United States
Environmental Protection
Agency
EPA-600/8-83-027
July 1983
Environmental
Monitoring!
Reference Manual
for Synthetpc Fuels
Facilities
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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
environmental 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 SPECIAL REPORTS series This series is
reserved for reports which are intended to meet the technical information needs
of specifically targeted user groups Reports in this series include Problem Orient-
ed Reports, Research Application Reports, and Executive Summary Documents
Typical of these reports include state-of-the-art analyses, technology assess-
ments, reports on the results of major research and development efforts, design
manuals, and user manuals
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161
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EPA-600/8-83-027
July 1983
ENVIRONMENTAL MONITORING REFERENCE MANUAL
FOR
SYNTHETIC FUELS FACILITIES
EPA Project Officers:
D. Bruce Henschel
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
and
James T. Stemmle
Office of Environmental Processes and Effects Research
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, D.C. 20460
Prepared for:
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C. 20460
U.S. Environmental Protection Agency
Region V, Library
230 South Dearborn Street
Chicago, Illinois 60604
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Disclaimer
This document has been reviewed in accordance with U.S. Environmental
Protection Agency policy and approved for publication. Mention of trade names
or commercial products does not constitute endorsement or recommendation for
use.
In preparing this manual* the Environmental Protection Agency has con-
sulted with the U.S. Synthetic Fuels Corporation. Release of the manual does
not reflect Its endorsement by the Corporation.
********#**##*#####*#*****
* NOTICE *
* This manual will be revised 1f necessary based upon 1n1- *
* tlal experience with Its use 1n the development and *
* review of environmental monitoring plans and plan out- *
* lines. Comments for consideration 1n any such revisions *
* of the manual should be provided by October 31> 1983» to: *
* . *
* D. Bruce Henschel *
* Industrial Environmental Research Laboratory (MD-61) *
* U.S. Environmental Protection Agency *
* Research Triangle Park, N.C. 27711 *
* (919) 541-4112 *
lronmental Protection
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Foreword
This Environmental Monitoring Reference Manual for Synthetic Fuels Facil-
ities 1s Intended to aid applicants to the Synthetic Fuels Corporation (SFC)—
and to aid other developers of synthetic fuels plants—1n developing Environ-
mental Monitoring Plans (and outlines of such plans) covering source and ambi-
ent monitoring. The manual is also intended to assist Federal and State agen-
cies in reviewing these monitoring plans and plan outlines. This manual is
provided as one component of the Agency's input to the consultation process
specified in Section 131(e) of the Energy Security Act.
This manual is not Intended to provide rigorous specifications for an
"acceptable" monitoring plan. The ultimate acceptability of a plan is
determined by the SFC. Nor 1s the manual intended as a comprehensive defini-
tion of the compliance monitoring that will be required by permits. Rather,
the manual describes approaches that can be considered, and issues that need
to be addressed, in the development of a monitoring plan or outline for a syn-
thetic fuels plant. The exact content of the monitoring plan or outline for
any specific facility would have to be developed taking into consideration the
particular circumstances associated with that plant.
As developers and reviewers of monitoring plans and outlines begin to use
this manual, potential improvements 1n the content or format might become
apparent which would enable the manual to better achieve its intended pur-
pose. If the Agency receives substantive comments from Initial users, the
manual will be revised as appropriate.
Users of the manual are therefore encouraged to submit—by October 31,
1983—any comments that they feel should be considered in the revision of this
document. Comments should be directed to:
D. Bruce Henschel
Industrial Environmental Research Laboratory (MD-61)
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
(919) 541-4112
Donal d)0. JE^eth «£aetTfig"~D1 rector
Off 1 ce/oK^nvi ronmental Engi neerl ng
ind Technology
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Abstract
The Energy Security Act, which establishes the Synthetic Fuels
Corporation (SFC), specifies that applicants for SFC financial assistance must
develop a plan, acceptable to the Board of Directors, for the monitoring of
environmental and health-related emissions from the construction and operation
of the synthetic fuel project, following consultation with EPA and other
agencies. The SFC has published Interim Environmental Monitoring Plan Guide-
lines outlining SFC policy for preparation of the required monitoring plans.
This Environmental Monitoring Reference Manual 1s Intended as a technical aid
to the applicants and to reviewers 1n developing and reviewing the environmen-
tal monitoring plans for coal-, oil shale- and tar sand-based synthetic fuel
plants, consistent with the Act and the SFC guidelines. It also should be
useful for plants processing peat and heavy oil. The manual considers source
and ambient monitoring; 1t does not address Industrial hygiene, wildlife,
water consumption or sodoeconomlc monitoring.
This manual outlines some features which could be considered 1n develop-
ing an environmental monitoring plan (or monitoring plan outline). These fea-
tures Include approaches for selecting discharge streams and ambient media to
be monitored, substances/survey procedures to be addressed 1n the various
streams and media, sampling and monitoring techniques, and monitoring fre-
quencies. A phased approach Is emphasized, 1n which an initial comprehensive
"survey" (Phase 1) monitoring phase Identifies the species which should be
addressed 1n a subsequent reduced extended-term (Phase 2) monitoring program.
The manual addresses both regulated and unregulated substances. Nothing in
the manual supercedes compllance-requlred monitoring.
This reference manual 1s not Intended to provide specifications for an
"acceptable" monitoring plan. The exact content of the monitoring plan for
any specific synfuels plant would have to be developed, in consultation with
agencies specified 1n the Energy Security Act, for application to the partic-
ular conditions associated with that plant. However, the manual does describe
practical approaches to consider 1n developing an effective monitoring plan
(or plan outline) tailored to the needs of a specific facility.
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TABLE OF CONTENTS
Foreword iii
Abstract iv
Figures vi ii
Tables ix
Acknowledgments xi i
1. INTRODUCTION 1-1
1.1 Purpose 1-1
1.2 Background 1-1
1.3 Scope and Content 1-2
1.4 Use of Manual 1-5
1.5 Other References 1-11
2. MONITORING CONCEPTS 2-1
2.1 Approach to Monitoring 2-1
2.2 Integration of Source and Ambient Monitoring 2-4
3. QUALITY ASSURANCE 3-1
3.1 Organization of QA/QC 3-2
3.2 Sampl ing Qua! ity Control 3-3
3.3 Analytical Quality Control 3-5
3.4 Method Verification 3-8
3 .5 Sampl e Management 3-10
3.6 References for Section 3 3-11
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TABLE OF CONTENTS (Continued)
4. SOURCE MONITORING 4-1
4.1 Discharge Stream and Control Technology Data Base
Suggestions 4-5
4.1.1 Discharge Streams of Interest 4-6
4.1.2 Discharge Stream Data Base Suggestions 4-18
4.1.3 Control Technology Monitoring 4-39
4.2 A Phased Approach for Data Base Development 4-48
4.2.1 Phase 1 Monitoring 4-50
4.2.2 Phase 2 Monitoring 4-74
4.3 Alternative Monitoring Approaches 4-111
4.3.1 Option I - Phase Monitoring Approach Using
Indicator Parameters in Phase 2 4-112
4.3.2 Option II - Phased Monitoring Approach with
Deletions Following Phase 1 4-114
4.3.3 Option III - Non-Phased Monitoring Approach:
Continued Survey 4-116
4.4 Monitoring Procedures 4-118
4.4.1 Suggested Phase 1 Survey Techniques 4-119
4.4.2 Alternative Techniques 4-120
4.5 References for Section 4 4-151
5. AMBIENT MONITORING 5-1
5.1 Ambient Monitoring Data Base Suggestions 5-2
5.1.1 Monitoring Suggestions to Define the Data
Base 5-2
5.1.2 Location of Ambient Sampling Sites 5-4
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TABLE OF CONTENTS (Continued)
5.2 Approaches for Ambient Monitoring 5-5
5.2.1 Pre-constructlon Monitoring 5-5
5.2.2 Construction Monitoring 5-6
5.2.3 Operational Monitoring 5-9
5.3 Alternative Ambient Monitoring Procedures 5-13
5.4 Special Regional Considerations 5-13
5.4.1 Acidity/Alkalinity 5-14
5.4.2 Sulfur and Trace Elements 5-14
5.4.3 Radioactive Materials 5-15
5.4.4 Arid Environments 5-15
5.5 References for Section 5 5-16
APPENDICES
A. Measurement Methods A-l
B. Statistical Issues B-l
C. Discussion of Ambient Pollutants C-l
D. Ambient A1r Monitoring Techniques D-l
E. Ambient Water Monitoring Techniques E-l
F. Ambient Soil Monitoring Techniques F-l
G. Groundwater Monitoring Techniques G-l
H. Special Biological Monitoring Techniques H-l
I. SFC Guidelines 1-1
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LIST OF FIGURES
Number Page
3-1 Example method verification scheme 3-9
4-1 Generalized block flow diagram of synthetic fuels
f aci 1111 es 4-16
4-2 Schematic diagram of approach for selecting Phase 1
monitoring frequency and duration 4-69
4-3 Determining indicator/parameter relationships 4-89
4-4 Example chart for determining number of tests required
in Phase 2 monitoring 4-100
4-5 Schematic diagram of approach for designing Phase 2
monitoring and updating Phase 1 data base 4-108
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LIST OF TABLES
Number
4-1 Generic Categories - Gaseous Discharge Streams 4-7
4-2 Generic Categories - Aqueous Discharge Streams 4-10
4-3 Generic Categories - Solid Discharges 4-13
4-4 Data Base Suggestions for Gaseous Discharge Streams 4-19
4-5 Data Base Suggestions for Aqueous Discharge Streams 4-22
4-6 Data Base Suggestions for Solids Discharges 4-24
4-7 Water Quality Parameters of Interest 1n Synfuels
Wastewaters 4-26
4-8 Organic Species of Special Interest 1n Synfuels Discharge
Streams 4-26
4-9 Commonly Used Techniques for Determining the Biological
Activity of Specific Waste Streams 4-31
4-10 Organic Substances of Interest 1n Synfuels Waste Streams?. 4-33
4-11 Trace Elements of Interest in Synfuels Waste Streams? 4-36
4-12 Typical Synfuels Plant Control Devices and Key Operating
Variables — Gaseous Streams 4-42
4-13 Typical Synfuels Plant Control Devices and Key Operating
Variables — Aqueous Streams 4-45
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LIST OF TABLES (Continued)
Number Page
4-14 Typical Synfuels Plant Control Devices and Key Operating
Variables — Solid Waste 4-46
4-15 Suggested Phase 1 Monitoring Frequency - Gaseous Discharge
Streams 4-53
4-16 Suggested Phase 1 Monitoring Frequency - Aqueous Discharge
Streams 4-57
4-17 Suggested Phase 1 Monitoring Frequency - Solid Waste
Di scharges 4-60
4-18 Expected Confidence Intervals for a Parameter Mean as a
Function of Number of Samples (Measurements) 4-65
4-19 Precision of the Estimated Mean at a 95 Percent Confidence
Level for Various Sample Numbers (CV = 50%; Normal
Di stri buti on Model) 4-67
4-20 Types of Potential Indicators for Phase 2 Monitoring 4-77
4-21 Candidate Indicators for Organics of Interest in Synfuels
Waste Streams 4-80
4-22 Statistical Techniques and Their Applicability to the
Analysis of Monitoring Program Data 4-92
4-23 Example Application of Figure 4-4 4-102
4-24 Suggested Phase 1 Survey Techniques for Gaseous Streams... 4-123
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LIST OF TABLES (Continued)
Number Page
4-25 Suggested Phase 1 Survey Techniques for Aqeuous Streams... 4-125
4-26 Suggested Phase 1 Survey Techniques for Solid Streams 4-127
4-27 Monitoring Options for Gaseous Streams 4-130
4-28 Monitoring Options for Aqueous Streams 4-142
4-29 Monitoring Options for Solid Streams 4-148
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Acknowledgments
This reference manual represents the culmination of efforts of many Indi-
viduals. The source monitoring component (Section 4, Appendices A and B) was
prepared by the Industrial Environmental Research Laboratory 1n EPA's Office
of Research and Development (ORD), with technical support provided by Radian
Corporation (under Contract No. 68-02-3171, Work Assignment Nos. 69 and 77).
Arthur D. Little, Inc. provided assistance 1n revising Appendix A. Consulta-
tion on statistical considerations was provided by James E. Dunn. The
ambient monitoring component (Section 5 and related appendices) and an initial
Integrated draft were prepared by the Office of Environmental Processes and
Effects Research in ORD, with technical support provided by The MITRE Corpora-
tion. Descriptions of ambient sampling and analytical protocols for measuring
pollutants 1n air, water, and soil (Appendices D, E and F) were prepared by
ORD's Environmental Monitoring Systems Laboratory, with technical support pro-
vided by Research Triangle Institute. The Industrial Environmental Research
Laboratory coordinated the peer review process and the preparation of the
final report.
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SECTION 1
INTRODUCTION
1.1 PURPOSE
The purpose of this reference manual 1s to aid applicants to the U.S.
Synthetic Fuels Corporation (SFC) and other synthetic fuels plant developers
1n preparing environmental monitoring plans (and outlines of such plans)
covering source and ambient monitoring for coal-, oil shale-, and tar sands-
based synthetic fuels facilities. The manual 1s also Intended to assist
Federal and State agencies 1n reviewing these monitoring outlines and plans.
The manual 1s provided as one component of the Environmental Protection Agency
(EPA) consultation process 1n monitoring plan development, as specified 1n
Section 13He) of the Energy Security Act.
This manual 1s not Intended to provide specifications for an "acceptable"
monitoring plan. The ultimate acceptability of a plan 1s determined by the
SFC. Rather, the manual describes approaches to consider and Issues to
address 1n developing a plan or outline. The exact content of the monitoring
plan or outline for any specific facility would need to be tailored to meet
conditions associated with that particular plant.
1.2 BACKGROUND
The Energy Security Act of 1980 (PL 96-294)—which establishes the SFC—
Includes the following requirement (Section 131(e) of the Act):
"Any contract for financial assistance shall require the development
of a plan acceptable to the Board of Directors (of the SFC), for the
monitoring of environmental and health-related emissions from the
construction and operation of the synthetic fuel project. Such plan
shall be developed by the recipient of financial assistance after
consultation with the Administrator of the Environmental Protection
Agency, with the Secretary of Energy, and appropriate State
agencies."
1-1
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The Intent of Congress concerning Section 131(e) 1s discussed 1n the Joint
Explanatory Statement, Committee of Conference for this Act:
"The monitoring of emissions—gaseous, liquid or solid—and the
examination of waste problems, worker health Issues and other re-
search efforts associated with any synthetic fuel project receiving
assistance pursuant to this Part will help to characterize and
Identify areas of concern and develop an Information base for the
mitigation of problems associated with the replication of synthetic
fuel projects."
In Implementing Section 131(e), the SFC 1s using a two-stage approach 1n
which an applicant (1) develops an outline of the monitoring plan for Incor-
poration Into the financial assistance contract, and (2) develops the monitor-
ing plan Itself, based on the outline, after the financial assistance contract
1s executed. The SFC has published Interim Environmental Monitoring Plan
Guidelines (April 1, 1983), setting forth the procedural steps and the broad
substantive areas to be addressed 1n developing outlines and plans. (See
Appendix I.) These Interim Guidelines are subject to public comment; final
Guidelines will be prepared by SFC following receipt of public comments.
This manual 1s intended to serve as one component of the mandated con-
sultation process for monitoring plan development. Another component envi-
sioned 1n the process 1s direct contact between EPA and the applicants, 1n
which EPA assists them in applying the manual to the specific circumstances of
each proposed facility. The manual is designed to aid in the development and
review of both the outlines and the monitoring plans, consistent with the
intent of Section 131(e) and current SFC monitoring guidelines.
1.3 SCOPE AND CONTENT
The scope of the monitoring guidance 1s defined by the following topics.
Coal-, oil shale-, and tar sands-based synthetic fuels processes -
These processes Include coal gasification (high-, medium-, and low-Btu), coal
1-2
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liquefaction (Indirect and direct), oil shale mining and retorting, and tar
sands processing. In general, the manual also should apply to monitoring
heavy oil, peat and other synfuels processes.
Source monitoring and ambient monitoring - Source monitoring Includes
chemical and biological analyses on discharge streams (gaseous, aqueous,
sol Ids) Including fugitive discharges Inside the plant boundaries. Source
monitoring also Includes monitoring environmental control device performance.
Ambient monitoring Includes chemical and biological tests on the unconflned
environment 1n the vicinity of the synfuels plant (atmosphere, surface waters,
water 1n the unsaturated soil, surface aquifers, deep aquifers and the soil).
It 1s envisioned that source and ambient monitoring programs will be Inte-
grated. The manual does not address Industrial hygiene, wildlife, water
consumption, or sodoeconomlc monitoring.
Regulated and unregulated substances - The intent of the monitoring 1s
to develop a synfuels data base on environmental and health-related emissions
that will aid 1n mitigating problems in future technology replications.
Therefore, the monitoring should not be limited to the substances for which
regulations or standards already exist (either 1n related industries or the
ambient environment). Many substances which might be discharged from synfuels
plants are not currently regulated. Accordingly, the monitoring approaches
considered 1n this manual address unregulated substances as well as regulated
pollutants. This consideration of unregulated substances is consistent with
the provisions of the SFC monitoring plan guidelines.
Pre-construction. construction, and operational monitoring - Source
monitoring addresses monitoring only during plant operation, while ambient
monitoring is expected to occur during all three periods.
Monitoring Control Device Performance - As one component of source
monitoring, control device monitoring could address both the inlet and outlet
streams of a control device as well as suitably selected operating parameters.
The performance/reliability of conventional control techniques in synfuels
1-3
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plant applications has not been demonstrated 1n many cases. An Improved
understanding of control device performance, obtained by monitoring on Initial
synfuels plants, could help mitigate environmental problems 1n future replica-
tion of synfuels plants.
The manual provides the following Information to aid 1n developing moni-
toring plans and outlines.
Suggested Data Base Content - The manual presents 1n some detail a
suggested reasonable content for the "Information base" referred to 1n the
Congressional explanatory statement. The manual suggests which substances
might be analyzed in the various types of discharge streams in order to esta-
blish a sound Information base. The analyses for this data base Include both
(1) analyses for specific compounds, and (2) the use of survey analytical
techniques to screen for classes of compounds 1n streams where specific com-
ponents cannot be predicted a priori. The data base analyses include
biological and physical property tests as well as analyses for chemical com-
ponents.
The data base suggestions were derived by considering substances cur-
rently regulated in related industries and the ambient environment; substances
for which monitoring 1s typically specified in environmental permits for
related Industries; unregulated substances which have been observed in exist-
ing source test data from synfuels facilities; and unregulated substances
which are Included in various recognized pollutant lists and which might
reasonably be expected to be discharged from a synfuels plant. The data base
Includes suggestions concerning which specific substances/survey techniques/
bloassays might reasonably be considered 1n which streams (source monitoring)
or which ambient media (ambient monitoring) under different circumstances.
These considerations are addressed 1n Section 4.1 (source) and Section 5.1 and
Appendix C (ambient).
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Alternative Approaches to Monitoring - Several alternative approaches
to developing the data base are presented. Most Involve a phased monitoring
program 1n which a fairly comprehensive survey 1s done 1n the first phase
followed by a reduced second phase based on first-phase results. The moni-
toring frequency and duration for each phase can be based on site-specific
statistical considerations as described 1n Sections 4.2 and 4.3 (source) and
Section 5.2 (ambient).
SampHngj Sample Handling* and Analysis - Alternative monitoring proce-
dures are presented which can be considered for each substance to be analyzed
or each class of chemicals to be analyzed by a survey technique. Capabilities
of and estimated cost ranges for individual procedures are indicated in Sec-
tion 4.4 and Appendix A (source)* and Section 5.3 and Appendices D through H
(ambient).
Quality Assurance/Quality Control - Suggestions for a meaningful qual-
ity assurance/quality control program are also given in Sections 3.0 and
4.2.1.3 and the appendices describing monitoring procedures.
1.4 USE OF MANUAL
This manual does not provide specifications for an "acceptable" monitor-
Ing plan. Nothing in the manual constitutes a "requirement". The manual is
intended only to describe alternative approaches that can be considered 1n
developing the data base referred to in the Congressional explanation. These
alternatives can be considered in structuring a monitoring plan (or plan
outline) tailored to the needs of a specific facility.
The suggestions 1n this manual will in no way alter permit monitoring
requirements for a specific facility, nor relieve a facility from complying
with permit monitoring obligations. As a practical matter, most of the com-
pliance monitoring required by permits for a particular facility will gener-
ally be included in this manual. However, the monitoring approaches described
in the manual do not necessarily include, nor are they necessarily consistent
1-5
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with, every conceivable set of permit requirements that might be encountered
1n practice. These requirements will be established by the cognizant per-
mitting agency based on the conditions at a specific site.
The Interim SFC monitoring plan guidelines specify the content of moni-
toring plan outlines and of monitoring plans themselves. According to these
guidelines, the outline should Include:
• a summary of compliance monitoring obligations,
• the regulated and unregulated substances to be monitored (or,
where specific unregulated substances cannot be Identified
beforehand, an Indication of the classes of substances that
will be addressed),
• the general location of the monitoring (I.e., stream or ambient
medium),
• how the monitoring generally would be performed e.g., high-
volume sampler (where specific unregulated substances cannot be
Identified beforehand, the methods by which substances will be
Identified should be given),
• the duration of monitoring, and
• background Information on the synfuels project to enable review
of the outline (e.g., overall process description, process
block flow diagram, control system specifications, plot plans,
detailed site description, supporting environmental data,
etc.).
The monitoring plan should Include:
• any necessary further definition of the substances to be moni-
tored;
• detailed monitoring site locations;
• specific sampling/sample handling/analytical protocols, Includ-
ing equipment and methods;
• monitoring frequency for each substance at each monitoring
location; and
• background Information, as described for the outline above.
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This reference manual can be used to fulfill the above specifications for
monitoring plans and outlines for a specific plant by following the steps
11sted below:
1. Identify discharges and ambient media of concern - Review the
plant design drawings and flowsheet and the detailed site plan
to Identify discharge streams (and controls) and ambient media
of Interest. These are the streams/media to be sampled 1n the
monitoring program.
2. Classify the discharge steams - For source monitoring* class-
ify the streams of concern using the generic stream categories
defined 1n Tables 4-1, 4-2, and 4-3 (Section 4.1) for gases,
liquids, and solids, respectively. The stream categories are
logical and easy to understand. Category assignments will be
based on the following:
—Is the discharge a gas, liquid, or solid/sludge?
—Does the discharge contain organlcs? (1s 1t organic-rich
or organic-lean?).
—Is the discharge unique to synthetic fuel processing
(e.g. waste from raw reactor effluent cooling water
treatment), or non-unique (e.g. flue gas from coal-fired
boiler)?
3. Select substances to be analyzed - Use Tables 4-4 through 4-6
(gaseous, aqueous/liquid, and solid discharges) 1n Section
4.1.2 to select the specific substances to be analyzed 1n
samples from each discharge stream (or to select the chemical
classes of unregulated substances to be analyzed using survey
1-7
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analytical techniques if specific substances cannot be defined
beforehand). The same tables plus Appendix C can be used to
select substances to be monitored 1n ambient media.
The information in Tables 4-4 through 4-6, which are organized
by generic stream category, must be tailored to a specific
plant. The information needed to make plant-specific selec-
tions for monitoring includes:
—engineering assessment of expected compositions of
discharges from the plant,
—site- or process-specific test data on discharges and
their composition, and
—permit requirements.
4. Prepare a Test Matrix - Based on the selections made in 1
and 3 above, prepare a matrix of the streams (i.e., the source
monitoring locations) and ambient media to be sampled, the spe-
cies/classes to be analyzed in each, and the process data re-
quired to Interpret the monitoring data and define operating
conditions at the time of sampling.
5. Select Ambient Monitoring Locations - Use the comments 1n
Section 5.1.2 as a guide in the site-selection process for
ambient monitoring stations.
6. Select Sampling. Sample Handling, and Analysis Methods -
Refer to Section 4.4 and Appendix A (source) and to Section 5.3
and Appendices D through H (ambient) as a guide in selecting
sampling, sample handling, and analysis methods for each
species or class of chemicals in each stream or ambient medium.
Select potential source monitoring procedures for each sub-
stance from the alternatives in Tables 4-27 through 4-29.
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(Survey techniques used in screening for chemical classes when
specific substances cannot be defined beforehand are given 1n
Tables 4-24 through 4-26).
Find the descriptions of the candidate procedures 1n Appendix
A. The applications, limitations, and estimated costs are
discussed there for each procedure, and references are given.
An experienced analyst will be able to select suitable tech-
niques for a specific plant from the alternatives by taking
the following site-specific factors Into account:
—the analytical sensitivity needed for a component 1n a
specific stream,
—the potential presence of Interfering species, and
—the available analytical facilities and equipment.
Follow the same process for ambient monitoring procedures,
using the Information 1n Appendices D through H.
The level of detail 1n the appendices and tables provides a
general description of alternative techniques, which 1s ade-
quate for preparing the monitoring plan outline. However, 1n
some cases—1n particular, for complex organics—the descrip-
tion 1n the manual might not be adequate to define the specific
sampling/sample handling/analytical procedures 1n the detail
required for the monitoring plan. In these cases, an experi-
enced analyst will need to define the details (especially
sample handling/preparation techniques and sample size con-
siderations). The references given for each method should be
consulted for details.
7. Define Phased Monitoring Approach - The monitoring approach
that 1s chosen will Influence the selection of monitoring fre-
quency and duration. The monitoring approach emphasized 1n
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Section 4.2 employs the concept of phasing. Phase 1 Includes
monitoring needed Initially to define a baseline data base and
1s of limited duration. Phase 2 1s based on first-phase re-
sults and Involves a reduced monitoring effort for the remain-
der of the plant operating life to track the Phase 1 data base
using "Indicator" species to Identify deviations from the base-
line data. Two other possible approaches— one Involving a
different method of phasing and one not Involving phasing— are
described 1n Section 4.3. The user can adopt one of these
approaches or suggest an alternative. If an alternative ap-
proach 1s suggested, Its Impact on the resulting data base
should be evaluated carefully.
8. Select Monitoring Frequency and Duration - If the monitoring
approach 1n Section 4.2 1s employed, use the practical and sta-
tistical guidance 1n Sections 4.2.1.2 and 4.2.2.2 to select
monitoring frequency (for the plan) and duration (for the out-
line and plan). If a different approach 1s used, considera-
tions similar to those 1n Sections 4.2.1.2 and 4.2.2.2 can be
used to select frequency and duration.
Applying the statistical principles requires establishing cer-
tain decision criteria (e.g., desired accuracy). The manual
describes the types of statistical decisions and the Impacts on
sampling frequency and duration of monitoring. A tradeoff
between Improved statistical accuracy (Increased data quantity)
and reduced sampling frequency/duration (lower cost) must be
considered 1n selecting frequency and duration for the site-
specific monitoring plan.
The Interim SFC monitoring guidelines specify that outlines and monitor-
Ing plans should also address quality assurance/quality control (QA/QC) mea-
sures and data management and reporting procedures. QA/QC 1s discussed in
Section 3 of this manual. Data management and reporting are not specifically
1-10
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addressed 1n this manual (except 1n terms of statistical evaluation and Phase
2 design); EPA suggestions concerning data management/reporting will be
addressed separately.
The Interim SFC monitoring guidelines specify formation of a Monitoring
Review Committee comprised of representatives from the developers, the con-
sulting agencies and the SFC. This committee will review the monitoring
results and advise the SFC about any significant results and any resulting
adjustments 1n the monitoring program that might be warranted. If a phased
monitoring approach 1s used—wherein a reduced, second-phase program 1s
designed based on results from the first phase—the Monitoring Review Commit-
tee could be Involved 1n helping direct the Phase 2 design.
1.5 OTHER REFERENCES
In conducting a source and ambient monitoring program of the type out-
lined 1n this manual, Information from a large number of references might be
applicable. Key references are Included at the end of each section and
appendix.
In addition to this monitoring reference manual, the EPA-ORD synthetic
fuels program has generated another series of documents, the Pollution Control
Technical Manuals (PCTMs), which can be used 1n evaluating discharges and
control technologies for synthetic fuels facilities. Based on publicly avail-
able Information, the PCTMs estimate the compositions of the various waste
streams (prior to control), and describe alternative control techniques that
might be considered for application to each waste stream. PCTMs have been
prepared for the following synfuels technologies:
Lurgl-Based Indirect Coal Liquefaction and SNG (Report No.
EPA-600/8-83-006) - NTIS Accession No. PB83 - 214478
Koppers-Totzek-Based Indirect Coal Liquefaction (Report No.
EPA-600/8-83-008) - NTIS Accession No. PB83 - 214502
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Exxon Donor Solvent Direct Coal Liquefaction (Report No.
EPA-600/8-83-007) - NTIS Accession No. PB83 - 214486
Lurgl 011 Shale Retorting with Open Pit Mining (Report No.
EPA-600/8-83-005) - NTIS Accession No. PB83 - 200204
Modified In-S1tu 011 Shale Retorting Combined with Lurgl
Surface Retorting (Report No. EPA-600/8-83-004) - NTIS
Accession No. PB83 - 200121
TOSCO II 011 Shale Retorting with Underground Mining (Report
No. EPA-600/8-83-003) - NTIS Accession No. PB83 - 200212
Control Technology Appendices for Pollution Control Technical
Manuals (Report No. EPA-600/8-83-009) - NTIS Accession No. PB 83-
214734.
These PCTMs are available from the National Technical Information Service
(NTIS), 5285 Port Royal Road, Springfield, Virginia 22151.
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SECTION 2
MONITORING CONCEPTS
2.1 APPROACH TO MONITORING
The stated purpose of the Section 131(e) monitoring—to develop a data
base which can be used to Identify environmental problems—suggests the need
for a fairly broad monitoring program. A monitoring approach must be selected
which will allow this broad data base to be developed 1n a realistic and cost-
effective way.
Synthetic fuels processes could produce and potentially discharge a wide
array of organic compounds and any trace metals present 1n the feedstock.
While source tests have been conducted on the discharges from some synfuels
facilities (Including pilot plants and a few small commercial units)* these
data are not necessarily representative of large* commercial-scale plants. In
most cases* certain discharge streams that would be present 1n a commercial
facility were missing. And some of the streams present were not representa-
tive either because the facility was not a complete* Integrated plant, or
because the plant was not designed, operated, or controlled 1n a manner repre-
sentative of a modern commerlcal facility. Nevertheless, these data stm
suggest which classes of compounds might be present 1n discharges from a large
commercial facility. They cannot however, be used as a rigorous Indicator of
all substances that will be present or of substances that will always be pres-
ent 1n commercial discharge streams. Thus, the design of a monitoring program
that must develop a broad data base 1s complicated because a wide range of
substances might be present, and there 1s only a general (class) Indication of
what the actual substances might be.
A monitoring approach that addresses these concerns by monitoring speci-
fically for every potential substance that might be present would not be cost-
effective. On the other hand, a monitoring approach that monitored only for a
limited, preselected list of substances could overlook some Important sub-
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stances. And even after the substances present have been Identified, the num-
ber of substances might be so large that extended monitoring for all of the
substances could become expensive.
To overcome these potential difficulties* this manual presents the
following considerations:
• Where the specific (unregulated) substances cannot be
Identified beforehand, survey analytical procedures could
be employed during Initial monitoring to screen for the
substances which are actually present.
• The monitoring program could be phased so that the results
of the above-mentioned screening in the first phase could
be used to design a reduced second phase effort. The
second phase could be designed to monitor for fewer sub-
stances than were actually observed during Phase 1.
Three alternative monitoring approaches are discussed in this manual, all
of which Involve the use of survey analytical techniques, and two of which
Involve phasing. The designer of a monitoring plan/outline for a given plant
might Identify additional approaches, beyond these three, suitable for that
plant. The substances to be monitored, monitoring location, monitoring fre-
quency and duration, which must be specified 1n the monitoring plan and out-
line, would be determined by the overall monitoring approach. The choice of
monitoring techniques can also be influenced by the overall approach, 1f sur-
vey analytical procedures are called for. No matter what overall approach 1s
selected, monitoring for any regulated substances would continue as required
by permits.
The three alternative approaches discussed 1n this manual are summarized
below. These approaches are described in more detail in Sections 4.2 and 4.3.
If a different approach is proposed 1n the monitoring plan for a specific
plant, the plan should consider how the results from the new approach would
compare with those from the approaches discussed here.
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Phased approach using Indicators 1n Phase 2. Phase 1 monitoring would
Include: survey analytical procedures to screen for (unregulated) chemical
substances 1n selected classes when the substances cannot be defined before-
hand; specific component analyses for substances of Interest that can be Iden-
tified beforehand; and biological tests. These Phase 1 data would be col-
lected over an Initial period of steady state plant operation and would define
the "baseline" data base. These Phase 1 data would be statistically evaluated
to select particular substancest or parameters (such as COD), which might
serve as "Indicators" for the other substances/parameters observed during
Phase 1. Monitoring during Phase 2 would then proceed, addressing only the
Indicators. In theory, the entire baseline data base could thus be tracked
during Phase 2 by monitoring certain Indicators. Phase 1 measurements (for
the substances represented by a given Indicator 1n a given stream) would be
repeated 1f an excursion (of some pre-defined magnitude) 1n that Indicator
suggests that the baseline has shifted. The extended monitoring during Phase
2 would provide the data history needed for extrapolation of results 1n repli-
cation of synfuels technology. The frequency/duration of monitoring during
Phases 1 and 2 would be determined by the desired accuracy of the results, In-
cluding the accuracy of detecting baseline shifts during Phase 2. The advan-
tages of this approach are: 1) the use of survey analytical techniques avoids
the need to guess which substances will be present; 2) the use of phasing al-
lows a significant reduction 1n the monitoring effort after the first phase
and stm provides a broad baseline; and 3) the use of Indicators allows
tracking "baseline" data throughout Phase 2, and eliminates the need to decide
which of the substances observed 1n Phase 1 warrant continued monitoring. One
concern with this approach 1s the ability to define a suitable relationship
between potential Indicators and represented substances based on the Phase 1
results.
Phased approach with deletions following Phase 1. In this approach,
Phase 1 would proceed exactly as described above, during the Initial period of
steady state operation. However, the Phase 1 results would be Interpreted dif-
ferently. Rather than using Phase 1 results to select Indicators, the results
would be used to define which of the observed Phase 1 substances should con-
2-3
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tlnue to be monitored during Phase 2, and which should not. Phase 2 would
then address only those substances which were both a) observed during Phase 1,
and b) Judged to be significant enough to warrant extended monitoring. This
approach offers the benefits of survey procedures and phasing, as does the
previous approach, and avoids the potential difficulties Inherent 1n trying to
develop statistical relationships between Indicators and represented sub-
stances. However, this approach would require the sometimes-difficult deci-
sion about which substances warrant continued monitoring. Nor does this
approach assure that Phase 2 will represent the entire Phase 1 data base.
Ron-phased approach^ In the non-phased appr'oach, monitoring for the
entire data base (everything 1n Phase 1) would be continued with no effort to
reduce the monitoring as results become available. This approach would offer
the benefits of the survey analytical procedures, as 1n the approaches above,
and would avoid the difficulties Involved 1n designing a Phase 2 program.
However, this approach would not provide the advantage of potential reduc-
tions/cost savings from a reduced Phase 2. This approach would produce the
most comprehensive data set because Phase 1 monitoring for the total data base
would continue 1n place of the reduced Phase 2. Therefore, 1t might be desir-
able to select a total duration for the non-phased program which would be
shorter than for the phased approaches.
The phased approaches Involve data interpretation and decisions regarding
the Phase 2 content at the end of Phase 1. The Monitoring Review Committee—
described in the Interim SFC monitoring guidelines as an advisor to the SFC in
reviewing the monitoring data—could help direct the Phase 2 design activity.
2.2 INTEGRATION OF SOURCE AND AMBIENT MONITORING
Source and ambient monitoring are two complementary components of an
Integrated monitoring program. Source monitoring Identifies the substances
discharged to the environment. Ambient monitoring indicates where these sub-
stances actually appear/accumulate and suggests the transformations the
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substances might experience 1n the environment. One element of the review and
Interpretation of monitoring data should be comparison of the source and ambi-
ent results.
In this manual* 1t 1s assumed that the source and ambient monitoring pro-
grams use the same approach—I.e., Including survey analytical techniques and
perhaps phasing. Employing similar broad survey approaches 1n both programs
should help to Identify the relationships between source and ambient results.
As a practical matter* the results from source monitoring can be used to alert
the operators of the ambient program about the types of substances or trans-
formed substances that might be present. Conversely* excursions 1n the ambi-
ent results should alert source monitoring operators to look for the sub-
stances of concern 1n the pertinent discharges. This Integration will be of
particular Importance during Phase 2, when monitoring might be reduced and the
risk of failure to detect substances Increases. Continued Inconsistencies
between the source and ambient results that cannot be explained should be
Investigated.
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SECTION 3
QUALITY ASSURANCE
A well planned and executed Quality Assurance (QA) program 1s necessary
for the successful completion of any monitoring program. Monitoring efforts
are expended needlessly 1f the data obtained are of poor or unknown quality.
Normally* the quality of data 1s expressed 1n terms of five parameters: pre-
cision* accuracy* completeness* representativeness* and comparability. The
quality of data 1s affected by nearly every step 1n setting up and Implement-
Ing a monitoring program* from planning and executing the program to maintain-
ing data archives and analyzing the data.
An SFC applicant should note the principles of EPA's quality assurance
program. Under the EPA program, the absolute quality requirements for each
data set are not specified. It 1s the responsibility of the project personnel
to set reasonable goals. However, the EPA does Insist that the quality of the
data be known and well documented. This point 1s particularly relevant to
many of the pollutants associated with the synfuels Industry for which quality
assurance procedures have not been standardized or widely accepted. Under the
EPA quality assurance program, the quality of data obtained from all sampling
and measurement protocols must be known and documented, regardless of how
recently the procedures have been developed. The fundamental question asked
of a project monitoring director 1s "What makes you think your data are relia-
ble?'1 and "How reliable are they?". These questions are germane* no matter
how new or experimental the sampling or measurement protocol.
The essential elements which should be Included within a quality assur-
ance project plan are discussed 1n detail 1n the Interim guidelines document
available from EPA's Quality Assurance Management Staff, Office of Research
and Development (3-1).
3-1
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Broadly, quality control (QC) has to do with making quality what 1t
should be, and quality assurance has to do with making sure that quality con-
trol 1s what 1t should be. More precisely, quality control alms at providing
a quality of data, product or service that meets the needs of the users 1n
terms of adequacy, dependability and economy. The quality control system
Integrates the quality aspects of the specifications of what 1s desired, the
production to meet the specifications, the Inspection to determine 1f the
specifications were met and the review of usage for revision of specifica-
tions. The quality assurance program alms at providing assurance that the
overall quality control system 1s Implemented effectively. Quality assurance
requires an evaluation of the completeness and effectiveness of the quality
control and Initiation of corrective measures 1f necessary. Quality assurance
programs, therefore, Involve audits, verifications and evaluation of quality
factors for specification, production, Inspection and utilization (3-2).
A quality assurance plan should be developed, approved and Implemented
for each synthetic fuel plant monitoring program. The plan should be based on
four fundamental principles: (1) responsibility for quality assurance must
extend to all levels of management; (2) the specification of the quality of
data must be explicit, I.e., how good does the data have to be for the pur-
poses of the project; (3) the program must have adequate steps to assure that
data of the needed quality are obtained; (4) Implementable and effective
corrective actions must be taken when the data are of unacceptable quality.
Good statistical design of the sampling plan 1s of utmost Importance. The
quality assurance plan must address all of the activities which occur during
monitoring Including sampling, analysis, data reduction, and data Interpreta-
tion. The plan must also define a QA structure and the capabilities required
for QA and data management personnel.
3.1 ORGANIZATION OF QA/QC
The quality assurance and quality control functions should be organized
to Insure the generation of reliable and consistent analytical data to permit
the data Interpretation required for plant monitoring. The Quality Assurance/
3-2
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Quality Control (QA/QC) activities should be coordinated for consistent
review of the development and Implementation of the specific quality control
activities for sampling, organic analysis. Inorganic analysis, and data
management.
Specific QC protocols should be developed for the sampling program and
for each of the major analytical areas. Training sessions and scheduled QC
activities should be conducted. Reporting and record-keeping should be
defined expUdty, and QC data analysis documented. Mechanisms for detection,
reporting, and correction of any sampling or analytical problems should be
developed and maintained. These QC procedures should be audited through data
review and blind quality assurance analyses.
In a general monitoring program, QA activities will focus on: 1) sam-
pling, 2) analysis, 3) method verification, and 4) sample management. Exam-
ples of the quality assurance and quality control aspects to be considered for
a monitoring program are discussed for these four areas. Guidelines for spe-
cific quality assurance protocols can be found 1n the EPA quality control/
quality assurance and laboratory practice guideline documents listed 1n the
references (3-3 to 3-18).
3.2 SAMPLING QUALITY CONTROL
Detailed quality assurance procedures are essential to the successful
completion of sampling activities. The objectives of a sampling quality
assurance program are to:
• evaluate all aspects of .the sampling methodology, and
• Identify problems as they occur.
The Items to be addressed when developing specific QC procedures for
sampling Include:
3-3
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• facilities and equipment Inventory*
• training program*
• document control,
• quality control charts,
• supervision,
• materials Inventory and procurement,
• reliability and maintenance,
• data val1dat1on,
• equipment calibration, and
• correlation tests.
The types of sampling QC procedures which would be Implemented Include;
• Instructions which Insure proper Implementation of the
monitoring program design, correct use of all equipment, and
adherence to sampling protocols.
• Standardized data forms developed for each specific samplng
activity to aid 1n sampling documentation and record keeping.
The use of formatted data forms helps minimize recording errors
and Insures complete data.
• Quality control tests, I.e.:
- calibration checks at regular Intervals,
- use of blank or control samples to check for Interferences
and contamination,
- field spiking to evaluate recoveries,
- replicate and multiple time samples to evaluate the sources
of variation, and
- sampling checks for standardization of equipment and
personnel.
• Statistical analysis should be conducted and quality control
results reported during sampling activities. The quality
control tests should be followed by prompt determination of
results. If contamination of samples 1s occurring, it 1s
desirable to learn this before many samples have been taken.
Specific reporting of quality control data aids in continual
documentation of performance and allows rapid feedback of QC
results to sampling personnel for corrective action.
3-4
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• Independent quality assurance audits of field sampling tasks to
Insure adherence to sampling protocols* experimental design*
and quality control procedures. Audit procedures Include
checklists of key procedure Items, review of completed data
forms, and Initiation of additional quality control samples
such as standards and controls.
• Where possible, alternative sampling and analysis methods
provide added definition and control of data accuracy. Statis-
tical correlation techniques can be used to determine 1f
results from the two methods are Identical within expected
experimental reprodudbll 1ty.
These procedures may be modified for each type of sample or analysis 1n
the monitoring plan. For example, duplicate samples may be grab samples
collected at the same time, dual test runs, splits of composite samples, or
samples from similar process locations. Blanks must be analyzed to determine
analytical background arising from reagents, distilled water handled 1n the
field, and resins for collection of organlcs from gases.
3.3 ANALYTICAL QUALITY CONTROL
The quality control procedures for all analytical methods 1n the
monitoring program are critical for obtaining reliable and consistent data.
Analytical QC practices Include the use of standard methods when available,
calibrations, analysis of standard reference materials, and the frequent
analysis of QC check samples.
The quality control of all test results can be directly related to proper
calibration procedures. Calibration procedures and standards should be spe-
cified for all equipment and supplies used. TraceablHty to common standards
1s essential 1f analytical procedures are conducted 1n multiple laboratories.
Quality assurance procedures for standards and calibration Include the follow-
ing:
• written, detailed cal1brat1on Instructions,
• preparation procedures for secondary standards, when
applIcable,
3-5
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• requirements for frequency of calibration,
• record keeping of all calibrations and standards used,
• quality control charts for recording results from multiple
calibrations,
• evaluation of Internal standards,
• tolerances for calibration requirements,
• action when calibration requirements are not met.
All calibration results should be Included 1n the data base for review
and statistical analyses.
Each analytical protocol should have detailed requirements for equipment
and supplies. Reagents, solvents, and standards with specific levels of
purity should be defined within the monitoring program. Resins, GC column
materials, glassware, and sample handling equipment should also be specified.
The quality control procedures for equipment and supplies Include the
following:
• checklists for required supplies,
• documentation and reporting of all deviations from specified
equipment,
• procedures for testing for purity of reagents,
• tolerances for glassware, when applicable,
• purchasing h1gh-pur1ty d1 stmed-1n-glass solvents 1n large
quantities from a single lot,
• cleaning of glassware with chromic add or firing 1n a kiln,
and
• use of organic free water when appropriate.
Routine quality control samples analyzed concurrently with samples will
be a significant portion of laboratory quality control efforts. The purpose
of these checks are twofold:
3-6
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• to assure that samples being analyzed satisfy predetermined
standards of accuracy* and
• to measure and document actual levels of accuracy and
precision.
There are many different types of quality assurance samples which could
be used for these purposes. The correct combination will depend on the eco-
nomics and complexity of the analytical method and the desired degree of
accuracy. The following quality control parameters are general considerations
for field and laboratory analyses:
• Interferences - The analytical results may be affected by
Interferences from the glassware, solvents, reagents, sample
handling or sample matrix. Blank samples subjected to condi-
tions similar to actual samples can be used to evaluate Inter-
ferences from procedures, equipment or reagents. Frequency of
blank analysis will depend on the extent of the Interference
Indicated by Initial results and on the frequency of restocking
reagents and supplies. Blanks should be run routinely for
1mp1nger solutions, organic collection resins, filters and
extraction solvents. Positive or negative Interferences may
also arise from components 1n the sample matrix. Methods
should be verified for each matrix as discussed 1n Section 3.4
and periodically checked, particularly 1f changes 1n the pro-
cess operations Indicate potentially significant changes 1n the
sample matrix.
• Recovery - The accuracy of much analytical data 1s directly
related to the efficiency of analyte recovery through the
various steps 1n a measurement or preparative procedure such as
extraction or purging. Recovery can be measured using Internal
standards or spiked samples which are analyzed as any other
sample. Recovery efficiencies should be determined to define
deviations and compared to accuracy requirements for each
measurement technique.
• Precision - The precision or repeatability of a method 1s
required for proper Interpretation and weighting of the
resulting data. Repeat samples or standards can be used to
determine precision on a regular basis. The difference between
replicate analyses should be compared against predetermined
precision limits for acceptability. If repeated analyses are
not possible, for example with on-Hne process GC analyses,
then moving-ranges can be used to measure precision. The
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precision may be reported as a standard deviation of repeat-
ability statistic and may depend on the concentration of the
analytes.
• Reprodudbll 1ty - The reprodudbll 1ty of a method refers to the
repeatability over a period of time. How well will analyses
repeated a month later agree with today's results? Reproduc-
1b1l1ty will be measured by repeated analysis of samples from a
previous time period.
• Qualitative Specificity - In complex sample matrices with
multiple compounds, the use of some methods, such as GC, can
lead to m1s1dent1f1cat1on of compounds. The extent of mlslden-
t1f1cation can be estimated by repeated analysis of standards
containing compounds of Interest. Confirmation by alternate
methods, such as GC-MS provide a basis to evaluate m1s1dent1f1-
catlon problems.
The QA plan should Include procedures for establishing a "closed loop"
mechanism for analyzing QC data, reporting, and correcting problem areas. QC
reports should be sent regularly to appropriate personnel. Forms and proce-
dures will document QC results, report the results to the QA Coordinator or
monitoring project management, and document corrective actions taken to expe-
dite the production of meaningful data.
3.4 METHOD VERIFICATION
Analytical methods for a specific monitoring program should be verified
for application to expected sample matrices through a formal verification
procedure. Figure 3-1 summarizes an example verification procedure. This
verification will give accuracy and precision estimates for each method and
determine 1f the accuracy and precision are dependent on the concentration
levels and/or sample matrix effects. Each verification requires 24 analyses
by the method. Modifications to this example protocol may be required for
some specific methods. In the general verification protocol for aqueous
samples, clean water Is spiked at levels of 2, 5, 10 and 20 times the detec-
tion limit of the method. Each spiked sample 1s analyzed three times. A
3-8
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to
I
CLEAN WATER
1
SPIKE i
SAMPLE MATRIX
1
SPIKE i
LEVEL COMPUTE LEVEL j
Zx(dl) &• — 1- • »-
V V 1 v
XHI X||2 | x(1)
1
Sx(dl) • »• • I l
1
10x(dl) ^ — 1 — '•• •••• i
X|3I XU2 1 XU3
1
1
20x(UI) ^ 1
X|4I X|42 X|4J
X~n-0,,. ° | i
COMPUTE
s\
Jf21. a-,,.
X2n X212 1 X2|3
1
X22i X222 | Xj
1
y ^ IOX(X2|) ^ I J
"231 232 1
i
1
JT . a 2ox(x21) •»• • i
X24i X242 X,
23
233
»^ rr
X24.U 24-
t43
KEY:
dl = DETECTION LIMIT FOR METHOD
X,,k = ANALYTICAL RESULT FOR SAMPLE MATRIX I. SPIKE LEVEL |, AND ANALYSIS k
Y,,.= AVERAGE OF 3 ANALYTICAL RESULTS FOR EACH MATRIX AND LEVEL
01|. STAN DARD DEVIATION OF 3 ANALYTICAL RESULTS FOR EACH MATRIX AND LEVEL
Figure 3-1. Example method verification scheme
-------
process sample for which the method is intended should be obtained and ana-
lyzed in triplicate. The average of these analyses (*2,) w^ be used ^°
determine spiking levels for the parameter of Interest. This general verifi-
cation approach 1s applicable to vapor phase Impinger collection techniques
(the Impinger solution 1s spiked). For resin collection techniques an
analogous verification approach can be Implemented
The data from verification studies can be analyzed statistically to
determine:
• the type of error (constant versus proportional to concentra-
tion)
• accuracy (measured concentration versus spikes)
• precision (variation in measured concentrations)
• matrix effects (compare precision and accuracy of sample to
spiked clean water).
The results should be summarized as part of a written procedure for the
specific method.
3.5 SAMPLE MANAGEMENT
The control of storage and handling of samples 1s an important part of
the QA system. Samples should be tracked from the time they are collected
through storage and analysis.
The sample management and tracking identifies Information 1n three areas
for each sample collected:
• time of collection and basic descr1ption»
• sample status (location, splits),
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• analytical status of sample (analyses to be done and analyses
completed).
A master log of all process samples should be maintained for sample
coordination and data evaluation.
3.6 REFERENCES FOR SECTION 3
3-1. U.S. Environmental Protection Agency, Strategy for the Implementation
of the EPA's Mandatory Quality Assurance Program. QAMS-001/80.
Quality Assurance Management Staff, Office of Monitoring and Technical
Support, Office of Research and Development.
3-2. Statistics Technical Committee, Glossary and Tables for Statistical
Quality Control, American Society for Quality Control.
3-3. U.S. Environmental Protection Agency, Guidelines and Specifications for
Implementing Quality Assurance Requirements for EPA Contracts and
Interagency Agreements Involving Environmental Measurements. QAMS-
002/80. Quality Assurance Management Staff, Office of Monitoring and
Technical Support, Office of Research and Development.
3-4. U.S. Environmental Protection Agency, Quality Assurance Handbook for
A1r Pollution Measurement Systems, Volume I, Principles. EPA-600/9-76-
005. March 1976.
3-5. U.S. Environmental Protection Agency, Quality Assurance Handbook for
Air Pollution Measurement Systems, Volume II, Ambient A1r Specific
Methods. EPA-600/4-77-027a. May 1977.
3-6. U.S. Environmental Protection Agency, Quality Assurance Handbook for
A1r Pollution Measurement Systems, Volume III, Stationary Source Speci-
fic Methods. EPA-600/4-77-027b. August 1977.
3-11
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3-7. U.S. Environmental Protection Agency, The EPA Program for the Stan-
dardization of Stationary Source Emission Test Methodology—A Review.
EPA-600/4-76-044. August 1977.
3-8. U.S. Environmental Protection Agency, Handbook for Analytical Quality
Control 1n Water and Wastewater Laboratories. EPA-660/4-019. March
1979.
3-9. U.S. Environmental Protection Agency, Procedures for the Evaluation of
Environmental Monitoring Laboratories. EPA-600/4-78-017. March 1979.
3-10. U.S. Environmental Protection Agency, Interim Rad1ochem1stry
Methodology for Drinking Water. EPA-600/4-75-008; PB-253258/AS. March
1976.
3-11. U.S. Environmental Protection Agency, Manual for the Interim Certifica-
tion of Laboratories Involved 1n Analyzing Public Drinking Water
Supplies, Criteria, and Procedures. EPA-600/8-78-008. August 1978.
3-12. U.S. Environmental Protection Agency, Microbiological Methods for
Monitoring the Environment. EPA-600/8-78-017. December 1978.
3-13. U.S. Environmental Protection Agency, Methods for Chemical Analysis of
Water and Wastes. EPA-600/4-79-020. March 1979.
3-14. U.S. Environmental Protection Agency, Radioactivity Standards Distribu-
tion Program 1978-1979. EPA-600/4-78-033; PB-286981/AS. June 1978.
3-15. U.S. Environmental Protection Agency, Environmental Radioactivity
Laboratory Intercomparison Studies Program 1978-1979. EPA-600/4-78-
032; PB-284850/AS. June 1978.
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3-16. U.S. Environmental Protection Agency, Handbook for Analytical Quality
Control and Radioactivity Analytical Laboratories. EPA-600/7-77-088;
TVA-E-EP-77-4; PB-277254/9BE. August 1977.
3-17. U.S. Environmental Protection Agency, Manual of Analytical Quality
Control for Pesticides and Related Compounds 1n Human and Environmental
Samples. EPA-600/1-79-008. January 1979.
3-18. U.S. Environmental Protection Agency, Guides for Quality Assurance 1n
Environmental Health Research. EPA-600/1-79-013. January 1979.
3-13
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SECTION 4
SOURCE MONITORING
This section presents an approach to the development of the source moni-
toring portion of an effective, site-specific monitoring plan for a synthetic
fuels facility receiving assistance from the Synthetic Fuels Corporation. The
types of sources covered by this monitoring plan Include: 1) controlled dis-
charges of process effluents from discharge structures such as stacks, pipes,
or flares and 2) fugitive releases from processing, transportation, storage or
Impoundment facilities for feedstocks, products or solid/liquid wastes.
As Indicated 1n the Congressional explanation of the Energy Security
Act, Section 131(e) (reproduced 1n part 1n Section 1.0), 1t 1s Intended that
environmental and health-related monitoring conducted pursuant to this section
should "characterize and Identify areas of concern and develop an Information
base for the mitigation of problems associated with replication of synthetic
fuels projects." Thus, the objective of the monitoring program to be conducted
at each synthetic fuels facility receiving assistance 1s to develop a data
base. This data base must be adequate to characterize significant sources of
discharges to the environment. It also must provide a basis to help mitigate
problems 1n future facilities. To provide a comprehensive Identification of
"areas of concern", the data on emissions and discharges must be representa-
tive of major operating situations encountered during the Hfe of the plant
and must address both regulated and unregulated substances.
Mitigation of "problems associated with the replication of synthetic
fuels projects" can be accomplished through both administrative and technical
solutions. To support administrative solutions by state and federal
regulatory or permitting agencies, the data base should be adequate to
Identify situations which can be resolved 1n future projects by different
permit conditions, changes 1n existing regulations or development of new
regulations. To support technical solutions, the data base must be adequate
4-1
-------
to characterize the capabilities of existing pollution control technologies
and to Identify needs for developing modified or new control technologies.
Construction and operating permits Issued by the various local* state and
federal agencies will require monitoring of emissions and discharges to the
environment. Such monitoring will be done to demonstrate compliance with
limitations and performance requirements set forth 1n the permits. These
requirements will depend on both the location and design of the facility.
This section outlines the general source monitoring requirements needed to
develop a data base responding to the objectives discussed above for both
regulated and unregulated pollutants. As a practical matter, most of the
compliance monitoring required by permits for new facilities will be Included
1n this manual. However, the monitoring approach described here does not
necessarily Include all permit monitoring requirements, nor 1s the approach
suggested here guaranteed to be consistent with every conceivable set of
permit requirements. Permit monitoring requirements will be set by the
cognizant agency based on site-specific conditions. Accordingly, any sug-
gestions 1n this manual 1n conflict with permit monitoring requirements are
superceded by the permit requirements. Permit-required or compliance monitor-
Ing 1s expected to be a major source of the long term discharge characteriza-
tion data needed to fulfill a significant portion of the data base require-
ments.
Development of the source monitoring portion of a plan for monitoring
"environmental and health-related emissions" requires that a number of deci-
sions be made:
• selecting the streams and species to be monitored;
• determining process and control technology performance data to
support the discharge stream data;
• selecting the timing, frequency and duration of measurements;
4-2
-------
• selecting techniques and procedures for making the necessary
measurements; and
• selecting procedures for validating and analyzing the acquired
monitoring data.
The following sections provide suggestions, approaches and procedures to aid
1n these decisions. These are general discussions that apply to a number of
synthetic fuels technologies Including: oil shale mining and retorting,
direct and Indirect coal liquefaction, coal gasification, and tar sands (heavy
oil) recovery. Although this manual does not address all synthetic fuels
processes explicitly (for example monitoring needs associated with peat
processing are not discussed 1n detail) 1t 1s structured to be applicable to
any fossil fuel conversion process. The development of an environmental
monitoring plan 1s a very complex and highly site-specific task. The recom-
mendations and approaches given 1n this non-site-specific document will have
to be tailored by a facility operator to develop a plant-specific monitoring
plan.
To simplify the discussion of discharge streams for this wide variety of
technologies, generic stream categories have been developed. These are
described 1n Section 4.1 along with monitoring suggestions for each category.
A generic category Includes the streams from each technology which have simi-
lar characteristics, compositions and monitoring requirements. The monitoring
suggestions for a complete data base are then presented 1n the form of sub-
stance or property measurement needs for each generic stream category. In
most cases, the suggestions are to measure specific chemical substances or
properties. However, due to the large number of organic compounds of poten-
tial concern, survey analytical techniques that measure more than one com-
ponent of a class are suggested for many organlcs. If properly executed,
these techniques will provide data on the majority of compounds of environ-
mental or health concern.
4-3
-------
A general discussion of control technology performance monitoring 1s also
presented 1n Section 4.1. This discussion Includes the characteristics of
many of the control technologies which will be used 1n synthetic fuels
facilities. Recommended approaches for developing monitoring plans to charac-
terize removal efficiency for the design pollutant as well as other pollutants
of concern are provided. The design of a particular facility* performance
data availability and proprietary data restrictions will have a major Influ-
ence on the control technology monitoring aspects of any specific plan.
Alternative approaches for Implementing the monitoring suggestions for
the data base described 1n Section 4.1 are given 1n Sections 4.2 and 4.3. In
general, the alternatives describe options for phasing the monitoring effort.
A phased monitoring effort will allow the data base to be developed 1n the
most cost-effective manner. Other alternatives or phasing options which might
be suggested by those preparing specific monitoring plans should be acceptable
as long as they provide a data base covering major operating situations 1n the
detail needed to respond to the Intent of Section 131(e).
A two phase approach for developing the data base 1s described 1n some
detail 1n Section 4.2. Phase 1 of this suggested approach Involves an
Intensive monitoring effort to develop a complete data base representing
"normal" plant operating conditions. Phase 1 would be conducted for some
Initial period after plant shakedown. Preparation for Phase 1 monitoring 1s
accomplished during the start-up and shakedown period. Phase 2 Involves a
lower level-of-effort» long-term monitoring program 1n which a limited number
of "Indicator" species/parameters are monitored to "track" the data base
defined 1n Phase 1. During Phase 2, the detailed Phase 1 characterization
would be repeated when significant deviations from the conditions character-
ized 1n Phase 1 are observed through changes 1n Indicators.
Section 4.2 also shows how statistical principles can be used to define
the frequency and duration of monitoring. For the phased monitoring
approaches, Section 4.2 suggests that statistical techniques can be used to
analyze Phase 1 data and develop a Phase 2 monitoring plan design (I.e., to
4-4
-------
select Indicator species for Phase 2 monitoring). However* the extent and
nature of the data base collected 1n Phase 1 cannot be defined beforehand. It
1s possible that the results of Phase 1 data collection could fall to provide
a statistical basis for the selection of Indicator species for many Important
variables. If so, then an alternate approach to selecting Phase 2 monitoring
parameters might be required. Some of these alternate approaches are dis-
cussed 1n Sections 4.2 and 4.3.
In Section 4.4, alternative measurement techniques and procedures are
presented for each of the species or properties suggested for Inclusion 1n the
data base. Information 1s provided 1n enough detail to allow the Initial
selection of monitoring procedures for a monitoring plan. However, conditions
encountered 1n a particular facility and the potential for Interferences
require that the techniques be verified 1n preparation for Phase 1 monitoring.
It 1s likely that stream conditions or data quality control objectives will
require that at least some of the procedures be modified.
4.1 DISCHARGE STREAM AND CONTROL TECHNOLOGY DATA BASE SUGGESTIONS
The monitoring suggestions outlined in this section are designed to
provide the total data base needed to characterize discharges and control
technologies and to derive administrative and technical solutions to "repli-
cation" problems. This Includes both data required to comply with the
provisions of environmental permits and data on nonregulated pollutants.
This section presents information to aid 1n developing detailed source
specific monitoring plans. It Identifies the discharge streams of interest
(Section 4.1.1) and what data are desired for, or what species should be mea-
sured 1n, each stream (the "total" data base, Section 4.1.2). Section 4.1.3
discusses control technology monitoring.
4-5
-------
4.1.1 Discharge Streams of Interest
The synfuel technologies addressed 1n this manual Include coal gasifica-
tion, direct and Indirect coal liquefaction, oil shale mining and retorting,
and heavy oil production from tar sands. Based on a review of proposed
designs and publicly available data, a large number of potential discharge
streams were Identified. But even though the discharge streams arise from
different technologies or different parts of a facility, they have some char-
acteristics 1n common. Because of these similarities and the desire to
simplify the presentation of data needs 1n this manual, generic categories of
discharge streams were defined. A generic category 1s a group of streams with
similar characteristics and hence similar data needs.
The fifteen generic categories of discharge streams are presented 1n
Tables 4-1 through 4-3 for gases, liquids, and sol Ids, respectively. The
tables show: 1) examples of the types of streams 1n each generic category, 2)
components of Interest (environmentally significant species) 1n those streams,
3) the synfuels technologies that would be expected to generate the discharge
streams, and 4) clarifying comments. In some designs the example streams may
be routed to control devices. In these cases, the treated discharge should be
considered for monitoring.
The Information telling which synfuels technologies would generate the
example waste streams 1s based on an estimate of the probability ("usually",
"sometimes", or "rarely") that a stream will be found 1n a plant employing the
Indicated technology. Of course, the presence or absence of a stream 1n a
specific facility will depend on the design. For example, all synfuels tech-
nologies generate process-derived wastewater, but the design of the plant
water management system determines whether the wastewater 1s treated and
discharged to an outfall or reused within the plant.
4-6
-------
TABLE 4-1. GENERIC CATEGORIES - GASEOUS DISCHARGE STREAMS
Synfuels Technologies In which Discharge Stream
(see note a)
Generic Stream Categories
and Examples of Streams
Found In each Category
Environmentally
Significant Species
Potentially Present
Coal Gasification
or Indirect
Liquefaction
Direct
Liquefaction
011
Shale
May be Found
Tar
Sands
Comments
1. Boiler/furnace flue
gases resulting from the
combustion of conven-
tional fuels such as
coali fuel oil and natural
gas.
Criteria
pollutantsb;
Possible trace
elements (depends
on fuel)
This stream category
will be a major
potential source of
criteria pollutant
emissions and may be
regulated as such.
Emissions from these
types of sources have
been well character-
ized previously.
2. Bo1ler/furnace/1nc1n-
erator flue gases result-
ing from the combustion
of process-derived fuels
or waste streams such as:
a. flue gases from fuel-
gas-flred furnaces
b. flue gases from syn-
thetic distillate-fired
furnaces
c. flue gases from fur-
naces burning by-pro-
duct tars and oils
d. flue gases from waste
gas Incinerators
e. flue gases from sludge
Incinerators
f. flue gases from waste-
water Incinerators
Criteria
pollutants^;
Possible trace
elements (depends
on fuel)
Possible trace
organlcs, reduced
sulfur species
and reduced nitrogen
species (depends on
fuel and contusion
performance)
Fuels 1n this generic
category originate 1n a
process unique to a
synthetic fuels facil-
ity. Emissions from
3 these sources generally
are not well charac-
3 terlzed. Mixed fuel
combustors burning both
conventional and process-
1 derived fuels should be
treated as category 2
combustors for purposes
2 of monitoring. Some
flue gases will contain
2 organlcs and others will
not, depending on combus-
2 t1on/Incineration effi-
ciency.
