUMP
Figure 16. Diagrammatic presentation of connections for sorbent
cartridge to high-volume sampler.
87
-------
may often be obtained at a single site location using any of a variety of
commercially available vane type direction transmitters, cup anemometer
speed transmitters, and thermocouple or thermistor temperature transmitters
to provide continuous records on appropriate strip chart recorders.
5.3.2 Waterborne Fugitive Emissions
Stormwater runoff flowing overland is sampled using polyethylene, or
preferably Teflon, plug collectors similar to the one shown in Figure 17. A
network of plugs is driven into the ground so that the top face of each plug
is just below the surface of the surrounding material. Overland runoff
enters each plug through a screen in the top that removes large entrained
GROUND WATER
SEEPAGE
SURFACE WATER
ENTRANCE
Figure 17. Stormwater runoff sampling plug collector.
-------
particles but permits smaller suspended particulates to pass. These plugs
may also be used to collect groundwater seepage through channels around the
side surfaces by covering the openings in the top faces.
Stormwater runoff flowing in open channels can be sampled with plug
collectors if the flow rate is low, with an automatic sampler, or by dipping
collection bottles directly into the flowing stream. See Chapter 6 on
liquids for more details. In all instances, the sample for organic com-
pounds should be transferred to a dark glass bottle as soon after collection
as possible.
Rainfall is measured during the sampling period by making visual obser-
vations of a standard rain gauge at frequent intervals or by using a record-
ing gauge to provide a continuous record of rainfall rate. The resultant
overland runoff flow is estimated by multiplying the area drained by the
rainfall, either as total flow or a flow rate. An alternate method of
estimating the overland runoff is to measure the increased flow in the open
channels receiving it. Open channel runoff flow may be measured in a channel
using appropriate portable weirs or flumes installed as close to the sampling
points as possible.
5.4 SAMPLING PROGRAM PLANNING AND PERFORMANCE (refs. 1, 6, 36-44, 46-50)
A number of subjective evaluations may be required in determining which
sources are to be included in the assessment program and how they can best
be evaluated. The primary consideration for any source of fugitive emis-
sions is whether the emissions will migrate beyond the site boundaries. If
the planner is uncertain that the emissions from a specific source will have
an impact upon the ambient air outside the site, it is probably best to
exclude that source from individual source measurements and assume that its
emissions will be accounted for in the site source sampling data. If such
an assumption is made, the site source sampling methodology must be capable
of detecting all expected source compound classes. In categorizing specific
sources, those which are not clearly identifiable should be assigned to the
more general open source class to insure that reasonable overall measure-
ments are made rather than chance missing important data by sampling too
specifically. Consideration must also be given to eliminating specific
89
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sampling of sources whose emission characteristics or physical arrangements
are such that sampling can be conducted only under very limited conditions.
In such cases, the source emissions can again be assumed to be included in
the site source sampling data.
Sampler locations for enclosed or semienclosed sources will usually be
limited to one or possibly two alternatives that will permit the use of the
SASS train because the plume from such partially or fully enclosed sources
will normally only reach the atmosphere via a prescribed path. The SASS
train probe should be inserted into the plume as close to the source as
possible to minimize the required sampling duration.
Upwind samplers for site sources should be located as close to the site
boundary as possible to insure a reasonable estimate of background condi-
tions. Downwind samplers should be located far enough away from specific
sources at the site to eliminate any bias that might be introduced into the
measurements. Ideal locations for downwind samplers that will insure sam-
pling of a heterogeneous site source will usually be some distance downwind
of the site boundary, but should be close enough to provide a useful sample
size in a reasonable sampling period. The standard sampling duration is 8
hours of exposure time.
Stormwater runoff plugs should be installed as close to the source of
pollution as possible, typically at the base of storage piles where overland
flow is expected to be reasonably heavy and representative in makeup of the
total source runoff. Open channel runoff dip sampling should be planned so
as to avoid pool areas where suspended particulates may settle or highly
turbulent areas where suspended particulates may be exaggerated. Other
samplers such as the Quantum Science Limited automatic liquid sampler (U.S.
distributor—Kahlsico, El Cajon, CA) may be used advantageously in these
circumstances.
In preparing for the performance of the sampling program, the field
staff will utilize the information provided in the program plan and pretest
site survey to select the sampler locations best suited to the conditions
during the sampling period.
Once the samplers are satisfactorily installed, the sampling program is
carried out according to the schedule established in the program plan using
the procedures for the collection and handling of samples described in this
90
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manual. The collected samples are analyzed onsite and/or delivered to the
appropriate laboratory for analyses to determine their composition. The
organic and inorganic methods specified in this manual are to be used.
5.5 DATA REDUCTION
The analytically determined compositions, concentrations, and densities
of the sampled emissions are combined with the appropriate parameters of
flow rate, temperature, and flow direction of their transporting air to
yield quantitative concentrations at each sampling location. Measured back-
ground concentrations are then subtracted. The remaining concentrations are
used in appropriate diffusion equations to calculate the contribution from
each source of airborne materials. A library of computer programs is main-
tained at the User's Network for Applied Methods of Air Pollution (UNAMAP)
at the Environmental Protection Agency's Research Triangle Computer Center
to assist in the calculations.
Stormwater runoff pollutant concentrations are plotted against the
measured flow rates or as a function of time against the measured rainfall
rate to provide, by extrapolation, an estimate of the amount of any given
material that can be expected to be conveyed to a receiving body for any
given rainfall. Historical rainfall data can then be used to provide an
estimate of seasonal or annual materials transfer.
91
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CHAPTER 6
LIQUID AND SLURRY SAMPLING AND CHEMICAL ANALYSIS
6.1 INTRODUCTION (refs. 56-58)
In any given industrial process operation, the probability is high that
a number of the influent and/or effluent streams will exist in liquid or
slurry form. Considering the multiplicity of liquid streams in typical
plants, the number of possible sampling points becomes extensive. The
method chosen for Level 1 sampling is discussed below.
Once the samples are collected, they are analyzed onsite or packaged
for shipment and analysis at the laboratory (see Chapters 8 and 9). Streams
may be organic or aqueous or may contain water/organics/solids in miscible
or immiscible fractions. The handling of these solutions will affect the
reliability of the chemical or biological tests performed. Section 6.3
proposes a field separation scheme to prevent sample loss or adulteration.
This scheme is comprehensive enough to prevent sample loss, but is simple
enough to implement in the field.
6.2 PREPARING FOR SAMPLE COLLECTION
6.2.1 Personnel Requirements (ref. 59)
The liquid sampling techniques presented in this chapter are uncompli-
cated, and under favorable conditions only one person is needed to perform
the sampling effort. There are situations, however, that will require
additional manpower. Many streams will require that a crew member work
under conditions or in areas where the potential for physical mishap is
high. An additional crew member should be present to insure the safe com-
pletion of the task even though his active presence is not necessary for the
sampling effort.
92
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6.2.2 Dipper Sampling (refs. 31, 60-63)
The dipper sampling procedure is applicable to sampling sluices or open
discharge streams. The dipper is made with a flared bowl and an attached
handle long enough to reach the sluice or discharge areas. The bowl portion
must be coated with Teflon. A dipper sample is obtained by inserting the
dipper into the free-flowing stream so that a portion is collected from the
full cross section of the stream.
The pretest site survey will produce information on process cycles so
that the sampling times and points cover the most representative periods and
locations of discharge. The total amount of sample collected for chemical
analysis should be approximately 0.1 percent of the total stream flow up to
a maximum of 20 L. All individually collected samples from a given site
should be combined to produce one composite sample representing a complete
time integration. Individual aliquots are drawn from the composite for
further analysis. Whenever bioassay testing is programmed, greater volumes
of sample are required, i.e., 200 L for toxicity to fathead minnow.
6.2.3 Automatic Sampling
There are several types of automatic sampling devices that may be
employed in obtaining representative liquid samples for analysis. Some are
flow-proportional and others provide time-averaged samples. Options are
available for discrete increment collection and for refrigerated sample
holding. Depth-integrated samples may also be gathered using other instru-
ments. The type and advantage of these sample-gathering aids is site-
dependent. Their use is encouraged whenever it might improve the data
quality.
6.2.4 Heat Exchange Sampling Systems for High Temperature Lines
Many industrial systems utilize steam in their process applications.
Uses ranging from relatively clean steam power plant operations to polluted
lines resulting from stripping operations involving acid units, catalyst
regeneration, and scrubbing of polluted gas streams will be encountered. In
addition to pressurized process lines, various other process operations
exist that contain superheated vapors composed of effluents generally charac-
terizable as reaction products. The sampling techniques described in this
section pertain to all of the above systems; however, for the sake of brevity,
93
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the term high temperature (HT) line will be used to represent all applica-
tions unless otherwise indicated.
The principle used in the sampling of HT lines involves the use of a
water-cooled condenser system. Typical examples of apparatus used for this
purpose are illustrated in Figure 18. As can be seen in Figure 18, two
approaches are possible depending on whether the pressure in the line is
above or below atmospheric pressure. The condensate from the stream is
collected in a reservoir for later analysis.
In sampling HT lines, it should be kept in mind that stream constituents
will to some degree dissolve any substance contacted. For this reason, the
area of the surfaces exposed to the sample and the time that the sample is
in contact with these surfaces should be kept to a minimum. All tubing,
valves, nozzles, and containers must be constructed from materials of suffi-
cient strength to withstand the full pressure of the stream being sampled.
Tubing diameter must be small enough so that storage within coils and tubing
and the resultant time lag of the sample through the system are minimal.
The sampling operations presented in this section may be used safely pro-
vided that proper caution is exercised.
6.2.5 Tap Sampling (ref. 52)
Contained liquids may be divided into two broad categories: those that
are in motion (lines) and those that are not (tanks or drums). Usually, a
specific sampling technique, such as stratification, is applied to each of
these categories in order to accommodate the differences in sample charac-
teristics. A flowing stream containing particulate matter may be strati-
fied. A tank sample may also be stratified, but in the static sense rather
than in the fluid sense. Moving streams are traditionally sampled using a
technique called continuous sampling. This involves sample removal from a
tap connected to a probe inserted into the line. Static liquid samples
(tanks or large drums) are sampled using a technique called tap sampling.
For Level 1 purposes, the effort of inserting a probe into the line is
too time-consuming to be efficient. Consequently, all contained liquids
will be sampled using the tap method, as per ASTM D-270 (ref. 62), unless an
in-line probe already exists. Tap sampling, as discussed in this chapter,
94
-------
UD
on
PROCESS LINE
PROCESS LINE
NATURAL CIRCULATION SAMPLING SYSTEM
(HIGH PRESSURE, HIGH TEMPERATURE)
FORCED INJECTION SAMPLING SYSTEM
(SUBATMOSPHERIC PRESSURE, HIGH TEMPERATURE)
Figure 18. Sampling apparatus for high pressure high temperature lines.
-------
refers to a wide variety of grab techniques. In general, this type of
sampling implies that a sample is taken at a tap from a line or tank wall.
This approach is used for moving liquid or slurry streams. The procedure is
also applicable to streams under pressure or having elevated temperature,
provided the proper safety precautions are exercised. For systems under
pressure, valves should be opened very slowly to avoid injury caused by
sudden surge due to entrained air pockets or accumulated solids around the
valve opening. Streams with elevated temperatures should be sampled using a
heat exchanger system such as the one described in ASTM D-270 (ref. 62).
Tap samples are collected by inserting the sample line (a thoroughly
washed Teflon line) into the sampling bottle so that it touches the bottom
(after first flushing the sample line at a rate high enough to remove all
sediment and gas pockets). The sample bottle should be thoroughly rinsed
with sample prior to filling and the sample line flow must be regulated so
as not to exceed 500 mL/min. If sampling valves or stopcocks are not avail-
able, samples may be taken from water-level or gauge-glass drain lines or
petcocks.
6.3 LIQUID SAMPLE HANDLING AND SHIPMENT (ref. 64)
As mentioned previously in Section 6.1, sample handling is an important
consideration where liquids are involved. The entire spectrum of liquid
samples exists within the bounds of the following six categories:
a. Aqueous d. Aqueous/solid
b. Aqueous/organic e. Organic/solid
c. Organic f. Aqueous/organic/solid
Figure 19 shows a field handling scheme for liquid/slurry samples. Certain
of these samples must be stabilized prior to shipment for laboratory analysis;
Table 12 presents the most recent EPA-approved procedures for this sample
preservation. Consideration must also be given to the manner in which the
samples are to be packed and conveyed to the testing laboratory since Depart-
ment of Transportation regulations restrict shipment of certain materials on
commercial carriers (see ref. 65 for details on the chemicals involved and
packaging required). After preservation and packing, samples will be shipped
96
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WASTEWATER
SAMPLE
DISSOLVED 0.
pH
UNTREATED, SHIP TO LAB
FOR BIOTEST* BOD.
CONDUCTIVITY,
SUSPENDED SOLIDS
1 SHIP TO LAB FOR
I ORGANIC ANALYSIS*
*SEE CHAPTER 8.
tSEE CHAPTER 7
SEE CHAPTER 11.
SHIP TO LAB
1 FOR INORGANIC
I ANALYSIS*
1
ACIDIFY
pH<2
J
I— -* 1
[ SHIPTOLABFOR J
INORGANIC ANALYSIS1 ,
1 1
1
BASIFY
pHIZ
L.
l i
1 SHIPTOLABFOR '
1 CYANIDE ANALYSIS j
Figure 19. Sample handling summary.
97
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TABLE 12. RECOMMENDATION FOR SAMPLING AND PRESERVATION
OF SAMPLES ACCORDING TO MEASUREMENT1
Measurement
Acidity
Alkalinity
Arsenic
BOD
Bromide
COD
Chloride
Chlorine
Color
Cyanides
Dissolved oxygen
Probe
Winkler
Fluoride
Hardness
Iodide
MBAS
Metals
Dissolved
Suspended
Total
Mercury
Dissolved
Volume
required
(mL) Container2 Preservative
100
100
100
1000
100
50
50
200
50
500
300
300
300
100
100
250
200
100
i
100
p
p
p
p
p
p
p
p
p
p
G
G
P
P
P
P
P
P
, G
, G
, G
, G
, G
, G
, G
, G
, G
, G
only
only
, G
, G
, G
, G
, G
, G
None required
Cool, 4° C
HN03 to pH <2
Cool, 4° C
Cool, 4° C
H2S04 to pH <2
None required
Det. onsite
Cool, 4° C
Cool, 4° C
NaOH to pH 12
Det. onsite
Fix onsite
None required
Cool, 4° C
HN03 to pH <2
Cool, 4° C
Cool, 4° C
Filter onsite
HN03 to pH <2
Filter onsite
HN03 to pH <2
Filter
Holding
time3
24 h
24 h
6 mo
24 h
24 h
7 days4
7 days
No holding
24 h
24 h
No holding
4-8 h
7 days5
6 mo
24 h
24 h
6 mo6
6 mo
6 mo6
38 days
(glass)
13 days
(hard
plastic)
See footnotes at end of table.
(continued)
98
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TABLE 12 (continued)
Measurement
Total
Nitrogen
Ammonia
Kjeldahl,
total
Nitrate
Nitrite
NTA
Oil & grease
Organic carbon
pH
Phenol ics
Phosphorus
Orthophosphate,
dissolved
Hydro lyzable
Total
Total, dissolved
Volume
required
(ml)
100
400
500
100
50
50
1000
25
25
500
50
50
50
50
Container2
P, G
D f*
P, G
P, G
P, G
P, G
G only
P, G
P, G
G only
P, G
P, G
P, G
P, G
Preservative
HN03 to pH <2
Cool, 4° C
H2S04 to pH <2
Cool, 4° C
H2S04 to pH <2
Cool, 4° C
H2S04 to pH <2
Cool, 4° C
Cool, 4° C
Cool, 4° C
H2S04 or
HC1 to pH <2
Cool, 4° C
H2S04 to pH <2
Det. on site
Cool, 4° C
H3P04 to pH <4
1.0 g CuS04/L
Filter onsite
Cool, 4° C
Cool, 4° C
H2S04 to pH <2
Cool, 4° C
H2S04 to pH <2
Filter onsite
Cool, 4° C
Holding
time3
38 days
(glass)
13 days
(hard
plastic)
24 h4
24 h4 7
24 h
48 h
24 h
24 h
24 h
6 h
24 h
24 h
24 h4
24 h4
24 h4
(continued)
99
-------
TABLE 12 (continued)
Measurement
Residue
Filterable
Nonfilterable
Total
Volatile
Settleable matter
Selenium
Silica
Specific
conductance
Sulfate
Sulfide
Sulfite
Temperature
Threshold odor
Turbidity
Volume
required
CmL)
100
100
100
100
1000
50
50
100
50
500
50
1000
200
100
Container2
P, G
P, G
P, G
P, G
P, G
P, G
P only
P, G
P, G
P, G
P, G
P, G
G only
P, G
Preservative
Cool, 4° C
Cool, 4° C
Cool, 4° C
Cool, 4° C
None required
HN03 to pH <2
Cool, 4° C
Cool, 4° C
Cool, 4° C
2 ml zinc
acetate
Det. onsite
Det. onsite
Cool, 4° C
Cool, 4° C
Holding
time3
7 days
7 days
7 days
7 days
24 h
6 mo
7 days
24 h8
7 h
24 h
No holding
No holding
24 h
7 days9
See footnotes on following page.
100
-------
Source of this table is the National Environmental Research Center, Cin-
cinnati, Ohio (ref. 66). More specific instructions for preservation and
sampling are found with each procedure as detailed in this manual. A general
discussion on sampling water and industrial wastewater may be found in ASTM,
Part 31, pp. 72-82 (1976) Method D-3370.
2Plastic (P) or glass (G). For metals, polyethylene with a polypropylene cap
(no liner) is preferred.
3It should be pointed out that holding times listed above are recommended for
properly preserved samples based on currently available data. It is recog-
nized that for some sample types extension of these times may be possible,
while for other types these times may be too long. Where shipping regula-
tions prevent the use of the proper preservation technique or the holding
time is exceeded, such as in the case of a 24-h composite, the final
reported data for these samples should indicate the specific variance.
4Data obtained from National Enforcement Investigations Center, Denver,
Colorado, support a 4-week holding time for this parameter in Sewerage
Systems (SIC 4952).
5SDWA permits holding time of 1 month.
6Where HN03 cannot be used because of shipping restrictions, the sample may
be initially preserved by icing and immediately shipped to the laboratory.
Upon receipt in the laboratory, the sample must be acidified to a pH 2 with
HN03 (normally 3 mL 1:1 HN03/L is sufficient). At the time of analysis, the
sample container should be thoroughly rinsed with 1:1 HN03 and the washings
added to the sample (volume correction may be required).
7SDWA permits holding time of 14 days.
8If the sample is stabilized by cooling, it should be warmed to 25°QC for
reading, or temperature correction made and results reported at 25° C.
9SDWA requires analysis within 1 hr.
101
-------
by the most expeditious manner possible, and will not be delayed unneces-
sarily. Whenever there is danger of exceeding the recommended holding
times, consideration should be given to enlisting the services of a quali-
fied commercial testing facility nearer the sampling site to perform the
time-sensitive analyses.
Aqueous samples for organic content determination are first extracted
in convenient aliquots with high purity liquid chromatography grade methylene
chloride equal to 10 percent by volume of the aliquot to be extracted. Each
aliquot should be extracted two times at acid and alkaline pH (see Section
9.3.1). Following extraction, the individual volumes of methylene chloride
from the total sample are recombined to form one organic fraction for further
analysis. The above extraction may be performed in the laboratory or the
field, whichever is more convenient and most advantageous from the analytical
standpoint.
Filtration of the sample for suspended solid determination should be
performed using a preweighed Reeve Angel 934-A or 984 H or Gelman type A
glass fiber filter. This filtration procedure may be performed more effi-
ciently in the laboratory when the suspended solids content is high enough
to block the filter. When such is the case, provision must be made to
transport the cooled sample to the lab within the time frame of the most
sensitive test parameter to be determined. The filtrate from this process
may be used for anion and elemental analysis.
6.4 LIQUID ANALYSIS (ref. 67)
Certain liquid parameter analyses must be performed onsite for results
to accurately reflect the existing conditions. Such measurements as temper-
ature, pH, chlorine, ammonia, sulfide, dissolved oxygen, and other readily
changing concentrations may be determined in situ using calibrated thermo-
couples, standardized selective ion electrodes, and other sensors. When
there are no positive or negative matrix interferences, acceptable data (for
Level 1 purposes) may be produced using commercially available test kit
methods and freshly collected sample. Other liquid parameters such as
sulfate, phosphate, nitrate, nitrite, carbonate, chloride, fluoride, cyanide,
etc. , may be determined in the field by test kit methods or preferably at
102
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the laboratory using ion chromatography procedures and appropriately pre-
served samples. (See Table 12.) In either instance, perform these analyses
according to the equipment manufacturer's specifications and in conjunction
with known standard concentrations as a quality control measure.
Biochemical oxygen demand, chemical oxygen demand, suspended solids,
alkalinity, and acidity testing should be performed on unfiltered sample
aliquots using recognized techniques. Conductivity measurements may be
performed on either a filtered or unfiltered aliquot.
103
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CHAPTER 7
SOLID SAMPLING
7.1 INTRODUCTION (refs. 10, 67-69)
Solid sampling covers a broad spectrum of material sizes from large
lumps to fine powders and dusts. There is an equally diverse assortment of
potential sample sites including railroad cars, barges, trucks, large heaps,
plant hoppers, and conveyor belts. Obviously, no one sampling method or
piece of equipment can accommodate all possible situations. Furthermore,
all of the above sampling locations may contain products of widely varying
consistency. For the purposes of this chapter, the consistency of solid
samples ranges, by definition, from anhydrous or dry solids to thick, non-
flowing pastes.
The recommended Level 1 sampling technique is the modified grab sample.
This sample shall be taken with care to insure its representative nature and
may be composed of a time- or space-integrated series of smaller samples to
achieve this end. In general, the Level 1 and Level 2 solid sampling tech-
niques are identical except that, in the case of Level 2 sampling, a series
of grab samples is taken over a longer period of time from a conveyor belt
or over a larger area for stationary storage sites such as railroad cars or
large heaps. In cases of extreme sample variability, a larger grab sample
consisting of several increments or shovelfuls is required in Level 1. In
most cases, the difference between the Level 1 sample and a time-averaged
Level 2 sample is only a matter of degree rather than of technique.
The following sections present the sampling approaches applicable to
input and output solid streams and storage piles.
7.2 SOLIDS SAMPLING PROCEDURES
Level 1 solid sampling procedures use three manual grab sampling tech-
niques: shovel or grab sampling; boring techniques, which include pipe or
104
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thief sampling; and auger sampling. Data obtained from the pretest site
survey concerning the physical characteristics of the sample, together with
the optimum choice of sampling location, will determine the appropriate sam-
pling technique. Table 13 presents a sampling scheme showing the appro-
priate sampling technique as a function of physical characteristics and
actual location of the sampling points.
Each of the grab sampling techniques is discussed in detail in the
sections to follow.
7.2.1 Shovel Grab Sampling (refs. 33, 68, 70-74)
Raw material piles of relatively coarse lump size (ore piles, aggregate
piles, coal feed, etc.) are sampled using a fractional shoveling technique.
The shovel used in this procedure is of the square-edged variety measuring
12 in. wide.
In sampling from belt conveyors, one full cross section the width of
the shovel blade is taken as the sample.
Where ladder or tray conveyors are sampled, one shovelful from one com-
partment is removed.
Screw conveyors transfer sludge-type materials (such as ash effluents)
and are usually enclosed systems. The optimum sampling point for these sys-
tems is the conveyor exit. If this point is located in an unreachable posi-
tion, the sample must then be withdrawn from the entrance or exit area, de-
pending on whether the stream is influent or effluent, using a pipe, thief,
or auger technique (Section 7.2.2).
Duct conveyors consist of either gravity feed systems or chain-driven
scrapers and may be open-top or enclosed depending on the fineness of the
solid being transported. Open duct conveyors are sampled by removing one
shovelful of material from the top via the adjoining catwalk. Closed ducts
are sampled by taking one shovelful from the exit point. If these points
are unreachable, the sample must be taken from the storage pile using a
pipe, thief, or auger (Section 7.2.2).
7.2.2 Boring Techniques (refs. 33, 67, 75)
Pipe borers represent another class of solid sampling methods appli-
cable to materials stored in piles, silos, or bins. The pipe is inserted
105
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TABLE 13. LEVEL 1 METHODS FOR SOLID SAMPLING
o
en
Physical nature
of sample
Fine powder
Coarse powder
Coarse grain
Lump
Belt
conveyors
N/A
N/A
Cross
stream cut,
one shovel
Cross
stream cut,
one shovel
Ladder tray
conveyor
Shovel
grab from
one tray
Shovel
grab from
one tray
Shovel
grab from
one tray
N/A .