(Continued)
-------
TABLE 4-1. (continued)
00
Generic Stream Categories
and Examples of Streams
Found 1n each Category
3. Unccmbusted vent gases
(monitored directly If
vented* monitored before
combustion 1f flared)
a. coal feeder vent
gas
b. transient routine
vent gases
c. startup/upset vent
gases
d. sulfur recovery system
tall gases
e. CO _- rich vent gas from
selective AGR
4. Tank vents
a. product storage
b. by-product storage
c. process storage/
surge tanks
5. Process fugitive
emissions
a. pump and compressor
seal leaks
b. valve and flange leaks
Synfuels Technologies In which Discharge Stream
(see note a)
Environmentally Coal Gasification
Significant Species or Indirect Direct 011
Potentially Present Liquefaction Liquefaction Shale
Reduced sulfur and
nitrogen species, CO,
organlcs, possible
trace elements, pos-
sible parttculates 2 23
1 21
1 21
1 1 1
1 1 2
Dissolved gases.
VOC, reduced sulfur 2 11
and nitrogen species 2 22
1 1 1
CO, VOC,
reduced sul fur
and nitrogen
species 1 11
1 1 1
May be Found
Tar
Sands
3
2
2
1
2
1
2
1
1
1
Comments
Unlike the previous two
categories, these
streams may contain sig-
nificant quantities of
organlcs and reduced
sulfur and nitrogen
species.
These streams will con-
tain volatile species
present In the stored
fluids.
These types of emissions
have been well charac-
terized In the petroleum
refining and petrochem-
ical Industries; however
the frequency and compo-
sition might vary for
synfuels facilities.
Very little data are
available on nonhydro-
carbon emissions.
(Continued)
-------
TABLE 4-1. (continued)
Synfuels Technologies 1n which Discharge Stream May be Found
(see note a)
Generic Stream Categories
and Examples of Streams
Found In each Category
Environmentally
Significant Species
Potentially Present
Coal Gasification
or Indirect
Liquefaction
D1 rect
Liquefaction
Oil
Shale
Tar
Sands
Comments
6. Fugitive gaseous and
partlculate emissions
from waste Impouncfcnent.
storage or disposal
facilities
a. wastewater storage
ponds and treatment
vessels
b. storage, treatment
and disposal faci-
lities for solid waste
containing volatile
organlcs, e.g.. sludge
landfarms
Partlculates
(depends on source)
dissolved gases,
VOC, reduced sul fur
and nitrogen species
These waste streams are
distinguished from those
1n category 7 (below) by
the fact that they con-
tain volatile or reac-
tive species.
7. Fugitive partlculate Partlculates
emissions
a. oil shale mining/haul Ing
b. feed storage
c. crushing, screening,
sizing and conveying
operations
d. sol Ids (e.g., dry ash.
slag) Impoundment and
disposal areas
3
1
1
1
3
1
1
1
1
1
1
1
3
1
1
1
Some of these sources
will not be present In
facilities employing
1n-s1tu processing.
Codes refer to probability of occurrence: 1 = usually found; 2 = may be found depending upon the conversion processes or design
approaches used 1n a specific facility; 3 = seldom found.
Criteria Pollutants Include S0_, NO , CO. partlculate matter, ozone and lead.
-------
TABLE 4-2. GENERIC CATEGORIES - AQUEOUS DISCHARGE STREAMS
o
Synfuels Technologies 1n which Discharge Stream
Generic Stream Categories
and Examples of Streams
Found 1n Each Category
1. Wastewaters discharged
to outfalls, Impoundments,
or deep wells that are not
unique to synfuels plants
and have their origins 1n
an organic-laden environ-
ment. Source of the raw
wastewaters which comprise
this category Include:
a. sanitary sewer wastes
b. some laboratory wastes
c. some equipment cleaning
wastes
2. Wastewaters discharged
to outfalls. Impoundments,
or deep wells that are not
unique to synfuels plants and
have their origins In an
organic-lean environment.
Sources of the raw wastewaters
which comprise this category
Include:
a. demlnerallzer regeneration
wastes
b. cooling tower blowdown (1f
fresh water Is only source
of makeup)
c. coal pile runoff
d. boiler blowdown
e. boiler ash/slag quench or
sluice water blowdown
f. runoff from dust control
Environmentally
Significant Species
Potentially Present
Water quality
parameters'*,
extractable a!1-
phatlcs and
aromattcs, trace
elements
Water quality
parameters'5.
trace elements
Coal Gasification
or Indirect
Liquefaction
1
1
1
1
1
1
1
2
2
(see note a)
Direct 011
Liquefaction Shale
1 1
1 1
1 1
1 1
1 1
1 3
1 1
2 3
2 2
May be Found
Tar
Sands
1
1
1
1
1
3
1
3
2
Comments
This category Includes
organlcs-conta 1n1ng
waste streams with
characteristics simi-
lar to those of anal-
ogous waste streams
from non-synfuels facil-
ities.
This category Includes
organic-lean waste
streams with character-
istics similar to those
of analogous waste
streams from non-
synfuels facilities.
(Continued)
-------
TABLE 4-2. (continued)
Synfuels Technologies 1n which Discharge Stream
(see note a)
Generic Stream Categories
and Examples of Streams
Found 1n Each Category
Env1 ronmental ly
Significant Species
Potentially Present
Coal Gasification
or Indirect
Liquefaction
D1 rect
Liquefaction
011
Shale
May be Found
Tar
Sands
Comments
3. Wastewaters codlsposed
with solid wastes or dis-
charged to outfalls, Im-
poundments or deep wells
that result from the quench-
ing, cooling, upgrading, etc
of the plant's main product
streams. Sources of the
raw wastewaters which com-
prise this category Include:
a. raw product separation
condensates/quench waters
(e.g. Lurgl gas liquor,
EDS cold separator
water, retort water)
b, product purification/
upgrading condensates
(e.g. sour water from
atmospheric or vacuum
fractlonatlon, sour
water from oil, naphtha
or solvent hydrogenatlon,
AGR condensates and blow-
down solvents).
c. product upgrading waste-
waters (e.g. methanol or F-T
synthesis condensates).
d. process area runoffs
Water quality para-
meters, b dissolved
gases, trace ele-
ments, trace
organlcs.
This category Includes
a number of high volume
waste streams which
(In raw form) will
tend to be unique to
the synfuels techno-
logy from which they
originate. Generally,
these streams have
not been well char-
acterized to date,
so this category
Is of major Interest
In source monitoring.
These streams are
different from f
those Included In
category 4 (below)
because they are
likely to contain
organic as well as
Inorganic contami-
nants at levels of
Interest. The nature
of the discharge stream
resulting from the
treatment of these
wastes will be highly
variable depending
upon the nature of the
raw waste, the array of
treatment technologies
used and the extent of
water recycle/reuse 1n
the facility.
(continued)
-------
TABLE 4-2. (continued)
Synfuels Technologies 1n which Discharge Stream
(see note a)
Generic Stream Categories
and Examples of Streams
Found 1n Each Category
Environmental ly
Significant Species
Potentially Present
Coal Gasification
or Ind1 rect
Liquefaction
Direct
Liquefaction
011
Shale
Hay be Found
Tar
Sands
Comments
I
ro
4. Wastewaters codlsposed
with solid waste or dis-
charged to outfalls. Im-
poundments or deep wells
that are unique to synfuels
facilities but are not In-
cluded 1n category 3 above.
Sources of the raw wastewaters
which comprise this category
Include:
a. methanatlon condensates
b. gaslfer ash/slag quench
or sluice system blowdown
c. sulfur recovery system
tall gas treatment con-
densates
d. runoff from oil shale
mining/storage operations
(overburden piles)
e. collected leachate from
solid waste landfill sites
Water qual1ty para-
meters,'1 trace ele-
ments, dissolved
gases
These wastewaters are
distinguished from those
Included 1n category 3
by their origin In a
portion of the process
which does not come Into
contact with any raw or
upgraded product streams
containing high concen-
trations of water solu-
ble organlcs.
Codes refer to probability of occurrence: 1 = usually found; 2 • may be found depending upon the conversion processes and design
approaches used In a specific facility, 3 = seldom found.
Water quality parameters of Interest In synfuels facilities are listed In Table 4-7.
-------
TABLE 4-3. GENERIC CATEGORIES - SOLID DISCHARGES
Generic Stream Categories
and Examples of Streams
Found 1n Each Category
1. Organic-laden solid
wastes not unique to syn-
fuels facilities.
a. biological oxidation
sludge from treatment
of sanitary sewage
b. collected dust
(feed solids)
c. excess coal fines
2. Organic-free or
organic-lean solid
wastes not unique to
synfuels plants.
a. ashes from combus-
tors burning conven-
tional fuels
b. FGD sludges
c. makeup water treat-
ment sludges.
d. oil shale mining
overburden
Environmentally
Significant Species
Potentially Present
Leachable organlcs
and Inorganics,
1gn1tabtl1ty (coal
fines), trace
elements
Trace elements
Synfuels Technologies 1n which Discharge Stream
(see note a)
Coal Gasification
or Indirect Direct 011
Liquefaction Liquefaction Shale
2 22
1 1 1
2 23
1 1 3
2 22
1 1 1
3 32
Hay be Found
Tar
Sands Comments
Categories 1 and 2 both
contain streams that are
expected to be similar
2 to analogous waste
streams In related In-
dustries for which some
3 characterization Infor-
mation has been gathered.
3 The main difference
between these categories
1s that the category 1
streams are expected to
contain low levels of
organlcs.
3
2
1
3
(Continued)
-------
TABLE 4-3. (continued)
Synfuels Technologies In which Discharge Stream Hay be Found
(see note a)
Generic Stream Categories
and Examples of Streams
Found 1n Each Category
Env1 ronmental ly
Significant Species
Potentially Present
Coal Gasification
or Indirect
Liquefaction
D1 rect
Liquefaction
011
Shale
Tar
Sands
Comments
3. Organic-laden solid
wastes unique to synfuels
facilities.
a. biological treatment
sludge from treatment
of process wastewaters
b. oil/process water
separation sludges and
spent filter media
c. excess raw shale fines
d. processed shale/sands/
char (carbonaceous
retorted shale)
4. Organic-free or organic-
lean solid wastes unique to
synfuels plants.
a. gastfer ash/slag
b. Incinerator solids/
brines
c. spent catalysts
d. decarbonized retorted
shale
e. byproduct sulfur If
treated as solid waste
Leachable and extract-
able organlcs and
1norgan1cSt 1gn1t-
abH1ty. reactivity,
trace elements
Trace elements,
extractable allpha-
tlcs and aromatlcs
Category 3 and 4 waste
streams are distinguished
from those 1n categories
2 1 and 2 (above) by their
origin. They originate
In a unit operation
1 which Is either unique
to a synfuels plant or
has some features which
3 are unique. Very limited
1 characterization data on
most of these types of
streams have been
gathered to date. Most
of the waste streams 1n
category 3 result from
the treatment of process
3 derived wastewaters con-
2 talnlng high concentra-
tions of organlcs (cate-
2 gory 3 streams 1n Table
3 4-2). Category 4
streams should contain
2 very low levels of
organlcs because they
were subjected to a high
temperature, oxidizing
regime before release.
Codes refer to probability of occurrence: 1 = usually found; 2
approaches used 1n a specific facility, 3 * seldom found.
may be found depending upon the conversion processes and design
-------
Several criteria were used to develop the generic categories. First, the
streams were grouped according to physical state* I.e., gaseous, aqueous, or
solid. Then the streams were subgrouped according to composition. Often, the
main distinguishing factor was the presence or lack of organlcs. Finally,
streams were grouped on the basis of uniqueness to synfuels technologies. For
example, treated wastewaters originally derived from raw reactor effluent
cooling are considered unique to synfuels facilities, while flue gases from on-
slte coal combustion are not. (Coal combustion gases should be similar to the
flue gases from any coal-fired boiler firing the same coal.)
The reason for separating unique and nonunlque streams 1s that greater
emphasis 1s placed on monitoring suggestions for unique streams. It 1s the
unique streams for which the least amount of information is publicly avail-
able. This approach is not intended to imply that the nonunlque streams are
unimportant or that monitoring of these streams 1s not desirable. It simply
reflects the facts that (1) more is known about the nonunlque streams,
(2) monitoring of nonunique streams may be clearly required by law or permit,
and (3) facility designers and permit reviewers are more experienced 1n
developing monitoring plans for these streams.
Although there are many differences 1n the processing sequences and
equipment used 1n synfuels facilities, the five technologies considered here
can be represented generally by the block flow diagram 1n Figure 4-1. While
this diagram does not cover technology variations 1n detail, 1t shows 1n
general the major sources of waste streams expected from these facilities (as
listed in Tables 4-1 through 4-3).
As shown 1n Figure 4-1, raw feed (coal, shale or tar sands) received from
the mine may undergo pretreatment steps such as crushing and sizing (feed
preparation) to generate a feedstock suitable for the main reactors. In the
main reactors, the prepared feed reacts with other feed materials such as
steam, oxygen, hydrogen, hot water, hot combustion gases or pyrolysis product
gases. These reactions generally produce a raw reactor effluent stream (raw
product or synthesis gas), and a mineral residue (e.g., ash, char, spent shale
4-15
-------
SULFUR
RECOVERY
TAIL GASES
STORAGEI
PREPARATION
EMISSIONS
FEEDER AND
STARTUP/UPSET
EMISSIONS TO
FLARING/INCINERATION
BYPRODUCT
SULFUR
FUEL GAS TO
INPLANT USEi
OR SALE
SNG
STORAGE
PILE RUNOFF
REACTOR RESIDUES
(a g , ASH. SLAG,
PROCESSED SHALE)
AQUEOUS
CONDENSATES
OFF GASES TO
SULFUR RECOVERY
OH FUEL
LIQUID PRODUCTS
TO STORAGE
AQUEOUS
CONDENSATES
INITIAL WASTEWATER
TREATMENT (a g ,
OIL/WATER SEPARATION.
BULK ORGANICS
REMOVAL, DISSOLVED
GAS STRIPPING)
EXTENDED WASTEWATER
TREATMENT (eg,
BIOLOGICAL OXIDATION,
CARBON ADSORPTION. ION
EXCHANGE. INCINERATION)
SLUDGES TO
TREATMENT
OR DISPOSAL
BYPRODUCT
HYDROCARBON
LIQUIDS AND
AMMONIA
INCINERATOR
' OFF-GAS
SLUDGES TO
TREATMENT
OR DISPOSAL
TREATED PROCESS
WASTEWATERS TO
INPLANT USES OR
DISCHARGEJIMPOUNDMENT
Figure 4-1. Generalized block flow diagram of synthetic fuels facilities.
-------
or spent sands). An alternative processing scheme, 1n situ processing, avoids
several of these unit operations by using the original resource formation as
the reaction vessel. With this approach, the main reactant 1s Injected Into
the formation (after fracturing 1n the case of coal or oil shale) and the
produced raw products are withdrawn from the formation through another well.
Hot, raw products from the main reactors generally undergo a series of
quenching and cooling steps which produce a condensed wastewater and gaseous
and/or hydrocarbon-rich liquids stream(s). The gaseous and hydrocarbon
liquids streams undergo further processing Including purification (e.g.,
removal of add gases such as H-S and CCL from the gaseous stream), separation
(e.g., flashing and distillation of hydrocarbon liquids), and some upgrading
(e.g., gas oil hydrogenatlon). In Indirect coal liquefaction, the purified
and upgraded gaseous stream 1s further processed to produce liquid hydrocar-
bons (e.g., Flscher-Tropsch synthesis).
In addition to the main processing sequence, Figure 4-1 also shows two
Important pollution control systems - sulfur recovery and wastewater treat-
ment. The sulfur recovery system processes sulfur containing gases (HLS-
contalnlng gases removed from fuel-rich gas streams by add gas removal
units and dissolved H_S stripped from wastewater) and produces by-product
sulfur and a desulfurlzed tall gas for discharge to the atmosphere. The
wastewater treatment system receives wastewaters from various parts of the
plant (e.g., raw product cooling and liquids product separation and up-
grading). The wastewaters are treated, as appropriate, for removal of:
1) suspended sol Ids, tars, and oils, 2) bulk organlcs, 3) dissolved gases,
4) residual organlcs, and 5) dissolved solids. The processes and sequencing
1n the wastewater treatment system are determined mainly by two factors - the
composition of the untreated wastewaters and the desired quality of the
treated waters (which 1s dependent on whether they will be reused, discharged,
or Impounded).
4-17
-------
Auxiliary systems needed to support the main process operations are not
shown 1n Figure 4-1. Auxiliaries which could be present Include steam and
electricity generation, cooling water system(s), air separation units, raw
water treatment, product/by-product storage facilities, and waste treatment
operations such as flares, Incinerators and solid waste disposal facilities.
Also omitted from Figure 4-1 1s the mining operation often present 1n con-
junction with these facilities, especially for oil shale and tar sands opera-
tions.
4.1.2 Discharge Stream Data Base Suggestions
Tables 4-4, 4-5, and 4-6 show suggested monitoring that would define the
total data base for the species and properties of Interest 1n each generic
category of gaseous, aqueous and solid discharges. The monitoring suggested
1n these tables represents the total data base. Comments are given to explain
why each type of monitoring 1s suggested, to qualify the general requirements,
or to Identify data needs of particular Interest. Table 4-7 provides a
specific listing of water quality parameters which are referenced as a group
1n Table 4-5. Table 4-8 lists specific organic compounds of Interest, also
referenced 1n Tables 4-4 through 4-6.
Tables 4-4 through 4-6 define the total data base that might be consi-
dered. Sections 4.2 and 4.3 present alternative phasing options for develop-
ing this total data base. Most of these phasing approaches call for moni-
toring the total data base only during an Initial limited period (Phase 1).
Monitoring conducted after that Initial period would generally be a much-
reduced (Phase 2) effort. For example, Phase 2 might consist of monitoring a
limited number of "Indicators" which "track" the entire data base. Therefore,
1n considering the monitoring suggestions 1n Tables 4-4 through 4-6, the
monitoring plan developer should keep 1n mind that monitoring for the total
data base need not be conducted Indefinitely.
4-18
-------
TABLE 4-4. DATA BASE SUGGESTIONS FOR GASEOUS DISCHARGE STREAMS
Generic Stream Category
Survey Analytical
Techniques^
Monitor In? Suggestions
Specific Component
Suggestions
Comments
1. Boiler/furnace flue gases
from the combustion of
conventional fuels
2. Boiler, furnace, or Inciner-
ator flue gases from combustion
of process-derived fuels or
wastes
Analysis for trace
elements, e.g. ICP
Analysis for allphattcs
and aromatlcs, e.g.
TCO/GRAV, GC/MS
Analysis for nitrogenous
compounds, e.g. GC/MS,
GC-N specific
Criteria pollutants
(see note c)
Criteria pollutants
(see note c)
Total Hydrocarbons
(see note g)
Reduced sulfur species
(see note d)
Reduced nitrogen
species (see note e)
Volatile trace
elements (see note f)
Organlcs In Table 4-8
These streams are major potential sources of emissions
1n most synfuels facilities. However, these streams
are not unique to synfuels plants. Monitoring 1s In-
tended to be consistent with typical permits for flue
gases from conventional sources such as fossil-fuel
fired steam generators.
Monitoring Includes those parameters found In conven-
tional flue gases, (I.e., criteria pollutants), plus
monitoring to determine the degree of destruction of
synfuel-derlved pollutants In the feed. Parameter
selection should be Influenced by the composition of
the feed, e.g., flue gases from combustion of a sulfur-
free feed would not be monitored for sulfur species.
Monitoring the feed for trace elements may be more con-
venient than monitoring the flue gases. Monitoring for
organlcs should vary depending upon the source of the
combustor feed. Some feed streams will be derived from
essentially organic-free environments; others fron
organic-laden environments. Flue gases from fuel gas-
or synthetic distillate-fired furnaces might not war-
rant detailed organlcs analysis unless Initial screen-
Ing analyses for total vapor phase hydrocarbons give
high results. Off gases from tar-fired furnaces or
sludge Incinerators might suggest a greater need for
detailed organlcs analyses.
(continued)
-------
TABLE 4-4. (continued)
Generic Stream Category
Monitoring Suggestions—
Survey Analytical
Techniques"
Specific Component
Suggestions
Comments
3. Uncombusted vent gases
or feed gases to flares.
ro
O
4. Tank vents
Analysis for trace
elements, e.g. ICP
Analysis for al1phat1cs,
aromatfcs and oxygenates,
e.g. TCO/GRAV, GC/MS
Analysis for nitrog-
enous compounds,
e.g. GC/MS, GC-N
specific
Analysis for sulfur con-
taining compounds, e.g.
GC/MS, GC-S specific
Analysis for allphat-
1cs, arcmatlcs and
oxygenates, e.g.
TCO/GRAV, GC/MS
Criteria pollutants
(see note c)
Total Hydrocarbons
(see note g)
Reduced sulfur species
(see note d)
Reduced nitrogen
species (see note e)
Volatile trace
elements (see note f)
Organlcs 1n Table 4-8
Reduced sulfur species
(see note d)
Reduced nitrogen
species (see note e)
Total hydrocarbons
(see note g)
Organlcs In Table 4-8
Monitoring of flare feeds Is suggested due to the
difficulty 1n monitoring flare combustion products and
to Identify potential components for ambient monitor-
Ing. Many flaring events will be Intermittent and of
short duration, and source monitoring may not be prac-
tical. Monitoring the source of the flare feed may be
considered (I.e., monitor the source when 1t Is not
being flared). Flow rate data on flare feeds during
flaring should be obtained If practical. Organlcs
monitoring should vary depending on the feed source.
Some feeds are essentially organic-free.
Monitoring Is Intended to Identify volatile components.
Process vessels and product/by-product tankage con-
taining unstablllzed or unhydrotreated liquids may pro-
duce vent gases containing a wide variety of com-
ponents. Monitoring selections should consider
the characteristics of the fluids contained In the
tark(s).
5. Process fugitive
emissions
Analysis for allphat-
1cs, arcmatlcs and
oxygenates, e.g.
TCO/GRAV, GC/MS
Total hydrocarbons
(see note g)
Carbon monoxide
H2S
Any component 1n the fluids being processed can be
released as a fugitive emission. The species sug-
gested are Intended as Indicators of fugitive leaks.
This Information, along with composition of the fluid
being processed, allows approximate levels of non-
monitored species to be estimated. Repeated high
results for hydrocarbon measurements might trigger
detailed organlcs analyses.
(continued)
-------
TABLE 4-4. (continued)
Monitoring Suggestions
Generic Stream Category
Survey Analytical
Techniques
Specific Component
Suggestions
Comments
6. Fugitive emissions from
waste Impoundments/ storage.
or disposal facilities
Total Hydrocarbons
Parti culates
H2S
Off-site ambient monitoring may be the preferred
approach 1n many cases. In some cases, depending on
site design and on the wastes/materials stored In
Impoundments. h1-vol samplers might be placed on-s1te
around the Impoundment or the downwind transect method
might be used. Characterization of feedstreams to the
Impoundment 1s suggested to Identify potential com-
ponents of fugitive emissions.
7. Fugitive parttculate emissions
Particulates
t>0
Ambient monitoring for fugitive partlculates will be
the preferred approach In many cases. In some cases.
on-s1te monitoring of suspended partlculate from
fugitive sources using hl-vol samplers might be
desirable, depending on the location of off-site
ambient monitors and the nature/significance of the
fugitive partlculates.
Flow rates and temperatures should also be measured for each point source discharge. Key process data should also be collected as necessary for
Interpretation of results; In particular, coal/oil shale/tar sand feed rate to the plant, feedstock composition, fuel burned In multi-fuel boilers
nature and flow rate of uncombusted vent gases or flare feeds, nature of liquids contained In vented storage tanks, and nature of liquids/gases
In process components potentially contributing to fugitive emissions should be noted or measured.
For each entry 1n this column, a specific representative survey procedure Is presented In Table 4-24 (Section 4.4) which would be applicable 1n
most cases. Alternative procedures are listed 1n Table 4-27. When using these or the alternative techniques In Table 4-27, the extent of com-
pound specific Identification and quantification achievable at a reasonable cost 1s dependent on sample complexity and on the specific protocol
used (e.g. sample volume). The Indicated analyses should be performed on both vapor phase (volatile) samples and entrained partlculates.
ICP = Inductively Coupled Optical Emission Spectrometry
GC/MS = Gas Chromatography/Mass Spectrometry
GC-N specific = Gas Chromatography with Nitrogen specific detection
GC-S specific = Gas Chromatography with Sulfur specific detection
°Cr1ter1a pollutants Include SO,, N0x, CO, parttculates, ozone and lead.
Reduced sulfur species Include H2S, COS, CS2, and mercaptans.
Reduced nitrogen species Include NH3 and HCN.
Volatile trace elements Include antimony, arsenic, mercury, and selenium.
^Vapor phase, noncondensable hydrocarbons.
-------
TABLE 4-5. DATA BASE SUGGESTIONS FOR AQUEOUS DISCHARGE STREAMS
Generic Stream Category
Monitoring Suggestions
Survey Analytical
Techniques''
Specific Component
Suggestions
Comments
I
ro
ro
1. Wastewaters discharged to out-
falls* Impoundments or deep wells
that are not unique to synfuels
plants and have their origins In
an organic-laden environment.
2. Wastewaters discharged to out-
falls. Impoundments or deep wells
that are not unique to synfuels
plants, and have their origins
1n an organic-lean environment.
3. Wastewaters codlsposed with
solid wastes or discharged to
outfalls. Impoundments or deep
wells that result from the
quenching, cooling, purifying,
upgrading, etc. of the plant's
main products.
Analysis for trace
elements, e.g. ICP
Analysis for al Ipha-
tlcs and aromatlcs,
e.g. TCO/GRAV, GC/MS
Analysis for trace
elements, e.g. ICP
Analysis for trace
elements, e.g. ICP
Analysis for altpha-
tlcs, aromatfcs
and oxygenates, e.g.
TCO/GRAV, GC/MS
Analysis for nitrogenous
compounds, e.g. GC/MS,
GC-N specific on base/
neutral extract.
Analysis for sulfur con-
taining compounds, e.g.
GC/MS, GC-S specific
Biological screening
tests
Water Qual 1ty Para-
meters (see Table 4-7)
Water QualIty Para-
meters (see Table 4-7)
Water Qual1ty Para-
meters (see Table 4-7)
Volatile Trace Elements
(see note c)
Organlcs In Table 4-6
Water quality parameters suggested for monitoring are
Intended to be consistent with monitoring 1n typical
permits for similar streams In related Industries.
Water quality parameters suggested for monitoring are
Intended to be consistent with monitoring 1n typical
permits for similar streams In related Industries.
Monitoring Is Intended to Identify potential organic
and Inorganic contaminants. Organic monitoring should
reflect the characteristics of the raw wastewaters,
e.g. high temperature gasification produces wastewater
containing few organlcs while low or medium temperature
gasification produces Wastewaters high 1n organlcs.
Organlcs monitoring for a treated discharge should
reflect the level of organlcs In the raw wastewaters.
(Continued)
-------
TABLE 4-5. (continued)
Generic Stream Category
Monitoring Suggestions'
Survey Analytical
Techniques'*
Specific Component
Suggestions
Comments
4. Wastewaters codlsposed with
solid wastes or discharged to
outfalls. Impoundments or deep
wells that are unique to synfuels
facilities but not Included In
category 3.
Analysts for trace
elements, e.g. ICP
Analysis for allphatlcs
and aromatlcs, e.g.
TCO/GRAV, GC/MS
Biological screening
tests
Water Qua!1ty Para-
meters (see Table 4-7)
Volatile Trace Elements
(see note c)
Organlcs In Table 4-8
Organlcs monitoring 1s Intended to confirm the
absence or near absence of organlcs In these
discharges.
If streams from more than one category are combined, monitoring for the combined discharge should Include the procedures suggested for
each category present. Flow rates should also be measured for each discharge to an outfall, Impoundment or deep well. Key process data
should also be collected as necessary for Interpretation of results; 1n particular, coal/oil shale/tar sand feed rate to the plant,
feedstock composition, or special operating conditions of wastewater treatment systems (e.g., one unit In system malfunctioning) should
be noted.
-t^
00
For each entry In this column, a specific, representative survey procedure Is presented In Table 4-25 (Section 4-4) which should be applicable In
most cases. Alternative procedures are listed In Table 4-28. When using these or the alternative techniques In Table 4-28, the extent of com-
pound specific Identification and quantification achleveable at a reasonable cost Is dependent on sample complexity and the specific protocol
used (e.g. sample volume).
ICP = Inductively Coupled Optical Emission Spectrometry
GC/MS « Gas Chromatography/Mass Spectrometry
GC-N specific = Gas Chromatography with Nitrogen specific detection
GC-S specific « Gas Chromatography with Sulfur specific detection
cVolat11e trace elements Include antimony, arsenic, mercury, and selenium.
-------
TABLE 4-6. DATA BASE SUGGESTIONS FOR SOLID DISCHARGES
-p.
I
ro
Honltortna Suaaestlons
Generic Stream Category
1. Organic-laden solid wastes
not unique to synfuels plants.
2. Organic-free or organic-
lean solid wastes not unique
to synfuels plants.
3. Organic-laden solid
wastes unique to synfuels plants
Survey Analytical
Techniques3
Analysis for trace
elements, e.g. ICP
(whole sample and
leachate)
Analysis for leachable
aHphatlcs and aro-
matlcs, e.g. TCO/GRAV,
GC/MS b
Analysis for trace
elements, e.g. ICP
(whole sample and
leachate)
Analysis for trace
elements, e.g. ICP
(whole sample and
leachate)
Analysis for leachable
and extractable al 1-
phatlcs, aromatlcs and
oxygenates/ e.g.
TCO/GRAV, GC/MS b
Specific Component
Suggestions
Ultimate and proximate
RCRA hazardous waste
tests0
Particle Size
Radioactivity
Ultimate and proximate
RCRA hazardous waste
tests0
Particle Size
Radioactivity
Ultimate and proximate
RCRA hazardous waste
tests0
Particle Size
Radioactivity
TOC, COD In
leachate
Comments
Monitoring In categories 1 and 2 1s Intended to
characterize the physical and chemical properties of
the wastes and to Identify potentially leachable con-
stituents. The difference 1n monitoring 1s the inclu-
sion of leachable organlcs 1n Category 1. The main
purposes of these recommendations are to satisfy
regulatory (e.g. RCRA) constraints and to confirm that
these wastes are not unique to synfuels facilities.
All monitoring suggestions are not practical for each
stream type within the generic category. Judgment
should be exercised In selecting analyses for each
stream.
Monitoring 1n categories 3 and 4 1s Intended to
characterize physical and chemical properties and
to Identify the constituents which could be atmos-
pheric emissions (e.g. entrained partlculates) or
enter surface water or groundwater as leachates. The
difference 1n monitoring 1s the level of organlcs for
category 3. All monitoring suggestions are not
practical for each stream type within the generic
category. Judgment should be exercised In selecting
the analyses for each stream.
Analysis for leachable
and extractabTe nitro-
genous compounds,
e.g. GC/MS, GC-N
specific"
Analysis for leachable
and extractable sulfur
containing compounds,
e.g. GC/MS, GC-S
spec1f1cb
(Continued)
-------
TABLE 4-6. (continued)
Generic Stream Category
Monitoring Suggestions
Survey Analytical
Techniques3
Specific Component
Suggestions
Comments
4, Organic-free or organic-
lean solid wastes unique to
synfuels plants.
Analysis for trace
elements, e.g. ICP
(whole sample and
leachate)
Analysis for
extractable al 1pha-
ttcs and
aroraatfcs. e.g.
TCO/GRAV, GC/HS
Ultimate and proximate See comments for stream Category 3.
RCRA hazardous waste
testsc
Particle Size
Radioactivity
TOC, COD 1n leachate
en
For each entry In this column/ a specific, representative survey procedure Is presented 1n Table 4-26 (Section 4.4)
which should be applicable 1n most cases. Alternative procedures are listed 1n Table 4-29. When using these or the alterna-
tive techniques 1n Table 4-29, the extent of compound specific Identification and quantification achievable at a reasonable cost
1s dependent on sample complexity and the specific protocol used (e.g., sample volume).
ICP = Inductively Coupled Optical Emission Spectrometry
GC/MS = Gas Chromatography/Mass Spectrometry
GC-N specific = Gas Chromatography with Nitrogen specific detection
GC-S specific - Gas Chromatography with Sulfur specific detection
These analyses are suggested for leachates produced by neutral aqueous extraction and extracts produced using methylene
chloride or other suitable organic extractant.
CIncludes tests for toxldty and, where appropriate, 1gn1tab11 Ity, corrostvlty, and reactivity.
Monitoring should Include measurement of flow rates of discharge streams. Key process data should also be collected as
necessary for Interpretation of results; In particular, coal/oil shale/tar sand feed rate to the plant, feedstock
compositions, and any special operating features of solid waste generators (e.g. gaslfler operating atypically) should
also be noted.
-------
TABLE 4-7. WATER QUALITY PARAMETERS OF INTEREST IN SYNFUELS WASTEWATERS*
PH
Color
Acidity
Alkalinity
Conductivity
Total sol 1 ds
Settleable sol Ids
TSS
TDS
COD
TOC
BOD5
Phenols
011 and Grease
Ammonia (total)
Cyanides
Formates
Thlocyanates
Sul fides
Sulfltes
Sul fates
Chlorides
Fluorides
NO"/ NO"
Phosphorus (total)
Radioactivity (gross a and 3)
Dissolved oxygen
Chromium VI
Depending on the composition of the wastewater being analyzed,
some of these parameters will be of more Interest than others.
TABLE 4-8. ORGANIC SPECIES OF SPECIAL INTEREST IN SYNFUELS DISCHARGE STREAMS
Species
Reasons for Spec1al Interest
Regulation,Guide! 1ne
or Standard 1n Related
Industry or Contained
on Pollutant List
Toxic Properties,
Health Effects,
(References)
Comments
e
Benzene NESHAP, OSHA, Water
Quality, Priority,
RCRA VIII
Aniline OSHA
Anthracene/ OSHA, Water
phenanthrene Quality, Priority
Acute and chronic poison
causing blood disorders
(leukemia) 1n exposed
workers and chromosomal
aberrations (23, 24, 25
26, 27, 28)
Cases of acute and
chronic poisoning re-
ported, impalrs oxygen
transport ability (23,
24, 25, 29)
May be present In soot,
coal-tar, and pitch,
which are known to be
carcinogenic to man
(23, 25, 30)
Found 1n test
data, potential
indicator for
simple aro-
ma tics.
Found in test
data, potential
Indicator for
amines.
Found in test
data, potential
Indicator for
higher weight
polycycllcs
(Continued)
4-26
-------
TABLE 4-8. (continued)
Species
Reasons for Special Interest
Regulation,Guide! 1ne
or Standard 1n Related
Industry or
on Pollutant
Contained
List8
Toxic Properties!
Health Effects,
(References)
Comments
e
Phenol
Pyr1d1ne
Benzopyrene
OSHA, Water Quality,
EGD-ref1n1ng and
coking, NESHAP*,
Priority, RCRA VIII
OSHA, RCRA VIII
Water Qua!1ty,
Priority, RCRA VIII
Acute and chronic
poisoning, causing
damage to 1iver and
kidneys (23, 24, 26)
Skin irritant, causes
depression of central
nervous system, chronic
poisoning causes damage
to liver, kidney and
bone marrow (23, 25)
Active carcinogen, causes
chromosomal aberrations
1n mammalian cells (23,
24, 31)
Found in test
data, potential
Indicator for
oxygenates
Found in test
data, potential
indicator for
nitrogen-con-
taining hetero-
cyclics
Found 1n test
data, potenti al
indicator for
higher weight
polycyclics
Compounds on this list are Included because they are generally accepted as
toxic and hazardous compounds and/or are possible indicators of the
potential presence of similar compounds which are toxic and hazardous.
= National ambient air quality standards
NESHAP = National emissions standards for hazardous air pollutants
OSHA = OSHA toxic and hazardous air contaminants
Water Quality = Water Quality Criteria
EGO-reflning = Effluent Guidelines for petroleum refining
EGD-cok1ng = Effluent Guidelines for byproduct coking
"NhSHAP* = Compounds considered for regulations under NESHAP
Priority = Priority pollutants (NRDC vs. EPA)
RCRA VIII = RCRA Appendix VIII hazardous constituents
Numbers refer to references 1n Section 4.5.
indicates reference 4-23.
For example, if 23 is shown, it
e
For a full listing of compounds of concern for which these species may be
Indicators, see Table 4-20.
4-27
-------
Some of the data needs suggested 1n Tables 4-4 through 4-6 will be
satisfied by permit-required monitoring, depending on the requirements for a
specific plant. The discharge streams actually monitored at a specific plant
will depend on the design and circumstances of the plant. (Not all of the
streams 1n Tables 4-4 through 4-6 would have to be monitored at every plant.)
Not all of the monitoring suggestions are applicable to all streams 1n a
generic stream category. In addition, some plants might have multiple
discharges of the same type (e.g., vents from three product gasoline storage
tanks). In such cases, only one of the Identical multiple discharges would
have to be monitored to supply data base needs.
Tables 4-4 through 4-6 suggest three types of monitoring: (1) "survey"
analyses that can detect many species 1n a single sample (e.g. analysis for
allphatlcs and aromatlcs via gas chromatography/mass spectrometry);
(2) sampling and analysis for a specific chemical component or tests for a
specific property (e.g. analysis of H2S 1n uncombusted vent gases); and
(3) biological testing (Included under the "survey analytical techniques"
heading).
Monitoring suggestions of the first type ("survey" analytical techniques)
are emphasized as an effective means of screening for substances actually
present, without attempting to judge, a priori, which specific compounds
will ultimately prove to be present. The application of survey techniques
thus helps assure that the monitoring program 1s tailored to the needs of each
Individual site. If, 1n Heu of the survey procedures, a 11st of specific
preselected compounds were developed for Inclusion 1n all monitoring programs,
there would be a risk that:
some potentially significant compounds that are actually
present at a specific facility might be missed, because they
were not foreseen and not Included on the 11st (this concern
could result 1n any such 11st being conservatively long); and
some compounds which are not actually present might be
monitored repeatedly because they are on the 11st.
4-28
-------
The classes of substances addressed by the survey techniques Include
trace organlcs and trace metals. For these classes the operator of the
monitoring program would be likely to use the suggested survey procedures*
even 1f focusing on a pre-selected 11st. Therefore, the application of
survey techniques seems to offer a technically sound and cost-effective
approach.
The Intent of the survey technique approach 1s to limit the suggested
techniques to a few well-defined procedures that provide the maximum amount of
Information at reasonable cost. As shown 1n Tables 4-4 through 4-6, repre-
sentative survey techniques Include, for example, gas chromatography/mass
spectrometry for trace organlcs analysis, and Inductively-coupled optical
emission spectrometry for trace elements. These specific, representative
procedures—defined further 1n Section 4.4 (Tables 4-24 through 4-26)—can
detect many substances. However, 1n some cases, matrix effects and/or the
aggregate level of contaminants 1n a given sample could mask the presence, or
give erroneous quantltatlon, of some compounds which could be accurately
detected otherwise. For these and other reasons, 1t might be desirable to
select one of the alternatives to the survey procedures, listed 1n Tables 4-27
through 4-29.
Monitoring suggestions of the second type 1n Tables 4-4 through 4-6
(analysis for a specific component or property) Include:
• monitoring for substances which are regulated (e.g., criteria
air pollutants, RCRA hazardous waste tests) and substances
which, 1f not always covered by some discharge or ambient
quality standard, are conventionally Included for monitoring 1n
many permits (e.g., H_S, NHL, some of the water quality param-
eters); and
• monitoring for organic species of particular Interest (Table
4-8); these organlcs are Included because they are generally
recognized as toxic and/or are potential Indicators of similar
compounds which are toxic.
4-29
-------
Most of the organlcs listed 1n Table 4-8 will normally be detected using
the survey analytical techniques. In cases where the substances 1n Table 4-8
are effectively quantified by the survey procedures, further analyses are
unnecessary. However, where a particular sample does not permit the determi-
nation of one or more of these substances using the survey techniques (e.g.,
due to Interferences), then alternative analytical techniques aimed specifi-
cally at tne pertinent substances are suggested.
The third type of monitoring suggested 1n Tables 4-4 through 4-6 1s
biological testing. It 1s suggested only for the two generic wastewater
categories which Include streams unique to synfuels facilities. The use of
biological testing to Identify discharge streams having possible unique (and
potentially hazardous) Impacts can provide perspectives beyond those derived
from chemical testing. Biological tests are probably most useful 1n defining
relative Impacts of discharge streams and 1n detecting possible synerglstlc or
antagonistic matrix effects. Some typical biological screening tests employed
for these purposes are listed 1n Table 4-9. Impacts of discharges on aquatic
ecology can be defined using test organisms representative of those Indigenous
to the receiving water (e.g., minnows or daphnla) 1n a phased b1omon1tor1ng
program. A typical test sequence might Include (1) one or more acute toxldty
screening tests 1n undiluted effluent and one or more mutagenlclty screening
tests, (2) 96-hour flow through tests for effluents Identified as toxic 1n (1)
using minnows to determine LC , (3) bloaccumulatlon tests to determine chemi-
cal uptake over a specified time period, and (4) short-term chronic toxldty
tests.
A fourth type of monitoring or data gathering not explicitly suggested 1n
Tables 4-4 through 4-6 1s plant operating data such as unit feed rates,
product output rates, or process temperatures. Such measurements are of
course necessary to allow emission rates to be calculated and to allow proper
assessment of plant operating status during the monitoring effort. Suggested
monitoring for plant operating parameters 1s discussed further 1n Section
4.1.3.
4-30
-------
TABLE 4-9. COMMONLY USED TECHNIQUES FOR DETERMINING THE
BIOLOGICAL ACTIVITY OF SPECIFIC WASTE STREAMS
Test Objective
Test Designation Activity Measured
Test Organism
i
GO
Health Effects
Cellular
(1n-v1tro)
Aquatic Ecology
Whole Animal
(Vertebrate)
Whole Animal
(Invertebrate)
Algal
Ames
RAM
CHO
CHO/K1
CHO/SCE*
Acute Static
Bloassay (48 or
96 hr)
Acute Static
Bloassay (48 or
96 hr)
Algal growth
Mutagenesls
(point mutation)
Cytotoxldty EC™
Cytotox1c1ty EC™
Mutagenesls
(point mutation)
Mutagenesls
(gross genetic change)
Lethality, LC5Q
Lethality, EC5Q
Lethality, EC™
Growth Inhibition, EQ
'50
Salmonella Typh1mur1um
Rabbit Alveolar Macrophage
Chinese Hamster Ovary
Chinese Hamster Ovary
(Kl cell line)
Chinese Hamster Ovary
Fresh Water or Marine Minnow
Daphnla (fresh water) or
Shrimp (marine)
Algae:
Selenastrum caprlcornutum
(fresh water)
Skeletonema costatum
(marine)
*S1ster chromatid exchange
-------
In order to select appropriate survey techniques to develop the data base
for organlcs and trace elements* a number of data sources were reviewed to
Identify substances of Interest 1n synfuels waste streams. These sources
Included:
• regulations* standards* and criteria for similar discharge
streams from related Industries,
• lists of known pollutants, and
• synfuels test data.
The results of this review are summarized 1n Tables 4-10 (for organic
compounds/classes) and Table 4-11 (for trace elements). For each compound or
class, references are provided to show the specific regulations, pollutant
lists or test data which support the Inclusion of the substance 1n the tables.
Under most circumstances, the few survey techniques suggested 1n Tables 4-
4 through 4-6 (and further defined 1n Tables 4-24 through 4-26) should detect
most of the substances listed 1n Tables 4-10 and 4-11, plus other unlisted
substances 1n the same groups. The substances listed 1n these tables might be
considered as some of those to which the analyst might be alert when Interpre-
ting the results of survey techniques. The tables should not be construed as
a 11st of the substances that must be Individually determined during moni-
toring, nor as a comprehensive listing of the only substances that need to
be considered. If approaches other than the suggested survey techniques are
proposed 1n a monitoring plan, attention should be given to how well the
different approach would address the substances 1n Tables 4-10 and 4-11.
The organlcs 1n Table 4-10 belong to one of five chemical groups, based
on their dominant functional characteristic.
• allphatlcs
• aromatlcs
- simple aromatlcs (benzene/toluene/xylene)
- polynuclear aromatlcs (PNAs)
4-32
-------
TABLE 4-10. ORGANIC SUBSTANCES OF INTEREST IN SYNFUELS WASTE STREAMS'
OJ
CO
Compound
Altphatlcs
alkanes
cycloal kanes
alkenes
alkadlenes
Aromatlcs
Simple Aromatlcs
benzene
to! uene
alkyl benzenes
blphenyls
1 ndans/lndenes
Polynuclear Aromatlcs
naphthalenes
anthracenes/phenanthrenes
acenaphthenes
acenaphthylenes
benz(a)anthracenes
pyrenes/chrysenes
benzopyrenes
d1 benzanthracenes
benzoperylenes
dlbenzoperylenes
f 1 uorenes
fl uoranthenes
benzof luoranthenes
Indenopyrenes
cholanthrenes
Nitrogenous Compounds
Amines and Hetarocvcles
alkyl am 1nes/d( amines
aniline
alkylanlltnes
naphthyl amines
aromatic dtamlnes
amlnoblphenyls
aromatic amines
pyrldlnes
pyrroles
Indoles
carbazoles
qulnol Ines
acrldlnes
worphol Ines
CAS Registry
Number
00074-82-8
00074-85-1
00071-43-2
00106-86-3
00092-52-4
00496-11-7/
00095-13-6
00091-20-3
001 20-1 2-7/
00065 -01-fl
00083-32-9
00208-96-8
00056-55-3
00129-00-0/
00218-01-09
00086-73-7
00206-44-0
00062-53-3
00110-86-1
00109-97-7
00120-72-9
00086-74-8
00091-22-5
00260-94-6
00110-91-8
fl
Regulation* Guideline or Standard
Exists In Related Industry
OSHA
OSHA, FWPCA
OSHA, FWPCA
OSHA
OSHA, Hater Quality, FWPCA
OSHA, Water Quality, FWPCA
OSHA, Water Quality, FWPCA
OSHA
OSHA, Water Quality
OSHA, Water Quality, FWPCA
OSHA, Water Quality
Water Quality
Water Quality
Water Quality
Water Quality
Water Quality
Water Quality
Water Quality
Water Quality
Water Quality
Water Quality
Water Quality
Water dual 1ty
OSHA, FWPCA
OSHA, FWPCA
OSHA
OSHA
OSHA
FWPCA
OSHA
Contained on
Pollutant List
RCRA VIII, PWC
Priority, RCRA VIII
TSCAR
NESHW", Priority,
RCRA VIII, TSCAR
NESHAP», Priority,
RCRA VIII, TSCAR
PWC
Priority
Priority, RCRA VIII
Priority
Priority
Priority
Priority, RCRA VIII
Priority, RCRA VIII
Priority, RCRA VIII
Priority, RCRA VIII
Priority
Priority
Priority, RCRA VIII
Priority, RCRA VIII
Priority
RCRA VIII
RCRA VIII
RCRA VIII
RCRA VIII
RCRA VIII
Priority, RCRA VIII,
TSCAR
RCRA VIII
RCRA VIII
RCRA VIII
Found In Synfyels
Test Data"'1
1,2,5,6,7
1,2,8
1,2,8
1,2,8
1,2,4,6,12,13
1,2,4,6,12,13
1,2,4,6,8,12,13
2,8.12
1,2.4,13
1,2,4,5,8,12
1,2,4,13
2,12
4,5,13
2,6
1,2,4,13
2,4
6
S
1.2,4,12
1,2,4,13
4,14
6
1.2.5,8,11,12
2,5,8
5
5
1,2,4,5.6,7,8,10,11,12
1,2.5,8,12
1,2.4,5,8,12
2
2.4,5,6,8,12
2
(Continued)
-------
TABLE 4-10. (continued)
Compound
CAS Registry
Number
— Reason for Interest
Regulation, Guideline or Standard
Exists In Related Industry
Contained on
Pollutant List0'6
Found In Synfyels
Test Data0''
nitrogenous Compounds (continued)
Mltrlles/Isocvanatas
alkyl nttrlles
aromatic nltrlles
alkyl Isocyanates
aromatic dl f socyanates
Phenol Ics
phenol
alkyl phenols
naphthols
dlhydrlc phenols
Indanols/lndenols
benzofuranol s
Carboxvltc Acids
alkyl adds
aromatic adds
Other Oxvyenates,
alkyl ethers
dloxanes
aromatic ethers
alkyl alcohols
cyclo alcohol s
cellosol ves
alkyl ketones
cyclo ketones
aromatic ketones
alkyl aldehydes
aromatic aldehydes
alkyl esters
aromatic esters
phthalate esters
f urans
benzof urans
d1 benzof urans
00075-05-8
00100-47-0
00624-83-9
00108-95-2
00064-18-6
00065-85-0
00115-10-6
00067-5«-l
00067-64-1
00098-86-2
00050-00-6
00100-52-7
00079-20-9
00093-58-3
00131-11-3
00110-00-9
00271-89-6
00132-64-9
OSHA
FWPCA
OSHA
OSHA
OSHA, Water Qual tty.
EGD-reflnlng, EGD-coklng, FWPCA
OSHA, FWPCA
OSHA, FWPCA
OSHA, FWPCA
OSHA
OSHA
OSHA
OSHA
OSHA
OSHA
OSHA
OSHA
OSHA
OSHA, FWPCA
OSHA, FWPCA
OSHA, Water Quality, FWPCA
NESHAP', Priority,
RCRA VIII
NESHAP', Priority,
RCRA VIII
NESHAP', Priority,
RCRA VIII, TSCAR
RCRA VIII
RCRA VIII
NESHAP', RCRA VIII
RCRA VIII
RCRA VIII, PWC
RCRA VIII, Priority,
TSCAR
RCRA VIII
NESHAP', RCRA VIII,
TSCAR
RCRA VIII
Priority, RCRA VIII
RCRA VIII
PWC
1,12,13
8,12
1,2,3,4,5,6,8,9,10,11,12,13
1,2,4,5,6,8,9,10,11,12,13
1,2,4,5 ,8,10
2,4,5,10
4,5,8,10
10
1,2,9,10,11,12
5
1
1
12
2,5
1
1,8,10,12,13
8,12
12,13
12
s
12
2,4,5
1,2,8,12
1,2,12
1.2,12
(Continued)
-------
CO
en
TABLE 4-10. (continued)
Raason for Interest
Con pound
CAS Registry Regulation, Guideline or Standard
Number'' Exists in Related Industry0'"
Contained on
Pollutant List"'8
Found In Synfyels
Test Data"'*
Sulfur Con.tatn.lng Compounds
alky! mercaptans
alkyl dtsulftdes
tMophenes
benzothlophenes
PSO, OSHA, FWPCA
PSO, OSHA
RCRA VIII
00110-02-1
00095-15-8
1.6,7
1.2
1.7,8,12
1,2,8,12
aThls table should not be construed as a list of organic substances that must be determined Individually by monitoring, nor should It be construed
as a comprehensive list of all the substances that need be considered. Rather, 1t Is a suggestion of some substances an analyst might be alert to
when Interpreting results of survey analytical techniques. Survey analytical techniques are presented in Tables 4-4 through 4-6 and Tables 4-24
through 4-26 In Section 4.4.
Service (CAS) numbers are for the parent compound {e.g. the CAb number shown for alkyl alcohols Is for methanol although the
ls Is Intended to Include all alkyl alcohols. CAS numbers are not provided for entries where tne parent compound Is not
(e.g. benzopyrenes) .
Chemical Abstract
term alkyl alcoho
straightforward (e.g
CN£SHAP = National emissions standards for hazardous air pollutants (Section 112 of Clean Air Act)
PSD = Pollutants for which de mlnlmls values exist (may be part of a general class of compounds) relating to prevention of significant
deterioration regulations
OSHA '= OSHA toxic and hazardous air contaminants
Water Quality = Pollutants for which water quality criteria have been developed by EPA pursuant to Section 304 of the Clean Kater Act
EGD-refining - Effluent Guidelines for petroleum refining
EGD-coklng = Effluent Guidelines for byproduct coking
FHPCA = Pollutants addressed by Section 311 (Oil and Hazardous Substance Liability! of the Federal Hater Pollution Control Act
Seme of the classes of compounds listed 1n this table Include a number of single specific compounds, e.g.. alky {benzenes Includes ethy (benzene.
propyl benzene, Isopropyl benzene, and the butyl benzenes. When a regulation, standard, pollutant list, or test data source 1s cited for such a
class, 1t means that one or more members of the class but not all members are covered by the regulation, standard, or 11st.
eNESHAP» = Compounds considered for regulations under NEiHAP (Section 112 of Clean A1r Act)
Priority • Priority pollutants (NRDC vs. EPA)
RCRA VI11 • RCRA Appendix ¥111 hazardous constituents
PWC « Pollutants under consideration for development of water quality criteria pursuant to Section 304 of tne Clean Hater Act
TSCAR = Toxic Substances Control Act Review - committee to review compounds for possible EPA testing
Numbers refer to references In Section 4.5. For example. If 13 Is shown. It Indicates data are from reference 4-13.
-------
TABLE 4-11. TRACE ELEMENTS OF INTEREST IN SYNFUELS WASTE STREAMS'
Reason for Interest
Trace Element
CAS Registry
Number
Regulation, guideline or standard
exists In related Industry
Contained on
Pollutant List
Found In Synfuels Test Data
CO
cn
Antimony 07440-36-0 OSHA, FWPCA
Arsenic 07440-38-2 OSHA, Water Qualtty. FWPCA
Drinking Water, RCRA EP
Barium 07440-39-3 OSHA, Water Qual1ty, FWPCA
Drinking Water,RCRA EP
Beryllium 07440-41-7 NESHAP, PSD, OSHA,
Water Quality, FWPCA
Boron 07440-42-8 Water Qual 1ty
Cadmium 07440-43-9 OSHA, Water Quality,
Drinking Water, RCRA EP, FWPCA
Chlorine 07782-50-5 OSHA, Water Qual1ty,
Drinking Water, EGD-steam, FWPCA
Chromium 07440-47-3 OSHA, Water Qual1ty, Drinking Water,
EGD-ref1n1ng, EGD-steam, RCRA EP, FWPCA
Copper 07440-50-8 Water Qual 1ty, Drinking Water,
EGD-steam, FWPCA
Fluorine 07782-41-4 PSD, OSHA, Drinking Water, FWPCA
Iron 07439-89-6 Water QualIty, Drinking Water
EGD-steam, EGD-m1n1ng, FWPCA
Lead 07439-92-1 NAAQS, PSD, OSHA, Water Quality,
Drinking Water, RCRA EP, FWPCA
Manganese 07439-96-5 OSHA, Water Qual1ty, Drinking Water,
EGD-m1n1ng, FWPCA
Mercury 07439-97-6 NESHAP, PSD, OSHA, Water Quality,
Drinking Water, RCRA EP, FWPCA
Molybdenum 07439-98-7 OSHA
Nickel 07440-02-0 OSHA, Water Qual1ty, FWPCA
Phosphorus 07723-14-0 EGD-steam, FWPCA
Selenium 07782-49-2 OSHA, Water Qual 1ty, Drinking Water,
RCRA EP, FWPCA
Silver 07440-22-4 OSHA, Water Qual Ity, Drinking Water,
RCRA EP, FWPCA
Thallium 07440-28-0 OSHA, Water Qual1ty, FWPCA
Tin 07440-31-5 OSHA
Vanadium 07440-62-2 OSHA, FWPCA
Zinc 07440-66-6 Water Qual Ity, Drinking Water, EGD-
steam, FWPCA
Priority, RCRA VIII, TSCAR
Priority, RCRA VIII
RPAR, TSCAR
Priority, RCRA VIII, PWC
Priority, RCRA VIII
PWC
Priority, RCRA VIII, RPAR, TSCAR
PWC, RCRA VIII, TSCAR
Priority, RCRA VIII, TSCAR
Priority
RCRA VIII
RCRA VIII, PWC
RCRA VIII
Priority, RCRA VIII
NESHAP*, PWC
Priority, RCRA VIII, TSCAR
PWC
NESHAP*, Priority, RCRA VIII
RCRA VIII, PWC
Priority, RCRA VIII
Priority, RCRA VIII
Priority, RCRA VIII
RCRA VIII, PWC
RCRA VIII
2,7,9,13,17,19,21
1,2,6,7,13,14,15,16,17,18,19,20
21,22
1,2,7,13,14,15,16,17,18,19,22
13
1,2,7,13,14,15,16,17,18,19,20,22
3,6,7,13,15,18,19,22
1,2,3,6,7,13,15,16,17,18
1,6,13,14,15,16,17,18,19
1,2,3,6,7,13,15,16.17,18,19,21
6,7,13,14,16,17,18,19
1,2,3,7,13,15,16,17,18,19,20,21,22
3,6,13,15,16,17,18,19,22
1,2,13,14,15,16,17,18,19,21,22
2,6,13,14,16,17,18,19,21
3,13,17,18,19,20,21
1,3,6,13,14,15,16,17,18,19,21,22
2,7,13,16,17,18
1.2,6,7,13,14,15,16,17,18,19
1,7,13,15,18
7,13,15,17,18
2,13,15,18,19
1,2,3,6,13.14,15,16,17,18,19
(Continued)
-------
TABLE 4-11. (continued)
This table should be construed only as a suggestion of some of the substances an analyst might be alert to when Interpreting results of the survey
analytical techniques presented In Tables 4-4 through 4-6 and Tables 4-24 through 4-26 In Section 4.4
Includes the total quantity of element present. I.e., both the free element and Its compounds.
Chemical Abstract Service Registry Number
NAAQS = National ambient air quality standards
NESHAP = National emissions standards for hazardous air pollutants (Section 112 of Clean A1r Act)
PSD = Pollutants for which de m1n1m1s values exist (may be part of a general class of compounds) relating to prevention of significant
deterioration regulations
OSHA = OSHA toxic and hazardous air contaminants
Water Quality = Pollutants for »h1ch water quality criteria have been developed by EPA pursuant to Section 304 of the Clean Water Act
Drinking Water = Primary and Secondary Drinking Water Standard
EGD-ref1n1ng = Effluent Guidelines for petroleum refining
EGD-steam = Effluent Guldllnes for steam electric power generating
EGD-m1n1ng = Effluent Guidelines for coal mining
RCRA EP = RCRA Extraction Procedure for toxic pollutants
FWPCA = Federal Water Pollution Control Act 011 and Hazardous Substances listing for regulatory promulgation
eNESHAP« = Compounds considered for regulations under NESHAP (Section 112 of Clean Air Act)
Priority = Priority pollutants (NDRC vs. EPA)
RCRA VIII = RCRA Appendix VIII hazardous constituents
j-., PWC = Pollutants under consideration for development of water quality criteria pursuant to Section 304 of the Clean Water Act
I TSCAR = Toxic Substances Control Act Review - committee to review compounds for possible EPA testing
OJ RPAR = Rebutable Presumption Against Registration (Subject to manufacturing, transporting and use restrictions.)
Numbers refer to references 1n Section 4.5. For example, 1f 13 Is shown, 1t Indicates data found In reference 4-13.
-------
• nitrogenous compounds
- heterocycles and amines
- nitrlles and Isocyanates
• oxygenates
- phenols
- carboxyl 1c adds
- other oxygenated compounds
• sulfur containing compounds
Over seventy compounds or classes of compounds are listed 1n Table 4-10. If
each Individual compound 1n each class were listed* the number of entries
would be even greater. However» as Indicated 1n Tables 4-4 through 4-6, only
a few survey techniques are needed to Identify the five groups of organic
compounds 1n Table 4-10.
The regulations, standards, or criteria reviewed to develop the lists of
organlcs and trace elements of Interest Included 1) non-source-specific docu-
ments such as national ambient a1r quality standards, the OSHA 11st of air
contaminants, and water quality criteria, and 2) source-specific documents
such as new source performance standards and effluent guidelines for related
Industries. Pollutant lists reviewed for substances of Interest included the
11st of compounds considered for regulation under NESHAP, the priority pollu-
tant 11st, and the RCRA Appendix VIII hazardous constituents 11st.
Table 4-10 1s not a summary of all organic substances contained 1n the
regulations, standards, criteria, and pollutant lists reviewed. Many of the
substances found on those lists are not expected to be present 1n synfuels
discharge streams, and accordingly, were not included. Most of the substances
not included are manufactured chemicals or by-products of chemical manufac-
turing. For example, halogenated herbicides, pesticides, and insecticides—
major components 1n the priority pollutant 11st for aqueous streams—are not
Hkely to be present in synfuels waste streams and are not Included in Table
4-10.
4-38
-------
For the most part* the available synfuels test data referenced 1n Tables
4-10 and 4-11 were for raw waste streams and not treated discharges. The
assumption could be made that many of the substances found 1n test data for
raw waste streams would be either absent or present at very low or undetect-
able levels 1n treated discharges. However, this does not diminish the need
to establish the presence or absence and, 1f necessary, the concentration of
the substance 1n the treated discharge.
The synfuels test data review did not Involve an exhaustive search of
publicly available data. However, the data sources examined were adequate to
Identify the major classes of organlcs which could be present in synfuels
discharge streams. In developing monitoring plans, synfuels facility
developers are encouraged to use their own test data to supplement or modify
the data base requirements identified in this manual.
4.1.3 Control Technology Monitoring
Control technology monitoring involves collection of data that define
relationships between inlet stream characteristics, control device operating
conditions and outlet stream characteristics. While the major objective of
source monitoring 1s to characterize discharge streams, there are many bene-
fits to be gained from monitoring and reporting data for the Inlet streams to
control devices and the operating conditions of those devices (1n addition to
data on the resulting discharge stream):
• Synthetic fuel process developers and environmental agencies
would be better able to assess the performance of applied
control devices, thus improving the chances for mitigating
potential problems in future facilities. This assessment would
Include an evaluation of the performance of the device in
removing both regulated and unregulated species.
• The data would provide insight Into control device performance
problems and allow Identification of control technology design
Improvements and development needs for future facilities.
4-39
-------
• Facility operators might be able to reduce Phase 2 monitoring
costs by monitoring easy-to-mon1tor Inlet stream character-
istics and/or certain operating conditions Instead of discharge
stream characteristics. Of course, a good correlation between
Inlet stream compositions, operating condltlon(s), and
discharge stream compositions would be required to Implement
this approach.
In many cases, plant operators will routinely monitor control device Inlet
stream characteristics and operating conditions to control plant operations.
If so, the collection and reporting of these results might not significantly
Increase monitoring expenses.
The strongest justification for the acquisition of control process
performance data 1n addition to data on discharge stream characteristics 1s
related to the primary objective of the source monitoring program Itself,
I.e., to avoid environmental problems Identified 1n first generation facil-
ities 1n future replications of the technologies. There 1s currently a some-
what limited understanding of design requirements, performance capabilities,
and reliability of conventional control processes 1n a synthetic fuels plant
application. Early Identification of the sources of any control device per-
formance problems will help assure that future controls can be designed for
cost-effective and reliable performance.
In some cases, an Interest 1n monitoring the Inlet to a control device
might be stimulated by pollutant levels monitored 1n the outlet. For example,
high levels of organlcs 1n a control device outlet stream might make 1t
desirable to check for variations in inlet stream composition or control
device operating considerations to determine whether these factors were con-
tributing to high output levels.
Collection of data on control device operating conditions and inlet
stream composition might allow the development of simple performance models.
Such model development and validation could benefit both the facility operator
and environmental agencies. A data base would be provided for use in design-
Ing reliable controls and predicting performance of proposed controls. In
4-40
-------
addition, a facility operator might be able to demonstrate that emissions
would be expected to remain within a defined range as long as certain gross
Inlet composition parameters (e.g., VOC and incinerator temperature) are in
specified ranges.
While the benefits of control technology monitoring are readily apparent,
site specific constraints might limit the ability of a plant owner to gather
and/or report data on control device performance. These constraints Include:
Data on some Internal stream properties or control device
performance parameters may be proprietary.
Key inlet stream properties may be significantly different
(more complex matrix) or more highly variable than outlet
stream properties, complicating the monitoring effort.
In some cases, multiple control devices are linked in series to
produce a treatment "train". In such cases, the resources
required to monitor each Individual control device 1n the
series should be weighed against the value of the Information
gained by monitoring to determine whether monitoring every
device Is warranted.
The above factors suggest that control device monitoring program specifica-
tions must be established on a site specific basis.
Tables 4-12 through 4-14 are provided to aid 1n formulation of a control
technology monitoring program for gaseous, aqueous and solid stream controls,
respectively. These tables present:
• The major types of control devices that might be considered for
synfuels facilities.
• The major substances controlled by each device and typical
removal efficiencies. Inlet stream monitoring would
logically include the same array of substances/survey tech-
niques considered for the outlet stream (as listed in Tables
4-4 through 4-6), in order to provide a good data base for
4-41
-------
TABLE 4-12. TYPICAL SYNFUELS PLANT CONTROL DEVICES AND KEY OPERATING
VARIABLES—GASEOUS STREAMS
Stream Control Options Substances Controlled Emissions Levels
Typical Uncontrolled Typical Outlet/ Secondary Discharge
Control Levels
Streams
Major Control Device
Operating Parameters Affecting
Emission Levels
I
-fc>
ro
Stream. Type; Combustion Flue Gases (Generic Categories 1 and 2 In Table 4-11
Participate Controls
Baghouses Partlculates Up to 10 lb/106 Btu <0.10 lb/106 Btu Collected sol Ids
(for coal-fired
boilers)
ESPs
Wet Scrubbers
Mechanical Collectors
(cyclones)
Partlculates
Partlculates
(potentially S0
Partlculates
Up to 10 lb/106 Btu <0.10 lb/106 Btu Collected sol Ids
Up to 10 lb/10 Btu <0.30 lb/10 Btu
Up to 10 lb/10 Btu
lb/10 Btu
Collected sol Ids
(wet)
Liquid blow down
Collected sol Ids
Air/cloth ratio
Bag cleaning procedures.