Screw
conveyor
One shovel
from point
of exit
One shovel
from point
of exit
N/A
N/A
Duct
sample
One shovel
from exit
if enclosed,
from top if
open
Pipe,
from exit
if enclosed,
from top if
open
One shovel
from exit
if enclosed,
from top
if open
N/A
Open
piles
Pipe or
thief
Pipe,
thief, or
auger
Auger
Four
shovels,
one from
each side
Storage bins
or silos
Pipe or
thief
Pipe, thief, or
auger
Auger
Shovel or
auger
-------
into the material to be sampled at regular intervals. The method is fairly
reliable, providing that the pipe is long enough to reach the bottom of the
material. However, it is only applicable to fine or powdered dry materials,
because lumps or any stickiness will jam or plug the pipe. Small pipe
borers can be used to sample material in sacks or cans. There are primarily
two pipe designs that give best results. One is a simple pipe that is
tapered so the end first inserted is smaller in diameter than the handle
end. A more sophisticated design, known as a thief, makes the sample more
representative vertically. It consists of two close-fitting concentric
pipes sealed at the base in a conical point. Longitudinal slots are cut
along the side of each pipe. The thief is inserted with the slots turned
away from each other and then, when the sampler is in position, the outer
pipe is rotated, lining up the slots and allowing the inner pipe to fill
with sample. For proper results with any design of pipe borer, the opening
through which the sample material passes (slots or circular pipe ends) must
be larger than the largest particle size.
Auger samplers, a form of drill, pack the sample in the helical groove
of the auger and can be enclosed in a casing if the nature of the sample is
such that it will spill when the auger is removed from the hole. Like pipe
borers, they are simple to use and have the further advantage of being
applicable to a greater variety of materials. For example, augers work well
for materials that are packed too hard for the insertion of a pipe sampler.
For tightly packed materials, machine-driven augers are available. However, if
spillage is a serious problem, a thief type pipe sampler is the better
choice.
7.3 SAMPLE COLLECTION AND STORAGE (refs. 7, 33, 70, 72-76)
It is always preferable to sample a moving stream either in pipes or
off conveyor belts rather than from stationary storage sites. This is
particularly true if the sample has a wide particle size distribution.
Stored containers or heaped beds of material tend to settle, segregating the
particles according to size and density, and it is difficult to compensate
for this bias during sampling. Furthermore, large masses of stored material
are extremely difficult to handle. The interior portions are relatively
107
-------
inaccessible, and the amount of time and space needed to move the material
enough to take a representative sample can become prohibitive. However,
such situations can generally be avoided by a good sampling plan.
Typically, in a test for trace elements, the solid materials of interest
associated with a process are the feed materials and the residues from
particulate matter scrubbers such as baghouses, high energy Venturis, and
electrostatic precipitators. Raw feed stock, as it passes through the
process stream, may pick up other materials as contaminants and therefore
differs greatly in composition from the final feed to the process. Conse-
quently, samples should be taken at the last possible site before the stream
is fed into the process. This means that sampling will generally be con-
ducted from a feed hopper, if accessible, or from the pipes or conveyors
that feed the materials to the process. Similarly, scrubber residues can be
sampled from the collection hopper or from pipes going to the hopper. Extra
handling steps only increase the chances of the sample becoming contaminated.
When samples are taken from conveyor belts, the standard procedure is
to stop the conveyor at regular intervals (e.g., every 10 or 15 min) and
shovel off a section of the material. Flat-nosed shovels with straight
perpendicular sides are best for this type of sampling.
Samples collected in accordance with the above-prescribed procedures
should be stored in air-tight, glass containers with Teflon lids until ready
for analysis. If larger samples are necessary to provide a representative
sample, they should be placed in a series of these containers.
108
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CHAPTER 8
LEVEL 1 INORGANIC LABORATORY ANALYSIS TECHNIQUES
8.1 INTRODUCTION
The inorganic species to be measured in the Level 1 program include
certain inorganic gases; the major, minor, and trace element constituents of
a variety of samples; and certain simple and complex anions. Some of these
species will be measured in the field; the majority, however, will be meas-
ured in the laboratory.
The samples to be analyzed include gases, liquids, and solids (see
Figures 1 and 2). Inorganic gases to be measured are S02, S03, NO , CO,
CQ2, 02, N2, H2S, COS, NH3, HCN, and (CN)2. These gases are to be measured
in the field using gas chromatographic, spectrophotometric, and wet chemistry
procedures. The details of these procedures are provided in Chapter 3.
Both organic and aqueous liquids will be collected and analyzed. Solids to
be analyzed will include bulk solids and those filtered from liquid media.
An important source of liquid and solid samples will be the SASS and FAST
trains (see Chapters 4 and 5).
Elemental analyses are to be carried out in the laboratory on both
liquid and solid samples. Spark source mass spectrometry (SSMS), ion chro-
matography (1C), and atomic absorption spectrometry (AAS) are to be used in
this work. SSMS will be used for the analysis of the vast majority of the
elements. AAS will be used for all Hg determinations and for Sb and As
quantitation of the second and third SASS impinger solutions. 1C is^to be
used for the determination of the species F , Cl , N02, N03, S03, S04, and
POf. The type of commercial test kit discussed in Chapter 6 may be used
rather than 1C for determination of these ions if permitted by the EPA
project officer.
109
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8.2 SAMPLE PREPARATION AND ANALYSIS
The following text describes the protocols to be used in the analysis
of a variety of samples. These protocols are schematically represented in
Figures 20 and 21. It is assumed here that sample allocation has taken
place, that is, that the samples collected in the field have been appor-
tioned for the various analyses including organic analyses, inorganic analy-
ses, microscopy, and biotesting. Refer to Chapters 2 through 7 and especially
Chapter 4 for instructions regarding allocation.
8.2.1 Gases
The inorganic gases listed above will be measured in the field using
neat samples. Gases collected in traps in the SASS train are considered a
part of the appropriate solid or liquid SASS train samples and are, accord-
ingly, prepared as part of these latter samples.
8.2.2 Bulk Liquids
Two types of bulk liquids will be analyzed: organic and aqueous.
Organic liquids will include fuels, feedstocks, and waste solvents. One
gram of these liquids or a quantity having a heat of combustion <8.0 K
calories, whichever is less, must be combusted or "ashed" prior to analysis
for inorganic species. Use the Parr bomb procedure as outlined in Appendix
C. The combusted sample is then analyzed for trace element content using
SSMS and AAS as described above.
Aqueous bulk liquid samples should not usually require any preparation.
The exception might be a water stream contaminated with high levels of
organic residues. In this situation, the aqueous sample will have to be
extracted with methylene chloride as described in Chapter 6. The organic
extract will then have to be Parr bombed. Still another possibility is that
the aqueous sample contains insoluble particulate material. This will have
to be removed using filtration, also described in Chapter 6. The solids
collected will need to be Parr bombed if they contain significant amounts of
organic material (see Figure 20). The aqueous bulk liquid samples are to be
analyzed for trace element and anion content using SSMS, AAS, and 1C.
110
-------
*See Appendix E
Figure 20. Level 1 inorganic laboratory analysis plan for solid samples.
-------
MODULE
CONDENSATE
(extracted,
aqueous phase)
Hg(AAS)
S0= FrcCP
ETC. (1C)
°4'
•Liquids that are a mixture of water and organic substances
must be separated using extraction.
tSolids present in either of these types of liquids will have
to be removed by filtration and Parr bombed if they are,
in part, organic.
Figure 21. Level 1 organic laboratory analysis plan for liquid samples.
112
-------
8.2.3 Bulk Solids
Certain solids need no special preparation for analysis by SSMS. These
include flyash, bottom -ash, and inorganic minerals. Those solids that are
principally organic must be combusted (using the Parr bomb technique) prior
to SSMS analysis. For example, bulk organic materials and the XAD resin
from the SASS train must be combusted to avoid interference in mass spectral
analysis. Still other solids (e.g., coal) must be combusted, not so much to
remove interferences but to concentrate the inorganic constituents. A more
difficult question arises with "partially" organic samples. In these cases,
the sample is to be analyzed by SSMS without combustion. If the resultant
mass spectral data are not suitable for elemental analysis (i.e., element
signals are masked), then the sample is to be combusted and reanalyzed by
SSMS.
For the analysis of Hg (by AAS), the samples must be in solution form.
The samples resulting from Parr bomb combustion are in such form, and thus
are suitable for such analyses. Those samples that are not combusted must,
accordingly, be treated so as to release Hg. Aqua regia digestions are used
to dissolve these samples for Hg analysis. Also, particulate catches on the
glass fiber filters taken from the SASS and FAST trains will generally be
embedded in the pores of the filter and will require aqua regia digestion
for the SSMS analysis as well as for the Hg analysis. The aqua regia diges-
tion involves heating a mixture of the sample and aqua regia for about 6 h
and refluxing the acid. (See Appendix D for further details.)
Leachable anions and cations are to be released from bulk solids using
a cold water extraction procedure. The anions are to be determined using 1C
and the cations are to be determined using SSMS. The water extraction
procedure is described in Appendix E. The anions to be determined include
F", Cl", NOg, NOs, SOj, SOj, and PO^.
8.2.4 SASS Train Samples
Summaries of the SASS train sample analysis protocols are provided in
Figure 10. Discussions of the procedures to be used with these samples
follow.
8.2.4-1 Cyclone and Filter Catches—
The catches from the 10- and 3-um cyclones are to be weighed separately
and then combined. A portion of the resultant combination is taken for
113
-------
elemental analysis using SSMS. If the sample is high in organic content, it
will have to be Parr bombed prior to SSMS analysis. Another portion of the
combination (see Table 11) is to be digested in aqua regia. The resultant
solution is analyzed for Hg using AAS.
Both the filter and the 1-um cyclone catches are to be weighed. The
second step in the analysis depends upon the nature of the filter catch, as
described in Chapter 4. If the filter catch is loose, it is to be gently
shaken or tapped from the filter and combined with the catch from the 1-um
cyclone. Appropriate portions of this combination are to be analyzed using
SSMS and AAS as described in the preceding paragraph. If the filter catch
cannot be released from the filter, the filter is first to be apportioned by
cutting it into appropriate sections (see Chapter 4). The section for
inorganic analysis is then digested in aqua regia and the resultant solution
is analyzed using SSMS and AAS. When the filter is analyzed by itself, the
1-um cyclone catch is also analyzed by itself using the same protocol as is
used for the catch combinations described above.
8.2.4.2 Probe and Cyclone Washings--
The probe and cyclone washings combination is taken to dryness and
weighed. If the dried sample exceeds 10 percent of the total cyclone and
filter sample weight, then it is analyzed. Otherwise it is simply held in
reserve. If the sample is to be analyzed, a portion of it is analyzed by
SSMS. Again, a high organic content may require Parr bomb combustion prior
to SSMS analysis. Another portion of the sample is digested in aqua regia
and the resultant solution is analyzed for Hg using AAS.
8.2.4.3 XAD-2 Resin-
A 1-g portion of the homogeneously mixed XAD-2 resin is Parr bombed.
The resultant solution is analyzed using SSMS and AAS*.
8.2.4.4 XAD-2 Resin Module Condensate—
The contents of the XAD-2 resin module condensate reservoir are extracted
as described in Chapter 4. This extracted aqueous solution is then combined
with the solution from the first impinger. The resultant combination is
analyzed using SSMS and AAS*.
* Only Hg by AAS.
114
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8.2.4.5 APS Impinger Solutions—
The APS impinger solutions are combined and analyzed for Hg, Sb, and As
using AAS.
8.3 ANALYTICAL METHODOLOGIES
8.3.1 Elemental Analysis by Spark Source Mass Spectrometrv (refs. 77-87)
Spark source mass spectrometry (SSMS) has been chosen for elemental
analysis because (a) it provides multielemental analysis wherein sensitivity
does not vary greatly from element to element, and (b) the limit of detec-
tion is generally at the ppm level.
8.3.1.1 Instrumentation--
One source of difficulty in SSMS is the presence of organic materials
in the sample. Such materials may lead to masking of the elemental ion
signals by organic fragment ions. This problem is especially severe with
samples that are principally organic in nature; such samples must be com-
busted as described above. However, certain samples that are in part organic
will need combustion only if ion masking is significant. In order to mini-
mize this ion interference, and thus the need for combustion, the instrumen-
tal resolution* is to be at least 3000 in the Pb ion region; this value is
chosen on the basis of experience in the Level 1 program.
Another instrumental concern is ion detection. There are two general
types of SSMS detection systems: photographic plate and electrical detec-
tion. For Level 1 survey purposes, the photographic system will be applied.
All photoplates acquired as a part of Level 1 studies are to be retained for
a period of 2 years.
8.3.1.2 Electrode Preparation—
If the sample to be analyzed by SSMS is not already a conductor, it
must be placed in a conducting medium (graphite). The graphite to be used
shall be Ultra-1-N-USP from Ultracarbon Corporation, Bay City, Michigan, or
a graphite of equal purity. Figure 22 shows in schematic form how each
sample type is prepared for analysis by SSMS. Aqueous samples are prepared
"Instrumental resolution is defined as M/AM, where M is the average mass of
two ions just resolved (i.e., 50 percent valley between peaks) and AM is
the difference in their masses.
115
-------
PARTIALLY ORGANIC
SAMPLES. LIQUIDS
OR SOLIDS
FORM ELECTRODE FORM ELECTRODE
NO
Figure 22. Sample preparation for SSMS elemental analysis.
-------
by mixing 50 mg of graphite and an internal standard with 1 to 20 ml of the
sample. The amount of liquid used should be such that it yields 50 mg of
dry residue. Alcohol may be added to promote carbon "wetting." The slurry
formed is taken to dryness under a heat lamp. The remaining solid is mixed
thoroughly and formed into a set of three electrodes (two for sparking plus
a spare). Combusted, acid-digested, and water-extracted samples will be
prepared -for SSMS analysis in a manner analogous to that of the aqueous
samples. Nonconducting solids not requiring combustion will simply be mixed
in a 1:1 weight ratio with graphite. Again 50 mg of carbon, an internal
standard, and 50 mg of sample are mixed and formed into an electrode set.
If less than 50 mg of sample, either as a residue from a liquid sample or as
a solid, is available, all the sample that is available should be used for
electrode preparation.
8.3.1.3 Standards--
The method of internal standards is to be used for quantification in
SSMS. Elements that shall be used as internal standards are erbium, indium,
or rhenium. The standardization procedure involves first mixing one of
these elements with a known multielement mixture. This multielement mixture
should be prepared with commercially available oxides that are 99.99 or
99.999 percent pure. Commercially available mixtures (e.g., Spex Mix, Spex
Mix, Inc., Metuchen, N.J.), are to be used for those elements for which pure
oxides are unavailable.
Replicate standards of mid-range concentration are then prepared by
diluting portions of this multielement mixture with graphite. (Single point
standards are acceptable within the Level 1 framework.) These standards are
then analyzed using the "just disappearing line" technique. This technique
involves several steps. First, as the electrodes prepared from these samples
are sparked, a series of photoplate exposures of variable, total charge
accumulation are made. The plate is then developed and the charge values
corresponding to the lines from the internal standard and the elements of
interest just disappearing are noted. These charge values are then used to
determine the relative sensitivity coefficients (SR) of the elements of inter-
est to the internal standard. (See Section 8.3.1.5 for sample calculation.)
117
-------
8.3.1.4 Analysis of Environmental Samples--
As in the case of the standards, a known amount of an internal standard
is added to the sample prior to electrode preparation. The unknown or test
sample concentrations are determined by the "just disappearing line" tech-
nique, which in this case makes use of the SR values determined previously
with the standards. (See Section 8.3.1.5 for sample calculation.)
A matter of concern in using the "just disappearing line" technique is
the nature of the variation in the total charge accumulation from exposure
to exposure in the series. The maximum exposure for Level 1 work shall
correspond to 300 nanocoulombs of charge with subsequent exposures being
reduced by a constant factor, either 1/3 or 1/2. Typical series would thus
be 300, 100, 30, 10, 1, ... or 300, 150, 75, 37.5, 18.75, ... nanocoulombs.
Fifteen or sixteen exposures are to be made. The 1/2 factor, while slightly
more accurate, does not provide the range of detection that the 1/3 factor
does. When using the SSMS technique for the analysis of Level 1 samples,
all sample component concentrations up to 10 percent (by weight) must be
quantified. This will require that those contractors having SSMS spectrom-
eters built for exposure factors of 1/2 will have to prepare two samples for
each analysis, a normal sample allowing quantification from the sub-ppm
level to several hundred ppm and a second, more dilute sample for quantifi-
cation up to the 10 percent level.
8.3.1.5 Sample Calculation and Report Forms (See Sections 2.2.7-2.2.9)--
The calculation for an SSMS analysis, even using the disappearing line
technique, is moderately complex. An example calculation follows:
Standardization (Determination of Relative Sensitivity Coeffi-
cients)
To determine the relative sensitivity coefficients as discussed in
Section 8.3.1.3, the following equation is to be used:
g
« - _. ..
R C. E. wt. sample A. Wg M
SR = the experimentally determined relative sensitivity coefficient
to correct for other factors that bring about differences in
elemental sensitivity.
E = the estimate of the maximum exposure at which an isotope of
the internal standard present in known concentration "just
disappears."
118
-------
E = the similar estimate of the exposure for an isotope of the
element of interest in the standard mixture.
V_C = the product of the volume and stock concentration of the
s s
internal standard "spike."
wt. sample = the weight of the sample used in preparing the set of elec-
trodes.
A /A = the ratio of the isotopic abundances of the internal standard
isotope to the isotope of interest.
Wx/Ws = the ratio of the line widths of the mass of interest to that
of the internal standard; this is approximated in practice by
A b
M /M = the ratio of the mass of interest to that of the internal
standard, to convert from atomic concentration to weight
concentration.
To simplify a repetitive calculation, the various correction and conversion
factors may be regrouped in the following manner:
_ s / i _i , the elemental isotope dependent factors.
Fl= A, >s ' Ms
— - VsCs • js , the sample-dependent factors.
2 C. wt. sample E^
F, = can be calculated and tabulated for each isotope that is used
for analysis.
F? = is calculated for each sample
As a sample calculation, assume one is to determine SR for 59Co rela-
tive to 166Er+. The data are:
Ci = 10 ug/g
V C = (1 mL)(100 ug/mD = 100 ug
wt. sample = 0.0500 g (@ 10 M9/9)
Ei = 0.90 nC (est.)
E = 0.082 nC (est.)
then,
F 1 100 ug . 0-082 _ 18 2
2 " 10 ug/g ' 0.0500 g 0.90
SD = (18.2X0.0708) = 1-29.
K
119
-------
Analysis of an Unknown
The equation used to determine SR is now rearranged to determine C^;
that is,
c Es VsCs As
C — . . _ .
i wt. sample Ai T Ms Ms
Examples of completed SSMS forms are included as Figures 23, 24, and
25.
8.3.2 Atomic Absorption Spectrometry (refs. 88, 89)
While SSMS can theoretically be used to analyze any element, it has
been found that fairly volatile species such as Hg are poorly analyzed by
SSMS. Thus, Hg will be analyzed using atomic absorption spectrometry (AAS)
(see Figures 20 and 21). AAS will also be used to analyze for Sb and As in
the second and third impinger solutions taken from the SASS train; these,
plus Hg, are the only species of interest in this sample and using SSMS for
just two metals would be inefficient.
8.3.2.1 Mercury Analysis (ref. 90) —
The cold vapor mercury analysis procedure described here is applicable
for Level 1 determination of Hg in hydrogen peroxide and ammonium persulfate
impinger solutions, bulk liquids, dilute HN03 solutions resulting from the
Parr bomb combustion of fuels, and aqua regia solutions from the digestion
of particulates. The detection limit is 0.04 ug/L when using a 50-mL sample.
The cold vapor mercury analysis is based on the reduction of mercury
species in acid solution with stannous chloride and the subsequent sparging
of elemental mercury, with nitrogen, through a quartz cell where its absorp-
tion at 253.7 nm is monitored. Details of the procedure are provided in
Appendix F.
8.3.2.2 Arsenic Analysis (ref. 90)—
Arsenic analysis by AAS is applicable for Level 1 analysis of impinger
solutions. The detection limit for the procedure is 0.05 ug with a calcu-
lated sensitivity of 0.03 ug per 1 percent absorption.
The analysis procedure involves the reduction and conversion of arsenic
to its hydride through a reaction with fresh sodium borohydride (<4 h old).
The volatile hydride is swept from the reaction vessel, in a stream of
120
-------
SSMS ANALYSIS SHEET
Contractor John Doe Engineering
c,mnia«!it»
Sample bite
Acme Power Station
c . . ... _ 11/9/78
Sample Acquisition Date _ -li/Z//a
Stack
Type of Source
Test Number _
Sample Description 3 and 10 ym cyclone catch combination
Sample ID Number APS-JDE-11/2/78-510
Analyst Responsible I. M. Accurette
Calculations and Report Reviewed By sL
Date Analyzed 12/15/78 Time 9:00
Report Date 2/R./7Q
Instrument
MR7
Sequential Exposure Factor \f\
Resolution
3000
Carbon Type Used for Electrode Preparation Ultra-1-V-USP
Description of Multielement Calibration Standard Spex Mix
Internal Standard(s)
lndlum
Original Sample Volume or Mass f- ft™
Dilution Factor 1/2 (50 me carbon/50' mg participate)
Brief Description of Electrode Preparation Mix sample, graphite, and internal standard. Dry
and press into 3-electrode set. _ . _ ______
Figure 23. SSMS analysis sheet.
121
-------
ro
ro
Element
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Relative
Sensitivity
Coefficient
0.69
0.65
0.95
0.98
1.41
Concentration
of Calibration
Standard
10 ppm
10 ppm
10 ppm
10 ppm
10 ppm
Element
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Relative
Sensitivity
Coefficient
Concentration
of Calibration
Standard
Element
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulphur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
Relative
Sensitivity
Coefficient
Concentration
of Calibration
Standard
Figure 24. SSMS report — standardization results. (Note that this form is only partially
completed, but that it is to be completed in toto during an actual analysis.)
-------
fo
CO
Element
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
ridium
hmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Lin* Uwd
for
Estimate
(mass number)
238
232
207
208
205
NC
Uncorrected
Sample
Value
3.4
2.6
ND
68.7
2.3
NC
Blank
Value
ND
ND
ND
3.4
ND
NC
Corrected
Sample
Value
3.4
2.6
ND
65.3
2.3
NC
NOTE THAT THIS FORM IS ONLY
Assigned
Concentration*
3.4
2.6
ND
65.3
2.3
NC
PARTIALLY
At Source
Mass/Volume
mg/m^ or
MI/L
0.0002 me/tn
0.0002 mg/m
ND
0.004 mR/mJ
0.0001 mg/m
NC
COMPLETED, BUT THAT IT IS TO BE COMPLETED
IN TOTO
DURING A
CTUAL ANAL
YSIS.
Detection
Limit
1
1
0.7
1
0.6
18
•Results: pg/g (in original sample) or I - interference; NC • not computed; NG • sample value below blank; ND - not detectable «2a blank or baseline).
Figure 25. SSMS report—test sample results. (Note that Test Sample Results report
forms for the elements cerium through hydrogen are not included here
but are included in Appendix A.)
-------
argon, into an argon-hydrogen flame of an atomic absorption spectrophotometer.
There the hydride is decomposed and its concentration monitored at the
resonance wavelength 193.7 nm. Further details of the procedure are pro-
vided in Appendix F.
8.3.2.3 Antimony Analysis (ref. 90)--
Antimony analysis by AAS is applicable for the analysis of ammonium
persulfate solutions obtained from Level 1 samples. The detection limit for
the procedure is 0.05 ug when using a 10-mL sample.
Organic antimony-containing compounds are decomposed by adding sulfuric
and nitric acids and repeatedly evaporating the sample to fumes of sulfur
trioxide. The antimony liberated, together with the inorganic antimony
originally present, is subsequently reacted with potassium iodide and stan-
nous chloride and finally with sodium borohydride to form stibine. The
stibine is removed from solution by aeration and swept by a flow of nitrogen
into a hydrogen diffusion flame in an atomic absorption spectrophotometer.
The gas sample absorption is measured at 217.6 nm. Since the stibine is
freed from the original sample matrix, interferences in the flame are mini-
mized. Further details are provided in Appendix F.
8.3.2.4 Sample Calculation and Report Forms (see Sections 2.2.7-2.2.9)--
The procedures for determination of Hg, Sb, and As are similar. In
each case, the total metal content of an aliquot of sample is transported by
a carrier gas into the AAS. The calculation procedures are nearly identical
and are illustrated below:
Standard Solutions
Standard Solution No.
I
2
3
Blank Solution
Absorbance*
Concentration
of aliquot
s2
s3
Absorbance*
A
si
s2
*A double beam spectrophotometer is to be used, thus instrumental back-
ground signal is subtracted automatically.
124
-------
Unknown Solution
Absorbance*
AU,measured
From a linear regression analysis of the standards' data,
As,i = (Line sl°Pe) x (Cs p + (Intercept).
Calculate values of Cb]ank and C^^ from the standard calibra-
tion equation, and correct C for blank, i.e.,
C = C r
u,corrected u,measured V
The method for Sb analysis is not very reproducible; therefore a "check"
standard must be prepared with each set of samples, compared with the stand-
ard curve, and an appropriate correction made. That is,
Sb (cone) = A x H
where
A = concentration of Sb in sample aliquot as determined from cali-
bration equation
B = known concentration of "check" standard
C = concentration of "check" standard as determined from calibration
equation.
A typical report form for AAS analysis is given as Figure 26.
8.4 ION CHROMATOGRAPHY (refs. 91-94)
Ion chromatography is a new technique for the analysis of low levels of
both cationic and anionic species. It is a multielement technique with a
wide dynamic response range, 10 ppb to 1,000 ppm. Because it is so new, the
principles of the technique will be summarized here. An ion chromatograph
has three principal components: a first column for separation of the ions,
a second column for removal of the excess reagent used to elute the ions
from the first column, and a conductance cell and bridge for ion detection.
For anion separation, the first column would typically be an analytical
*A double beam spectrophotometer is to be used, thus instrumental back-
ground signal is subtracted automatically.
125
-------
AAS ANALYSIS SHEET
Contractor John Doe Engineering
Sample Ste Acme Power Station
Type of Source Stack
Test Number 1
Sample Acquisition Date
L/2/78
Sample ID Number APS-JDE-11/2/78-110
Sample Description Combined SASS Train Impinger Solutions
Original Sample Volume or Mass l.QQL
Analyst Responsible I. M. Accurette
Calculations and Report Reviewed By
Date Analyzed 12/2/78 Time 4:00
J. Doe
Report Date 2/8/79
Instrument Used
Wavelength Setting (nm)
Lamp Current (ma)
Fuel/Oxidizer Pressures (psi)
PM Voltage (volts)
Detection Limit (MO)
Sensitivity (abs. units/ppm/
sample volume)
High/Low Calibration Standards (ppm)
Sample Aliquot Volume (mL)
Dilution Factor
Unconnected Sample Aliquot Value (ppm)
Blank Value (ppm)
Corrected Sample Aliquot Value (ppm)
Assigned Concentration*
At Source Mass/Volume,
mg/m^oryg/L
As
PE 603
194
8 watts (EDL)
H0/Ar-8/30
800
0.2
0.2/0.013/20
.005/.020
25
1/2
0.015
0.006
0.009
0.018
0.0006 mg/m3
Hg
PE 603
254
6
-
800
.003
0.2/0.007/100
.001/.010
?5
none
0.002
0.002
_
ND
ND
Sb
PE 603
218
8 watts (ETyrA
H_/Ar-8/30
2.
800
0.1
0.2/0.025/20
.001/.015
100
none
0.003
0.000
0.003
0.003
0.0001 mg/m3
'Results: PPM value (in original sample) or I •
«2o blank or baseline).
interference; NC • not computed; NG - sample value below blank; ND - not detectable
Figure 26. AAS analysis sheet.
126
-------
anion exchange column. The anions would be eluted from this column using a
buffered weak base, e.g., NaHC03, Na2C03. The second column would contain
strong cation exchange resin in the H+ form, which would neutralize the
eluting base. The substance elating from this second column then is the
alkali metal-anion salt in a neutral or weakly ionized media. The conduct-
ance detector responds only to these salts and the output from the conduct-
ance bridge is taken as the analytical signal. The advantages of this
method are that it allows multielement (or multispecies) detection and that
it is fast, simple, and sensitive.
8.4.1 Sample Analysis
In the Level 1 assessment, 1C is to be used for determination of F~, Cl",
N03, N02, S03, 504, and PO^ in bulk aqueous liquids and also in the solution
resulting from the aqueous extraction of bulk solids.
A 4-L solution of distilled, deionized water containing 0.5 g each of
NaHC03 and Na2C03 is used as the eluent (i.e., 0.125 g/L). The sample is
first filtered and then injected into a sample loop (typically 1 to 2 mL
must be injected; 0.1 ml to fill the sample loop and the remainder to fill
the tubing leading to the sample loop). A pump rate of approximately 1.5
mL/min (300-400 psig) is used. The anions elute in the following order: F ,
Cl~, NOg, N03, P04, S03, and SO^. (Br~ will also elute if present.) The
anions of interest are then determined by either the method of standard
additions or by use of a calibration curve. The method of standard additions
should be used whenever the presence of interferences is suspected. These
include polyvalent cations such as Fe+3 and Al+ , which interfere by forming
complexes with F"; and iron, which will interfere with PO^ and CL through
complex formation.
As a final note and as stated previously, the type of commercial test
kit discussed in Chapter 6 may be used rather than 1C for determination of
these ions if permitted by the EPA project officer.
8.4.2 Sample Calculation and Report Forms (see Sections 2.2.7-2.2.9)
The calculation for ion chromatographic analysis is straightforward as
the following example shows.
127
-------
Standardization:
Standard solution no.
1
2
3
Concentration
'si
Peak height
Psl
Ps2
Ps3
A linear regression analysis of these data yields the standard calibra-
tion equation
P ,- = (Line Slope) x (C .) + (Intercept).
5,1 S , 1
The peak height for an unknown, P , is measured as well as that of a
blank, Pb« Concentrations GU measureci and C(-, are calculated using the
standard calibration equation and C corrected ^ Ca1cu1ated as
C = C - C
u, corrected u, measured b"
Typical report forms for 1C analysis are given in Figures 27 and 28.
Contractor
Sample Site
John Doe Engineering
Acme Power Station
Sample Acquisition Date
11/2/78
Type of Source Cool ing Hater
1
Test Number
Sample ID Number APS-JDE-11/2/78-210
Sample Description Grab sample from stream
Analyst Responsible
I. M. Accurette
Date Analyzed H/2/78 Time 3:00
Calculations and Report Reviewed By
Instrument Dionex
J. Doe
Report Date 2/8/79
Eluent
150 ml/hour
Column Flow Rate
100 UL
150 ml/hour
Pressure 400 psj
Sample Size
Attenuator Setting
Recorder Speed
30x
.5 cm/min
Original Sample Volume or Mass
Observations , ,
1 L
Multiple Standard Addition: Yes .
No
Figure 27. 1C analysis sheet.
128
-------
10
Ion
F ~
Cl~
Br~
NOj
"«3
so3=
soj
POf
Uncorrected
Sample Value
0.03
6.8
0.6
0.7
0.8
1.8
5.6
4.2
Blank
Value
0.03
0.7
0.6
0.7
0.1
0.7
1.5
0.4
Corrected
Sample Value
6.1
_
_
0.7
1.1
4.1
3.8
High/Low Calibration
Standards or Con-
centration Added
0.1/10
0.1/10
0.5/10
0.5/10
0.1/10
0.5/10
0.1/10
0.5/10
Dilution
Factor
None
1/10
None
None
None
None
None
None
Assigned
Concentration*
ND
61
ND
ND
0.7
1.1
4.1
3.8
Detection
Limit*
0.05
0.07
0.5
0.5
0.3
0.5
0.1
0.2
'Results: /ig/L values (in original sample or I — Interference; MC — major constituent, not quantified; NC — not computed; NG - sample value below
blank; ND - not detectable (<2 a blank or baseline).
Figure 28. 1C report—standardization and test sample results.
-------
CHAPTER 9
LEVEL 1 ORGANIC ANALYSIS TECHNIQUES
9.1 INTRODUCTION
The objective of Level 1 organic analysis is to identify the major
classes of organic compounds present in a process or effluent stream and to
estimate their concentrations. An example of the kind of information the
methodology is designed to provide is given in Table 14.
Samples obtained in accordance with the procedures outlined in Chapters
3 through 7 will be either gases, liquids, or solids. The multimedia analysis
flow scheme presented in Figure 29 shows how each of the sample types is
split for organic analysis.
In Level 1 organic analysis, quantitative information is provided by
gas chromatography (total chromatographable organics--TCO) and by gravimetry
(GRAV). Qualitative and semi quantitative information is obtained from
liquid chromatography fractionation, from infrared spectra, and from low
resolution mass spectra. In order to achieve a satisfactory characterization
of the sample, the analyst must integrate all of these data, as well as any
other available information about the source. Knowledge gained from any one
part of the analysis scheme (e.g., LC separation) should be used, to the
maximum extent possible, in interpreting the results from other parts (e.g.,
IR or LRMS spectrum). Table 15 summarizes the data expected from individual
samples undergoing Level 1 organic analysis.
9.2 LEVEL 1 ORGANIC ANALYSIS METHODOLOGY (ref. 95)
An overview of the methodology to be used for the Level 1 organic
analysis is shown in Figure 30. This methodology deals with the preparation
of the samples to provide a form suitable for analysis, and with their
subsequent analysis.
130
-------
TABLE 14. SUMMARY OF RESULTS FOR ORGANIC EXTRACTS FOR SASS TRAIN SAMPLE
co
2 • mg/m3
Part icul ate module
Categories
Aliphatic hydrocarbons
Aromatic hydrocarbons--
benzenes
Fused aromatics, MW <216
Fused aromatics, MW >216
Heterocyclic N
Heterocyclic S
Heterocyclic 0
Phenols
Esters
Carboxylic acids
Sulfur
Inorganics
Unclassified
Si li cones
Rinses* >3 urn
<0.06
0.25
0.25
0.31
<0.06
<0.06
0.06
0.18
<0.06
0.06
0.06
<3 urn
<0.04
0.15
0.15
0.19
<0.04
<0.04
0.04
0.11
<0.04
<0.04
0.04
Resin
0.3
0.6
6.3
4.2
0.6
0.4
0.2
0.1
0.1
0.3
0.1
0.2
Sorbent module
Rinse Condensatef
0.8
22
21
19
2
2
0.1
0.3
0.2
Totalf
1.1
0.6
29.
26.
20.
2.4
2.2
0.2
0.5
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.
tNo condensate was collected for this sample.
fRounded results.
-------
co
ro
SOLIDS
PARTICU-
LATES
OR ASH
METHYLENE
CHLORIDE
EXTRACTION
RINSES OF
SASS
TRAIN
ORGANIC
MODULE
METHYLENE
CHLORIDE
EXTRACTION
1. TCO/GRAV.
2. TOTAL SAM
PLE-IH
3. LC FRAC
TIONATED
SAMPLE-
IH/LRMS;
TCO/GRAV.
XAD2
SORBENT
TRAP
RINSES OF SASS
TRAIN PROBE AND
PARTICIPATE
MODULES
PORTION FOR
INORGANIC
ANALYSIS
1. GRAV.
2. TOTAL SAMPLE
-IR
3. LC FRACTION-
ATED SAMPLE
-IR/LRMS;
GRAV.
M
CO
•ANALYSIS ENDS HERE IF RESIDUE < 10 PERCENT OF TOTAL PARTICULATE CATCH.
Figure 29. Multimedia organic analysis overview.
-------
TABLE 15. SUMMARY OF EXPECTED DATA FROM LEVEL 1 ORGANIC ANALYSIS
Onsite
Sample GC Weigh Extract TCO GRAV IR LC*
Gases—grab sample V
SASS
>10 urn parti cul ate ,/ I / / / /
> V V v V
3-10 pro particulate V \
1-3 urn particulate V ) / i i i
\ V V V V
<1 urn particulate J j
Rinse of particulate
modules and probe V Vt Vt Vt Vt
XAD-2 resin combined
with rinse of
sorbent module
Sorbent module
condensate
SOLIDS
Flyash; clinker
Organic feed stock
Coal
LIQUIDS
Effluent water
Organic feed stock
Fuels
V
V
V V
V V
V V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
^
V
V
V
V
V
V
V
V
V
Includes GRAV + IR and TCO on all fractions; perform LRMS when criteria
are exceeded.
tDo analysis if gravimetric results are greater than 10 percent of the total
particulate catch.
133
-------
Organic Extract
or
Neat Organic Liquid
Concentrate
Extract
Infrared Analysis
Gravimetric
Analysis
Aliquot Containing
15-100 mg
Solvent
Exchange
Liquid
Chromatographic
Separation
Seven Fractions:
Infrared Analysis
Low Resolution
Mass Spectra
Analysis
TCO*
Analysis
Repeat TCO*
Analysis
if Necessary
TCO* and
Gravimetric
Analysis
'See section 9.4.1.
Figure 30. Organic analysis methodology.
134
-------
As indicated in Figure 29, the extent of the sample preparation required
varies with sample type. The low molecular weight, volatile species (boiling
point <100° C) are determined by gas chromatography onsite and require no
preparation. Organic liquids, such as fuel oils, will not need pretreatment
and are placed directly into the analysis scheme. However, the majority of
the samples, including the SASS train components, aqueous solutions such as
scrubber waters, and bulk solids such as coal or slag, require extraction
with solvent prior to analysis. This extraction separates the organic
portion of the samples from the inorganic species. The analysis of organic
extracts or organic liquids then proceeds to initial quantitative analyses
of volatile (TCO) and nonvolatile (GRAV) organic material and a preliminary
infrared (IR) spectral analysis. The IR spectrum provides an indication of
the types of functional groups present in the sample and a control check-
point for subsequent analyses. All functional groups identified in this
total sample should be accounted for in the succeeding steps.
The sample extract or organic liquid is separated by silica gel liquid
chromatography (LC) using a 7-fraction solvent series of varying polarity.
TCO and gravimetric analyses of each fraction are done to determine the
distribution of the sample by the various class types. An IR spectrum is
then obtained on each LC fraction for determination of the types of func-
tional groups present. Low resolution mass spectra (LRMS) are also obtained
on all fractions that exceed the concentration threshold in order to deter-
mine the principal compound types present in each fraction. For the sample
streams identified in the Level 1 scheme, these threshold concentrations
are:
a. Gas streams sampled with the SASS system--0.5 mg/m3 computed at
the source;
b. Aqueous slurry or solid samples—dependent on extract concentra-
tion;
c. Organic liquids--! mg/LC fraction.
The decision is based on the sum of the TCO and GRAV analyses (Section 9.4)
for each fraction.
It should be emphasized that sample contamination and solvent impur-
ities are common problems in organic analysis. The best possible laboratory
135
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procedures must be used along with verified pure solvents. Blanks and
controls are to be run for each stage in the analysis scheme, as specified
in Chapter 2.
9.3 PREPARATION OF SAMPLE EXTRACTS
This section presents sample preparation procedures that are appropriate
for most samples. The specific solvent indicated for the extraction is
methylene chloride, which was selected because of its good solvent properties
and high volatility (to facilitate concentration). This solvent should be
used except in cases with unusual requirements, for which an alternative
procedure can be suggested and used after approval by the project officer
and by the Process Measurements Branch, IERL-RTP.
Procedures for concentration and analysis of extracts are presented in
Section 9.4.
9.3.1 Aqueous Solutions
Extraction of aqueous solutions should be carried out with methylene
chloride using a standard separatory funnel fitted with a Teflon stopcock.
The pH of the aqueous phase should be adjusted first to 2.0 ±0.5 with hydro-
chloric acid and subsequently to 12.0 ±0.5 with sodium hydroxide, using
multirange pH paper for indication. Two extractions are to be done at each
pH, using a 250-mL volume of methylene chloride for each of the four extrac-
tions of a 10-L sample. The extractions may be performed in several batches
on convenient-sized sample portions with corresponding amounts of solvent,
but the entire 10-L sample must be extracted.
For the SASS train sorbent module condensate, the volume of aqueous
solution should be measured and the quantity of methylene chloride adjusted
proportionately.
To avoid the necessity of shipping large quantities of water, the
extractions should preferably be done onsite whenever facilities will permit
contamination-free conditions. If formation of emulsions is encountered,
the samples may be shipped to the laboratory for extraction. Centrifugation
at about 2,000 rpm has been found to be an effective way to break the emul-
sion in several studies.
136
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9.3.2 Solids, Particulate Matter, and Ash
All solid material including waste products, raw materials, cyclone,
probe and filter particulate, and ash are extracted for 24 h with methylene
chloride in a Soxhlet apparatus. When sample quantities are limited, such
as in the case of SASS cyclone catches, the designated solid sample aliquots,
remaining after a small portion has been set aside for inorganic and particle
morphology analysis, should be taken for the extraction. (See Table 11,
Chapter 4.) When kilogram quantities of the sample material are available,
optimal sample sizes should be used for these determinations. Bulk lumpy
solids, such as coal, should be crushed to a size that will pass a 60-mesh
screen before extraction, using a procedure such as that in ASTM D 2013,
"Preparing Coal Samples for Analysis" (ref. 74). The sample is held in the
thimble with a plug of glass wool and a stainless steel screen during the
extraction to avoid carryover of the sample.
9.3.3 Slurries and Sludges
The sludge/slurry sample category can span a tremendous range, in-
cluding slurries and solid or semisolid sludges containing up to 95 percent
water. Some of these materials are very difficult to handle and no one
procedure will work for all of them. The basic Level 1 approach is to
determine whether the sample is best treated as a solid, a liquid, or by a
combination of procedures. The protocol will involve, in most cases, tests
on small portions of the 1-kg sample to determine the best procedure prior
to committing the entire sample. The stepwise protocol follows.
If the physical character of the sample permits, treat
it as a solid by transferring the whole sample to a Soxhlet
thimble and extracting for 24 h with methylene chloride. Do
not dry sample before extracting. Determine wet weight of
sample taken by weighing sample container before and after
transferring sample to thimble. If an aqueous phase is
noticed in the organic extract, this should be separated and
removed prior to concentration.
If the sample state does not appear compatible with
direct Soxhlet extraction (i.e., wet sludge/slurry of high
liquid content), select a treatment procedure as follows:
1. Take a 10-mL portion of the sample (shaking vigorously
first, if necessary, to facilitate a fairly representa-
137
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tive sampling) and place in a 15-mL centrifuge tube.
Add 2 ml methylene chloride. Shake well and allow to
settle for at least 30 min. Then:
a. If sample dissolves completely, treat the sample
like a neat organic liquid—no sample preparation
is required.
b. If a clean two-phase (organic-aqueous) separation
is achieved, treat the sample like an aqueous
sample.
c. If a clean two-phase separation is not achieved
(i.e., if an emulsion forms, or if the apparent
solvent recovery is low, or if a three-phase system
with solids suspended in organic layer or between
organic and aqueous layers is present), centrifuge
the mixture. If a clean two-phase system then
results, treat sample as in l.b. above. If not,
test sample as suggested in 2., below.
2. Take a 10-mL portion of the sample (shaking vigorously
first, if necessary, to facilitate a fairly representa-
tive sampling) and place in a 15-mL centrifuge tube.
Centrifuge. If phases separate, treat the solid phase
by Soxhlet extraction. The liquid phase is treated like
an aqueous sample or, if organic, like a neat organic
liquid. The several extracts generated for this type of
sample should be recombined—taking the same fraction of
each—prior to organic analysis.
Occasionally a sludge/slurry sample may be encountered for which none
of the above methods will be satisfactory. In those instances, the EPA
project officer and appropriate PMB personnel should be consulted for guid-
ance.
9.3.4 SASS Train Rinses
For each SASS train run there are two samples of this type, one from
the rinse of the particulate portions (cyclones and filters), and a second
from the rinse of the sorbent module. The solvent mixture used for the
particulate rinses is 1:1 (v:v) methylene chloride:methanol. This rinse
should be dried and weighed. If the residue quantity is greater than 10
percent of total filter and cyclone catch, the full complement of analytical
tests should be performed. (See Figure 29.) The rinse for the gas condi-
tioner and sorbent module is methylene chloride alone. It should be added
to the Soxhlet solvent reservoir prior to XAD-2 extraction. This will
138
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result in a combined rinse and extract characterization for organic com-
pounds. (See Figure 29.)
9.3.5 Sorbent Trap
The XAD-2 resin from the sorbent trap is removed from the SASS train
cartridge and homogenized, and a 5-g portion is removed for the inorganic
analysis. The balance of the resin is extracted with methylene chloride to
remove the organic material. A large Soxhlet extraction apparatus, avail-
able from several manufacturers*, must be used to extract the 400 ml of
resin. The resin is transferred to a previously cleaned glass extraction
thimblef. A glass wool plug and stainless steel screen are used to secure
the resin, which would otherwise float on the methylene chloride. Approxi-
mately 1 L of methylene chloride is added to the 2-L reflux flask. (The
dumping volume of an appropriate commercial extractor is 750 ml.) A larger
Soxhlet extractor may be used if available and an appropriate increase in
the reflux solvent volume made. The boiling solvent in the flask should be
examined periodically because additional methylene chloride may be needed to
replace that lost by wetting the resin and by volatilization. The resin is
extracted for 24 h. If water is extracted from the XAD-2 resin during this
procedure, as evidenced by two phases in the liquid portion, segregate them
with a separatory funnel before concentrating the methylene chloride. The
aqueous fraction from this separation is added to the condensate catch
before it is extracted at the two pH levels.
9.4 ANALYSIS OF SAMPLES FOR ORGANICS
The analysis of each of the prepared or isolated samples for organic
compounds follows the scheme introduced in Figure 30. The overall scheme is
based upon an initially recommended scheme (ref. 95), which has been revised
with information from subsequent laboratory evaluations (ref. 96).
Qualitative analyses of organic compounds are accomplished by the
LC/IR/LRMS procedure, which will provide reliable data on the compound types
*For example, Ace Glass Incorporated (catalog No. 6810-10) or Lab Glass
(catalog No. LG-6910-100).
fThimbles of borosilicate glass with fritted glass discs must be specially
fabricated for this size Soxhlet extractor. Do not use cellulose thimbles.
139
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present in the sample or organic extract. However, compounds with boiling
points below about 100° C will not be captured in the SASS train or retained
in the organic extracts. Consequently, a separate field gas chromatography
procedure has been included for the analysis of this range of materials (see
Chapter 3), which gives a limited amount of qualitative information (reten-
tion times) as well as quantitative information.
Quantitative analysis of moderately volatile materials (bp 100° C to
300° C) is achieved by a gas chromatographic procedure applied to various
organic solvent extracts, organic liquids, and SASS sorbent module rinses.
This Total Chromatographable Organics (TCO, Section 9.4.1) analysis is not
appropriate for extracts from samples that do not contain low boiling or-
ganics, such as SASS particulate material collected at 200° C. Quantitative
analysis of nonvolatile organic sample components (bp >ca. 300° C) in all
extracts is achieved by evaporating an aliquot of extract to dryness and
weighing the residue (GRAV procedure).
In summary, TCO analyses of extracts and organic liquids are performed
prior to any concentration step. It is then necessary to obtain an IR on a
portion of this material, to do a gravimetric analysis on an aliquot, and
to concentrate the extract for the LC separation. The appropriate stage to
conduct each of these steps (gravimetric analysis, IR, concentrate) will
depend on the quantity and solubility of the sample as described in the
following sections. For many samples, quantitative analyses (TCO and/or
GRAV) may be required both before and after concentration.
9.4.1 Total Chromatographable Organics (TCO) Analysis
As previously stated, the TCO analysis is necessary for quantification
of materials with boiling points in the range of 100° to 300° C. This
analysis is applied to all samples that might contain compounds in this
volatility range. These include organic liquids, many solid sample extracts,
aqueous sample extracts, extracts from the SASS train sorbent module samples,
and LC fractions obtained for those samples. However, particulate samples
collected at the specified 205° C SASS train oven temperature or residues
from high temperature processes do not require TCO analysis. If, for some
special circumstance, the front half of the sampling train is run at a
140
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temperature lower than 200° C, then both the TCO and the gravimetric proce-
dures should be applied to the extracts of cyclone particulate catch.
Because materials in the TCO volatility range may be lost to varying
degrees during solvent evaporation, it is important that this analysis be
performed on extracts and solutions prior to any concentration step. It
will also frequently be desirable to repeat the TCO analysis later on the
concentrated extract. When the original analysis shows a low TCO value,
corresponding to a concentration of less than about 40 mg/L in the extract,
the TCO analysis should be repeated on a concentrated extract. This will
give a more reliable estimate than that obtained by multiplying the original
low concentration estimate by the large volume of unconcentrated extract.
For determination of TCO, a 1- to 5-uL portion of the extract is ana-
lyzed by GC using a flame ionization detector. A 1.8 m x 3 mm 0.0. (6 ft x
1/8 in.) column of 10 percent OV-101 on 100/120 mesh Supelcoport has been
used successfully for this analysis. Other silicone phases (OV-1, etc.) may
work as well, but a 10 percent loading is recommended. The GC is operated
isothermally at about 30° C--or room temperature—for 6 min after sample
injection and then programmed at approximately 20° C/min to 250° C and held
at 250° C as long as necessary for complete elution of sample. Injector
temperature of 275° C and detector temperature of 300° C are appropriate.
Slight modifications in the temperature and duration of the initial hold
period may be necessary to accommodate variations in individual GC systems.
Quantitative calibration of the TCO procedure is accomplished by use of
mixtures of known concentrations of the normal hydrocarbons C8, C12, and
C16. The quantitative calibration standards should be prepared to cover the
concentration range to be studied. Retention time limits corresponding to
the TCO range of boiling points are defined by the peak maxima for n-heptane
(C7, bp 98° C) and n-heptadecane (C17, bp 303° C). Therefore, integration
of detector response should begin at the retention time of C7 and terminate
at the retention time of C17. By this procedure, the integrated area will
cover material in the boiling range of 100° C to 300° C. (The C7 and C17
peaks should not be included in the quantitative calibration.)
In the TCO analyses, it is important that the observed values of total
integrated area for samples be corrected by subtracting an appropriate
141
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solvent blank prepared (i.e., concentrated) in the same manner as the sam-
ples. The blank should be checked on each of the seven LC solvent mixtures.