Pressure drop
Precipitation rate (function
of parttcule resistivity,
particle size distribution,
gas velocity distribution,
rapping frequency, electri-
cal factors)
Specific collection area
(plate area)
Gas flow rate
Partlculate loading
L1qu1d-to-gas ratio
Gas velocity
Energy consumption
Particle size distribution
and loading
Inlet gas velocity (perfor-
mance affected greatly by
large load swings)
Particle size distribution
and loading
(Continued)
-------
TABLE 4-12. (continued)
Typical Uncontrolled
Stream Control Options Substances Controlleda Emissions Levels
Typical Outlet/
Control Levels
Secondary Discharge
Streams
Major Control Device
Operating Parameters Affecting
Emission Levels
Stream Type: Combustion Flue Gases (Generic Categories 1 and 2
1n Table 4-1)
SO. Controls
Wet Scrubbers
I
-p.
OJ
so2
(potentially partlculates)
Up to 10 lb/10 Btu
50-90-Kt removal
Spray Dryers
SO, Up to 10 lb/10 Btu
(and partlculates In
downstream solids
collection device)
50-80* removal
Fuel Pretreatment
(e.g. desulfurtzed
fuel gas)
H2S, RSH,
N/A
Up to 9M removal
Calcium based sludge
(from 11me, limestone
and dual alkal1 pro-
cesses) ; or sulfur or
H.SO. (from regener-
aole systems such as
Wellman-Lord); or
aqueous wastes (high
TDS blow down streams
from sodium-based
scrubbing systems)
Dry sol Ids (sodium
or calcium based
salts and any par-
tlculate matter 1n
the feed stream
such as bo1ler fly
ash)
Rich add gases or
sulfur
S0_ Inlet concentration
Gas residence time
Gas/11qu1d contact area
L1qu1d-to-gas ratio
Liquid phase aikalinity
(key soluble species 1n
1 Iquld phase)
SO- Inlet concentration
Sorbent type (sodium or
calcium-based) and sorbent/
S02 ratio
Gas residence time
L1qu1d-to-gas ratio
Dryer outlet temperature
Dry solids recycle
Same as controls for AGR
offgases (see below)
Combustion Modifications NO
(e.g. LEA, SC, FGR)
Post Combustion Controls N0x
Ammonia Injection
Catalytic reduction
<1 lb/10 Btu 10-50* reduction Must be careful to
control potential
Increases 1n CO,
participate, and
HC emissions wltn
combustion mods
<1 lb/106 Btu 40-80* NH.HSO. deposits on
outlet duct and
air preheater
surfaces
Excess air, fuel N content
OFA port location.
Burner design
Gas reclrculatlon rate
NO Inlet concentration
NH? Injection rate, mixing
temperature
Space velocity, catalyst
activity, NH3/NOx ratio
(Continued)
-------
TABLE 4-12. (continued)
Typical Uncontrolled Typical Outlet/
Stream Control Options Substances Controlled8 Emissions Levels Control Levels
Secondary Discharge
Streams
Major Control Device
Operating Parameters Affecting
Emission Levels
-p.
I
Stream Type: Sulfur Recovery System Offgases (Generic Category 3 1n Table 4-1)
Bulk Sulfur Recovery Processes
Claus
H2S
RSH
5-20+*
100 ppm
90% total S
Stretford
Ta.11 G3S Treatment PrQcessqs.
(e.g. Beavon, SOOT,
Wellman-Lord)
H2S
HCN
RSH
Up to 5*
100 ppm
100 ppm
<10 ppm
>90*
up to 90*
Depends on process
-------
TABLE 4-13. TYPICAL SYNFUELS PLANT CONTROL DEVICES AND
KEY OPERATING VARIABLES—AQUEOUS STREAMS
-pi
en
Process
Biological 0x1 da t Ion
Carbon Adsorption
Chemical Oxidation
Wet Air Oxidation
Thermal Oxidation
Gravity Separation
Chemical Precipitation
Dissolved Gas Stripping
Filtration
Membrane Separation
Forced Evaporation
Typical Control
Substances Controlled8 Efficiency
Phenols, TOC, 90+J phenolic
COD, BOD compounds
800, TOC, some S5+* BOO
trace metal s,
specific organlcs
TOC, COD, some 80+*
trace metal s,
spec! f Ic organlcs
COD, TOC, 5% CN~, 80+*
Nrt^* specific
organfcs
COD, TOC, S . CN , 90+*
specific organlcs
TOG, red S/N, 99X (organlcs)
specific organlcs
Tars/Oils 60+*
TSS 10+*
Trace metals, 50+* (hardness)
dissolved solids
NHj* C02» H2S, 50+*
HCN, VOC
TSS 30-60*°
TDS, TOC N/A
TDS, TOC N/A
Secondary Discharge
Streams
Recovered phenols
Spent filter media
Sludge
Air emissions
Spent carbon
of fgases
Backwash stream
Sludge
Evolved gases
Offgases
Sludge
Flue gas
Ash
Byproduct tars/oils
Recovered sol Ids/sludge
Sludge
Stripped gases
Spent filter media;
backflush water
Recovered condensate;
wastewater concentrate
Recovered condensate;
wastewater concen-
trate, noncondensl bl e
gases
Major Control Device Operating
Solvent type, S/W ratio, pH, temperature.
operation
Hydraulic residence time, sludge age,
aeration rate, F/M ratio, sudden changes
In Influent composition
Nature of po1 1 utants present, temperature,
pH, contact time, regeneration efficiency
0x1 da nt/ feed ratio, temperature, residence
time* pressure
water composition
Temperature, residence time, excess atr»
atomlzatlon
Temperature, residence time, relative density
differences, particle size
Reagent dosage, temperature* liquid composi-
tion
Steam/feed ratio, number of stages, pH of
feed liquor* reflux ratio, temperature,
pressure
Filter media type, nature of solids, filtra-
tion rate, backwash frequency and
effectiveness
Membrane properties* nature of pollutants
present, osmotic pressure
Recovery rate, demisting efficiency, conden-
sate composition
Monitoring In the Inlet stream to a control device could Include the same substances/survey techniques considered for the outlet stream
(Table 4-5). However, the emphasis for Inlet stream monitoring might be placed on the major substances the device was designed to control. The
"specific organlcs" mentioned In this column Include the allphatlcs, aromatlcs, oxygenates, nitrogenous compounds and/or sulfur containing com-
pounds appropriate for each stream (see Table 4-5).
Control device operating parameters to be monitored might be chosen from this column.
cW1thout pretreatment (flocculatlon/coagulatlon).
With pretreatroent (flocculatlon/coagulatlon).
-------
TABLE 4-14. TYPICAL SYNFUELS PLANT CONTROL DEVICES AND
KEY OPERATING VARIABLES — SOLID WASTE
Process
Typical Controlled
Substances Controlled Efficiency
Secondary Discharge
Streams
Major Control Device Operating
Parameters Affecting Emission Levels
Landfill
Incineration
Stabilization
Land Treatment
All
Organlcs
All
Organlcs
N/A
>90X
N/A
Unknown
Leachate
Atmospheric emissions
Flue gas
Residual ash
Leachate (at reduced
levels)
Atmospheric emissions
Volatile organtcs as
atmospheric emissions
Leachate
Waste handling techniques
Waste characteristics
Site specific factors such as climate, topo-
graphy, geology, hydrology
Waste characteristics
Temperature
Residence time
Excess air
Type of process used
Characteristics of wastes
Characteristics of wastes
Site specific factors
The solids/sludges entering these processes should be monitored according to the suggestions 1n Table 4-6. The "outlet" collected leachate from
landfill should be monitored as suggested 1n Table 4-5 (generic stream Category 4). The flue gas and residual ash from Incineration should be
monitored as suggested 1n Table 4-4 (generic stream Category 2) and Table 4-6 (Generic Stream Category 4), respectively.
-------
future control design decisions. However/ 1n selecting sub-
stances to be monitored in the Inlet stream* emphasis might be
placed upon the main substances that the device was designed to
control).
• The major control device operating parameters that affect
discharge levels. (If the control device falls to operate as
anticipated* the cause of the problem 1s likely to be reflected
by one or more of these operating parameters.)
• Certain other Information of possible Interest in the design of
the monitoring program (e.g., Inlet pollutant loadings*
secondary discharge streams).
The 11st of control devices 1n these tables does not necessarily Include
every control that might appear 1n a synfuels plant. Nor are the lists of
Important operating parameters necessarily exhaustive. However, the tables
should provide a basis for selecting monitoring that might be considered
around control devices in most cases. Additional Information on control
devices 1s given 1n the PCTM references mentioned 1n Section 1.5.
4-47
-------
4.2 A PHASED APPROACH FOR DATA BASE DEVELOPMENT
In Section 4.1, suggestions were provided regarding the possible extent
of a data base for synthetic fuels plants. In Section 4.2, a specific phased
monitoring approach 1s suggested by which a data base might be developed 1n a
cost effective manner. In Section 4.3, additional, alternative monitoring
approaches (some of which also envision some form of phasing) are described.
The total data base (e.g., as described 1n Tables 4-4 through 4-6) 1s
reasonably extensive, and 1t will be costly to conduct this full monitoring
program over an extended period. However, 1f the data base Is to be useful 1n
controlling the Impacts of future synfuel plant replications, 1t 1s Important
that the data base be developed over an extended operating period. The data
base would then reflect a range of plant cycles/operating conditions, and pro-
vide a sufficient data history for reliable extrapolation of the data base to
other synfuel facilities. To satisfy the need for an extended monitoring per-
iod, while at the same time controlling monitoring costs, a phased approach 1s
suggested.
If a two-phased approach 1s used, 1t would be reasonable for the first
phase (Phase 1) to Include:
• permit-mandated compliance monitoring,
• monitoring for the full ("baseline") data base for discharges
(as defined 1n Tables 4-4 through 4-6) during routine plant
operation (after shakedown), and
• monitoring of the performance of control technologies, as
described 1n Section 4.1.3.
Phase 1 would continue only long enough to address practical considerations
(e.g., to cover seasonal or other variations), and to provide a data base of
sufficient accuracy and completeness for a specific facility. The results of
the Phase 1 monitoring would be evaluated to select a limited number of "Indi-
cator" substances or parameters, which are shown 1n the Phase 1 data to be
suitable (perhaps even semi-quantitative) Indicators of fluctuations 1n
4-48
-------
other data base substances/parameters. This limited number of Indicators
would then be monitored 1n Phase 2, to represent the total data base.
Accordingly, the content of Phase 2 would Include:
• continued permit-mandated compllance monitoring*
• tracking the total discharge data base through the monitoring
of a limited number of Indicator substances/parameters* and
• tracking control technology performance* through the monitoring
of major pollutants 1n and out* and perhaps monitoring of
Indicators and/or key operating parameters.
If fluctuations 1n a Phase 2 Indicator suggest that the substances represented
by that Indicator have deviated outside of some expected range (I.e.* that the
Phase 1 baseline might have shifted), then Phase 1 analyses for the substances
represented by that Indicator might be repeated. The baseline would then be
updated. Even 1f the Indicators do not suggest such a deviation during Phase
2, periodic repeats of the Phase 1 analyses are suggested throughout Phase 2
to assure that the baseline has not shifted without being reflected 1n the
Indicators.
This phased approach should be developed to provide the data base
described 1n Section 4.1 1n a cost-effective manner. It 1s suggested the
statistical procedures be used as a basis for developing Phase 1 of this plan
(as described 1n the following sections). The use of statistical techniques
to analyze Phase 1 data and then develop the Phase 2 plan 1s also suggested;
however, 1t must be recognized that the extent (data quality and quantity) of
the actual Phase 1 data base collected (which cannot be defined before Imple-
mentation) :
• will limit the type of statistical analysis that can be
performed, and
« may require a restructuring of the overall approach to Phase 2
monitoring, especially 1f Indicator species cannot be selected
for a large number of "significant" parameters.
4-49
-------
Although Phase 1 monitoring would not begin until shakedown 1s completed*
monitoring should be useful during the shakedown period to:
• validate and perfect monitoring procedures, as part of quality
assurance,
• train personnel, and
• initiate compliance monitoring as required by permits.
The suggested bases for selecting the frequency, timing and duration of
Phase 1 monitoring according to this approach are described in Section 4.2.1.
These bases Include consideration of statistical principles to aid in the
selection. Startup monitoring is addressed in Section 4.2.1.3. Phase 2
monitoring is discussed 1n Section 4.2.2.
4.2.1 Phase 1 Monitoring
As discussed previously, the intent of Phase 1 1s to develop the total
data base described in Section 4.1. This data base would then (with periodic
updating) serve as the baseline for a reduced monitoring effort during
Phase 2.
This section contains a discussion of the possible bases for selecting:
• the timing of Phase 1—when it might start, under what condi-
tions monitoring might be considered,
• the frequency and duration of Phase 1 monitoring, considering
both practical and statistical concerns, and
• the pre-Phase 1 monitoring that might be conducted during the
plant startup period.
4.2.1.1 Phase 1 Timing
The objective of the Phase 1 monitoring is to develop "baseline" levels
for parameters of interest. Thus, most of the Phase 1 monitoring should be
conducted during routine operation after shakedown. However, the end of the
4-50
-------
shakedown period and the beginning of routine operation may not be a well-
defined point. It 1s likely that different sections of a plant will follow
different schedules 1n progressing through the shakedown process. The com-
ments made 1n this section appear to assume that all Phase 1 measurements will
be made at the same time. In practice* however* startup and llneout activi-
ties 1n a large, complex facility such as a new synthetic fuels plant are not
likely to be simultaneous. TMs could be either Intentional or the result of
problems 1n sections of the plant. In either case, to be consistent with the
objectives of the overall monitoring program, Phase 1 monitoring (1n a given
plant section) can be started as soon as the plant Cor plant section) 1s lined
out at design (or anticipated "normal") operating conditions.
In general, Phase 1 sampling should be performed when the plant 1s
operating routinely within design parameters. Usually, data would not be
collected during transient operations. However, a limited amount of Informa-
tion might be gathered during selected periods of scheduled transient
performance to evaluate the effect of the transient on the baseline.
Even 1f plant operating variations prevent sample collection at exactly
the planned frequency, the sampling should be performed at a fairly uniform
rate (e.g., 1f six samples are desired over a one-year period, the samples
should be collected at approximately bi-monthly Intervals, rather than all
samples being collected 1n a one-month period).
4.2.1.2 Frequency and Duration of Phase 1 Monitoring
The monitoring frequency should be selected for the various substances/
parameters 1n the various streams based upon two major considerations:
« the availability of monitoring techniques—Including their
capabilities, turnaround time and costs, and
• the quality desired 1n the Phase 1 measurement data base for a
specific site.
4-51
-------
When the variability of a given substance or parameter 1s known (I.e., the
standard deviation of analyses of a given stream 1n a given facility over a
specific period of time), one can use statistical principles to estimate the
number of measurements required to provide a desired accuracy for the mean
estimate of that substance/parameter. The greater the variation 1n a param-
eter, and the greater the desired accuracy, the greater will be the necessary
number of measurements. This number of measurements determines the relation-
ship between the monitoring frequency and the duration over which monitoring
1s conducted. Because monitoring frequency and duration are linked 1n this
manner, they are discussed together fn this section.
The Phase 1 monitoring duration is also Influenced by two major
considerations:
• the desired accuracy, as discussed above
• practical considerations, Including the desire to Include
within Phase 1 a reasonable range of plant operating condi-
tions, and the desire to complete Phase 1 within some reason-
able time period.
Thus, a number of factors must be weighed In order to decide upon a
reasonable Phase 1 frequency and duration.
In Tables 4-15 through 4-17, a range of Phase 1 monitoring frequencies is
suggested for the analyses and specific components listed in Tables 4-4
through 4-6. The availability of monitoring techniques and the significance
of the stream categories were considered in defining the frequency ranges.
Also considered was the need to keep monitoring costs to reasonable levels
while obtaining a sample set which will provide data of reasonable accuracy.
A rationale for the suggested frequency ranges is presented for each generic
stream category listed in Tables 4-15 through 4-17. In addition, some
criteria are given as a basis for choosing the appropriate frequencies.
4-52
-------
TABLE 4-15. SUGGESTED PHASE 1 MONITORING FREQUENCY - GASEOUS DISCHARGE STREAMS
Generic Stream
Category
Monitor 1ng
ency Suggestions
Test Results
of
Interest
Possible
Frequency
Ranges*
Cements
1. Boiler/Furnace flue
gases from the combustion
of conventional fuels
Criteria
Pollutants
I
cn
CO
Bol1er/furnace> or
Incinerator flue gases from
the combustion of process-
derived fuels or waste
streams
Crlterla
Pollutants
Reduced Sulfur
and Nitrogen
Species
Volatile Trace
Elements
Trace Elements
Al Iphatlc and
Aromatic
Organlcs
TCO/GRAV
Nitrogenous
Organic
Compounds
Organlcs In
Table 4-8
Q-M
Q-M
Q-M
Q-M
Q-M
.Ra.tlQ.nAle; Continuous monitors are available for some criteria pollutants such as
SO-, NO , and partlculates. In some cases, continuous monitoring may be less costly
than periodic sample collection and analysts. Frequent monitoring may also be
required by permit conditions. Quarterly monitoring represents the lowest frequency
bound, because four samples In a one-year period are felt to be the minimum
statistically desirable number.
Continuous monitoring Instruments are available for some criteria
pollutants. In some cases, continuous monitoring may be simpler and less expensive
than periodic sampling collection and analyses. Continuous or frequent monitoring
of criteria pollutants may be required by permit conditions. Analyses of trace
elements, sulfur/nitrogen species, and complex organlcs are somewhat more difficult*
time consuming, and expensive. For that reason, monthly monitoring for these
materials Is the suggested upper frequency bound. Quarterly monitoring represents
the lowest frequency bound, because four samples over a one-year period are felt
to be the minimum statistically desirable number.
Considerations: Continuous monitoring of criteria pollutants may be required by
permits. If not required, lower frequency of monitoring might be acceptable. Con-
tlnuous monitoring will provide more data than periodic sampling/analyses. More
frequent monitoring of species, particularly heavy organlcs 1s Important 1f heavy
fuels (such as sludges, tars, and heavy waste gases) are being burned. Frequent
sampling provides greater accuracy and better definition of baseline values.
Sources 1n which synthetic fuel gases are being burned are less likely to have
heavy organlcs present In flue gases. Monitoring of these streams for organlcs
could be less frequent. It may be desirable to monitor flue gases more frequently
during Initial stages of monitoring. Frequency could be reduced later If the
results of monitoring Indicate a Justification for less monitoring. The levels of
some pollutants 1n the flue gases are generally related to process parameters such
as feed stream properties, excess air rate» combustion temperature and furnace
residence time. If adequate correlations can be developed, process parameter
monitoring may reduce the need.
(Continued)
-------
TABLE 4-15. (continued)
Generic Stream
Category
Monitoring
Frequency Suggestions
Test Results Possible
of Frequency
Interest Ranges
3. Uncombusted vent gases or
feed gases to flare
I
cn
Criteria
Pollutants
NMHC
Q-M
Reduced Sulfur Q-M
and Nitrogen
Species
Volatile Trace O-M
Elements
Trace Elements Q-M
Aliphatic, Aro- Q-M
matlc and Oxy-
genated Organlcs
TCO/GRAV
Q-M
Nitrogenous and Q-M
Sulfur Contain-
ing Organic
Compounds
Qrganlcs tn
Table 4-8
Q-M
Continuous monitoring Instruments are available for some criteria
pollutants* and continuous or frequent monitoring of these compounds may be required
by permit conditions. In some cases, continuous monitoring may be simpler and
less expensive than periodic sample collection and analyses. Analyses or trace
elements. sulfur/nltrogen species* and complex organlcs are somewhat more d1 f f 1-
cult, time consuming* and expensive. Thus» monthly monitoring for these materials
1s the suggested upper frequency bound. Quarterly mon1toring represents the
lowest frequency bound* because four samples over a one-year period are felt to be
the minimum statistically desirable number.
Conslderations: Continuous monitoring of criteria pollutants from some of
the vent gas streams may be required by permit. If not required/ lower frequency of
criteria pollutant monitoring might be acceptable. Continuous monitoring will
provide more data than periodic sampling/analyses. More frequent sampling (s
Indicated for those streams which can be expected to vary as a result of varying
feed composition, feed rates, or discharge rates. It 1s virtually Impossible to
measure flare emissions at the source. The feed to the flare Is generally Mghly
variable, so monthly monitoring should be considered. Compounds of particular
Interest 1n the flare feed are sulfur/nitrogen compounds, volatile trace elements,
and refractory organic compounds which are less easily combusted. It may be
desirable to monitor some of the vent streams more frequently during the early
stages of the monitoring effort. The frequency could be reduced later In the
program for those streams which contain consistent and/or low levels of pollutants.
4. Tank Vents
Reduced Sulfur SA-BM
and Nitrogen
species
Total Hydro- SA-BM
carbons
Volatile SA-BM
Allphatlcs, Aro-
natlcs and Oxy-
genates
NMHC
SA-BM
Organlcs In SA-BM
Table 4-8
Rationale: Tanks can be present 1n relatively large numbers 1n synfuels plants.
Thus, frequent sampling of these sources can be expensive and time consuming. Tanks
are generally dedicated to particular liquid services, and the composition of the
vented gases will only change significantly with the tank temperature and the
composition of the contents. The composition of the tank vent gases can be expected
to change somewhat over the year as the ambient temperature changes. Bimonthly
sampling should be sufficient to detect significant composition differences (If they
exist) throughout the year. If composition changes are not significant, or If the
hydrocarbon content of the vapor Is low. the monitoring frequency could be reduced
as low as twice a year.
Considerations; Fixed-roof tanks generally are used to store hydrocarbon liquids
of relatively low volatility. Obvfously, the most volatile of these liquids can be
expected to produce vented gases with the highest concentrations of hydrocarbons.
Examples of relatively volatile liquids which might be stored In fixed-roof tanks
are unstablllzed or unhydrotreated products and by-products. The composition of the
vapor above the liquid at any given temperature and pressure Is a function of the
liquid composition. The results of early monitoring efforts could be used to define
the accuracy and consistency of these relationships between liquid and vapor
compositions. If the relationships are valid, liquid samples could be periodi-
cally analyzed to confirm that no significant changes In the concentration of com-
ponents of Interest have occurred. Vapor analyses could thus be significantly
reduced or even replaced by liquid analyses.
(Continued)
-------
TABLE 4-15. (continued)
Generic Stream
Category
Monitoring
Frequency Suggestions
Test Results Possible
of Frequency
c&
Interest
Ranges*
Comments
5. Process Fugitive Emissions
cn
cn
6. Fugitive emissions from
waste Impoundments, storage
and disposal facilities
Total VOC
Concentration
SA-Q
Carbon Monoxide SA-Q
HS SA-Q
SA-Q
Volatile
Allphatics
and Aromatic
Compounds
VOC
Partfculates
SA-BM
SA-BM
SA-BM
RatIpnajfl: Process fugitive emissions can be controlled through a periodic leak
detection and repair (LDAft) program. The cost of this type of program can be quite
significant, although for some sources (such as valves), the cost can be partially
or completely offset by the value of the recovered material. The major cost Hern is
the monitoring or detection segment of the program, and this cost rises
exponentially as the frequency of monitoring Increases. The program becomes
particularly costly at monitoring Intervals of less than three months (quarterly).
Results of a LDAR program may well show that the leak frequency and/or leak
occurrence rate for some sources Is quite low. In these cases, the monitoring
frequency may be reduced as low as twice a year.
Cons 1 derations: Sources In service on streams consisting of light (volatile)
hydrocarbons and gases are most prone to emit fugitive emissions. Streams con-
taining less than 10 percent of combined hydrocarbon, CO, H S, and NhL can generally
be exempted frcm monitoring. Careful records of the results of the monitoring
program should be kept. Such records may Indicate particular streams or sources
which have very low leak frequencies and leak occurrence rates. Petroleum refinery
and chemical plant studies have shown that processes in which heavy liquids are
dominant have low rates of fugitive emissions. Examples are vacuum distillation,
lube oil processing, and asphalt production. Monitoring results In these types of
units can be expected to Justify semi-annual monitoring frequencies.
More frequent monitoring of streams containing toxic and/or noxious components (such
as H S and NH_) may be desirable to keep fugitive emissions of these compounds at a
low fevel.
between the cost of sampling and the need for accuracy. Initial monitoring may
only small degrees of variation with time, and the monitoring frequency could be
reduced to as low as twice a year. Semi-annual sampling 1s felt to be the lower
bound of monitoring frequency to obtain samples 1n at least two different season
of the ear (such as hot/cold, wet/dr)
f the year (such as hot/cold, wet/dry).
Considerations: Experience In petroleum refineries and chemical plants has
Indicated that sources with large exposed areas 1n which organic material Is
directly exposed to the air (uncovered oil-water separators, dissolved air flotation
units, land treatment sites) may emit significant quantities of VOC and other
volatile compounds. Aerated sources such as aeration ponds* biological oxidation
units, aerated activated sludge units, and dlssol ved-al r flotation units can also be
expected to emit detectable quantities of VOC and other volatile compounds. More
frequent monitoring (particularly 1n the early stages of the monitoring program)
should be considered for these sources.
In some cases, the VOC content of the water, sludge, etc. being processed 1n these
sources can be determined. This may also guide the selection of Initial monitoring
frequencies. The absence of significant amounts of VOC In the water and/or waste
material may Justify a lower monitoring frequency.
(Continued)
-------
TABLE 4-15. (continued)
Generic Stream
Category
Monitoring
frequency Suggestions
Test Results Possible
of Frequency
Interest Ranges
Comments
7. Fugitive Participate
Emissions
Partlculates SA-BH RatlpnaAa'* Participate emissions are a function of trie source properties, level
at which the source Is being worked/disturbed, and weather conditions. Since
partlculate sampling Is relatively costly, bimonthly monitoring was selected as a
compromise between the need for accuracy and the monitoring cost. The results of
Initial testing may Justify reduction of that frequency as low as send-annually
because of either consistency of emissions or low emissions levels.
emissions as accurately as practical.
Those sources such as reserve coal storage* and wet coal/coke/shale piles can be
expected to emit participates at a low rate, and even Initial monitoring of such
sites may be done at frequencies less than bimonthly.
I
en
A * annual, SA = semiannual* Q " quarterly. BH = bimonthly, M * monthly, BH « bi-weekly, H * weekly, C » continuous
NOTE: Flow rates and temperatures of discharge streams should be monitored at the same frequency as tne chemical
composition. Likewise* major pertinent process variables should be monitored at this same frequency (e.g.,
feedstock feed rate to plant* feedstock composition).
-------
TABLE 4-16. SUGGESTED PHASE 1 MONITORING FREQUENCY-AQUEOUS DISCHARGE STREAMS
Generic Stream
Category
Monitoring
Frequency Suggestions
Test Results Possible
of Frequency
Interest
Ranges
a
Comments
1. Wastewaters discharged to
outfalls* Impoundments* or
deep wells that are not
unique to synfuels plants
and have their origins 1n
organic-laden environment
Water quality SA-BM
parameters
Aliphatic and SA-BM
aromatic
organic
compounds
Trace elements SA-BM
These wastewaters are not unique and are expected to be relatively
benign 1n nature. In the absence of more stringent permit (NPDES) requirements,
bimonthly monitoring during Phase 1 should be sufficient to Include most operating
conditions which are subject to seasonal variations. Initial results may justify a
reduction 1n sampling frequency to a level as low as two times per year. Statis-
tical and practical considerations suggest semiannual sampling as the minimum
useful sampling frequency.
I
cn
2. Wastewaters discharged to
outfalls. Impoundments, or
deep wells that are not
unique to synfuels plants,
and have their origins 1n an
essentially organic-free
environment
Water qual1ty
parameters
SA-BM
Trace elements SA-BM
Considerations: NPDES permit requirements may dictate the monltotlng frequency
for these streams. In selecting a monitoring frequency for a given stream, the
time constraints (or residence times) of various surge vessels/ponds should be
considered. Another consideration 1s the known or anticipated nature of the
stream. Since these streams are not unique to synfuels processing, some Indica-
tion of their quality can be obtained from examining the nature of similar streams
1n other Industries (such as the petroleum refining, petrochemical, and organic
chemical Industries). Initial monitoring frequencies as low as quarterly may be
Justified. However, test results should be carefully analyzed, and the presence
of any unexpected compounds may Indicate a need for additional or more frequent
monitoring to verify water quality and organlcs content. If any of the stream
parameters are to be considered as an Indicator, the more frequent monitoring
schedule Is advisable.
(Continued)
-------
TABLE 4-16. (continued)
Generic Stream
Category
Monitoring
Frequency Suggestions
Test Results Possible
of Frequency
c "
Interest
Ranges
Comments
3. Wastewaters discharged to
outfalls, Impoundments, or
deep wells that result from
the quenching, cooling,
purifying, upgrading, etc.
of the plant's main products
-P»
CO
Water quality Q-W
Trace elements Q-M
Aliphatic, Q-M
aromatic, and
oxygenated
organic
compounds
Nitrogenous Q-M
organic
compounds
Sulfur- Q-M
containing
organic
compounds
Volatile trace Q-M
elements
Biological
screening
Organlcs 1n
Table 4-8
Because of the generally unknown nature of these wastewaters and the
uncertainty of wastewater treatment technologies 1n synfuels service, more frequent
monitoring 1s suggested, particularly 1n the early stages of the plant operation.
The cost of these tests must be weighed against the benefits achieved with larger
sample populations. The highest monitoring frequencies suggested here represent a
compromise between cost and data needs. The water quality parameter analyses are
rather costly, but such testing 1s often an Integral part of the wastewater
treatment system operation. Weekly monitoring Is suggested In the early stages of
the plant operation, since both the water quality and the effectiveness of
treatment will likely be uncertain and/or fluctuating. Monthly monitoring for
other compounds should provide data over the range of seasonal variations (n
processing, ambient conditions, and product specifications. Twelve data sets per
year provide sufficient data to statistically evaluate the quality and content of
the effluent water as well as the effectiveness of wastewater treatment processes.
Continuous biological screening Is a relatively cost-effective method for
determining the overall ecological effect of the treated wastewater on marine life.
Other health and ecological tests should be performed on a bimonthly to quarterly
frequency during the Initial stages of plant operation.
Quarterly sampling provides enough data sets for statistical purposes, particularly
If variability 1s not great. However, Initial monitoring frequencies should be
greater until the range and variability of some of the parameters have been defined,
or at least estimated,
Considerations; The quality of the effluent water 1s a function of the plant
processes and their operation, as well as the performance of the wastewater
treatment system. Both the processing and the treatment may be quite variable
during the first phases of the plant operation, and the higher frequency monitoring
should be emphasized during this period. Some monitoring frequencies may also be
dictated by permit (such as NPDES) requirements.
High temperature gasification processes produce wastewaters which contain relatively
low concentrations of organic compounds. On the other hand, the wastewaters from
liquefaction and low/medium temperature gasification processes can be expected to
contain higher levels of organlcs. Thus, 1t 1s particularly Important that the
effluent wastewater from these latter processes be monitored for organic compounds
on a frequent basis.
Those parameters which are considered as potential Indicator compounds/parameters
should be monitored at the higher frequencies to provide correlations/relationships
of the highest possible accuracy.
Results of the testing should be analyzed on a regular basts to determine If and
when the frequency of monitoring can be reduced. Statistical analyses of the data
should provide considerable guidance In defining the variability of the results and
an acceptable level of reduced monitoring (If such a reduction Is justified at all).
(Continued)
-------
TABLE 4-16. (continued)
Generic Stream
Category
Mon1tortng
Frequency Suggestions
Test Results Possible
of Frequency
Interest
Ranges
a
Comments
4. Wastewaters discharged to
outfalls. Impoundments/ or
deep wells that are unique
to synfuels facilities, but
not Included 1n Category 3
I
01
Water qualIty
parameters
Q-W
Trace elements Q-M
Al Iphatlc and
arcmatlc
organic
compounds
Volatile trace
el ements
Biological
screening
Organlcs 1n
Table 4-8
Q-M
Q-M
SA-C
Q-M
jj_g: Much of the rationale discussed under Category 3 1s applicable here.
Although the levels of organlcs are expected to be low, this Is not a certainty, and
reasonably frequent monitoring (monthly) should provide data for a practical
statistical assessment of the water quality and the levels of the various compounds
1n the effluent wastewater. At the same time, this level of monitoring should not
be excessively costly. In general, the higher frequency level 1s suggested for
Initial definition of the wastewater quality and Its expected variability. The
lower suggested frequencies may be applicable 1n later stages of plant operation.
Quarterly monitoring Is the recommended lower limit for the monitoring frequencies.
This level of monitoring still provides enough Information for statistical
evaluation and reasonably accurate water quality estimates (provided that the
variability 1s not too great).
Considerations: NPDES (and possibly
specific monitoring frequencies. More
during the Initial phases of plant ope
pollutants/contaminants will probably
organic compounds 1n these streams are
verifies this expectation, the organic
decreased to four times per year at a
maintain higher monitoring frequencies
Indicator compounds/parameters.
other) permit requtrments may require
frequent monitoring should be performed
ration, since the water quality and levels of
be quite variable. The concentrations of
expected to be very low. If Initial testing
compound monitoring frequency could be
relatively early date. It may be desirable to
for those parameters which are to serve as
The results of the testing and analyses should be periodically reviewed to define
both the levels and the variability of the water quality parameters and pollutants
of concern. Those parameters/pollutants which have low variabilities or which are
present at very low levels may be monitored at lower frequencies.
NPDES (and possibly other) permits may require specific monitoring tests and
frequencies. Obviously, these requirements would take precedence over the
tests/frequencies suggested here If the suggested monitoring 1s less stringent than
required In the permlt(s).
A = annual, SA - semiannual, Q = quarterly, BM = bimonthly, M = monthly, BW = bi-weekly, W = weekly, C = continuous
NOTE: Flow rates of discharge streams (to outfalls. Impoundments, or deep wells) should be monitored at the same
frequency as the chemical composition. Likewise, major pertinent process variables should be monitored at
this same frequency (e.g., feedstock feed rate to the plant, feedstock composition).
-------
TABLE 4-17. SUGGESTED PHASE 1 MONITORING FREQUENCY - SOLID WASTE DISCHARGES
01
o
Monitoring
F reqi lency Suggest tons
Test Results Possible
Generic Stream of Frequency
Category Interest Ranges
1. Organic-laden solid wastes Trace elements
not unique to synfuels pi ants (whol e sampl e
and leachate)
Leachable
al Iphatlc and
aromatic organic
compounds
TCO/GRAV
Ultimate and
proximate
analyses
RCRA hazardous
Particle size
Radioactivity
2. Organic-free or organic- Trace elements
lean solid wastes not unique (whole sample
to synfuels plants and leachate)
Ultimate and
proximate
analysis
RCRA hazardous
waste tests
Particle size
Radioactivity
SA-BM
SA-BM
SA-BM
SA-BM
SA-BM
SA-BM
SA-BM
SA-BM
SA-BM
SA-BM
SA-BM
SA-BM
Comments
Rationale: These streams are expected to be relatively benign In nature. The
primary purpos of the monitoring Is to define tne physical and chemical properties
of the wastes nd to Identify potentially Teachable constltutents. Bi-monthly
monitoring dur ng the Initial phases or the plant operation should satisfy these
needs. Six da a sets 1n the first year of monitoring should provide the basis fora
statistically ound estimate of the various parameters and properties. A high
degree of accu acy Is not required for these parameters. Semi-annual monitoring Is
suggested as a lower frequency limit. This provides tne minimum number of annual
samples which can be statistically evaluated. The lower frequency should only be
Initiated for tnose nonhazardous streams which have relatively constant and/or low
values for the parameters of Interest.
.Conslderallpris: Two of the main objectives ot the monitoring are to satisfy
estimates of their composition may be developed from an examination of similar
chemical Industries). If Initial monitoring confirms these levels. It may be
possible to Justify reduced frequencies for monitoring at a relatively early period
of plant operation.
All of the monitoring tests suggested for Category 1 and 2 streams may not be
practical or appropriate for all of the Individual streams within the generic
categories. The various monitoring tests required for tne Individual streams will
have to be selected on an Individual basis.
(Continued)
-------
TABLE 4-17. (continued)
Generic Stream
Category
Monitoring
Frequency Suggestions
Test Results Possible
of Frequency
Interest Ranges
Comments
3. Organic-laden solid wastes
unique to synfuels plants
CT>
Extractable Q-M
nitrogenous and
sul fur-containing
organic
compounds
Trace elements Q-M Rationale; Solid waste streams In this category will be significant discharge
(whole sample sources and should receive major emphasis In a solid discharge characterization
and leachate) program. The suggested upper monitoring frequency of monthly sampling/analysis 1sa
compromise between the need for characterization data and the high cost ot frequent
Extractable Q-M monitoring. Monthly monitoring will provide twelve data sets 1n a year. This data
aliphatic, base should be sufficient to provide statistically valid estimates of the various
aromatic, and parameters at a reasonable cost. At later stages of plant operation, after many of
oxygenated the solid waste characteristics have been reasonably well defined, the monitoring
organic frequencies may be reduced. Quarterly monitoring 1s suggested as a lower Unit.
compounds Four samples per year still provide enough data to allow statistical evaluations.
Monitoring at frequencies less than four times a year Is not suggested because of
TCO/GRAV Q-M the potential Importance of these discharges and the need to maintain a continual
awareness of any changes that may occur 1n the wastes.
Considerations! Some of the streams 1n this generic category may only be
available Intermittently (spent catalysts* for example), and these streams
should be sampled as they are available to obtain the desired number of
samples. It may not be practical to perform all the desired tests on every
waste discharge In this category. The monitoring tests required for each
Ultimate and Q-M specific stream will have to be selected on an Individual basis.
proximate
analysis High temperature gasification processes will tend to produce discharge streams
containing relatively low concentrations of organic compounds. Conversely,
RCRA hazardous Q-M discharge streams from liquefaction and low/medium temperature gasification
waste tests processes can be expected to contain higher levels of organic components. It Is
particularly Important, therefore, that the solid waste streams from these latter
Particle size Q-M processes be monitored for organic compounds on a frequent basis.
Radioactivity Q-M The data from the sampling and analysis program should be examined frequently to
Identify those streams for which the monitoring frequencies can be reduced. Some
Selected water Q-M streams may contain very low levels of some of the compounds under Investigation.
quality In other cases, some of the compounds and/or parameters may be found to be quite
parameters for consistent during plant operation. In these cases, reduced frequency of monitoring
leachates can be Justified after early stages of plant operation.
Those parameters which are potential Indicator compounds/parameters should be
monitored at the higher frequencies to develop correlations and other relationships
having the greatest possible accuracy.
(Continued)
-------
TABLE 4-17. (continued)
Generic Stream
Category
Monitoring
Frequency Suggestions
Test Results Possible
of
Interest
Frequency
Ranges4
Comments
4. Organic-free or organic-
lean solid wastes unique to
synfuels plants
I
CT>
Trace elements Q-M Rationale: Much of the discussion of rationale presented for the Category 3
streams (see above) 1s also applicable here. The levels of organic compounds 1n the
Extractable Q-M Category A solid waste discharge streams are expected to be quite low. Since tnls
aliphatic and assumption 1s not a certainty, however, reasonably frequent (monthly) monitoring 1s
aromatic organic suggested during the Initial phases of plant operation. Monitoring at these
compounds frequencies should provide data for a practical statistical assessment of the levels
of organic compounds present 1n the solid waste discharge streams. At the same
Ultimate and Q-M time, the monitoring costs should not be excessive.
proximate
analyses The higher monitoring frequencies are suggested during the early phases of plant
operation to provide an Initial characterization of solid waste discharge stream
RCRA hazardous Q-M properties and the variabilities of these properties. The suggested lower
waste tests frequencies may find application during later plant operations. Quarterly
monitoring 1s suggested as a lower limit for the monitoring frequencies. This level
Particle size Q-M of monitoring can still develop enough Information for statistical evaluations with
reasonably accurate estimates of the solid waste parameters/properties (provided
Radioactivity Q-M that the variability 1s not too great).
Selected water Q-M Considerations; The more frequent monitoring 1s most applicable during the first
quality phases of plant operation. This monitoring will allow reasonably accurate
parameters for definition of baseline values for many of the solid waste stream parameters of
leachates concern. At the same time, the more frequent monitoring will provide some
assessment of the variability of the solid waste properties.
The concentrations of organic species In these solid wastes are expected to be low,
by definition. In particular, those streams associated with high temperature coal
conversion should be particularly low 1n or free of organic compounds. If Initial
monitoring verifies the expected low organic levels, the monitoring of organic
compounds could be decreased to a frequency as low as four times per year at a
relatively early stage of plant operation.
It may be desirable, however, to maintain the higher frequencies for those
parameters which are potential Indicator parameters/compounds.
A = annual, SA « semiannual, Q = quarterly, BM - bimonthly, M « monthly, BW • bi-weekly, W » weekly, C « continuous
-------
Tables 4-15 through 4-17 address monitoring frequencies for discharge
streams only. Where monitoring 1s being conducted around environmental con-
trol devices* ft 1s expected that monitoring of the control Inlet and key
operating parameters (as discussed In Section 4.1.3) will be conducted at the
same time as monitoring of the control discharge.
The number of measurements required 1n Phase 1 Is a function of two major
factors:
• the variability of the parameters being measured (as reflected*
for example, by the standard deviation of the parameter).
There are several contributing components to variability:
variability of both the environmental sampling procedures and
the analytical effort; and both short-term and long-term varia-
bility 1n the synfuels process Itself;
• the desired quality of the data base from Phase 1 measurements.
The data base quality can be selected to fit the needs of a
specific parameter at a specific site and, as such* can be
controlled by the program designer.
Since the selection of the quality level of the Phase 1 data base can
play a major role 1n determining the number of measurements, this selection is
an Important responsibility of the program designers. The quality of the
Phase 1 data base impacts not only the confidence 1n the baseline data base,
but also the accuracy and the approach with which the baseline can be tracked
during Phase 2 (see Section 4.2.2.2). The intent of the following paragraphs
is to provide background that will aid the user in selecting the desired data
base quality for a parameter. An expanded discussion of the concepts des-
cribed in this section is included in Appendix B.
The quality of the data base for a specific parameter 1s concerned with
how well actual measured values reflect variations in actual discharge param-
eters or emission levels over the time period represented by the data base. A
set of measured values is usually summarized in terms of the central tendency
(mean) and the dispersion (standard deviation) for the parameter. The mean
and standard deviation can be used 1n conjunction with an appropriate distri-
bution model to represent expected parameter levels.
4-63
-------
Confidence intervals (see Appendix B) can be used to evaluate the ex-
pected precision of estimates of the mean for a parameter using the Phase 1
data base. A confidence interval for the mean is a set of end points about
the average obtained from sample measurements that is believed, with a speci-
fied degree of confidence, to include the parameter mean. The parameter mean
is defined here as the value which would be obtained if continuous measure-
ments were made and averaged for the period. The confidence level for a
confidence interval indicates the expected percentage of the time that a
constructed interval will actually include the parameter mean. For a particu-
lar distribution model, the width of the confidence interval for the mean
depends on:
• the variability of the measurement (standard deviation or
coefficient of variation),
• the confidence level (90%, 95%, 99%, etc.), and
• the sample size (number of measurements made during Phase 1).
The relationship between data variability and the number of samples
required to establish a given level of precision for the parameter mean at the
95 percent confidence level is given in Table 4-18. This table shows the
effects of variability and number of samples or data points on the expected
confidence interval around a calculated mean. The variability is expressed in
terms of a known coefficient of variation. This coefficient is defined as the
ratio of the known standard deviation and the known mean, and it is expressed
as a percent.
An example of how to use Table 4-18 follows. This example is for a
parameter having a coefficient of variation of 50 percent for which the normal
distribution is an appropriate model. If six measurements were made (n=6) the
95 percent confidence Interval (from Table 4-18) has an expected range of
+52 percent of the mean of the six measurements. That is, the expected
confidence interval ranges from 0.48 times and 1.52 times the mean of the six
measurements.
4-64
-------
I
CT>
cn
TABLE 4-18. EXPECTED CONFIDENCE INTERVALS FOR A PARAMETER MEAN
AS A FUNCTION OF NUMBER OF SAMPLES (MEASUREMENTS)
Expected
VarlabH 1ty of
Measurement
(Coefficient
of Variation)
5*
10*
25*
SOX
100*
200*
5005!
1000*
10000*
95* Confidence Interval About the .
Mean Estimate for Phase 1 (oercent)
Distribution
(Model)
Normal Model
Lognormal Model
Normal Model
Lognormal Model
Normal Model
Lognormal Model
Normal Model
Lognormal Model
Normal Model
Lognormal Model
Lognormal Model
Lognormal Model
Lognormal Model
Lognormal Model
n » 4
(Quarterly)0
+8.0
+8.1, -7. 5
+15
±17, -15
±40
+4B.-32
±80
+110, -53
±160
+280, -73
+650, -87
+1700, -94
+3000, -96
+13000.-99
Coefficient of variation Is the ratio of the standard deviation
A known value for the coefficient 1s assumed 1n this table.
If the coefficient of variation Is greater than 100*, the normal
n • number of samples or data points.
n « 6
(Bi-monthly)
±5.2
+5. 4, -5.1
+11
+11, -9. 9
+26
+29,-23
+52
+62, -39
+110
+104, -58
+280, -74
+570, -85
+900.-90
+2300.-96
n = 12
(Monthly)
±3.2
+3 .2, -3.0
+6.4
+6. 5, -6.1
±16
+17 ,-14
+32
+35, -26
±64
+70, -41
+124, -55
+220, -6 8
+300, -75
+5 90, -85
n - 24
(Semi-monthly)
±2.1
+2.1, -2.0
±4.2
+4. 3 ,-4.1
±11
+ll,-9.9
+21
+22, -18
+42
+42, -30
+71, -42
+120, -53
+150, -60
+260, -72
n - 52
(Weekly)c
+1.4
+1.4
+2.8
+2. 8, -2. 7
+6.9
+7.1, -6. 6
±14
+14, -12
+28
+26, -21
+43, -30
+65, -40
+82, -45
+130, -57
n • 365
(Dallyf
+0.5
±0.5
+1.0
±1.0
±2.6
+Z.6.-2.5
' +5.2
+5.0, -4. 8
+11
+9.0.-8.2
+14, -12
+20 ,-17
+24, -20
+37, -27
to the mean expressed In percent.
model 1s not realistic.
°Mon1tor1ng frequencies required for the specific value of n If the duration of Phase 1 was one year.
-------
Confidence Intervals are shown 1n Table 4-18 for both normal and lognor-
mal distribution models (Appendix B). Most populations of discharge stream
measurements can be represented reasonably well by one of these cases. Dis-
charge stream parameters which tend to have low values and be limited on the
"bottom end" by zero, but which can assume occasional high values as well
(e.g., fugitive emission leak rates), frequently follow a log normal distribu-
tion. Other parameters will not be limited to some minimum value and will
more often follow a normal distribution pattern.
The confidence Intervals given 1n Table 4-18 can be used to evaluate
alternative Phase 1 testing frequency and duration decisions. The product of
the frequency and the Phase 1 duration will determine the sample size avail-
able for estimating the mean. Table 4-18 contains confidence Interval widths
expressed as a percent of the mean. Sample sizes range from n = 4 to n = 365.
Variabilities range from a coefficient of variation (CV) of 5 percent to a CV
of 10,000 percent.
To further Illustrate the use of Table 4-18, consider a variable that
varies symmetrically about Its mean value (normal distribution) with an
assumed coefficient of variation of 50 percent. The fourth row 1n Table 4-18
describes data with a CV of 50 percent. Reading across the fourth row, one
can see that the width of the confidence Interval decreases as more samples
are taken. If 6 samples are taken, the 95 percent confidence Interval 1s
±52 percent. With 365 samples, the Interval 1s reduced to ±5.2 percent.
Table 4-19 summarizes this example. Tables such as this can be used to eval-
uate trade-offs between the cost of testing and the precision of the estimated
mean (both of which Increase as the sample size Increases).
As another example of using Table 4-18, suppose 1t 1s Important to esti-
mate the parameter mean within a confidence Interval of about 50 percent.
Table 4-18 can be used to determine the number of samples required to maintain
this confidence Interval (with a confidence level of 95 percent) for para-
meters with different variabilities (CVs). The results shown below are
applicable for either a normal or log-normal model.
4-66
-------
Required Test Frequency
Number of Samples For Phase 1 Duration
CV of Parameter Required (n) of One Year
<2S% 4 quarterly
25 - 50% 6-12 bi-monthly
50 - 100% 24 semi-monthly
100 - 500% 52 weekly
>500% 365 dally
The calculations reflected in Table 4-18 can be repeated for other sets
of conditions (e.g., for other confidence levels, CV's, or sample sizes). The
equations used for making these calculations are presented in Appendix B. It
is generally felt that a 95% confidence level is reasonable for this type of
analysis.
Table 4-18 focuses on how well a parameter mean can be estimated (I.e.,
the confidence Interval about the mean). Confidence Intervals can also be
calculated for the standard deviation to evaluate how well the variability of
a parameter can be estimated from the data base. A statistician should be
contacted for this type of analysis.
TABLh 4-19. PRECISION OF THE ESTIMATED MEAN AT A 95 PERCENT CONFIDENCE LEVEL
FOR VARIOUS SAMPLE NUMBERS (CV = 50%; NORMAL DISTRIBUTION MODEL)
Number of
Samples
6
12
24
52
365
Frequency for a
One Year Duration
bi-monthly
monthly
semi-monthly
weekly
daily
Precision of Estimated Mean
±52%
±32%
±21%
±14%
+5%
monitoring frequency required to obtain the indicated number of samples
1f Phase 1 duration is one year
4-67
-------
The coefficient of variation for the various parameters 1n synfuels plant
discharges 1s likely to vary from parameter to parameter. It 1s expected that
the coefficient of variation for many synfuels parameters will be reasonably
high (over 30%).
The manner 1n which the monitoring program designer might utilize these
statistical concepts 1n selecting Phase 1 frequency and duration 1s suggested
schematically 1n Figure 4-2. The steps 1n this procedure Include:
• estimate (order of magnitude) the coefficient of variation for
the various parameters. Since the coefficient will Hkely be
different for every parameter, the designer might wish to
assume one or more gross values for the coefficient and cate-
gorize the parameters of Interest according to which gross
value most reasonably might apply.
• select the desired accuracy for estimating the parameter mean
during Phase 1. This step would Involve selection of the
desired confidence level (e.g., 9556) and confidence interval
(e.g., ±50%). This selection of Phase 1 accuracy could
Influence (or be Influenced by) the desired accuracy and ap-
proach for tracking the parameters during Phase 2, as discussed
in Section 4.2.2.2.
• select the reasonable number of measurements (from Table 4-18
or equivalent), considering the estimated coefficients of
variation and the desired accuracy. As a practical matter,
this selection will likely be a judgment made by the designer
after reviewing the sample number versus confidence interval
tradeoff reflected in Table 4-18.
• select the frequency and duration, based upon the selected
sample number. Here again, the program designer will need to
make judgments concerning the frequency-versus-duration trade-
off, based upon the particular circumstances. The availabi-
lity/costs of monitoring techniques, and the desire for the
Phase 1 duration to encompass a reasonable period of time, will
undoubtedly influence these judgments.
• conduct the Phase 1 monitoring, and Interpret the results
(Including calculation of the parameter mean, coefficient of
variation, and confidence interval).
4-68
-------
For Each Stream
and Parameter
Estimate the expected
(order-of-magnitude) coefficient of
variation and concentration level
Select desired accuracy
(confidence interval width)
Select the number of measurements
(from Table 4-18 or equivalent)
necessary to give desired accuracy
Select reasonable frequency and duration
in order to achieve this number of measurements
Conduct Phase 1 testing.
Calculate actual coefficients of variation
and parameter mean
Were concentration levels
nd variability as expected?
Determine if the
accuracy of the
actual data base
is acceptable
Conduct additional
Phase 1 testing,
if necessary, to
achieve acceptable
accuracy
Figure 4-2. Schematic diagram of approach for selecting
Phase 1 monitoring frequency and duration.
4-69
-------
• 1f the observed parameter levels are substantially different
than expected* the Impact of this discrepancy should be
assessed. If the coefficient of variation is actually much
higher than was anticipated* and if the attained confidence
Interval 1s thus much broader than had been desired* it might
be decided that a larger number of Phase 1 measurements is
needed to achieve the desired confidence Interval. In this
case. Phase 1 testing for that parameter might be continued for
an additional period.
Sample numbers, monitoring frequencies and durations derived using the
above approach would be tailored to each site, and would provide Phase 1
results of known quality. While the decisions for any one site will vary
depending upon the site, some typical considerations are discussed below:
• Sample number. Although calculations such as Table 4-18
might suggest a certain number of measurements as being
adequate (e.g., n=6 for S0_), it might be more convenient (or
required by permit) that a greater number of samples be taken
in some cases (e.g., continuous monitoring for SCL). Con-
versely, for more difficult measurements (e.g., GC/MS for
complex organlcs), it might be reasonable to limit sample
number to, e.g., 4 to 12, 1n order to keep cost and duration
reasonable, even if this number results 1n an accuracy somewhat
lower than desired. As Indicated earlier, Phase 1 sample
number can also be influenced by the method selected for
Interpreting Phase 2 data.
• Duration. A reasonable duration would have to be selected
for each site based upon statistical considerations, as
discussed above, and based upon practical considerations, such
as the desire to cover a reasonable range of plant operating
conditions, and the desire to limit Phase 1 to a reasonable
length. While the selection of duration 1s site specific, a
duration of approximately one year might be reasonable 1n many
cases. This duration would cover any seasonal variations and
many other long-term process variations, and could provide time
for a reasonable number of sampling events.
• Frequency. The frequency ranges shown 1n Tables 4-15 through
4-17 reflect both practical considerations (e.g., the capabi-
lities, turnaround times and costs of monitoring techniques)
and the intuitive significance of the stream categories in-
volved. The selection of a monitoring frequency from within
these ranges would be based upon the circumstances of each
specific synfuels facility, Including the statistical consider-
ations described previously. In some cases, 1t might be desir-
able to select a frequency outside of the range indicated on
4-70
-------
the table (e.g., 1f a substance of partialuar concern has a
high coefficient of variation, or 1f a permit specifies a
particular frequency outside the range).
Stability of the Phase 1 Baseline
The discussion 1n this section assumes that the concentration levels for
a particular parameter and stream during Phase 1 can be represented by a
single baseline distribution. The variation observed 1n parameter concentra-
tions during Phase 1 1s assumed to be due to random causes (I.e., sampling and
analytical variability and random process variability). A single mean and
coefficient of variation (or standard deviation) can thus be used to charac-
terize the Phase 1 baseline data.
If 1n fact, a synfuels plant operates at systematically different con-
ditions during Phase 1, more than one baseline may be appropriate. For
example, two different types of coal might be used for the feedstock (e.g.,
low-sulfur and high-sulfur coal). Certain parameter discharge levels may be
systematically affected by the change 1n coal type. The parameter concentra-
tions would thus form two different distributions depending on the types of
coals used during the monitoring period. These distributions would have
different means and possibly different variations. The statistical considera-
tions discussed 1n this section would then be applicable to each distribution.
For the affected parameters, separate baselines for each condition should be
evaluated against the Incremental costs of developing multiple data bases.
There may be other Important changes 1n operating conditions during Phase
1, 1n addition to coal type, that could also affect measured parameter values.
During the Interpretation of the Phase 1 results, statistical procedures can
be used to evaluate stability, 1f adequate measurements are available. For
example, 1f twelve or more data points are available, a control chart (refer-
ence 4-32) can be constructed to evaluate the stability of the process. The
control chart will Identify segments of the data which should be described by
different baselines. When a large amount of data 1s available (e.g., from
dally testing or continuous monitors) more sophisticated techniques, such as
4-71
-------
time series analysis (reference 4-33) or response surface analysis can be used
to evaluate the effects of changes in plant operating conditions or parameter
levels. A statistician should be consulted for these analyses.
As discussed later* shifts in the baseline can have beneficial impacts in
some cases. Data obtained at more than one baseline can aid in the statis-
tical selection of Indicators to represent the data base during Phase 2 moni-
toring (see Section 4.2.2.1).
4.2.1.3 Monitoring During the Plant Startup Period
The intent of Phase 1 monitoring is to develop a representative,
"baseline" data base for the synfuels facility. Thus, a comprehensive Phase 1
testing program would not normally be proposed during the startup period,
because the facility would be expected to be operating at non-representative,
transient conditions during this period. However, some monitoring would be of
value during startup to:
• validate and refine monitoring procedures, as part of the QA/QC
program (discussed 1n Section 3.0),
• train personnel,
• conduct permit-required compliance monitoring.
The data collected during the startup monitoring may not contribute
directly to the "baseline" data base. However, the startup monitoring results
should be reviewed as a possible aid 1n the design/conduct of Phase 1. These
results can also serve as an indication of possible startup discharges from
future replications of the synfuels technology.
Validation and refinement of the monitoring procedures are necessary for
several reasons. The exact characteristics of many synfuel plant discharge
streams cannot be established until some operating experience with the speci-
fic process is obtained. As a result, some of the monitoring procedures that
the program designer might expect to apply, might have to be adjusted or
4-72
-------
changed to be more compatible with the substances which are present. For
example, the nature of the organlcs actually present could Influence the
analyst's selection of an extraction method; or the presence of Interfering
compounds could Influence the selection of an appropriate detector. Other
validation procedures are described 1n Section 3.0.
To accomplish this validation/refinement, 1t 1s suggested that two
separate monitoring campaigns be conducted during the plant startup period.
Each campaign would consist of a full Phase 1 effort (as defined by the survey
techniques and specific component analyses Identified 1n Tables 4-4 through
4-6). These campaigns should Involve a review of the performance of the tech-
niques and monitoring personnel/ and a review of the results, 1n order to
assess whether any of the techniques should be modified.
For a complete OJ\/QC program, these two startup monitoring campaigns
might also Include elements aimed at determining sampling and analytical
variability. A discussion of these elements 1s presented 1n Section 3.0.
The first of the two startup monitoring campaigns would logically be
Initiated as soon as possible after plant startup, and the second conducted
within 3 to 6 months after the first. The sampling might be conducted during
"reasonable" plant operating conditions, but the plant will likely be opera-
ting at transient or part-load conditions during the startup period.
If startup of a section of the plant extends beyond 3 to 6 months, 1t
might be desirable to continue monitoring for major substances 1n key streams
during startup of that section after the two campaigns discussed above are
completed. This continuing startup monitoring might logically Include only
the specific substances listed 1n the column, "Specific Component Sugges-
tions", 1n Tables 4-4 through 4-6. Continued analysis for trace metals or
complex organlcs Identified through the survey techniques might not be
4-73
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warranted during the transient startup periodf unless the surveys during the
two startup campaigns suggest consistently high levels of some substance of
particular concern.
During the startup, limited monitoring might also be conducted around
some of the major control devices. This would be aimed at assuring that the
controls are operating basically as anticipated. The monitoring would not be
intended to characterize control performance during the non-representative
startup period. The testing would logically address only the major pollutants
that the control device was designed to remove, as distinguished from the
entire list of survey techniques/specific components listed in Tables 4-4
through 4-6. Such pre-Phase 1 control monitoring would help assure that the
controls will be operating properly when routine operation begins after start-
up, and that routine operation will not be delayed by inadequate control
performance. It might be expected that this type of control performance
checking during startup would normally be conducted by the plant operator 1n
any event.
4.2.2 Phase 2 Monitoring
During the Phase 1 monitoring effort, a comprehensive, "baseline" data
base will be developed. The intent of Phase 2, in the approach being
described here, 1s to monitor this total data base without having to monitor
for every parameter contained 1n the data base. The method suggested to
accomplish this goal 1s the use of a limited number of "Indicator parameters"
to represent everything in the data base. These indicators will be selected,
to the extent possible, from the relationships observed in the Phase 1 data
between the indicators and the parameters they represent. In theory, if the
selected Indicator remains at its observed Phase 1 level throughout Phase 2,
then the represented parameters can also be assumed to remain at their Phase 1
level. If, during Phase 2, the indicator varies from Its Phase 1 level, a
single Phase 1 monitoring program might be conducted for the stream in which
the excursion occurred and for the substances represented by the indicator
4-74
-------
that varied. The baseline data base would thus be continually updated* based
upon the Phase 2 results for the Indicator parameters and the Phase 1 repeats
for the varying parameters.
Due to the Inherent uncertainties 1n selecting Indicators and 1n measur-
ing the Indicators during Phase 2, 1t 1s possible that the baseline might
shift without being reflected by an excursion of the Indicators outside of the
accepted limits. To guard against such an undetected baseline shift, Phase 1
testing might be repeated periodically during Phase 2, even 1f not triggered
by an Indicator excursion.
This section contains a discussion of:
• methods for selecting Indicator parameters and steps that might
be taken 1f effective Indicator relationships are not apparent,
• criteria for deciding when a Phase 2 Indicator result suggests
that the baseline has shifted,
• frequency of Phase 2 monitoring needed to detect Important
baseline shifts with reasonable confidence, and,
• periodic repeats of Phase 1 to assure that an undetected base-
line shift has not occurred.
4.2.2.1 Selection of Indicator Parameters for Phase 2
A key element 1n the phased approach 1s the selection of a limited number
of Indicators which can effectively represent the total Phase 1 data base.
The relationship between the Indicator and the species 1t represents should be
developed from review of the Phase 1 data.
Indicators might Include: Individual chemical compounds; some measure of
a class of compounds; gross chemical parameters, such as COD or TOC; plant or
control device operating conditions; perhaps even bloassays. Conceivably, an
Indicator could provide an Index for several classes of species. By
definition, the Indicator would have to be monitored during Phase 1.
4-75
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The selection of candidate Indicators can be based on:
c observed statistical relationships between the Indicator
and the substances 1t represents as developed from the
Phase 1 data* or
• theoretical correlations from engineering analysis or
fundamental chemistry.
If a theoretical correlation 1s employed, 1t would be desirable to test
the relationship as additional data become available from Phase 2.
Statistical principles can be used to determine Indicator relationships.
As will be discussed, the nature of the relationship between an Indicator and
the parameters 1t represents can vary. In a few cases, a true quantitative
relationship might be apparent; I.e., 1f the Indicator changes 1n concentra-
tion by a certain amount, then the represented parameter changes by a certain
corresponding and predictable different amount. More often, the relationship
will be "semi-quantitative"; I.e., 1f, during Phase 2, the Indicator remains
within Its range observed during Phase 1, then the represented parameters also
might be expected to remain within their Phase 1 ranges. In some cases, a
parameter might show JQO_ correlation with any other potential Indicator
(I.e., 1t would have to be Its own Indicator for a time).
The procedure for selecting Indicators basically consists of two steps:
1) Identification of which observed Phase 1 parameters might be considered,
from a practical point of view, to be suitable potential Indicators; and 2)
exploring alternative statistical correlations to see 1f relationships might
be Identified between the observed parameters and the potential Indicators.
Identification of Potential Indicators
Table 4-20 1s Intended to aid 1n the Identification of potential Indica-
tors. The types of potential Indicators are presented in Table 4-20 and are
discussed below 1n order of Increasing specificity.
4-76
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TABLE 4-20. TYPES OF POTENTIAL INDICATORS FOR PHASE 2 MONITORING
Indicator
Basts of Relationship
Class or Category of
Compounds Potentially Indicated
o OPERATING PARAMETERS
- Main Reactor
Feedstock composition:
ultimate, proximate* trace elements
Steam/02 ratio
Reactor temperature and pressure
Reactant and product flowrates
- Raw Reactor Effluent Cooling
Recycle, blow down, makeup rates
D1 fferentlal pressures
Operating temperatures and pressures
- Gas Purification and Upgrading
Flowrates
Operating temperatures and pressures
01fferentlal pressure
Recycle, blowdown, makeup rates
Regeneration steam rates
- Liquid Product Separation and Upgrading
Flowrate of aqueous and hydrocarbon phases
Operating temperatures and pressures
- Products Synthesis
Reactant and product flowrates
Operating temperatures and pressures
- Control Technologies
See Tables 4-12, 4-13, and 4-14 for operating
parameters affecting emission levels
o NON-SPECIFIC CHEMICAL ANALYSES
Total Organic Carbon (TOO
Total Inorganic Carbon (TIC)
Chemical Oxygen Demand (COD)
Total Chromatographable Organlcs (TOO)
Gravimetric Organic Loading (GRAV)
Total Hydrocarbon Analysis
Changes In feedstock composition,
operating conditions and flowrates
may result 1n changes 1n emission
levels; for example; If feed
volatile carbon Increases, organic
loading may Increase} or 1f product
flowrate decreases, trace element
emissions nay decrease.