The results of each TCO analysis should be reported as one number, in
milligrams, corresponding to the total quantity of material in the 100° to
300° C boiling range in the original sample collected (see Figure 31). The
TCO data are thus analogous to the results obtained by gravimetric analysis.
The chromatograms themselves contain some additional data beyond the TCO
values (i.e., retention times and areas of individual peaks) and should be
retained until the Level 1 sampling and analysis effort has been completed.
9.4.2 Gravimetric (GRAV) Analysis
The gravimetric analysis is used for quantification of organic sample
components with boiling points higher than 300° C. This analysis should be
done after the sample extract has been concentrated, since it is recommended
to weigh at least 10 mg of sample in a gravimetric analysis, when possible.
Weighing to a precision of ±0.1 mg is adequate for purposes of Level 1
analysis. Sample and tare weights should be obtained by drying to "constant
weight" (±0.1 mg) in a desiccator over silica gel or Drierite. In perform-
ing a gravimetric analysis on a large volume sample (i.e., >50 mL), no more
than 5 mL of extract should be evaporated to dryness. For extracts concen-
trated to 10 mL, a 1-mL aliquot is taken for GRAV analysis. The GRAV results
should be reported as one number for the entire sample (see Figure 31). The
infrared analyses called for in Level 1 organic analysis can be performed on
the residues from the GRAV procedure, provided that the weighing dishes were
successively rinsed with distilled water, methanol, and methylene chloride
before use.
9.4.3 Concentration of Extracts and Solvent Exchange Procedure
After the initial TCO* analysis, it will usually be necessary to concen-
trate the organic extracts to a volume of 10 mL for subsequent analysis. It
is recommended that concentration to slightly less than 10 mL volume (i.e.,
8 or 9 mL) be accomplished using a Kuderna-Oanish apparatus with a 3-ball
Snyder column for volumes less than 1 L, and a rotary evaporator for volumes
*0n all samples except SASS particulate fractions and residues from high
temperature processes.
142
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that initially exceed 1 L. It is essential that the extract not be reduced
to dryness at this point in the' scheme to prevent loss of TCO range material.
The concentrated extract should then be transferred to a convenient graduated
container (e.g., Kuderna-Danish receiver or centrifuge tube) and the volume
restored to 10 ml. The concentration process should be stopped if material
begins to drop out of solution. In that case, the extract should be restored
to a convenient volume in which the material is redissolved. The original
TCO* analysis may provide guidance as to the degree of concentration that is
required for each particular sample. The objective is to achieve a final
concentration of not more than 100 mg/mL and a final volume of not less than
10 ml.
At this stage in the analysis sequence, a GRAV determination is done
and the TCO* determination is repeated.f A 1-mL aliquot is used for the
GRAV analysis and a 5-|jL aliquot is used for the TCO. If the sum of TCO
plus GRAV is <15 mg for the total sample, the LC separation is not performed
and the Level 1 analysis is concluded by obtaining IR and LRMS spectra on the
sample. If the sum of TCO plus GRAV is >15 mg, the LC separation is per-
formed. An IR spectrum is also obtained on the residue from the GRAV analy-
sis or on a separate aliquot of extract. A portion of the concentrated
extract that contains about 100 mg of organic material, if possible, is
taken for the LC. Smaller quantities down to a lower limit of 15 mg may be
used if necessary.
The LC separation procedure requires that both methylene chloride
solvent and water be eliminated before the sample extract is applied to the
silica gel column. Otherwise, the required aliphatic/aromatic and subse-
quent compound class separations will not be achieved. Extracts that do not
contain low boiling organics, such as SASS train particulate materials or
other materials collected at temperatures exceeding 200° C (400° F), can be
evaporated to dryness with silica gel, as detailed below, before LC analysis.
*0n all samples except SASS particulate fractions and residues from high
temperature processes.
tUnless the initial TCO values for the unconcentrated extract exceeded the
guideline of 40 mg/L (TCO).
143
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Extracts containing appreciable quantities of TCO material (>2 mg) must be
transferred to the LC columns without being evaporated to dryness. For
these samples, a solvent exchange procedure is required to minimize losses
of volatile sample components. An aliquot of the methylene chloride solu-
tion containing 15 mg (minimum) to 100 mg (preferred) of sample is taken for
solvent exchange into cyclopentane; the detailed procedure is given below.
Normal hydrocarbon solvents are not to be substituted for the cyclopentane;
pentane boils too low (36° C, below methylene chloride) and hexane boils too
high (68° C) for the solvent exchange. The solvent exchange and removal of
water from the sample extracts is accomplished as described in Section
9.4.4.3.
9.4.4 Liquid Chromatographic (LC) Separation
All sample extracts, neat organic liquids, and SASS-train-dried probe/
cyclone rinse extracts are subjected to LC separation if sample quantity is
adequate. An aliquot of the concentrated extract containing 100 mg of
organic matter is preferred for the LC, but smaller quantities down to a
lower limit of about 15 mg may be used. The sample components are separated
according to polarity on silica gel using a step gradient elution technique.
The detailed procedure for the LC separation is given below:
Column: 200 mm x 10.5 mm ID, glass with Teflon stopcock, water-
jacketed with inlet water temperature in the range of
18° to 22° C and sufficient flow to maintain this tempera-
ture through to the outlet.
Adsorbent: Davison, Silica Gel, 60-200 mesh, Grade 950 (available
from Fisher Scientific Company) is to be used; no other
types or grades of silica gel can be substituted. This
material should be cleaned prior to use by sequential
Soxhlet extractions with methanol, methylene chloride,
and pentane. This adsorbent is then activated at 110° C
for at least 2 h just prior to use, and cooled in a
desiccator.
144
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Drying Agent: Sodium Sulfate (Anhydrous, Reagent Grade). Clean by
sequential Soxhlet extraction for 24 h each with methanol,
methylene chloride, and pentane. Dry for at least 2 h
at 110° C just prior to use and cool in a desiccator.
9.4.4.1 Procedure for Column Preparation—
The chromatographic column, plugged at one end with a small portion of
glass wool, should be slurry packed with 6.0 g of freshly activated silica
gel in n-pentane. A portion of properly activated silica gel weighing 6.0
±0.2 g occupies 9 ml in a 10-mL graduated cylinder. The total height of the
silica bed in this packed column is 10 cm. The solvent void volume of the
column is 2 to 4 ml. When the column is fully prepared, allow the pentane
level in the column to drop to the top of the silica bed so that the sample
can be loaded for subsequent chromatographic elution.
After packing the silica gel column, add 3 g ±0.2 g clean sodium sul-
fate to the top of the column. Vibrate for 1 min to compact. The sodium
sulfate should occupy 2 ml in a 10-mL graduated cylinder. The sodium sul-
fate will remove small quantities of water from the organic extract; how-
ever, appreciable quantities of water will solidify the sodium sulfate,
inhibiting proper flow through the column. Therefore, it is advisable that
if enough water is present in the sample to form two layers, it should be
removed by another method—pipette or separatory funnel.
9.4.4.2 Evaporation of Sample Extracts with Low TCO (<2 mg original
sample)—
For these samples, the aliquot of extract containing 15 mg (minimum) to
100 mg (preferred) of material is added to a small amount of silica gel, the
solvent is allowed to evaporate, and the residue plus silica gel is trans-
ferred to the LC column with the aid of a microspatula. The container is
rinsed as described in Section 9.4.4.5.
9.4.4.3 Solvent Exchange of Sample Extract with High TCO (>2 mg original
sample)--
An aliquot of methylene chloride extract containing 15 mg (minimum) to
100 mg (preferred) of material is added to 200 mg of silica gel in a grad-
uated receiver. The volume of extract is carefully reduced to 1 mL at
ambient temperature under a gentle stream of nitrogen (tapped from a liquid
145
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nitrogen cylinder, if possible, to minimize impurities). The solvent evap-
porates rapidly so it is important that this operation be done under con-
stant surveillance to insure that the volume is not reduced below 1 mL It
is also necessary to warm the samples slightly, either by hand or water
bath, at <40° C, to prevent condensation of atmospheric moisture in the
sample due to evaporative cooling. One milliliter of cyclopentane is added
and mixed by gentle agitation. The volume is reduced to a total of 1 ml as
before. A second milliliter of cyclopentane is added, mixed, and the volume
is again reduced to 1 ml. The exchange is repeated with a third milliliter
of cyclopentane. After the volume has been reduced to 1 ml for this last
time, the solvent mixture will be £5 percent methylene chloride. This is
sufficiently low to prevent breakthrough of aromatic sample components into
the aliphatic hydrocarbon fraction, LCI.
The cyclopentane and silica gel are transferred to the top of the
previously prepared LC column using a Pasteur pipette. The container is
rinsed as described in Section 9.4.4.5.
9.4.4.4 Neat Organic Liquids—
A 100-mg sample is weighed into a tared glass weighing funnel and mixed
with about 200 mg of silica gel using a microspatula. The sample is then
transferred to the top of the column. The container is rinsed as described
in Section 9.4.4.5.
When neat organic liquids are fractionated by the liquid chromatography
scheme, they have the same theoretical gravimetric detection limitations as
other samples separated by this means, 0.1 mg/100 mg or 0.1 percent of the
sample applied. Since these aliquots are neat samples and do not have
concentration factors as multipliers, the resultant detection limits for
minor components are 1 g/kg at best.
9.4.4.5 Chromatographic Separation into Seven Fractions—
Table 16 shows the sequence for the Chromatographic elution. In order
to insure adequate resolution and reproducibility, the column elution rate
is maintained at 1 mL/min.
146
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TABLE 16. LIQUID CHROMATOGRAPHY ELUTION SEQUENCE
Fraction
I
2
3
4
5
6
7
Solvent composition
Pentane
20% Methyl ene chloride in pentane
50% Methyl ene chloride in pentane
Methyl ene chloride
5% Methanol in methyl ene chloride
20% Methanol in methyl ene chloride
50% Methanol in methyl ene chloride
Volume (mL)
25
10
10
10
10
10
10
The volume of solvents shown in Table 16 represents the solvent volume
added to the column for that fraction. If the volume of solvent collected
is less than the volume actually added due to evaporation, restore the
fraction volume to the proper level with fresh solvent. In all cases, the
solvent level in the column should be at the top of the gel bed, i.e., the
sample-containing zone, at the end of the collection of any sample fraction.
The fractions are retained as solutions for TCO analyses.
After the first fraction is collected, rinse the original sample con-
tainer or weighing funnel with a few milliliters of Fraction 2 solvent (20
percent methylene chloride/pentane) and carefully transfer this rinsing into
the column. Repeat with each successive solvent mixture in turn.
Add each new solvent to the column slowly to minimize disturbing the
gel bed and eliminate the trapped air bubbles, particularly in the zone of
the sample-containing silica gel.
After each sample is collected, an aliquot (1 to 5 uL) is taken for TCO
analysis of each fraction (unless the sample taken for LC had a TCO of <2
mg). Also, an aliquot (10 ml for Fraction 1 and 5 mL for Fractions 2-7) is
transferred to a tared aluminum micro weighing dish for evaporation and
gravimetric analysis. The GRAV data for Fraction 7 must be corrected for a
blank contributed by a small quantity of silica gel that dissolves in the
highly polar eluent. The blank value is determined by running an LC column
to which no sample is added; it is on the order of 0.9 ±0.1 mg in LC7 (10 mL).
147
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After TCO and GRAV determinations, the fractions are analyzed by IR and,
when the quantity is sufficient, by LRMS (see Section 9.4.6).
The objective of the LC procedure is to separate the sample into frac-
tions of varying chemical class type to facilitate subsequent analyses. The
LC separation procedure is not a high resolution technique and, consequently,
there is overlap in class type between many of the fractions. Figure 31
shows a sample LC report with a number of compound classes represented in
the eluent.
The results of the LC fractionation procedure include quantitative
estimates of TCO and GRAV range materials in each of seven fractions. In
most cases, the quantity of material actually taken for the LC separation is
only a portion of the total sample, and the amount taken should be stated in
the report. The actual, measured TCO and GRAV values for the LC fractions
should be multiplied by the appropriate factor (total sample quantity T
quantity taken for LC) to give the corresponding total sample values. It is
then useful to convert these quantitative estimates into equivalent concen-
trations at the source in order to facilitate comparisons with various
decision criteria. Figure 31 illustrates the format for reporting LC frac-
tionation data, with an example from a SASS train sorbent trap extract.
Note that GRAV analyses involve weighing to the nearest 0.1 mg. TCO values
are reported to the nearest 0.1 mg, also.
9.4.5 Infrared Analysis
The total sample extract, or neat liquid, and the 7 LC fractions are
analyzed by infrared (IR) spectrophotometry. A grating spectrophotometer
should be used and the following instrument conditions adhered to.
1. Resolution: For dispersively measured spectra, the spectral
slit width should not exceed 4 cm through at least 80 percent
of the wave number range.
:cur
-1
2. Wave number accuracy: ±4 cm below 2,000 cm'1 and ±15 cm"1
above 2,000 cm
3. Noise level: No more than 2 percent peak to peak.
4. Baseline flatness: The IQ or 100 percent line must be flat to
within 5 percent across the recorded spectrum.
148
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LC REPORT
SAMPLE: 11-3 SORBENT TRAP EXTRACT
Total Sample*
Taken for LC^
Recovered^
TCO
mg
106
23
17
GRAV
mg
386
84
74
TCO + GRAV
Total mg
492
107
91
Concentration
mg/ (m3, L, or kg)
82
18
15
VQ
Fraction
1
2
3
4
5
6
7
Sum
TCO in mg
Found in
Fraction
0.3
3.3
12.0
0.1
0.2
0.7
0.1
16.7
Blank
0.0
0.1
0.6
0.0
0.1
0.0
0.0
0.7
Cor-
rected
0.3
3.2
11.5
0.1
0.1
0.7
0.1
16.0
Total*
1.4
15.0
54.0
0.5
0.5
3.2
0.5
75.1
GRAV in mg
Found in
Fraction
2.5
1.0
56.4
2.2
6.8
3.6
0.6
73.1
Blank
0.0
0.1
2.5
0.1
0.5
0.2
0.0
3.4
Cor-
rected
2.5
0.9
53.9
2.1
6.3
3.4
0.6
69.7
Total4
11.5
4.1
247.9
9.7
29.0
15.6
2.8
320.6
TCO +
GRAV
Total mg
12.9
19.1
301.9
10.2
29.5
18.8
3.3
395.8
Concentration
mg/
O
(m ,L. or kg)
1.9
3.2
50.0
1.7
4.9
3.1
0.6
65.9
1. Quantity in entire sample, determined before LC
2. Portion of whole sample used for LC, actual mg
3. Quantity recovered from LC column, actual mg
4. Total mg computed back to total sample
Figure 31. Sample LC report.
-------
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 ued in a double beam
mode.
6. Spectral range: Spectra should be recorded, without gaps, over
the spectral range 3,800-600 cm"1.
7. False radiation: Not to exceed 2 percent.
IR spectra are obtained in absorbance units on samples held between two NaCl
salt plates using methylene chloride to transfer the sample to the plates.
KBr pellets can also be used if films (from MeCl2) will not give satisfactory
spectra, i.e., material is a crystalline solid. Sample quantity and instru-
ment parameters are adjusted so that the maximum signal of the strongest
peak is less than 1.0 absorbance.
Spectra are interpreted in terms of functional group types present in
the sample or LC fraction. The many reference texts (refs. 96-101) in this
area are of considerable help in interpreting the IR spectra. The interpre-
tation of the spectra should also be guided by consideration of the LC
fractionation scheme and the LRMS results (when available).
The results of the IR analysis should be reported in the format shown
in Figure 32 according to the following guidelines:
a. The frequency reported should be the peak maximum, or a range may
be reported instead for broad peaks with no well-defined maximum.
b. Absorbance values should be measured by baseline technique. The
intensity is reported relative to the strongest peak in the spec-
trum on a percentage absorbance basis.
S = strong, 70-100 percent of the absorbance value of the
strongest peak.
M - medium, 30-70 percent of the absorbance value of the
strongest peak.
W = weak, 0-30 percent of the absorbance value of the
strongest peak.
When a peak is of borderline intensity, it should be labeled "m."
Finer intensity ratings such as M-S or W-M are not appropriate.
150
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IR REPORT
SAMPLE: H-3-LC6
Wave-Number
(cm'1)
3400
3050
2850, 2920
1710
1680
1600
1450
1060
740
Intensity
M
W
M
S
M
M
M
S
M
Assignment
OH,NH
Comments
Broad
unsat'd CH
sat'd CH
acid, ketones
amide, ketones
aromatic C = C
CH2
Si-O, ether
Broad
subst. pyridine, C— Cl
Figure 32. Sample IR report.
c. The assignment/comments column indicates the functional group(s)
to which the peak is attributed*. This column may also contain
single-word descriptors of peak shape such as "broad," "doublet,"
"shoulder."
d. All weak, medium, and strong peaks must be reported.
e. A copy of the infrared spectrum should be retained at the labor-
atory for 3 years should further reference to it be needed.
As a matter of quality control, the IR bands observed with each LC
fraction should be compared to those observed with the total sample. Addi-
tional bands in any of the fractions would indicate the introduction of
impurities or decomposition on the column. The IR bands observed with the
total sample but not with any of the LC fractions would indicate loss of
material onto the column.
*A11 features of the IR spectrum, such as presence or absence of bands at
other related IR frequencies, should be considered in making the functional
group assignments.
151
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9.4.6 Low Resolution Mass Spectrometry (refs. 102-105)
A low resolution mass spectrum (LRMS) is obtained on each LC fraction
that has sufficient quantity (TCO plus GRAY), when referenced back to the
source, to exceed decision criteria concentrations. The Process Measure-
ments Branch guidelines recommended for general Level 1 purposes are:
Gas--SASS train samples 0.5 mg/m3
Ambient air--particulate 1 |jg/m3
Solids 1 mg/kg
Aqueous solutions 0.1 mg/L
An LRMS analysis is to be done on any LC fraction that corresponds to a
source concentration higher than these levels.
In the event that other, more stringent criteria are determined to be
appropriate for a particular environmental assessment, then the cutoff point
for performing LRMS will change accordingly. For example, if MEG/MATE
(Multimedia Environmental Goals/Minimum Acute Toxicity Effluent) concen-
tration values are to be used in making Level 1 decisions, then LRMS must be
done on all LC fractions for a SASS sample. This is because MATE values are
sufficiently low that in each LC fraction there is at least one compound
-category that might be present whose level of concern would be exceeded by
any detectable quantity of material.
In order to minimize the cost of the Level 1 organic analysis, it is
desirable to keep the total number of LRMS analyses required as low as
possible. An LRMS analysis must always be run on any LC fraction that
exceeds the Level 1 concentration criteria given above. However, if the
more stringent (MEG/MATE) cutoff criteria are used, it is acceptable, for
LRMS purposes only, to combine fractions falling below the Level 1 concen-
tration criteria, according to the following scheme:
LCI = LRMS-1
LC2 plus LC3 = LRMS-2, 3
LC4 plus LC5 = LRMS-4, 5
LC6 plus LC7 = LRMS-6, 7
This will allow LRMS results to be obtained on all LC fractions in a minimum
number of separate LRMS analyses. The IR data obtained with each LC fraction
should be considered before making the decision to combine fractions. If
the IR spectra of two fractions considered for combination are vastly dif-
152
-------
ferent,( those fractions should probably not be combined as the LRMS of the
mixture will be especially difficult to interpret.
The mass spectrometer used in this determination should have a resolu-
tion (M/AM) of 800 to 1,000, batch and direct probe inlet, variable ionizing
voltage source, and electron multiplier detection. Samples with significant
quantities of TCO range material (>2 mg) should be analyzed by insertion in
the batch inlet. All samples that meet the decision criteria for quantity
(TCO plus GRAV) will require analysis via the direct insertion probe. A
small quantity of sample is placed in the probe capillary and inserted into
a cool source. The temperature is then programmed up to vaporize the sample.
Spectra are recorded periodically through this period. Spectra are normally
obtained at 70 eV ionizing voltage, but low voltage (10 eV) spectra may
provide much simpler data and thus aid in interpretation in some cases.
The mass spectroscopist should integrate the interpretation of the
batch and probe mass spectra obtained on a particular sample to provide one
report describing sample chemistry. Details of quantitation of LRMS data
are too numerous to be addressed in this manual.
Interpretation of the mass spectra is guided by knowledge of the LC
separation scheme, the IR spectra, and other information about the source.
In reporting the results of the LRMS analysis, the basic philosophy is to
present increasingly more specific data as the complexity (or simplicity) of
the spectra will allow. The first level of reporting is to ident'ify compound
classes. If possible, or appropriate, one should then attempt to identify
the subcategory compound classes present in the fraction. Finally, specific
compounds should be identified, if possible to do so from the spectra.
Where possible, the molecular weight range and composition of each category
should be estimated with a rating of 100 = major, 10 = minor, and 1 = trace.
It should be possible, using this methodology, to account for nearly
all observed species by selection from a relatively small list of compound
categories and subcategories. A tentative list of such categories has been
assembled in Table 17. The primary reference for selecting these categories
was the MEG list, which seems to do an adequate job of representing all
probable major compound classes. Some few categories were not in the MEG
list and have been added here.
153
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TABLE 17. CATEGORIES FOR REPORTING LRMS DATA
en
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)
Most probable
LC fraction*
1
1
1
1
1,2
1,2
1,2
2,3
2,3
2,3
4,5
2,3
2,3
2,3
4
4
4
4
3,4
4
4
4
6
6
6
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
Carboxyl ic acids
Silicones
Phosphates
Most probable
LC fraction*
6
6
6
6
6
6
6
6
6
6
6
4
6
6
6
6
4
7
6
6,7
2,3,4
5,6,7
*Possible assignments. Fractions 4-5, 5-6, 6-7 generally overlap to a considerable extent. Also, addi-
tional components of a particular molecule may cause it to elute in an LC fraction other than that ex-
pected. For example, a short-chain ester would probably elute in LC fraction 5 or 6 whereas a long-
chain ester would elute in Fractions 3 or 4.
-------
The list in Table 17 is also organized somewhat differently than the
MEG list to be more compatible with the nature of the mass spectrometry
data. It should be strongly emphasized that the list probably does not
include all identifiable compound categories. If interpretation of the
spectra yields the identification of a category not included in this table,
the category should be reported. At the same time, EPA/PMB should be noti-
fied of the need to add that category to the list. It will be possible in
most cases to identify the spectra in terms of the compound categories
listed in Table 17, but one should avoid force fits if another category
seems more appropriate.
Interpretation of the mass spectral data should take full advantage of
all other information known about the sample source, i.e., LC fraction and
IR spectra. Since the LC separation does a reasonable job of dividing
compound classes, the categories listed in Table 17 have been listed in
order of their possible elution from the LC column. Where possible, some
indication has been made as to the LC fraction in which the category might
elute. These fraction assignments are known to be correct in some cases and
are only estimates in others. Sometimes the sample characteristics will
have minor effects on the fraction elution behavior. Again, the LC fraction
indications should only be taken as a guideline. Figure 33 gives a completed
example of a reporting format for the LRMS data. Blank forms may be found
in Appendix A.
It is once again emphasized that interpretation of the LRMS data is
best done using all available information, such as what one knows about the
chemistry of the source being sampled, what species generally elute in the
LC fraction being examined, and functional group data derived from the IR
spectra.
9.5 ORGANIC ANALYSIS SUMMARY TABLES
At the end of the Level 1 organic analysis procedure, there will be an
LC report, seven IR reports, and up to seven LRMS reports for each organic
extract or neat organic sample. This is an unwieldy body of data from which
to make a decision. The first step in reducing these data to a workable
form is to prepare a single table that summarizes the organic analysis
155
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LRMS REPORT
SAMPLE: H-3-LC6
Major Categories
Intensity
100
100
10
10
10
Category
Ke tones
Heterocyclic Nitrogen Compounds
Esters
Carboxylic Acids
Phenols
MW Range
180-280
167-253
Sub-Categories, Specific Compounds
Intensity
100
100
10
10
10
10
10
10
10
10
10
10
10
Category
Acridine
Fluorenone
Phenol
Cresol
Ben zoic Acid
Carbazole
Me thylacridine
Me thv 1 f luo renone
Anthraquinoline
Benzan throne
Dibenzofluorenone
Dibutylphthalate
MP fhy 1 Tipn 7.ffn f_h ron e
m/e
179
180
94
108
122
167
193
194
229
230
280
278
244
Composition
CT3H9N
CJ.AO
C6H6°
C?HQ0
C7Hfi02
C12H9N
C14H11N
C14H10°
C17HUN
C17H10°
C21H12°
C16H22°4
C18H12°
Other
Figure 33. Sample LRMS report.
156
-------
results for each extract. Figure, 34 illustrates the organization of this
table and the following paragraphs describe the various entries.
Space is allotted in the table heading for a sample identification
code. It is assumed that each laboratory will have devised its own coding
system (see Chapter 2) for uniquely identifying the various samples. It may
be desirable to include the date, the name of the analyst, or other similar
information.
The body of the table includes one column for each of the LC fractions
and one column for summing the data. The first set of data entries is the
quantitative analysis, transcribed from the LC report. The calculated total
organic loading corresponding to each fraction is entered in the first row.
This value is used in estimating the abundance of the various organic com-
pound classes. The next two rows contain the estimated TCO and GRAV values
to indicate the distribution of total volatile (bp 1QO°-300° C) and nonvola-
tile (bp >300° C) organic materials. This information can be useful later
in the selection of appropriate decision criteria (Level 1, MATE, etc.)
values for comparison with the Level 1 results. The results of the compound
category analysis (primarily from LRMS data) are summarized in the bottom
columns.
For those LC fractions that contained sufficient quantity to have been
analyzed by LRMS, the results of the LRMS analyses are summarized in the
table as follows: The major categories present in LC fraction 1 are listed
at the left-hand side of the table and the approximate intensity (100, 10,
or 1) for each category is entered in the LCI column. To convert the LRMS
intensity index to a concentration estimate for each organic compound cate-
gory, the individual intensity value is divided by the sum of all intensities
for the LC fraction and then multiplied by the total organic loading (mg/m3)
estimated for the fraction. This procedure is then repeated for the other
LC fractions. Examples are worked in Figure 35 for two LC fractions, LC2
and LC4, of the same XAD-2 extract.
The results presented in Figure 34 illustrate the considerable overlap
in chemical class composition that can be expected between some fractions in
the Level 1 LC scheme. As noted earlier, this is not a high resolution
separation technique and the various compound categories cannot be uniquely
157
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ORGANIC EXTRACT SUMMARY TABLE
Sample Sorbent Extract-ll-3
Total Organics, mg
TCO, mg
GRAV, mg
LCI
18.2
5.2
13.
LC2
22.3
19.
3.3-
LC3
253
73.
180.
LC4
29.7
6.7
23.
LC5
11.0
3.7
7.3
LC6
46.3
5.3
41.
LC7
15.1
0.1
15.
2
390
110
280
Category Assigned intensity--mg/, (m3, L, or kg)*
Sulfur
Aliphatic HC's
Aromatics— Benzenes
Fused Arom 216
Fused Arom 216
Heterocyclic S
Heterocyclic N
Carboxylic Acids
Phenols
Esters
•
„
*Concentration for gas samples mg/mj, for liqui
actual m3, L, or kg value.
^Estimated assuming same relative intensities as L
100-0.6
10-0.06
10-0.06
100-0.6
10-0.06
10-0.06
100-4
100-4
10-0.4
d samples = mg/L, for solid samples = m
C6, since IR spectra of LC5 and LC6 are
100-0.5
100-0.5
10-0.05
10-0.05
g/kg. Fill in
very similar.
-0.1*
-0.1*
-0.1 f
-0.01*
-0.01*
100-0.7
10-0.07
100-0.7
10-0.07
10-0.07
10-0.02
100-0.2
10-0.02
10-0.02
O.ff
0.06
0.06
5.
5.
0.5
1.
0.3
1.0
0.1
0.08
on
00
Figure 34. Organic extract summary table.
-------
LC 2
Total organics = 0.57 mg/m3
Aromatic HC's-benzenes 10
Fused Arom <216 MW 100
Fused Arom >216 MW 10
Heteroyclic S Compounds 10
LC 4
Total organics =6.6 mg/m3
Fused Arom <216 MW 100
Fused Arom >216 MW 100
Heterocyclic S Compounds 10
Heterocyclic 0 Compounds 10
en
Calculation of Concentration Estimates by Category
intensities =130 S intensities = 220
Aromatic HC's - benzene: y^j- x 0.57 = 0.04 mg/m3
100
Fused Arom <216 MW:
Fused Arom >216 MW:
x 0.57 = 0.4 mg/m3 Fused Arom <216 MW:
x 0.57 = 0.04 mg/m3 Fused Arom >216 MW:
100
x 6.6 = 3 mg/m3
x 6.6 = 3 mg/m3
Heterocyclic S Cmpds: -r^g- x 0.57 = 0.04 mg/m3 Heterocyclic S Cmpds: ^ x 6-6 = 0-3
Heterocyclic 0 Cmpds:
10
x 6.6 = 0.3 mg/m3
Figure 35. Sample calculations of concentration estimates from LRMS data.
-------
assigned to particular LC fractions. The data do show the expected trend,
in that LC2 is relatively richer in light aromatics (benzene and fused
species with MW <216) than is LC4. The fact that adjacent LC fractions can
be expected to show gradual changes in chemistry can serve as a useful guide
for the analyst in detecting contamination. Very abrupt changes in apparent
composition or the appearance of a compound class in an entirely unexpected
fraction (i.e., phthalates in LC2 or paraffins in LC6) should be regarded
with suspicion.
The overlap between fractions can also be used in estimating the composi-
tion of those fractions that did not contain sufficient material to trigger
an LRMS analysis. For any LC fraction that was not analyzed by LRMS, it is
suggested that the IR spectrum be compared with the IR's of the adjacent
fractions. If a close correlation is found between two IR spectra, then
this, together with the known behavior of the LC scheme, suggests that the
two LC fractions have similar, though not identical, qualitative composi-
tion. It is therefore suggested that the total organics in the non-LRMS LC
fraction be distributed over the same classes and in the same proportion as
was done for the adjacent LC fraction whose IR spectrum was the best match.
The error introduced by this procedure into the overall description of
sample chemistry will be small, since only fractions with small amounts of
material are excluded from the LRMS.
Concentrations estimated by this procedure should be identified with an
asterisk in the organic extract summary table and an explanatory footnote
should be included.
For those LC fractions for which only IR data are available, the proce-
dure for estimating concentrations by compound class is as follows:
1. List all categories from Table 17 that could be in that fraction.
2. Assign a weighting factor of 100 to each category that appears to
be present in the sample based on the IR spectrum.
3. Assign a weighting factor of 10 to each category for which func-
tional groups were not identified.
Then, in the absence of evidence to the contrary, assume that cate-
gories with an intensity of 100 may constitute up to 50 percent of the total
sample and those with an intensity of 10 up to 10 percent. Clearly, this
160
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procedure may "account for" more than 100 percent of the total sample.
However, this conservative method of estimation seems necessary because it
is not always possible to determine from the IR spectrum of a mixture alone
how the various functional groups are assembled into molecules or classes.
Table 18 illustrates this procedure for an LC5 sample, assuming only IR
and LC data were available. Concentrations estimated on the basis of IR and
LC data only should be footnoted with a dagger in the organic extract summary
table and an explanatory footnote should be included.
Once concentrations have been estimated for all compound categories
identified in the seven LC fractions for a particular organic extract, or
neat organic liquid, these values are summed across each row of the table.
(See Figure 34.) This procedure condenses the information obtained on the
various LC fractions to provide an integrated description of the chemical
composition. In the case of liquid and solid samples, the summation column
represents the total concentration/compound category information for the
stream sampled. For gaseous streams, the summary report for each component
of the SASS train must be added to determine the stream composition, as was
shown in Table 15.
9.6 QUALITY CONTROL IN LEVEL 1 ORGANIC ANALYSIS
This discussion has been written for the analytical chemist, who can be
presumed to be familiar with generally accepted standards of good laboratory
practice. It is worthwhile, however, to reemphasize the importance of some
procedures, in addition to sample preparation and analysis per se, which
have a very significant impact on the overall quality of the analytical
results. Some of those procedures, in particular those related to prevent-
ing and/or recognizing sample contamination, are especially critical in a
Level 1 environmental assessment.
To insure adequate data quality, it is essential that blanks (controls)
be analyzed along with the samples, as discussed in Chapter 2. There is no
reliable way to identify spurious results and/or sample contamination other
than by finding the same contaminant in a control sample.
161
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TABLE 18. ESTIMATION OF FRACTION COMPOSITION FROM IR AND LC DATA ONLY
Sample LC 5
IR Report
Wave number
cm l
3,400
3,050
2,850-2,950
2,230
1,700
1 t
^ 1,600
1,530
1,420-1,450
1,050-1,300
700-850
I
S
M
S
M
S
S
M
S
M
S
Ass i gnments/comments
OH or NH (broad)
Aromatic CH
Aliphatic CH
C=N or CsC, cyanates or
isocyanates
Ketone, carboxylic acid,
aldehydes
Conj. C=C or aromatic
C=N, N-N02, C-N=0,
Carboxylate
C=N, C-N02
CH3, NH4+, CH2, Si-phenyl
carbonates
Alcohol C-0, phenol C-0,
ether C-0, C-F, various
P-0 compounds, various Si-0
or Si-C compounds
Subst. benzene rings, some
olefinic C-H, C-C1 , CF-CF,
some peroxides
Total Organics = 0
Categories most probable
in LC 5
Heterocyclic N compounds
Heterocyclic S compounds
Sul fides, disul fides
Nitriles
Ethers
Aldehydes, ketones
Nitroaliphatics
Alcohols
Nitroaromatics
Amines
Phenols
Esters
.28 mg/m3
Assigned
weighting
factor
100
10
10
100
100
100
100
100
100
100
100
10
Estimated
possible
concentration
(mg/m3)*
0.14
0.03
0,03
0.14
0.14
0.14
0.14
0.14
0.14
0.14
0.14
0.03
Total organics = 0.28 mg/m3.
-------
Control sample, of course, means more than a simple reagent blank for
the analysis itself. The control sample and its handling throughout the
laboratory sequence should be identical to the real sample and Us handling,
except that the real sample has been exposed to a process stream in a sam-
pling procedure. For instance, an unexposed XAD-2 cartridge must be dumped,
homogenized, and a 5-g aliquot reserved for the Parr bomb ashing and trace
element assays. The remainder must be Soxhlet extracted and the extract
subjected to the entire organics analysis sequence.
The procedures for cleaning the XAD-2 resin prior to use are specified
in Appendix B. The quality control checks described in the appendix should
be applied to each batch of resin before it is used in a field study.
Each lot of organic solvent (i.e., each new batch number) must be
checked for contamination. A volume of solvent equivalent to that used in
sample extraction should be evaporated to dryness. The residue should be
weighed and examined by IR. If any significant quantity of organic contam-
ination is found, the solvent batch must be redistilled or rejected entirely.
Solvents used should be Burdick and Jackson "distilled in glass" or equiva-
lent quality. Note that use of chemicals of the specified grade does not
eliminate the necessity of performing checks on the quality of each new
batch of material used. However, use of high-quality reagents is important
to minimize the probability of acquiring unsatisfactory lots of material,
which would require repurification or replacement. Sodium sulfate and
silica gel used in the LC separation will frequently require cleanup by
extraction with organic solvent prior to use, as described in Section 9.4.4.
These controls and blanks should permit the analyst to identify the
source of any background contaminant and to make corrections to the results
of sample analyses. If contamination is excessive (more than 10 percent of
the sample level), the source should be traced and the contamination elimi-
nated, if possible. Note that silicones (from lubricants/sealants) and
phthalates (from plastics) are major potential interferences and must be
avoided entirely in collection, storage, and handling of samples for organic
analysis.
163
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CHAPTER 10
PARTICULATE MORPHOLOGY AND CLASSIFICATION
10.1 INTRODUCTION (refs. 71, 106-113)
The solid samples taken in Level 1 environmental assessment studies
(fly ash, SASS samples, fugitive emissions, slags, etc.) have physical
properties that are extremely useful in classifying their origins and/or
assisting in evaluating their pollution potential. These physical prop-
erties are readily determined by personnel trained in using basic light and
polarized light microscopy techniques. For example, a photomicrograph of
glassy spheres from combustion source effluent material suggests the pres-
ence of inorganic matter transformed at high temperature. Information on
the refractive index, size, and inclusions further defines the probable
material. Similarly, fugitive emission catches may be compared with feed
stock materials and the various particulate process effluents for a good
idea of the type and source of these emissions.
10.2 HANDLING PARTICULATES FOR MICROSCOPIC EXAMINATION
Since analytical determinations are actually made on nanogram quanti-
ties of the material, care must be taken to avoid introducing contamination
during sample procurement, handling, storage, and preparation. For large
solid samples, such as slags and coals, a representative portion must be
chipped and ground to a fine powder prior to the examination. A description
of all size reduction procedures must accompany any particulate characteri-
zation. Conversely, for solid samples of fine particulate matter such as
SASS cyclone catches, fly ash, etc., care must be taken to avoid crushing or
grinding the individual particles prior to examination. For suspended
solids in liquid, microscopic examination may be performed on the neat
sample and on evaporated deposits on a slide.
164
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10.3 EQUIPMENT SPECIFICATIONS
Adequate observations of particles may be made using any of a variety
of good compound microscopes with the following minimum requirements. The
microscope must have strain-free achromatic lenses with a numerical aperture
rating for the objective lens of less than 1/100 x the total system magnifica-
tion. Objective lens magnifications of X-10 and X43 are sufficient while
that of the ocular should be X10 or greater. The microscope should have a
uniform illumination source. Polarized light microscopy must be performed
using an instrument with a rotating stage having a marked scale or substage
polarizer and analyzer lenses. All combinations of lenses and camera attach-
ments should be calibrated for dimensional analysis with an ocular graticule
or sealer and an etched stage micrometer.
10.4 MOUNTING OF SAMPLE MATERIALS
Sample mounting techniques have a great influence on the appearance of
the sample materials being viewed. There are three procedures that shall be
used to examine a solid sample. The first is dry mounting, which provides
the least chance for introducing artifacts into the preparation and the best
condition for observing true reflected light. Deposit about a milligram of
well-mixed sample and spread it about the center of the slide with a needle
in concentric motion. The ideal area coverage of the material in the micro-
scope field would be about 5 percent. View the slide without a covers!ip.
The particles should be separated, not clumped or aggregated.
A second mounting procedure entails mixing the sample with a drop of
high refractive index (RI) mounting material such as Canada balsam (RI =
1.535). This may allow better definition of shape and size.
The third mount is the microscopist's choice. He or she may choose to
blank out certain particles or background interference by using a mounting
medium with a refractive index that is within 0.002 of that material. Thus,
a quartz fiber filter with a 1.460 RI will be rendered optically transparent
when mounted in a medium with a similar index of refraction. All other
material with a higher or lower RI will be visible when it is trapped on the
filter. Given different sample types, the mounting media would be chosen to
accentuate other special features.
165
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A fresh preparation should be made for analytical determinations since
sample changes, such as aggregations, color change, etc., may occur over
time in prepared material. Permanently mounted preparations should be kept
on file for future reference along with any photograph locator coordinates
to specific fields.
10.5 SAMPLE VIEWING
Mounted samples should first be viewed under low power (i.e., with
4-10X stereoscope) followed by higher magnification for general orientation
and to determine the samples' particulate types and size classes. The next
step involves a description of each specific type of particle present and an
estimate of its abundance as a percentage of the total material present.
This description should include shape, preliminary sizing (range), color of
transmitted light, color of reflected light (if available), surface features,
morphology, aggregation, transparency, cleavage, etc. A summary sheet as
shown on page A-46 should report all aspects of each particle type along
with a definition of the viewing system used in examining the sample. Any
questionable determinations should be noted with qualifying comments to
alert the reader to the possibility of alternate interpretations. The
analyst should make any other observational comments secondary to the above
requested class characterization information. Other comments might include
a tentative particle identification if accompanied by supportive evidence.
The primary objective again is to achieve particle classification and charac-
terization with secondary emphasis on identification. Level 2 investigation
will provide more detailed size analysis and positive particulate identifi-
cation.
10.6 GRAPHIC ILLUSTRATIONS
Photomicrographs of the three sample preparations provide good documen-
tation of sample characteristics and should be included in the particle
description report. High contrast black and white film may be used for
shape definition and enumeration. Color film (polaroid or photomicrographic)
is required for polarized light photomicrographs and can also be used for
the other micrographs. Provide a tick mark as a sealer on prints, i.e., 1
urn =1 1 . In all instances, the mounting and viewing specifications must
be included to provide background for the graphic interpretation.
166
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CHAPTER 11
BIOLOGICAL ASSESSMENT
11.1 INTRODUCTION
A principal role of the Industrial Environmental Research Laboratory in
environmental protection is to assure that the types and levels of indus-
trial emissions that are regulated are limited to those that might prove
harmful to ecology or health. One of the most effective means of providing
this information is through direct biological testing of the industrial
process emissions for their toxic, mutagenic, or other adverse effects upon
sensitive organisms and test systems. Biotesting has not been developed to
the extent of being an absolute criterion for site clearance or for estab-
lishing regulatory status. Rather, these procedures complement the chemical
and physical investigations in the Level 1 phased approach by providing a
selective, biologically integrated appraisal of complex sample reactions
with various test systems. The combined information from the respective
areas of investigation—physical, chemical, and biological—will permit a
rational identification of sources of greatest environmental concern. From
this information base, further testing or control activities can be effec-
tively planned.
The following discussion outlines the principles of the biological
testing procedures. Result report forms for the various biological tests
are included in Appendix A of this manual to further illustrate the nature
of the Level 1 biological assessment. Additional forms and details of the
procedures are found in the IERL-RTP Procedures Manual: Level 1 Environ-
mental Assessment Biological Tests for Pilot Studies, EPA 600/7-77-043 (ref.
114) and its revisions. Testing must be performed in approved laboratory
facilities by qualified and experienced professionals adhering to strict
quality control measures. Samples must be tested as soon after being taken
as possible.
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11.2 SAMPLING
Biological testing for environmental assessment Level 1 purposes in-
volves a survey technique using extract and whole sample incorporation of
representative solids, liquids, or gaseous discharges. The diverse sample
types and selective test systems used in their characterization are sum-
marized in Figure 36. General guidelines for sampling and sample handling
are presented in the biological test manual and in the preceding chapters of
this manual. Precise instructions for obtaining samples and performing
testing cannot be produced to cover every circumstance encountered in envi-
ronmental assessment testing; however, sampling methods used for acquisition
of samples presented in this manual are usually sufficient.
The following brief descriptions outline the various testing methods
applicable to the Level I environmental assessment survey. Selections of
appropriate test types for particular samples obtained must be made with the
combined guidance of the project officer and the biological procedures
manual. The interpretation of test results will be the responsibility of
the biological committee until such time as guidelines for this activity are
published. Results from the bioassays will be reported according to the
format explained in the biological procedures manual.
11.3 HEALTH EFFECTS TESTS
11.3.1 Salmonella/Microsome Mutagenesis Assay (Ames) (refs. 115-118)
The Ames test will be used as a primary screen to determine the muta-
genic potential of complex mixtures or component fractions. It has recently
been demonstrated that most carcinogens act as mutagens. The Ames Assay is
based on the property of selected Salmonella typhimurium mutants to revert
from a histidine-requiring state to prototrophy due to exposure to various
classes of mutagens. The test can detect nanogram quantities of mutagens.
It has also been adapted to mimic some mammalian metabolic processes by the
addition of aryl hydrocarbon hydroxylase activity from a mammalian liver
9,000 G microsomal fraction (S-9). In extensive testing, the Ames assay has
demonstrated 90 percent accuracy in detecting known carcinogens as mutagens.
Certain known carcinogens are negative (e.g., asbestos and metals) or weakly
positive in the test. False positive results are also known—substances
168
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SAMPLE FOR BIOLOGICAL ANALYSIS
GASES AND SUSPENDED
PARTICULATE MATTER
GASEOUS
GRAB SAMPLES
CTi
PARTICIPATES
> 3 Aim
(MICROBIAL
MUTAGENESIS)
(CYTOTOXICITY)
(STRESS ETHYLENE)
SORBENT
EXTRACT
AQUEOUS
ORGANIC)
•3 urn
EXTRACTED WITH
METHYLENE CHLORIDE
MICROBIAL
MUTAGENESIS,
RODENT ACUTE
TOXICITY.
CYTOTOXICtTY,
SOLIDS
MICROBIAL
MUTAGENESIS,
CYTOTOXICITY
MICROBIAL MUTAGENESIS,
CYTOTOXICITY,
RODENT ACUTE TOXICITY,
ALGAL BIOASSAY,
FISH BIOASSAY,
INVERTEBRATE BIOASSAY
v>
•a
30
m
•o
J*
MICROBIAL
MUTAGENESIS,
CYTOTOXICITY,
RODENT ACUTE
TOXICITY
ALGAL
BIOASSAY,
FISH
BIOASSAY
INVERTEBRATE
BIOASSAY
NOTE: BIOLOGICAL TESTS SHOWN IN PARENTHESES ARE OPTIONAL.
Figure 36. Biological analysis overview.
-------
that are mutagenic in the Ames system but are noncarcinogenic in mammals.
Continued improvement of the present bacterial strains, addition of new
strains, and revaluation of the conventional animal carcinogenesis data are
expected to reduce this level of test error even further in the near future.
11.3.2 Clonal Toxicity Assay
In some cases, a toxicity assay is employed for comparative purposes
utilizing an appropriate cell type, e.g., CHO cells. This technique involves
the plating of a specified number of cells per tissue culture dish, generally
100 to 1,000 in increments of 100. Following cell attachment, replicate
plates are exposed to particulate or soluble (aqueous or limited organic)
toxicants for 24 to 48 h. The cultures are then washed free of toxicant,
resupplied with fresh growth medium, and allowed to develop discrete "clonal"
colonies of cells. After 10 to 16 days (time depends upon the cell line),
the cultures are fixed, stained, and counted,
11.3.3 Cytotoxicity Assays
Cytotoxicity assays employ mammalian cells in culture to quantitatively
measure the cellular metabolic impairment and death resulting from in vitro
exposure to soluble and particulate toxicants. Mammalian cells derived from
various tissues and organs can be maintained as short-term primary cultures
or, in some cases, as continuous cell strains or lines. The Cytotoxicity
assays, available as part of Level 1 analysis, employ primary cultures of
rabbit alveolar (lung) macrophages (RAM) and maintenance cultures of strain
WI-38 human lung fibroblasts. The alveolar macrophage constitutes an essen-
tial first line of pulmonary defense by virtue of its ability to engulf and
remove particulate materials that are deposited in the deep lung. It is
appropriate, therefore, that this cell type be used to define the acute
cellular toxicity of airborne particulates and associated chemicals. It has
been possible to "rank" the toxic response to a series of industrial particu-
lates collected on a cyclone sampling train similar to the SASS train (ref. 6).
The strain WI-38 human lung fibroblasts are perhaps the best characterized
diploid human cells available for Cytotoxicity screening. These cells exhibit
the major pathways of DNA, RNA, and protein synthesis common to all dividing
cells and can be shown to possess a number of inducible enzyme systems.
170
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11.3.4 Acute In-Vivo Test in Rodents
Since the major objective of the Level 1 biological testing procedure
is to identify toxicology problems at minimal cost, it is recommended that a
two-step approach be taken to the initial, in vivo toxicological evaluation
of unknown compounds. The first is based on the quanta! (all-or-none)
response of 10 rats to a single 10-g/kg dose administered by gavage. Toxico-
logical effects are also noted over the following 14-day period. Normally,
the quanta! test is used to determine the necessity to carry out the quanti-
tative assay. Should one or more of these test animals die or exhibit gross
toxic effects in this experiment, a second, more extensive test involving a
quantitative (graded) response may be performed. In this series, 80 rats
are divided into groups, each of which receives a fraction of the original
dose. LDj-Q and other toxicological information is again noted over the
following 14 days.
11.4 AQUATIC ECOLOGICAL EFFECTS TEST
11.4.1 Freshwater Algal Assay Procedure: Bottle Test
An algal assay is based on the principle that growth is limited by the
nutrient that is present in shortest supply with respect to the needs of the
organism. The test is designed to be used to quantify the biological re-
sponse (algal growth) to changes in concentrations of nutrients and to
determine whether or not various effluents are toxic or inhibitory to algae.
These measurements are made by adding a selected test alga to the test water
and determining algal growth at appropriate intervals.
11.4.2 Bioassay with Unicellular Marine Algae
The community of unicellular algae is a very important constituent of
marine ecosystems because of the photosynthetic production of most of the
food and oxygen used by other members of the community. It is comprised of
a variety of species that have different growth rates, photosynthetic rates,
nutrient requirements, etc. Thus, relevant environmental parameters regu-
late species composition and diversity.
171
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This sensitivity to environmental changes is used as a test index.
Species may be inhibited or stimulated by pollutants. In a community, a
pollutant may affect some species but not others, thereby causing changes in
species diversity and composition. This can be followed by changes in
composition of the animal community and altered routes of flow of energy and
materials. Often, the altered ecosystem is undesirable from the human
standpoint. In this test, selected marine algae species, such as Skeletonema
costatum, are exposed to waters or contaminants in question and the growth
response is monitored.
11.4.3 Acute Static Bioassays with Freshwater Fish and Daphnia
The fathead minnow (Pimephales promelus) is the primary vertebrate used
in all tests carried out under this protocol for the environmental assessment
studies. The invertebrate choice is Daphnia magna, which should be used if
additional toxicity data are desired or if it is impossible to use the
fathead minnow. These representative aquatic organisms will integrate
synergistic and antagonistic effects of all the components in the aqueous
test sample over the duration of their exposure. The test is scored by the
number of dead or affected organisms after a specified period, i.e., every
24 h after the beginning of the test. More frequent observations may be
desirable, especially at the beginning of the test.