Organlcs and Inorganics
Provides Indication of change 1n
total aqueous organic loading
Provides Indication of change In
total aqueous Inorganic carbon loading
Provides Indication of change In
total aqueous organic loading
Provides Indication of change 1n
total extractable organic
loading
Provides Indication of change 1n
total extractable organic
loading
Provides Indication of change In
total vapor phase organic
loading
Organlcs and some water quality
parameters
Carbonate, bicarbonate, and some
water quality parameters
Organlcs and some water quality
parameters
Organlcs
Organlcs
Organlcs
(Continued)
-------
TABLE 4-20. (continued)
Indicator
Basis of Relationship
Class or Category of
Compounds Potentially Indicated
I
^1
00
Methane/Nonmethane Hydrocarbon Analysis by FID
Infrared Analysis (IR)
GC-Photolonlzatlon Detection
Ultraviolet Analysts
Fluorescence Spot Test
GC-NHrogen Specific Detection
Colorlmetry <4-am1noant1pyr1ne)
GC-Sulfur Specific Detection
o SPECIFIC COMPONENTS
- Permit Required Monitoring
Will vary with specific permit requirements.
Could Include* for example, CO
- Non-Regulated Components
Hexane
Benzene
Napthalene
Aniline and Carbazole
Acetonltrtle
Phenol
Acetic Add
2-Hexanone and Dlbenzofuran
Benzothlophenes
Provides Indication of change 1n
total vapor phase organic
loading
Provides Indication of change In
organic class distribution or
composition
Provides Indication of change 1n
aromatic organic distribution or
composition
Prov1des 1ndlcatlon of change In
polynuclear aromatic organic dis-
tribution or composition
Provides Indication of change 1n
polynuclear aromatic organic dis-
tribution or composition
Provides Indication of change In
nitrogenous organic distribution
or composition
Provides Indication of change 1n
distribution or composition of
phenolIcs
Provides Indication of change 1n
distribution or composition of
sulfur containing compounds
Might provide Indication of change 1n
emission composition or distribution.
For example, a change 1n flue gas CO
levels could Indicate a change 1n
combustion efficiency that would also
affect organic emissions
May serve as Indicator of change 1n
concentration of members of a class
of analogous compounds
Organlcs
Aliphatlcs, aromatlcs, oxygenates
(ethers, esters, ketones, carboxyllc
acids)
Simple aromatlcs
Polynuclear aronatlcs
Polynuclear aromatlcs
Nitrogenous compounds
Sulfur containing compounds
Specific permit monitoring require-
ments might provide Indications for
organlcs ana/or Inorganics
AHphatlcs
Simple Aromatlcs
Polynuclear Aromatlcs
Amines and heterocycllc nitrogen
compounds
NJtrlles/lsocyanates
Phenol Ics
Carboxyllc acids
Other oxygenates
Sulfur containing compounds
-------
Operating conditions are the simplest type of parameter which may serve
as Indicators of change 1n stream compositions and emission levels. For exam-
ple, Incinerator temperature changes may Indicate changes 1n the organlcs 1n
the off-gas. The operating parameters listed 1n Table 4-20 may prove to be
suitable potential Indicators for organic and/or Inorganic components.
Non-specific chemical analyses may serve as Indicators for certain cate-
gories of compounds. For example, a change 1n TOC may Indicate a change 1n
specific organlcs 1n a wastewater stream. Several potential Indicators of
this type are shown In Table 4-20.
Specific components may also serve as Indicators for classes of compounds
or homologous series of compounds. Some of these specific components may be
monitored as a result of permit requirements or they may be non-regulated.
Examples of these specific components and the classes of compounds they may
Indicate are also shown 1n Table 4-20. An advantage to utilizing less speci-
fic Indicators 1s that they often are less expensive or time consuming to
Implement than the more specific Indicator analyses.
Since many organic compounds may potentially be present 1n some streams,
the Indicator compounds given 1n Table 4-20 may not be sufficient to represent
complex mixtures. Therefore, Table 4-21 presents additional potential Indica-
tor compounds which may be explored as potential Indicators for the organic
substances of Interest 1n synfuels waste streams listed 1n Table 4-10. Fur-
ther details for the use of non-specific chemical analyses as Indicators are
also given 1n Table 4-21. Table 4-21 follows the same organic compound
classification as Table 4-10. Alternative potential Indicator compounds and
non-specific chemical analysis Indicators (where applicable) are shown for
each organic classification. To provide additional Information for the user,
some specific examples of compounds previously Identified 1n synfuels waste
streams are Included under the appropriate categories 1n this table. Often,
4-79
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TABLE 4-21. CANDIDATE INDICATORS FOR ORGANICS OF INTEREST IN SYNFUELS WASTE STREAMS
Category of Organlcs
Compound Name
Non-SDeclftc Chemical Analysis"
Indicators
Specific Compounds
oo
o
(Subcategory)
ALIPHATICS
AROMATICS
(Single-ring)
(Multi-ring, non-fused)
General
(Specific Example Compounds)
Alkanes
(Pentane)
(Hexane)
(Heptane)
(Octane)
Cycloalkanes
(Cyclohexane)
(Methyl Cyclohexane)
Alkenes
Alkadlenes
(Butadiene)
(Cyclohexene)
(Benzene [BP 80*C3)
Alky! Benzenes
(Ethyl Benzene [BP 136'C]>
(Methyl Styrene)
(Toluene)
(Xylene [BP 137-144'C])
Blphenyls
(Blphenyl [BP 245-255'C])
(Dlmethylblphenyl)
(Methylblphenyl)
Infrared Analysis at
characteristic wavelength
GC/PID (Retention time window
corresponding to organtcs with
boiling points 65'C to 200*C)
GC/PID (Retention time window
corresponding to organlcs with
boiling points 200'C to 300'C)
Hexane
Elcosane
Benzene
Blphenyl
(Multi-ring, fused)
Indanes/Indenes
(Indan [BP 176'C])
(1H Indene)
GC/PID (retention time window
corresponding to organlcs with
boiling points 100'C to 350'C,
melting point 300*C
Indan
(Continued)
-------
TABLE 4-21. (continued)
Category of Organlcs3
Compound Name
Non-Specific Chemical Analysts
Indicators
Specific Compounds
POLYNUCIEAR AROMATICS
I
OO
Naphthalenes
(Methyl naphthalene)
(Dimethylnaphthal ene)
(Ethylenenaphthalene)
(Naphthalene [BP 218'C])
(Trfmethyl naphthalene)
(Tetramethylnaphthal ene)
(Phenylnaphthalene [PB 324-325'C])
Anthracenes/Penanthrenes
(Anthracene [BP 312'C])
(Phenanthrene [BP 336'C])
(Chrysene [BP 448'C])
(4H-Cyclopenda(def)phenanthrene)
(D1 methy 1phena nth rene/D1 methy 1anth racene)
(Dimethylpyrene)
(Methyl anthracene/Methylphenanthrene)
(Methyl benz(a)anthracene)
(Methyl chrysene)
(Methy 1cy cl ope nta(def)phenanthrene)
(Methylpyrene)
(Pyrene [BP 393'C])
(Trlmethylanthracene)
(Trtmethlphenanthrene/Trimsthy 1anthracene)
Acenaphthenes
(Acenaphthene [BP 279'C])
(Acenaphthylene [BP 280'C])
(Methylacenaphthene)
(Dimethylancenaphthene)
(Blmethylacenaphthene)
Benzfa(anthracenes
(Benz(a)anthracene [MP 160'C])
(Benz(a)anthracene/Chrysene)
(7,12-D1methy1benz(a)anthracene)
Benzo Pyrenes
(Benzo(a)pyrene [MP 179'C])
(Methylbenzo(a)pyrene)
Fluorescent Spot Test
Naphthalene
Phenylnaphthalene
Anthracene/Phenanthrene
Pyrene
Acenaphthene
Benzopyrene
(Continued)
-------
TABLE 4-21. (continued)
Category of Organtcs
Compound Name
Non-Specific Chemical Analysis
Indicators
Specific Compounds
POLYNUCLEAR AROMATICS (Continued)
I
CO
ro
NITROGENOUS COMPOUNDS
Amines and Heterocycles
(Amines)
Dlbenz Anthracenes
(D1benz(a,h)anthracene CMP 226'C])
Perylenes
(Perylene [sub 350/450'C])
(Benzotg.h. Dperylene)
(Dlbenzoperylene)
Fluorenes
(Benzofluorene [MP 209-102'CJ)
(11H Benzo(a)fluorene)
(Dimethylfluorene)
(Ruorene [BP 298'C])
(Methylfl uorene)
Fluoranthenes
(Fluoranthene [BP 394'C])
(Methylf1uoranthene)
(Dlmethylfluoranthene)
Benzofluoranthenes
(Benzo(k)fluoranthene)
Indenopyrenes
Choianthrenes
(Methylcholanthrene [MP 179-180'CD)
Perylene
Fluoranthene
Anil1nes
(Aniline [BP 184-186'C])
Alkyl An 1Hnes/D1 amines
Naphthylamlnes
(2-Naphthylam1ne [BP 306'C])
Aromatic Amines
Am1nob1phenyls
Morphol1nes
(Morphollne [BP 129*C)
GC/N specific (retention time window
corresponding to organlcs with
boiling points SO'C to 400'C)
Methy 1cholanth rene
Aniline
2-Naphthylam1ne
(Continued!
-------
TABLE 4-21. (continued)
Category of OrgaMcs
Compound Name
Indicators
Non-Soec1f346'C])
Pyrroles
(Pyrrole [BP 130-131'C])
Indoles
(Indole [BP 253'C])
Phenols
(Phenol [MP 35-40'C])
Alky! Phenols
(Dimethyl Phenol)
(Methyl Phenol)
(Tetramethylphenol)
(Trlmethyl Phenol)
Naphthols
(2-Naphthol [122-123'C])
(Methyl Naphthol)
Dthydrlc Phenols
(Resordnol [HP 109-110'C3)
Benzofuranols
GC-N specific (retention time
window corresponding to organlcs
»1th boiling points 50'C to 400'C)
Col or1metry(4-am1noant1pyrene)
Pyrfdlne
Carbazole
Phenol
Naphthol
(Continued)
-------
TABLE 4-21. (continued)
Category of Organtcs
Compound Name
Non-specific Chemical Analysis'
Indicators
77T6
Specific Compounds
I
CO
OXYGENATES (Continued)
Carboxyl 1c Adds
Other Oxygenates
(Ethers)
(Alcohols)
(Ketones)
(Aldehydes)
(Esters)
Alkyl Acids
(Formic Add [116-118'C])
(Acetic Add [100.8'C])
Aromatic Acids
(Benzole Acid [122-123'C])
Alkyl Ethers
Aromatic Ethers
Oloxanes
Alkyl Alcohols
(Butanol)
Cycloalcohols
Cellosolves
(2-Ethoxyethanol [BP 135'C])
Alkyl Ketones
(2-Butanone)
(2-Heptanone [BP 149-150"C])
(3-Heptanone CBP 146*C])
(2-Hexanone [BP 127'C])
(4-Methyl-2-pentanone
[BP 117-118'C])
(5-Methyl-3-heptanone)
(2»6-D1methyl-4-heptanone [169'
(2-Pentanone)
(2-Propane)
Cycloketones
Aromatic Ketones
Formaldehyde
Alkyl Aldehydes
Aromatic Aldehydes
Alkyl Esters
Aromatic Esters
(Phthalate Esters)*
Infrared Analysis at characteristic
wavelength
Infrared Analysis at characteristic
wave!ength
Infrared Analysis at characteristic
wavelength
Infrared Analysis at characteristic
wavelength
Infrared Analysis at characteristic
wavelength
Infrared Analysts at characteristic
wavelength
Acatfc Acid
Benzole Add
Butanol
Cellosolve
4-Hethyl-2-pentanone
Benz aldehyde
(Continued)
-------
TABLE 4-21. (continued)
Category of Organtcs
Compound Name
Non-Specific Chemical Analysis
Indicators
Specific Compounds
CO
en
OXYGENATES (Continued)
(Heterocycl1c Oxygen)
SULFUR CONTAINING
(Mercaptans and Sulffdes)
(Heterocycl(c Sulfur)
Furans
(Furan [BP 32'C])
Benzofurans
(Methylbenzofuran CBP 197'C])
Dlbenzofurans
(dbenzofuran [BP 285*C])
(Dimethy1d1benzofuran)
(Methyldlbenzofuran)
Alkyl Mercaptans
(Methyl Mercaptan [BP 6'CD)
(Ethyl Mercaptan)
(Butyl Mercaptan [BP 64-98'C])
Alkyl Dlsulfldes
(Methyldlsulflde [BP 110'C])
Thlophenes
(Thlophene [BP 64'C])
None available (possibly GC/PID)
GC-S specific (retention time window
corresponding to organlcs with
boiling points 5'C to ISO'C)
GC-S specific (retention time window
corresponding to organlcs with
boiling points 75'C to MP 200'C)
Benzothlophenes
(Benzo(b)thlophene [BP 221'C])
(Benzo(b)naphtho(l,3-d)th1ophene)
[MP 186'C])
Furan
Dlbenzofuran
Ethyl Mercaptan
Thlophene
Benzothlophene
As listed 1n Table 4-10.
bG1ven In Table 4-20.
•Generally present as artifacts of sample handling and exposure to plastics. Not anticipated to be produced In synthetic fuels processes.
-------
non-specific chemical analysis results will be adequate to confirm any compo-
sitional changes or Indicate the absence of a class of organic compounds; and
more rigorous and quantitative analyses for specific Indicator compounds will
not be necessary.
No specific Inorganic Indicator compounds have been suggested for the
elements listed 1n Table 4-11. Since the elements listed 1n Table 4-11 will
most often be Identified not as compounds but as total elemental concentra-
tion, the element will most commonly serve as an Indicator for Itself. Most
of the elements listed 1n Table 4-11 can be Identified rapidly 1n an ICP
analysis of each sample; therefore, no selection of Indicator elements for
classes of elements (analogous to Table 4-21) has been made. Analysis of some
volatile elements, arsenic, antimony, selenium and mercury, by AA 1s stm
most commonly applicable; and 1t will probably be necessary to quantify each
of these elements Individually by AA. Once elements of Interest have been
selected from the Phase 1 data, the details of Implementation for the analyt-
ical techniques (e.g., ICP) may change 1n Phase 2 to focus on these specific
elements. If Indicators beyond those suggested 1n Table 4-20 are desired for
the elements listed 1n Table 4-11, the selection of those Indicators should be
based on an analysis of both the process design and process chemistry.
When Tables 4-20 and 4-21 are used for a specific Phase 1 data set, the
program designer would review the Phase 1 data base to Identify the classes of
organlcs and to determine 1f potential Indicator compounds have been observed.
The program designer then might employ the statistical data Interpretation
techniques, discussed later, to determine 1f the Phase 1 data set reflects
suitable relationships between the potential Indicators and the compounds or
groups of compounds the Indicators were to represent. An assessment would be
made to determine 1f operating parameters might be used as Indicators. Then,
the program designer might determine 1f non-specific chemical analyses may be
appropriate as Phase 2 Indicators. Tables 4-20 and 4-21 then would be applied
to select potential Indicators. For compounds observed 1n a specific Phase 1
data set but not listed 1n Table 4-21, judgments would be necessary to cate-
gorize the observed compounds. Selection of potential Indicator compounds
4-86
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would be made using Table 4-21 as a guide. If no indicators can be Identi-
fied, then rigorous definition of indicators will be delayed until further
data become available.
The selected indicators should have some practical, as well as statis-
tical, relationship to the parameters being represented. For example, the
indicator might be a member of a homologous series of organic compounds repre-
senting other compounds in that series; it might be a gross organic parameter
(non-specific chemical analysis), such as TOC representing specific organics
in a wastewater stream; or it might be an operating parameter, such as incin-
erator temperature representing organic compounds in the off-gas.
Exploring Alternative Correlations between Potential Indicators and
Represented Parameters
A variety of statistical procedures are available for quantifying indica-
tor/parameter relationships from monitoring data. (These procedures are
discussed later.) The appropriate statistical procedure will depend on the
form of the available data and the expected indicator relationship.
Some Potential Difficulties in Developing Indicator Relationships. The
development of suitable relationships between potential indicators and Phase 1
parameters that they might represent during Phase 2 might be complicated by
two factors:
• the relatively small amount of data which may be available from
Phase 1, especially for those parameters for which monitoring
is expensive and time consuming.
• the variability of the sampling and analysis procedures rela-
tive to the range in concentration of the parameters during the
Phase 1 period. To evaluate potential indicator relationships,
the range of the parameter concentrations during the Phase 1
period should be much larger than the analytical variability.
Since Phase 1 tests might be at a single set of "baseline"
operating conditions for the plant (i.e., at a stable base-
line), some parameter values might not vary significantly
4-87
-------
during Phase 1. Thus, 1t 1s possible that data obtained from
Phase 1 might not be adequate to develop quantitative Indicator
relationships for some parameters.
The nature of this problem 1s Illustrated 1n Figure 4-3, where measured
values for a hypothetical parameter of Interest are plotted against a poten-
tial Indicator for that parameter. A series of measurements at "normal's or
baseline* plant operating conditions are Indicated 1n the figure by the letter
N. As shown* any correlation that might exist between the parameter and the
potential Indicator Is hidden by the effects of sampling and analytical vari-
ability. However* 1n this hypothetical example* if plant operation were
changed to a different set of conditions (a new baseline), representing an
"excursion" from the original baseline (represented by the letter E 1n the
figure), the effect of this change might be large enough to override the
effects of sampling and analytical variability. Then the nature of the over-
all relationship might be revealed. The Initial Phase 1 monitoring will be
limited 1n duration, and might be deliberately aimed at a single set of "base-
line" conditions. It Is possible that the range of plant operating conditions
during Phase 1 might not be great enough to effectively reveal some relation-
ships which might 1n fact exist. The potentially limited number of samples
obtained during Phase 1 would only exacerbate this problem.
To validate indicator/parameter relationships* 1t would be desirable to
collect data over a wide range of operating conditions. The parameters of
Interest should vary as widely as possible for the purpose of defining any
Indicator relationships. If a synfuels plant 1s being operated at a different
set of conditions as part of the plant operating plan, then Phase 1 monitoring
(of potential Indicators and represented parameters) could profitably be
scheduled to occur during operations at these different conditions. Such
Phase I monitoring might be conducted during the Initial Phase 1 period, 1f
the baseline shift occurs then, or it could be one of the Phase 1 repeats
scheduled during Phase 2 (discussed later).
4-88
-------
CO
LU
QC
UJ
cc
<
a.
10 -
9 -
8 -
7 -
6 -
5-
4 -
3-
2-
1
0 -
N
NN
N
N
N
N NORMAL PLANT OPERATING CONDITIONS
E EXCURSION FROM NORMAL CONDITIONS
34567
POTENTIAL INDICATOR
10
Figure 4-3. Determining indicator/parameter relationships.
4-89
-------
Development of Indicator Correlations when Data Permits. If available data
Include adequate variations for both the parameters and potential Indicators,
statistical procedures can be used to evaluate and quantify the form of the
relationship between a parameter to be represented and Its potential Indica-
tor. Various statistical techniques might be applied to the Phase 1 data 1n
exploring potential qualitative and quantitative relationships between the
alternative candidate Indicators and the parameters to be represented. Some
of these more useful techniques are summarized 1n Table 4-22.
When quantitative data sets are available, techniques such as correlation
analysis, regression analysis and several of the multlvarlate procedures are
most applicable 1n analyzing the potential Indicator/parameter relationships.
Multlvarlate techniques are also useful for screening multiple candidate
Indicators. The strength of an Indicator/parameter relationship can be
defined using correlation analysis. Regression analysis 1s useful 1n develop-
ing quantitative relationships (1f present) between Indicators and the repre-
sented parameters.
Many of the parameters of Interest 1n synfuels plants will be present at
levels which logically fall Into discrete ranges of values. A good example of
this type of behavior 1s the presence of compounds of Interest 1n concentra-
tions at or below analytical detection limits. Discriminate analysis and
categorical data analysis procedures are useful when dealing with this type of
data.
Approach when Data do not Permit Statistical Indicator Correlations. If
Indicators cannot be Identified from the Phase 1 data/results, alternative
approaches can be developed for proceeding with Phase 2 testing. For example,
Indicator/parameter relationships can be developed based on fundamental chem-
istry considerations or derived from an engineering analysis of the plant/
process operation. Alternately, Phase 2 could proceed and "temporary" indica-
tors could be used. As discussed later, the complete Phase 1 testing should
4-90
-------
TABLE 4-22. STATISTICAL TECHNIQUES AND THEIR APPLICABILITY
TO THE ANALYSIS OF MONITORING PROGRAM DATA
Technique
Applicability
Result of
ApplIcatlon
Limitations
References
1. Correlation Analysis
2. Regression Analysis
(Method of least
squares)
I
IO
3. Discriminant analysis
To Indicate the degree to
which variations 1n one
parameter are "tracked"
by corresponding varia-
tions 1n another para-
meter (e.g.i a candidate
Indicator). This 1s pro-
bably one of the most
familiar, easily applied
and useful tests of the
strength of an Indicator/
monitored parameter
relationship.
2. To develop a quantitative
expression for the rela-
tionship between a moni-
tored parameter and Its
1nd1cator(s). This tech-
nique will provide a more
definitive Indication of
Indicator/parameter rela-
tionships than that pro-
vided with correlation
analysis.
3. To develop a relationship
between a potential Indi-
cator and substances 1t
might represent, when the
represented substances fall
Into discrete classes
(e.g., detected vs. not
detected) and where the
potential Indicator Is
quantified (numerical
values available).
A correlation coefficient, r,
1s calculated by the methods
described 1n Appendix B. r2
1s then used as a measure of
the degree to which two
variables "track" one another.
r^ > 0.9 Indicates a strong
correlation (good Indicator/
parameter relationship).
r < 0.1 Indicates a poor
correlation. Utility of values
between 0.1 and 0.9 would
depend upon situation.
An equation which can be
used to predict the value
of a parameter of Interest
given a set of assumed or
measured Indicator para-
meter values.
A relationship which
describes the probability
of a parameter falling
Into some class or range
of values given a known
set of quantitative values
for appropriate Indicators.
3.
Data for both the parameter 4-34
and the Indicator must be
quantitative (I.e., not sim-
ply detected/not detected or
Iow-medtum-h1gh). Since this
technique assumes a linear
relationship. Initial cross-
plots may be needed to deter-
mine the best possible corre-
lation form. Data, transforma-
tions (e.g., to log domain)
may be useful 1n establishing
the strongest possible
correlatlons.
The existence of a statist!- 4-34
cally significant Indicator/
parameter relationship which
can be quantified through an
equation, may Imply more of
a cause-effect relationship
than Is appropriate; see
also limitations 1 and 3.
A lot of analysis can 4-35
be required to develop
appropriate correlation
forms, select appropri-
ate class ranges, etc.;
see also limitation 2.
(Continued)
-------
TABLE 4-22. (continued)
Technique
ApplIcabtllty
Result of
Appl (cation
Limitations
References
-p.
I
rvi
4. Categorical Data
Analysis
(Ch1-square test)
5. Other Multtvarlate
Procedures
(e.g., canonical
correlation, prin-
cipal component
analysis, factor
analysis, cluster
analysis)
4. To develop a relationship t
between a potential Indi-
cator and substances 1t
might represent, when the
represented substances fall
Into discrete classes (e.g.,
not detected, detected,
quantified) and where the
Indicator parameter Itself
1s expressed as an element
of a discrete class of
values, (e.g., low, medium,
or high).
5. To analyze relationships 5
among multiple parameters
and Indicators simul-
taneously. Can be valuable
1n screening alternative
Indicator/parameter rela-
tionships and 1n select-
Ing the best single Indi-
cator or group of Indica-
tors for larger classes
or groups of monitored
parameters.
A definition of whether
a statistically signifi-
cant relationship exists
and a definition of error
rates for specific
Indicator/parameter
relationships.
Depends on technique; allows
quick screening of alterna-
tives; Indicator Indexes can
be developed.
Similar to limitations
for technique 3.
4-36
Requires a large data
base compared to some
of the other techniques
to establish meaning-
ful correlations.
4-35
-------
be periodically repeated throughout Phase 2 1n order to determine whether the
baseline has shifted without excursions 1n the Indicators. To aid 1n Indica-
tor selection, these Phase 1 test programs could be scheduled when the plant
1s operating (at steady state) at conditions quite different from those of the
Phase 1 baseline conditions (I.e., deliberately scheduled for a time when the
baseline might likely have shifted). Improved Indicator relationships might
be developed using the additional data, and these Improved Indicators might
then replace the "temporary" Indicators.
A number of alternatives can be considered for selecting "temporary"
Indicators. The Individual parameter can be considered its own "temporary"
Indicator. Phase 2 monitoring would thus Include the Individual parameter
Itself (or perhaps the same survey techniques used 1n Phase 1). This approach
might be useful, particularly when only a few parameters are not represented
by Indicators.
Another alternative 1s to select temporary Indicators which are broadly
representative of that class/group of substances which Includes the parameter
of Interest. Some possible temporary Indicators of this type are analytical
techniques listed under the heading of "non-specific chemical analysis" 1n
Table 4-21. Temporary Indicators should be meaningful and should also have
advantages over the Phase 1 survey technique for the parameter of Interest.
For example, the testing required to obtain temporary Indicators should be
cheaper and/or simpler than that for the parameter. Otherwise, there 1s no
point to choosing an Indicator Instead of the parameter Itself.
Each periodic Phase 1 repeat during Phase 2 would Increase the number of
Phase 1 measurements, and would possibly provide data at a baseline different
from the Phase 1 baseline. Both of these factors Increase the probability
that suitable Indicator/parameter relationships might be Identified. The data
should be reviewed after each Phase 1 repeat to Identify whether any Indica-
tor/parameter correlations have become apparent with the new data set.
4-93
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It 1s possible that—even after substantial additional data becomes
available during Phase 2—no suitable parameter/Indicator relationship will be
found for some particular parameter(s). In these cases, the choice must be
made concerning whether Phase 2 monitoring for this parameter should be con-
tinued Indefinitely. Such a choice will be a function of several factors
Including:
• parameter level,
• Importance, hazard, toxldty,
• cost of sampling/analysis,
• accuracy of analysis,
• variability of the parameter,
• the number of parameters for which no Indicator relationships
are apparent.
4.2.2.2 Methods for Conduct of Phase 2
The Intent of Phase 2 1s to track the total Phase 1 data base, using a
limited number of Indicators, and to repeat the pertinent portions of Phase 1
when an Indicator excursion suggests that a shift 1n the Phase 1 baseline has
occurred. Once Indicators are selected, the key Issues that need to be
addressed 1n designing the Phase 2 program to achieve these goals are:
• the method by which the Phase 2 results are compared against
the Phase 1 results for each Indicator,
• the magnitude of the excursion 1n the Phase 2 Indicator which
is necessary before a repeat of Phase 1 1s warranted for the
parameters represented by that Indicator in the stream for
which the excursion occurred, and
• the frequency of the Phase 2 monitoring for each Indicator.
4-94
-------
These three Issues—plus the number of measurements made during Phase 1
(the quality of the Phase 1 baseline)—can be related by statistical
principles.
A number of statistical considerations must be factored Into the
resolution of the above Interrelated Issues. These statistical
considerations* which must be determined for each site. Include:
• the acceptable degree of risk of a Type I error (false
positive); I.e., the risk of concluding that the Phase 1
baseline has shifted when 1n fact 1t has not. The concern
about a false positive, of course, is that it would suggest
that a Phase 1 repeat is necessary when 1n fact it 1s not.
Suitable selections of the method for comparing Phase I/Phase 2
results, the accepted magnitude of the Phase 2 excursion, and
(1n some cases) the number of Phase 1 measurements can control
the risk of a Type I error.
• the acceptable degree of risk of a Type II error (false nega-
tive); I.e., the risk of concluding that the baseline remains
at the Phase 1 level when 1n fact 1t has changed. Another way
of phrasing this is, What 1s the desired "power" of this Phase
2 program, the level of confidence that it will indeed detect
baseline shifts? As will be discussed later, Type II error can
be controlled by the number (frequency) of Phase 2 samples, the
number of Phase 1 samples 1n some cases, and other factors,
depending upon the nature of the method selected for comparing
the Phase I/Phase 2 results.
• the desired sensitivity in detecting baseline shifts during
Phase 2. How small a shift 1n the baseline should be detected?
This sensitivity can be controlled by the number (frequency) of
Phase 2 and Phase 1 samples.
The decisions concerning the issues and the considerations listed above,
will be Influenced by a variety of statistical and practical factors:
• the practical limitations on the number of Phase 1 samples (and
hence limitations on the accuracy of the Phase 1 mean and
standard deviation);
4-95
-------
• the coefficients of variation of the various Indicators; the
higher this variation, the greater the number of Phase 1 and/or
Phase 2 samples needed to control the Type II error.
• the significance of the indicator or parameter; the more
Important the substance, the more accurately 1t might be
tracked.
• the complexity and cost of available sampling and analytical
techniques; 1f a substance requires more difficult or expensive
techniques, this fact could Influence the selected Phase 2
frequency.
• the accuracy of the available sampling/analysis techniques
(also reflected in the coefficient of variation, above).
• the precision of the statistical relationship between the
Indicator and the substances it represents. If the indicator
relationship is weak, and if 1t 1s desired to use the Indicator
to track the represented substances with a certain power, 1t
might be necessary to select a greater power for monitoring the
Indicator.
Thus, the selection of the most desirable monitoring frequencies is not a
precise quantitative process. The ability to detect changes 1n the baseline
parameter values 1s the primary factor affected by monitoring frequencies.
The ability to detect changes is also Influenced by the decision criteria used
to detect baseline shifts.
The first decision that must be made 1n designing the Phase 2 program is
the method that will be used to compare the Phase 2 and Phase 1 results.
Several alternative methods, and variations of methods, are available. One
key criterion 1n selecting a suitable method from the list of alternatives 1s
the number of Phase 1 measurements that can be made (I.e., the accuracy with
which the Phase 1 mean and the standard deviation are known). Ideally, it
would be desirable to make a fairly large number of measurements during Phase
1, so that the mean and the standard deviation for a substance would be
accurately known. For substances measured fairly frequently in Phase 1 (e.g.,
continuously or weekly), this will be possible. However, 1f the number of
4-96
-------
Phase 1 samples is limited by practical considerations, metnous utilizing
small-sample theory might be necessary. The methods that will be discussed
here are the following:
• control chart analyses (most effective when number of Phase 1
samples is 1arge),
• t-test (number of Phase 1 samples is small),
• nonparametric procedure (no distribution model is appropriate)
The issues listed at the beginning of Section 4.2.2.2 are now discussed
for each of these three alternative statistical methods for comparing the
Phase 1 and Phase 2 results. Different Phase I/Phase 2 comparison methods,
different "acceptable" Phase 2 excursions, and different Phase 2 monitoring
frequencies might be considered for different indicators, based upon differ-
ences in the practical number of Phase 1 samples, in the significance of the
indicators, and other factors.
Control .Chart .Analysis
If the indicator involved is amenable to frequent Phase 1 monitoring
(e.g., bi-weekly, weekly, or even more frequently)—so that 25-50, or even
more, Phase 1 measurements are realistically possible—then a fairly accurate
Phase 1 mean and standard deviation can be determined. In control chart
analyses, a decision criterion is selected—e.g., 3a — and Phase 1 for an
Indicator is repeated once each time a single Phase 2 measurement of that
Indicator (or, if desired, the average of multiple Phase 2 measurements)
varies from the Phase 1 mean by an amount greater than this decision crite-
rion. This approach is statistically most reliable when the mean and the
standard deviation are fairly accurately known. (Application of the control
chart approach when only a limited number of Phase 1 measurements are avail-
able is discussed in Reference 4-38).
In this approach, the Type I error is controlled by the selection of the
decision criterion (the size of the accepted Phase 2 excursion). The larger
the excursion that is allowed in Phase 2, before conducting a Phase 1 repeat,
4-97
-------
the smaller will be the likelihood of a false positive vrewer "unnecessaiy"
Phase 1 repeats) and the greater will be the likelihood of a Type II error
(lower power or confidence). Thus* after selecting the decision criterion to
control Type I error, Type II error is controlled by the selection of the
Phase 2 monitoring frequency (number of Phase 2 samples). If a relatively
large accepted excursion were selected in order to reduce the likelihood of
false positives, then a higher Phase 2 monitoring frequency might be selected
1n order to compensate for the resulting risk of false negatives. The sensi-
tivity of this approach in detecting baseline shifts for a given indicator
depends upon the standard deviation (or the coefficient of variation) for that
indicator, as measured in Phase 1, and upon the number of samples obtained In
Phase 1 and Phase 2.
This approach is often used in traditional quality control applications.
The formulas/procedures governing this approach are described in Reference
4-37.
In order to decide whether control chart analysis might be suitable for
the Phase 2 program on a given indicator, the program designer should consider
the following points:
• Is it reasonable to obtain a fairly large number of samples
during Phase 1 (e.g., 25 to 50)? Without a minimum number of
samples, the Phase 1 mean and standard deviation might not be
known with sufficient accuracy to use this approach. (See
Reference 4-38 for cases where the Phase 1 sample number 1s
limited.)
• Is a distribution model appropriate for the substance (e.g.,
normal, lognormal)? The control chart approach requires the
use of a distribution model. (In general, a distribution model
can be selected if 25 to 50 Phase 1 measurements are made.)
If this approach were selected, a procedure that might be utilized in
applying the approach could be as follows.
4-98
-------
Select the decision criterion which will provi 1e &,• acceptable
Type I error. Traditionally, a value of 3a is employed in
quality control applications (Reference 4-32). This value
results in only a small chance of a Type I error (3 out of
1000), while providing a reasonable opportunity to reduce Type
II errors through suitable selection of Phase 2 monitoring fre-
quency/ sample numbers. By comparison, the use of a 2o criter-
ion would achieve a lower Type II error rate, but would result
in a higher Type I error rate (up to about 5 %). The use of
4a criterion would reduce the risk of Type I errors to a
negligible value, but would result in poor power (large Type II
errors). Accordingly, a decision criterion of 3o seems reason-
able. Phase 1 monitoring for the substances represented by an
Indicator in a given stream would be repeated during Phase 2
once each time a single measurement of that Indicator varied
from its Phase 1 mean by more than ±3o.
Select the number of Phase 2 samples (the sampling frequency)
needed for each indicator in order to control the Type II error
rate (achieve acceptable power) and obtain the desired sensi-
tivity. The calculated sample number will depend upon the
variability (standard deviation) of the individual indicator.
The relationship among all of these variables is illustrated in
Figure 4-4, which assumes that Type I error has been controlled
by the selection of a 3a decision criterion (and that the
distribution is normal). This figure shows the power of the
test (probability of detecting baseline shift) as a function of
an index b/o, which is the the baseline shift (desired sensi-
tivity) divided by the standard deviation of the indicator.
The effect of Phase 2 sample number is shown by a parametric
series of curves. As an example of the use of this figure, if
the Phase 1 mean for an indicator is represented by the symbol
\i f suppose that it were decided that a baseline shift of 50%
of the Phase 1 mean (i.e., a sensitivity of b = 0.5y) in an
indicator having a coefficient of variation of 25% (i.e., o/y =
0.25, or a = 0.25p) should be detected with a power of 95%
(likelihood of Type II error of 5%). Referring to Figure 4-4,
for a value of b/o = 0.5y/0.25y = 2.0, and for a 95% probabil-
ity, it is apparent that 20 samples would be statistically
necessary. In other words, if 20 Phase 2 measurements were
made for this particular indicator, and if none of them varied
from the Phase 1 mean by more than +3 a, then one could be 95%
confident that the Phase 1 baseline had in fact not varied by
more than 50%. If it is desired to maintain this confidence on
an annual basis, then the 20 Phase 2 measurements would need to
be made in the period of one year, suggesting a bi-weekly
frequency.
Another manner of presenting this same information is presented
in Table 4-23. In this table, the power (probability of
detecting a baseline shift) is presented as a function of the
desired sensitivity (shift in baseline mean) and the number of
4-99
-------
100 n
o
o
lil
01
z
_l
LU
CO
CO
tu
CO
X
0-
z
t
X
CO
o
z
01
fc
Q
CD
<
m
O
cc
a.
m = NUMBER OF TESTS
0-
BASELINE SHIFT/STANDARD DEVIATION
Figure 4-4. Example chart for determining number of tests
required in Phase 2 monitoring.
-------
samples, for the specific case of an indicator having a coeffi-
cient of variation of 50%. This table—which is designed to
illustrate more clearly the effects of sensitivity in the
selection of sample numbei—is derived directly from Figure 4-
4, recognizing that the percentage baseline shift is 100 x b/y,
and the coefficient of variation is 100 x o/n. As an example
of the meaning of the table, if one wished to detect a 100%
shift from the Phase 1 baseline for this particular indicator,
then one could only be 50% confident of detecting the shift if
only 4 samples were taken (and were compared against the ±3a)
but one could be 97% confident if 20 samples were taken.
Assuming again that it is desired to maintain this confidence
on an annual basis, this example illustrates the impact upon
power of a quarterly versus a biweekly sampling frequency.
Figure 4-4 and Table 4-23 (or comparable figures for, e.g.,
distributions other than normal decision criteria other than
3«, etc.) can be used for the interrelated decisions concerning
sample number, desired Type II error and desired sensitivity
for a particular synfuels plant.
The power of this procedure also depends upon the number of
indicator measurements made during each Phase 2 "test event".
If a test event consists of multiple measurements—and if it is
an average of these Phase 2 measurements that is compared
against the Phase 1 mean—then the power of the procedure could
be increased.
Since only one Phase 2 measurement would need to vary beyond
the 3a decision criterion in order to trigger a Phase 1 repeat
for an indicator, by the example discussed in this section, it
would be expected that the Phase 1 repeat would be conducted
immediately, even if the excursion occurs before the full
number of Phase 2 measurements is made. In such a case, the
mean for the affected indicator would be recalculated based
upon the data from the Phase 1 repeat, as discussed later; the
Phase 2 monitoring would then "begin over again" using the new
mean.
t-Test Procedure
The t-test is appropriate if either a normal or log-normal distribution
model is known to apply for the indicator (or parameter) data (see Appendix
B). In this approach, the average of the full set of measurements (2 or more)
from the Phase 1 period are compared to the average of a set of measurements
4-101
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TABLE 4-23. EXAMPLE APPLICATION OF FIGURE 4-4.
Number of
Samples
1
2
4
8
20
ProbabU
50%
Shift
2%
5%
9%
17%
38%
1ty of Detecting a Shift 1n the Mean
Yalue Within A Year of Occurrence
Percentage Shift
75%
Shift
7%
13%
24%
42%
75% .
of Basel 1ne Mean
100%
Shift
16%
29%
50%
75%
97%
Basel 1ne
200%
Shift
84%
97%
99%
100%
100%
Coefficient of variation = 50%
Decision criterion = 3 a
Normal distribution model
(1 or more) from each Phase 2 sampling event. The t-stat1st1c (Reference 4-
39) 1s used to evaluate the statistical significance of the difference. The
Type I error 1s controlled by the selection of the appropriate t-stat1st1c.
The Type II error 1s controlled by the sample size 1n Phase 1 and 1n each
Phase 2 test event. Reference 4-40 can be used to evaluate the Type II error
for alternative sample sizes 1n the two time periods.
The larger the sample sizes (number of measurements) 1n Phases 1 and 2,
the greater the power of the test to detect differences between the means 1n
the two periods. The basic assumptions of the t-test Include 1) the distri-
bution model 1s normal, 2) each measurement during Phase 1 and Phase 2 1s
Independent or the others, and 3) the variability of the measurements is the
same during Phase 1 as during Phase 2. If the log-normal distribution model
1s appropriate, then the data should be transformed (by taking logarithms of
the measurements) prior to applying the test.
4-102
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In making a decision to apply this testf the program designer should
consider the following points:
1) Is the number of Phase 1 measurements limited to the point
that the control chart analysis procedure might not be
preferred?
2) Is 1t reasonable to assume the normal or lognormal model
to describe the Indicator data?
If the t-test 1s to be used* the user would need to make decisions concerning
the following factors:
1) What are appropriate levels for the Type I and Type II
errors (the t-stat1st1c would be selected to provide the
desired Type I error);
2) What magnitude of change 1n the mean level 1s 1t necessary
to detect (I.e., what 1s desired sensitivity);
3) What number of measurements should be made during Phase 1,
and what number during each Phase 2 test event* 1n order
to achieve the desired Type II error and the desired
sensitivity 1n detecting shifts;
4) Are data transformations needed; and
5) The frequency with which Phase 2 test events should occur*
and the duration of each Phase 2 event (e.g., 1f Phase 2
samples from a given event are collected over a period of
one week, the t-test would be comparing that Phase 2 week
against the total Phase 1 period.).
In the t-test approach, each Individual Phase 2 test event confirms the
presence, or lack, of an excursion from Phase 1 within the designed Type I and
Type II errors over the duration of the Phase 2 test event. The frequency
with which Phase 2 events are conducted, therefore, depends upon how often the
program designer wishes to check for a possible excursion.
One common approach 1s to select two as the number of measurements for
each Phase 2 test event (the "two-sample t-test"). As an example of applying
the two-sample t-test, suppose 1t were desired to maintain the Type I error at
4-103
-------
S%, and the Type II error at 10%. Suppose, 1n addition that 1t were Important
to detect any excursion of greater than 100% from the Phase 1 mean each time a
test event was done during Phase 2. If the coefficient of variation for the
Indicator of Interest were 40% (and two measurements were made for each Phase
2 test event)* then 23 measurements (samples) for that Indicator would be
necessary during Phase 1 to maintain the desired levels for the Type I and
Type II errors.
Nonparametrlc Tests
If the number of Phase 1 measurements 1s limited, and 1f a data distribu-
tion model (e.g., normal or lognormal) for the parameter of Interest 1s not
known, then nonparametrlc tests may be appropriate to compare the results from
Phase 2 with the results from Phase 1. As with the t-test, small sample non-
parametric tests focus on changes 1n the Indicator between Phases 1 and 2,
rather than on the absolute value of the Indicator. Nonparametrlc tests do
not require strict assumptions on the form of a distribution model for the
measurement data. In general, a nonparametrlc test will not be as powerful 1n
detecting differences as a test which assumes a distribution model (such as
the t-Test). Thus, 1f a distribution model 1s appropriate for the data, a
test such as the Two-Sample t-Test should be used.
The nonparametrlc test can be applied to any number of measurements taken
during Phase 1 and during each Phase 2 test event. Reference 4-41 Includes a
number of nonparametrlc test approaches which are appropriate for comparing
Phase 2 results against Phase 1. Typically, the test criteria are based on
percentHes (e.g., are the Phase 2 measurements from a single Phase 2 test
event 1n the upper or lower quartlle of the Phase 1 data, or above or below
the Phase 1 median, etc.) or on order statistics (e.g., are all or some of the
Phase 2 measurements from a single Phase 2 test event greater than the second-
highest Phase 1 value, or below the minimum Phase 1 value, etc.). The Type I
error 1s controlled by the selection of an appropriate critical value (tabu-
lated) or by the selection of the particular percent He or order statistics.
The Type II error is controlled by the sample sizes in Phase 1 and in each
4-104
-------
Phase 2 test event. For most nonparametrlc tests it is not possible to quan-
tify the Type II error without assuming a distribution model for the parameter
(I.e. to quantify the magnitude of the excursion or mean drift).
In deciding whether to utilize nonparametrlc procedures, the program
designer should consider the following:
1) Is the number of Phase 1 measurements limited to the point
that the control chart analysis procedure might not be
preferred?
2) Is the distribution model describing the indicator/
paramater data uncertain? (These are the conditions under
which nonparametrlc tests would be applied.)
If a nonparametrlc test is to be used to compare the Phase 1 and Phase 2
data, the user will need to make decisions concerning the following factors:
1) appropriate levels for Type I and Type II errors;
2) the type of changes from Phase 1 that one wishes to detect
1n the Phase 2 data (e.g., Is it desired to detect a shift
in the Phase 1 mean?);
3) the direction of the changes that one wishes to detect in
Phase 2 (e.g., just an upward shift of the mean, just a
downward shift, or a shift in either direction);
4) the percentile or order statistic, and the number of sam-
ples 1n Phase 1 and in each Phase 2 test event, 1n order
to achieve the desired Type I and Type II errors, and in
order to detect the desired type and direction of changes
1n the Phase 2 data;
5) the frequency with which Phase 2 test events should occur
and the duration of each Phase 2 event.
As in the t-test approach, each individual Phase 2 test event in the non-
parametric approach confirms the presence, or lack, of an excursion from Phase
1 within the designed Type I and Type II errors over the duration of the Phase
4-105
-------
2 test event. The frequency with which Phase 2 events are conducted, there-
fore, depends upon how often the program designer wishes to check for a possi-
ble excursion.
As a representative example of a nonparametrlc Phase 2 design, suppose
that the order statistic 1s selected to be the second largest Phase 1 measure-
ment for an Indicator, the total number of Phase 1 measurements 1s 10, and the
number of Phase 2 measurements 1s 2 for each test event. If a Phase 1 repeat
1s triggered only when both Phase 2 measurements exceed the second largest
Phase 1 measurement, then one would be 90 percent confident (I.e., 10 percent
chance of Type II error) that a Phase 1 repeat would 1n fact be triggered
every time the mean for the Indicator Increased above the Phase 1 baseline by
2.8o or more. In this example, there would be only a 5 percent chance of a
Type I error (repeating Phase 1 when the baseline really had not shifted). In
this example, the logistic distribution was used 1n defining the baseline
shift of 2.8a. Downward shifts 1n the baseline would not be detected 1n this
example.
4.2.2.3 Updates of the Baseline Data. Base
During the course of the Phase 2 monitoring program, data will be ob-
tained which will enable the Initial Phase 1 data base to be updated.
• Data will be obtained on a continuing basis for the Indi-
cators which were selected for Phase 2 monitoring.
• Data on parameters represented by certain Indicators will
be obtained occasionally when an excursion 1n those Indi-
cators suggests that the baseline has shifted for those
Indicators.
• One set of measurements for the total data base (Tables 4-
4 through 4-6) might be repeated periodically, even 1f
Indicators do not experience excursions, to confirm that
the data base has not dramatically shifted without this
shift having been reflected by the indicators.
4-106
-------
The manner in which the data from these sources might be used to update the
Phase 1 data base is illustrated schematically in Figure 4-5.
Continuing Phase 2 data on Indicators. The measurements of indicators
that are made on a continuing basis throughout Phase 2 can be used to refine
the baseline mean values and standard deviations for those indicators* based
upon the increasing number of measurements. Statistical procedures to recom-
pute the values are given in Appendix B.
Occasional data base monitoring triggered bv indicator excursions.
Occasional excursions will occur during Phase 2 in individual indicators in
individual streams. If a Phase 2 excursion cannot be explained as being due
to temporary* nonrepresentative variations in plant operation (e.g., equipment
malfunction), the excursion should trigger one set of measurements for the
substances represented by that indicator in that stream. Such a set of mea-
surements would be conducted immediately after the indicator excursion is
observed. This testing would effectively increase the Phase 1 data base (for
the affected indicator and the parameters it represents) by one set of mea-
surements. The results from each such set of measurements can be used as fol-
lows:
• For that indicator in that stream, one can now recalculate
the relationship between the indicator and the parameter
it represents. The uncertainty in the indicator/parameter
relationship should be reduced, due to the increased num-
ber of "Phase 1" measurements now available. This im-
proved certainty should enable an increased confidence
(power) in tracking the various parameters using this
Indicator. Does the indicator/parameter relationship
appear to be changing? Does it seem that some individual
parameters are no longer represented well by this indi-
cator? Are new indicator/parameter relationships appar-
ent?
• Can the method of comparing Phase 1 and Phase 2 data be
changed/improved with these additional data? For example,
is it now possible to use the control chart approach
rather than small sample theory for that indicator?
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I Initial Phase 1
i Basel me Data Base
Conduct
periodic
repeats of
Phase 1 ,
Select parameters which can serve as
indicators for other parameters during
Phase 2 (e.g.. Table 4-20, Statistical
Analysis, etc.). Identify where parame-
ter must serve as own indicator.
Select method to be used for comparing
Phase 1 and Phase 2 data, based upon
criteria in Section 4.2.2.2.
Use Phase 1 data base to calculate factors
necessary for Phase 2 method (e.g., Phase 1
mean, standard deviation).
Select factors necessary for design of
Phase 2: acceptable Type I error, acceptable
Type II error.
Design Phase 2
Phase 1 repeat,
(e.g. , decision criteria
monitoring frequency).
for
Can
action
be taken to
return parameter
levels to
baseline?
Are
results for
parameters within
acceptable limits'
Figure 4-5. Schematic diagram of approach for designing
Phase 2 monitoring and updating Phase 1 data base.
4-108
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• For that Indicator, one can now recalculate the Phase 1
mean and standard deviation (or, e.g., the order statistic
used 1n the nonparametric approach), and can use these new
values 1n the continuation of Phase 2.
• Depending upon the Impact of the new "Phase 1" results, 1t
might now be practical to select, e.g., the reduced accep-
table Type II error, because the Increased number of Phase
1 samples could enable this reduced error to be achieved
using a reasonable sample number/frequency.
Periodic repeats of total data base monitoring. Periodic repeats of
monitoring for the total data base—consisting of one full set of the measure-
ments listed 1n Tables 4-4 through 4-6—woul d be useful throughout Phase 2.
Such periodic repeats would help Indicate whether the baseline had 1n fact
shifted without the Indicators having varied outside of their selected limits.
The frequency of such total data base repeats would be selected for the circum-
stances of the specific synfuels facility; the more variable the facility, the
greater the variation 1n operating conditions (e.g., 1n feedstock, 1n product
slate), the more frequent such repeats might be warranted. A frequency of
approximately one repeat per year would seem generally reasonable. It might
be useful to schedule such full repeats after major scheduled operating
changes, because: a) that 1s when baseline shifts might logically be
expected; b) that 1s when Indicator excursions might most likely trigger
repeats anyway; and c) obtaining additional data at such shifted conditions
might Improve the opportunity for defining Indicator/parameter relationships,
as discussed 1n connection with Figure 4-3.
The results from each total data base repeat can be used as follows:
• To Improve the Indicator/parameter relationships for all
indicators in all streams, through the increased number of
Phase 1 measurements now available. In particular, 1f the
new data are at a different set of conditions (per Figure
4-3), current Indicator/parameter correlations might be
Identified for parameters which were not previously rep-
resented by an Indicator (other than the parameter It-
self). The validity of indicator/parameter correlations
could be improved, and any changes in the relationship
identified.
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To change/improve the method of Phase I/Phase 2 data com-
parison, 1f possible (e.g., can the control chart approach
now be used?).
To recalculate the Phase 1 mean and standard deviation,
etc., for use 1n the continuation of Phase 2.
If warranted, to select new values for acceptable Type II
errors.
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4.3 ALTERNATIVE MONITORING APPROACHES
The phased monitoring program concept described 1n Section 4.2 represents
one of a number of possible approaches that would satisfy the monitoring re-
quirements of Section 131(e). In developing monitoring plans and outlines/
SFC applicants might consider approaches different from the Section 4.2 ap-
proach. To Illustrate the flexibility available 1n selecting the monitoring
appraoch, the Section 4.2 approach and two alternative approaches are dis-
cussed 1n this section. The discussion focuses on the advantages and disad-
vantages of each approach and some of the Issues to consider 1n selecting the
most appropriate approach.
The Intent of monitoring 1s to develop an Information base that can be
used to Identify potential environmental problem areas. The monitoring pro-
gram designed to accomplish this objective should be reasonable and cost-
effective. The monitoring approach for a specific plant could depend upon a
number of plant- and site-specific factors, such as:
• the extent and applicability of existing data on the
processes proposed fop use 1n the new facility. If much
of the desired Information base had already been
addressed—e.g., through testing on earlier commercial-
scale versions of the same process—this fact could Influ-
ence the monitoring approach selected.
• the tradeoff between an Increased data Interpretation
effort (for Phase 2 program design) versus an Increased
sampling/analysis effort 1n Phase 1. A phased approach
will often permit a more confident characterization of the
data base with a reduced total monitoring effort. How-
ever, this approach will require some judgment and Inter-
pretation of Phase 1 results 1n the design of Phase 2. If
the data base were to be developed with a non-phased
approach, less data Interpretation would be needed, but
the sampling/analysis effort might be greater. The cost-
effectiveness of these tradeoffs would need to be con-
sidered on a case-by-case basis.
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The monitoring approach described In Section 4.2 should be a responsive
and cost-effective long-term approach for new synfuels facilities. Other
approaches can satisfy the monitoring requlrementsi and might be preferred
under various conditions. The three approaches discussed below are not a
comprehensive compilation of all possible approaches. Rather* they are pre-
sented to Indicate the flexibility available 1n selecting approaches. If an
alternative approach 1s proposed 1n the monitoring plan for a specific plant*
the test plan developer should evaluate how the results from the alternative
approach would compare with those from the approaches described 1n this sec-
tion. The plan should discuss how the results from the alternative approach
will f111 the data and Information requirements of Section 131(e).
4.3.1 Option I - Phased Monitoring Approach Using Indicator Parameters In
Phase 2
This 1s the approach described 1n Section 4.2. Phase 1 monitoring—
conducted during the Initial period of steady state plant operation—would
develop a broad baseline data base using both survey analytical procedures
and analyses for specific components. The survey procedures would screen for
both regulated and unregulated chemical substances within selected classes,
where these substances cannot be defined beforehand. In the design of Phase
2, the Phase 1 data would be statistically evaluated to select substances or
parameters which might serve as "Indicators" for the other substances/parame-
ters observed during Phase 1. Monitoring during Phase 2 would proceed, ad-
dressing only the indicators. In theory, the entire baseline data base could
thus be tracked during Phase 2 by monitoring a limited number of indicators.
Phase 1 measurements (for the substances represented by a given indicator 1n a
given stream) would be repeated during Phase 2 if an excursion of some pre-
defined magnitude 1n that Indicator suggested that the baseline had shifted.
Section 4.2 suggests the specific substances that might be monitored, and
the survey analytical procedures that might be employed, in developing the
Phase 1 baseline data base, together with the streams of possible Interest.
4-112
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The section also discusses the practical and statistical principles that can
be used to select the Indicators for Phase 2 and the monitoring frequency and
duration for both phases. The frequency/duration would depend upon the
desired accuracy of the results, Including the accuracy of detecting baseline
shifts during Phase 2.
This monitoring approach offers a number of advantages and disadvantages.
The advantages Include the following.
• The use of survey analytical procedures allows a broad
data base to be effectively developed and avoids the need
to guess which substances are going to be present. These
survey procedures are particularly useful because com-
mercial synfuels streams have not been well characterized
and might contain a wide array of substances.
• The phasing concept enables a significant reduction 1n the
monitoring effort after the first phase and stm provides
a broad data base. Long term monitoring 1s effectively
focused on the substances actually present.
• The use of Indicators allows the entire data base to be
tracked throughout Phase 2, while greatly reducing the
Phase 2 monitoring effort and eliminating the need for
decisions about which of the substances observed 1n Phase
1 warrant continued monitoring.
• The application of statistical principles 1n selecting
Phase 1 measurement frequency and designing Phase 2 would
provide a defensible data base with known accuracy.
There are also several potential disadvantages associated with this approach.
• The phasing concept necessarily delays design of part of
the monitoring program (the extended Phase 2 portion)
until after Phase 1 1s completed. This factor prevents a
complete definition of scope and duration at the outset of
the monitoring program.
• The Phase 2 design could require a fair degree of statis-
tical data Interpretation following Phase 1. A mechanism
for making decisions at the end of Phase 1 1s also
required.
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• The Phase 1 results might not provide an adequate rela-
tionship between some of the observed substances and
potential Indicators for those substances. If a good
Indicator relationship 1s not apparent for some substances
from the Phase 1 data, 1t might be necessary to continue
monitoring for those substances during Phase 2.
• A baseline shift might occur during Phase 2 without a
simultaneous excursion 1n Phase 2 Indicators. The risk of
occurrence depends on the strength of the relationship
between the Indicator and the represented substances and
on the statistical design of the monitoring program (the
sensitivity 1n detecting baseline shifts). To guard
against such undetected shifts. Section 4.2 suggests that
Phase 1 monitoring be repeated periodically throughout
Phase 2.
4.3.2 Option II - Phased Monitoring Approach with Deletions following
Phase 1
In this approach, Phase I would proceed as described for Option I above.
However, the Phase 1 results would be Interpreted differently 1n the design of
Phase 2. Rather than using Phase 1 results to select Indicators, the results
would be used to decide which of the substances observed 1n Phase 1 should
continue to be monitored during Phase 2. Phase 2 would then address only
those substances which were both a) observed during Phase 1, and b) felt to be
present at levels significant enough to warrant extended monitoring.
A major Issue 1n this approach is the method for deciding which of the
measurements are "significant." The criteria for establishing significance
would need to be defined 1n the monitoring plan. Examples of factors to
consider Include the concentration at which the substance was observed, the
consistency with which It was observed, the presence of the substance on
recognized pollutant lists and the potential health and ecological effects of
the substance (e.g., toxldty, mutagenlclty, tendency for bioaccumulatlon,
etc.). "Trigger values"—concentrations which, 1f exceeded 1n Phase 1, would
trigger monitoring for a given substance during Phase 2—might be agreed upon.
4-114
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The major advantages of this monitoring approach are as follows.
• The use of survey analytical procedures allows a broad
data base to be collected under conditions where the
composition 1s not well understood beforehand* as 1n
Option I above.
• The use of phasing should allow a significant long-term
reduction 1n, and focusing of, the monitoring effort* as
1n Option I.
• There 1s no need to Identify Phase 2 Indicators* so the
risk of being unable to define suitable Indicators for
some substances 1s avoided, as 1s the statistical effort
required to define the Indicators.
• Statistical principles can be employed to provide a defen-
sible data base.
Some potential disadvantages of this approach are:
• The use of phasing prevents the Phase 2 part of the pro-
gram from being defined until Phase 1 1s completed, as 1n
Option I.
• A mechanism and criteria for decisions concerning Phase 2
design at the end of Phase 1 will be necessary, although
less statistical analysis might be required 1n comparison
with Option I.
• Judgments about the "significance" of the various sub-
stances observed during Phase 1 would be required for the
Phase 2 design. The decision concerning which Phase 1
substances warrant continued monitoring would likely
require a fair amount of evaluation. One option might be
that Phase 2 would address every substance seen above
detection limits during Phase 1. This approach would
eliminate the requirement for judgments about signifi-
cance, but could result 1n a relatively large Phase 2
program.
• The Phase 2 effort might not address the total baseline
(Phase 1) data base. If the substances deemed "signifi-
cant" cover only a portion of the data base, the Phase 2
monitoring would not provide Information on changes 1n the
other portion of the data base. Therefore, 1t would be
useful (as 1n Option I) to repeat the full Phase 1 program
periodically to confirm that baseline shifts are not
causing discharges of other "significant" substances.
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4.3.3 Option III - Non-Phased Monitoring Approach; Continued Survey
In this non-phased approach, monitoring of all Phase 1 parameters would
continue with no attempt to reduce monitoring as results became available.
The repeated monitoring of the total data base would Include survey analytical
techniques and specific component analyses as used 1n the first two "phased"
approaches. In this, however, "Phase 1" monitoring would continue for some
extended period, with no attempt to design a reduced Phase 2.
This non-phased approach would produce a more comprehensive data set than
the phased approaches, because the total "Phase 1" monitoring effort would
be continued for an extended period while the other two approaches call for a
reduced Phase 2. In view of this more comprehensive data set, 1t might be
possible to conclude the non-phased monitoring effort at an earlier time than
either of the phased approaches might be concluded. (The total duration of
the monitoring program must be acceptable to the SFC and other consulting
agencies.) In any case, 1t should be of adequate duration to establish a
complete data history, addressing a broad range of plant conditions.
The non-phased approach offers several advantages.
• The use of survey analytical procedures allows a broad
data base to be collected under conditions where stream
properties are not well known beforehand, as 1n Options I
and II above.
• Since no changes will be made 1n the monitoring program
after 1t 1s Initiated (I.e., a Phase 2 program will not be
designed after a Phase 1 1s completed), the exact nature
of the total monitoring program can be defined at the
outset.
• Potential difficulties associated with the design of a
Phase 2 program are avoided; I.e., no extensive statisti-
cal Phase 1 data Interpretation/Phase 2 design, no uncer-
tainties concerning the selection of Indicators, no judg-
ments required concerning which observed substances are
"significant," etc.
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This option provides the most comprehensive data set,
since simplifying assumptions (e.g., regarding the ability
of a limited number of Indicators to track the total data
base, as 1n Option I) are not required. The total data
base 1s monitored repeatedly.
This approach has two major disadvantages:
Since no attempt 1s made to reduce the monitoring effort
based on the Initial results, this approach could result
1n a more substantial and expensive monitoring effort.
If the duration of monitoring under Option III 1s less
that that under Options I or II, then Option III would not
provide the longer-term coverage features of the other
approaches. Such features allow detection of significant
shifts in the plant operating baseline, so that additional
monitoring data can be gathered.
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4.4 MONITORING PROCEDURES
In Tables 4-4 through 4-6 (Section 4.1.2), general analytical procedures
and specific components were suggested for the monitoring data base. As a
result of Phase 1 monitoring, Indicators such as those listed 1n Tables 4-20
and 4-21 might be selected for monitoring 1n Phase 2. This section outlines
monitoring procedures that might be considered for conducting Phase 1 and
Phase 2.
Tables 4-24 through 4-26 (Included at the end of this section) present
specific procedures which are suggested for the Phase 1 survey analytical
techniques referenced 1n Tables 4-4 through 4-6 (for gaseous, aqueous and
solid streams). Tables 4-27 through 4-29 (also at the end of this section)
11st alternative techniques for:
• the specific components listed 1n Tables 4-4 through 4-6
• additional components that may be monitored,
• those compounds from which Phase 2 Indicators are expected
to be selected, and
• alternative Phase 1 survey analytical techniques (1n
addition to those given 1n Tables 4-24 through 4-26).
The commonly applicable techniques are marked 1n Tables 4-27 through 29 with
an asterisk. If any of the Phase 1 techniques suggested 1n Tables 4-24
through 4-26 are not applicable 1n a specific synfuels plant. Tables 4-27
through 4-29 are a starting point for alternative technique selection.
The procedures listed 1n Tables 4-24 through 4-29 are described 1n
further detail 1n Appendix A. Each entry 1n the tables Includes an Index
term, which Involves a letter (S for sampling method, P for preservation and
preparation methods, A for analytical method and T for test method) and two
digits; this Index term can be used to locate the more detailed discussion of
the method 1n Appendix A. In the Appendix, the S entries are presented first,
the P entries second, and so on.
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The procedures 1n the tables are broken down according to three major
steps: sampling* sample preservation/preparation* and analysis or testing.
Often, the steps 1n the monitoring sequence are linked 1n a specific manner
(e.g., specific analyses requires specific sample preparation method). These
linkages are shown 1n the tables.
The Information presented reflects the key elements of each sampling,
preservation/preparation, and analysis or test procedure. Further detail
would be necessary for the procedure to be Implemented; for example, what pH
or what solvent might be used for an extraction, or what sample volume is
needed for the desired sensitivity. These details must be defined as part of
a specific monitoring program and will depend upon the circumstances associ-
ated with specific samples. The procedural constraints which Influence these
details are discussed in Appendix A.
4.4.1 Suggested Phase I Survey Techniques
The suggested Phase 1 survey techniques in Tables 4-24 through 4-26 were
selected to provide the broadest coverage of a wide array of potential compo-
nents, using the most limited number of procedures. These techniques are pre-
sented in the same format as they appeared 1n the corresponding Tables 4-4
through 4-6. Also shown in Tables 4-24 through 26 are the generic stream
categories for which the technique was suggested in Tables 4-4 through 4-6.
In general, for each group of components of interest, one sampling method, one
preservation/preparation method and one analytical method are shown, consti-
tuting a suggested approach. Where multiple entries are shown, the meaning is
as follows.
• volatile versus non-volatile organlcs—although a single
entry 1s shown for organic survey techniques 1n Tables 4-4
through 4-6, this single entry requires two approaches:
one for volatile compounds, and one for non-volatile
compounds. The techniques for volatile versus non-
volatile usually differ slightly (I.e., sample collection
techniques vary, therefore preservation/preparation tech-
niques are different).
4-119
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• multiple entries under sample preparation—where more than
one preparation technique 1s listed, each preservation/
preparation step 1s often necessary and they are generally
executed 1n the order listed.
• multiple entries under analytical method—where more than
one analytical technique 1s listed, each analytical proce-
dure 1s often necessary to obtain useful Information for a
monitoring data base. The procedures are listed 1n order
of Increasing specificity and most often are performed 1n
the sequence shown.
Although the techniques suggested 1n Tables 4-24 through 4-26 will be
reasonable selections, there might be circumstances under which one or more of
these techniques 1s not be applicable. The sampling conditions (temperatures,
pressures, etc.) and the stream compositions (with resulting analytical Inter-
ferences) will vary significantly from one plant to the next. Accordingly, 1n
some cases, alternative techniques will need to be selected. Alternatives
might be selected from Tables 4-27 through 4-29. For example, 1f a sample
contains non-volatile components that are not amenable to gas chromatography
(e.g., GC/MS) then a HPLC technique might be used Instead.