11.4.4 Static Bioassays with Marine Animals
The method recommended for static bioassays on marine animals uses
juvenile sheepshead minnows (Cyprinodon variegatus) and adult grass shrimp
(Palaemonetes pugio or P. vulgaris) as the test species. These species
adapt easily to a wide range of salinity and temperature in static bio-
assays. This method has proven satisfactory for ranking industrial effluents
relative to their toxicity to other marine animals.
11.5 TERRESTRIAL ECOLOGY TESTS
Terrestrial bioassays have been developed relatively recently, and show
great promise in evaluating complex industrial effluents. These techniques
are under review by IERL-EPA, and their current status is subject to change.
Interested parties should contact the PMB staff of IERL or refer to the
172
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latest edition of the Level 1 Biological Tests Manual if there are questions.
11.5.1 Stress Ethylene/Foliar Injury Plant Response
This test is based on the well-known plant response to environmental
stress that involves the release of elevated levels of ethylene. Under
normal conditions, plants produce low levels of ethylene. By exposing
plants to various levels of gaseous effluents and subsequently quantitating
the ethylene released relative to the control conditions, the stress ethylene
release attributable to the effluent can be determined in a graded response.
11.5.2 Seed Germination/Seedling Growth Test
These tests allow evaluation of toxic chemicals from environmental
samples that are inhibitory to seed germination and root elongation. The
tests are well documented for pure compounds and have been validated for use
by the Office of Toxic Substances. The tests are particularly suited for
aqueous effluents and aqueous leachates from solid samples. The test evaluates
the effect of a sample on a variety of seed species; its advantages are that
it is short-term, inexpensive, and requires minimum space for testing.
11.5.3 Soil Respiration/Nitrogen Fixation Test
This combination of tests can be performed on any solid or liquid waste
material and is particularly applicable to material destined for overland
distribution or for landfill operations. The test is based on changes in
normal respiration of C02 by general microbial activity of a soil sample and
general ability of microbes to take up nitrogen surrogates. Soil respiration
and nitrogen fixation are classic tests best suited to detecting the severe
effects of toxic insults to soils.
11.5.4 Insect Bioassays
The objective of the insect bioassays being considered is to measure
the acute toxicity of a solid, liquid, or gaseous sample on sensitive insect
species. Two insect species are being considered for Level 1 biological
testing, the honeybee and the fruitfly- The advantages of insect tests are
their relative low cost, short-term analysis time, and small sample size
requirements.
173
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79. Ahearn, A., Ed. Trace Analysis by Mass Spectrometry. 1st ed. , Aca-
demic Press, New York, New York, 1972. 460 pp.
80. Javorskii, F. F. Anal. Chem. 46:2080, 1974.
81. Von Lehmden, D., K. Jungers, and R. Lee, Jr. Anal. Chem., 46:239,
1974.
82. Kessler, T. , A. Sharkey, and R. Friedel. Spark Source Mass Spectrom-
eter Investigation of Coal Particles and Coal Ash. Bureau of Mines
Technical Progress Report 42, Pittsburgh, Pennsylvania, 1971. 15 pp.
83. Jacobs, M. L., S. L. Sweeney, and C. L. Webster. In: Keystone Coal
Industry Manual. 1975 ed., G. F. Nielson, Ed., McGraw-Hill Mining
Publications, New York, New York, 1975. pp. 243-245.
84. Brown, R., M. L. Jacobs, and H. E. Taylor. American Laboratory, 4:29,
1972.
85. Brown, R., and H. E. Taylor. The Application of Spark Source Mass
Spectrometry to the Analysis of Water Samples. Proceedings of the
American Water Symposium No. 18, American Water Resources Association,
Urbana, Illinois, 1974. p. 72.
86. Bringham, K. A., and R. M. Elliott. Anal. Chem., 43:43, 1971.
87. Guidoboni, R. J. Anal. Chem., 45:1275, 1973.
88. Dean J. A., and T. C. Rains. Flame Emission and Atomic Absorption
Spectrometry in Components and Techniques. Vol. 2, Marcel Dekker,
Inc., New York, New York, 1971. Chapter 10.
180
-------
89. Angino, E. E., and G. K. Billings. Atomic Absorption Spectrometry in
Geology. Elsevier Publishing Company, New York, New York, 1967.
144 pp.
90. Yu, C. L. Atomic Absorption Analysis of Arsenic for Level 1. Docu-
ment No. 28055-6008-TU-OO, TRW Defense and Space Systems Group, Redondo
Beach, California, March 24, 1978 (Draft).
91. Sawicki, E. , J. D. Mulik, and E. Wittgenstein, eds. Ion Chromatographic
Analysis of Environmental Pollutants. Ann Arbor Science Publishers,
Ann Arbor, Michigan, 1978.
92. Boyoucos, S. A. Anal. Chem., 49(3):401, 1977.
93. Small, H. , T. S. Stevens, W. C. Bauman. Anal. Chem., 47(11):1801,
1975.
94. Mulik, J. , R. Puckett, D. Williams, and E. Sawicki. Anal. Lett.,
9(7):653, 1976.
95. Jones, P., A. Graffeo, R. Detrick, P. Clarke, and R. Jacobsen. Tech-
nical Manual for Analysis of Organic Materials in Process Streams.
EPA-600/2-76-072, U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina, 1976.
96. Levins, P. L. , A. B. Caragay, K. E. Thrun, J. L. Stauffer, and L.
Guilmette. Evaluation of Alternative Level 1 Organic Analysis Methods.
Draft Report on EPA Contract No. 68-02-2150, U.S. Environmental Pro-
tection Agency, Research Triangle Park, North Carolina, June 1976.
pp. 1-8.
97. ASTM Committee D-2. Petroleum Products-LPG, Aerospace Materials,
Sulfonates, Petrolatum, Wax. 1971 Annual Book of ASTM Standards, Part
17, D2887-70T, American Society for Testing and Materials, Philadelphia,
Pennsylvania, 1971. pp. 1072-1081.
98. Rao, C. N. R. Chemical Applications of Infrared and Raman Spectros-
copy. 1st ed., Academic Press, London, England, 1963. 683 pp.
99. Colthup, N. B., H. D. Lawrence, and S. E. Wiberley. Introduction to
Infrared and Raman Spectroscopy. 1st ed., Academic Press, London,
England, 1964. 511 pp.
100. Cross, A. D. An Introduction to Practical Infrared Spectroscopy. 1st
ed., Butterworth, Inc., Washington, D.C., 1964. 86 pp.
101. Kendall, D. N. Applied Infrared Spectroscopy. 1st ed., Reinhold
Publishing Corporation, New York, New York, 1966. 560 pp.
102. Reed, R. I. Applications of Mass Spectrometry to Organic Chemistry.
1st ed., Academic Press, New York, New York, 1966. 256 pp.
181
-------
103. Budzikiewicz, H., C. Djerassi, and D. Williams. Mass Spectrometry of
Organic Compounds. 1st ed., Holden Day, Inc., San Francisco, Cali-
fornia, 1976. 690 pp.
104. Imperial Chemical Industries, Ltd. Eight Peak Index of Mass Spectra.
1st ed., Mass Spectrometry Data Center, Alder Maston, Reading, United
Kingdom, 1970.
105. Texas A & M University. Selected Mass Spectral Data. API Research
Project No. 44, College Station, Texas, 1975.
106. McCrone, W. C., and J. C. Dilly. The Particle Atlas. 2nd ed., Ann
Arbor Science Publishers, Ann Arbor, Michigan, 1973. Volumes I-IV.
107. West, P. W. The Chemist Analyst, 34:76, 1945.
108. West, P. W. The Chemist Analyst, 35:4, 1946.
109. Herdon, G. Small Particle Statistics. 2nd ed., Academic Press, New
York, New York, 1960, 520 pp.
110. Orr, C., and J. M. Dalla Valle. Fine Particle Measurement, Size,
Surface and Pore Volume. 1st ed., Macmillan Publishing Company, New
York, New York, 1960. pp. 83-91.
111. Chamat and Mason. Handbook of Chemical Microscopy. Volume II, John
Wiley and Sons, New York, New York, 1959.
112. American Society for Testing and Materials. Recommended Practices for
the Analyses by Microscopical Methods. ASTM: Part 23 and 30, Phila-
delphia, Pennsylvania, 1973.
113. Shillaber, C. P. Photomicrography. John Wiley and Sons, New York,
New York, 1944.
114. Duke, K. M., M. E. Davis, and A. J. Dennis. IERL-RTP Procedures
Manual: Level I Environmental Assessment Biological Tests for Pilot
Studies. EPA 600/7-77-043, U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina, April 1977.
115. Ames, B. W., E. G. Gurney, J. A. Miller, and H. Bartsch. Proc. Nat.
Acad. Science, 69:3128, 1972.
116. Ames, B. W., F. D. Lee, and W. E. Durston. Proc. Nat. Acad. Science,
70:782, 1973.
117. Ames, B. W., W. E. Durston, E. Yamasaki, and F. D. Lee. Proc. Nat.
Acad. Science, 70:2281, 1973.
118. Ames, B. N., J. McCann, and E. Yamasaki. Methods for Detecting Carcino-
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Test. Mutation Research, 31:347-364, 1975.
182
-------
APPENDIX A
DATA SUMMARY FORMS
A-l
-------
I. GENERAL
Ditt of Survey
Company Name .
Address
PRETEST SITE SURVEY
Telephone
SIC Number
Name
CONTACTS
Title
Telephone
Process
Batch
Operating Schedule
or Continuous
Best Time to Test
Signature Required on Passes
Waivers
Description of Pollution Control Equipment and Operation
Name
MOTELS
Location
Rate
Telephone
R*(ttunnn Atnibhl*
Airport
Distance to Plant
A-2
-------
SITE MAP
A-3
-------
II. SAMPLING
A. Sample Typato be Collected:*
1. Raw Materials
2. Product
3. Make-Up Water
4. Fuel
Si Process Stream
& Scrubber Water
Individual Sample Points:
a. Description:
Location:
7. Ash
8. Water Effluent
9. Airborne Fugitive
10. Surface Fugitive
11. Control Equipment Effluent
12. Other
How to Sample: .
b. Description:
Location:
How to Sample:.
c. Description:
Location:
How to Sample:
d. Description:
Location:
How to Sample: .
e. Description:
Location:
How to Sample:
f. Description:
Location:.
How to Sample:
'Check type to be collected. Stack effluent described under Individual Sample Description.
A-4
-------
B. Stack Effluent
1. Stack Data
Properties of
Sampling Locations
Purpose of stack
Height ft.
Width ft (Top/Bottom)
Length ft.
Diameter at port ft., I.D.
Wall thickness in.
Material of construction
Existing Ports:
a. Size opening
b. Distance from platform
Straight distance before port
Type of restriction
Straight distance after port
Type of restriction
Environment
Work space
Ambient temperature °F
Average pitot reading, r^O, in inches
Approximate stack velocity ft/min.
Approximate std flow, ft^/min.
Approximate moisture % by volume
Approximate stack temperature °F
Approximate particulate loading gr/SCF
Approximate particle size
Approximate composition gases present
Approximate stack pressure ^0, in inches
Water sprays
Approximate dilution air
Elevator
Stack #1
Stack #2
Stack #3
Stack #4
,
A-5
-------
2. Sketch of slack to be sampled showing locations of port opening, water sprayers, flow interferences, dilution air inlets, and scaffolding
or platform erection dimensions. Attach photograph if available.
A-6
-------
III. SUPPORT MATERIALS
A. Available at Plant
1. Parking facilities
2. Electrical extension cords
1 Electrician
4. Ice
5. Weighing balance
B. Electricity Sources
1. Number of circuits
2. Amperage per circuit
1 Location of fuse box
6. Cleanup area
7. Laboratory facilities
8. Scaffolding
9. Restroom
10. Rope
4. Extension cord lengths
5. Adaptors needed —
C. To be Purchased or Rented
1. Ice
Location
2. Scaffolding
Height _
Vendor
Address
Telephone
Quantity
Telephone
Size
' Two 30-A circuits or four 15-A circuits are required to operate the SASS train.
A-7
-------
IV. SAFETY CHECKLIST
A. Medical:
1. Plant first aid available (yes/no)
If available give location of unit and telephone number.
2. Phone number for ambulance:.
1 Phone number for hospital: .
4. Comments:
B. Test Site Checklist (Check if OK)
\. Udders:
General conditions Rest stops Cage
Comments:
2. Scaffolds/Platforms:
General conditions Guardrails
Toeboards _ Screening .
Comments:
C. Personnel Protection Equipment (check if needed):
1. Safety glasses : Side shields
Face shields Goggles Hard hat
Safety shoes Electrical hazard shoes
Life belt and safety block Hearing protective devices Ladder climbing devices.
2. Respiratory equipment:
Air purifying Air supplied Self-contained
Other
3. Body protection:
Chemical protection garments.
Heat protective garments
Chemical gloves
Heat resistant gloves _
Other
D. Are Fire Extinguishers Available at Site ?
E. Special or Unusual Test Procedures and Safety Precautions Necessary:
A-8
-------
ORGANIC COMPOUNDS (bp <100° C)
Contractor
Simple Site
Type of Source
Test Number
Simple Description
Analyst Responsible
Calculations and Report Reviewed By
1. Column Flow Rate (mL/min)
1 Full Scale (mV)
5. Electrometer Set (A/mV)
7. Sample Size (ml)
9. Flame Flow Rates (mL/min): H?-
111 Attenuation
12. Observations
Sample Acquisition Date
.Time
Sample ID Number
Data Analyzed
Time
Report Date
Workup
2. Recorder Speed
4. Column Pressure (psi) -
6. Calibration Date —
8. Oven Temperature (°C)
Air
11. Range
Results: PPM value (in original sample) or I — interference; NC - not computed; NG - sample value below blank;
ND - not detectable (<2a blank or baseline).
Gas
.BC,
GCj
6C3
GC4
«C5
GC6
GC7
Uncorrected
Sum of Peak
Areas
,
Blank
Valve
Retention
Time
Corrected
Sum of Peak
Areas
Cone.
(%)
Sensitivity*
High/Low Calibration
Standards
Cone.
(ppm)
A-9
-------
IMOX FIELD DATA
Type nf Source
Sampling Location
Sample Number
Temperature
Analyst Responsible
Calculations and Report Reviewed By
Date Taken Time
Rarntnptrir , Statir Pressure
Date Analyzed Time
Report Date
Sampling Flask Number
(volume of flask plus valve, ml)
g (volume of acidic, oxidizing solution)
: (initial flask temperature, °K)
Ph ; (barometric pressure prior to sampling)
u,i —
APm j (manometer reading prior to sampling)
P; (absolute internal flask pressure prior to sampling) = Ph ; - &Pm;
i u,i 111,1
Tf (flask temperature at sample recovery, ° K)
Pjj f (barometric pressure at sample recovery)
APm f (manometer reading at sample recovery)
(absolute internal flask pressure at sample recovery) = P - AP
m f
A-10
-------
INORGANIC GASES ANALYSIS SHEET
Contractor .
Sample Site.
Sample Acquisition Date
Type of Source
Test Number .
Sample ID Number
Sample Description
Obtained By Grab:
.Yes
.No
Time Integrated From:
Original Sample Volume or Mass
Analyst Responsible
Date Analyzed
Time
To
Time
Calculations and Report Reviewed By
Type of Sampling Container
Report Date
Sampling Container Purged or Cleaned Prior to Sampling
A-ll
-------
SULFUR SPECIES
1. Column Flow Rate (mL/min).
3. Full Scale (mV)
5. Electrometer Set (A/mV)
7. Sample Size (ml)
9. Attenuation
11. Observations
12. Specify type of sampling container
13. Are sample responses bracketed with standards?
14. Analyst Responsible
15. Calculations and Report Reviewed By
2. Recorder Speed
4. Column Pressure (psi)
6. Calibration Date
8. Oven Temperature (°C)
10. Range
Date Analyzed
Report Date
Time
Gas
COS
HZS
so2
cs2
Unco meted
Sum of
Peak Areas
Blank
Value
Retention
Time
Corrected
Sum of
Peak Areas
Cone.
(%)
Sensitivity
High/Low
Calibration
Standards
Cone.
(ppm)
Results: PPM value (in original sample) or I • interference; NC - not computed; NG • sample value below blank;
NO • not detectable «2a blank or baseline).
A-12
-------
FIXED GASES
1. Column Flow Rate (mL/min)
3. Full Scale (mV)
5. Electrometer Set (A/mV)
7. Sample Size (mL) .
9. Attenuation
11. Observations
12. Analyst Responsible
13. Calculations and Report Reviewed By
2. Recorder Speed
4. Column Pressure (psi)
6. Calibration Date
8. Oven Temperature (°C)
10. Range
Date Analyzed
Report Date
Time
Gas
°2
C02
CO
«2
Uneorrected
Sum of
Peak Areas
Blank
Value
Retention
Time
Corrected
Sum of
Peak Areas
Cone.
<%)
Sensitivity
High/Low
Calibration
Standards
Cone.
(ppm)
Results: PPM value (in original sample) or I - interference; NC • not computed; NG • sample value below blank;
ND • not detectable «2 a blank or baseline).
A-13
-------
NOV ANALYSIS REPORT FORM
X
Sample =
Comments
1.1 Standardization
1.1.1 pH of standard solutions
1.1.2 A1 (absorbance of the 100 pg N02 standard)
A2 (absorbance of the 200 pg N02 standard)
A3 (absorbance of the 300 /Jg N02 standard)
A£ (absorbance of the 400 /ig N02 standard)
1.1.3 K_ (calibration factor)
= 100
= 100
A., + 2A2
3(
Date analyzed
Time
Analyst Responsible
Calculations and report checked by
Report Date
1.2 Test Solution Analysis
1.2.1 Vf (volume of flask plus valve, ml)
V, (volume of acidic, oxidizing solution)
Tj (initial flask temperature, °K)
(barometric pressure prior to sampling)
(manometer reading prior to sampling)
(absolute internal flask pressure prior to sampling) = f^ • - AP =
A-14
-------
1.12 Tf (flask temperature at sample recovery, °K)
(barometric pressure at sample recovery)
(manometer reading at sample recovery)
Pf (absolute internal flask pressure at sample recovery) = Pfa « - A? f
1.2.3 VSG (sample volume, dry basis, standard conditions, ml)
P • P
/
(
°-3858
Vsc =
1.2.4 Final test solution pH
A (test solution absorbance)
F (dilution factor, as needed to reduce the absorbance into the range of calibration
m (total jug N02 per sample)
= 2K.AF
I*
- (2) { ) ( ) ( )
m =
1.2.5 C (sample concentration, dry basis, standard conditions, mg/m )
m
Vsc
( )
A-15
-------
Sample Site
FUGITIVE EMISSIONS FIELD DATA
GENERAL
Type of Source
Sampling Location
Test Number _
Date Taken
Type of Sample: Air
Sample Description
Sample Number
Water
Analyst Responsible
Date Analyzed.
Time
Calculations and Report Reviewed By:
Report Date
SAMPLING DATA - AIR SAMPLE
Sampling Device
Size of High Volume Sample Filter
ANALYTICAL DATA - AIR SAMPLE
Sample Number
Sample Mass on
Particulate Filter
Gross
Tare
Net
Gross
Tare
Net
Gross
Tare
Net
Gross
Tare
Net
A-16
-------
Flow Rate _ Sampling Time
Type and Size of Adsorbent Bed
Sample Location: Upwind Downwind
Wind Speed _ Wind Direction
Ambient Temperature
Distance From Source ,
SAMPLING DATA - WATER SAMPLE
Sampling Device
Sample Volume ——
Composite Sample: Yes No
If Composite, Number and/or Volumes of Portions of Composite _ / —
Sample Description: Fluid Viscous Hot Cold : Flowing
Still Homogeneous Heterogeneous Color
A-17
-------
LIQUIDS FIELD DATA
GENERAL
Sample Site
Type of Source
Sampling Location
Sample Type: Aqueous Slurry Organic _
Sample Number Date Taken
Analyst Responsible
Calculations and Report Reviewed By Report Date
Sampling Device Sample Mass or Volume
Composite Sample: Yes or No .
If Composite, Number and/or Volume of Portions of Composite: /
Sample Description: Fluid Viscous Hot Cold Flowing Still
Homogeneous Heterogeneous Color
Sampling Problems
A-18
-------
FIELD WATER ANALYSIS
Contractor
Sample Site
Type of Source
Test Number
Sample Description
Analyst Responsible
Calculations and Report Reviewed By
Sample Acquisition Date
Sample ID Number
Date Analyzed
Report Date
Time
Parameter
Flow
PH
Cond
TSS
Hard
Alk
Acidity
NH3-N
N03--N
Cyanide
P04-P
so3
so4
Uncorrected
Sample Value
Blank
Value
Corrected
Sample Value
Sensitivity
High/Low Calibration
Standards or Con-
centration Added
Assigned
Concentration
m3/h
jumhos/cm
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
Results: Concentration measured in original sample on I - interference; NC - not computed; NG - sample value below blank;
NO - not detectable «ff blank or baseline).
A-19
-------
SOLIDS FIELD DATA
GENERAL
Sample Site
Type of Source
Sampling Location
Sample Type: Inorganic Organic __
Sample Number Date Taken
Analyst Responsible
Calculations and Report Reviewed by: Report Date
Sampling Device Sample Mass or Volume .
Composite Sample: Yes or No .
If Composite, Number and/or Volume of Portions of Composite: /
Sample Description: Homogeneous Heterogeneous Powder Small Pieces
Large Pieces Color Wet Dry
Sampling Problems
A-20
-------
SASS FIELD DATA
Plant
Date
Sampling Location
Source I.D
Run Number
Operator
Probe Length and Type
Nozzle, I.D.
Ambient Temperature
Barometric Pressure _
Static Pressure, (Pj) _
Filter Number(s)
Assumed Moisture, % —
XAD-2 Module Number
Meter Box Number
Meter AH
C Factor
Oven Number
Probe Heater Setting
Oven Setting
Reference AP
Calculations and Report Checked By
. Report Date
SCHEMATIC OF TRAVERSE POINT LAYOUT
READ AND RECORD ALL DATA EVERY MINUTES
TRAVERSE
point
NUHttR
TOTAL
AVEMOC
\
SAMPLING
TlMEjHIH
•
CLOCK TIKt
m HR CLOCK)
\
e
•
MS METER READING
°F
"l»
®
OUTLET
«.WF
•
PUHP
VACUUM
IN Hg
•
«
OVEN
TtMPCftATUR
°F
•
«
IWlHCfH
TCIPCRATURE
OF
&
®
tORBEHI
mf
TEHPERATURE
«f
®
0
PHOBI
IEKPEIU11KE
°F
®
®
COPMKIS
-------
EXAMPLE OF AN ACCEPTABLE SYSTEM OF
SAMPLE CODING WITH COMMENTS FOR SAMPLE PACKING SHEETS
1C 1 -3ju cyclone catch
3C 3-1 OM cyclone catch
10C > 10ju cyclone catch
PF-a Participate filter(s)
PR CH2CI2/Methanol probe and cyclone rinse
MR CH2CI2 organic module rinse
XR XAD-2 resin
XRB XAD-2 resin blank
CD-0 Neat condensate
CD-LE CH2CI2 extract of condensate
CD-AE Acidified, extracted condensate
HM HMO, module rinse
HMB HN03 blank
HI First (H202) impinger - Special handling. See Chapter 2
HIB First (HnO?) impinger blank - Special handling
Al 2nd and 3rd (APS) impinger composite
AM B 2nd (First APS) impinger blank
AI-2B 3rd (Second APS) impinger blank
MCB CH2CI2 blank
MMB CH2CI2/Methanol blank
FF Liquid (oil) fuel feed
CF Solid (coal) fuel feed
FA Fly ash
BA Bottom ash
A-22
-------
SAMPLE PACKING SHEET
ro
GO
Samp
Date
Shipp
Date
Carrie
• Site
Sampled
lid By
Shipped
r
Sample No.
Collected
(yes/no)
Date
Recovered /Prep
Time
Weight (g)
of Volume (mi)
< - . ••
IP M.imhor T«t NM"l^r
Invoice RlMmhff
n«t«> Rrrfnifd
Reeehied Ry
Hnnditinn
Field Adjustments/Observations
Signature
Page 3 of
-------
SAMPLE PACKING SHEET
ro
Sample Site _
Date Sampled
Shipped By
Date Shipped
Carrier
10 Number
Invoice Number
Date Received _
Received By
Condition
Test Number
Sample No.
MR
HM
1C
3C
IOC
PR
GC
GF
GP
PF-a
Collected
(yes/no)
Date
Recovered /Prep
Time
Weight (g)
or 'Volume (ra£)
Field Adjustments /Observations
Page 2 of
-------
SAMPLE PACKING SHEET
ro
en
Sample Sitt _
Date Sampled
Shipped By
Date Shipped
Carrier
ID Number
Invoice Number
Date Received _
Received By
Condition
Test Number
Sample No.
MCB
MAB
HFIB
HIB
A I -IB
AI-2B
XRB
CD-0
CD-LE
CD-AE
HI
AI
XR
Collected
(yes /no)
Date
Recovered /Prep
Time
Weight (g)
or Volume (m.0)
Field Adjustments/Observations
Page
of
-------
PARTICULATE LOADING DATA
D tie Weighed!