4.4.2 Alternative Techniques
Tables 4-27 through 4-29 11st alternative procedures that might be con-
sidered for the full array of monitoring: techniques for Individual Phase 1
components; alternative techniques for Phase 1 surveys; and techniques for
Phase 2 Indicators. Some of the listed methods are for components currently
regulated 1n other Industries, and/or are EPA reference methods or, APHA or
ASTM methods. Where a technique can be Implemented with a commonly-known pro-
cedure such as an EPA reference method, this fact 1s Indicated 1n the refer-
enced procedure 1n Appendix A. Although all of the techniques listed for mon-
itoring could be appropriate under various circumstances, the commonly appli-
cable techniques are marked with an asterisk.
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In Tables 4-27 through 4-29, the listings for Individual substances (such
as SCL, H_S, etc.) Include both grab sample approaches and Indicate available
continuous monitoring. Continuous monitoring will often be the most cost-
effective approach 1f the necessary sampling/analysis frequency 1s high.
If Tables 4-27 through 4-29 are used to select a procedure for monitoring
a Phase 2 Indicator, 1t would be necessary to Identify the component or class
to which the particular Indicator belongs. For example, 1f the particular
Indicator 1s a non-volatile oxygenate 1n an aqueous stream, the user would
review the procedures listed for non-volatile oxygenates 1n Table 4-28. Know-
Ing the specific indicator compound of Interest, and knowing the other (poten-
tially Interfering) compounds present 1n the stream, the experienced analyst
could select a set of suitable procedures from the 11st of alternatives. Then
the operating details could be determined to tailor the approach to define the
compound of Interest most effectively. The selected procedure for the Phase 2
Indicator probably could be related to the Phase 1 technique (for oxygenates
1n this example). Generally, with the technique aimed at a specific compound,
1t would be determined more reliably. Potentially, the cost of Implementation
would be less than the Phase 1 approach.
If a Phase 1 survey technique different from those listed in Tables 4-24
to 4-26 1s needed, the appropriate component or class 1n Tables 4-27 through 4-
29 would be referenced. The experienced analyst could select from the Table 4-
27 alternatives, a technique which would circumvent the difficulty encountered
with the Table 4-24 approach. For example, 1f the Table 4-24 sampling tech-
nique for volatile nitrogen compounds (Tenax resin) 1s not appropriate in a
specific gas stream, then one would review the alternatives for volatile
nitrogen compounds in Table 4-27. After reviewing the descriptions in
Appendix A and the references cited, one might select trapping on charcoal.
In this example, if charcoal were selected, the sample probably would be
solvent extracted (different preparation step from that for Tenax) and
analyzed by GC/MS and/or GC with a nitrogen specific detector (a variation on
the analysis step in Table 4-24).
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While the techniques listed in Tables 4-24 through 4-29 are conventional
procedures in common usage* their applicability to a specific synfuels stream
might vary, depending upon a number of factors (the best example being stream
composition, which could lead to Interferences from other components in the
stream). Accordingly, method evaluation and verification should be performed
during the plant startup period, as discussed in Section 3.4 and 4.2.1.3.
This evaluation/verification would be one component of a good sampling and
analytical quality assurance program. Although historical data on limitations
and interferences are available for the methods 1n the tables, some of these
analyses will be employed in matrices different from those on which historical
data are available. Some modification of existing methods might be needed.
One Issue of particular interest is the sensitivity with which the com-
ponents are detected. For many techniques, sensitivity depends on implementa-
tion and sample size. For example, if a large aqueous sample 1s taken and
extracted for organics, the organic compounds will be detected with a greater
sensitivity than 1f a smaller aliquot were extracted. This issue is discussed
further at the beginning of Appendix A (see Table A-l). Because of the poten-
tial variation 1n sensitivity, the sensitivity figures in Appendix A are often
presented as a range.
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TABLE 4-24. SUGGESTED PHASE 1 SURVEY TECHNIQUES FOR GASEOUS STREAMS*
• urvry Tc^f.nlque
(Listed In Table 4-4)
Generic
Stream
Sampling
Preparation
Analysis or Test
Analysis for Trace Elements
Analysts for Altphatfcs and
Aromatlcs
- Condensable
Analysis for Altphatlcs, Aromatlcs 3,4
and Oxygenates
- Volatile
- Condensable
Implnger (S07D)
Tenax sorbent
resin (S05)
XAD-2 sorbont
resin (505)
Tenax sorbent
resin (SOS)
XAD-2 sorbent
resin (SOS)
Acidic preservation (Pll)
and Acid digestion (P12)
Thermal
desorptlon (P03)
Cool (Pll) and
extract (POD both
sorbent and condensate
follo*ed by LC
fracttonatton (P05)c
Thermal
desorptlon (P03)
Cool (Pll) and
extract (P10) both
sorbent and condensate
folloned by LC
fractlonatlon (P05)°
AA (AdO) for As, Sb, Se, Hg.
ICP (A40) for other elements
of Interest
GC/MS (All)3'
d
TCO (A121+GRAV (A13)
GC/MS (All)
and GC-PID (A19)
TCO (A121+GRAV (A13)
GC/MS (All) .
and GC-PID (A19)
(Continued)
-------
Survey Technique
(Listed In Table 4-4)
Analysis for Nitrogenous
Compounds
- Condensable
TABLE 4-24.
Generic
Stream Swipl 1 ng
2, 3
resin (S05)
XAD-2 sorbent
resin (S05)
(continued)
Preparation Analysis or Test
desorpti on (P03 )
Cool (Pll) and TCO (A12J+GRAV (A13)d and
extract (POD both GC/MS (All)
Analysis for Sulfur
Containing Compounds
- Condensable
Tenax sorbent
resin (SOS)
XAD-2 sorbent
resin (S05)
sorbent and
condensate, fol lowed
by fractlonation (P05)c
Thermal
desorption (P03)
cool (Pll) and
extract (POD both
sorbent and condensate,
folloned by LC
fractlonatton (P05)
and GC-N specific (A10)e
a,f
GC/MS (AID
TCO (A12)+GRAV (A13) and
GC/MS (All)
and GC-S specific (A18)
ro
For survey analysis of entrained participate, see solids techniques In Table 4-26.
aAnalys1s of Tenax resin al Iquots Is often hampered by contamination during homogenatlon and aliquot preparation. Therefore, multiple analysis
techniques are not recommended.
Although GC-PID 1s often more sensitive for the detection of simple aromatlcsi If compound confirmation is desired, GC/MS Is tne more appropriate
technique.
Fractlonatlon may be appropr'ate for complex samples. Fraction or fractions of Interest can be selected prior to analysis. If capillary GO 1s
Implemented, fractlonation will be necessary less frequently.
TCO ana GRAV or TCO may be useful to determine organic loading prior to specific analyses.
Although GC-N specific (HECD-N or NPD) Is often more sensitive for the detection of nitrogenous compounds* If compound confirmation 1s desired*
GC/MS Is the more appropriate technique.
Although GC-S specific (HECD-S or FPD) Is often more sensitive for the detection of the sulfur containing compcdndsj If compound confirmation Is
desired, GC/MS 1s the more appropriate technique.
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TABLE 4-25. SUGGESTED PHASE 1 SURVEY TECHNIQUES FOR AQUEOUS STREAMS
;„rvey TechnIque
(Listed In Table 4-5)
Generic
Stream
Sampl1ng
Preparation
Analysis or Test
Analysis for Trace Elements
1.2, 3, 4
Composite (S10)
Acidic preservation (Pll)
and add digestion (P12)
AA (A40) for As, Sb, Se, Hg.
ICP (A40) for other elements
of Interest
ro
en
Analysis for AHphatlcs and 1.4
Aromatlcs
- Volatile
- Extractable
Analysis for AHphatlcs, Aromatlcs 3
and Oxygenates
- Volatile
- Extractables
Grab (Sll)
Composite (S10)
Grab (Sll)
Composite (S10)
Cool (Pll), purge and trap
(P03)
Cool (Pll), extraction
(POD, base/neutral extract
GC/MS (All)a'b
TCO (A121+GRAV (A13)C and
GC/MS (All)
followed by LC fractlonatlon and GC-PID (A19)
(P05)6
Cool (Pll), purge GC/MS (All)a'b
and trap (P03)
Cool (Pll), extraction (POD TCO (A12)+GRAV (A13)c and
add extract analyzed for GC/MSb
-------
TABLE 4-25. (continued)
Survey Technique
(Listed In Table 4-5)
Generic
Stream
Sa/npl f ng
Preparation
Analysts or Test
ro
cr>
Analysis for Nitrogenous
Compounds
- Volatile
- Extractable
Analysis for Sulfur
Containing Compounds
- Volatile
- Condensable
Grab (Sill
Composite (S10)
Grab (Sll)
Composite
-------
TABLE 4-26. SUGGESTED PHASE 1 SURVEY TECHNIQUES FOR SOLID STREAMS
"i r vry Technique
'Listed In Table 4-6)
Generic
Stream
SamplIng
Preparation
Analysis or Test
I
ro
Analysis for Trace Elements
- Whole sample
- Leachable
Analysis for Leachable
Allphatlcs and Arcmatlcs
- Volatile
- Extractable
Analysis for Extractable"
Allphatlcs and Aromatlcs
Analysis for Leachable Allphatlcs,
Aromatlcs and Oxygenates
- Volatile
- Extractable
1. 2. 3, t
Composite (SOI)
(Leachate)
(Leachate)
(Leachate)
Composite (SOD
(Leachate)
(Leachate)
Fusion (P09) and/or acid
digestion (P10)
Acidic preservation (Pll)
and acid digestion (P12)
AA (A40) for As, Sb, Se,
Hg. ICP (A40) for other
elements of Interest
AA (A40) for As, Sb, Se,
Hg. ICP (A40) for other
elements of Interest
Cool (Pll), extraction (POD TCO (A121+GRAV (A13) and
followed by LC fractionatlon GC/HS (All) and
(P05) on base/neutral GC-PID (A19?
extract
Extraction (POD, followed
by LC fractlonatton (P05)
on base/neutral extract
TCO (A12HGRAV (A13)
GC/MS (All) and
GC-PID
-------
TABLE 4-26. (continued)
Survey Technique
(Listed In Table 4-6)
Gener1c
Stream
Samp!Ing
Preparation
Analysis or Test
(Vl
00
Analysis for Extractable*
Allphatlcs, Aronatlcs and
Oxygenates
Analysis for Leachable
Nitrogen Containing
Compounds
Composite (SOI)
Extraction (POD, acid
extract analyzed for
phenols and carboxyllc
acids . Base/neutral
extract followed by LC
fracttonatlon (P05)a
TOO (A121+GRAY (A13) and
GC/MS (All) and
GC-PIO (A19)
- Volatl le
- Extractables
Nitrogen Containing
Compounds
Analysis for Leachable 3
Sulfur Containing
Compounds
- Volat! le
- Extractable
(Leachate) ""
(Leachate) Cool (Pill, extraction
(POD, LC fractlonatlon (EOS)
on base/neutral extract '
Composite (SOD Extraction (POD. LC
fracttonatlon on (P05)
(Leachate) ••
Uaachate) Cool (Pll), Extraction
(POD, followed by LC
f ractlonatlon on base/
• •
TOO (A121+GRAV (A13)b
GC/MS (All) and GC-N
specific (AID)
TCO (A121+GRAV (A13)b
GC/MS (All) and GC/N
specific (A10)
UK
and
and
TOHA12HGRAV (A13)b and
GC/MS (All) and
GC-S specific (A18)9
(Continued)
-------
TABLE 4-26. (continued)
Survey Technique Generic
(Listed In Table 4-6) Stream Sampling Preparation Analysis or Test
Analysis for Extractable* 3 Composite (SOI) Extraction (POD, followed TCO (A12)+GRAV (A13)b and
Sulfur Containing by LC fractionation on GC/MS (All) and GC-S
Compounds base/neutral extract specific (A18)^
Purging or thermal desorptlon techniques, which define volatile organic fractions for liquids or gases, are not generally appropriate for solids.
Therefore, no volatile classification 1s shown.
Analysts for volatile organlcs present In a leachate would follow the same suggested guidelines as for volatile organlcs from aqueous streams
(see Table 4-25). However, 1f volatlles remain In the solid waste and are leached, they would most likely be lost during the leaching
procedure.
Fractlonatton may be appropriate for complex samples. Fraction or fractions of Interest can be selected prior to analysis. If capillary GC Is
Implemented, fracttonation will be necessary less frequently.
TCO and GRAV or TCO may be useful to determine organic loading prior to specific analyses.
Although GC-PIU Is often more sensitive for the detection of simple arcmatlcsj If compound confirmation is desired, GC/MS 1s tne more appropriate
technique.
d
Although GC-N specific (HECD-N or NPD) Is often more selective for nitrogenous compounds, 1f compound confirmation Is desired, GC/MS Is tne more
appropriate technique.
Phenols can be analyzed directly with appropriate GC column selection. Carboxyllc acids may require derlvltlzatlon to be chromatographable.
Many nitrogenous compounds are chromatographable without derlvltlzatlon with appropriate GC column selection.
Although GC-S specific (HECD-S or FPD) Is often more selective for sulfur containing .compoundsi If compound confirmation 1s desired, GC/MS Is the
more appropriate technique.
-------
TABLE 4-27. MONITORING OPTIONS FOR GASEOUS STREAMS
Property or
Specie
GeneM c
Stream
Sampl1ng
Options
Preparation
Options
Analysis or
Test Options
Major Gases
CO
1,2,3
continuous monitoring, or
gas bomb* or bag (S13)
screen1ng(S!2)« or
bagg1ng(S14)+ gas
bonb(S13>
part/aerosol removal(S06) GC-TCD(A03)*
+H20 removal (S04)» or
part/aerosol removal(S06) orsat(A03)
NA detector tubes(S12)»
NA GC-TCD(A03)
CO
o
CH,
1,2,3
1,2,3
1,2,3
1,2,3
1,2,3
Moisture
1,2,3,4
gas bomb* or bag (S13)
continuous monitoring, or
gas bomb* or bag(S13)
gas bomb* or bag(S13)
gas bomb(S13)
continuous monitoring, or
gas bomb* or bag(S13)
continuous monitoring, or
gas bomb* or bag(S13)
screen1ng(S08)*, or
bagg1ng(S!4)+ gas
bomb (S13)
Silica gel(S02)»
part/aerosol removaI(S06) GC-TCD(A03)»
+H 0 removal(S04)» or
part/aerosol removal(S06) orsat(A03)
part/aerosol removal(S06) GC-TCD(A03)«
+H20 removal (S04)» or,
part/aerosol removal(S06) GC-TCD(A03>
part/aerosol removal(S06) GC-TCD(A03)
+H20 removal(S04)«
part/aerosol removal(S06) orsat(A03)
part/aerosol removal(S06) GC-TCD(A03)*
+H20 removal(S04)*, or
part/aerosol removal(S06) orsat(A03)
part/aerosol removal(S06) GC-TCO(A03)*, or
+H20 removal(S04)» or GC-F1DIA02)*
part/aerosol removal(S06) orsat(AU3)
NA portable FIO(S08)«
NA GC-FIDCA02)
part/aerosol removal(S06)» gravimetr1c(S02)*
(Continued)
-------
TABLE 4-27. (continued)
Property or
Specie
Generic
Stream
Sampl 1ng
Options
Preparation
Options
Analysis or
Test Options
Sulfur Gases
1,2
1,2,3,4
continuous monitoring, or
1mp1nger(S07F)«
gas bomb* or bag(S13)
cool (PIDpart/aerosol
removal (S06)»
turbldlmetrlc SO(A35)*
part/aerosol removal(S06) GC-FPu(AOl)* or
+H.O removal(S04>* GC-TCD(A03)
H S
2,3,4,6
continuous monitoring, or
1mp1nger(S07E)*, or
gas bomb or bag (S13)
screen1ng(S12)*, or
bagg1ng(S!4) + gas
bomb (S13)
f1lter(Pll>, + tttratlon S (A29)*
part/aerosol removal(S06)»
part/aerosol removal(S06) GC-FPU(A01) or
+H20 removal (S04)
NA
NA
GC-TCDCA03)
detector tUDes(512)*
GC-FPU (AOD
COS
cs2
Mercaptans
2,3,4,6 gas bomb* or bag(S13)
5 baggtng(S14)+ gas
bomb(S13>*
2,3,4,6 gas bomb* or bag(S13)
5 bagg1ng(S!4)+ gas
bomb(S13)»
2,3,4,6 gas bomb* or bag(S13)
5 bagg1ng(S14)+ gas
bomb(S13)«
part/aerosol removal (S06)
+H_0 removal (S04)*
part/aerosol removal(S06)*
part/aerosol removal (S06)
+H20 removal (S04)*
NA
part/aerosol removal (S06)
+H20 removal (S041*
NA
GC-FPU (AOD*
GC-FPD(AOD*
GC-FPU(AOD*
GC-FPO(AOD*
GC-FPU(AOD*
GC-FPU (AOD*
(Continued)
-------
00
ro
Property or
Sped e
Nitrogen Gases
NH,
Generl c
Stream
2,3,4,6
HCN 2,3,4,6
S
NOX 1,2,3
Halogen Gases
HF 1,2,3
HC1 1,2,3
Particles/Aerosols
Opacity 1,2,3
TABLE 4-27. (continued)
Sampl 1ng
Options
Preparation
Options
Analysis or
Test Options
1mp1nger(S07B)»
gas bomb or bag(S13)
bagg1ng(Sl4)-Mmp1nger
(S07B), or
screenlng(SlZ)*
1mp1nger(S07A)«
bagg1ng(S!4)+
1mp1nger(S07A), or
screen1ng(S12)»
continuous monitoring, or
titip1nger(S07C>«
1mp1nger(S07H)»
1mp1nger(S07G)»
part/aerosol removal(S06) tltratlon NH (A27)»
+ac1d1c,cool(Pll)«
part/aerosol removal(506) GC-TCO(A03)
+ HO removal (S04)
ac1d1c,cool(Pll) tltratlon Nh
detector tuoes(S12)»
part/aerosol removal(S06) colorlmetrlc CN~(A28)«
+bas1c, cool(Pll)«
part/aerosol removal(S06) colorlmetrlc CN~ (A28)
+bas1c, cooHPll)
NA
detector tubes(S12)«
part/aerosol removal(S06)* spectrometr1c(A4l)*
part/aerosol removal(S06)» SIE F~(A31)«
part/aerosol removal(S061* potentlometrlc C1~(A33)*
continuous monitoring, or
NA NA
visual determ1nat1on(T2D*
Loading
Size Distribution
Composition
1,2,3
6,7
1,2,3
6.7
1,2,3
6,7
1sok1net1c(S03)«
high voKSIS)*
1sok1net1c(S03)«
high vol(S15)»
1soMnet«
high vol(S15)«
NA
NA
NA
NA
**
ftft
grav1metr1c(S03)»
grav1metrtc(Sl5>*
grav1metr1c(S03)*» or
m1croscopy(A08)
grav1metr1c(S!5)*, or
m1croscopy(A08)
«x
«*
(Continued)
-------
TABLE 4-27. (continued)
Property or
Specie
Generlc
Stream
Sa/npl Ing
Options
Preparation
Options
Analysis or
Test Options
Trace and Minor Elements
Total 1,2,3
1mp1nger(S07D)"
part/aerosol removal(S06) AA/ICP(A40)«
+ac1d1c(Pll),
+ac1d dtgest1on(Pl2)»
Volatile
1,2,3
1mp1nger(S07D)«
ac1d1c(Pll)+
add d1gest1on(P!2)»
AA/ICP(A40)«
Radioactivity
Gross alpha, beta
2,3
1mptnger(S07D)»
ac1d1c(Pll)«
alpha, beta count1ng(A36)»
OJ
CO
Organlcs
Total Hydrocarbons
1,2,3,4,6
5
gas bomb* or bag(S13)
screenfng(S08)*, or
bagg1ng(S!4)+gas
bomb(S13)
part/aerosol removal(S06) GC-FID(A02)»
•W0 removal (S04>*
NA
NA
portable FID(S08)«
GC-FID(A02)
Hydrocarbons 2,3,4,6
gas bomb* or bag(S13)
part/aerosol removal(S06) GC-FID(A02)»
+H20 removal(S04)»
Volatile Organlcs
o Functional group 2,3,4,6
screening
sorbent(S05)«
extraction (POD, or
extractlon(POl) +
LC separation(P05)», or
part1t1on1ng(P04)
spectrometr1c(A!4)
spectrometr1c(A14)»
spectrometr1c(A!4)
o AHphatlcs
(crcio'
2,3,4,6
gas bomb(S13)», or
sorbent(SOS)
part/aerosol removal(S06) GC-FIO(A02)»
+H20 removal*
thermal desorpt1on(P03) GC/MS1A11), or
GC-FID(A12)
(Continued'
-------
TABLE 4-27. (continued)
Property or Generic
Specie Stream
o Aroma tics
- Slmple(BTX) 2,3,4,6
- Polynuclear 2,3,4,6
Samp! Ing
Options
gas bomb(S13)> or
sorbent(SOS), or
sorbent(SOS)*
sorbent(SOS), or
Preparation
Options
part/aerosol removal (S06)
•HUO removal (S04)
extract1on(POl),or
part1t1ontng(P04),
thermal desorpt1on(P03)»
extractlon(POl) or
Analysis or
Test Options
GC-FIDCA02)
GC-FID(A02)Vor GC/MS(All)+/or
GC-FID(A12)+/or GC-PID(A19)
GC-FID(A02)+/or GC/MS(All)«+/or
GC-FID(A12)Vor GC-PID(A19)«
GC/MS(A11), GC-FID(A12),
aromatfcs
o Nitrogenous
Compounds
- Nitrogen
Hetero/Amlnes
2,3,4,6
- Nltrlles,
Isocyanates
2,3,4,6
sorbent(S05)«
sorbent(SOB), or
sorbent(S05)»
sorbent(S05). or
extraction (POD +
LC separation (P05) or
partit1on1ng(P04)
thermal desorpt1on(P03)»
extract)on(POl), or
extraction (POD +
LC separation (P05), or
partitioning (P04)
thermal desorpt1on(P03)*
extraction (POD, or
extract ton (POD+der1v-
H1zat1on(P02), or
part1t1on1ng(P04), or
GC-PIO(A19), HPLC(A16),
GC/MS-SCM(A15)+/or
GC/MS(A1D, GD-FIDIA12),
GC-PID(A19), HPLC(A16),
GC/MS-SCM(A15)+/or
GC/MS(A1D, GD-FID(A12),
GC-PID(A19), HPLC(A16),
GC/MS-SCM(A15)t/or
GC/MS(A1D«, GD-FID(A12).
GC-PID(A19), HPLC(A16),
GC/MS-SCM(A15)
GC/MS(All)+/or GC-FID(A12)+/or
GC-NP/HECD-N1A10)
GC/MS(AlD+/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)
GC/MS(AlD+/or GC-FIU(A12) Vor
GC-NP/HECD-N(A10)
GC/MS(AlD«+/or GC-FID(A12)+/or
GC-NP/HEUD-NIA10)*
GC/MS(AH)+/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLC(A16)
GC/MS(AlD+/or GC-FID(A12) +/or
GC-NP/HECO-N(AlO)+/or
HPLC(A16)
GC/MS(AH)+/or GC-FID(A12)+/or
GC-rlP/HEr;D-N(A10)+/or
HPLC(A16)
(Continued)
-------
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-------
TABLE 4-27. (continued)
Property or
Sped e
Generlc
Stream
Samp!Ing
Options
Preparation
Options
Analysts or
Test Options
- Carboxyl1c
Adds
2,3,4,6
sorbent(SOS)
extractlon(POl), or
extract1on(POl)+
LC separatlon(POB), or
extraction(P01)+
LC separat1on(P05)+
derfv1t1zatton(P02), or
GC/MS(AllH/or GC-FID(A12H/or
HPLC(A16)
GC/MS(All>+/or GC-FID(A12)+/or
HPLC1A16)
GC/MS(Aim/or GC-FID(A12)+/or
HPLC(A16)
extract1on(POl)+
der1v1t1zat1on(P02), or
parttt1on1ng(P04), or
GC/MSIAlDVor GC-FID(A12H/or
HPLC(A16)
GC/MS(All)Vor GC-FID(A12)+/or
HPLC(A16)
part1t1on1ng(P04)+
der1v1t1zat1on(P02)
GC/HS(All)+/or GC-FID(A12)+/or
HPLC(A16)
- Other
2,3,4,6
sorbent(S05),or
extraction (POD, or
GC/MS(All)+/or GC-FID(A12)+/or
HPLC(A16)
CO
cn
extraction (POD +
LC separatlon(POS), or
extraction (P01H
LC separat1on(P05)+
der1v1t1zat1on(P02), or
GC/MS(All)+/or GC-FIO(A12)+/or
HPLC(A16)
GC/MS(All)+/or GC-FID(W2)+/or
HPLC(A16)
extract1on(POl)+
oer1v1t1zat1on(P02), or
part1t1on1ng(P04), or
GC/MS(All)+/or GC-FID(A12)+/or
HPLC(A16>
GC/MS(All)+/or GC-FIO(A12)+/or
HPLC(A16)
part1t1on1ng(P04H
der1v1t1zat1on(P02)
GC/MS(All)+/or GC-FIU(A12)4-/or
HPLCCA16)
sorbent(S05>*
thermal desorpt1on!P03)"
GC/MS(All)»+/or GC -FlLI(A12)+/cr
HPLC(A16)
o Sulfur Con-
taining
Compounds
2,3,4,6
sorbent(SOB), or
extraction (POD, or
part1t1on1ng(P05), or
GC/MS(All)+/or GC-FID(A12)+/or
GC-FPU/HECD-S(A18)
GC/MS(All)Vor GC-FIU(A12)+/or
GC-FPD/HECD-S(A18)
axtract1on(POl)+
LC separation(P05)
GC/MS(All)+/or GC-i-'IU(A12)+/or
GC-FPD/HECD-S(A18)
corbent(S05)«
thermal desorpt1on(P03)«
GC/MstAll>»+/or GC-FID(A12)*'or
GC-Fr-D/HE'JD-S(A18)»
(Continued)
-------
TABLE 4-27. (continued;
Property or
Specie
Generic
Stream
Sampl 1ng
Options
Preparation
Options
Analysis or
Test Options
I
OJ
Condensable Organlcs
o Loading 2,3,4.6
o Functional Group 3,6
Screenlng
o AHphatlcs
2,3,4,6
o Aromatlcs
- Simple (BTX) 2,3,4,6
- Polynuclear 2,3,4,6
sorbent(S05)«+/or
1mp1nger
-------
TABLE 4-27. (continued)
Property or
Specie
Generic
Stream
Sampl 1ng
Options
Preparation
Options
Analysis or
Test Options
o Nitrogenous Compounds
- Nitrogen
Hetero/Am1nes
2,3,4,6
sorbent(S05)»/or
tmp1nger(S09>
cool(Pll)+extract1on
(POD*, or
cool(Pll)+extract1on
(POD-H.C separation
(P05)
GC/MS(All)»+/or GC-FID(A12H/or
GC-NP/HECD-N(A10)»
GC/MS(All>+/or GC-FID(A12)+/or
GC-NP/HECD-N(A12)
cool(Pll)+part1t1on1ng
(P04)
GC/MS (All )-i-/or GC-FIO(A12)+/or
GC-NP/HECD-N(A12)
N1tr1les,
Isocyanates
2,3,4,6
sorbent(S05)*+/or
1mp1nger(S09), or
cool(Pll)+extract1on
(P01)«, or
GC/MS(A11)» +/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)» +/or
HPLCIA16)
cool(Pll)+extract1on
(POD+LC separation
(P05), or
GC/MS(All)+/or GC-FIU(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLC(A16)
CO
OD
cool(Pll)+extract1on
(P0l)+der1v1t1zat1on
(P02), or
cool(Pll)+extract1on
(POD+LC separation
(P05)+der1v1t1zat1on
(P02), or
cool (Pll)-i-partltlonlng
(P04), or
GC/MS(All)+/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLC(A16)
GC/MS(All)+/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLC(A16)
GC/MS(All)+/or GC-FID(A12)+/or
GC-NP/HECD-N (Alt) )+/or
HPLC(A16)
cool (Pll)-Hnlcroextrac-
t1on(P06), or
GC/MS(All)-t-/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLC(A16)
cool(Pll)+m1croextrac- GC/MS(All)+/or GC-FID(A12)+/or
t1on(P06),+der1v1t1zat1on GC-NP/HECD-N(A10)+/or
(P02), HPLC(A16)
1mp1nger(S09)
cool(PI 1)
aqueous 1nj.(A09)
(Continued)
-------
TABLE 4-27. (continued)
Property or
Specie
Generic
Stream
Sampl1ng
Options
Preparation
Options
Analysis or
Test Options
o Oxygenates
- Phenols
2,3,4,6
sorbent(S05)*+/or
1mp1nger(S09)
I
OJ
cool(PD)+extract1on
(POD*, or
cool (PID+extractlon
(POD+LC separation
(POS), or
cool (PID+extractlon
(POD+der1v1t1zat1on
(P02), or
cool (PlD+extract1on
(POD+LC separation
(P05)+der1v1t1zatton
(P02), or
cool (PlD+part1tton1ng
(P04), or
cool (PlD+m1croextrac-
t1on(P06), or
GC/MS(AlD»+/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLC(A16)+/or GC-PID(A19)
GC/MS(AlD+/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLC1A16)
GC/MS(AlD+/or GC-FIU(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLCIA16)
GC/MS(AlD+/or GC-FID(A12)+/or
GC-NP/HECO-N(A10)+/or
HPLC(A16)
GC/MS(AlD+/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLC(A16)
GC/MS(AlD+/or GC-FID(A12)+/or
GC-NP/HECD-N(A10)+/or
HPLC(A16)
cooKPlD+mlcroextrac- GC/MS(AlD+/or GC-FlL)(A12)+/or
t1on(P06),+der1v1t1zat1on GC-NP/HF.CD-N(A10)+/or
(P02), HPLC(A16)
- Carboxyltc
Adds
2,3,4,6
sorbent(S05)*+/or
1mp1nger(S09)
cool (PlD+extract1on
(POD, or
cool (PlD+extract1on
(POD+LC separation
(POS), or
cool (PlD+extract1on
(POD+der1vtt1zat1on
(P02)», or
cool(Pll)+extract1on
(POD+LC separation
(P05)+der1v1t1zat1on
(P02), or
GC/MS(AlD+/or GC-FID(A12)+/or
HPLC(A16)
GC/MS(AlD+/or GC-FID(A12)+/or
HPLC(A15)
GC/MS(AlD»+/or GC-FID(A12)+/or
HPLC(Alfi)
GC/MS(AlD+/or GC-FIU(A12)+/or
HPLC(A16)
(Cont;nuc1)
-------
TABLE 4-27. (continued)
Property or
Specie
Generlc
Stream
Sampl1ng
Options
Preparation
Options
Analysis or
Test Options
1mp1nger(S09)
cool(Pll)+part1t1on1ng
(P04), or
cool(Pll)+m1croextrac-
t1on(P06), or
cool(Pll)+m1croextrac-
t1on(P06),+der1v1t1zat1on
(P02),
cool(Pll)
GC/MS(All)+/or GC-FID(A12)Vor
HPLCCA16)
GC/MS(All)+/or GC-FID(A12)+/or
HPLC(A16)
GC/MS(Aim/or GC-FID(A12)+/or
HPLC(A16)
aqueous 1nJ.(A09)
- Others
2,3,4.6
I
O
sorbent(S05)*+/or
1mp1nger(S09)
1mp1nger(S09)
cool(PllHextractlon
(P01)«, or
cool(PllHextractlon
(P01HLC separation
(P05), or
cool(Pll)+extract1on
(POlHder1v1t1zat1on
(P02), or
cool(Pll)+extract1on
(POD+LC separation
(P05)+der1v1t1zat1on
(P02), or
cool(Pll)+part1t1on1ng
(P04), or
cool(Pll)+m1croextrac-
t1on(P06), or
cool(Pll)+m1croextrac-
t1on(P06),+der1v1t1zat1on
(P02),
cool(Pll)
GC/MS(All)*+/or GC-FID(A12)+/or
HPLC(A16)
GC/MS( Aim/or GC-FID(A12)+/or
HPLCCA16)
GC/MS(All)+/or GC-FID(A12)+/or
HPLC(A16)
GC/MS(All)+/or GC-FID(A12)+/or
HPLCCA16)
GC/MS(All)+/or GC-FID(A12)+/or
HPLC(A16)
GC/MS(All)+/or GC-FIU(A12)+/or
HPLC(A16)
GC/MS(All)+/or GC-FID(A12)+/or
HPLC1A16)
aqueous 1nJ.(A09)
o Sulfur Containing 2,3,4,6
Compounds
sorbent(S05)*+/or
1mp1nger(S09)
cool(Pll)+extract1on
(P01)«, or
cool (PllHextractlon
(POD+LC separation
(P05), or
cool(Pll)+part1t1on1ng
(P04), or
cool(Pll)+m1croextrac-
t1on(P06).
GC/MS(All)*+/or GC-FID(A12)+/or
GC-FPU/HECD-S(A18)«
GC/MS(All)+/or GC-FID(A12H/or
GC-FPUXHECD-S(Alb)
6C/'MS(All)+/or GC-FIO
-------
TABLE 4-27. (continued)
FOOTNOTES:
Fractlonatlon may be appropriate for complex organic samples. Fraction or fractions of Interest can be
selected prior to analysis. If capillary GC 1s Implemented, fractlonatlon (as Indicated 1n Table 4-24)
will be necessary less frequently.
GENERIC STREAMS:
1. Flue gases from conventional fuel combustion
2. Flue gases from process-derived fuel or waste combustion
3. Uncombusted vent gases or feed gases to flares
4. Tank vents
5. Process fugitive emissions
6. Impoundment, storage or disposal emissions
7. Fugitive partlculate emissions
NA - not applIcable
"Techniques expected to be most commonly applicable are marked with an asterisk
**See Table 4-29 for Solids Methods.
-------
TABLE 4-28. MONITORING OPTIONS FOR AQUEOUS STREAMS
I
ro
Property or
Specie
pH
Conductivity
Alkal1n1ty/Ac1d1ty
AmmoM a
Cyan) de
01 1 and Grease
Dissolved Oxygen
Chloride
Fluoride
Nitrate/Nitrite
Sulfate
Sulflte
Sulflde
Biological Oxygen
Demand
Chemical Oxygen
Demand
Phosphate
Thlocyanate
Formate
Total Organic
Carbon
Total Inorganic
Carbon
Generic
Stream
1,2,3,4
1,2,3,4
1,2,3,4
1,2,3,4
1,2,3,4
1,3
1,2,3,4
1,2,3,4
1,2,3,4
1,2,3,4
1,2,3,4
1,2,3,4
1,2,3,4
1.2,3,4
1,2,3,4
1,2,3,4
1,2,3,4
1,2,3,4
1,3,4
1,2,3,4
Sampl 1ng Options
grab(Sll)*
grab(Sll)«
compos 1te(SlO)» or grab(Sll)
composite (S10) or grab(Sll)»
composite; S10) or grab(Sll)»
composlte(SlO) or grab(Sll)*
composlte(SlO)* or grab(Sll)
compos1te(S10)« or grab(Sll)
composlteCSlO)* or grab(Sll)
compos) te(S10> or grab(Sll)*
ccmposlte(SlO)* or grab(Sll)
compos) te(S10) or grab(Sll)*
composlte(SlO) or grab(Sll)*
composHe(SlO) or grab(Sll)1
composlte(SlO) or grab(Sll)*
ccmposfte(SlO) or grab(Sll)«
composlte(SlO) or grab(Sll)*
composlte(SlO) or grab(Sll)*
compostte(SlO) or grab(Sll)»
compos1te(SlO)» or grab(Sll)
Preparation
Options
NR
cool(Pll)*
cooKPll)*
acidic + cool (Pill «
basic + cool(Pll)*
acidic + cool(Pll)«
cool(Pll)»
NR
NR
acidic + cool(Pll)*
cooHPll)*
cooKPll)"
f1lter(Pll)»
cooKPll)*
ac1d1c(Pll)»
phosphate forms
separat1on(A38)»
cooKPll)*
cooKPll)*
acidic + cool (Pll)»
cool CPU) «
Analysts or
Test Options
electrode(A20)«
electrode(T09)«
t1trat1on(A39)»
t1trat1on(A27)«
color1metr1c(A28)«
grav1metr1c(A37)»
electrode(A44)»
t1trat1on(A33)»
SIECA31)"
color1metr1c(A32)»
turb1t)metr)c(A3S)*
t)trat1on(A34)»
t)trat)on(A29)«
1ncubat1on(A25)»
ox1dat)on(A24)»
color1metr1c(A38)«
color)metr)c(A30)*
)on chromatography (A45>*
NDIR-FID(A42)»
NDIR(A43!«
Trace and Minor Elements
o Total
o Soluble
Radioactivity
Total Suspended
Sol Ids
Total Dissolved
Sol Ids
Total Sol Ids
Total Volatile
Solids
1,2,3,4
1.2,3,4
3.4
1,2,3,4
1,2,3,4
1,2,3,4
1,2,3,4
compos1te(S!0)« or grab(Sll)
compos 1te(SlO)» or grab(Sll)
composite (S10)» or grab(Sll)
compos! te(S10) or grab(Sll)«
composlte(SlO) or grab(Sll)»
composlte(SlO) or grab(Sll)'
composlte(SlO) or grab(Sll)*
addlc(Pll) +
add digestion (P20)»
filter + acldlc(Pll) +
add digest) on (P20)»
ac1d)c(Pll)«
cool (?!!)«
cool(Pli)«
cool (Pill*
cool(Pll)«
AA/ICP (A40)«
AA/ICP (A40)»
a.B counting (A361*
gravimetric (A23)*
gravimetric (A22)»
gravimetric (A2)>*
gravimetric (A21)»
(Continued)
-------
TABLE 4-28. (continued)
CO
Property or
Specie
Generic
Stream
SamplIng Options
Preparation
Options
Analysts or
Test Options
Settleable Solids 1,2,3,4
Solids Composition 3,4
Oroanlcs
o Loading
1,2,3,4
o Total Organic 3,4
Halogens
o Functional 1,3,4
Group Screening
o Phenollcs 1,2,3,4
o Volatile Organfcs
- AHphattcs 1,3,4
- Aromatics
. Slmple(BTX) 1,3,4
Polynuclear 1,3,4
Aromatics
Nitrogenous
Compounds
. Nitrogen
Hetero/ 3,4
Amines
. N1tr1les,
Isocyanates 3,4
Oxygenates
. Phenols 3,4
Carboxyllc 3,4
Adds
Other
3,4
composite!S10) or grab(Sll)* cool(Pll)»
compos1te(SlO>* or grab(Sll) **
compostte(S10> or grab(Sll)« cool(Pll) + extract1on(P01)»
composlte(SlO) or grab(Sll)* cool(Pll)*
composlte(SlO) or grab(Sll)» cool (Pll) + extraction CP01), or
cool (Pll) + extraction (POD
+ LC separation (P05)», or
cool (Pll) + mlcroextractlon (P06), or
cool (Pll) + partitioning (P04)
composlte(SlO) or grab(Sll)* acidic + cool(Pll)«
composlte(SlO) or grab(Sll)* cool(Pll) + purge ana trap (P031*
coraposlte(SlO) or grab(Sll)» cool(PH) + purge and trap (P03)»
composlte(SlO) or grab(Sll)* cool(Pll) + purge and trap(P031*
composlte(SlO) or grab(Sll)« cool(Pll) + purge and trap(P03>*
composite(S10) or grab(Sll)' cool(Pll) + purge and trap(P03)»
compostte(SlO) or grab(Sll)* cool(Pll) + purge and trap(P03)»
"o,tipos1te(SlO> or grab(Sll)* cool (Pll) + purge and trap(P03)»
:-,ip03lte(S10) or grab(Sll)* cool (Pll) + purge and trap(P03)«
sed1mentatton(A46)»
grav1metr1c(Al3) + GC-FID(A12)"
TOX(A17)«
spectrometr1c(A14)
spectrometr1c(Al4)*
spectrometr1c(A!4)
spectrometr1c(A14)
color1metr1c(A26)»
GC/MS(A11)« +/or GC-FIO(A12)
GC/MS(A11)» +/or GC-FID(A12)
+/or 6C-PID(A19)«
GC/MS(A11)« +/or GC-FID(A12) +/or
GC-PID(A19) +/or hPLC(A16) +/or
GC/MS-SCWA15)
GC/MSIA1D* +/or GC-FIDIA12) Vor
GC-NP/HECD-NMA10)
GC/MS(A11)» +/or GC-FID(A12) +/or
GC-NP/HECD-N(A10)»
GC/MS(A11)» +/or GC-FIDCA12) Vor
GC-PID(A19)« +/or GC/MS-SCM(A15)
GC/MS(A11)« Vor GC-FKKA12) +/or
GC-PID(A19) +/or HPLC(A16) +/or
GC/MS-SCM(A15)
GC/MS(A11)» +/or GC-^'j'.H':)
GC/MS(A19) +/or GC/MS-SCM(nlS)
(Continued)
-------
TABLE 4-28. (continued)
Property or
Specie
Generlc
Stream
SamplIng Options
Preparation
Options
Analysts or
Test Options
- Sulfur Con-
taining
Compounds
o Nonvolatile
Organlcs
- AHphatlcs
3,4
1,3,4
- Aroma tics
. Slmple(BTX) 1,3,4
Polynuclear 1,3,4
Aromatlcs
Nltrogeneous
Compounds
. Nitrogen 3,4
Hetero/Am1nes
composlte(SlO) or grab(Sll)« cool(Pll) + purge and trap(P03)«
composlte(SlO)* or grab(Sll) cool (Pll) + extraction (POD*, or
cool (Pll) + extraction (POD
+ LC separation (P05), or
cool (Pll) + partitioning (P04), or
cool (Pll) + mlcroextractlon (P06)
compos1te(S10)» or grab(Sll) cool (Pll) + extraction (POD«, or
cool (Pll) + extraction (POD
+ LC separation (FOB), or
cool (Pll) + partitioning (P04), or
cool (Pll) + mlcroextractlon (P06)
compos1te(S!0)» or grab(Sll) cool (Pll) + extraction (POD*, or
cool (Pll) + extraction (POD
+ LC separation (POS), or
cool (Pll) + partitioning (P04), or
cool (Pll) + mlcroextractlon (P06)
compos!te(SlO)* or grab(Sll) cool (Pll) + extraction (POD*, or
cool (Pll) + extraction (POD
+ LC separation (POS), or
cool (Pll) + partitioning (P04), or
cool 'D1D + mlcroextractlon (P06)
GC/MS(A11)» +/or GC-FID(A12> +/or
GC-FPD/HECD-S(A18>»
GC/MS(A11)» +/or GC-FIDIA12)
GC/MS(A1D +/or GC-FID(A12)
GC/HS(A11) +/or GC-FIDCA12)
GC/MS(A1D +/or GC-FID(A12)
GC/MS(A1D* +/or GC-FID(A12) +/or
GC-PID(A19)»
GC/MS(A1D +/or GC-FID(A12) +/or
GC-PID(A19)
GC/MS(A1D +/or GC-FID(A12) +/or
GC-PID(A19)
GC/MS(A1D +/or GC-FID(A12) +/or
GC-PID(A19)
GC/MS(A1D* +/or GC-FID(A12) Vor
GC-PID(A19) +/or HPLC(A16)
GC/MS(A1D +/or GC-FID(A12) +/or
GC-PID(A19) +/or HPLC(A16)
GC/MS(A11) +/or GC-FID1A12) +/or
GC-PID(A19) +/or HPLC(A16)
GC/MS(A11) +/or GC-FID(A12) +/or
GC-PID(A19) +/or HPLC(A16)
GC/MS(A11)« +/or GC-FIDtAU! +/or
GC-NP/HECD-N(A10)» +/or HPLC(A16)
GC/MS(AU) +/or GC-FIO(A12)
GC-NP/HECO-N(A10) +/or HPLC'A16)
GC/HS(A11) +/or GC-FIO(A12)
GC-NP/HECO-N(A10) +/or HPLC;A16)
GC/HS(A11) Vor GC~FID:A12) t/or
GC-NP/HECO-N(A10) .-/o. HPLC(A16)
(Continued)
-------
TABLE 4-28. (continued)
Property or
Specie
Generic
Stream
Samp!1ng Options
Preparation
Options
Analysis or
Test Options
N1tr1les, 3,4
Isocyanates
I
en
Oxygenates
. Phenols 3,4
composlte(SlO)* or grab(Sll) cool (Pll) + extraction (POD*, or
cool (Pll) + extraction (POD
+ der1v1t1zat1on (P02), or
cool (Pll) + extraction (POD
+ LC separation (P05), or
cool (Pll) + extraction (POD
+ LC separation (P05) +
der1v1t1zat1on (P02), or
cool (Pll) + partitioning (P04), or
cool(Pll) + mlcroextractlon(P06), or
cool (Pll) + mlcroextractlon (P06)
+ der1v1t1zat1on (P02),or
cool(Pll)
compos1te(S!0)« or grab(Sll) cool (Pll) + extraction (POD», or
cool (Pll) + extraction (POD
+ der1v1t1zat1on (P02), or
cool (Pll) + extraction (POD
+ LC separation (P05), or
cool (Pll) + extraction (POD
+ LC separation (P05) +
derlvltlzatlon (P02), or
cool (Pll) + partitioning (P04), or
cool (Pll) + mlcroextractlon (P06), or
cool (Pli: + mlcroextractlon (P06)
+ derlvltlzatlon (P02)
GC/MS(A11>* +/or GC-FIDIA12) +/or
GC-NP/HECD-N(A10)« +/or HPLC(A16)
GC/MS(A11) +/or 6C-FID(A12) +/or
GC-NP/HECD-N(A10) +/or HPLC(A16)
6C/MS(A11) +/or GC-FID(A12) +/or
GC-NP/HECD-N(A10) +/or HPLCIA16)
GC/MS(A11) +/or GC-FID(A12) +/or
GC-NP/HECD-N(A10) +/or HPLC(A16)
GC/MS(A1D +/or GC-FID1A12) +/or
GC-NPXHECO-N(AIO) +/or HPLC(A16)
GC/MS(A11) +/or GC-FID(A12) +/or
GC-NP/HECO-N(A10) +/or HPLC(A16)
GC/MS(A1D +/or GC-FID(A12) +/or
GC-NP/HECD-N(A10) +/or HPLC(A16)
aqueous 1nj.(A09)
GC/MS(A1D* +/or GC-FID(A12) +/or
GC-PID(A19)« +/or HPLC(A16) +/or
GC/MS-SCM(A15)
GC/MStAll) +/or GC-FIO(A12) +/or
GC-PID(A19) +/or HPLC(A16) +/or
GC/MS-SCM(A15)
GC/MS(A1D +/or GC-FID(A12) t/or
GC-PID1A19) +/or HPLC(A16) +/or
GC/MS-SCM(A15)
GC/MS(A1D +/or GC-FID(A12) +/or
GC-PID(A19) +/or HPLC(A16) Vor
GC/MS-SCM(A15)
GC/MS(A11) +/or GC-FID(A12! +/or
GC-PID(A19) Vor HPLC(A16) +/or
GC/MS-SCM(A15)
GC/MSIA1D +/or GU-FICIA12) +/or
GC-PID(A19) +/or hPLC(A16) +/or
GC/MS-SCM(A15)
GC/MS(A1D +/or &--FILMA12) +/or
GC-PIO(A19) +/or HflC'Ale) +/or
GC/MS-SCM(A15)
(Continued)
-------
Property or
Specie
Generic
Stream
TABLE 4-28. (continued)
Sampl1ng Options
Preparation
Options
Analysts or
Test Options
Carboxyllc 3,4
Adds
CTt
Other
3,4
composl i(S10)» or grab(Sll) cool [Pill + extraction (P01)«, or
cool (Pll) + extraction (POD
+ derlvltlzatlon (P02), or
cool (Pll) + extraction (POD
+ LC separation (P05), or
cool (Pll) + extraction (POD
+ LC separation (P05) +
derlvltlzatlon (P02), or
cool (Pll) + partitioning (P04), or
cool (Pll) + mlcroextractlon (P06), or
cool (Pll) + mlcroextractlon (P06)
+ derlvltlzatlon (P02), or
cool(Pll)
conposlte(SlO)* or grab(Sll) cool (Pll) + extraction (P01)«, or
cool (Pll) + extraction (POD
+ dertvltlzatlon (P02), or
cool (Pll) + extraction (POD
+• LC separation (P05), or
cool (P1D + extraction (POD
+ LC separation (P05) +
derlvltlzatlon (P02), or
cool (Pll) + partitioning (P04), or
cool (Pll) + mlcroextractlon (P06), or
cool (Pll) + mlcroextractlon (P06)
+ aer1v1t1zat1on (P02),or
cool(Pll)
GC/MS(A11)» +/or GC-FID(A12) +/or
HPLC(A16I»
GC/MSIA11) +/or GC-FID(A12) +/or
HPLC(A16)
GC/MS(A11) +/or GC-FID(A12) +/or
HPLC(A16)
GC/MS(A11) +/or GC-FID(A12) +/or
HPLC(A16)
GC/MS(A11) +/or GC-FID(A12) +/or
HPLC1A16)
GC/MS(A11) +/or GC-FID(A12) +/or
HPLC(A16)
GC/MS(A1D +/or GC-FID(A12) +/or
HPLC(A16)
aqueous 1nj.(A09)
GC/MS(A11)» +/or GC-FID(A12) +/or
HPLC(A16)
GC/MS(A1D +/or GC-FID(A12) +/or
HPLC(A16)
GC/MS(A1D +/or GC-FID(A12) +/or
HPLC(A16)
GCXMS(All) +/or GC-FID(A12) +/or
HPLC(A16)
GC/MS(A1\) Vor GC-FID(A12) +/or
HPLC(A16)
GC/MS(A1D +/or GC-FID(A12) +/or
HPLC(A16)
GC/HS(A1D +/or GC-FID1A12! +/or
HPLC(A16)
aqueous mj.(A09)
(Continued)
-------
TABLE 4-28. (continued)
Property or
Specie
Generic
Stream
Safnpl 1 ng Opt 1 ons
Preparation
Options
Analysis or
Test Options
Sulfur Con- 3,4
taln1ng
Compounds
ccropostte(SlO)" or grab(Sll) cool(Pll) + extractlon(POl)*, or
cool(Pll) + part1t1ontng(P04), or
cool(Pll) + extractlon(POl) +
LC separatlon(POS), or
cool(Pll) + m1croextract1on(P06)
GC/MSIA11)* +/or
GC-FIDCA-12) «/or
GC-FPD/HECO-S(A18>"
GC/HSIA11) +/or
GC-FID(A-12) */or
GC-FPD/HECD-S(A18)
GC/MS(A11) +/or
GC-FID(A-12) Vor
GC-FPD/HECO-S(A16)
GC/MSIA11) +/or
GC-FIOIA-12) +/or
GC-FPO/HECD-S(A18)
Health Effects 3,4
Ecological Effects 3,4
compos1te(S10)» or grab(Sll) cool(Pll)*
conpos1te(S10)« or grab(Sll) cool(PI 1)"
cellular, mammalian
IT121"
algal,
vertebrate!T13)«
FOOTNOTES:
Fractlonatlon may be appropriate for complex organic samples. Fraction
or fractions of Interest can be selected prior to analysis. If capillary
GC Is Implemented, fractlonatlon (as Indicated In Table 4-25) «tll be
necessary less frequently.
Generic Stream Types
1. Wastewater streams containing nonunlque streams from organic sources
2. Wastewater streams containing nonunlque streams from organic-free
or organic-lean sources
3. Wastewater streams containing unique streams from organic-laden sources
4. Wastewater streams containing unique streams from organic-free or
organic-lean sources
•Expected to be most ccmnonly applicable.
•"See Table 4-29, MONITORING OPTIONS FOR SOLID STREAMS
NR - none required
-------
TABLE 4-29. MONITORING OPTIONS FOR SOLID STREAMS
Property or
Specie
Proximate
Ultimate
Ash Mineral
Analysis
Trace and Minor
Elements
ASTM Leachab1l1ty
RCRA EP
LeachablHty
Crystalline forms
Particle S1re
Surface Area
Particle Morphology
Reactivity
Ign1tab1l1ty
Corros1v1ty
Radioactivity
Viscosity
Specific Gravity
Bulk Density
Permeabll 1ty
Organ,1cs***
• Loading
• Functional
Group
Screening
• AHphatlcs
• Aroma tics
- Slmple(BTX)
- Polynuclear
Aromatlcs
Generic
Stream
1,2,3,4
1,2,3.4
1,2,3.4
1,2,3.4
1,2,3.4
1,2,3,4
3,4
1,2.3.4
3,4
3,4
1,2,3.4
1,2,3.4
1,2,3,4
1,2,3,4
1.2,3.4
1,2,3,4
2,4
2.4
1,3,4
1.3,4
1,3,4
1,3,4
1.3,4
Sampl Ing
Options
composite* or grab (SOI)
composite* or grab (SOI)
composite* or grab (SOI)
composite* or grab (SOD
composite* or grab (SOI)
composite* or grab (SOI)
composite* or grab (SOD
composite* or grab (SOI)
composite* or grab (SOD
composite* or grab (SOD
composite* or grab (SOD
composite* or grab (SOD
composite* or grab (SOI)
composite* or grab (SOD
composite* or grab (SOI)
composite* or grab (SOD
composite* or grab (SOD
composite* or grab (SOI)
composite* or grab (SOD
composite* or grab (SOD
composite* or grab (SOD
composite* or grab (SOD
composite* or grab (SOI)
Preparation
Options
NR
NR
fus1on(P09)» +/or
add d1gest1on(P!0)»
fus1on(P09)» +/or
add dlgestlon(PlO)*
Analysis or
Test Options
ASTM(A04>*
ASTMA05)*
AA/ICP1A40)*
AA/ICP(A40>*
neutral extract1on*
extraction (POD*, or
extraction (POD +
LC separatlon(POS)
extrart1on(POl>«, or
extraction (POD +
LC separatlon(POS)
extractlon(POl)*, or
extractlon(POl) +
LC separatlon(POS)
**
XRCKA07)*
SEM(A08)» or sieve and
sedlmentatlon(TOS)
BET(Tll)*
SEM(A08)*
reaction with H_0
(T02)*
Pensky-Martens cup
(T03J*
steel coupon(TOl)*
a, 8, Ra226 counting
(A06)»
vlscometer(TlO)*
d1splacement(T06)*
dens1tometer(TQ7)»
H20 conduct1v1ty(T04)»
grav1metr1c(A!3)+
GC-FID(A12)*
spectrometrl c(A14)
spectrometrl c ( A14 ) *
GC/MS(A11>* +/or
GC-FIDCA12)
GC/MS(A1D +/or
GC-FID(A12)
GC/MS(A1D* +/or
GC-FID(A12) +/or
GC-PIDCA19)*
GC/MS(A11) +/or
GC-FID(A12) +/or
GC-PID(A191*
GC/MS(A1D* +/or
GC-FID(A12) +/or
GC-PID(A19) +/or
HPLC(A16) +/or
GC/MS-SCM(A15)
GC/MSiAll) +/or
GC-FID(A12) +/or
GC-PID(A19) +/or
HPLC(A16) +/or
GC/MS-SCM(A15)
(Continued)
4-148
-------
TABLE 4-29. (continued;
Property or
Specie
Gener! c
Stream
Sampl Ing
Options
Preparation
Options
Analysis or
Test Options
Nitrogenous
Compounds
- Nitrogen
Hetero/
Amines
3.4
- N1tr1les.
Isocyanates
3,4
composite* or grab(SOl) extractlon(POl)*, or
extraction (POD + LC
separatlon(POS), or
extraction (POD +
der1v1t1zat.1on(P02) ,or
extraction (POD + LC
separatlon(POS) +
der1v1t1zat1on(P02)
composite* or grab(SOl) extract1on(POD*» or
extraction (POD + LC
separatlon(POS),
extraction (POD +
der1v1t1zat1on(P02),or
extraction (POD + LC
separatlon(POS) +
der1v1t1zat1on(P02)
• Oxygenates
- Phenols
3,4
composite* or grab(SOl)
extractlon(POl)*, or
extraction (POD + LC
separatlon(POS).
extraction (POD +
der1v1t1zat1on(P02),or
extraction (POD + LC
separatlon(POS) +
der1v1t1zat1on(P02)
GC/MS(A1D* +/or GC-FID(A12)
+/or GC-NP/HECD-N(A10)» +/or
HPLC(A16)
GC/MS(A11) +/or GC-FID(A12)
+/or GC-NP/HECD-N(A10) +/or
HPLC(A16)
GC/MS(A1D +/or GC-FID(A12)
•^/or GC-NP/HECD-N(A10) +/a-
HPLC(A16)
GC/MS(A11) +/or GC-FID(A12)
+/or GC-NP/HECD-N(A10) +/or
HPLC(A16)
GC/MS(A1D* +/or GC-FID(A12)
+/or GC-NP/HECD-N(A10)« +/or
HPLC(A16)
GC/MS(A11> +/or GC-FID(A12)
+/or GC-NPXHECD-N(AIO) +/or
HPLC(A16)
GC/MS(A1D +/or GC-FID(A12)
+/or GC-NP/HECD-N(A10) +/or
HPLCIA16)
GC/MS(A1D +/or GC-FID(A12)
+/or GC-NP/HECD-N(A10> +/or
HPLCIA16)
GC/MS(A1D* +/or
+/or GC-PID1A19)* +/or
HPLC(A16) Vor GC/MS-SCM(A15)
GC/MS(A1D +/or GC-FID(A12)
+/or GC-PID(A19) +/or
HPLC(A16) +/or GC/MS-SCM(A15)
GC/MS(A1D +/or GC-FIU(A12)
+/or GC-PID(A19) +/or
HPLC(A16) +/or GC/MS-SCM(/;S)
GC/MS(A1D +/or GC-FID(A'2i
+/or GC-PIO(A19) +/or
HPLC(A16) +/or
(Continued)
4-149
-------
TABLE 4-29. (continued)
Property or
Specie
Gener!c
Stream
SamplIng
Options
Preparation
Options
Analyils or
Test Options
Carboxyllc 3,4
Acids
composite* or grab(SOl)
- Other
3,4
o Sulfur Con- 3,4
talnlng
ptoassav
Health Effects 3,4
Ecological Effects 3,4
composite* or grab(SOI)
composite* or grab(SQl)
composite* or graMSOU
composite* or grab(SOl)
composite* or grab(SOI)
extractlon(POl)*, or
extractton(POl) + LC
separatlon(POS),
extractlon(POl) +
der1vtt1zat1on(P02),or
extractlon(POl) + LC
separat1on(P05! +
der1v1t1zatton(P02)
extractlon(POl)*, or
extractlon(POl) + LC
separatlon(POS),
extractlon(POl) +
der1v1t1zat1on(P02),or
extract1on
extractlon(POl)*, or
extractlon(POl) + LC
separation (P05)
neutral extraction
(POB)«
composite* or grab (SOD neutral extraction
(P08)»
GC/MS(A1))« +/or GC-FIO(A12)
+/or HPLC(A16>* +/or GC-PIP
(A19)
GC/MSC11) -f/or GC-FID(A12)
+/or HPLC(A16) +/or GC-PID
(A19)
GC/MS(A11) +/or GC-FIO(A12)
+/or HPIC1A16) +/or GC-PID
(A19)
GC/MS(A11) */or GC-FID(A12)
t/or HPLC(A16) +/or GC-PID
(A19)
6C/MS*
algal,
vertebrateCn.3)
algal,
»ertebrate(T13)*
FOOTNOTES:
Fractlonatlon may be appropriate for complex organic samples. Fraction or fractions of Interest can be selected prior
to analysis. If capillary GC Is Implemented, frsrtlonatlon (as Indicated In Table 4-26) «111 be necessary less
frequently.
FOOTNOTES
F
t
frequently
Generic Stream Types
1. Nonunlque organic-laden solid wastes
2. Nonunlque organic-free or organic-lean solid wastes
3. Unique organic-laden solid wastes
4. Unique organic-free or organic-lean solid wastes
•Expected to be most commonly applicable.
"See Table 4-28 MONITORING OPTIONS FOR AQUEOUS STREAMS
t««purgflng or thermal desorptlon techniques (P03), which define volatile organic fractions for liquids and
gases, are not generally appropriate for solids. Therefore, no volatile organic classification
1s shown for solids.
NR - none required
4-150
-------
4.5 REFERENCES FOR SECTION 4
4-1. Hlttman Associates, Inc., personal communication concerning source test
campaign on Exxon Donor Solvent Coal Liquefaction pilot plant.
Columbia, MD, June 1982.
4-2. Hlttman Associates, Inc., personal communication concerning source
test campaign on Fort Lewis SRC Coal Liquefaction pilot plant.
Columbia, MD, October 1981.
4-3. Reap, E. J., G. M. Davis, M. J. Duffy, and J. H. Koon, "Wastewater
Characteristics and Treatment Technology for the Liquefaction of Coal
Using H-Coal Process," Presented at the 32nd Annual Purdue University
Waste Conference, West Lafayette, IN, May 1980. 38 pp.
4-4. Thlelen, C. J., R. A. Magee, and R. V. Collins, On-S1te GC/MS Analysis
of Chapman Gasification Separator Liquor. EPA-60Q/7-81-136;
PB82-107285 Radian Corporation, Austin, TX, August 1981.
4-5. Lewis, D. S. Addendum to Environmental Assessment: Source Test and
Evaluation Report — Chapman Low-Btu Gasification. EPA-600/7-80-178;
PB82-107285. Radian Corp., Austin, TX, October 1980.
4-6. Lee, K. W., et al., Environmental Assessment: Source Test and Evalua-
tion Report - Lurgl (Kosovo) Med1um-BTU Gasification. EPA-600/7-81-
142; PB82-114075. Radian Corp., Austin, TX, August 1981.
4-7. Page, G. C., Environmental Assessment: Source Test and Evaluation
Report—Chapman Low-Btu Gasification. EPA-600/7-78-202; PB-289 940.
Radian Corp., Austin, TX, October 1978.
4-151
-------
4-8. Stamoudls, V. C., and R. G. Luthy, Biological Ren.ovo, of Organic Con-
stituents 1n Quench Waters from H1gh-Btu Coal-Gasification Pilot
Plants. ANL/PAG-2. Argonne National Lab., Energy and Environmental
Systems Division, Argonne, IL, February 1980.
4-9. Woodall-Duckham Ltd., Trials of American Coals 1n a Lurgl Gas1f1er at
Westfleld, Scotland. Final Report. Research and Development Report
No. 105; FE-105. Crawley, Sussex, England, November 1974.
4-10. Gremlnger, D. C., and C. J. King, Extraction of Phenols from Coal Con-
version Process Condensate Waters. LBL-9177. Lawrence Berkeley Lab.,
California University, Berkeley, CA, June 1979.
4-11. Wlnton, S. L., and M. D. Matson, Lurgl Process Wastewaters - Projected
Characteristics and Treatment Alternatives. Radian Technical Note 218-
001-15-02. Radian Corp., Austin, TX, June 1980.
4-12. Pellizzari, E. D., et al., "Identification of Organic Components 1n
Aqueous Effluents from Energy-Related Processes," in: Symposium on the
Measurement of Organic Pollutants 1n Water and Wastewater, Denver, CO,
19-20 June 1982. ASTM Special Technical Publication No. 686. ASTM,
Philadelphia, PA, 1979. pp. 256-275.
4-13. KHeve, J. R., and G. D. Raw lings. Assessment of Oil Shale Retort
Wastewater Treatment and Control Technology: Phases I and II. EPA
600/7-81-081; PB81-187288. Monsanto Research Corp., Dayton, OH, AprT!
1981.
4-14. Tanis, F. J., B. N. Haack, and R. B. Fergus, "Potential Environmental
Problems Associated with In-S1tu Gasification of the Antrim Shale," in:
Eleventh 011 Shale Symposium Proceedings, Golden, CO, 12-14 April 1978.
Colorado School of Mines Press, 1978. pp. 47-54.
4-152
-------
4-15. U.S. Environmental Protection Agency, Pollution Control Technical
Manual for Exxon Donor Solvent Direct Coal Liquefaction, EPA-600/8-83-
007. EPA, Washington D.C., April, 1983.
4-16. Forney, A. J., et al., Trace Element and Major Component Balances
Around the Synthane PDU Gas1f1er. PERC/TPR-75-1. Pittsburgh Energy
Research Center, ERDA, Pittsburgh, PA., August 1975.
4-17. Bombaugh, K. J., Analyses of Grab Samples from Fixed-Bed Coal Gasifica-
tion Processes, Final Report. EPA-600/7-77-141; PB 276608. Radian
Corp., Austin, TX, December 1977.
4-18. Farrier, D. S., et al., "Environmental Research for In-Situ Oil Shale
Processing," in: Eleventh Oil Shale Symposium Proceedings, Golden, CO,
12-14 April 1978. Colorado School of Mines Press, 1978. pp. 81-99.
4-19. TRW and Denver Research Institute, Trace Elements Associated with Oil
Shale and Its Processing. EPA-908/4-78-003. Redondo Beach, CA, and
Denver, CO, May 1977.
4-20. Occidental 011 Shale, Inc., Environmental Assessment: DOE/Occidental
Oil Shale, Inc., Cooperative Agreement. Phase II, Oil Shale Retorting,
Logan Wash Site, Garfield County, Colorado. DOE/EA-0095. Grand
Junction, CO, November 1979.
4-21. Fruchter, J. S., et al., Source Characterization Studies at the Parahc
Semlworks 011 Shale Retort. PNL-2945. Battelle Pacific Northwest
Labs., Richland, WA, May 1979.
4-22. Bates, E. R., and T. L. Thoem, eds., Perspective on the Emerging Oil
Shale Industry. EPA-600/2-80-205a. January 1981.
4-153
-------
4-23. Cleland, J.G., andG.L. Klngsbury, Multimedia Environmental Goals fo/
Environmental Assessment. Volume II. MEG Charts and Background
Information. EPA-600/7-77-1365. Research Triangle Institute, Research
Triangle Park, NC, November 1977.
4-24. Chrlstensen, H.E., and E.J. Fa1rch1ld, Registry of Toxic Effects of
Chemical Substances: 1976 Edition. HEW Publication No. (NIOSH)76-191.
National Institute for Occupational Safety and Health.
4-25. American Conference of Governmental Industrial Hyg1en1sts. Documen-
tation of the Threshold Limit Values for Substances in Workroom Air
with Supplements, Third Edition. American Conference of Governmental
Industrial Hygienlsts, Cincinnati, OH, 1974.
4-26. Sax, N.I., Ed. Dangerous Properties of Industrial Materials, Fourth
Edition. Van Nostrand Relnhold Co., New York, NY, 1975.
4-27. Occupational Safety and Health Administration. Occupational Exposure
to Benzene: Emergency Temporary Standards, Hearing. Department of
Labor. OSHA Title 29, Part 1910. 1n: Federal Register, Vol. 42, No.
85, 1977. pp. 22516-22529.
4-28. National Institute for Occupational Safety and Health. Criteria for a
Recommended Standard: Occupational Exposure to Benzene. PB 246 700.
1974.
4-29. Hamblln, D.O., Aromatic N1tro and Amino Compounds. In: Patty, F.A ,
Ed., Industrial Hygiene and Toxicology, Second Revised Edition, Vol. 2.
Interscience Publishers, New York, NY, 1963.
4-154
-------
4-30. Searle, C.E., Ed. Chemical Carcinogens. ACS Monograph 173. American
Chemical Society, Washington, D.C., 1976.
4-31. Flshbein, L., W.G. Flamm, and H.L. Falk. Chemical Mutagens:
Environmental Effects on Biological Systems. Academic Press, New York,
NY, 1970.
4-32. Grant, E.G., and R.S. Leavenworth, Statistical Quality Control, Fifth
Edition. McGraw-Hill, New York, NY, 1980. pp. 286-287.
4-33. Box, E.P., and G.M. Jenkins, Time Series Analysis: Forecasting and
Control. Hoi den-Day, Inc., San Francisco, CA, 1976.
4-34. Droper, N.R., and H. Smith, Applied Regression Analysis. John Wiley
and Sons, Inc., 1968.
4-35. Morrison, D.F., Multivariant Statistical Methods. McGraw-Hill, New
York, NY, 1967.
4-36. Goodman, L.A., Analyzing Quantitative/Categorical Data. Able Books,
MA, 1978.
4-37. American National Standards Institute, Guide for Quality Control and
Control Chart Method of Analyzing Data. ANSI, Inc., New York, NY,
1959.
4-38. Hlllier, F.S., "X Chart Control Limits Based on a Small Number of
Samplings," in: Industrial Quality Control. 1974. pp. 24-29.
4-39. Miller, I., and J.E. Freund, Probability and Statistics for Engineers.
Prentice-Hall, NJ, 1965. pp. 167-170.
4-155
-------
4-40. Beyer, W.H., Handbook of Tables for Probability an-1 Statistics.
Chemical Rubber Company, Cleveland, OH, 1966. pp. 83-88.
4-41. Hollander, M., and D.A. Wolfe* Nonparametrlc Statistical Methods. John
Wiley and Sons, Inc., New York, NY. pp.67-82.
4-156
-------
SECTION 5
AMBIENT MONITORING
Ambient monitoring 1s a key link defining the relationship between
emissions from synthetic fuels production and Impacts on human health and f-.e
environment. Ambient monitoring Identifies potential contaminants 1n the
environment, 1n the vicinity of the potential receptor, so that transport and
potential degree of exposure to emissions can be estimated. Ambient monitor-
Ing Includes chemical analyses and biological studies (genotoxic, mutagenic*
and aquatic and terrestrial effects) on samples obtained from the environment
1n the vicinity of a synfuel facility. The biological component of the
ambient program should provide help 1n identifying effects associated with
plant discharges. The media which act as pathways for pollutant movement and
which require monitoring Include water within soil (I.e., vadose or unsatur-
ated zone), surface aquifers, deep aquifers, surface waters, and the atmos-
phere. Ambient monitoring, as considered here, also Includes monitoring of
the soil itself.
While a large body of literature exists on the subject of ambient moni-
toring, certain references are of particular importance. Key references deal-
Ing with groundwater and the unsaturated zone are: 5-1, 5-2, 5-3 and 5-4; for
the analyses of organic compounds: 5-5, 5-6, 5-7, 5-8, 5-9 and 5-10; for bio-
accumulation: 5-11 and 5-12; for genotoxlns: 5-13, 5-14, 5-15, 5-16, and
5-17; for analysis of complex mixtures: 5-18; and for an overall approach to
monitoring a synthetic fuel facility: 5-19 and 5-20.
This section on ambient monitoring has a format similar to Section 4 for
source monitoring. Section 5.1 describes suggested total data base needs to
consider in designing the ambient portion of a monitoring plan or outline
(analogous to Section 4.1), including substances of potential Interest for
monitoring and criteria for selecting locations for ambient monitoring
stations. Section 5.2 describes approaches for conducting the ambient moni-
toring program (including the concept of phasing and discussions of the timing
5-1
-------
and frequency of monitoring), analogous to Sections 4.2 and 4.3. Section 5.3
addresses possible alternative ambient sampling and analytical techniques,
analogous to Section 4.4. Section 5.4 discusses regional considerations in
selecting aspects to be emphasized 1n ambient monitoring. Section 5.5 con-
tains references for the whole section. While source monitoring occurs only
during plant operation, ambient monitoring also includes the pre-constructlon
and construction periods.
5.1 AMBIENT MONITORING DATA BASE SUGGESTIONS
5.1.1 Monitoring Suggestions to Define the Data Base
011 shale, coal and tar sands, the basic resources for synthetic fuels
plants, are of sedimentary origin. They are largely organic substances rich
1n heterocycllc nitrogen, oxygen, and sulfur compounds; polycycllc aromatic
compounds; and inorganic mineral Impurities. The oil shale, coal or tar sands
processed at a specific site will contain varying amounts of complex organo-
metallic materials depending on the meteorological, biological, and physical
forces affecting bed formation. Consequently, each synfuel facility will have
Its own chemical "signature" depending on the ratios of these resource con-
stituents and the manner in which they are converted into organic and inor-
ganic pollutants 1n various solid, aqueous and airborne emissions.
In view of the wide array of potential site-specific emissions, the
monitoring suggestions 1n Section 4.1.2 for the source discharge data base
include the following elements:
• survey analytical techniques—well-defined screening
procedures for a variety of substances. The survey
approach avoids the need to judge, j priori, which
specific substances might be discharged to the ambient
environment from a specific synfuels plant.
• specific component analyses—analyses for individual sub-
stances (or properties, such as BOD) of regulatory or
other interest.
5-2
-------
• biological tests
In selecting the scope of the data base for ambient monitoring around a
facility, the monitoring plan designer should:
• pay close attention to plans for the source monitoring
data base (survey techniques, specific component analyses,
bioassays); and
• consider the groupings of chemicals defined in Appendix C
and specific biological tests (Appendices D and H) which
are of particular concern for evaluating possible impacts
on human health and the environment.
The survey techniques, specific component analyses and bio-assays
suggested for source monitoring are summarized in Tables 4-4 through 4-6
(supplemented by Tables 4-7 through 4-9). A list of some specific substances
likely to be detected in source surveys is Included in Tables 4-10 and 4-11.
The needs of the ambient monitoring program might vary from these source
tables 1n some cases due to applicability of techniques and transformation/
dilution of substances in the ambient environment. However, much of the
Information can be useful 1n the ambient program design, and use of the tables
should provide a basis for correlating the results of source and ambient
monitoring.
The ambient monitoring effort may have different emphasis from the source
effort. For example, differences might arise due to chemical transformation
in the environment, dilution of the substances through dispersion, and media
effects (e.g., substances emitted in gaseous form might appear/accumulate in
surface waters or soil). Accordingly, in addition to the substances listed in
the source monitoring tables, the ambient monitoring effort should consider
the groups of chemicals described in Appendix C. Most of these chemicals
should, if present, be detected by the survey techniques mentioned previously,
as well as those listed in Appendices D, E, and F. In addition to the acute
bioassays listed in Table 4-9, the ambient program might also address the
extended, ambient bioassays described in Appendix H (including terrestrial
effects, perlphyton, and aquatic bioaccumulation monitoring).
5-3
-------
As noted above, the source monitoring techniques presented in Tables 4-4
through 4-6, in Section 4.4, and in Appendix A will be applicable to most sub-
stances or classes of compounds of interest in ambient monitoring. In partic-
ular, the methods of analysis will be applicable to samples collected in both
the source and ambient monitoring programs (criteria pollutants in ambient air
are an exception; special requirements are described in Appendix D).
Different sample collection and preparative methods, however, will be
required for the ambient monitoring program. The concentrations of substances
of Interest generally will be much lower in ambient media than in source dis-
charge streams. Therefore, larger sample volumes, longer sample collection
periods, and techniques for concentrating samples to bring analytes into the
detectable range will be required for ambient samples. Methods of sample col-
lection and analysis for ambient air, surface water, soil and groundwater are
discussed in detail 1n Appendices D, E, F, and G.
5.1.2 Location of Ambient Sampling Sites
A key element In developing the ambient data base is placement of sam-
pling stations. Monitors should be sited so that any substances from the syn-
fuels plant that affect the environment are detected, and so that the Impacts
of the plant can be distinguished from those of neighboring facilities.
In addition to obvious considerations such as accessibility, availability
of electrical power, and relationship to possible Interfering pollutant
sources, Important factors 1n selecting sampling sites are meteorology and
topography. Dispersion modeling, if required to support PSD permit applica-
tions, will provide site-specific predictions of emission transport patterns
that will be useful in siting air monitoring stations. The unidirectional
movement of rivers and most groundwaters will, to a large extent, limit
choices 1n placement of water samplers. However, both air and water monitor-
Ing will require site-specific strategies that provide both background
5-4
-------
(upstream, upwind) data and impact (downstream, downwind) data on the contri-
bution from the synfuels plant. The approach to monitoring controlled emis-
sions is well established and a detailed discussion is beyond the scope of
this brief document. Detailed Information can be found in references 5-21
through 5-32.
It 1s Important that air monitoring stations provide data that are repre-
sentative of background conditions (upwind of plant) and impact conditions
(downwind of plant). If a wind rose pattern indicates that wind direction
variations are seasonal* a number of stations may be needed around the perl-
meter of the facility. If a downwind impact station regularly samples emis-
sions from other local sources, relocations should be considered. Meterologi-
cal data should be collected to provide a basis for data interpretation.
5.2 APPROACHES FOR AMBIENT MONITORING
5.2.1 Pre-construction Monitoring
Pre-constructlon monitoring should be conducted to characterize the
nature and extent of existing substances 1n the air, water, and soil in the
vicinity of a proposed synfuel facility. Knowledge of these background con-
centrations is needed to assess the Impact of the proposed source. Baseline
meteorological and hydrological conditions should be monitored in addition to
the substances expected to be emitted from the facility. Sampling sites
should be located at the points of maximum expected concentrations due to
emissions from the proposed facility, from existing sources, or the combined
effects of both.
It would be desirable in most cases to conduct pre-construction monitor-
ing for the pertinent portions of the entire suggested (chemical and biologi-
cal) data base, as described in Section 5.1.1. The frequency and duration of
pre-construction monitoring would depend upon the capabilities and costs of
available ambient monitoring techniques (discussed in Appendices D through H),
and on expected seasonal variations in meteorology and hydrology. The
5-5
-------
selected frequency also would depend on the precision of the ambient measure-
ments and the desired statistical accuracy of the pre-construction results.
The statistical considerations in selecting source monitoring frequency and
duration discussed in Section 4.2.1.2 should also apply to ambient monitoring.
It is important that pre-construction monitoring begin early enough and
last long enough (preferably at least one year) to collect data that are
representative of normal seasonal changes. If a longer pre-construction moni-
toring period is possible and if additional accuracy in results is desirable,
the duration might be lengthened as discussed in Section 4.2.1.2 for source
monitoring. High priority should be placed on preparing and implementing the
pre-construction portion of the monitoring plan, so it can be underway while
detailed plant design and other pre-construction planning efforts proceed.
5.2.2 Construction Monitoring
Although the period of construction of a synfuel facility is brief com-
pared to its operational life, it 1s during construction that the most
dramatic alterations to the site, and on occasion to adjacent areas, will
occur. Such large-scale activities, which are by nature relatively uncon-
trolled, require careful and continuous monitoring to assess the impact on the
surrounding environment.
Construction monitoring is conducted from the initial phases of site
preparation through completion of facility construction. It is essentially a
continuation of the baseline monitoring initiated in the pre-construction
phase. Its main function 1s to detect changes in environmental conditions
that may be attributable to construction activities in order to minimize
adverse impacts. Data acquired during construction will not only aid in the
identification of impacts associated with construction activities per se,
but also will expand the base of available background data collected in pre-
construction monitoring. While construction monitoring requirements generally
will be defined by the permitting process, they also should be addressed spe-
cifically in the monitoring outline and plan.
5-6
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Ambient Impacts from the construction of synfuels plants will be very
similar to impacts from the construction of fossil fuel processing plants* and
the same is true for the associated construction monitoring. Typical con-
struction activities such as blasting* excavation, hauling, clearing and
burning of vegetation, open pit dumping, and stock-piling of sand, gravel and
other materials on site can result in excessive partlculate emissions. In
general, emissions of gaseous pollutants will not be significant during the
construction phase. However, the use of diesel engines in both construction
machinery and electrical generators will contribute to increased emissions of
NO , CO and unburned hydrocarbons. If pre-constructlon monitoring indicates
X
that levels of these pollutants are approaching National or state air quality
standards, monitoring downwind of the site should be planned.
As noted 1n 5.1.1, the organic resources used as raw materials for
synthetic fuel processes can be rich in sulfur, nitrogen, and organo-metall ic
compounds. In the event these compounds are exposed to the atmosphere, either
through test burns (e.g., during in-situ retort construction) or as waste
materials removed from the site, appropriate monitoring should be done. Such
monitoring should be designed to account for the specific emission expected
from construction or pre-operational activities. For example, sulfur dioxide
and particulate monitoring would be performed when combustion trials occur,
and elemental analyses of particulate samples and ambient NMHC measuremets
would be done 1f mine waste or other residual organic materials were allowed
to accumulate on site.
The schedule and duration of ambient air monitoring should correspond to
the character of the activities at the construction site. At a minimum,
upwind-downwind particulate sampling sites should be established and operated
on an every-s1x-day schedule. If significant N02 levels have been measured
during pre-constructlon monitoring, a downwind continuous NO.- monitoring pro-
gram should also be considered. Early 1n the construction phase, special pur-
pose upwind-downwind property line studies would be useful in determining the
5-7
-------
Impact of specific participate sources such as loading facilities, truck traf-
fic on access roads, and excavation and blasting. Finally, special activities
at the site (e.g., disposal of waste materials by burning), should be moni-
tored by the appropriate method at the time of occurrence.
Anticipated Impacts to the soil and surface/ground-water systems from
synfuels facility construction are also similar to those expected in conven-
tional plant construction. Necessary modifications to the existing topography
associated with site preparation, road and pipeline construction, etc., could
result 1n Impacts on runoff, erosion, and sedimentation rates. Accidental
spills of oil, grease, or other materials on-site during construction activi-
ties could result in environmental contamination. Other potential sources of
construction phase contaminants Include wastewater from sanitary facilities
and mine dewaterlng (where applicable), and landfill of construction waste.
Potential impacts specific to synfuels production are due to the nature
of the raw materials and the modes of extraction peculiar to the industry.
The extremely large volumes of material Involved in either surface retorting
or 1n-s1tu gasification of oil shale present a unique set of potential envi-
ronmental problems. Stockpiled raw materials (surface-mined coal or lignite,
oil shale, etc.) and/or overburden removed during mine construction could
potentially generate add, alkaline or trace element contaminated runoff or
leachate. In-situ extraction technologies requiring fracturing of source
materials prior to gasification could contribute to deterioration of ground-
water quality if resulting fractures hydraulIcally connect shallow potable and
deeper saline aquifers. Thus, the construction monitoring program might
1nclude:
• stream gaging - to identify variations in surface water
flow beyond expected seasonal/episodic fluctuations;
• surface water quality monitoring - including chemical
analysis, turbidity, and sedimentation rate determina-
ti ons;
5-8
-------
• ground-water monitoring - including sampling and water
quality analysis and water table measurement;
• soil sampling and analysis - especially in the vicinity of
known spills;
• runoff from overburden - special emphasis should be placed
on the analysis of soluble metals (e.g.» Se, As, Mo) under
the alkaline runoff conditions potentially present in
western soils.
5.2.3 Operational Monitoring
It is suggested that ambient monitoring conducted during plant operation
employ a phased monitoring approach. A phased approach offers the opportunity
to tailor the monitoring program to the specific site, providing extended
coverage of a fairly extensive data base while reducing the extent and cost of
the monitoring program. One concept for a phased source monitoring program is
discussed in detail in Section 4.2; some alternatives (including an alterna-
tive involving no phasing) are addressed in Section 4.3. These concepts
should apply to the ambient monitoring program as well.
5.2.3.1 Phase 1 Monitoring
When a synthetic fuels plant has achieved normal operation* the compre-
hensive Phase 1 ambient monitoring program might logically begin. In Phase 1,
samples from all media (vadose zone, surface aquifers, deep aquifers, surface
waters, the atmosphere and the soil) are surveyed for the pertinent portions
of the total data base. As described in Section 5.1.1, this data base includ-
es the application of survey analytical techniques, specific component analy-
ses ana biological testing. The Phase 1 design would include tests applicable
to each medium. Permit-required monitoring would be superimposed on this sur-
vey monitoring.
The focus of this phase would be to identify those substances actually
present in the ambient environment as a result of plant operation. The
results of this Phase 1 program would be used for two purposes:
5-9
-------
• to compare the results to the pre-construction monitoring
data base, to develop initial conclusions regarding the
environmental Impact of the synfuels plant;
• to design a reduced Phase 2 operational monitoring
program, as discussed 1n Section 5.2.3.2.
The frequency with which the various monitoring techniques (survey
analytical techniques, specific component analyses, and biological tests) are
conducted during Phase 1 depends on both practical and statistical considera-
tions. From a practical standpoint, the frequency will be influenced by the
capabilities and the costs of the applicable ambient monitoring techniques,
described 1n Appendices D through H. From a statistical standpoint, the
frequency (and the duration) of Phase 1 will be Influenced by desired accuracy
of the results, the variability in concentrations of the substances being
monitored, and variations 1n hydrologic and meterologic conditions at the
site. The suitable frequency might vary from substance to substance. Statis-
tical considerations in selecting monitoring frequency and duration for source
monitoring discussed in Section 4.2.1.2 should be applicable to ambient moni-
toring as well.
Phase 1 monitoring would continue for some limited period after routine
plant operation begins. The duration of Phase 1 could be selected based on
practical and statistical considerations and should Include major seasonal
variations 1n meteorological and hydrological conditions. A reasonable mini-
mum duration will probably be about one year for most substances in most
media, but a longer period might be required for groundwater monitoring,
depending on pollutant migration rates.
Initial operation of a synfuels plant will generally involve a phased
startup period. During startup plant discharges will not be representative of
routine operation. In particular, excursions in the compositions of plant
discharges are likely to occur; hence the startup period would not generally
be suitable for Phase 1 (data base development) monitoring. Monitoring during
the startup period can be used to validate ambient sampling and analytical
5-10
-------
procedures and to train monitoring personnel in preparation for formal Phase 1
monitoring. These startup results can also be used to gain an understanding
of the substances present in the ambient environment due to plant operation,
and to test the relationships between data collected by source and ambient
monitoring. Compliance monitoring required by permits would proceed as
scheduled during the startup period.
Possible methods of designing a startup source monitoring effort that
will achieve appropriate quality assurance/protocol validation objectives are
discussed in Section 4.2.1.3.
5.2.3.2 Phase 2 Monitoring
The intent of Phase 2 is to provide extended-term tracking of the Phase 1
data base, through a monitoring effort that is reduced in comparison with the
Phase 1 program. The Phase 2 program should provide a data base reflecting a
range of plant cycles/operating conditions. It should also provide a suffi-
cient data history to enable reliable extrapolation of the data base to future
facilities.
Three alternative approaches are discussed in Sections 4.2 and 4.3 for
design of Phase 2 of the source monitoring program. The same approach can be
applied to ambient monitoring.
• Use the Phase 1 results to select a limited number of
"indicator" parameters to represent the data observed
during Phase 1. Phase 2 monitoring would then address
only those indicators. Portions of Phase 1 would be
repeated if an excursion in an indicator suggests that the
represented substances might also have varied.
• Use the Phase 1 results to decide which of the substances/
parameters observed in Phase 1 should continue to be
monitored; discontinue monitoring for the other sub-
stances, unless subsequent data suggest that monitoring
for these (or additional) substances should be resumed.
5-11
-------
• Continue the full Phase 1 program for some period (several
years), without attempting to design a reduced Phase 2
program.
The first alternative approach above Involves several decisions:
What criteria can be used to determine when one substance/
parameter might serve as a Phase 2 Indicator for others?
Suggestions concerning this Issue are presented 1n Section
4.2.2.1 (Including a discussion of statistical considera-
tions, and including Table 4-20, which suggests certain
substances that might be Investigated as potential indica-
tors). Where substances of particular interest in the
ambient monitoring program (Appendix C) are not specifi-
cally listed in Table 4-20, potential indicators might be
selected for these substances based on the results of
Phase 1 monitoring and chemical and engineering judgment.
How frequently should Phase 2 monitoring be conducted?
This Issue 1s decided based on practical and statistical
considerations, as discussed in Section 4.2.2.2 as well as
variations in meteorological and hydrologlcal conditions.
How should Phase 1 and Phase 2 results be compared, and
how large an excursion might be permitted in the Phase 2
indicator before Phase 1 is repeated for the substances
represented by that Indicator? Statistical considerations
for addressing this Issue are discussed in Section
4.2.2.2.
With the Phase 2 indicator approach, the Phase 1 data base would be updated on
a number of occasions, as discussed in Section 4.2.2.3.
The preceding discussion concerning phased approaches applies primarily
to monitoring for chemical substances/parameters and to some short-term
bio-assays. By comparison, some of the biological tests (such as the aquatic
bio-accumulation test) might be inherently long-term, and hence not amenable
to the type of phasing envisioned here.
5-12
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5.3 ALTERNATIVE AMBIENT MONITORING PROCEDURES
A wide variety of alternative sampling and analytical procedures can be
considered for the development of the data base described in Section 5.1.1* in
all of the media of interest (vadose zone, surface aquifers, deep aquifers,
surface waters, the atmosphere and the soil). Alternative procedures are
described in Appendices D (air monitoring), E (water monitoring) and F (soil
monitoring). Appendix G discusses some techniques for groundwater monitoring
(of special concern for 1n-situ synfuels processes and some solid waste dispo-
sal operations).
Screening procedures for the determination of organic compounds 1n air
and water, including sample collection, extraction, purification, and analysis
are provided in Appendices D, E, and F.
Biological tests for the presence of airborne genotoxic and mutagenic
agents are discussed in Appendix D. Special terrestrial and aquatic monitor-
ing techniques which are suggested for incorporation into an ambient monitor-
ing plan are described in Appendix H.
5.4 SPECIAL REGIONAL CONSIDERATIONS
Although 1t 1s important to survey the environment near synthetic fuels
facilities for all groups of compounds of concern, certain pollutants or
monitoring needs are likely to warrant special regional attention. Such
variations in regional emphasis need to be considered in each monitoring plan
and in any trend toward standardization of monitoring plans for all U.S.
synfuels facilities. A few of these regional concerns are highlighted In this
section. They should be viewed as examples of inherent variations in the
relative importance of certain substances or characteristics from a geograph-
ical perspective.
5-13
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5.4.1 Acidity/Alkalinity
The oxidation and dissolution of pyrite with the liberation of acid is
responsible for the acid mine drainage problems which are a concern associated
with the development of coal resources in the eastern United States. In the
West, excessive amounts of alkaline calcite and dolomite in overburden mate-
rial, coupled with sulfides, result in high total dissolved solid concentra-
tions in surface waters and groundwaters. While decreasing the mobility of
most metal species by increasing pH values, this process enhances the trans-
port of other potential contaminants such as molybdenum, fluoride, boron,
arsenic, selenium, and sulfate. These elements and their compounds may pose
long-term detrimental environmental effects associated with chronic leaching
of alkaline spoils (5-33, 5-34).
5.4.2 Sulfur and Trace Elements
Western lignites and subbitumlnous coals are low in sulfur content (usu-
ally less than 0.5 percent by weight), whereas the bituminous formations in
the midwest may contain up to eight times as much sulfur (as high as 4.0
percent by weight, Reference 5-35). This disparity in sulfur levels can have
a direct bearing on the magnitude of both water discharges and airborne
emissions of inorganic and organic sulfur compounds.
Generally, coals in western states contain lower concentrations of envi-
ronmentally objectionable trace elements than do the coals of eastern or
midwestern states. However, the highest concentrations of arsenic, antimony,
beryllium, cadmium, and selenium generally occur in coals from western states,
and lead, mercury, and zinc are highest in eastern states. Appalachian coals
also can be unusually high in beryllium, whereas the Powder River Basin coals
of southeastern Montana and northwestern Wyoming are unusually low in most
environmentally hazardous trace elements (5-36). For a current comprehensive
review of trace elements of health and environmental concern in U.S. coals,
see Reference 5-37.
5-14
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5.4.3 Radioactive Materials
Radioactive Isotopes can be found 1n coals of all ranks and are more
prevalent 1n some lignite formations from uran1um-r1ch areas such as the
southwest. Such formations are covered with uran1um-r1ch overburden. In some
places, high levels of uranium together with Inorganic sediment/ sand, dirt,
ana other impurities extend downward into the lignite formation.
Extraction, combustion, gasification and/or liquefaction of such a
resource can result in the release of trace quantities of radioactive substan-
ces. Radioactivity monitoring should be included in the ambient monitoring
plan for all synfuels plants. Depending on the concentration of radioactive
isotopes in the feedstock (coal, oil shale, or tar sands), an Increased
emphasis on radioactivity monitoring might be warranted for some sites.
5.4.4 Arid Environments
Synthetic fuel development in the West will occur largely 1n arid or semi-
arid areas lacking substantial amounts of uniformly distributed water. Syn-
fuels facilities will require large amounts of process water, and the heat and
pressures required for processing cause additional water loss through evapora-
tion. These water losses could have a significant long term impact on
ground/surface water flows, pollutant mobility and transformation, and diver-
sity of natural biota near project sites. Detection of such effects may
require increased emphasis on the ancillary monitoring of meteorological
conditions such as humidity, solar and terrestrial radiation, and precipita-
tion, and on the monitoring of terrestrial effects.
5-15
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5.5 REFERENCES FOR SECTION 5
5-1. Everett, L.G. Groundwater Monitoring Guidelines and Methodology for
Developing and Implementing a Groundwater Quality Monitoring Program.
General Electric Company* Schenectady, NY, 1980.
5-2. U.S. Environmental Protection Agency. Monitoring 1n the Vadose Zone:
A Review of Technical Elements and Methods. EPA-600/7-80-134,
Environmental Monitoring Systems Laboratory, Las Vegas, NV, 1980.
5-3. National Water Well Association. Manual of Ground Water Quality
Sampling Procedures. 500 West Wilson Bridge Rd., Worthlngton, OH,
1981.
5-4. A series of 1981-1983 articles on Methods for Monitoring Pollutant
Movement in the Vadose Zone. Ground Water Monitoring Review Vol. 1(2):
44-51; Vol. 1(3): 32-41; Vol. 2(1): 31-42; and Vol. 3(1):155-166.
5-5. U.S. Environmental Protection Agency. Identification and Analysis of
Organic Pollutants 1n Water. L.H. Keith, ed. (ISBN-0-250-40131-2) Ann
Arbor Science Publishers, Inc., Ann Arbor, MI, 1979.
5-6. U.S. Environmental Protection Agency. Master Scheme for the Analysis
of Organic Compounds 1n Water - Interim Protocols. Environmental
Research Laboratory, U.S. Environmental Protection Agency, Athens, GA,
1980.
5-7. American Chemical Society. Monitoring Toxic Substances. D. Schuetgle,
ed. ACS Symposium Series 94, Washington, DC, 1979.
5-8. Jolley, R.L. Concentrating Organlcs 1n Water for Biological Testing.
Environmental Science and Technology, 15(8)-.874-880, 1981.
5-16
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5-9. U.S. Environmental Protection Agency. Procedures for Level 2 Sampling
and Analysis of Organic Materials. EPA-600/7-79-033 (NTIS PB 293 800),
Industrial Environmental Research Laboratory, Research Triangle Park,
NC, 1979.
5-10. Klngsbury, G.L., J.B. White, and J.S. Watson. Multimedia Environmental
Goals for Environmental Assessment. Volume 1, Supplement A.
EPA-600/7-80-041, Industrial Environmental Research Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC, 1980.
5-11. Hamellnk, J.L., and J.G. Eaton. Proposed Standard Practice for Con-
ducting B1oconcentrat1on Tests with Fishes and Saltwater Bivalve
Molluscs. ASTM Committee F-47, American Society for Testing and
Materials, Philadelphia, PA, 1981.
5-12. Frlant, L., and J.W. Sherman. The Use of Algae as Biological Accumu-
lations for Monitoring Aquatic Pollutants. In: Second Interagency
Workshop on In-S1tu Water Quality Sensing: Biological Sensors.
Pensacola Beach, FL, April 28-30, 1980. EPA/NOAA/USACE/USGS, 1980.
pp. 285-306.
5-13. PelHzzarl, E.D. Integratory Microbiological and Chemical Testing 1n
the Screening of Air Samples for Potential Mutagenldty. In: Proceed-
ings, Second Symposium on Application of Short-term Blossays 1n the
Fract1onat1on and Analysis of Complex Environmental Mixtures.
WllHamsburg, VA, March 4-7, 1980. Plenum Press, NY, 1981.
5-14. Lentas, J. Overview: Assay and Exposure Technology of In Vitro M1cro-
blal Assay Systems Applied to Airborne Agents. In: Proceedings,
Symposium on the Genotoplc Effects of Airborne Agents, Brookhaven
National Laboratory, February 9-11, 1981. Available from Plenum Press,
NY. (In Press).
5-17
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5-15. Kolber, A., et al. Collection, Chemical Fractionatlon, and Muta-
genlclty Bloassay of Ambient A1r Participate. In: Proceedings, Second
Symposium on Application of Short-term Bioassays 1n the Fractionatlon
and Analysis of Complex Environmental Mixtures. W1ll1amsburg, VA,
March 4-7, 1980. Plenum Press, NY, 1981.
5-16. Ames, B.N., J. McCann, and E. Yamasaki. Methods for Detecting
Carcinogen and Mutagens with the Salmonella/Mammal1an-M1crosome
Mutagen1c1ty Test. Mutation Research, 31:347-364, 1975.
5-17. U.S. Environmental Protection Agency. Short-term Tests for
Carcinogens, Mutagens, and Other Genotoxlc Agents. EPA-625/9-70-003,
Health Effects Research Laboratory, Research Triangle Park, NC, 1979.
5-18. Natusch, David F.S., and Phillip K. Hopke. Analytical Aspects of
Environmental Chemistry. John WHey and Sons, NY, 1983.
5-19. U.S. Environmental Protection Agency. Environmental Perspective on the
Emerging 011 Shale Industry, E.R. Bates and T.L. Thoem, eds.
EPA-600/2-80-205a, Industrial Environmental Research Laboratory, U.S.
Environmental Protection Agency, Cincinnati, OH, 1981.
5-20. Dal ton, Dal ton, and Newport. Draft Technical Monitoring Reference
Manual for Commercial Low/Medium Btu Coal Gasification Plants.
Contract No. 68-03-2755, prepared for U.S. Environmental Protection
Agency, Washington, DC, 1981.
5-21. Langley, G.J., and R.G. Wetherold. Evaluation of Maintenance for
Fugitive VOC Emissions Control. EPA-600/2-81-080 (NTIS PB 81-206-005),
Industrial Environmental Research Laboratory, Cincinnati, OH, 1981.
5-22. Goulden, P.O. Environmental Pollution Analysis. Heyden and San, Ltd.,
London, 1978.
5-18
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5-23. Dal ton, Dal ton, and Newport. Draft Technical Monitoring Reference
Manual for Commercial Low/Medium Btu Coal Gasification Plants. Con-
tract No. 68-03-2755, prepared for U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1978.
5-24. Office of A1r Quality Planning and Standards. Ambient Monitoring
Guidelines for Prevention of Significant Deterioration (PSD).
EPA-450/2-78-019 (NTIS PB-283696). U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1978.
5-25. World Health Organization. Selected Methods of Measuring Air
Pollutions, Geneva, Switzerland, 1976.
5-26. American Chemical Society. Proceedings of the Fourth Joint Conference
of Sensing of Environmental Pollutants. Washington, DC, 1978.
5-27. U.S. Environmental Protection Agency. Quality Assurance Handbook for
Air Pollution Measurement Systems. Volume I—Principles. EPA-600/9-76-
005, Environmental Monitoring and Support Laboratory, Research Triangle
Park, NC, 1976.
5-28. U.S. Environmental Protection Agency. Quality Assurance Handbook for
A1r Pollution Measurement Systems. Volume II-Amb1ent Air Specific
Methods. EPA-600/4-77-027a. Environmental Monitoring and Support
Laboratory, Research Triangle Park, NC, 1977.
5-29. U.S. Environmental Protection Agency. Quality Assurance Handbook for
Air Pollution Measurement Systems. Volume Ill-Stationary Source
Specific Methods. EPA-600/4-77-027b. Environmental Monitoring and
Support Laboratory, Research Triangle Park, NC, 1977.
5-19
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5-30. U.S. Environmental Protection Agency. Handbook for Analytical Quality
Control and Radioactivity 1n Analytical Laboratories.
EPA-600/7-77-088, Environmental Monitoring and Support Laboratory* Las
Vegas, NV, 1977.
5-31. U.S. Environmental Protection Agency. Manual of Analytical Quality
Control for Pesticides and Related Compounds 1n Human and Environmental
Samples. EPA-600/1-79-008, Office of Research and Development,
Washington, DC, 1979.
5-32. National Research Council. Airborne Particles. University Park Press,
Baltimore, MD, 1979.
5-33. Brown, R. Environmental Effects of Coal Technologies: Research Needs.
MTR-79W159-03 (NTIS No. 81-220824). The MITRE Corporation, McLean, VA,
1981.
5-34. Brown, R. Health and Environmental Effects of Synthetic Fuel Facili-
ties: Research Priorities. MTR-80W348 (NTIS PB 81-212474). The MITRE
Corporation, McLean, VA, 1981.
5-35. Office of Technology Assessment. The Direct Use of Coal. Congress of
the United States, Washington, DC, 1979.
5-36. Zubonic, P. Geochemistry of Trace Elements 1n Coal. In: F.A. Ayer,
ed. Symposium Proceedings: Environmental Aspects of Fuel Conversion
Technology, II. EPA-600/2-76-149, (NTIS No. PB257-182). Industrial
Environmental Research Laboratory, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 1976.
5-37. National Research Council. Trace-Element Geochemistry of Coal Resource
Development Related to Environmental Quality and Health. National
Academy Press, Washington, DC, 1980.
5-20
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APPENDIX A
MEASUREMENT METHODS
Introductory Discussion A-6
Samp! 1 ng Methods A-12
S-01 Solid Waste Streams A-12
S-02 Sampling for Determination of Vapor Phase Moisture A-18
S-03 Isok1net1c Collection of Particles from Gas Streams
to Determine Mass Loading (Grain Loading) or Parti-
cle Size Distribution A-20
S-04 Removal of Moisture A-22
S-05 Vapor Phase Organlcs Collection by Sorbent Trapping A-24
S-06 Particle/Aerosol Removal from Gas Streams A-26
S-07 Collection of Vapor Phase Samples by Liquid Trapping
(Implnger Collection) A-28
S-08 Fugitive Screening for Hydrocarbons A-33
S-09 Collection of Vapor Phase Organlcs 1n Implngers A-35
S-10 Composite Sample Collection from Aqueous Streams A-37
S-ll Grab Sample Collection from Aqueous Streams A-39
S-12 Collection/Determination of Vapor Phase Components by
Sol 1 d Adsorpti on A-42
S-13 Collection of Vapor Phase Samples for Direct Analyses
(Bag or Bomb Collection) A-44
S-14 Collection of Fugitive Emissions by Bagging A-47
S-15 Collection of Fugitive Particulate Emissions A-49
A-l
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Preparative Methods A-51
P-01 Solvent Extraction of Moderately Volatile Organlcs A-51
P-02 Der1v1tlzatlon of Organic Compounds 1n Sample Extracts A-54
P-03 Thermal Desorptlon of Volatile Organic Species A-58
P-04 Solvent Partitioning of Semlvolatlle Organlcs A-61
P-05 Organic Fract1onat1on by Column (Sorbent) Separation A-64
P-06 M1croextract1 on A-67
P-01 RCRA Tox1c1ty Test Extraction Method for Solids A-70
P-08 ASTM Batch Extraction of Sol Ids A-73
P-09 Ashing, Fusion and Digestion of Solid Samples A-75
P-10 Mixed Add Digestion of Solid Samples A-77
P-ll Preservation of Aqueous Samples A-79
P-12 Add Digestion for Aqueous Samples A-83
Analytlcal Methods A-85
A-01 Gas Chromatography - Flame Photometric Detection,
Vapor Phase Samples A-85
A-02 Gas Chromatography - Flame lonization Detection,
Vapor Phase Samples A-88
A-03 Gas Chromatography - Thermal Conductivity Detection,
Vapor Phase Samples A-90
A-04 Proximate Analysis of Solid Samples A-92
A-05 Ultimate Analysis of Solid Samples A-94
A-06 Measurement of Radioactivity in Solids A-97
A-07 X-Ray Diffraction Spectrometry for Qualitative Identi-
fication of Crystalline Phases in Solid Samples A-100
A-08 Optical or Scanning Electron Microscopy (SEM) and Scanning
EM Plus Energy Dispersive Analysis of X-rays A-102
A-2
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Analytical Methods (continued)
A-09 Direct Aqueous Injection Gas Chroma tography A-104
A-10 Gas Chromatography - Nitrogen Specific Detection A-106
A-ll Gas Chromatography - Mass Spectrometrlc Detection (GC/MS)... A-109
A-12 Gas Chromatography - Flame Ion1zat1on Detection (GC/FID).... A-113
A-13 Gravimetric Estimation of Organic Content in Solvent
Extracts A-116
A-14A Estimation of Quantities of Organics by Infrared Analysis
Total Species Method A-119
A-14B Estimation of Quantities of Categories of Organics by
111 travi ol et Spectroscopy A-125
A-14C Category Identification of Organics by Low Resolution Mass
Spectrometry A-128
A-15 Specific Compound Monitoring by GC-MS A-132
A-16 High Pressure Liquid Chromatography (HPLC) A-135
A-17 Total Organic Halogen Determination (TOX) A-139
A-18 Gas Chromatography - Sulfur Specific Detection A-141
A-19 Gas Chromatography - Photoionization Detection A-143
A-20 pH Measurement A-145
A-21 Total Sol Ids Measurement A-147
A-22 Total Dissolved Solids Measurement A-149
A-23 Total Suspended Sol Ids Measurement A-151
A-24 Determination of Chemical Oxygen Demand (COD) A-153
A-25 Determination of Biological Oxygen Demand (BOD) A-156
A-26 D1 still ati on/Col orimetry (4-am1 noantipyri ne) A-158
A-27 D1 still ati on/Ti trati on A-161
A-28 Di sti 11 ati on/Col orimetry A-164
A-29 Preci pi tati on/Ti trati on A-167
A-30 Col orimetry A-170
A-3
-------
Analytical Methods (continued)
A-31 Specific Ion Electrode A-172
A-32 Cadmium Reduction/Spectrophotometry A-174
A-33 Silver Nitrate Titration with Potentiometrlc
End-point Determination A-177
A-34 lodometric Titration A-180
A-35 Turbidimetric Analyses A-182
A-36 Radioactivity A-184
A-37 Extraction/Gravimetric Analyses A-186
A-38 Ascorbic Acid Colorimetric Method for Dissolved*
Hydrolyzable or Total Phosphorous A-189
A-39 Acid/Base Titration A-192
A-40 Elemental Analysis by Inductively Coupled Optical
Emission Spectroscopy (ICP) or Atomic Absorption
Spectroscopy (AA) A-195
A-41 Spectrophotometric Determination of Nitrogen Oxides
in Vapor Phase Samples A-198
A-42 Instrumental Methods for Total Organic Carbon A-201
A-43 Infrared Analysis for Inorganic Carbon A-204
A-44 Membrane Electrode Measurement A-206
A-45 Ion Chromatography A-208
A-46 Sedimentation Solids A-211
Test Methods A-213
T-01 Laboratory Corrosion Testing of Metals A-213
T-02 Reactivity (RCRA) A-215
T-03 Pensky-Martens Closed-Cup Method for Ignitability
of Sol i ds A-217
T-04 Permeability (Hydraulic Conductivity) of Solid Waste
Samp! es A-219
A-4
-------
Test Methods (continued)
T-05 Particle-Size Distribution of Solid Samples A-221
T-06 Specific Gravity of Solid Samples A-223
T-07 In-Place Bulk Density of Solids A-225
T-08 Moisture-Density Relations of Sol Ids (Optimum
Moisture at Maximum Dry Bulk Density) A-227
T-09 Specific Conductance (Conductivity) of Aqueous
Samp! es A-230
T-10 Viscosity (Fluid Friction) Determination 1n Liquids,
Tars and Sludges A-232
T-ll Determination of Specific Surface Area of Solids A-234
T-12 Bloassay for Health Effects A-237
T-13 Bloassay Testing for Ecological Effects A-240
T-14 Opacity Measurement A-243
A-5
-------
The methods summarized 1n this appendix are grouped 1n four categories;
• Sampling - general methods for sample acquisition and
sample conditioning.
• Preparative - techniques for the Isolation of species for
analysis, or to convert the sample to a form suitable for
analysis.
• Analysis - procedures by which chemical species, classes
or groups of compounds are quantified or qualitatively
Identified.
• Test - methods which measure a physical property, charac-
teristic or effect.
Each method summary contains (where applicable):
• T1 tl e
• Analyte - components, classes of compounds, or
characteristics for analyses or test methods
• Description - brief, general discussion of the method
• Application - appropriate streams or sample types for the
method
• General Method Parameters - more detailed description of
method, reagents, equipment and Implementation. These
details are given only for generally applicable,
standardized methods and may not be appropriate for all
sample matrices or laboratory situations.
A-6
-------
• Limitations - known common interferences or problems that
may be encountered. The detailed procedures referenced
contain more extensive listings or discussions of
limitations.
• Sensitivity - the general range of precision of the
technique or instrumental detection limit.
• External Cost - the estimated cost range for an outside
contractor or service laboratory to provide a single
analytical determination, to Implement a preparative
procedure or test method for one sample, or to collect a
single sample. Travel or freight expenses are not
included.
• Internal Cost - 1) the estimated manhour range required
within the owner/operator organization for
the completion of a single analysis, test.
preparative procedure or sample collec-
tion.
2) the estimated cost range for the
acquisition of Instruments and equipment
required to perform sampling, analysis,
preparation or test methods.
• References - information sources necessary for review
prior to protocol selection and implementation. Primary
references contain specific Information which rigorously
defines each procedure.
• Alternates - method title and reference for well known
alternative approaches which may be required by the sample
matrix or data needs.
A-7
-------
The cost and sensitivity of the techniques are of such general Interest that
they may require further explanation. The external costs are the costs esti-
mated for an external (Independent) organization to perform specific tasks.
These estimates cover a range from the cost for straightforward Implementation
of the method to the cost for a complex sample or Implementation requiring
procedure validation. The external cost estimate also covers the range from a
single sample basis (more expensive) to the cost per sample on a multiple
sample basis when economy of scale 1s a factor. The external cost range 1s
relatively broad 1n many cases, but 1t should cover most situations.
The Internal costs cover the estimated range of manhours necessary for
the work to be performed within the owner or operators facility by his staff.
Like the external cost range, Internal labor estimates cover both straight-
forward and complex situations and single or multiple determinations. The
manhours given 1n Internal costs cannot be compared directly to the external
cost. External costs reflect not only a labor rate which varies with the
level of skill required by the technique* but also the various overhead bur-
dens that associated equipment costs would generate for each method. The
estimated range of capital equipment costs that the owner/operator would Incur
to provide Internal facilities for sampling* and analysis are given as addi-
tional Internal costs.
The sensitivity of each method 1s presented as the Imposed Instrumental
detection or precision limit. Many analytical techniques contain steps to
allow for sample dilution or concentration. Many of the sampling techniques
allow collection of larger samples to give more total sample mass for analy-
sis. Therefore 1t 1s difficult, 1f not misleading, to supply minimum detect-
able quantities 1n terms of stream concentrations. As a guide, however, Table
A-l gives example relationships between instrument mass detection limits,
stream concentrations and illustrative sample volumes.
The majority of the suggested methods are widely used standard
techniques. The techniques for gaseous streams rely heavily upon Title 40 of
the Code of Federal Regulations, Part 60, which contains stationary source
A-8
-------
TABLE A-l. EXAMPLE STREAM CONCENTRATIONS FROM DETECTION
LIMITS AND SAMPLE VOLUMES
Detection Limit
Gaseous*
1-10 ng
1-10 ng
10-100 ng
10-100 ng
10-100 yg
10-100 yg
Liquids
1-10 ng
1-10 ng
10-100 yg
10-100 mg
Solids
10-100 ng
1-10 mg
10-100 yg
1-10 yg
Sample Volume
1 Nm3
100 Nm3
100 Nm3
1 mL
100 Nm3
1 L
10 mL
1 L
1 L
1 L
1 9
1 9
1 kg
10 g
Stream Concentration
0.5-5 ppt (v/v)
50-500 ppt (v/v)
0.5-5 ppb (v/v)
5-50 ppm (v/v)
0.5-5 ppm (v/v)
5-50 ppm (v/v)
0.1-1 ppb (w/v)
1-10 ppt (w/v)
10-100 ppb (w/v)
10-100 ppm (w/v)
10-100 ppb (w/w)
0.1-1% (w/w)
10-100 ppb (w/w)
0.1-1 ppm (w/w)
*Assume MW ~ 50.
A-9
-------
emissions sampling and analysis methods. The IERL-RTP. Procedures Manuali
Level I Environmental Assessment was used as a primary reference for
sampling* preparative and analysis techniques for non-regulated components.
Most of the methods suggested for liquid streams are 1n the Federal Register
(vol. 44, no. 233, December 3, 1979) which cites the 1975 edition of Part 31
of the American Society for Testing and Materials (ASTM) Annual Book of ASTM
Standards* the American Public Health Association 14th edition of Standard
Methods for the Examination, of. Water and, Wast.ewa.ter and the EPA Methods .of
Chemical Analysis of Water and Wastes.. The methods suggested for solid
streams are primarily ASTM techniques. Methods for analysis of sol Ids, after
preparative ashing or digestion, follow the aqueous analytical techniques
outlined above. The suggested analytical techniques for organic species from
aqueous and solid samples also follow the Federal Register (vol. 44, no. 233,
December 3, 1979).
Some cross-references to sampling, preparative and analytical methods are
included in the method descriptions. Many combinations can be made between
preparative options for organlcs and organic analysis techniques, as shown in
Figure A-l.
A-10
-------
Preparative Techniques
Solvent Extraction (P-01)
1 Col umn
1-Clean Up (P-05)
Sol vent
Partitioning (P-04)
LDeMvitizatlon (P-02)
EXTRACT
Analytical Techniques
-GC-MS (A-ll)
-GC-FID (A-12)
-GC-PID (A-19)
-GC-FPD/HECD-S (A-18)
-GC-NP/HECD-N (A-10)
-HPLC (A-16)
-GC-MS-SCM (A-15)
-SPECTRA (A-14)
LGRAV (A-IS)
Purge and Trap (P-03)
Thermal
Desorptlon (P-03)
-GC-MS (A-ll)
-GC-FID (A-12)
-GC-PID (A-19)
-GC-FPD/HECD-S (A-18)
-GC-NP/HECD-N (A-10)
-GC-MS-SCM (A-15)
M1croextraction (P-06)
EXTRACT
-GC-MS (A-ll)
-GC-FID (A-12)
-GC-PID (A-19)
-GC-FPD/HECD-S (A-18)
-GC-NP/HECD-N (A-10)
-GC-MS-SCM (A-15)
Direct
Aqueous
Injection (A-09)
-GC-MS (A-ll)
-GC-FID (A-12)
-GC-PID (A-19)
-GC-FPD/HECD-S (A-18)
-GC-NP/HECD-N (A-10)
-GC-MS-SCM (A-15)
( ) Method number for general description of technique
Figure A-l. Organic Preparative and Analytical Technique
Associative Flow-Chart
A-ll
-------
METHOD NUMBER: S-01
SAMPLING METHOD: Solid Waste Streams
DESCRIPTION: There are several variations of sampling appropriate for
solid waste. The simplest is simple random sampling which is
accomplished by collecting a one-time grab sample. If the stream
is stratified, a number of grab samples or a cross section such as
a coring technique should be used to collect a representative sample
of the stratifications (unless only a particular part of the stream
is of interest). If the stream varies or is stratified and an
"average" sample is needed, systematic random sampling is required.
The final variation of grab sampling is composite sampling which is
systematic grab sampling as a function of time or location with a
resultant summation (compositing) of samples for the designated
time period. Compositing can be accomplished by a combination of
mixing and random splitting of the total material from the grab
samples.
APPLICATIONS: Any of the sampling methods described above may be
appropriate; the method is selected according to the testing
objective and homogeneity of the stream. Systematic random and
composite sampling provide an average sample which is sometimes
required for compliance testing and provide a statistically
defensible sampling approach. In most instances, composite
sampling is the method of choice, unless the stream is known to
be homogeneous with respect to the components of interest. A
stream should be presumed to be heterogeneous, especially with
respect to low level (<500 ppm) components, unless there are data
to the contrary. However, if a stream is known to be essentially
constant in composition, a simple random sampling may be as repre-
sentative as systematic or composite sampling. A series of simple
grab samples, also, is appropriate when a significant change in an
effluent stream needs to be monitored to define variation in
A-12
-------
METHOD NUMBER: S-01
effluent composition. Various sampling devices are available
for different physical forms and sample consistencies.
SAMPLING METHOD PARAMETERS: One of the following three typical solid
sampling devices and procedures will usually be applicable.
Thief (Grain) Sampler: The thief is inserted into the solid to be
sampled, the inner tube rotated to open the sampler, and then
agitated to encourage flow of the sample. The sampler is closed
and the sample withdrawn. A thief sampler is useful for powdered
or granular solids. It has limited utility when the solid diameter
is greater than 0.6 cm.
Trowel (Scoop): The trowel is constructed from stainless steel or
a polypropylene scoop. Prior to collecting a sample, the top half-
inch of the solid must be removed. Kg-sized samples are obtained
by combining subsamples taken at several locations. The trowel
is generally used for dry materials and surface soil. It is not
applicable to sampling deeper than 8 cm. Obtaining reproducible
samples is sometimes difficult.
Trier (Sample Corer/Waste Pile Sampler): The sample corer (trier)
is fabricated from PVC pipe or sheet metal as described in SW-846.
(The waste pile sampler is a larger version.) The sampler is
inserted into the solid material at an angle of 0-45°, rotated to
cut a core of the solid or sludge, and removed with the concave
side upward. The trier is also applicable to powdered or granular
material.
REPRESENTATIVE ALIQUOTS FROM FIELD SAMPLES: Field samples are composited
in order to obtain representative aliquots for analysis. Procedures
for compositing solids and sludges are given as follows:
A-13
-------
METHOD NUMBER: S-01
Sludges: Samples are homogenized and aliquots removed. Aliquots
are then combined and mixed.
Solids: If necessary, the sample is ground to reduce the particle
size (20 mesh screen) using agate or alumina equipment. The
sample is then riffled through a steel or aluminum riffler;
appropriate aliquots are combined, cone-blended three times or
roll-blended by an auger, and coned and quartered.
LIMITATIONS: With many solid waste streams, heterogeneity in the
sample makes obtaining a representative sample difficult. Since
solids are often sluiced, the compositions of the solids are also
affected by leaching during processing causing compositional varia-
bility in the samples for analysis. For sluiced solid streams, the
procedures described under liquid waste sampling (Methods S10, Sll)
will generally be applicable. Some solid wastes will change in
composition upon long exposure to air. While major constituents
may be constant for most solids, trace species may vary greatly.
SENSITIVITY: The sensitivity of solid waste sampling will vary with
stream characteristics and sampling program. Sensitivity is deter-
mined by both sample size and the analytical finish used. Typically,
for metals analyzed by ICAP, a mg/kg concentration range in the
solid sample can be expected to be detectable. For organics,
detection limits on the order of 10 mg/kg should be generally
attainable. These levels assume that approximate kg size samples
are collected and that 10-100 g aliquots are taken for analysis.
QA/QC: All field samples should be collected in replicate. Duplicates
of simple random grab samples or of field composites are the minimum
acceptable. At least one sample from each pair will be analyzed;
the second will serve as a contingency sample in the event of
A-14
-------
METHOD NUMBER: S-01
breakage or of apparently anomolous analysis results on the first
sample. If stream heterogeneity is expected to be a major problem,
three or more replicates should be collected and analyzed separately.
At least one blank should be generated for each set of samples.
This will generally be a field blank, consisting of appropriate
sample container(s), taken to the field and handled (container
opened, contents transferred, etc.) like the samples. If contam-
ination from the field environment is expected to be a major problem,
a trip blank should be prepared in addition to the field blank.
The trip blank consists of sample container(s) taken to the field,
unopened, and returned to the laboratory for analysis. Comparison
of trip and field blanks allows assessment of contamination from
the field environment vs. that due to shipment, storage, or post-
sampling laboratory work-up.
REQUIREMENTS FOR ANALYTICAL TECHNIQUES: Generally, solids should be
analyzed as soon as possible following collection. If vapors from
solids are part of the analytes, solids must be stored in glass
bottles to prevent diffusion through plastic. For greatest compo-
sitional stability, samples should be stored at 4°C, in the absence
of air. Generally, chemical preservation is unnecessary. However,
for solids containing large liquid fractions, filtrations or other
separation of phases on-site may be required to maintain the original
phase of components. Typically, sample aliquots for organic analysis
are stored in borosilicate glass containers with Teflon-lined screw
caps, and the aliquots for volatile organic analysis are stored so
that there is no headspace above the sample. Sample aliquots for
inorganic analysis may be stored in high-density, linear polyethylene
containers. Specific sample collection techniques and preservation
are listed with individual analyte test methods, and these steps
should be performed according to analytes of interest-
A-15
-------
METHOD NUMBER: S-01
EXTERNAL COST:
Preparation for Simple Grab Sample: per single sample $30-$100
Preparation for Systematic Grab Sample: per single sample $700-$!500
Preparation for Composite Grab Sample: per single sample $700-$1500
INTERNAL COST:
Preparation for Simple Grab Sample: manhours/sample 2-8
Preparation for Systematic Grab Sample: manhours/sample 24-48
Preparation for Composite Grab Sample: manhours/sample 24-48
Capital Equipment:
Grain Sampler $100-$500
Trier (Sample Corer/Waste Pile Samples) $50-$200
Trowels, Dipper $10-$30
Pumps (Slurry Sampling) $200-$500
Shovel $20
Grinder $100-$6,000
Auger $100-$200
Riffler $50-$200
PRIMARY REFERENCE: U.S. Environmental Protection Agency, Office of
Solid Waste and Emergency Response, "Test Methods for Evaluating
SoVid Waste—Physical/Chemical Methods," SW-846, Washington, D.C.,
1982
ADDITIONAL REFERENCES: American Society for Testing and Materials,
Philadelphia, Pennsylvania, "Annual Book of ASTM Standards,"
Method No. E-300-37, Parts 29 and 30, 1973
A-16
-------
METHOD NUMBER: S-01
Berl, W.G. (ed.)» Physical Methods In Chemical Analysis,
Academic Press, New York, Vol. Ill, 183-217, 1956
Kennedy, W.R. and J.F. Woodruff (eds)., Symposium on Sampling
Standards and Homogeneity, Los Angeles, California, June 25-30-, 1972,
American Society for Testing and Materials, Philadelphia, Pennsylvania,
1973
A-17
-------
METHOD NUMBER: S-02
SAMPLING METHOD: Sampling for Determination of Vapor Phase Moisture
DESCRIPTION: A known volume of gas is passed through a knock-out to
remove entrained water, and then a silica gel trap to determine
moisture content gravimetrically.
APPLICATIONS: This sampling method is applicable to gaseous streams,
with a wide range of pressures and temperatures, in which moisture
determinations are needed.
SAMPLING METHOD PARAMETERS: The silica gel is weighed prior to sampling.
A known volume of sample is drawn through a tared silica gel trap.
The trap is then reweighed on a high capacity analytical balance
and the amount of absorbed species determined. A knockout must be
used upstream of the silica gel trap to remove entrained water.
LIMITATIONS: Hydrogen sulfide or organic species sorption may bias
data if either are present in appreciable concentrations. The
method may yield questionable results when applied to saturated gas
streams that contain water droplets.
SENSITIVITY: Weight gains of 1% can be measured with some accuracy.
QA/QC: A blank portion of silica gel not used for sampling should be
weighed as a control. The balance used should be calibrated regularly.
Use of indicating silica gel is strongly recommended to insure that
the capacity of the drying tube is not exceeded.
The length of sampling lines should be minimized to prevent conden-
sation losses, and the silica gel trap be cooled to a temperature of
68°F or less.
A-18
-------
METHOD NUMBER: S-02
EXTERNAL COST:
Per single sample $3--$60
INTERNAL COST:
Manhours/sample 0.5-1
Capital Equipment:
Analytical Balance $1,000-$2,000
Pump, Meter $3,000
PRIMARY REFERENCE: Tital 40 Code of Federal Regulations, Part 60,
Appendix A, 1980. [Method 4 - Determination of Moisture Content
in Stack Gases]
A-19
-------
METHOD NUMBER: S-03
SAMPLING METHOD; Isok1net1c Collection of Particles from Gas Streams to
Determine Mass Loading (Grain Loading) or Particle Size Distribution
DESCRIPTION: The gas sample 1s obtained at the same flow rate as that oc-
curring within the process pipe or duct (the 1sok1net1c rate). The par-
ticles are removed by filtration or by dynamic particle sizing devices
such as an Impactor or a series of cyclones. Cross-sectional area of
probe orifice (nozzle) and acquisition rate may be varied to cover a wide
range of stream velocities. Sample collection device and sample trans-
port lines are heated to remain above dew point of gas stream sampled.
APPLICATIONS; Generally applicable to a wide range of process pressures and
temperatures.
LIMITATIONS; Streams at elevated temperatures and pressures will require
modifications of general techniques. Access to the flowing stream for
determination of velocity profile and point of average velocity or trav-
ersing to average stratification is required. Aerosol tars and oils will
be collected 1f present. Entrained moisture, 1f vaporized in the collec-
tion device, may leave salt residues that bias results. Non-1soklnetic
sampling rates produce bias in particle loading or size distribution de-
termlnation.
SENSITIVITY; Mass collected must be sufficient for accurate gravimetric
results, 10-100 g 1s the lower level of detection. Gas volumes can be
measured to 0.1 scf with accuracy.
.QA/Q£: Determination of stream velocity profile, temperature, pressure,
moisture content and volumetric flow rate must be made prior to sample
acquisition (EPA Methods 1, 2, 3 and 4, reference 1). Calibration of gas
metering equipment, pi tot tubes, temperature probes and equipment leak
check are necessary.
A-20
-------
METHOD NUMBER: S-03
EXTERNAL COST:
Per single sample $500-$2500 (depending on partlculate concen-
tration)
INTERNAL COST:
Manhours/slngle sample 2-12 (depending on partlculate concentra-
tion)
Capital Equipment:
Probe* console, meter, pump $10,000-$20,000
Probe, high volume pump, metering system $25,000-$50,000
PRIMARY REFERENCE: Title 40, Code of Federal Regulations, Part 60, Appendix
A, 1980. [Method 5 - Determination of Partlculate Emissions from Sta-
tionary Sources]
Accurex, Aerotherm. Operating and Service Manual. Mountain View, CA.
April, 1976.
ALTERNATE REFERENCE:
Lentzen, D. E., D. E. Wagoner, E. D. Estes and W. F. Gutknecht, "EPA/IERL-
RTP Procedures Manual: Level 1 Environmental Assessment, Second Edi-
tion," EPA-600/7-78-201 (January 1979), NTIS No. PB 293795/AS.
A-21
-------
METHOD NUMBER: S-04
SAMPLING METHOD: Removal of Moisture
DESCRIPTION: Devices for removal of vapor phase moisture are used
upstream of particulate sampling devices for protection of equip-
ment or minimization of interferences. In some cases, knockout
traps are used for removal of water in aerosol form.
APPLICATIONS: Vapor phase moisture removal by desiccants is appropriate
for the protection of gas sampling and metering equipment. Condensa-
tion is appropriate immediately after resin collection and prior to
gas scrubbing by impingers. Dilution and permeation are recommended
as "polishing techniques" when gas streams must be sufficiently dry
for introduction into continuous on-line analyzers. For fixed gases,
entrained moisture is usually removed by placing a knockout prior to
sample collection.
GENERAL METHOD PARAMETERS: Desiccants (e.g., silica gel, drierite)
may be packed into a tube or cartridge inserted upstream of the
device to be protected, for collection of vapor phase water.
Knockout traps for water in aerosol form may be similarly inserted.
Permeation-type dryers may be used, especially with on-line instru-
mental methods of analysis.
LIMITATIONS: Choice of device is dependent upon species of interest,
and a different sampling train may be necessary. Desiccants may
absorb some of the components of interest as well as the water
vapor. Knockout traps may also remove some species if they are
condensable in the same temperature range as water. Permeation
devices may be permeable to some species other than water (e.g.,
ammonia) resulting in non-quantitative recovery of those compounds.
A-22
-------
METHOD NUMBER: S-04
QA/QC: Leak check each device per manufacturer's instructions.
EXTERNAL COST:
Per single sample $15-$30
INTERNAL COST:
Manhours/sample 1-2
Capital Equipment:
Permeation drier $500-$2,000
PRIMARY REFERENCE: Fougler, B.E., and P.G. Simmonds, "Drier for
Field Use in the Determination of Trace Atmospheric Gases,"
Anal. Chem., 51(7)=1089-1090, June 1979
A-23
-------
METHOD NUMBER: S-05
SAMPLING METHOD: Vapor Phase Organlcs Collection by Sorbent Trapping
DESCRIPTION; Gas stream 1s passed through a cartridge or canister filled
with porous polymeric resin beads or granules. Vapor phase organlcs are
sorbed by the resin. Both XAD-2 resin (for moderately volatile com-
pounds) and Tenax-GC resin (for volatile compounds) are very widely used.
Additionally, XAD-8, Carbotrap, Carboselve, and the Chromosorbs have been
used successfully as have other less common sorbents. Specific sorbent
traps are recently available for nitrosamlnes.
APPLICATIONS: Broad range of volatile organic compounds are collected.
Generally, highly polar compounds are sorbed less efficiently. The tech-
nique 1s effective to collect organlcs present at low levels; large gas
volumes can be concentrated for analysis of very low stream concentra-
tions.
PREPARATIVE REQUIREMENTS: Gas stream should be cooled (^20°C), particles/
aerosols removed (S-06) and free of entrained moisture (S-04). Resins
should be cleaned (appropriately for the recovery technique, extraction
or thermal desorptlon) prior to use.
LIMITATIONS: Low organic content streams «100 ppb) require long sampling
times (high gas volumes) for accumulation of sufficient mass for analy-
sis. If aqueous or organic condensates are produced by gas clean-up/con-
densation, aliquots must be analyzed in an analogous manner to the resin
catch for an accurate determination of total vapor phase stream composi-
tion.
SENSITIVITY: Technique sensitivity primarily a function of analytical de-
tection technique (see introduction, Table A-l).
QA/QC: Collected sample may be spiked for recovery data. Significant prob-
lems exist 1n accomplishing accurate spiking of the stream to determine
A-24
-------
METHOD NUMBER: S-05
sorptlon efficiency. Collection efficiency can be determined by serial
collection and multiple analyses. Resin blank analyses are required.
Collection system must be rigorously cleaned prior to sampling. Good
sampling practices, leak check, meter calibration, accurate volume mea-
surement, must be followed. Well mixed or representative sample recom-
mended.