Oito Weighed G
Balance Used
Analyst Responsible
Date Analyzed
Time
Calculations end Report Reviewed By
Report Date
Give Gross (G), Tare (T). and Net (N) Weights and Units for All Applicable Samples
Sample No.
and Site Name
and Location
•
Particulate Filter
G
T
N
G
T
N
G
T
N
G
T
N
G
T
N
1(A Cyclone
G
T
N
G
T
N
G
T
N
G
T
N
G
T
N
3p, Cyclone
G
T
N
G
T
N
G
T
N
G
T
N
G
T
N
1(V Cyclone
G
T
N
G
T
N
G
T
N
G
T
N
G
T
N
Probe Rinse Solids
G
T
N
G
T
N
G
T
N
G
T
N
G
T
N
3>
on
-------
SASS ANALYTICAL DATA
Plant
Sampling Location_
Recovered By
Comments
Sample No.
Run No.
Recovery Date
Run Date
Analyst Responsible
Calculations and Report Reviewed By
Report Date
FILTERS USED
CYCLONES
No.
Used Pretared Container
(yes/no) (No.)
in
IMPINGER VOLUMES
Initial
Final
First (H202)
Second (APS + AgK03)
Third (APS + AgN03)
. TOTALS
mJl
Gain
SILICA GEL WEIGHTS
Initial
Final
J,
_g
_g
TOTALS
Gain
CONDENSATE
TOTAL VOLUME COLLECTED
Volume Neat
Volume Extracted
Volume CHC^ Extract (3 x
Extracted Condensate: pH Neat
Amount 967. HN03 added
pH Final
TOTAL GAIN
mi,
A-27
-------
SSMS ANALYSIS SHEET
Sample Sftp
Type of Snurre
Tart Numhpr
Sample Dfisr.riptinn
Analyst Responsible
Calculating and Repnrt Reviewed By
Instrument
Sfimplp Acquisition Datfi
Sample ir) Number
Date Analyzed Time
Rppnrf Hate
Resnlntinn
Sequential Exposure Factor Carbon Type Used for Electrode Preparation
Description of Multielement Calibration Standard
Internal Standard(s)
Original Sample Volume or Mass
Dilution Factor
Brief Description of Electrode Preparation
A-28
-------
3>
r\3
Time at
start and
finich
Photo-
plale
exposure
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Exposure
«10»
coulombs
Range factors
Int.
Man.
Meter
or
counter
Pulse
repetition
rate c/s
Pulse
length
microsec
Spark
volt
%
Magnet
current
mA
Accelerating
voltage
kV
Anal.
pressure
" torr "
Source
pressure
"torr "
,
Remarks
Operator:
-------
co
o
Element
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Indium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutecium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
Terbium
Gadolinium
Europium
Samarium
\leodymium
Praseodymium
Lin* Used
for
Estimate
(mass number)
Uncorrected
Sample
Value
Blank
Value
Corrected
Sample
Value
""
Assigned
Concentration*
At Source
Mass/Volume
mg/m3 or
W/L
Detection
Limit
•Results: fig/g (in original sample) or I - interference; NC • not computed; NG - sample value below blank; ND • not detectable «2o blank or baseline).
-------
I
Co
Element
Cerium
Lanthanum
Jarium
Cesium
iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Una Used
for
Estimate
(mass number)
Uncorrected
Sample
Value
Blank
Value
Corrected
Sample
Value
Assigned
Concentration*
At Source
Mass/Volume
mg/m3 or
WI/L
Diuction
Limit
* Results: jug/g (in original sample) or I - interference; NC - not computed; NG - sample value below blank; ND - not detectable «2o blank or baseline).
-------
I
CO
ro
Element
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulphur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
.ithium
lydrogen
Line Used
for
Estimate
(mass number)
Uncorrected
Sample
Value
Blank
Value
Corrected
Sample
Value
Assigned
Concentration*
At Source
Mass/Volume
rng/m^ or
WJ/L
Detection
Limit
•Results: jug/g (in original sample) or I - interference; NC • not computed; NG • sample value below blank; ND - not detectable «2a blank or baseline).
-------
AAS ANALYSIS SHEET
Contractor
Sample Site
Type of Source
Test Number
Sample Description
Original Sample Volume or Mass
Analyst Responsible
Calculations and Report Reviewed By
Sample Acquisition Date
Sample ID Number
Date Analyzed
Time
Report Date
Instrument Used
Wavelength Setting (nm)
Lamp Current (ma)
Fuel/Oxidizer Pressures (psi)
PM Voltage (volts)
Detection Limit fog)
Sensitivity (abs. units/ppm/
sample volume)
High/Low Calibration Standards (ppm)
Sample Aliquot Volume (mL)
Dilution Factor
Uncorrected Sample Aliquot Value (ppm)
Blank Value (ppm)
Corrected Sample Aliquot Value (ppm)
Assigned Concentration*
At Source Mass/Volume,
mg/m^orAtg/L
As
Hg
Sb
•Results: PPM value (in original sample) or I - interference; NC - not computed; NG - sample value below blank; ND - not detectable
«2a blank or baseline).
A-33
-------
Contractor .
Sample Site
1C ANALYSIS SHEET
Type of Source
Test Number
Sample Description .
Analyst Responsible
Calculations and Report Reviewed By
Instrument
Sample Acquisition Date
Sample ID Number
Date Analyzed
Time
Report Date
Eluent.
Column Flow Rate
Sample Size
Original Sample Volume or Mass
Observations
Pressure
Recorder Speed
Attenuator Setting
Multiple Standard Addition: Yes
No
A-34
-------
co
en
Ion
F ~
Cl~
Br~
NO^
NtfJ
so3=
soj
POf
Uncorrected
Sample Value
Blank
Value
Corrected
Sample Value
High/Low Calibration
Standards or Con-
centration Added
Dilution
Factor
Assigned
Concentration*
Detection
Limit*
Results: /ufl/L values (in original sample or I - Interference; MC
blank; ND - not detectable (<2 a blank or baseline).
major constituent, not quantified; NC - not computed; NG - sample value below
-------
LC ANALYSIS REPORT
Contractor
Sample Site
Type of Source
Test Number
Sample Description.
Original Sample Volume or Mass
Analyst Responsible
Calculations and Report Reviewed By
Acquisition Date
Sample ID Number
. Date Analyzed
.Report Date.
Time
Column Flow Rate
Observations
Column Temperature
Total Sample1
Taken for LC2
Recovered3
TCO
mg
GRAV
mg
TCO + GRAV
Total mg
Concentration
mg/ (m3, L, or kg)5
Fraction
1
2
3
4
5
6
1
Sum
TCO in mg
Found in
Fraction
Blank
'
Cor-
rected
Total4
GRAV in mg
Found in
Fraction
Blank
Cor-
rected
Total4
TCO +
GRAV
Total mg
Concentration
mg/
(m3,L, or kg)5
1. Quantity in entire simple, determined before LC
2. Portion of whole sample used for LC, actual mg
3. Quantity recovered from LC column, actual mg
4. Total mg computed back to total sample
5. Supply values for both sample size and concentration
A-36
-------
ANALYSIS REPORT
Contractor
881111116 Site Sample Acquisition Date
Type of Source
Test Number _ ^mpte ID Number.
Sample Description
Analyst Responsible Date Analyzed Time
Calculations and Report Reviewed By Report Date
Instrument Sample Cell Type
Utilized Max/Win Signal Intensity Values
Observations
A-37
-------
IR REPORT
SAMPLE:
Wave Number
- (cm'1)
Intensity
Assignment
Comments
A-38
-------
LRMS ANALYSIS REPORT
Contractor
831111118 Ste — Sample Acquisition Date
Type of Source
Test Number . _ amph , D Numbfir
Sample Description
Analyst Responsible Date Ana|yzed
.Time
Calculations and Report Reviewed By Report Date
Instrument __
Resolution
Sample Size Batch Inlet Probe Inlet
Observations
A-39
-------
LRMS REPORT
SAMPLE:
Major Categories
Intensity
Category
MW Range
Sub-Categories, Specific Compounds
Intensity
Category
m/e
Composition
Other
A-40
-------
ORGANIC EXTRACT SUMMARY REPORT
Contractor
Sample Site Sample Acquisition Date
Type of Source
Test Number Sample ID Number.
Sample Description
Original Sample Volume or Mass
Analyst Responsible — Date Analyzed _ Time
Calculations and Report Reviewed By _ _— Report Date .
A-41
-------
ORGANIC EXTRACT SUMMARY TABLE
Total Organics, mg
TCO, mg
GRAV. mg
LCI
LC2
LC3
LC4
LCS
LC6
LC7
2
Category
Assigned intensity - mg/ (m^, L, or kgr
i
-p»
ro
1 Concentration for gas samples = mg/m3, for liquid samples = mg/L, for solid samples - mg/kg. Fill in actual m^, L, or kg value.
-------
ALGAL BIOASSAY DATA SHEET
Sample ID Number
Test Date.
Date Sample Received
Test Number
Report Date
Culture Medium
pH of Medium
Temperature
Collection Data (Time-Date)
Illumination Source.
Other Pertinent Sample Information
Investigator
Calculations and Report Reviewed By
Intensity
Duration
RESULTS
Sample
Flask
No.
Cone.
INCUBATION TIME-DAYS
3
Cells/mL
Dry wt.
mg/L
Other
5
Dry st.
Cells/mL mg/L Other
7
Dry wt.
Cells/mL mg/L Other
(Etc. for 9, 13,
17,21 Days)
REMARKS:
Maximum Specific Growth Rate:
Maximum Standing Crop:
EC SO (12 Day or Other Days of Importance)
A-43
-------
BIOASSAY RECORD SHEET
Dilution Water Analysis
Date
Hardness
mg/L
as CaCoj
Alkalinity
mg/L
as CaC<>3
Specific
Conductance
PH
Suspended
Solids
mg/L
TOC
mg/L
Un-ionized
Ammonia
mg/L
Residual
Chlorine
mg/L
Total Organo
Phos. Pesti-
cides
mg/L
Total Organo
Chlor. Pesti-
cides + PCB's
mg/L
-Ji.
-Ji.
-------
MICROSCOPIC PARTICLE CHARACTERIZATION
Contractor
83011118 Slte Sample Acquisition Date
Type of Source
Test Number Sample ID Number
Brief Sample Description
Wlicroscopist Date Analyzed
Calculations and Report Reviewed By Report Date
Prepare a separate data sheet for each mounting or particle type.
Gross Sample Appearance ,
A-45
-------
Article Type
Percent by Number
Materials Preparation
Mounting Media _
Microscope Used: _
Illumination: Type
PHYSICAL PROPERTIES
Shape
% Estimated.
Objective Lens
Ocular Lens
Source
Combined Magnification
Size Range of This Particle Type
Aggregation: Clustered
Homogeneity: Homogeneous
Heterogeneous
Inclusions _
Surface Texture: Glassy
Other
Other Comments
OPTICAL PROPERTIES
Transparent
, Distinct
, Other
Laminar
, Polycrystalline
, Smooth.
Porous.
, Rough
, Translucent
, Opaque
Color Observed from Transmitted Light
Color Observed of Reflected Light
Luster: Metallic , Adamantine.
., Vitreous
., Resinous
., Greasy
Brilliance: Splendent
Isotropic .
., Shining
, Glistening
., Glimmering
Dull
. Silky
, Anisotropic.
Refractive Index Estimate
Other
Birefringence Estimate.
Photographs Attached
or Negative #
Scale Indication
A-46
-------
Wl-38 CELLULAR TOXICITY TESTING
Sample ID Number
Date Sample Received
Description of Sample
Date Tested
Report Date
Passage of Cells
Seeding Population of Cells
Incubation Time
Incubation Temperature
EC5Q VALUES
Cell Count
Viability _
Viability Index
Protein
ATP
Other
Investigator
Calculations and Report Reviewed By
TEST RESULTS
Tube
No.
Test Sample
Cone.
wg/mL)
orfoL/mL)
pH
Initial
After
Incut).
Cell No. as
X of Control
Viable
Cells
Viability
Index
ATP
Protein
A-47
-------
ALVEOLAR MACROPHAGE TOXICITY TESTING
Sample ID Number
Date Sample Received-
Description of Sample
Date Tested
Report Date
No. Rabbits Used
Remarks About Rabbits
Total No. Cells Recovered _
Seeding Population of Cells
Incubation Temperature _
Calculations and Report Reviewed By.
DIFFERENTIAL
Macrophages
Neutrophils
Other
Incubation Time
ECCn Values _
Cell Count
Viability _
Viability Index
Protein
Other
Investigator
TEST RESULTS
Tube
No.
Test Sample
Cone.
Mg/mL)
orbiLVmL)
PH
Initial
After
Incun.
Cell No. as
% of Control
Viable
Cells
Viability
Index
ATP
Pratttn
A-48
-------
GENERAL FORMAT FOR RECORDING MUTAGENICITY DATA
Data Simple Roeihnd , .
Samnlt ID Number
Incubation Timpinrtnr*
tneuhatinn Start
Incubation End
Report Pat*
Datt Ttrted
Pat* R'pntwf
Comments, i.e.. Solvent Extraction or Sample Pretreatment etc.
InuKtigatnr Tettor Strain IU«H r.ln..l.tinn> .ml n.nnrt n.ui<««u< Rv
Test Condition Sample Type
......... Adjusted Index of
Revertants or colonies on Individual Plates Average Relative
Am^int Number Mumbor Roncat Roncat Averase Hevertants Mutagemcity
kg/plate) 1 2 3 4 1&2 3&4 1&2 3&4 1&2 3&4
Nanactivation Positive control
Solvent control
Sample Plate ID
Toxicity test
Induced activation
Positive control
Solvent control
Sample Plate ID
Toxicity test
-------
STATIC BIOASSAY RECORD SHEET
Sample ID Number
Investigator
Test Number
Source
Date Sample Received
Source of Dilution Water
Test Species
Date/Time Initiated
Date/Time Completed.
Temperature Range
Number Individuals Per Percent Waste
Calculations and Report Reviewed By
Start
Report Date
| Comments
Percent waste
DO
Temperature
pH
Specific
conductance
Number
surviving
% survival
DO
Temperature
PH
Number
surviving
% survival
DO
Temperature
PH
Number
surviving
% Survival
DO
Temperature
pH
24 hours
48 hours
96 hours
Control
•
*
LC50/EC50
,
* Method used for calculating.
A-50
-------
APPENDIX B
PREPARATION OF XAD-2 SORBENT RESIN
B-l
-------
APPENDIX B
PREPARATION OF XAD-2 SORBENT RESIN
B.I SCOPE AND APPLICATION
XAD-2 resin, as supplied by the manufacturer, is impregnated with a
bicarbonate solution to inhibit microbial growth during storage. Both the
salt solution and any residual extractable monomer and polymer species must
be removed before use. The resin is prepared by a series of water and
organic extractions followed by careful drying.
B.2 EXTRACTION
B.2.1 Method 1
The procedure may be carried out in a giant Soxhlet extractor, which
will contain enough XAD-2 for a single SASS module. An all-glass thimble
(55-90 mm OD x 250 mm deep [top to frit]) containing an extra-coarse frit is
used for extraction of XAD-2. The frit is recessed 10-15 mm above a crenu-
lated ring at the bottom of the thimble to facilitate drainage. The resin
must be carefully retained in the extractor cup with a glass wool plug and
stainless steel screen since it floats on the final solvent, methylene
chloride. This process involves sequential extraction in the following
order.
Solvent Procedure
Water Initial rinse with 1 L H20 for 1 cycle, then
discard H20
Water Extract with H20 for 8 hours
Methyl alcohol Extract for 22 hours
Methylene chloride Extract for 22 hours
Methylene chloride (fresh) Extract for 22 hours
B-2
-------
B.2.2 Method 2
As an alternate to Soxhlet extraction, a continuous extractor has also
been fabricated for the extraction sequence and is described in Figure B-l.
This extractor has been found to be acceptable. The particular canister
used for the apparatus shown in Figure B-l contains about 500 g of finished
XAD-2 or enough for more than three sorbent modules. Any size may be con-
structed; the choice is dependent on the needs of the sampling programs.
The XAD-2 is held under light spring tension between a pair of coarse and
fine screens. Spacers under the bottom screen allow for even distribution
of clean solvent. The three-necked flask should be of sufficient size (3 L
in this case) to hold solvent equal to twice the dead volume of the XAD-2
canister. Solvent is refluxed through the Snyder column and the distillate
continuously cycled up through the XAD-2 for extraction and returned to the
flask. The flow is maintained upwards through the XAD-2 to allow maximum
solvent contact and prevent channeling. A valve at the bottom of the can-
ister allows removal of solvent from the canister between changes.
Experience has shown that it is very difficult to cycle sufficient
water in this mode. Therefore, the aqueous rinse is accomplished by simply
flushing the canister with about 20 L of distilled water. A small pump may
be useful for pumping the water through the canister. The water extraction
should be carried out at the rate of about 20-40 mL/min.
After draining the water, subsequent methyl alcohol and methylene
chloride extractions are carried out using the refluxing apparatus. An
overnight or 10- to 20-hour period is normally sufficient for each extrac-
tion.
All materials of construction are glass, Teflon, or stainless steel.
Pumps, if used, should not contain extractable materials. Pumps are not used
with methanol and methylene chloride.
B.3 DRYING
(_
After evaluation of several methods of removing residual solvent, a
fluidized-bed technique has proven to be the fastest and most reliable
drying method.
A simple column with suitable retainers as shown in Figure B-2 will
serve as a satisfactory column. A 10.2-cm (4-in.) Pyrex pipe 0.6 m (2 ft)
B-3
-------
0.32 cm Union
Air Jacketed
Snyder Column
Fine Screen
Coarse Plate
•Teflon Gaske|
Retaining Spring
Coarss Plate
Fine Screen
Drain
1
Optional Pump
Figure B-1. XAD-2 cleanup extraction apparatus.
B-4
-------
Loose Weave Nylon
Fabric Cover
10.2 cm
(4 Inch) Pyrex
Pipe
Liquid Take off
5.
0.95 cm (3/8 in) Tubing
Liquid Nitrogen
Cylinder
(1602)
^£^^*W*£y/Co3rs3 Support
Heat Source
Figure B-2. XAD-2 fluidized-bed drying apparatus.
B-5
-------
long will hold all of the XAD-2 from the extractor shown in Figure B-l or
the Soxhlet extractor, with sufficient space for fluidizing the bed while
generating a minimum resin load at the exit of the column.
B.3.1 Method 1
The gas used to remove the solvent is the key to preserving the clean-
liness of the XAD-2. Liquid nitrogen from a regular commercial liquid
nitrogen cylinder has routinely proven to be a reliable source of large
volumes of gas free from organic contaminants. The liquid nitrogen cylinder
is connected to the column by a length of precleaned 0.95-cm (3/8-in.)
copper tubing, coiled to pass through a heat source. As nitrogen is bled
from the cylinder, it is vaporized in the heat source and passes through the
column. A convenient heat source is a water bath heated from a steam line.
The final nitrogen temperature should only be warm to the touch and not over
40° C. Experience has shown that about 500 g of XAD-2 may be dried over-
night consuming a full 160-L cylinder of liquid nitrogen.
B.3.2 Method 2
As a second choice, high purity tank nitrogen may be used to dry the
XAD-2. The high purity nitrogen must first be passed through a bed of
activated charcoal approximately 150 ml in volume. With either type of
drying method, the rate of flow should gently agitate the bed. Excessive
fluidization may cause the particles to break up.
B.4 QUALITY CONTROL PROCEDURES
For both Methods 1 and 2, the quality control results must be reported
for the batch. The batch must be reextracted with methylene chloride if the
residual extractable organics are greater than 20 ug/mL or the gravimetric
residue is greater than 0.5 mg/20 g XAD-2 extracted.
Three control procedures are used with the final XAD-2 to check for (1)
residual methylene chloride, (2) extractable organics (TCO), and (3) residue
(GRAV).
B.4.1 Procedure for Residual Methylene Chloride
B.4.1.1 Description--
A 1 ±0.1 g sample of dried resin is weighed into a small vial, 3 mL of
B-6
-------
toluene are added, and the via! 1s capped and well shaken. Five microliters
of toluene (now containing extracted methylene chloride) are injected into a
gas chromatograph, and the resulting integrated area is compared to a refer-
ence standard.
The reference solution consists of 2.5 uL of methylene chloride in
100 ml of toluene, simulating 100 ug residual methylene chloride on the
resin. The acceptable maximum content is 1,000 ug/g resin.
B.4.1.2 Experimental—. u ^ —
6 ft. x 1/8 in. SS column containing 10% OV-101 on 100/120 Supel-
coport
Helium carrier at 30 mL/min
FID operated on 4 x lo'11 A/mV
Injection port temp 250° C, detector temp 305° C
Programmed: 30° C (4 min) 40°/min 250° C (hold)
Program terminated at 1000 seconds.
B.4.2 Procedure for Residual Extractable Qrganics
B.4.2.1 Description--
A 20 ±0.1 g sample of cleaned, dried resin is weighed into a precleaned
alundum or cellulose thimble which is plugged with cleaned, glass wool.
(Note that 20 g of resin will fill a thimble, and the resin will float out
unless well plugged.) The thimble containing the resin is extracted for
24 h with 200 ml of pesticide-grade methylene chloride.*
The 200-mL extract is reduced in volume to 10 ml using a nitrogen
evaporation stream. Five microliters of that solution are analyzed by gas
chromatography using the TCO analysis procedure. The concentrated solution
should not contain more than 20 ug/mL of TCO extracted from the XAD-2. This
is equivalent to 10 ug/g °f Tco in tne XAD"2 and would correspond to 1.3 mg
of TCO in the extract of the 130-g XAD-2 module. Care should be taken to
correct the TCO data for a solvent blank prepared (200 •»• 10 ml concentra-
tion) in a similar manner.
B.4.2.2 Experimental —
Use the TCO analysis conditions described in the revised Level 1 manual
*Burdick & Jackson pesticide grade or equivalent purity.
B-7
-------
B.4.3 Methodology for Residual Gravimetric Determination.
After the TCO value is obtained for the resin batch by the above
procedures, dry the remainder of the extract in a tared vessel. There must
be less than 0.5 mg residue registered or the batch of resin will have to be
extracted with fresh methylene chloride again until it meets this criteria.
This level corresponds to 25 ug/g in the XAD-2 or about 3.25 mg in a resin
charge of 130 g.
B-8
-------
APPENDIX C
PARR BOMB COMBUSTION PROCEDURE
C-l
-------
APPENDIX C
PARR BOMB COMBUSTION PROCEDURE
C.I SCOPE AND APPLICATION
Parr oxygen combustion is applicable for the preparation of all combus-
tible materials for inorganic analysis. For Level 1 samples, samples prin-
cipally organic in nature are to be combusted, for example, fuel oil, coal,
and XAD-2 resin. Significant background quantities of Cr, Fe, Ni, and Mn
can be encountered as a result of attack on and leaching of stainless steel
bomb components during combustion. To eliminate this background, samples
for SSMS analysis are combusted by a more rigorous method using platinum
electrodes and a quartz cup and lid to line the bomb.
C.2 APPARATUS
Parr oxygen bomb--342-mL capacity
Quartz cup and lid as bomb liner
Platinum firing wire
Oxygen supply and regulator
Parr pellet press and die
Vycor sample cups
Glass beakers, 250 mL and 100 mL
Watch glasses
Whatman filters, #41
Nalgene funnels
Mortar and pestle, ceramic
C.3 REAGENTS
4 percent collodion in amyl acetate or equivalent.
1:1 HN03, H20
Benzoic acid
C-2
-------
C.4 SAMPLE PREPARATION
Two general types of sample will be analyzed: organic liquids and
organic solids. A special sample type is the XAD-2 resin. No special
preparation is necessary for the organic liquids; however, the other two
sample types will require the following steps to insure complete combustion.
C.4.1 Organic Solids
Weigh 1.0 g solid or a quantity having a heat of combustion <8.0 Kcal,
whichever is less, into a Vycor sample cup; add 0.25 g of benzoic acid and
mix. Transfer contents to a pellet die and press the sample into a pellet.
C.4.2 XAD-2 Resin
Weigh 1.0 g of resin into a Vycor sample cup. Add ~1 mL of collodion
solution, mix, and flatten the sample into a pellet. Place the sample in an
oven at 110° C for -20 min.
C.5 COMBUSTION PROCEDURE
C.5.1 SSMS Analysis Samples
Place ]£ml_ of 1:1 HN03 in a quartz cup and place in a Parr bomb. Place
the Vycor cup with sample in a Pt holder and attach the platinum firing
wire, being certain contact is made with the sample. The quartz cup and lid
should fit the bomb snugly. Care must be taken when placing the quartz lid
down onto the cup to assure that the lid forms a seal with the cup. Assemble
the bomb and pressurize to 30 atm with 02. Insert the bomb in a calorimeter,
attach electrical leads, and ignite. Allow to cool for -15 minutes and
slowly release the pressure. Disassemble bomb and wash the bottom of the
quartz lid and the contents of the Vycor sample cup into the quartz cup.