EXTERNAL COST:
Per single sample $500-53000 (depending on sample volume)
INTERNAL COST;
Manhours/sample 1-12 (depending on sample volume)
Capital Equipment:
Probe, meter, console, pump $10,000-$15,000
High-volume sampling system $30,000-$40,000
PRIMARY REFERENCE: Lentzen, D. D., D. E. Wagoner, E. D. Estes and W. F.
Gutknecht. EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment, Second Edition. EPA-600/7-78-201, USEPA, RTP, NC, January
1979. CNTIS No. PB 293795/AS].
BIBLIOGRAPHY; Title 40, Code of Federal Regulations, Part 60, Appendix A,
1980. [Method 1 - Sample and Velocity Traverse for Stationary Sources,
Method 2 - Determination of Stack Gas Velocity and Volumetric Flow Rate].
Gallant, R. F., J. W. King, P. L. Levins, and J. F. Plecewlcz. Charac-
terization of Sorbent Resins For Use 1n Environmental Sampling. EPA-
600/7-78-054, USEPA, RTP, NC, March 1978.
A-25
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METHOD NUMBER: S-06
SAMPLING METHOD: Particle/Aerosol Removal from Gas Streams
DESCRIPTION: Participate removal is achieved by filtration, use of
cyclones, or electrostatic precipitation. If the particles are not
to be retained for analysis, isokinetic collection or access to traverse
the stream are unnecessary.
APPLICATIONS: This method is used whenever a particular sampling
device or procedure requires a particulate-free gas stream sample.
Particulate removal is necessary for most on-line monitors of
gaseous species. Particulate material is also removed prior to
collection of vapor phase materials in impingers or solid sorbent
devices.
SAMPLING METHOD PARAMETERS: A filter, cyclone, or electrostatic
precipitator is inserted into the sampling train upstream of the
device to be protected.
LIMITATIONS: Tar or soil aerosols can rapidly plug filter surfaces.
Electrostatic precipitation may be more effective for these
situations. Extremely high particle loadings may require high
capacity filters (large surface area or thimbles) to avoid
frequent changes or unacceptable pressure drop. Particulate
removal devices may also remove some fraction of the species
sought.
QA/QC: Preliminary consideration must be given to the possibility
that some of the analyte of concern may be removed by the particluate
removal device. It may be possible to ascertain this from first
principles. In cases where there is doubt, however, (for example,
when sampling acid gases from a stream that may contain alkaline
A-26
-------
METHOD NUMBER: S-06
participate material), it will be necessary to conduct laboratory
experiments to confirm that the quantitative collection of the
species sought is not affected by the particulate removal device.
EXTERNAL COST:
Per single analysis $250-$2,500 (depending on
removal technique)
INTERNAL COST:
Man-hours/sample 1-12 (depending on removal
technique)
Capital Equipment:
Filter holder $75-$300
Cyclones $600-$3,000
Electrostatic precipitator $2,000-$8,000
PRIMARY REFERENCE: Lentzen, D.E., D.E. Wagoner, E.D. Estes, and
W.F. Gutknecht. EPA/IERL-RTP Procedures Manual: Level 1
Environmental Assessment, Second Edition. EPA-600/7-78-201, USEPA,
RTP, NC, January 1979 [NTIS No. PB 293795/AS]
ADDITIONAL REFERENCE: Title 40, Code of Federal Regulations, Part 60,
Appendix A, 1980. [Method 5 - Determination of Particulate Emissions
from Stationary Sources]
A-27
-------
METHOD NUMBER: S-07
SAMPLING METHOD: Collection of Vapor Phase Samples by Liquid Trapping
(Implnger Collection)
ANALYTE: HCN, NHV NO . minor and trace elements, radioactive species, H0S,
_> X ^
SO^, HC1, HF, some organic components.
DESCRIPTION,; The gas stream 1s passed through a series of 1mp1ngers which
contain aqueous solutions of specific reagents (see Table 1 for specifics
and subdeslgnations S-07A, S-07B, etc.) to sorb or react with a target
vapor phase component. Solutions are kept cool to provide Increased col-
lection efficiency. The vapor phase specie can be concentrated 1n the
Implnger solutions by Increasing the total volume of gas sampled.
APPLICATIONS: Applicable to a wide range of stream temperatures and pres-
sures. Full access to traverse the stream 1s not required although sam-
ples obtained at a point of average velocity or from a well mixed stream
are recommended. Vapor phase organlcs can be trapped 1n solvent solu-
tions.
PREPARATIVE REQUIREMENTS: Entrained moisture or condensable organlcs which
could be collected 1n the 1mp1ngers must be removed by prior condensation
or 1mpact1on 1f analytical Interferences are a potential. Particles/
aerosols should be filtered from the gas stream prior to sample collec-
tion (S-06). Implnger solutions should be prepared and prewelghed under
the best laboratory conditions available prior to sampling. Commonly
used sorptlon solutions are listed 1n Table 1.
LIMITATIONS: General limitations and comments for collection of specific
analytes are given 1n Table 1. The limitations of Implnger collection
techniques 1n general are 1) the difficulty involved in preparing a
spiked gaseous stream to verify technique applicability and assess the
potential of unanticipated interferences; 2) serial collection, and mul-
tiple analyses are required to determine the collection efficiency of the
A-28
-------
METHOD NUMBER:
S-07
TABLE 1. COMMON TRAPPING SOLUTIONS FOR IMPINGER SAMPLE COLLECTION
S-07
Subdesi (nation
Anslyte
Solution
Comments
HCN
5% Sodium Hydroxide
Final solution pH nnst be <10 to avoid poor
retention of HCN. High CO, «20%) will produce
sodium carbonates which can cause plnggage. poor
gas-liquid contact, decreased solution pH. Not
selective for HCN.
10% Calcium Hydroxide
10% Sodium Acetate
NHi 5% Sulfuric Acid
NOx Saltiman Solution
[glacial acetic acid,
sulfanilic acid,
N-(l-naphthyl) othylone
diamine dihydrochloride]
Minor I Trace HiOi. Ammonium persnlfate/
Elements, silver nitrate
Radioactive
Species
Calcium carbonate solids from high COi «20%) cause
fewer collection and handling problems than the
sodium carbonates from NaOH collection. Final
solution pH must be <10. Not selective for HCN.
Applicable to OOi-rich streams, solids formation
hindered by buffering. Final solution pH must be
<10. Not selective for HCN.
Other acids also applicable. Final solution pH
influences retention of ammonia. Other basic species
sorbed also.
Possibly non-stoichiometric reaction see (A-41),
EPA Method 7 (evacuated bomb) more generally
recommended.
Multi-reagent impinger series, most applicable to
combusted streams, silver and sulfur cannot be
determined due to solution composition
10% Nitric acid.
deionixed water
Multi-reagent impin
HiS
SO,
Peroxide, CdS04
2% Zinc Acetate
Cd(OH),
80% Isopropanol, 3%
hydrogen peroxide
Potassium tetra-
chl or omer curate
Multi-reagent impinger series, appropriate for low
levels of H>S (EPA Method 11)
ZnOAc preferable for high levels of snlfide,
oxidation losses occur at low levels. CdS04
(above) more appropriate to low levels.
Like Method 11 (above) appropriate for low level HsS
Multi-reagent impinger series, free ammonia inter-
feres (EPA Method 6)
Modified West-Gaeke method, solutions thermally
unstable above 4*C
HC1
HF
2% NaOH
2% NaOH
SPADNS/Zirconium
Lake
Carbonate formation in high C0» streams causes
handling difficulties, effects solution pH. Other
caustics applicable if necessary.
Carbonate formation in high COj streams causes
handling difficulties, effects solution pH. Other
canstics applicable if necessary.
EPA Method 13
Phenols
0.1 N NaOH
Formaldehyde Sodium tetrachloro—
mercurate
Carbonate formation in COa-rich streams can cause
sampling difficulties and alter solution pH. Not
specific for phenolics, heavily substituted phenols
not collected efficiently. Other canstics applicable.
Modification of West-Gaeke technique.
A-29
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METHOD NUMBER: S-07
technique; and 3) the potential for analyte loss or compositional changes
to occur during gas clean-up, filtration, moisture or condensate removal,
prior to analyte collection.
SENSITIVITY: Vapor phase detection levels detemlned by analysis techniques:
HCN (A-28), N0x (A-41), minor and trace elements (A-40), radioactive
species (A-36), H2$ (A-29), S02 (A-35), HC1 (A-33), and HF (A-31) or as
given by EPA methods cited. Very large gas sample volumes may be ob-
tained to determine very low stream concentrations.
QA/QC: Good sampling practice requires accurate measurement of volumes, 1m-
plnger collection techniques require low flow rates (0.1-0.5 scfm for 500
ml 1mp1ngers) to allow adequate gas-l1qu1d contact. Equipment leak check
and meter calibrations are necessary. Solution blanks must be retained
for analysis.
EXTERNAL COST:
Per single sample $500-$2500 (depending on stream concentration)
INTERNAL CQSTt
Manhours/sample 1-12 (depending on stream concentration)
Capital Equipment:
Probe, pumps, meter, console $8,000-$12,000
PRIMARY REFERENCE.S: Scarengell 1s, F. P., B. E. Saltzman, and S. A. Frey.
Spectrophotometrlc Determlnation of Atmospheric Sulfur Dioxide. Anal.
Chem. 39 1967. pp. 1709-1719.
A-30
-------
METHOD NUMBER; S-07
Title 40, Code of Federal Regulations, Part 60, Appendix A, 1980. [Meth-
od 6 - Determination of Sulfur Dioxide Emissions from Stationary Sources,
Method 7 - Determination of Nitrogen Oxide Emissions from Stationary
Sources, Method 11 - Determination of Hydrogen Sulflde Content of Fuel
Gas Streams 1n Petroleum Refineries, Method 13 - Determination of Total
Fluoride Emissions from Stationary Sources, SPADNS Zirconium Lake Meth-
od].
Lentzen, D. D., D. E. Wagoner, E. D. Estes and W. F. Gutknecht. EPA/IERL-
RTP Procedures Manual: Level 1 Environmental Assessment, Second Edition.
EPA-600/7-78-201,USEPA, RTP, NC, January 1979. CNTIS No. PB 293795/AS],
ALTERNATIVE REFERENCES: Title 40, Code of Federal Regulations, Part 60,
Appendix A, 1980. [Method 15 - Determination of Hydrogen Sulflde, Car-
bony! Sulflde, and Carbon D1sulf1de Emissions from Stationary Sources;
Method 16 - Semicontinueus Determination of Sulfur Emissions from Sta-
tionary Sources; Method 20 - Determination of Nitrogen Oxides, Sulfur
Dioxide, and Oxygen Emissions from Stationary Gas Turbines],
USEPA. Proposed Rules. Federal Register, 46(117):31905-31909, June 18,
1981. [Method 16A - Determination of Total Reduced Sulfur Emissions from
Stationary Sources].
USEPA. Proposed Rules. Federal Register, 46(25):11498-11500, February
6, 1981. [Appendix I - Determination of Sulfur Dioxide Emissions from
Fossil Fuel Combustion Sources (Continuous Bubbler Method)].
USEPA. Proposed Rules. Federal Register, 46(16):8359-8364, January 26,
1981. [Performance Specification 2 - Specifications and Test Procedures
for S0~ and NOx Continuous Emission Monitoring Systems 1n Stationary
Sources],
A-31
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METHOD NUMBER; S-07
USEPA. Proposed Rules. Federal Register, 46(138):37289, July 20, 1981.
[Performance Specification 5 - Specifications and Test Procedures for TRS
Continuous Emission Monitoring Systems 1n Stationary Sources],
BIBLIOGRAPHY; Lelthe, W. and A. A11ver-Humphrey. 1970. The Analysis of A1r
Pollutants. Science Publishers, London.
Lyles, G. R., F. B. Dowllng and V. J. Blanchard. Quantitative Determina-
tion of Formaldehyde 1n the Parts-per-100 Million Concentration Level.
J. A1r Pollution Control Assoc., 15, 1965.
A-32
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METHOD NUMBER: S-08
SAMPLING METHOD: Fugitive Screening for Hydrocarbons
DESCRIPTION: Vapor phase sample is pulled into the analyzer by a
small pump and the hydrocarbon concentration determined without
speciation by flame ionization detection.
APPLICATIONS: Samples may be obtained from open or semi-open sources
or in vicinity of potential leak sources (valves, flanges, etc.).
SAMPLING METHOD PARAMETERS: After the vapor phase sampler is allowed to
stabilize, the instrument is calibrated using an appropriate calibra-
tion gas of known concentration. The probe inlet of the sampler is then
placed at the surface to be monitored. The probe is moved along the
interface until a maximum meter readout is obtained. The probe inlet
is held at the maximum reading location for approximately two times
the instrument response time. Results are usually reported as
parts-per-billion.
LIMITATIONS: A total detector response is obtained; sample
components are not separated and quantified as separate species.
Response of the FID is reasonably uniform for hydrocarbons;
response for compounds containing oxygen or other hetero-elements
is more variable. Pulling of variable amounts of dilution air
from the ambient environment can affect the quantitative validity
of the measurements.
SENSITIVITY: 10 ppb-100 ppm depending on instrument and attenuation
capabilities.
QA/QC: Frequent calibrations and analysis of known blends must be
performed.
A-33
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METHOD NUMBER: S-08
EXTERNAL COST:
Per single sample $10-$20
INTERNAL COST:
Man-hours/sample ^0.1
Capital Equipment
Portable FID $4,00.0-$6,000
PRIMARY REFERENCES: USEPA. Title 40, Code of Federal Regulations,
Part 60, Appendix A. December 5, 1980. [Method 25 - Determination
of Total Gaseous Organic Concentration Using a Flame lonization
Analyzer]
USEPA. Proposed Rules. Federal Register, 45(224). December 17,
1980. [Method 25A, Method 25B]
A-34
-------
METHOD NUMBER: S-09
SAMPLING METHOD: Collection of Vapor Phase Organics in Impingers.
ANALYTE: Acidic, basic or reactive organic species.
DESCRIPTION: A measured volume of gas is collected in a solution
containing an appropriate solution (e.g., dilute caustic for
acidic compounds).
APPLICATIONS: This method is used for organic species that are not
efficiently collected on solid adsorbent sampling devices.
Examples are highly polar organic acids and bases or reactive
species such as formaldehyde.
SAMPLING METHOD PARAMETERS: Impingers containing appropriate reagents
are inserted into a sampling train (See Method S-03). For organic
acids, 0.1-1 N HC1 is appropriate. For organic bases, 0.1-1 N NaOH
may be employed. For formaldehyde, an acidic solution of 2,4-
dinitrophenylhydrazine is used.
LIMITATIONS: Specific solutions must be selected for each group of
compounds to be collected. The collection efficiency for various
species can be highly variable and must be validated. Use of
organic solvents for collection of neutral organic species is a
technique formerly used, but generally inferior to use of solid
adsorbents.
REQUIREMENTS FOR ANALYTICAL TECHNIQUES: Samples may require solvent
extraction after a treatment step to free the organic moiety
(e.g., pH adjustment).
A-3b
-------
METHOD NUMBER: S-09
QA/QC: Good sampling practice requires accurate measurement of gas
volume. The sampling system should be constructed to prevent
organic contamination, e.g., Tygon tubing, greases, plastic-
ware cannot be used. Spike studies should be performed by
spiking the impinger solution and sampling zero grade air to
determine loss during sampling.
EXTERNAL COST:
Per single sample $250-$!,000 (depending on
stream concentration)
INTERNAL COST:
Man-hours/sample 2.5 - 10 (depending on stream
concentration)
Capital Equipment:
Probe, pumps, meter, $5,000-$!0,000
console, glassware
PRIMARY REFERENCE: Arthur D. Little, Inc. Sampling and Analysis
Methods for Hazardous Waste Incineration. EPA Contract No.
68-02-3111, USEPA, February 1982.
A-36
-------
METHOD NUMBER: S-10
SAMPLING METHOD: Composite Sample Collection from Aqueous Streams
DESCRIPTION: Composite samples may be collected either as a series of
manual grab samples or by continuous automatic sampling. Either
flow proportional sample collection or time compositing of individual
samples can be done. The frequency of collection must be determined.
If an automated sampler is utilized, the collection rate is
determined from the compositing time and total sample volume required.
APPLICATIONS: This technique is applicable when it is desirable to
mix several individual samples to determine the average representative
composition of a stream or to minimize the number of samples to be
analyzed.
SAMPLE METHOD PARAMETERS: Samples are collected as described in
Method S-ll. Samples are homogenized and an aliquot removed.
Appropriate aliquots are combined and mixed in a container.
LIMITATIONS: The composite sampling approach does not provide
information concerning the variability of stream composition.
Preservation reagents or cooling may be required to avoid sample
degradation during long compositing periods (P-ll).
QA/QC: All field samples should be collected in replicate.
Duplicates of simple random grab samples or of field composites
are the minimum acceptable. At least one sample from each pair
will be analyzed; the second will serve as a contingency sample
in the event of breakage or of apparently anomolous analysis
results on the first sample. If stream heterogeneity is expected
to be a major problem, three or more replicates should be collected
and analyzed separately. At least one blank should be generated
for each set of samples. This will generally be a field blank,
consisting of appropriate sample container(s), taken to the field
A-37
-------
METHOD NUMBER: S-10
and handled (containers opened, contents transferred, etc.) like
the samples. If contamination from the field environment is expected
to be a major problem, a trip blank should be prepared in addition
to the field blank. The trip blank consists of sample container(s)
taken to the field, unopened, and returned to the laboratory for
analysis. Comparison of trip and field blanks allows assessment of
contamination from the field environment vs. that due to shipment,
storage, or post-sampling laboratory work-up.
EXTERNAL COST:
Per single sample $200-$800
INTERNAL COST:
Man-hours/sample 2-10
Capital Equipment:
Automatic samplers $1,000-$2,000
PRIMARY REFERENCES: USEPA Technology Transfer. Handbook for
Monitoring Industrial Wastewater, Washington, DC, August 1973.
USEPA-EMSL. Handbook for Sampling and Sample Preservation of
Water and Wastewater. EPA-600/4-82-029, Cincinnati, OH,
September 1982.
A-38
-------
METHOD NUMBER: S-ll
SAMPLING METHOD: Grab Sample Collection from Aqueous Streams
DESCRIPTION: Grab samples may be collected manually or automatically
from the water stream using a pump or other suitable device. The
grab sample volume required depends upon the total number of separate
analyses that must be made; however, for a detailed characterization,
a 4-liter sample is usually sufficient.
APPLICATIONS: The technique is applicable to aqueous streams providing
that there is a long residence time in a vessel or pond or that
stream characteristics are relatively constant. Multiple grab
samples taken over time provide a means to determine stream
variability. Grab samples are recommended for analysis of components
which may be lost or degraded during long compositing periods.
SAMPLING METHOD PARAMETERS:
Preparative Requirements: Clean bottles for collection and appro-
priate reagents and equipment for on-site preparation and preser-
vation (P-ll).
Method:
Tap: A sample line is inserted into the collection vessel. The
sample line and bottle must be thoroughly rinsed with the liquid
stream prior to isolating the sample. (This material must be
disposed of in an appropriate manner.) A sample is collected over
a sampling time which exceeds 5 minutes.
Weighted Bottle: A stoppered bottle is lowered to the appropriate
depth, the stopper removed, and a sample collected. After the
bottle is filled, the sample bottle is capped and wiped off.
A-39
-------
METHOD NUMBER: S-ll
Dipper (Pond Sampler): The beaker inserted into the liquid with the
opening downward, until the desired depth is reached. The beaker
is then turned right side up, filled with sample, the dipper
raised, and the sample transferred to a storage vessel. A
2-4 L sample is collected.
Coliwasa Sampler: The Coliwasa sampler is inserted in the closed
position into the liquid. The sampler is then opened, filled,
capped, and removed.
LIMITATIONS: A grab sample may not be representative of the average
stream conditions over time. Grab samples may not provide a
representative sample of suspended solids from a stream in which
solids stratification is prevalent.
QA/QC: All field samples should be collected in replicate.
Duplicates of simple random grab samples or of field composites
are the minimum acceptable. At least one sample from each pair
will be analyzed; the second will serve as a contingency sample in
event of breakage or of apparently anomolous analysis results on
the first sample. If stream heterogeneity is expected to be a major
problem, three or more replicates should be collected and analyzed
separately. At least one blank should be generated for each set of
samples. This will generally be a field blank, consisting of
appropriate sample container(s), taken to the field and handled
(container opened, contents transferred, etc.) like the samples. If
contamination from the field environment is expected to be a major
problem, a trip blank should be prepared in addition to the field
blank. The trip blank consists of sample container!s) taken to
the field, unopened, and returned to the laboratory for analysis.
Comparison of trip and field blanks allows assessment of contamination
from the field environment vs. that are due to shipment, storage,
or post-sampling laboratory work-up.
A-40
-------
METHOD NUMBER: S-ll
EXTERNAL COST:
Per single sample $20-$200 (depending on access
to stream)
INTERNAL COST:
Man-hours/sample 0.5-8 (depending on access
to stream)
Capital Equipment:
Pump, sample lines, $200-$400
general equipment
PRIMARY REFERENCES: USEPA Technology Transfer. Handbook for
Monitoring Industrial Wastewater. Washington, DC, August 1973.
USEPA-EMSL. Handbook for Sampling and Sample Preservation of
Water and Wastewater. EPA-600/4-82-029, Cincinnati, OH,
September 1982.
ADDITIONAL REFERENCES; U.S. Environmental Protection Agency/Office
of Solid Waste, Washington, DC, "Test Methods for Evaluating Solid
Waste - Physical/Chemical Methods," SW-846 (1980).
deVera, E.R., B.P. Simmons, R.D. Stephens and D.L. Strom, "Samplers
and Sampling Procedures for Hazardous Waste Streams," EPA-600/2-80/018
(January 1980), NTIS No. PB8Q-1355353.
American Society for Testing and Materials, Philadelphia, Pennsylvania,
"Annual Book for ASTM Standards," Method D-270 (1975).
American Society for Testing and Materials, Philadelphia, Pennsylvania,
"Annual Book of ASTM Standards," Method E-300 (1973).
A-41
-------
METHOD NUMBER: S-12
SAMPLING METHOD: Collection/Determination of Vapor Phase Components
by Solid Adsorption.
DESCRIPTION: Gas sample is pulled through commercially-available,
specific sorbent-filled tubes. Sorbents selectively react with
specific components of interest. Widely used for CO, HLS,
NH3> HCN.
APPLICATIONS: Fugitive emission sampling, atmospheric pressure
streams, and general screening.
SAMPLING METHOD PARAMETERS:
Method: A gas sample is collected through a sorbent tube at a
flow rate of 1 L/min.
LIMITATIONS: This technique is generally not applicable to pressurized
streams. Tubes are generally not available for high level components
or high capacity sampling. Tubes are usually not quantitative.
The gas matrix should be evaluated for interferences for each
species of interest and sorbent.
SENSITIVITY: 1-100 ppm depending on tube reagents, analyte and
gas sample volume.
QA/QC: Tubes must be protected from breakage and contamination.
Field blanks must be verified for potential degradation or
contamination.
A-42
-------
METHOD NUMBER: S-12
EXTERNAL COST:
Per single sample $10-$50
INTERNAL COST:
Man-hours/sample 0.2-1
Capital Equipment:
Small volume pump and tubes $300-$700
PRIMARY REFERENCE: USHEW, Public Health Service, Center for
Disease Control, National Institute of Occupational Safety and
Health. The Industrial Environment—Its Evaluation and Control,
1973, pp. 188-195.
A-43
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METHOD NUMBER: S-13
SAMPLING METHOD: Collection of Vapor Phase Samples for Direct
Analysis (Bag or Bomb Collection).
DESCRIPTION: The gas sample is collected at low flow rates from a
pressurized stream or pumped into an inert bag (Teflon, Tedlar,
polyethylene) equipped with a shut-off valve. Glass sample bombs
may be either previously evacuated and filled, or at atmospheric
pressure and purged to atmospheric or slight positive pressure
Atmospheric pressure bombs must be purged with 8-10 residence
volumes prior to sample collection. High pressure steel bombs
provide larger sample volumes and are durable.
APPLICATIONS: Generally applicable to a range of process pressures
if pressure reduction and flow control are included upstream of
sample container.
SAMPLING METHOD PARAMETERS:
Preparative Requirements: Sample should be dry and particle/aerosol
free prior to collection (S-04, S-06).
Method:
Gas Bag (Used for Unreactive Gases): The probe on the gas bag is
inserted into the center of the sample source and a sample is
collected.
Gas Bulb (Used for Reactive Gases): A gas bulb is purged with the
gas to be sampled prior to isolating the sample. The bulb is then
re-evacuated, the valve opened, a gas sample collected, and the
valve closed.
A-44
-------
METHOD NUMBER; S-13
LIMITATIONS: Some polymeric bags lose light gaseous species (e.g.,
hydrogen) by diffusion. Reactive species may be lost if inert bags
or pre-passivated glass bombs are not employed. Condensable
species are not recovered from the bag or bomb. Condensates or
particles/aerosols provide sorption surfaces and active sites for
reactive species. Metallic sample bombs may provide active sites
and loss of reactive species. Metal carbonyls may be formed in situ
if metal sample bombs are used for streams containing carbon
monoxide at high pressure.
SENSITIVITY: Volumes generally from 2 L to 10 L can be collected
unless pressurized steel bombs are used. 10 psig is maximum
pressure for glass bombs. Steel bombs are available for pressures
up to 3,000 psig.
QA/QC: In addition to general good sampling practice, bombs or bags
must be rigorously cleaned and analytically checked for background
contamination prior to use.
EXTERNAL COST:
Per single sample $30-$100
INTERNAL COST:
Man-hours/sample 0.5-2
Capital Equipment:
Probe, drier, pump, regulators $500-$!,000
Glass bombs or bags $20-$100
Steel bombs $100-$500
A-45
-------
METHOD NUMBER: S-13
PRIMARY REFERENCES: Lentzen, D.E., D.E. Wagoner, E.D. Estes, and
W.F. Gutknecht. EPA/IERL-RTP Procedures Manual: Level 1 Environmental
Assessment, Second Edition. EPA-600/7-78-201 USEPA, RTP, NC,
January 1979, [NTIS No. PB 293795/AS]
USEPA. Proposed Rules. Federal Register, 45(77):26682, April 18,
1980. [Method 110 - Determination of Benzene from Stationary
Sources]
USEPA. Title 40, Code of Federal Regulations, Part 60, Appendix A.
December 5, 1980. [Method 3 - Gas Analysis for Carbon Dioxide,
Oxygen, Excess Air and Dry Molecular Weight]
A-46
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METHOD NUMBER: S-14
SAMPLING METHOD: Collection of Fugitive Emissions by Bagging
DESCRIPTION: Fugitive emissions from a point source are collected by
enclosing the source in a flexible inert bag (Tedlar, Teflon, etc.).
The concentration in the bag can be increased by collection over
time or most often by pulling ambient air over the source and into
the bag. The bag contents may then be analyzed as a vapor phase
sample.
APPLICATIONS: Discrete sources of such size or location as to be
practically and reliably enclosed.
SAMPLING METHOD PARAMETERS: The probe on the gas bagging equipment
is inserted into the center of the source and a sample is
collected.
LIMITATIONS: Some sources cannot be enclosed. Levels of components
close to ambient background are not reliably quantified.
Condensation of the components of interest within the bag biases
data.
QA/QC: Good sampling practices dictate that the bag and any materials
that contact the bag be clean and not introduce bias or interferences,
Background levels must be determined.
EXTERNAL COST:
Per single sample $75-$250
A-47
-------
METHOD NUMBER: S-14
INTERNAL COST:
Man-hours/sample 1-3
Capital Equipment:
Small pump, meter, $1,000-2,000
bagging material
PRIMARY REFERENCES: Title 40, Code of Federal Regulations, Part 61,
Appendix B, 1980. [Method 106 - Determination of Vinyl Chloride
from Stationary Sources]
USEPA. Proposed Rules. Federal Register, 45(77)-.26677-26682,
April 18, 1980. [Method 110 - Determination of Benzene from
Stationary Sources]
A-48
-------
METHOD NUMBER: S-15
SAMPLING METHOD: Collection of Fugitive Participate Emissions
DESCRIPTION: High volume sample acquisition of ambient air within
the industiral site is employed using a prepared glass filter for
the collection of ambient airborne particulate material. Sample
can be collected for both mass loading or chemical characterization.
A split stream may be passed through a condenser or resin canister.
APPLICATIONS: Technique can be utilized in a grid pattern to profile
a site, upwind/downwind of an emission source or in any required
alternate site locations. Appropriate for fugitives of open or
semi-open origin.
SAMPLING METHOD PARAMETERS: An EPA-approved high-volume sampling system
is used for collection of particulate material. If collection of
organics is also required, an IERL/RTP Fugitive Assessment Sampling
Train (FAST) may be substituted. Samples of ambient air are
drawn through the train at a sampling rate of 5 cu ft/hr or greater.
Careful location of sampling devices in upwind/downwind locations
is required. In order to allow interpretation of the data,
meteorological information must be collected during the sampling
period.
LIMITATIONS: Long term sampling (8 hours or more) required for
collection of sufficient mass for chemical characterization.
The FAST sampling is bulky, and requires a trailer. A modified
standard hi-vol sample requires a filter change whenever a .10%
reduction in flow (from design criteria) is observed.
QA/QC-' Good sampling practices and routine checks on collector
operation are sufficient.
A-49
-------
EXTERNAL COST:
METHOD NUMBER: S-15
Per single sample
$500-$!,000 (depending on
duration of sampling)
INTERNAL COST:
Man-hours/sample
10-40 (depending on duration
of sampling)
Capital Equipment:
FAST Sampling System
Hi-Vol Sampler (unmodified)
$2,000~$10,000
<$1,000
PRIMARY REFERENCES:
Kolnsberg, H. Technical Manual for the
Measurement of Fugitive Emissions. EPA 600/2-76-089-A Wethersfield,
CT, 1976.
Lentzen, D.E., D.E. Wagoner, E.D. Estes, and W.F. Gutknecht. EPA/
IERL-RTP Procedures Manual: Level 1 Environmental Assessment,
Second Edition. EPA-600/7-78-201, USEPA, RTP, NC, January 1979,
[NTIS No. PM 293795/AS]
A-50
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METHOD NUMBER: P-01
PREPARATIVE METHOD: Solvent Extraction of Moderately Volatile Organics
DESCRIPTION: Organic species are removed from a solid or liquid sample
matrix by extraction with a suitable solvent. A drying step through
N32S01+ and a concentration step is usually required to remove water
and enrich the organic content in the solvent.
APPLICATIONS: This preparation method is used in combination with GC,
HPLC, GC/MS, MS, IR and is applicable to gas samples collected on sor-
bents and impingers and to solids, sludges, organic liquids, and
aqueous samples.
DRYING AND CONCENTRATING: Sample extracts are passed through anhydrous
Na2S04 and may subsequently be concentrated by evaporative techniques
(Kuderna Danish). Concentration or dilution of a sample extract prir>
to further analysis, such as GC/MS, may be determined by such techni-
ques as TCO (A-12) and GRAV (A-13).
LIMITATIONS: The extraction efficiency depends on the solvent selected,
the sample matrix, and the organic functional groups present. Solvents
other than methylene chloride may be used if preliminary laboratory
data suggests that all organic species are not being extracted optimally,
Solvents should also be selected on the basis of compatibility with
the detector used for analysis. Possible alternatives are diethyl ether
for acidic organics and hexane for non-polar species. The extract
may require additional treatment to remove interferences and/or
increase sensitivity, derivatization (P-02), solvent on column
separation (P-05) before analysis.
SAMPLING REQUIREMENTS: Samples should be stored in glass, stainless
steel or Teflon® containers to minimize contamination and should be
A-51
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Method Number: P-01
kept cold (4°C) to minimize degradation. Relatively large volumes
of sample (1-3 L of water, 1-2 kg of solids) are required to extract
detectable quantities of low level organic components.
QA/QC: Preliminary QC should check the method using standards. The
recovery and precision should be calculated. As ongoing QC, blanks
(reagent and method), blank spikes, matrix spikes, and matrix
replicates are extracted with every sample set.
Samples should be extracted within a short time to minimize degrada-
tion.
EXTERNAL COST:
Per single sample $50-$200
INTERNAL COST:
Manhours/sample 1-8
Capital Equipment:
Specialized glassware and related lab
equipment $1,000-$5,000 (typical
start-up
cost)
REFERENCES: US EPA, Office of Solid Waste and Emergency Response. Test
Methods for Evaluating Solid Waste--Physical/Chemical Methods. SW-846.
Washington, D.C., 1982
A-52
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Method Number: P-01
Arthur D. Little, Inc. Sampling and Analysis Methods for Hazardous
Waste Combustion. EPA Contract No. 68-02-3111, US EPA, February 1983
Radian Corporation. Assessment, Selection and Development of Procedures
for Determing the Environmental Acceptability of Synthetic Fuel Plants
Based on Coal, May 1977 (NTIS FE-1795-3)
Keith, L.H. ed. Identification and Analysis of Organic Pollutants in
Water. Ann ArborScience, Ann Arbor, MI, 1977
A-53
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METHOD NUMBER: P-02
PREPARATIVE METHOD: Derivatization of Organic Compounds in Sample
Extracts.
DESCRIPTION: By chemical reaction with a derivatization reagent, polar
or high boiling organic compounds are changed into species which are
more easily analyzed (e.g., converting a carboxylic acid into a
methyl ester). This technique can also be used to add a functional
group to a compound which enables selective detection. For example,
phenols can be fluorinated to allow gas chromatographic detection by
electron capture with an increase in sensitivity over flame
ionization detection.
APPLICATIONS: This preparation method can be used in combination with
HPLC, GC, and GC/MS analysis techniques. It is generally used to
reduce interferences, increase sensitivity, or shorten analysis time.
Of the species expected to be important in synfuel plant effluents,
aldehydes and carboxylic acids are the two categories most likely to
require derivatization; most others can be analyzed as is. Procedures
for derivatizing aldehydes and carboxylic acids are given below.
GENERAL METHOD PARAMETERS:
Derivatization of Aldehydes: Aldehydes are derivatized using
dinitrophenylhydrazine (DNPH) prior to extraction, and analysis
by GC/MS, GC or HPLC. A sample aliquot is taken for derivatization/
extraction. If the matrix is"a DNPH impinger reagent which has
been used for collection of aldehydes, it is immediately extracted
with methylene chloride and n-pentane. If the sample is an
aqueous liquid such as a scrubber water or an extract prepared from
a waste stream or comprehensive stack sampling train, it is
treated by mixing with DNPH reagent (2,4-dinitrophenylhydrazine in
2N HC1) for 10 minutes prior to extraction. After extraction,
A-54
-------
METHOD NUMBER: P-02
the combined methylene chloride/pentane layers are washed with
2N HC1 and then distilled water. The extracts are then evaporated
to dryness and the residue dissolved in acetonitrile. These
solutions are analyzed as the DNPH derivatives of the aldehydes
by GC/MS or by HPLC procedures.
Derivatization of Carboxylic Acids: Carboxylic acids are esterfied
prior to analysis by GC or GC/MS. After the sample is extracted
into methylene chloride, the extract is transferred through a
funnel plugged with glass wool into a (K-D) flask equipped with
a 10 ml graduated receiver with liberal washings of solvent. The
acids in the extract are esterified using either diazomethane or
boron trifluoride.
Diazomethane: The extract is evaporated to <5 mL. An aliquot
of diazomethane is added to the extract. The mixture stands for
10 minutes with occasional swirling and subsequently rinsed with
diethyl ether.
Boron Trifluoride: An aliquot of benzene is added to the extract.
The extract and benzene are evaporated to a small volume. The ampule
is removed and further concentrated using a two-ball micro-Snyder
column. After cooling, boron trifluride methanol reagent is added
to the benzene solution. This mixture is held at 50°C for 30
minutes on the steam bath. After cooling, neutral 5% sodium sulfate
is added and the flask stoppered, shaken and allowed to stand
for three minutes for phase separation. The solvent layer is
transferred to a small column packed with sodium sulfate over
florisil adsorbent and eluted with benzene. The final eluent
volume is adjusted with benzene. The extracts are analyzed as
the methyl esters of the Carboxylic acids using GC/MS or GC
procedures.
A-55
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METHOD NUMBER: P-02
LIMITATIONS: Sufficient quantity of reagent must be added to
completely derivatize the analytes. This can only be determined by
analyzing samples spiked before derivatization to determine percent
recovery.
QA/QC: Preliminary QC should check the method using standards. The
recovery and precision should be calculated. As ongoing QC,
blanks (reagent and method), blank spikes, matrix spikes, and
matrix replicates are derivatized with every sample set.
EXTERNAL COST:
Per single analysis $5-$200
INTERNAL COST:
Man-hours/sample 0.1-10
Capital Equipment:
Specialized glassware, $50-$!,000 (depending on
reagents, general equipment availability
laboratory equipment in existing laboratory)
PRIMARY REFERENCES: Radian Corporation. "Assessment, Selection, and
Development of Procedures for Determining the Environmental
Acceptability of Synthetic Fuel Plants Based on Coal," Austin,
TX, May 1977 [NTIS FE-1795-3]
U.S. Environmental Protection Agency, Office of Solid Waste and
Emergency Response. "Test Methods for Evaluating Solid Waste
Physical/Chemical Methods," Washington, DC, July 1982, 2nd Edition.
Arthur D. Little, Inc. "Sampling and Analysis Methods for
Hazardous Waste Combustion." EPA Contract No. 68-02-3111,
U.S. Environmental Protection Agency, February 1983.
A-56
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METHOD NUMBER: P-02
/
Keith, L.H., ed. "Identification and Analysis of Organic Pollutants
in Water," An Arbor Science, Ann Arbor, MI, 1977.
Kuwata, K., M. Uebori, and Y. Yamasaki, "Determination of
Aliphatic and Aromatic Aldehydes in Polluted Airs as their
2,4-Dinitrophenylhydrazones by High Performance Liquid Chromatography."
J. Chromatogr. Sci.. 17, 264-268 (1979).
Smith, A.E., "Uses of Acetonitrile for the Extraction of Herbicide
Residues from Soils." J. of Chrom.. 129, 309-314 (1976).
A-57
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METHOD NUMBER; P-G3
PREPARATIVE METHOD; Thermal Desorptlon of Volatile Organic Species
DESCRIPTION); The sample which has been trapped cryogenlcally or on a
suitable sorbent 1s thermally desorbed Into the analytical Instrument.
For aqueous and solid samples a purging step onto a trap 1s required to
remove the volatile organlcs from the sample matrix. In general, the
method 1s appropriate for non-polar compounds with boiling points of
150°C or less (e.g., benzene, xylenes). This range can be extended by
higher desorptlon temperatures and longer purge and desorptlon times to
Include compounds such as naphthalene and pyrldlne.
APPLICATIONS; For gas samples collected on sorbents, the method 1s appli-
cable to only species which are retained on the sorbent and can be ther-
mally desorbed. For aqueous and solid samples, the method 1s further
limited by the ability to purge the compound from the sample matrix.
LIMITATIONS; This method requires a series of sample handling steps which
can be labor and equipment Intensive as compared to mlcroextractlon
(P-06). These handling steps may also produce some analytical difficul-
ties due to the complexity of the method. Contamination from volatile
species 1n the sample container or 1n the room air 1s a major concern.
The purging and desorptlon times and temperatures must be carefully opti-
mized to allow measurement of the higher boiling volatile species such as
benzene and xylene while preventing loss of the highly volatile species.
QA/Q£; Frequent blanks should be analyzed to Insure uncontamlnated system
due to carryover from previous analytes. Back-up sorbent traps (serial
samples) should be analyzed to determine analyte break-through. Good
laboratory practice 1s essential. Spiking studies are recommended.
SAMPLING REQUIREMENTS; Sorbent samples should be 1n sealed tubes and stored
1n a freezer until the time of analysis. The technique does not allow
for re-analysis, therefore duplicate samples are required. Also, sorbant
A-58
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METHOD NUMBER: P»03
samples should be collected at various gas volumes (e.g., 1 mL, 50 mL,
1000 mL) 1f the concentration of analytes 1s unknown. Aqueous samples (5-
50 ml) should be collected 1n glass vials with no headspace.
EXTERNAL COST;
Per single sample $20-$250
INTERNAL COST:
Manhours/sample 0.5-4
Capital Equipment:
Thermal desorptlon unit $2,000-$10,000
PRIMARY REFERENCES: Bellar, T. A., and J. J. Uchtenberg. Determining Vol-
atile Organlcs 1n M1crogram-per-L1tre Levels by Gas Chromatography. J.
American Water Works Assoc., 66(12): 739-744, December 1974.
USEPA. Proposed Rules. Federal Register, 44(233): 69468-69478, Decem-
ber 3, 1979. [Method 601 - Purgable Halocarbons, Method 602 - Purgable
Aromatlcs]
ALTERNATE REFERENCES: Arthur D. Little, Inc. Sampling and Analysis Methods.
for Hazardous Waste Incineration. Cambridge, MA, February 1982.
USEPA, Office of Solid Waste and Emergency Response. Test Methods for
Evaluating Solid Waste Physical/Chemical Methods. Washington, D.C., July
1982.
A-59
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METHOD NUMBER: P-03
Keith, L.H., ed. Identification and Analysis of Organic Pollutants
in Water. Ann Arbor Sciences, Ann Arbor, MI, 1977
Keith, L.H., ed. Advances in the Identification and Analysis of
Organic Pollutants in Water. Ann Arbor Science, Ann Arbor, MI, 1981
REFERENCE: Miller, H.C., R.H. James and W.R. Dickson, "Evaluated
Methodology for the Analysis of Residual Wastes," Report prepared
for U.S. Environmental Protection Agency/Effluent Guidelines
Division, Washington, D.C., by Southern Research Institute, Birmingham,
Alabama under Contract No. 68-02-2685 (December 1980)
U.S. Environmental Protection Agency, Federal Register, 44, 69464-
69575 (December 3, 1979)
A-60
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METHOD NUMBER: P-04
PREPARATIVE METHOD: Solvent Partitioning of Semivolatile Organics
DESCRIPTION: Solvent partitioning is used as a cleanup procedure
prior to analysis in order to eliminate interferences and
potential erroneous results. Organic species are separated by pH
adjustment and/or selection of appropriate solvents e.g., phenols
can be separated from neutral species.
APPLICATION: This preparation method can be used in combination with
GC, HPLC and GC/MS analysis techniques and it is generally useful
for isolating a particular category of organics (e.g., phenols)
from a sample containing other organic sepcies, therefore reducing
interferences. This method should be considered when: (1) the
organic species of interest are at low concentrations relative to
the other organics, i.e., 10 ppb of phenanthrene in a sample contain
ing 10 ppm phenol, or (2) the analytical method is non-specific,
e.g., GC-FID (A-12) and many other organic species could interfere,
This method should be considered an extension of the general
solvent extraction method (P-01).
GENERAL METHOD PARAMETERS:
Organic Acids and Bases: An aliquot of the sample extract or organic
liquid is shaken with an aqueous solution at pH 12-13 to extract
organic acids and/or at pH 2 to extract organic bases into the
aqueous phase. The pH of the aqueous phase is then readjusted to
pH 2 in the case of acids and/or to pH 12-13 for bases. The
aqueous phase is then reextracted with a solvent, such as methylene
chloride as described in Method P-01.
A-61
-------
METHOD NUMBER: P-04
Neutral Species: An aliquot of the sample extract or organic liquid
is shaken with a non-miscible organic solvent such as acetonitrile,
The organic phase containing the compound of interest is separated
and concentrated if necessary.
LIMITATIONS:
Selection of a solvent system that will achieve the
desired class separation(s) can be difficult. All steps of the
procedure must be validated by spiking into the sample matrix.
This procedure can be labor intensive and may not be necessary
for relatively clean sample extracts or for analytical techniques
with sufficient specificity, such as GC/MS (A-ll), nitrogen-
specific detection (A-10), sulfur-specific detection (A-18), etc.
C: Preliminary QC should check the method using standards.
The recovery and precision should be calculated. As ongoing
QC, blanks (reagent and method), blank spikes, matrix spikes and
matrix replicates are extracted with each sample set.
EXTERNAL COST:
Per single analysis
$20-$200
INTERNAL COST:
Man-hours/sample
1-10
Capital Equipment:
Specialized glassware and
related lab equipment
$1,000-$5,000 (typical start-
up cost)
PRIMARY REFERENCES:
U.S. EPA, Office of Solid Waste and Emergency
Response. Test Methods for Evaluating Solid Waste Physical/Chemical
Methods. Washington, DC, July 1982, Method 3530.
A-62
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METHOD NUMBER: P-04
Radian Corporation. Assessment, Selection and Development of
Procedures for Determining the Environmental Acceptability of
Synthetic Fuel Plants Based on Coal. Austin, TX, May 1977.
[NTIS FE-1795-3].
Miller, H.C., R.H. James and W.R. Dickson, "Evaluated Methodology
for the Analysis of Residual Wastes," Report prepared for U.S.
Environmental Protection Agency/Effluent Guidelines Division,
Washington, DC, by Southern Research Institute, Birmingham, Alabama,
under Contract No. 68-02-2685 (December 1980).
McKown, M.M., J.S. Warner, R.M. Riggen, M.P. Miller, R.E. Heffelfinger,
B.C. Garrett, G.A. Jungclaus, and T.A. Bishop, "Development of
Methodology for the Evaluation of Solid Wastes." Report prepared
for U.S. Environmental Protection Agency/Effluent Guidelines
Division, Washington, DC, by Battelle Columbus Laboratories,
Columbus, OH, under Contract No. 68-03-2552 (January 1981).
U.S. Environmental Protection Agency, Federal Register, 44, 69464-
69575 (December 3, 1979).
A-63
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METHOD NUMBER; P--Qf*
PREPARATIVE METHOD: Organic Fract1onat1on by Column (Sorbent) Separation
DESCRIPTION; The sample extract 1s eluted through a column containing
sorbent to selectively separate classes of organic species. The most
commonly used sorbents are alumina* florlsH and silica gel. Ion ex-
change chromatography and gel permeation chromatography (GPC) are related
techniques which are used 1n special cases.
APPLICATIONS! This method 1s used to Isolate a particular organic group*
e.g., PNAs, from a sample extract (P-01). Compound separation 1s gener-
ally based on polarity. This method 1s very useful for "clean-up" of
extracts prior to analysis by non-specific methods such as GC-FID (A-12),
and provides an additional measure of reliability 1n Identification.
LIMITATIONS; Some compounds can Irreversibly absorb on the column. The
elutlon time of the compound group of Interest must be established. Sep-
aration can be effected 1n samples containing high concentrations of
organic species.
SENSITIVITY; Column techniques range from macro (capable of fractionating
grams of sample) to micro (capable of fractionating 1-2 mg of sample).
QA/QC; Sorbents must be reprodudbly conditioned (activated). The activa-
tion of each lot should be checked by a standard. The sorbent can gener-
ate artifacts; blanks are essential.
EXTERNAL COST;
Per single sample $25-$200
A-64
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METHOD NUMBER: P-05
INTERNAL COST:
Manhours/sample 2-10 (depending on ease of fractionation)
Capital Equipment:
Glass columns $50-$200
Fraction collector $1,000-$6,000
REFERENCES: Arthur D. Little, Inc. Sampling and Analysis Methods for
Hazardous Waste Combustion. EPA Contract No. 68-02-3111, US EPA,
February 1983.
US EPA, Office of Solid Waste and Emergency Response. Test Methods
for Evaluating Solid Waste-Physical/Chemical Methods. SW-846.
Washington, DC, 1982.
Keith, L.H., ed. Identification and Analysis of Organic Pollutants
in Water. Ann Arbor Science, Ann Arbor, MI, 1977.
Keith, L.H., ed. Advances in the Identification and Analysis of
Organic Pollutants in Water. Ann Arbor Science, Ann Arbor, MI 1981.
Radian Corporation. Assessment, Selection and Development of Pro-
cedures for Determining the Environmental Acceptability of Synthetr''
Fuel Plants Based on Coal. Austin, TX, May 1977 [NTIS FE-1795-3].
Lentzen, D.E., D.E. Wagoner, E.D. Estes and W.F. Gutknecht, "EPA/IERL-
RTP Procedures Manual: Level 1 Environmental Assessment (second editinn)
"EPA-600/7-78-201 (October 1978). NTIS No. PB293795/AS.
A-65
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METHOD NUMBER: P-05
U.S. Environmental Protection Agency, Federal Register, 44, 69464-
69575 (December 3, 1979).
Miller, H.C., R.H. James and W.R. Dickson, "Evaluated Methodology
for the Analysis of Residual Wastes," Report prepared for the U.S.
Environmental Protection Agency/Effluent Guidelines Division,
Washington, DC, by Southern Research Institute, Birmingham, Alabama,
under Contract No. 68-02-2685 (December 1980).
A-66
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METHOD Ml lpj:R_ P-'.ly
PREPARATIVE METHOD: Microextraction
DESCRIPTION: A small amount of an organic solvent is mixed with the
sample (e.g., 100 ml of an aqueous sample with 1 ml of solvent). The
solvent extract containing the organic species generally requires no
further concentration prior to analysis.
APPLICATIONS: This preparation method is used in combination with GC,
GC/MS and HPLC analysis techniques. This method is useful for
the long-term monitoring of compounds with high partition coefficients
and which have been identified previously; it can be used for most
solid and liquid samples. For example, the method has been used
for determining the following: volatiles in water, phenols in
water, PNAs collected on filters, and benzene collected on charcoal.
Because the method is not labor or equipment intensive, it is well
suited for field and/or long-term analyses.
GENERAL METHOD PARAMETERS: Aqueous: Surrogates are added to an aliquot
of the sample saturated with Na2SOi+. The sample is then transfer^.-:'
to a volumetric flask. Hexane (for neutral organics) or diisopropyl-
ether (for acidic organics) is added to the flask inverted on a
mechanical shaker and the content shaken. The contents are allowed
to settle and the measured sample extract is transferred to a labeled
container.
Filters and sorbents: Surrogates are added to the filter or sorbent.
The sample is then extracted with a small amount of solvent, typically
using sonification.
LIMITATIONS: Microextraction may not recover the analytes as efficiently
as the solvent extract procedures (Method P-01) due to low sample-to-
sol vent ratio. When using microextraction as compared to P-01, the
solvent is usually not further concentrated, thus volatility losses
are decreased, and few interferences are extracted.
A-67
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METHOD NUMBER: P-Q6
SENSITIVITY: Other preparative procedures such as solvent extraction
(P-01) or thermal desorption (P-03) will probably allow for better
sensitivity, assuming the same analytical detection technique is
employed.
QA/QC: Preliminary QC should check the method using standards. The
recovery and precision should be calculated. As ongoing QC, blanks
(reagent and method), blank spikes, matrix spikes, and matrix re-
plicates are extracted with every sample set. Internal standards
or surrogates are generally required for quantification.
SAMPLE REQUIREMENTS: In general, this method requires a small
volume of sample, e.g., 100 mL for aqueous samples, 0.1-1 g for
solid samples. The samples should be collected in glass, Teflon®
or stainless steel containers to minimize contribution from other
organics. Standard procedures for organic sample handling (keep
cold, etc.) should be followed. Aqueous samples containing volatile
analytes should be collected in sample bottles with no headspace.
Other samples with volatile analytes (sorbents, solids, etc.)
should be sealed to prevent loss of the volatile species.
EXTERNAL COST:
Per single sample $10-$50
INTERNAL COST:
Manhours/sample 0.5-2
Capital equipment: negligible
A-68
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METHOD NUMBER P-06
REFERENCES: Keith, L.H., ed. Advances in the Identification and
Analysis of Organic Pollutants in Water. Ann Arbor Science, Ann
Arbor, MI, 1981
A-69
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METHOD NUMBER: P-07
PREPARATIVE METHOD: RCRA EP Toxicity Test Extraction Method for Solids
DESCRIPTION: The Extraction Procedure (EP) Toxicity Test is designed
to simulate the leaching a waste would undergo if it were disposed
in an improperly designed landfill. Solid phase samples are ex-
tracted with deionized water maintained at a pH of 5 +_ 0.2 using
acetic acid. The extract is then analyzed for the species of
interest. The Resource Conservation and Recovery Act (RCRA)
stipulates subsequent eight analysis for eight metals (arsenic, barium,
cadmium, chromium, lead, mercury, selenium, silver) and six pesti-
cides (Endrin, Lindane, Methoxychlor, Toxaphene, 2,4,5-TP Silvex).
APPLICATIONS: This preparation method is used to determine the
Teachability of certain analytes from solid samples. The technique
is applicable to solid wastes containing more than 0.5% solids.
Wastes that contain less than 0.5% are not subjected to extraction,
but are analyzed directly.
GENERAL METHOD PARAMETERS: If the waste contains free liquids, aliquots
are filtered prior to extraction. The filtered solids are then ex-
tracted for 24 hours with aqueous acetic acid at pH 5. The solid and
liquid phases are allowed to settle and the liquid portion is filtered.
Analysis of metals in leachate is accomplished by either AA or ICAP u;
specified in the following methods under Method A-40.
A-70
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METHOD NUMBER: P-07
Metal Method
Arsenic AAS
Barium I CAP or AAS
Cadmium ICAP or AAS
Chromium ICAP or AAS
Lead AAS
Mercury AAS
Selenium AAS
Silver ICAP or AAS
LIMITATIONS: The presence of acetic acid may make survey analysis for
additional organics difficult.
SENSITIVITY: The Teachability of each analyte varies with the sample
matrix and the chemical form of the analyte in the solid.
QA/QC: Preliminary QC should check the method using standards. The
recovery and precision should be calculated. As ongoing QC, blanks
(reagent and method), blank spikes, matrix spikes and matrix
replicates are extracted with every sample set.
SAMPLE REQUIREMENTS: Technique is applicable for all types of random
or composite samples (S-01). A sample of 100 g is necessary per
analysis. The sample should be representative of the waste. It
must not have preservatives added to it. Samples can be refrigerates
if it is determined that refrigeration will not affect the integrity
of the sample.
EXTERNAL COST:
Per single sample $25-$200
A-71
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METHOD NUMBER: P-07
INTERNAL COST:
Manhours/sample 3-5
Capital Equipment:
Extractor $100-$!,000
Pressure filter $400-$!,000
Compaction tester $100-$500
REFERENCES: US EPA. Rules and Regulations. Federal Register, 45 (98):
33127-33137, May 19, 1980. Subpart C - Characteristics of Hazardous
Waste, Appendix I - Representative Sampling Methods, Appendix II -
EP Toxicity Test Procedure.
US EPA, Office of Solid Waste and Emergency Response. Test Methods
for Evaluating Solid Waste--Physical/Chemical Methods. SW-846.
Washington, DC 1982 [Method 1310].
A-72
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METHOD NUMBER: P-08
PREPARATIVE METHOD: ASTM Batch Extraction of Solids
DESCRIPTION: A representative sample of the solid is mixed with 20
times its weight of water, agitated for two days and filtered. The
filtrate is analyzed for the species of interest.
APPLICATIONS: This technique is applicable to all solid wastes.
GENERAL METHOD PARAMETERS:
Method: The sample is dried for 18 hours at 105°C, then cooled to
room temperature in a dessicator. A representative portion of
the material is placed in a container. Distilled water is added
and the closed container is agitated continuously for 48 hours at
20°C. The bulk is separated from the aqueous phase by decantation,
centrifugation or filtration, as appropriate. The filtrate is
transferred and preserved for analysis.
LIMITATIONS: Solid is not ground or further divided in order to
maintain representativeness with the actual waste. It may be
difficult to obtain representative samples of solids that are very
coarse.
SENSITIVITY: The Teachability of components varies with sample
matrix and chemical composition.
QA/QC: Preliminary QC should check the method using standards. The
recovery and precision should be calculated. As ongoing QC, blanks
(reagent and method), blank spikes, matrix spikes and matrix replicates
are extracted with every sample set.
A-73
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METHOD NUMBER: P-08
SAMPLING/SAMPLE HANDLING REQUIREMENTS: This technique is applicable
for all types of random or composite samples (S-01). A sample of
70 g is necessary per analysis. The sample should be representative
of the waste and should not have preservatives added.
EXTERNAL COST:
Per single analysis: $20-$200
INTERNAL COST:
Manhour/sample 1-5
Capital Equipment:
Pressure filter $400-$!,000
PRIMARY REFERENCE: American Society for Testing and Materials.
ASTM Batch Extraction Method A-l (proposed by ASTM Committee D34
on Solid Wastes). Philadelphia, PA.
A-74
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METHOD NUMBER: P-09
PREPARATIVE METHOD; Ashing, Fusion and Digestion of Solid Samples
DESCRIPTION; Solid waste 1s ashed and Ignited. A portion 1s fused with
NaOH and dissolved 1n HC1 for the analysis of S10 and Al_0_. Another
portion of the ash 1s digested 1n HLSO., HF, and HNO_ and analyzed for
the remaining elements (Fe_0g, T102, P?0?' Ca°» M9°» Na2°' K20>'
APPLICATIONS; This technique 1s applicable to solid wastes, primarily ashes
and slags.
LIMITATIONS; Some losses may occur during Ignition, fusion and digestion
procedures.
QA/QC; Duplicates and blanks should be analyzed for all analytes.
SAMPLING/SAMPLE HANDLING REQUIREMENTS; Technique 1s applicable for all
types of random and composite samples (S-01). The sample should be rep-
resentative of the waste and stored without preservatives. Approximately
5 g of dry, ground sample are required per test.
EXTERNAL COST;
Per single sample $10-$100
INTERNAL COST;
Manhours/sample 2-4
Capital Equipment:
Muffle furnace $500-$2,000
A-75
-------
METHOD NUMBER: P-G9
REFERENCES; American Society for Testing and Materials. Annual Book of
ASlM Standards, Part 26. Philadelphia, PA, 1975. [Method D2795 -
Analysis of Coal and Coke Ash]
A-76
-------
METHOD NUMBER; P-10
PREPARATIVE METHOD; Mixed Add Digestion of Solid Samples
DESCRIPTION: Solid samples are brought Into solution using a digestion pro-
cedure employing a mixture of adds. The sample 1s treated with a mix-
ture of nitric and hydrofluoric adds and heated. Perchloric add 1s
added and the digestion 1s taken to dryness. The residue 1s dissolved
using hydrochloric add and diluted with delonlzed water to a known vol-
ume then analyzed for specific analytes.
APPLICATIONS- This technique 1s applicable to all solid wastes.
LIMITATIONS; No spedatlon of Individual elements as compounds can be de-
termined on this digest. Occasionally* losses during digestion occur to
spattering behavior of solids during heating. Volatile elements may be
lost during drying.
£A/££: Duplicate determinations for digestion should be performed, and
quality control measures suggested 1n the appropriate analytical methods
should be followed. Perchloric add should be used with extreme caution.
Explosive conditions can occur.
SAMPLING/SAMPLE HANDLING REQUIREMENTS. Technique 1s applicable for all
types of random or composite solid samples (S-01).
EXTERNAL COST-
Per single sample $30-$150
A-77
-------
METHOD NUMBER: P-10
INTERNAL COST:
Manhours/sample 3-5
Capital Equipment:
Hood $500-$!,500
Oven $200-$!,000
REFERENCES: US EPA, Office of Solid Waste and Emergency Response.
Test Methods for Evaluating Solid Waste—Physical/Chemical Methods.
SW-846. Washington DC, 1982 (Methods 3010, 3020, 3030, 3040, 3050,
3060).
McQuaker, N.R., D.F. Brown, and P.O. Kluckner. Digestion of
Environmental Materials for Analysis by Inductively Coupled
Plasma-Atomic Emission Spectrometry. Analytical Chemistry
51 (7):1082-1084, 1979.
A-78
-------
METHOD NUMBER: P-ll
PREPARATIVE METHODS: Preservation of Aqueous Samples
DESCRIPTION: Aqueous samples are preserved as soon as possible to
ensure that the analytes are stabilized. In addition, holding times
are usually specified to prevent decomposition of unstabilized
samples prior to analysis.
APPLICATIONS: These techniques are applicable to grab (S-ll) or
composited (S-10) aqueous samples.
LIMITATIONS: The approach will minimize sample decomposition. Pre-
servation is only as successful as the effort expended in rapidly
stabilizing samples and completing the analyses. The proposed
methods have not all been validated for maximum holding times.
GENERAL PARAMETERS: Analysis procedures are listed below along with
the appropriate preservation technique.
PH
Conductivity
T«. Samples should be stored in plastic
containers at 4°C. For BOD, samples
i should b6 filtered prior to storage.
I OO
Alkalinity
BOD
I
The pH of the sample is adjusted to
less than 4 using H3P04. One gram
Phenolics per liter of copper sulfate is added
to the sample which is stored in amber
glass.
A-79
-------
METHOD NUMBER:
P-ll
COD
TOO
Phosphorus
Ammonia
Nitrite/Nitrate
Oil and Grease
Extractable Organics
The pH of the sample adjusted to
less than 2 using I^SO^. The samples
are stored in glass at 4°C. Filtra-
tion before preservation is necessary
for ammonia, phosphorus, nitrate,
and nitrite.
The pH is adjusted to less than 2
using HC1. The samples are stored
in glass at 4°C.
Samples are stored in amber glass
bottles at 4°C.
Trace Elements
Radioactivity
Sulfide
Sulfite
Cyanide
Thiocyanate
Chloride
Fluoride
Sulfate
\
The pH is adjusted to less than 2
with HN03 and the samples are stored
in plastic. If necessary, filtering
should be done before preservation.
The sample is filtered and then
preserved by addition of zinc acetate.
They are stored in plastic at 4°C.
Lead acetate is added to the samples
which are then filtered. The pH
is then adjusted to greater than 12
using sodium hydroxide. Samples are
then stored at 4°C in plastic.
No preservation is necessary.
A-80
-------
METHOD NUMBER: P-11
SAMPLING/SAMPLE HANDLING REQUIREMENTS: A flow chart applicable to
aqueous sample preservation are presented in Figure 1.
EXTERNAL COST:
Per sample set shown in Figure 1 $25-$100
INTERNAL COST:
Manhours/sample set shown in Figure 1 2-8
Capital Equipment
Bottles, filtering apparatus, chemicals $100-$400
REFERENCES: US EPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. (Amendment to 40 CFR 136)
US EPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes. EPA-625/6-74-003, Washington, DC, 1974.
(NTIS No. PB 297686/AS) 298 pp. (Introduction, Tables)
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APHA, Washington
DC, 1976
US EPA. Handbook for Sampling and Sample Preservation of Water and
Wastewater. EPA-600/4-82-029, Cincinnati, OH, September 1982
A-81
-------
00
CO
Cool, 4°C
[Plastic]
pH
Conducitn
TS
TDS
TSS
Alkalinity
BOD
Cool. 4°C
[Plastic]
• (BOD)
HiP04, pH <4,
1 g/L CuS04.
Cool, 4°C
[Amber Glass]
city • Phenol ics
HaS04, p
Cool. 4°
r [Glass]
Aqueous Sample
1
HC1. pH <2,
Cool. 4°C
[Glass]
• Oil and
Grease
H <2
Cool, 4°C Cool, 4°
[VOA Bottle] [Amber G
C HNOi, pH <2
lass] [Plastic]
• Volatile • Extractable • Trace Elements
Organics Organics • Radioactivity
C
Filter
• COD
• TOC
• Phosphorous
No
Preservation
Required
[Plastic]
• Chloride
• Fluoride
• Snlfate
BaS04. pH <2 Pb(OAc)a, Zn(OAc)a
Cool, 4°C filter, NaOH, Cool, 4°
[Glass] pH >12 [Plastic
Ammonia
(COD)
Phosphorous
(TOC)
Nitrite/Nit]
cool, 4wc
[Plastic] • Sulfi
• Sulfi
• Cyanide
• Thiocyanate
rate
, HNOa, pH <2
C [Plastic]
J
• Trace Elements
de • Radioactivity
te
o
o
DO
m
-a
i
Figure 1. Preservation Procedures for Water Samples
-------
METHOD NUMBER: P-12
PREPARATIVE METHOD: Acid Digestion for Aqueous Samples
DESCRIPTION: Aqueous samples are digested for elemental analysis
(A-40) by gentle heating in the presence of HN03- A mixture of
HN03 and HC1 may be used.
APPLICATION: Aqueous samples and impinger solutions can be prepared
for analysis by this technique.
LIMITATIONS: Volatile elemental species may be lost during digestion.
Incomplete digestion may occur in samples having high organic
content or high solids content.
SENSITIVITY: A minimum of 25 mL of sample is required for digestion,
100 mL of sample is generally used.
QA/QC: Preliminary QC should check the method using standards.
Recovery and precision should be calculated. As ongoing QC,
blanks (reagent and method), blank spikes, matrix spikes and
matrix replicates are prepared with each sample set.
EXTERNAL COST:
Per single analysis $10-$50
A-83
-------
METHOD NUMBER: P-12
INTERNAL COST:
Manhours/sample Q.I - 0.3
Capital Equipment:
Hot plate, beakers $100-$300
PRIMARY REFERENCE: U.S. Environmental Protection Agency, Office
of Technology Transfer, Methods for Chemical Analysis of Water
and Wastes, EPA-625/6-74-003, Washington, DC, 1974
[NTIS No. PB 2976861 AS].
A-84
-------
METHOD NUMBER; A-01
ANALYTICAL METHOQ* Gas Chromatography - Flame Photometric Detection, Vapor
Phase Samples
ANALYTES; H S, COS, SO ; minor volatile sulfur components: CH SH, C^hLSH,
CS2» (CH_)2S, thlophenes, etc.