Remove the quartz cup, wash the contents into a Nalgene bottle, and make up
to 50 ml. Label the sample.
C.5.2 Other Samples (not sensitive to Parr bomb contamination)
Place 10mL of 1:1 HN03 in the bottom of the Parr bomb. Place the
sample cup in the holder and attach the platinum firing wire, being certain
contact is made with the sample. Assemble the bomb and pressurize to 30 atm
C-3
-------
with 02. Insert the bomb in a calorimeter, attach electrical leads, and
ignite. Allow to cool for ~15 minutes and slowly relieve pressure. Dis-
assemble bomb and wash contents into 250-mL beaker, cover with a watch
glass, and digest on a hot plate for 30 min; do not allow to boil. Cool and
filter through a #41 Whatman filter, supported in a Nalgene funnel, into a
100-mL Nalgene volumetric. Dilute to volume and label.
C-4
-------
APPENDIX D
AQUA REGIA DIGESTION PROCEDURE
D-l
-------
APPENDIX D
AQUA REGIA DIGESTION PROCEDURE
D.I SCOPE AND APPLICATION
Aqua regia digestion is applicable for the preparation of loose partic-
ulate, participate collected on glass fiber filters, and bulk solids (e.g.,
fly ash and bottom ash) for inorganic analysis. This method is appropriate
for elements such as Hg, and anions such as S04, POJ, and F, which are
soluble in aqua regia.
D.2 APPARATUS
Distillation flasks, flat-bottom, 200 ml
Condenser, Liebig or Allihn type
Hot plate
Volumetrics, Nalgene, 100 mL
Filter funnels, Nalgene
Filter paper, Whatman #41
D.3 REAGENTS
Constant boiling aqua regia—4 parts concentrate HN03 + 1 part
concentrate HC1; mix fresh daily
D.4 PROCEDURE
The weighed sample aliquot is placed in the distillation flask. Sixty
milliliters of constant boiling aqua regia solution are added, the condenser
is attached, and the apparatus is secured over a hot plate. The acid is
refluxed for ~6 hours at which time the apparatus is removed from the hot
plate and allowed to cool. Rinse the contents of the condenser into the
distillation flask using 10 ml of deionized water and disconnect the con-
denser. Filter the contents of the distillation flask through a #41 Whatman
filter supported by a Nalgene funnel. Collect the filtrate in a Nalgene
volumetric and wash the filter with two 10-mL volumes of deionized water.
Fill the volumetric to volume and label.
D-2
-------
APPENDIX E
PROCEDURE FOR LEACHING OF BULK SOLIDS
E-l
-------
APPENDIX E
PROCEDURE FOR LEACHING OF BULK SOLIDS*
E.I SCOPE AND APPLICATION
The procedure described here is to be used to leach, or extract, trace,
minor, and major soluble species from bulk solids. The procedure is intended
as a means of obtaining solutions for the estimation of the relative environ-
mental hazard inherent in the Teachings of these bulk solids.
E.2 SUMMARY OF METHOD
A known weight of solid is shaken with deionized and distilled water.
The aqueous phase is then separated by filtration and analyzed using SSMS
and AAS.
E.3 APPARATUS
Agitation equipment - Agitation equipment of any type that will
produce constant movement of the aqueous phase equivalent to that
of a reciprocating platform shaker operated at 60 to 70 one-inch
(25-mm) strokes per minute without incorporation of air is suitable.
Equipment used shall be designed for continuous operation without
heating the samples being agitated.
Membrane filter assembly - A borosilicate glass or stainless steel
funnel with a flat, fritted base of the same material and membrane
filters.
Containers - Round, wide-mouth bottles of composition suitable to
the nature of the waste and the analyses to be performed. One-
gallon (or 4-L) bottles should be used with 700-g samples and
%-gal (or 2-L) bottles with 350-g samples. Multiples of these
sizes may be used for larger samples. These sizes were selected
to establish suitable geometry and provide that the sample plus
liquid would occupy approximately 80 to 90 percent of the container.
Bottles must have a watertight closure. Containers for samples
'"Proposed Method for Leaching of Waste Materials, ASTM, 1916 Race St. ,
Philadelphia, Pennsylvania 19103.
E-2
-------
where gases may be released should be provided with a venting
mechanism. Containers should be cleaned in a manner consistent
with the analyses to be performed.
E.4 REAGENTS
Test water—reagent grade; deionized plus distilled.
E.5 PROCEDURE
1. Grind the material, if necessary, to pass through a 9.5-mm (3/8-
in.) standard sieve.
2. Dry the sample 18 ±2 h at 104 ±2° C. Cool to room temperature in
a dessicator.
3. Weigh a representative 700- or 350-g portion of the material to be
tested. Record the value to ±0.1 g.
4. Place the weighed portion of sample into the container to be used
in the shake test.
5. Add to the container a volume of test water equal in milliliters
to four times the weight in grams of the sample used in 4.
6. Close the container and place it on the agitation equipment.
7. Agitate continuously for 48 h ±0.5 h at 20 ±2° C.
8. Open the containers. Observe and record any changes in the sample
and leaching solution.
9. Separate the bulk of the aqueous phase from any solid or nonaqueous
phases by decantation, centrifugation, or filtration through
filter paper, as appropriate. Vacuum filter the aqueous phase
through a 0.45-um membrane filter.
10. Transfer the filtrate to sample bottles of a size such that the
entire bottle is filled. Close and label. Preserve the filtrate
in a manner consistent with the chemical analyses to be performed.
E-3
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APPENDIX F
ATOMIC ABSORPTION SPECTROMETRIC
PROCEDURES FOR Hg, Sb, AND As
F-l
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APPENDIX F
ATOMIC ABSORPTION SPECTROMETRIC PROCEDURES
FOR Hg, Sb, AND As
F.I MERCURY ANALYSIS
F.I.I Scope and Application
The cold vapor mercury analysis described here is applicable for Level 1
determination of Hg in hydrogen peroxide and ammonium persulfate impinger
solutions, bulk liquids, dilute HN03 solutions resulting from the Parr bomb
combustion of fuels and XAD-2 resin samples, and aqua regia solutions from
the digestion of particulates. Sensitivity and detection limits are 0.004
and 0.001 ug, respectively, with an upper limit of 0.25 ug.
F.I.2 Summary of Method
The cold vapor mercury analysis is based on the reduction of mercury
species in acid solution with stannous chloride and the subsequent sparging
of elemental mercury, with nitrogen, through a quartz cell where its absorp-
tion at 253.7 nm is monitored.
F.I.3 Apparatus
Mercury reduction apparatus—The usual design, consisting of a jar
incorporating a two-hole rubber stopper through which a gas bubbler
tube and a short gas outlet tube pass, can be used. A U tube with
a glass frit on one side has been found to be satisfactory. The
frit serves as a mixing device as well as the gas bubbler, thus
eliminating the need for a separate magnetic stirrer and a stirring
bar to mix the reductor contents.
Atomic absorption spectrophotometer—Use a mercury hollow cathode
lamp at a wavelength of 253.7 nm (or equivalent).
Absorption cell—A cylindrical tube approximately 25 mm I.D. x
125 mm long, with quartz windows, and incorporating inlet and
outlet side arms to permit introduction and discharge of carrier
gas. This type of cell is available commercially from several
F-2
-------
manufacturers of atomic absorption equipment, or it may be con-
lll'clu fh°miHeHdi!y aVai'1able mate"ials. in the latter case,
««2 i ?h b?1t!sted carefully for possible leakage after
assembly. The cell 1S mounted in the optical path of the AAS.
Flowmeter--Capable of measuring a gas flow on the order of 1.9
L/min (4 ftd/h).
Scavenging tube—This tube is filled with soda lime and is con-
nected between the gas outlet tube of the reduction vessel and the
inlet side arm of the absorption cell with Tygon tubing. The soda
lime is replaced.every 25 determinations; otherwise a loss in
sensitivity occurs.
Erlenmeyer flasks--125 ml.
Beakers--150 ml.
Pellet press.
Funnels.
Filter paper--Whatman #41.
F.I.4 Reagents
Stock mercury solution, approximately 1 g/L (1,000 ppm)—Weigh 1 g
of pure, elemental mercury to the nearest 0.1 mg and dissolve in a
solution consisting of 150 ml deionized water and 50 ml concen-
trated HN03 (specific gravity of 1.42). Dilute this solution to
1,000 ml with deionized water. The final solution contains approxi-
mately 1,000 ppm mercury (record exact concentration) in a matrix
of 5 percent (v/v) nitric acid. A commercially obtained 1,000 ppm
Hg solution can also be used.
Standard mercury solutions—Prepare working standard solutions of
mercury down to 1 ppm by serial dilutions of the 1,000 ppm Hg
stock solution with 5 percent (v/v) HN03. Such solutions can be
assumed to be stable for up to one week. Below 1 ppm Hg, standard
solutions should be prepared daily and diluted with 5 percent
(v/v) HN03 and/or deionized water as appropriate so the final
solution matrix is approximately 1 percent (v/v) HN03.
1:1 Nitric acid solution—Dilute 500 ml concentrated nitric acid
to 1,000 ml.
Stannous chloride solution—Dissolve 20 g of SnCl2-H20 in 20 ml
concentrated HC1 (warm the solution to accelerate the dissolution
process) and dilute to 100 ml.
Potassium permanganate solution—Dissolve 5.0 g KMn04 in deionized
water and dilute to 1 L.
F-3
-------
Nitrogen carrier gas.
Nitric acid, concentrated.
Hydrochloric acid, concentrated.
Benzole acid.
F.I.5 Procedure
F.I. 5.1 Standardization--
Standards in the range of 1-10 ppb are made. To the reduction vessel,
transfer 10 ml 1:1 nitric acid solution, 3 ml concentrated H2S04, 5 ml of a
standard solution, and deionized water to bring the volume to a total of
50 ml_. Add 5 ml of stannous chloride solution. Close the system and immedi-
ately initiate the nitrogen flow. The optimum flow rate will vary from
system to system; therefore, several flow rates should be tried until maximum
sensitivity is obtained. Repeat the procedure for varying concentrations of
mercury throughout the specified range. The glass frit is cleansed between
analyses by flushing with 1:1 nitric acid followed by deionized water.
Blanks should be run using deionized water. Plot absorption (peak height)
against standard concentration to obtain a calibration curve.
F.I.5.2 Analysis--
In the determination of mercury by the cold vapor technique, certain
volatile organic materials may absorb at 253.7 nm. If this is expected, the
sample should be analyzed by the regular procedure and again under oxidizing
conditions, i.e., without the addition of stannous chloride. The true
mercury concentration can be obtained by taking the difference of the two
values.
Aqueous samples are analyzed by the same procedure as that used
for standardization. If a larger sample size is used resulting in
a total volume greater than 50 ml, a new calibration curve must be
constructed using the new total volume.
30 percent H202 has shown an interference by consuming the stan-
nous chloride reducing agent. This problem is circumvented by
decomposing the excess H202 with permanganate prior to stannous
chloride addition. Pipet an aliquot into a 125-mL Erlenmeyer and
add 10 ml concentrated HN03. Add KMn04 solution, stirring until
the Mn02 precipitate that forms will not redissolve. At this
point add 2 ml concentrated H2S04 and 1 drop 30 percent H202.
F-4
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ST P ! redissolved, continue adding KMn04 dropwise
rd,,t? Permanen* reddlsh Co1°r ^ obtained. Transfer contents to
P^r i apparatus and adjust volume to approximately 50 ml.
Proceed as per the standardization procedure.
The presence of the silver nitrate catalyst in the ammonium per-
suirate solution has been shown to yield low Hg recoveries.
Removal of Ag by addition of Cl followed by filtration has been
round to be an effective procedure for the removal of this inter-
Terence. Pipet an aliquot into a 150-mL beaker. Add 10 mi_ concen-
trated HN03 and 2 mL HC1. Filter through #41 Whatman filter.
Wash several times with deionized water and dilute filtrate to
approximately 50 ml. Transfer filtrate to reduction vessel and
proceed as per standardization procedure.
In analyzing organic solids, aliquots from Parr bomb decomposition
over acid are used. If there is doubt as to whether the sample
has undergone complete oxidation during combustion, add 5 percent
potassium permanganate solution dropwise until a pink color per-
sists. Proceed with the determination as described under stand-
ardization. As the bomb ages, there may be a tendency for mercury
to become trapped in the bomb wall fissures during combustion. In
addition, if the same bomb is used for normal calorimetry work,
there may be a tendency for mercury to accumulate in the bomb with
time. Consequently, before a series of mercury determinations is
undertaken, several blank determinations should be made by firing
benzoic acid pellets (approximately 1 g) in place of the sample.
Benzoic acid firings should be repeated until a stable, consis-
tently low blank value is obtained. This final blank value is then
used to correct the mercury values obtained for subsequent samples.
The condition of the interior of the bomb should be inspected at
frequent intervals. If evidence of significant pitting or corrosion
is observed (usually indicated by erratic mercury values for
samples or benzoic acid blanks), the bomb should be returned to
the manufacturer for reconditioning.
To analyze particulates, aliquots from the aqua regia digestion
are used. Proceed with the determination as described under
standardi zati on.
F.I.6 Precision and Accuracy
Mercury at a concentration of 0.4 ug/L yields a precision of ±21.2
percent RSD with a relative error of 2.4 percent.
F-5
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F.2 ANTIMONY ANALYSIS
F.2.1 Scope and Application
This method is applicable for the determination of antimony in the
ammonium persulfate solutions obtained from SASS train impingers.
F.2.2 Summary of Method
Organic antimony-containing compounds are decomposed by adding sulfuric
and nitric acids and repeatedly evaporating the sample to fumes of sulfur
trioxide. The antimony liberated, together with the inorganic antimony
originally present, is subsequently reacted with potassium iodide and stan-
nous chloride, and finally with sodium borohydride to form stibine. The
stibine is removed from solution by aeration and swept by a flow of nitrogen
into a hydrogen diffusion flame in an atomic absorption spectrometer. The
gas sample absorption is measured at 217.6 nm. Since the stibine is freed
from the original sample matrix, interferences in the flame are minimized.
F.2.3 Apparatus
Stibine vapor generator—(Figure F-l) consists of: (1) a 100-mL
capacity three-neck round-bottom flask; (2) gas dispersion tube,
coarse frit (Scientific Glass Apparatus Co. No. JG-8500 has been
found satisfactory); and (3) 2-ml capacity medicine dropper, or
5-mL capacity automatic pipetter.
Atomic absorption spectrophotometer--Use an antimony hollow cathode
lamp at a wavelength of 217.6 nm. A three-slot burner or equivalent
is to be used. The fuel is hydrogen (hydrogen diffusion flame)
and nitrogen is used as the stibine carrier.
F.2.4 Reagents
Antimony standard solution I, 1.00 ml = 100 |jg Sb--Disso1ve 274.3
mg antimony potassium tartrate, (SbO)KC4H406-l/2H20, in deionized
water and dilute to 1 L with deionized water.
Antimony standard solution II, l.QO ml = 10 ug Sb—Dilute 50.0 ml
antimony solution I to 500.0 ml with deionized water.
Antimony standard solution III, 1.0 mL = 0.10 ug Sb—Dilute 5.0 ml
antimony standard solution II to 500.0 ml with deionized water.
Prepare fresh before each use.
F-6
-------
EYE DROPPER FOR
NaBH4 ADDITION
TOAA
GAS DISPERSION TUBE
100 ML THREE NECK
ROUND BOTTOM FLASK
Figure F-1. Hydride evolution apparatus.
F-7
-------
Hydrochloric acid, concentrated (specific gravity 1.19)
Nitric acid, concentrated (specific gravity 1.41).
Potassium iodide solution. 15 g/lOQ mL—Dissolve 15 g KI in 100 ml
deionized water. This solution is stable when stored in an amber
bottle.
Sodium borohydride solution, 4 g/100 mi—Dissolve 4 g NaBH4 pellets
in 100 ml deionized water (Alfa Products No. 14122 has been found
satisfactory). Prepare fresh just before each use.
Stannous chloride solution, 4.6 g/100 ml concentrated HC1--
Dissolve 5 g SnCl2-H20 in 100 ml concentrated HC1 (specific gravity
1.19). This solution is stable if a few pieces of mossy tin are
added to prevent oxidation.
Sulfuric acid 9M--Cautious1y, and with constant stirring and
cooling, add 250 ml concentrated H2S04 (specific gravity 1.84) to
250 ml deionized water.
F.2.5 Procedure
1. Prepare, in 150-mL beakers, a blank and sufficient standards
containing from 0.0 to 1.5 |jg Sb by diluting 0.0 to 15.0 ml por-
tions of antimony standard solution III to 100 ml with deionized
water. Place 25-mL aliquots of the impinger solution into beakers
and add water as with the blank and standards.
2. To each beaker add 7 ml 9M H2S04 and 5 ml concentrated HN03. Add
a small boiling chip and carefully evaporate to fumes of S03.
Maintain an excess of HN03 until all organic matter is destroyed
as evidenced by a clear solution. This prevents darkening of the
solution and possible reduction and loss of antimony. Cool, add
25 ml deionized water, and again evaporate to fumes of S03 to
expel oxides of nitrogen.
3. Cool, and adjust the volume of each beaker to approximately 50 ml
with deionized water.
4. To .each beaker, add successively, with thorough mixing after each
addition, 4 ml concentrated HC1, 1 ml KI solution, and 0.5 ml
SnCl2 solution. Allow about 15 min for reaction.
5. To set the N2 carrier gas flow rate, place 55 ml of deionized
water in the round-bottomed flask and put a rubber stopper in
place of the medicine dropper. Increase the N2 flow slowly until
a maximum is reached that still avoids carrying liquid into the
tubing leading to the AA instrument. Empty the flask and begin
analyzing the samples by transferring the contents of each beaker,
one at a time, to the flask and proceeding with the NaBH4 reaction.
F-8
-------
6. Fill the medicine dropper with ~1 ml NaBH4 solution and insert
into a one-hole rubber stopper that has been tightly fitted into
the center neck of the three-neck round-bottom flask. Press the
dropper and rubber stopper both in tightly.
7. Quickly add the NaBH4 solution all at once to the sample solution.
After^the absorbance has reached a maximum and has returned to the
baseline as measured by the AAS instrument, remove the flask.
Rinse the gas dispersion tube in deionized water before proceeding
to the next sample. Treat each succeeding sample, blank, and
standard in a like manner.
F-9
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F.3 ARSENIC ANALYSIS
F.3.1 Scope and Application
Arsenic analysis by hydride generation and atomic absorption spectro-
metric detection is applicable for the analysis of ammonium persulfate
solutions obtained from SASS train impingers. Detection limit for the
procedure is 0.1 ug with a calculated sensitivity of 0.8 ug. Either of two
arsine evolution methods can be used: gas can be generated in a reaction
with stannous chloride and zinc slurry, or in a reaction with sodium boro-
hydride. Some interferences have been reported for this arsenic procedure.
In particular, it has been found that excess HN03 must be removed prior to
the addition of either the Zn slurry or NaBH4.
F.3.2 Summary of Method
The procedure entails the reduction and conversion of arsenic to its
hydride in acid solution with either SnCl2 and metallic Zn or NaBH4. The
volatile hydride is swept from the reaction vessel, in a stream of argon,
into an argon-hydrogen flame in an atomic absorption spectrophotometer.
There the hydride is decomposed and its concentration monitored at the
resonance wavelength 193.7 nm.
F.3.3 Apparatus
Arsine vapor generator—The apparatus used for the generation of
stibine may be used here. Connect the outlet of the reaction
vessel to the auxiliary oxidant input of the spectrophotometer
burner with Tygon tubing and connect the inlet of the reaction
vessel to the outlet side of the auxiliary oxidant control valve
of the instrument.
Atomic absorption spectrophotometer—Use an arsenic hollow cathode
lamp at a wavelength of 193.7 nm. A Boling burner head is to be
used; the flame source is argon-hydrogen (about 8 L/min each).
Argon (~ 1 L/min), connected as the auxiliary oxidant, serves to
carry the arsine into the flame.
F.3.4 Reagents
Potassium iodide solution—Dissolve 20 g KI in 100 mL deionized
water.
F-10
-------
solution—Dissolve 100 g SnCl2 in 100 mL concen-
dust (200 mesh) to 100 mL deionized
10° mL 18 N H2S°4 and 400 ml concentrated HC1 to
ml deiomzed water in a 1-L volumetric flask and bring to
volume with deionized water.
Sodium borohydride solution—Dissolve 5 g NaBH4-H20 in 100 mL
deionized water. Make fresh prior to each use.
Arsenic solutions—
1. Stock arsenic solution—Dissolve 1.3209 g arsenic trioxide,
As203, in 100 ml deionized water containing 4 g NaOH and
dilute to 1,000 ml with deionized water. 1.00 ml solution
contains 1.00 mg As.
2. Intermediate arsenic solution—Pipet 1 ml stock arsenic
solution into a 100-mL volumetric flask and bring to volume
with deionized water containing 1.5 ml concentrated HN03/L
1.00 ml solution contains 10 ug As.
3. Standard arsenic solution—Pipet 10 ml intermediate arsenic
solution into a 100-mL volumetric flask and bring to volume
with deionized water containing 1.5 mL concentrated HN03/L.
1.00 mL solution contains 1 ug As.
F.3.5 Procedures
F.3.5.1 Sample Preparation—Ammonium Persulfate Samples—
To a 25-mL aliquot in a 150-mL beaker, add 5 mL concentrated HN03 and
6 mL 18 N H2S04. Evaporate to S03 fumes. To avoid the loss of arsenic,
maintain oxidizing conditions at all times by adding small amounts of nitric
acid whenever the red brown N02 fumes disappear. Cool, transfer to a 50-mL
volumetric, add 20 mL concentrated HC1, and dilute to volume.
F.3.5.2 Preparation of Standards--
Transfer 0.5, 1.0, 1.5, and 2.0 mL of standard arsenic solution to
100-mL volumetric flasks and bring to volume with diluent to obtain concen-
trations of 5, 10, 15, and 20 ug/L arsenic.
F-ll
-------
F.3.5.3 Treatment of Samples and Standards--
Transfer a 25-mL portion of prepared sample or standard to the reaction
vessel and add 1 mL potassium iodide solution. If the Zn slurry addition
method is to be followed, add 0.5 ml SnCl2 solution. Allow at least 10 min
for the metal to be reduced to its lowest oxidation state. Initiate the
argon flow. Fill the medicine dropper either with 1.50 ml zinc slurry that
has been kept in suspension with the magnetic stirrer, or with 1.50 ml NaBH4
solution. Firmly insert the stopper containing the medicine dropper into
the side neck of the reaction vessel. Squeeze the bulb to introduce either
the zinc slurry or the NaBH4 solution into the sample or standard. The
metal hydride will produce a peak almost immediately. When the recorder pen
returns to the baseline, remove the reaction vessel, empty, and proceed with
the next sample.
Please note that if Zn is used, a IQ-cm long polyethylene tube filled
with glass wool should be connected to the generator exit tube in order to
keep particulate matter out of the burner.
F.3.6 Precision and Accuracy
Replicate 10-ug/L samples exhibit a relative standard deviation of ±6.0
percent and a relative error of ±1.0 percent.
F-12
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REPORT NO.
EPA-600/7-78-2Q1
TECHNICAL REPORT DATA
incase read Instructions on the reverse before completing)
2.
3. RECIPIENT'S ACCESSION NO.
PLE
IERL-RTP Procedures Manual: Level 1 Environmental
Assessment (Second Edition)
5. REPORT DATE
October 1978
6. PERFORMING ORGANIZATION CODE
D.E.Lentzen, D.E.Wagoner, E.D.Estes and
W.F.Gutknecht
8. PERFORMING ORGANIZATION REPORT NO.
'ERFORMING ORGANIZATION NAME AND ADDRESS ~~
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
TNE624
11. CONTRACT/GRANT NO.
68-02-2156, T.D. 21300
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD CC
Task Final; 12/76 - 1/78
COVERED
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES JERL-RTP project officer is L.D.Johnson, Mail Drop 62, 919/541-
2557. The report cancels and supersedes EPA-600/2-76-160a.
. ABSTRACT
Tne report gives revised Level 1 environmental assessment procedures (re-
commended by EPA's Industrial Environmental Research Laboratory, Research Tri-
angle Park) for personnel experienced in collecting and analyzing samples from indus-
trial and energy producing processes. The strategy provides a framework for deter-
mining industrial process and stream priorities on the basis of a staged sampling and
analysis technique. Level 1 is a screening phase that characterizes the pollutant poten-
tial of process influent and effluent streams. The manual is divided into two major
sections, according to procedure used. Chapters 3-7 discuss sampling procedures for
gases, fugitive emissions, liquids (including slurries), and solids. The remainder of
the manual is divided into three chapters on procedures for inorganic , organic , and
particle analyses. Chapter 11 briefly discusses bioassay procedures. Biological asses-
sment techniques are detailed in a companion procedures manual.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Assessments
Sampling
Analyzing
Industrial Processes
Energy Conversion Techniques
Pollution Control
Stationary Sources
Environmental Assess-
ment
Level 1 Procedures
13B
14 B
13H
10A
13. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
279
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA form 2220-1 (9-73)
279
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