DESCRIPTION; Direct Injection gas chromatography using porous polymer or
cyano-coated conventional or carbonaceous supports and flame photometric
detection. Temperature programming usually required for separation of
components. Techniques provides both quantification and spedatlon.
APPLICATIONS; Generally applicable to vapor phase samples of process and
emission streams.
PREPARATIVE REQUIREMENTS; Gas sample should be moisture and particulate
free (S-04, S-06). The presence of condensates and aerosols 1s also
unacceptable. Sample contact with metal or plastic must be minimized or
eliminated.
LIMITATIONS; Due to the,reactivity of the analytes of Interest, grab sam-
ples must be analyzed as soon as possible. Contact with non-pass1vated
metal or glass surfaces should be eliminated or minimized. Contact with
plastics, moisture, condensates or aerosol tars must be reduced as far as
practical. Carbon dioxide causes some reduced detector response, carbon
monoxide and methane cause severe reductions 1n detector response under
most procedures. Detector linear dynamic range 1s limited.
SENSITIVITY* Detector linear response range usually no greater than 1 to
100 ng (as sulfur). Sample size can be adjusted to provide an effective
detection range from "0.1-2500 vppm. Multiple analyses may be required
1f components are present at both sensitivity extremes.
A-85
-------
METHOD NUMBER: A-01
The linear range of the detector must be defined through analysis of
standards prior to sample analysis. Detector stability should be veri-
fied by frequent analysis of reference standards. Sample stability
should be assayed for each matrix or samples analyzed Immediately. Use
of permeation standards will require that flow calibrations be performed.
Duplicate analyses are recommended.
SAMPLING REQUIREMENTS; Applicable to moisture and particle free (S-04, S-
06) grab or continuous samples (S-13).
EXTERNAL COST;
Per single analysis $50-$200
INTERNAL COSTt
Manhours/analysls 0.5-2
Capital Equipment:
Non-continuous gas chromatograph, temperature $9*000-16*000
programmable* flame photometric detector
REFERENCES: Title 40, Code of Federal Regulations, Part 60, Appendix A
1980. [Method 15 - Determination of Hydrogen Sulflde, Carbonyl Sulflde,
and Carbon D1sulf1de Emissions from Stationary Sources].
Lentzen, D. D., D. E. Wagoner, E. D. Estes and W. F. Gutknecht. EPA/
IERL-RTP Procedures Manual: Level 1 Environmental Assessment. EPA-600/7-
78-201, RTP, NC, January 1979. CNTIS No. PB 293795/AS],
A-86
-------
METHOD NUMBER; A-01
ALTERNATE REFERENCES- Title 40, Code of Federal Regulations, Part 60,
Appendix A, 1980. [Method 2 - Determination of Stack Gas Velocity and
Volumetric Flow Rate (Type S P1tot Tube), Method 5 - Determination of
Partlculate Emissions from Stationary Sources, Method 6 - Determination
of Sulfur Dioxide Emissions from Stationary Sources, Method 11 - Determi-
nation of Hydrogen Sulflde Content of Fuel Gas Streams 1n Petroleum Re-
fineries, and Method 16 - Semi continuous Determination of Sulfur Emis-
sions from Stationary Sources],
A-87
-------
METHOD NUMBER; A-02
ANALYTICAL METHOD: Gas Chromatography - Flame Ion1zat1on Detection, Vapor
Phase Samples
ANALYTES; C. to C._ vapor phase hydrocarbons.
DESCRIPTION; Direct Injection gas Chromatography generally using porous
polymer, carbon, or methyl s1H cone-coated packed or capillary columns.
Temperature programming normally required for component resolution. Cryo-
genic trapping allows for sample concentration.
APPLICATIONS: Generally concentrations from 1 vSB to 1 vppm may be analyzed
directly by adjusting Injection volume.
PREPARATIVE REQUIREMENTS; Sample should not contain particles, aerosols or
condensates (S-04* S-06). High concentrations of vapor phase moisture
may have deleterious effects on the analytical column.
LIMITATIONS; Multiple analyses may be required for accurate quantification
of high and low concentration ranges within a single sample. Cyanide
Interferes with the analysis of Cj-CU hydrocarbons 1n some specific pro-
cedures. CO Interferes with CH. 1n some procedures. Sample Integrity 1s
a concern 1f condensable quantities of C.-C.. compounds present. Speda-
tlon of every potential Isomer generally not attainable.
£A/£IC: In addition to recommended laboratory practice, calibration checks
and reference mixture analysis, condensation of less volatile components
must be avoided or assessed.
SAMPLING REQUIREMENTS; Grab (S-13) or continuous samples may be analyzed.
EXTERNAL
Per single analysis $50-$100
A-88
-------
METHOD NUMBER; A-02
INTERNAL COST;
Manhours/analysls 0.5-1
Capital Equipment:
Non-continuous gas chromatograph, temperature $10-12,000
programmable with flame 1on1zat1on detector
PRIMARY REFERENCES; D. E. Lentzen, D. E. Wagoner, E. D. Estes and W. F.
Gutknecht, "IERL-RTP Procedures Manual: Level I Environmental
Assessment," (Second Edition), EPA-600/7-78-201, January 1979.
ALTERNATE REFERENCES; American Society for Testing and Materials. Annual
Book of ASTM Standards. Philadelphia, PA, 1977. [Method DD3416-75T].
Title 40, Code of Federal Regulations, Part 60, Appendix A, 1980. [Meth-
od 25 - Addendum I. System Components].
USEPA. Proposed Rules. Federal Register, 45(77):26677-26682, April
1980. [Method 110 - Determination of Benzene from Stationary Sources].
Byron Hydrocarbon Analyzer or Equivalent (continuous monitor, methane/non-
methane).
A-89
-------
METHOD NUMBER; A-03
ANALYTICAL METHOD; Gas Chromatography - Thermal Conductivity Detection,
Vapor Phase Samples
°2» H2' "V C0' C02' CH4* H2S
DESCRIPTION; Direct Injection GC. Columns generally non-coated porous pol-
ymers and/or molecular sieves.
APPLICATIONS: Applicable for major gas species analysis at 0.5-100 v*.
PREPARATIVE REQUIREMENTS; Sample should not contain particles, aerosols,
condensates (S-06). Vapor phase moisture generally unacceptable (S-04).
LIMITATIONS ; H S (>0.5-lfc) 1s an Interference with some specific protocols.
NH- O0.5-15B) 1s an Interference with some specific protocols. Argon usu-
ally not resolved from 02< Sample stability 1s not a general concern 1f
preparative requirements achieved.
SENSITIVITY; Usually >.0.1-0.05* for all species except »2 (MDL ^5% unless
platinum furnace detection) and CH.< 0.5-lfc.
QA/QC; Good laboratory practice Including dally calibration verification
and reference sample analyses usually sufficient. Duplicate determlna-'
tlons recommended.
SAMPLING REQUIREMENTS; Technique applicable for moisture and particle free
(S-04, S-06) grab or continuous samples (S-13).
EXTERNAL COST;
Per single analysis $30-$60
A-90
-------
MFTHQD NUMBER; A-03
INTERNAL COST»
Manhours/analysls 0.5-1
Capital Equipment:
Non-continuous gas chromatograph with $4»000-$12,000
thermal conductivity detector
REFERENCES; Lentzen, D. D., D. E. Wagoner, E. D. Estes and W. F. Gutknecht.
EPA/IERL-RTP Procedures Manual: Level 1 Environmental Assessment, EPA-
600/7-78-201, RTP, NC, January 1979. CNTIS No. PB 293795/AS].
ALTERNATE REFERENCE; Title 40, Code of Federal Regulations, Part 60, Appen-
dix A, 1980. [Method 3 - Gas Analysis for Carbon Dioxide Oxygen, Excess
A1r, and Dry Molecular Weight; Method 10 - Determination of Carbon
Monoxide Emissions from Stationary Sources; and Method 11 - Determination
of Hydrogen Sulflde Content of Fuel Gas Streams 1n Petroleum Refineries].
A-91
-------
METHOD NUMBER:
A-04
ANALYTICAL METHOD; Proximate Analysis of Solid Samples
ANALYTES; Moist ure, volatile matter , ash, fixed carbon
DESCRIPTION * Moisture 1s determined from weight loss under controlled heat-
Ing conditions; ash 1s determined by residue weight after burning. Vola-
tile matter 1s determined by weight loss corrected for moisture. The
fixed carbon 1s a calculated value resulting from the summation of per-
centages of moisture, ash, and volatile matter subtracted from 100.
APPLICATIONS; This technique can be applied to all solid wastes; the re-
sults for ashes and slags may not be as useful as proximate analyses of
other solid wastes. Moisture determination coupled with ultimate analy-
sis (A-05) results for ashes and slags may provide more reliable Informa-
tion on those materials.
PREPARATIVE REQUIREMENTS; The sample should be representative of the waste,
and 1t should be gathered 1n a glass bottle to maintain sample Integrity
of volatlles.
LIMITATIONS; Inhomogenelty 1n the waste can cause major variations In re-
sults.
SENSITIVITY; Acceptable Precision:
Repeatability Reproduc1b1l1ty
Moisture
Ash
Volatlles
5
1
0.5
1
2
A-92
-------
METHOD NUMBER; A-04
QA/QC; Duplicates per batch should be performed. Heating program of muffle
furnace should be checked regularly.
SAMPLING REQUIREMENTS- Technique 1s applicable for all types of random or
composite samples (S-01). Each test requires about 1 gram of sample.
EXTERNAL COST-
Per single analysis $30-200
INTERNAL COSTi
Manhours/analysls 3-4
Capital Equipment:
Muffle furnace $1,000-55,000
Analytical balance $2,000-$5,000
PRIMARY REFERENCES: American Society for Testing and Materials. Annual
Book of ASTM Standards, Part 25. Philadelphia, PA, 1975. [Methods
D013, D346, D3173, D3174, D3176]
American Society for Testing and Materials, Philadelphia, PA, "Annual
Book for ASTM Standards, Method 0-1888-78, Part 31 (1979)
Kopp, J.F. and 6.D. McKee, "Methods for Chemical Analysis of Water
and Wastes," EPA-600/4-79-020 (March 1979). [NTIS No. PB 297686/AS]
American Society for Testing and Materials, Philadelphia, PA, "Annual
Book of ASTM Standards," Method D-1888-78, Part 31 (1979)
A-93
-------
METHOD NUMBER: A-05
ANALYTICAL METHOD: Ultimate Analysis of Solid Samples
ANALYTES: Carbon and hydrogen in gaseous combustion products; sulfur,
nitrogen and ash in the whole material; and oxygen by difference.
DESCRIPTION: Carbon and hydrogen are determined by burning the sample
in a closed system and fixing the products. Nitrogen is determined
by the Kjeldahl-Gunning method in which the nitrogen is converted
into ammonium salts, decomposed, distilled, and titrated. The
sulfur can be determined by the Eschka method, bomb washing method,
or high-temperature combustion.
APPLICATIONS: This technique can be applied to all solid wastes.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples representative of the waste should
be stored in glass bottles. Technique is applicable for all types
of random or composite samples (S-01). Approximately 10 gms of
sample are necessary for ultimate analysis.
Method:
Reference Measurement
Carbon ASTM D-3178-73 (1979) C02 and H20 on combustion
Nitrogen ASTM D-3179-73 (1979), N~ by Kjeldahl
E-258-67 (1977) c
Oxygen ASTM D-3176-76 (1979) Difference method
Sulfur ASTM D-3177 (1975), Sulfate titration
D-129-64 (1978)
A-94
-------
METHOD NUMBER: A-05
LIMITATIONS: The carbon values include carbon in carbonates and
hydrogen in the moisture and water of hydration of silicates. A
modified Kjeldahl method must be used for nitrogen determination
in oily wastes. Analysis of high ash content materials often
varies.
SENSITIVITY: Acceptable precision (% difference):
Sulfur 0.10
Carbon 0.3
Hydrogen 0.07
Nitrogen 0.05
Ash 0.5
QA/QC: Blanks, standards and matrix replicates should be analyzed
with each sample set. The precision of the analysis should be
reported.
EXTERNAL COST:
Per single analysis $100-$250
INTERNAL COST:
Manhours/analysis 2-6
A-95
-------
METHOD NUMBER: A-05
Capital Equipment:
Analytical balance $2,000-$5,000
Kjeldahl distillation unit $200-$500
Carbon/hydrogen train $1,000-$3,000
Sulfur apparatus $2,000-$!0,000
Tube furnace $200-$500
Muffle furnace $1,000-$5,000
Automated C,H,0,N,S, analyzer $25,000-$35,000
PRIMARY REFERENCE: American Society for Testing and Materials,
Philadelphia, PA, "Annual Book of ASTM Standards," Methods for
each element, as specified above.
A-96
-------
METHOD NUMBER: A-06
ANALYTICAL METHOD: Measurement of Radioactivity in Solids
ANALYTES: Gross a, Gross B, Radium-226
DESCRIPTION: For gross alpha and beta, a pulverized sample is
slurried onto a 47 mm filter, dried and counted for emissions with
a gas proportional counter. For Ra-226, a solid sample is ashed,
digested and then the solution is measured for Ra-226 using the
methods for liquid samples.
APPLICATIONS: This technique should only be applied to streams
expected to concentrate radioactivity. In most cases, this will
apply to ashes.
GENERAL METHOD PARAMETER:
Preparative Requirements: The sample should be representative of
the waste, and solids and liquids should not be separated. The
technique is applicable for all types of random or composite
samples (S-01). Approximately 300 g of sample is required for
testing.
Method: The solid is ground to a fine powder with a mortar and
pestle. Transfer a maximum of 100 mg fixed residue for alpha
2
assay and 200 mg fixed residue for beta assay for each 20 cm of
counting pan area. The residue is distributed uniformly in the
pan by dispersing the dry residue of known weight that is spread
with acetone and a few drops of Lucite solution. This is oven-
dried at 103°C to 105°C weighed and counted using an internal
proportional counter or geiger counter.
A-97
-------
METHOD NUMBER: A-06
LIMITATIONS: The minimum limit of concentration for gross alpha
and gross beta depends on sample size, counting system character-
istics, background, and counting time. Only a thickness of
2
5 mg/cm can be deposited in the counting planchet; therefore,
only the radioactivity associated with that sample size can be
analyzed. Limitations of the Ra-226 method include analytical
precision during ashing and loss during alkaline borate fusion
and acid dissolution followed by BaSO^ and PBS04 precipitation,
and reprecipitation from EDTA.
SENSITIVITY: The sensitivity for measuring radioactivity in solids
is very dependent on the sample size and counting system character-
istics. Lower detection limits can be achieved by increasing
counting time.
QA/QC: For absolute gross alpha and gross beta and Ra-226 measure-
ments, the detectors must be calibrated to obtain the ratio of
count rate to disintegration rate, appropriate standards used, and
the appropriate corrections made for system characteristics,
background, self-absorption due to water, and geometry and particle
counting efficiencies.
EXTERNAL COST:
Gross a Per single analysis $50-$200
Gross B Per single analysis $50-200
Ra-226 Per single analysis $75-$150
INTERNAL COST:
Gross a Manhours/analysis ^1
Gross B Manhours/analysis ^1
Ra-226 Manhours/analysis ^4
A-98
-------
METHOD NUMBER: A-06
Capital Equipment:
Gas-flow proportional counting system $5,000-$20,000
Scintillation detector system $5,000-$20,000
PRIMARY REFERENCES: American Society for Testing and Materials.
Annual Book of ASTM Standards, Part 26. Part 45. Philadelphia,
PA, 1979.
Harley, J.H., N.A. Hallden, and I.M. Fisenne. Beta Scintillation
Counting with Thin Plastic Phosphors. Nucleonics 20, 1961.
p. 59.
Halden, N.A., and J.H. Harley. An Improved Alpha-Counting
Technique, Analytical Chemistry, 32, 1960. p. 1861.
Nuclear Science Series, USAEC Report, NAS-NS-301 to NAS-NS-3111,
1960-1974.
A-99
-------
METHOD NUMBER: A-07
ANALYTICAL METHOD: X-Ray Diffraction Spectrometry for Qualitative
Identification of Crystalline Phases in Solid Samples.
DESCRIPTION: Ground, solid sample is exposed to an x-ray beam. The
intensity and pattern of peaks at diffraction angles from the
rotated sample are used to identify compounds by special arrange-
ment of atoms within the crystalline structure, using Bragg's Law.
APPLICATIONS: This technique is applicable only to completely dry
solids expected to be crystalline, i.e., ashes, slags, and dewatered
inorganic sludges.
PREPARATIVE REQUIREMENTS: The sample should be representative of
the waste and should not be preserved chemically. Samples must
be ground to minus 400 y. Random or composite samples (S-01) may
be analyzed using this method. Approximately 1 g of sample is
required for each analysis.
LIMITATIONS: If the sample contains large amounts of amorphous
material, background interference will be high. If numerous
crystalline phases are present, diffraction patterns will be
too complex for unquestionnable identification.
SENSITIVITY: In highly crystalline materials containing mixtures of
several compounds, XRD can be both quantitative and qualitative.
If the sample is primarily amorphous, this technique is imprecise.
QA/QC: Standard alignment procedures for generator, goniometer,
and detector should be performed regularly. Alpha-quartz standards
should also be analyzed. If quantitative results are required,
standard method of additions must be employed. Duplicates in each
batch should also be determined.
A-100
-------
METHOD NUMBER: A-07
EXTERNAL COST:
Per single analysis $40-$500 (depending on diffraction
pattern complexity)
INTERNAL COST:
Manhours/analysis 4-20 (depending on diffraction
pattern complexity
Capital Equipment:
XRD Unit $20,000-$75,000
Grinder $200-$6,000
PRIMARY REFERENCE: Azaroff, L.V., Elements of X-Ray Crystallography,
McGraw-Hill, New York, 1968.
A-101
-------
METHOD NUMBER: A-08
ANALYTICAL METHOD: Optical or Scanning Electron Microscopy (SEM)
and Scanning EM plus Energy Dispersive Analysis of X-rays.
ANALYTES: Bulk elemental chemistry (XRF) and particle morphology or
particle size distribution.
DESCRIPTION: Small sample of dry solid is covered with vacuum-
evaporated metal on carbon film, allowing secondary emission when
placed in SEM and targeted by electron beam. While CRT is used
to view magnified surface characteristics or size, x-ray fluorescence
emission can be used to identify bulk elemental composition of
specific or bulk surface areas. Optical microscopy provides a
similar morphology and size data with less magnification.
APPLICATIONS: This technique is applicable to only dry solids. It
is not applicable to tars or sludges.
GENERAL METHOD PARAMETERS:
Preparative Requirements: The sample should be as representative as
possible. Aggregates should be maintained if possible. No chemicals
should be added to the sample when collected. Samples from vapor
phase streams should be collected isokinetically (S-03) on
Nucleapore or equivalent filter substrates. For solid emission
streams, technique is applicable for all types of random or
composite samples (S-Q1). Less than 1 gram of sample is
necessary for bulk XRF analysis.
LIMITATIONS: Samples viewed are on microscopic level; therefore,
inhomogeneity in the solid sample can lead to great variability.
It is important that the specimen is prepared such
that it is truly representative of the sample. Elements
A-102
-------
METHOD NUMBER: A-08
detected by the associated energy dispersive spectrometer range
in atomic number from sodium to uranium.
SENSITIVITY: Elements present at 5% or greater in the bulk sample
will produce discernable XRF emission for elemental identification,
Magnification on most SEM instruments can go up to 50.000X.
QA/QC: XRF standards should be run to assure proper detection of
emission spectrum. Alignment to prevent optical abberations in
viewed images should be performed before each sample batch.
EXTERNAL COST:
Per single analysis $100-$!,000
INTERNAL COST:
Manhours/analysis 1-4
Capital Equipment:
Scanning Electron Microscope $50,000-$200,000
Vacuum Evaporator $1,000-$2,000
PRIMARY REFERENCE: Goldstein, H.I. and J. Yakowitz. Practical
Scanning Electron Microscopy. Planum Press, New York, 1975.
A-103
-------
METHOD NUMBER; A-09
ANALYTICAL METHOD; Direct Aqueous Injection Gas Chromatography
ANALYTES: Non-extractable, non-purgeable organic compounds 1n water, e.g.,
carboxyllc adds, alcohols, polyols, and other low molecular weight,
polar compounds.
DESCRIPTION: Aqueous sample 1s Injected directly Into a gas chromatographlc
system which has a water compatible GC column. A variety of GC detectors
can be used Including mass spectrometry.
APPLICATIONS: Aqueous solutions of organic analytes Including 1mp1nger sol-
utions and leachates. Not applicable for low sample concentrations.
LIMITATIONS; Effective detection limits may be larger than usually obtained
since no extraction-concentration step 1s used. The water can be an In-
terference depending on the analytical conditions.
SENSITIVITY; 1-200 ng on column (1-50 mg/L sample). Sensitivity varies
with analytes, sample matrix, and Instrument.
SAMPLING REQUIREMENTS; Only 1-5 vL are commonly used for analyses. General
practice would be to obtain a 5-20 ml sample 1n a glass vial. The sample
should not contain suspended sol Ids or oils. General organic sample
handling practices should be followed.
EXTERNAL COST;
Per single analysis $25-$300 (depending on matrix and GC detection
technique employed)
A-104
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INTERNAL COST:
METHOD NUMBER: A-09
Man-hours/analysis
1-3 (depending on matrix and
GC detection technique
employed)
Capital Equipment:
Gas Chromatograph/
Mass Spectrometer
Gas Chromatograph with
variety of alternate
detectors
$90,000-$300,000
$5,000-$20,000
PRIMARY REFERENCES:
DiCorcia, A. and R. Samperi, "Gas Chromatographic
Determination of Glycols at the Parts-Per-Million Level in Water
by Graphitized Carbon Black," Anal. Chem.. 51 776-778 (1979)
Harris, L.E., W.L. Budde, and J.W. Eichelleyer. Analytical
Chemistry, Vo. 46, No. 13, pp. 1912-1917, 1974.
A-105
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METHOD NUMBER: A-10
ANALYTICAL METHOD: Gas Chromatography - Nitrogen Specific Detection
ANALYTES: Nitrogen containing organic compounds, such as amines,
nitriles, isocyanates, heterocyclic nitrogen compounds (e.g.,
pyridines, carbazoles, quinolines)
DESCRIPTION: The sample or extract is injected onto a gas chromato-
graphic column interfaced to a nitrogen/ phosphorus specific
detector (NPD), or a Hall electrolytic conductivity detector
(HECD/N) in the nitrogen specific mode. Organic species which
elute from the GC column are detected and a chromatogram obtained.
The chromatogram is used to (1) determine if any nitrogen containing
organic species are present (screening); (2) obtain an estimate of
the total chromatographable nitrogen loading (total species method);
or (3) determine the presence or concentration of selected compounds
by comparison to an analytical standard.
APPLICATIONS: Generally applicable to all types of sample extracts
containing nitrogen compounds.
GENERAL METHOD PARAMETERS:
Preparative Requirements: The sample is introduced by thermal desorption
(P-03) or as an extract (P-01). Cleanup procedures, such as column
separation (P-05) or solvent partitioning (P-04), are used particularly
for complex samples as they remove interferences providing for more
reliable identification and quantification of species present.
Total Species Methods: Nitrogenous organics are analyzed within
a boiling point range of 50°C to 400°C. Nitrogenous organics are
A-106
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METHOD NUMBER: A-10
used for qualitative retention time and for quantitative detector
response calibration.
Specific Organics; Specific nitrogenous organics are analyzed
using the procedure given above or in the references. GC conditions
are determined from the analysis of calibration standards containing
the analytes of interest.
LIMITATIONS: The analytes must be chromatographable. High concentra-
tions of other organics can interfere with the analysis. Solvents,
such as hexane, pentane, or iso-octane, compatible with the detector
are used. The detector stability is established and verified prior
to sample analysis.
SENSITIVITY; 10-100 ng of each component tested.
QA/QC: Calibration standard solutions containing the component(s)
of concern must be prepared and analyzed to generate a calibration
curve. Blanks, calibration standards and matrix replicates should
be analyzed along with every sample set. In the case where the
sample complexity is sufficiently low to permit the use of GC/NPD
for the determination of specific compounds, blank spikes, and
matrix spikes should also be prepared and analyzed. The recovery
and precision of the analysis should be reported.
EXTERNAL COST:
Per single analysis $50-$200 (depending on
qualitative or quantitative
application and sample matrix)
A-107
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METHOD NUMBER: A-10
INTERNAL COST:
Man-hours/analysis 1-6 (depending on
qualitative or quantitative
application and sample matrix)
Capital Equipment:
Gas chromatograph with nitrogen/
phosphorus or Hall Electrolytic
conductivity detector $12,000-$17,000
REFERENCES: USEPA. Proposed Rules. Federal Register, 44(233):69496-
69500, December 6, 1979. [Method 607 - Nitrosamines]
Thrun, K.E., J.C. Harris, C.E. Rechsteiner, D.J. Sorlin,
USEPA/IERL-RTP, "Methods for Level 2 Analysis by Organic Compound
Category," EPA-600/57-81-029, July 1981
A-108
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METHOD NUMBER: A-11
ANALYTICAL METHOD: Gas Chromatography - Mass Spectrometric
Detection (GC-MS)
ANALYTES: Virtually any organic species which can be chromatographed
including the following categories of organics of interest to
synfuel effluents: aliphatics, aromatics, polynuclear aromatics,
oxygenates (e.g., alcohols, ketones, phenols), nitrogenous and
sulfur containing organics.
DESCRIPTION: The sample or sample extract is introduced into the GC/MS
system. The organic species are separated by GC and a mass spectrum
of each compound obtained. A computerized data system is typically
used to acquire the data. Various computer programs can then
normally be used to (1) identify compound by comparison to reference
standards, (2) identify unknowns by comparison against computerized
libraries, or (3) determine the concentration of the identified
species. Unknown or unusual compounds may require manual
interpretation.
APPLICATIONS: This method is best suited for providing a broad base
of data concerning the composition and concentration of organics in
waste samples, where this data is lacking. This method also provides
reliable data concerning identification of compounds in support of
other techniques, e.g., GC/FID.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples can be introduced by thermal
desorption (P-03) or as an extract [solvent extraction (P-01)].
Cleanup procedures such as column Chromatography (P-05) and solvent
partitioning (P-04) are useful for complex samples as they provide
for more reliable identification and quantification by removal of
interferences.
A-109
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METHOD NUMBER: A-11
Method: For a survey analysis, the GC/MS is operated in the full mass
range scanning mode with electron impact ionization. The extract
(Method P-04), with or without additional cleanup procedures
(Method P-05) of the semi volatile fraction of the sample or the
sorbent trap (P-03), is spiked with an internal standard, such
as phenanthrene-d-jQ. The total ion chromatogram for the sample is
examined for the 20 most intense peaks, or for all peaks with an
intensity of more than 1% of the total ion intensity (after
eliminating background due to the GC column). Qualitative
identification is attempted for all of the designated peaks by
either computerized library searching or manual spectral
interpretation.
Detection Limit
5 -20 ng of each compound, injected on-column
Other procedures are given in the references.
LIMITATIONS: Quantitative data is generally not as precise as that
from conventional GC detection techniques. Low molecular weight
compounds (MW <45) or compounds which have only low mass fragments
can be difficult to measure due to the air background. Analysis
of specific organics may be achieved using Method A-15.
SENSITIVITY: 1-100 ng per component on column.
QA/QC: The instrument is tuned routinely, e.g., DFTPP. Surrogates
are typically added to the sample before preparation, in order to
assess the overall method recovery and precision. Calibration
solutions containing the analyte(s) of concern (if known), the
surrogates and the internal standards are prepared and analyzed to
A-110
-------
METHOD NUMBER: A-ll
generate a calibration curve. Blanks, calibration standards and
matrix replicates should be analyzed with each sample set. The
recovery of surrogates and precision of the analysis should be
reported.
EXTERNAL COST:
Per single analysis
$500-$!200 (depending on
sample complexity and
necessity of manual
interpretation)
INTERNAL COST:
Man-hours/analysis
2-20 (depending on
sample complexity and
necessity of manual
interpretation)
Capital Equipment:
Gas chromatograph/mass spectrometer $90,000-$400,000
PRIMARY REFERENCES: USEPA, Office of Solid Waste and Emergency
Response. Test Methods for Evaluating Solid Waste Physical/
Chemical Methods. SW-846. Washington, D.C., 1982.
USEPA. Proposed Rules. Federal Register, 44 (233):69464-69575,
December 3, 1979. [Method 624 - Purgeables; Method 625 - Base/Neutrals,
Acids and Pesticides]
A-lll
-------
METHOD NUMBER: A-ll
Arthur D. Little, Inc. Sampling and Analysis Methods for Hazardous
Waste Combustion. EPA Contract 68-0311, USEPA, February 1983
Keith, L.H., ed. Identification and Analysis of Organic Pollutants
in Water. Ann Arbor Science, Ann Arbor, MI, 1977
Keith, L.H., ed. Advances in the Identification and Analysis of
Organic Pollutants in Water. Ann Arbor Science, Ann Arbor, MI, 1981
A-112
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METHOD NUMBER; A-12
ANALYTICAL METHOD; Gas Chromatography-Flame Ion1zat1on Detection (GC-FID)
ANALYTES; Virtually any organic species which can be chromatographed
Including allphatlcs, aromatics, phenols, PNAs, etc. Formaldehyde and
formic add are the notable exceptions.
DESCRIPTION; The sample or sample extract 1s Introduced Into a gas chromato-
graph having a FID. Organic species which elute from the GC column are
detected and a record (chromatogram) obtained. The chromatogram can be
used to 1) determine 1f any organic species are present, (screening) 2)
obtain an estimation of the total chromatographable organic loading
(TOO), or 3) determine the presence or concentration of selected com-
pounds by comparison to an analytical standard. A variety of GC columns
are used. In general, these columns separate oganlcs by boiling point,
or polarity. Both packed and capillary columns may be used.
APPLICATIONS: Applicable to gas samples collected on sorbents or 1n 1m-
plnger solutions, as well as aqueous and solid samples. This method Is
well suited for long term monitoring of streams with a relatively consis-
tent composition. The application of the method and the Interpretation
of data are relatively easy as compared to other techniques such as GC-
MS, (A-ll). The ease of application, when combined with the relatively
low capital equipment cost, results 1n a broad range of analytical utili-
zation and capability.
PREPARATIVE REQUIREMENTS-. Numerous preparative methods for organlcs, previ-
ously described, are routinely employed [thermal desorptlon (P-03) and
solvent extratlon, (P-01) etc.]. The column separation (P-05), solvent
partitioning (P-04) and der1v1t1zat1on (P-02) methods are particularly
useful for complex samples as they provide for more reliable
Identification and quantltatlon by removal of Interferences.
A-113
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METHOD NUMBER: A-12
LIMITATIONS; Method 1s not specific for any compounds. Identification 1s
based on retention time only. This method cannot be used to unequivo-
cally Identify unknowns or provide any specific Information about the
unknown except estimated boiling point.
SENSITIVITY: 1-100 ng per component Injected.
JW££: Analyst must run adequate controls and generally use good lab
practices. Analytical checks by alternate methods* e.g. GC-MS, 1s a
recommended practice* especially 1f changes are observed.
EXTERNAL COST:
Per single analysis $20-$150 (depending on sample complexity and
level of quantification required)
INTERNAL COST;
Manhours/sample 1-4 (depending on sample complexity and
(level of quantification required)
Capital Equipment:
Gas chromatograph, temperature $5,000-$15,000
programmable, with flame 1on1zat1on
detector
REFERENCES; Lentzen, D.D., D.E. Wagoner, E.D. Estes and W.F. Gutknecht.
EPA/IERL-RTP Procedures Manual: Level 1 Environmental Assessment, EPA-
600/7-78-201, RTP, NC, January, 1979. [NTIS No. PB 293795/AS].
A-114
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METHOD NUMBER; A-12
USEPA. Proposed Rules. Federal Register, 44(233):69464-69575, December
3, 1979. [Method 603 - Acrol e1n-Acrylon1tr1le, Method 604 - Phenols,
Method 606 - Phthalate Esters, Method 610 - Polynuclear Aromatic Hydro-
carbons].
USEPA, Office of Solid Waste and Emergency Response. Test Methods for
Evaluating Solid Waste—Physical/Chemical Methods. SW-846. Washington,
D. C., July 1982.
A-115
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METHOD NUMBER: A-13
ANALYTICAL METHOD: Gravimetric Estimation of Organic Content in
Solvent Extracts.
ANALYTES: Virtually all organic species with boiling points greater
than 250-300°C.
DESCRIPTION: An aliquot of the sample extract is evaporated at
room temperature in a tared weighing dish and weighed to constant
weight. The gravimetric estimate can be used to (1) determine if
any organic species with boiling points greater than 250-300°C are
present (screening), or (2) obtain an estimate of the organic
gravimetric content (GRAV).
APPLICATIONS: Applicable to extracts from gas samples collected on
sorbents or in impinger solutions, as well as aqueous and solid
samples. This method is well suited for long-term monitoring of
streams with a relatively consistent composition, particularly when
in combination with the GC/FID (TCO) technique (see Method A-12).
The ease of application, when combined with the low cost of analysis,
provides a rapid estimation of the total organic content (BP greater
than 250-300°C) of a sample.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Solvent extracts of samples are used for GRAV
estimation (see solvent extraction Method P-01). The column
separation (P-05) method is particularly useful for complex samples
as they provide for more reliable identification and quantification
by removal of interferences.
An aliquot corresponding to one-tenth of the concentrated sample
extract, prepared according to the procedures in Methods P-01 and
P-06 of this manual, is taken for gravimetric analysis.
A-116
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METHOD NUMBER: A-13
Method: The aliquot is transferred to a clean, tared aluminum
weighing dish and evaporated in a desicator at room temperature
to constant weight (+ 0.1 mg). The GRAV results are reported as
mg of GRAV range organics (BP~>300°C) per ml of extract and also
per L (kg) of waste.
LIMITATIONS; Limitations include specific components are not identified;
volatile organics (typically with boiling points less than 250°C) are
not identified (see Method A-12 for quantification of more volatile
species); and a relatively large quantity of extractable material is
needed for the analysis.
SENSITIVITY: Sensitivity varies with sample size. Requires about
1 mg or more of residue.
QA/QC: Blanks and at least one pair of matrix replicates should be
analyzed along with each sample set. The precision of analysis
should be reported.
EXTERNAL COST:
Per single analysis $20-$40
INTERNAL COST:
Manhours/analysis 0.5-1
Capital Equipment:
Analytical balance $1,000-$3,000
A-117
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METHOD NUMBER: A-13
PRIMARY REFERENCE: Lentzen, D.E., D.E. Wagoner, E.D. Estes and
U.F. Gutknecht. EPA/IERL-RTP Procedures Manual: Level 1 Environ-
mental Assessment, Second Edition. EPA-600/7-78-201, RTP, NC,
October 1978. [NTIS No. PB 293795/AS]"
A-118
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METHOD NUMBER: A-14-A
ANALYTICAL METHOD: Estimation of Quantities of Categories of Organics
by Infrared Analysis Total Species Method
ANALYTES: Aliphatics (including alkenes) and oxygenated organics
(including alcohols, ketones, aldehydes, ethers, esters and
carboxylic acids) have been chosen for class quantification by
this method.
DESCRIPTION: Solution spectroscopy is a widely-accepted technique
for quantitative analysis, as it provides a reproducible molecular
environment. Correlations between vibrational frequencies and
molecular structure are most valid when a material is examined in
dilute solution in an inert, non-polar solvent.
Beer's law is applicable in the low concentration range of non-
interacting solvents which makes infrared spectroscopy an ideal
method for monitoring the concentration of known constituent in
a stream.
APPLICATIONS: The time required for analysis is relatively short
once the calibration curves are prepared. The technique can also
provide reliable qualitative data about a sample containing few
compounds at a low cost.
GENERAL METHOD PARAMETERS:
Preparative Requirements: An extract (P-01) of the solvent sample
must be obtained before analysis. Solvent partitioning (P-04) or
column separation (P-05) methods can be used to reduce the complex-
ity of the spectra generated by this method.
A-119
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METHOD NUMBER: A-14-A
Method Description: A general solution method with the procedure for
quantification dependent on knowledge of the sample to be analyzed
is described. The method is applied to monitor the concentration
of a group of similar compounds, for instance n-alkanes. A cali-
bration curve is prepared, using the specific organic compound
identified for each general compound class, i.e., for alkyl ethers
use butyl ether as a reference. If another alkyl ether is known
to be present, then the calibration curve could be prepared using
the known ether.
Table 14-A-l lists analytes, solvents to use, analytical bands and
reference compounds. One of two solvents has been suggested for
each compound class, based on the frequencies chosen for analysis.
Tetrachloroethylene is recommended for the 4000-1400 cm range
and hexane for the 1300-800 cm range. These spectrophotometric
solvents are virtually transparent in the chosen frequency ranges.
The calibration curve should be based on a minimum of three concen-
tration levels, prepared on a weight-volume basis and examined in
the same solution cell. The cell should be thoroughly cleaned
with the solvent and the calibration solutions run in increasing
concentration order.
The recommended cell path is 0.1 mm; for this cell path, 10% (10
grams per 100 cc) is the highest useful concentration. Therefore,
1%, 5%, and 10% concentrations are recommended. Prepare the cali-
bration curve based on the starred (see Table 14A-1) peak maxima at
each concentration level,, using the specific organic recommended
or the specific organic known to be present!
The ratio test should first be applied to test for interferences.
The sample spectrum is recorded "neat", i.e., between KBr plates
as a capillary film or in a KBr pellet of a solid. The absorbance
intensities ratio of the two analytical bands is compared to the
A-120
-------
METHOD NUMBER: A-14-A
ratio obtained for the reference organic. If the ratios are more
than 20% different, this indicates probably interferences and the
infrared method should not be used. If less than-20% different,
the total species concentration can be determined using this
method.
The sample or sample extract is then weighed and dissolved in the
same solvent at a concentration that is near the mid-point of
the calibration range. Several dilutions may be necessary to
reach the optimum 0.2-0.7 absorbance range. Record the spectrum
using the same cell as for the calibration curve. Note whether
1
the peak maxima are within 10 cm of the maxima for the organic
reference compound. If not this may also indicate interferences.
Read the analyte concentration from the calibration curve, using
the intensity at peak maximum and extrapolate the sample concen-
tration before dilution.
LIMITATIONS: This method requires a skilled analyst for preparation
of solutions and construction of calibration curves. Application
of the ratio test may require judgment based on some experience.
The analyte should be in as pure a state as possible, since the
reliability of the information obtained decreases as the number
of components increases. Presence of unexpected functionalities
in the spectrum is considered a strong interference. The ratio
test is an indication of interference by a similar functionality.
For instance, carbonyl functionality is not unique to a particular
category; thus presence of an ester may interfer with ketone
quantification.
SENSITIVITY: 50 yg to several milligrams.
A-121
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METHOD NUMBER: A-14-A
JA/QC: Calibration solutions are prepared and analyzed to generate
a calibration curve. Spectroquality solvents should be used for
solution preparation. The solvents should be examined in the cell
for cleanliness. As noted in the Description Section, the cell should
be thoroughly cleaned with the solvent and the calibration solution
run in increasing concentration order. The baseline method for
2
quantitative analysis, as described in Potts , should be used for
peak intensity measurement. Parameters for the IR spectrophoto-
meter should be optimized as recommended by the manufacturer.
A-122
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TABLE 14A-1
ro
CO
Category
Aliphatics
Alcohols
Ke tones
Aldhydes
Ethers
Esters
Carboxylic Acids
Analytes Infrared Solvent Analytical Bands
Allcanes
Cycloalkanes
Alkenes
Alkadiene
Alkyl Alcohols
Cycloalcohols
Cellosolves
Alkyl Ketones
Cycloketones
Aromatic Ketones
Alkyl Aldehydes
Aromatic Aldehyde
Alkyl Etners
Aromatic Ethers
Dioxanes
Alkyl Esters
Aromatic Esters
Alkyl Acids
Aromatic Acids
c2ci4
c2ci4
c2ci4
c2ci4
c2ci4
c2ci4
c2ci4
c2ci4
c2ci4
c2ci4
c2ci4
c2ci4
C6H14
C6H14
C6H14
c2ci4
c2ci4
c2ci4
c2ci4
*2920/1470
*2920/1445
3080/1650*
3040/1640*
*3350/1065
*3350/1060
*3420/1055
*1 725/1 170
*1695/1200
*1660/1275
2710/1725*
2715/1700*
2960/1120*
3015/1095*
2840/1 1*0*
1740/1180*
1730/1275*
*1710/1275
*1680/1285
Reference Compound
Hexane
cyclohexane
1-octene
1 ,7 - octadiene
butanol
cyclohexanol
cellosolve
2-pentanone
cycl ooctanone
benzophenone
butyraldehyde
benzaldehyde
butyl ether
benzyl ether
p dioxane
ethyl butyrate
di-2-ethylhexyl phthala
acetic acid
benzoic acid
* The starred band absorbance intensity is to be used in preparing the calibration curve;
both bands are used for the ratio test.
-------
METHOD NUMBER: A-14-A
EXTERNAL COST:
Per single analysis $30-$2,000 (depending on complexity
of sample, spectroscopic
technique and level of
interpretation)
INTERNAL COST:
Manhours/analysis 1-40 (depending on complexity of
sample, spectroscopic technique
and level of interpretation)
Capital Equipment: $10,000-$20,000 (to $100,000 for
IR spectrometer Fourier-Transform IR)
REFERENCES: Lentzen, D.E. , D.E. Wagoner, E.D. Estes, and W.F. Cutknecht.
EPA/IERL-RTP Procedures Manual: Level 1 Environmental Assessment,
Second Edition, EPA-600/7/78-201, RTP, NC, October 1978 (NTIS No.
PB 293795/A.S)
Potts, W.J., Jr., Chemical Infrared Spectroscopy, Vol. 1, Techniques,
John Wiley and Sons, Inc. (1963)
Smith, A.L., Applied Infrared Spectroscopy, John Wiley and Sons (1979)
A-124
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METHOD NUMBER: A-14-B
ANALYTICAL METHOD: Estimation of Quantities of Categories of Organics
by Ultraviolet Spectroscopy.
ANALYTES: UV for category identification is useful for material with
functionalities such as aromatics, conjugated unsaturation, and
conjugated carbonyls.
DESCRIPTION: The ultraviolet region of the electromagnetic spectrum is
usually divided into two regions, the vacuum UV and the quartz UV.
The quartz UV region, from 200 to 400 mm, is used for analytical
measurements which are based on electronic transitions in the
analytes. Samples and sample extracts are dissolved in UV trans-
parent solvent, the absorbance at a specific wavelength measured,
and the concentration extrapolated. As in infrared, Beer's Law
is applicable for low concentrations in non-interacting solvents
allowing quantities of compound categories to be determined.
GENERAL METHOD PARAMETERS:
Preparative Requirements: An extract (P-01) of the sample is dissolved
in a non-UV absorbing solvent. Solvent partitioning (P-04) or
column separation (P-05) can be used to reduce the number of compo-
nents.
Method Description: In order to quantify the amount of material in a
sample, a calibration curve for the material is necessary. Three
solutions of known concentrations of an analytical standard are
made up and the absorption at a specific wavelength is measured.
The absorption is plotted against concentration of the standards.
The standards are usually run in a 1 cm path length quartz cell
with a blank (cell and solvent) in the reference beam. The
standards are run in ascending concentration order with ample
A-125
-------
METHOD NUMBER: A-14-B
washing of the cell between runs. The sample is then analyzed
in the same cell, the absorbance at the recommended wavelength
measured and the concentration determined from the calibration
curve and extrapolated to an undiluted sample.
The analytical wavelength to be used for the analysis should be
determined during the Phase I monitoring program by ascertaining
a xmax for each sample type. Reference compounds for calibration
curves can be chosen on the basis of a material most similar to
those found in the stream of interest.
LIMITATIONS: Measurements can only be accurately made on samples
containing components with large extinction coefficients (E max^
5000). Components with similar chromophoric groups (conjugated
ketones and aldehydes) will overlap and may cause interference
problems in the analysis.
SENSITIVITY: The expected sensitivity will vary with the extinction
coefficient of the analytes and the cell path length. Typically,
10 yg to 100 mg can be determined.
QA/QC: Calibration solutions are prepared and analyzed to generate a
calibration curve. Spectral quality solvents should be used for
all analyses. This is particularly important if UV absorbances
are low and solvents might cause interferences. Cells should be
well cleaned and both cell blanks and solvent blanks should be
run. Optimum instrument parameters, as specified by the instrument
manufacturer should be used.
EXTERNAL COST:
Per single analysis $30-$2,000
A-126
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METHOD NUMBER: A-14-B
INTERNAL COST:
Manhours/analysis 2-3 (depending on complexity of
sample, technique and level of
interpretation)
Capital Equipment $5,000 - $50,000 (depending on
resolution and automation)
PRIMARY REFERENCES: Lentzen, D.E., D.E. Wagoner, E.D. Estes, W.F.
Gulknecht. IERL-RTP Procedures Manual: Level 1 Environmental
Assessment, Second Edition. EPA-600/7-78-201, EPA, RTP, NC,
October 1978, [NTIS No. PB 293795/AS).
Bauman, R.P., Absorption Spectroscopy. John Wiley, New York, 1962.
A-127
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METHOD NUMBER: A-14-C
ANALYTICAL METHOD: Category Identification of Organics by Low
Resolution Mass Spectrometry.
ANALYTES: All chemical classes may be determined by Low Resolution
Mass Spectrometry (LRMS). In a complex mixutre, clean-up of the
sample may be helpful,
DESCRIPTION: LRMS plays an important role in the determination of
the chemical composition ,of organic mixtures. By this method, one
can identify a chemical class and give an order of magnitude
quantisation. Complimentary information available from liquid
chromatographic separations (Method Number P-05) and from inter-
pretation of infrared spectra of the mixture may be useful for
interpretation.
APPLICATIONS: The technique can be used for qualitative identification
of various species. Interpretation of complex spectra may be diffi-
cult and time consuming. The analysis results obtained by LRMS are
reported primarily as chemical classes and molecular weight ranges
of those classes, with subcategory or specific compound or compo-
sition designation whenever possible.
GENERAL METHOD PARAMETERS:
Preparative Requirements: An extract (Method P-01) of the sample is
usually analyzed. Solvent partitioning (P-04) or column separation
(P-05) can be used to reduce the complexity of the spectra.
Method Description: The detail that may be obtained from the mass
spectrum of multicomponent mixtures is dependent both on the
complexity of the spectrum itself, and on the amount of supplemental
information that is available. The precision of the identification
A-128
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METHOD NUMBER: A-14-C
that may be obtained will vary accordingly, ranging from specific
compound or composition assignments for all of the spectrum, to
simply an indication of the chemical classes that are present.
The task confronting the analyst of the mass spectra of multi-
component mixtures is to discover the correct combination of
individual spectra that will adequately account for the experi-
mentally observed spectrum. The additive nature of superimposed
mass spectra assures that this is possible, and the multi-peak
nature of electron impact mass spectra makes it practical in most
cases. The combination of the two aspects ensures that if the
observed mass spectrum is fully accounted for by the combined
individual assignments, than those assignments are an accurate
indication of the chemical class makeup of the sample.
Two principal techniques are used to provide clues to the analyst
for tentative individual chemical class or compound assignments.
The first and most important of these is the fractional distilla-
tion of the sample that occurs as the direct insertion probe is
slowly taken through its complete temperature cycle from cool to
hot. The second is the use of both high (70 eV electron impact),
and low (10 to 20 eV) electron impact or chemical ionization modes,
at or near the same probe temperature.
The thermal distillation provides a separation into successive
molecular weight ranges, and the change of ionization mode
differentiates between parent and fragment ions. All of the data,
taken in combination, provides enough information for overall
spectral interpretation.
Tentative assignments, made on the basis of the above information,
are confirmed or modified in the confirmation phase of the analysis.
A-129
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METHOD NUMBER: A-14-C
In the confirmatory phase, standard spectra obtained either from
the literature, or from reference compounds are used to evaluate
how completely the experimentally observed mass spectrum is
accounted for by the combined tentative individual assignments.
Several interpretation aids can be helpful in the analysis of the
LRMS data. The first of these is a table of mass numbers and
associated Z values, where the Z value is given by the relationship:
MW - CnH(2n + Z)
A Z value for any ion in the spectrum can be correlated with a
limited range of possible chemical classes, and a very limited
range of possible chemical compositions. Mass values for PAH
species can be correlated to specific chemical compositions and
numbers of rings, although not to specific isomers. In most
cases, similarly specific chemical composition assignments can
be made to individual mass values for aza-arenes, and for oxygen
or sulfur containing polycyclic species.
LIMITATIONS: The complexity of a sample and the time necessary for
interpretation are severe limitations to the technique. The
reliability of the information obtained decreases as the complexity
of the sample increases.
SENSITIVITY: 50 ng to 10 yg depending on matrix and sample type.
QA/QC: Since the technique is very sensitive, care should be taken
not to introduce contamination during the preparation steps. To
account for contamination, field and method blanks should be
analyzed with each sample set.
A-130
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METHOD NUMBER: A-14-C
EXTERNAL COST:
Per single analysis $100-$2,000 (depending on
complexity of sam-
ple and level of
interpretation)
INTERNAL COST:
Manhours/analysis 1-40 (depending on complexity
of sample and level of
interpretation)
Capital Equipment
Mass Spectrometer $90,00-$400,000(depending on
resolution and
automation)
PRIMARY REFERENCES: Lentzen, D.E., D.E. Wagoner, E.D. Ester, and
W.F. Gutknecht. IERL-RTP Procedures Manual: Level 1 Environmental
Assessment, Second Edition. EPA-600/7-78-201, EPA, RTP, NC,
October 1978, [NTIS No. PB 293795/AS].
"Eight Peak Index of Mass Spectra", 4 volumes, 2nd edition,
published by Mass Spectrometry Data Centre, AWRE, Aldermaston,
Reading, RG7 4PR, United Kingdom, 1974
Heller, S.R.; and Milne, G.W.A., "EPA/NIH Mass Spectral Data Base",
5 volumes, U.S. Department of Commerce/National Bureau of Standards,
NSRDS-NBS 63, December 1978.
Stauffer, J., "Interpretation of Low Resolution Mass Spectra for
Level 1 Analysis of Environmental Mixtures" Report prepared for US
EPA/IERL, N.C., Contract No. 68-02-311, September 1980.
A-131
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METHOD NUMBER: A-15
ANALYTICAL METHOD: Specific Compound Monitoring by GC/MS
ANALYTES: Virtually any organic species which can be chromatographed
including the following categories of organics of interest to synfuel
effluents: aliphatics, aromatics, polynuclear aromatics, oxygenates
(e.g., alcohols, ketones, phenols), nitrogenous and sulfur containing
organics.
DESCRIPTION: The GC/MS system is operated in a selective mode
(commonly termed SIM or MID) which allows better sensitivity and
specificity for selected compounds. The analytical sensitivity and
specificity are improved by increasing the dwell time on character-
istic ions (representative of key fragments) of the compound. This
procedure is similar to method A-ll, however, it is directed towards
the analysis of specific organic(s).
APPLICATIONS; This technique is generally used for 1) measuring low
levels of compounds expected to be present or 2) measuring specific
compounds in the presence of high concentrations of other com-
ponents.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples may be prepared for analysis by
virtually any of the preparative techniques described (solvent
extraction (P-01), derivatization (P-02), thermal desorption
(P-03), solvent partitioning (P-04), column clean up (P-05), or
microextraction (P-06) ). Extensive clean-up techniques are usually
not necessary because of the specificity of the method.
Method: For the analysis of specific organics, the GC/MS is operated
in the selected ion monitoring mode with electron impact ionization.
A-132
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METHOD NUMBER: A-15
An internal standard, such as phenanthrene-d,Q is added to the
sample, as a retention time marker and may also be used to determine
relative responses for quantification. Typical GC/MS conditions for
volatile and semi-volatile organics are given in Method A-ll.
LIMITATIONS: Within a sample the technique is generally limited to
a small group (<20) of compounds such as PNAs. Identification of
species is often not as reliable as full scan GC/MS. Mass spectral
data for identification of other organic species is not obtained
during specific compound monitoring.
SENSITIVITY; 5-20 ng of each compound injected on column (50 ng for
mixtures like PCBs).
QA/QC: The instrument is tuned routinely, e.g., DFTPP. Surrogates
are typically added to the sample before preparation, in order
to assess the overall method recovery and precision. Calibration
solution(s) containing the analytes of concern, the surrogates and
the internal standard are prepared and analyzed to generate a
calibration curve. Blanks,calibration standards, blank spikes,
matrix spikes and matrix replicates should be analyzed with each
sample set. The recovery and precision of the analysis should be
reported.
EXTERNAL COST:
Per single analysis $200-$! ,000
INTERNAL COST:
Manhours/analysis 2-4
A-133
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METHOD NUMBER: A-15
Capital Equipment:
Gas chromatograph/mass spectrometer $90,000-$400,000
PRIMARY REFERENCES: Radian Corporation, Assessment, Selection and
Development of Procedures for Determining the Environmental
Acceptability of Synthetic Fuel Plants Based on Coal. Austin, TX,
May 1977. [NTIS FE-1795-3]
U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, DC, "Test Methods for Evaluating Solid Waste Physical/
Chemical Methods," SW-846 (1980)
U.S. Environmental Protection Agency, Federal Register, 44, 69464-
69575 (December 3, 1979)
A-134
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METHOD NUMBER: A-16
ANALYTICAL METHOD: High Pressure Liquid Chromatography (HPLC)
ANALYTES: Various polar, non-volatile or heat labile analytes such
as PNAs, phenols, alcohols and carboxylic acids.
DESCRIPTION: The sample extract and/or aqueous and organic (effluent)
samples are injected onto a high performance liquid chromatographic
column. Eluting analytes are detected and measured by detectors re-
lying on UV abosrbance, fluroescence, electrochemical oxidation or
refractive index. This method can sometimes provide specific identi-
fication of isomers which cannot be resolved by gas chromatography.
The choice of column and solvent system is dependent upon the parti-
cular species being analyzed.
APPLICATIONS: This analysis method is applicable to aqueous samples and
extracts from all types of samples. Detector selection is based both on
the sensitivity required and the compounds analyzed as shown in Table A-2.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Sample must be in solution in a non-
interferring solvent. Sample may require column cleanup (P-05),
solvent partitioning (P-04), or derivitization techniques (P-02) to
remove interferences.
Method: Generally, a HPLC method using a reversed-phase C,g column
is applicable for analyzing a number of categories of organics,
including polynuclear aromatics, phenols, carboxylic acids, nitro-
cresols, nitrogen containing organics and aldehydes. The analytes
are typically eluted from the column using a water/acetonitrile
(or methanol) solvent system. For carboxylic acids and some phenols,
it is necessary to add acetic acid to the solvent system. For
aldehydes, the organics are reacted to form Dinitrophenyl Hydrazine
(DNPH) derivatives (Method P-02).
A-135
-------
TABLE A-2. HPLC DETECTOR CHARACTERISTICS
CO
cr>
Detector
DV Absorbance
Fixed X
Variable X
Fluorescence
Electrochemical
Principle
Analyte detected by its UV
•obile phase. UV wavelength
is fixed.
UV wavelength available
through use of a prism or
gravity montchromator.
Analytes detected by light
irradiated with UV light.
Analyte is oxidized or re-
Approx. Sensitivity
for strong UV
absorbers
10- '-10-* g
analyte injected
Ifl— *—10— * g
10-" -10-' g
Applieationa
Compounds showing UV
length of instrument
measurement usually 254
urn (PNAs)
Compounds having UV
length e.g., 200-400
urn (PNAs, phenol a,
aroma tics)
Compounds which fluo-
flnoreace e.g., indolea,
PNAs, etc. Relatively
apecif ic.
Phenols, amines, catechola,
and other eaailv oxidized
Limitations
Response factors may vary
widely. Mobile phase must
Response factors vary widely.
parent.
Fluorescence may be inhibited
pound specific, narrow linear
range.
Compound specific, narrow
linear ranee. Reanirea nolar
Approx.
Coat
$3,000
$5-10,000
$10-20,000
12-5.000
Differential
Refractometer
(i) ia Measured in
• icroasipa.
Analytes detected by their
refractive index in solution.
analyte injected
or reduced species.
Most general detector
available. Potentially
applicable to all apeciea
of compounds, low speci-
ficity.
mobile phase.
Low aensitivity. Cannot vary
mobile phase composition.
$3-5,000
n:
o
DO
m
CTi
-------
METHOD NUMBER:
A-16
Polynuclear aromatics and aldehydes are two categories or organics
expected to be present in synfuel effluents. The HPLC techniques
described below for these two categories, are highly specific and,
therefore, are recommended particularly for monitoring.
Sensitivity: 0.1 ng to 100 ng each PNA on column. 5 to 20 ng each
aldehyde on column.
LIMITATIONS:
Often less sensitive than GC methods, but more specific.
Detector response varies widely for different analytes. Requires
use of standards for quantitation and identification. Some analytes
may require derivatization. Unequivocal compound identification is
not usually achieved.
SENSITIVITY:
Varies widely with nature of analyte and detectors.
Approximately 10 ng to 10 yg of injected components.
EXTERNAL COST:
Per single analysis
$75-$200 (depending on sample matrix
and degree of quantitation)
INTERNAL COST:
Manhours/analysis
1-3 (depending on sample matrix and
degree of quantitation)
Capital Equipment:
High Performance
Liquid Chromatograph
$15,000-$50,000
A-137
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METHOD NUMBER: A-16
PRIMARY REFERENCES: Dillon, H.K., R.H. James, H.C. Miller, and A.K.
Wensky (Battelle Columbus Laboratories, Columbus, Ohio). POHC
Sampling and Analysis Methods. Contract No. 68-02-2685, Report
prepared by Southern Research Institute, Birmingham, AL, USEPA/
IERL, RTP, NC, December 1981
Kuwata, K., M. Uebori, and Y. Yamasaki. Determination of Aliphatic
and Aromatic Aldehydes in Polluted Airs as Their 2,4-Dinitrophenyl-
hydrazones by High Performance Liquid Chromatography. J. Chromatogr.
Sci., 17, 1979, pp. 264-268
US EPA. Proposed Rules. Federal Register, 44(233):69514-69517,
December 3, 1979. [Method 610 - Polynuclear Aromatic Hydrocarbons]
A-138
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METHOD NUMBER: A-17
ANALYTICAL METHOD: Total Organic Halogen Determination (TOX)
ANALYTES: Halogenated Organics (nonspecific)
DESCRIPTION: Halogenated organics are combusted and analyzed in a
microcoulometric titration cell.
APPLICATION: Aqueous samples
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples are kept cool (4°C). Grab (S-ll)
or composite (S-10) aqueous samples are analyzed using this method.
Method: Halogenated organic compounds are sorbed on activated carbon.
The carbon is rinsed with nitric acid to remove inorganic halide
components. The micro carbon plug is placed in a combustion furnace
and organohalide compounds converted to gaseous acid halides which
are swept into a microcoulometric titration cell. The halides are
titrated with a standard silver nitrate solution.
LIMITATIONS: Samples with high inorganic halide levels (brines, sea-
water) will result in positive interference due to incomplete
inorganic halide removal.
.SENSITIVITY: 5-100 yg/L.
QA/QC: Calibration solutions are prepared and analyzed to generate a
calibration curve. Blanks, calibration standards, blank spikes,
matrix spikes and matrix replicates should be analyzed with each
sample set. The precision and recovery of analysis should be
reported. Carbon columns in series may be analyzed in order to
check for halogenated organic breakthrough.
A-139
-------
METHOD NUMBER: A-17
EXTERNAL COST:
Per single analysis $25-$100
INTERNAL COST:
Manhours/analysis 1-3
Capital Equipment:
TOX analyzer $10,000-$20,000
REFERENCE: US EPA. Office of Research and Development, EMSL, Physical
and Chemical Methods Branch. Total Organic Halide, Interagency
Method 450.1. Cincinnati, OH. November 1980
Kopp, J.F. and G.D. McKee, "Methods for Chemical Analysis of
Water and Wastes," EPA-600/4-79-020 (March 1979). NTIS No. PB297585/AS
A-140
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METHOD NUMBER: A-18
ANALYTICAL METHOD- Gas Chromatography - Sulfur Specific Detection
ANALYTES,; Sulfur containing organic compounds: e.g., ,th1ophenes» benzothlo-
phenes. etc.
DESCRIPTION; Sample or sample extract 1s Injected Into a gas chromatograph
equipped with a flame photometric detector (FPD) or a Hall electrolytic
conductivity detector configured 1n the sulfur mode (HECD-S). Either the
detector 1s specific for sulfur containing compounds.
APPLICATIONS: Method can be used to screen samples for sulfur compounds or
to determine Individual species.
PREPARATIVE REQUIREMENTS; Thermal desorptlon (P-03) or solvent extraction
(P-01) methods are generally most appropriate.
LIMITATIONS; High concentrations of other organlcs can Interfere. The
stability of the detector 1s varlble. Solvent must be detector compati-
ble.
SENSITIVITY; i-io ng per component Injected.
QA/QC; Frequent calibration, 1n addition to good general laboratory
practices.
EXTERNAL COST;
Per single analysis $50-$250 (depending on sample matrix and degree of
quantification)
A-141
-------
METHOD NUMBER: A-18
INTERNAL COST:
Manhours/analysis 1-6 (depending on sample matrix and degree
of quantification)
Capital Equipment:
Gas chromatograph with either $10,000-$17,000
flame photometric or HECD(S) detector
REFERENCE: Keith, L.H., ed. Energy and Environmental Chemistry - Fossil
Fuels. Ann Arbon Science, Ann Arborn, MI, 1982. 443 pp.
US EPA/IERL, RTF, "Methods for Level 2 Analysis by Organic Compound
Category," EPA-600/57-81-029, July 1981.
A-142
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METHOD NUMBER; A-19
ANALYTICAL METHOD; Gas Chromatography - Phot1on1zat1on Detection
ANALYTES: Aromatic species such as benzene, toluene, naphthalenes, xylenes,
anilines.
DESCRIPTION• Sample 1s Injected or purged Into gas chromatograph equipped
with phot1on1zat1on detector (PID). Aromatic compounds are selectively
detected 1n presence of aliphatic hydrocarbons. Method can be used quan-
titatively or as a screening technique.
APPLICATIONS; Generally applicable to sample extracts and volatile species
collected on sorbents.
PREPARATIVE REQUIREMENTS: Thermal desorptlon (P-03) and solvent extraction
(P-01) are the most common preparative methods.
LIMITATIONS; Not applicable to compounds which have no ultraviolet chromo-
phores. High concentrations of other organic species can Interfere.
SENSITIVITY; 0.2 to 1 ng analyte Injected.
QA/QQ; Good laboratory practices and multipoint calibrations necessary for
quantltatlon.
EXTERNAL COST;
Per single analysis $50-$300 (depending on sample matrix and degree
of quantltatlon)
INTERNAL COST;
Manhours/analysls 1-6 (depending on sample matrix and degree of
quantltatlon)
A-143
-------
METHOD NUMBER; A-19
Capital Equipment:
Gas chromatograph with $10,000-115,000
photo1on1zat1on detector
REFERENCES; USEPA. Proposed Rules. Federal Register, 44(233):69474-69478,
December 3, 1979. [Method 602 - Purgeable Aromatlcs],
Cox, R. D., and R. F. Earp. Determination of Trace Level Organlcs 1n
Ambient A1r by High-Resolution Gas Chromatography with Simultaneous Pho-
to1on1zat1on and Flame Ion1zat1on Detection. Anal. Chem., 54(13):2265,
1982.
John H. Drlscoll, et. al. The Photo1on1zat1on Detector 1n Gas Chromato-
graphy, American Laboratory, 10, 1978. p. 137.
A-144
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METHOD NUMBER: A-20
ANALYTICAL METHOD: pH Measurement
ANALYTES: H ion concentration
DESCRIPTION: The pH is determined using a glass electrode.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: This analysis method is applicable to grab
samples (S-ll) and continuous sampling (S-10)
Method: The pH of the sample is determined electronically using
either a glass electrode in combination with a reference potential
or a combination electrode, as specified in SW-846.
LIMITATIONS: The sample pH may change with time, therefore, pH should
be determined as soon as possible after collection. If not deter-
mined within 6 hours, the time of determination after collection
shall be referenced.
SENSITIVITY: Depends upon pH meter - usually 0.01 to 0.1 pH units
Samples should be analyzed in duplicate. The pH meter and
electrode(s) should be calibrated using aqueous buffers at a
minimum of 2 pH levels; at least one calibration pH should be
within 2 pH units of the sample value. Grab samples (S-ll) or
continuous sample (S-10).
EXTERNAL COST:
Per single analysis $5-$15
A-145
-------
METHOD NUMBER: A-20
INTERNAL COST:
Manhours/analysis 0.1-0.2
Capital Equipment:
pH meter with electrodes $300-$!,300
REFERENCES: US EPA. Proposed Rules Federal Register, 44 (233).
December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1981. p. 178. [Method
D-1293 - pH of Water and Wastewater] (1981)
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Evaluation of Water and Wastewater, 14th edition. APHA, Washington,
D.C., 1976. p. 460, [Method 424 - pH Value].
U.S. Environmental Protection Agency/Office of Solid Waste,
Washington, D.C., "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods," SW-846 (1980), Section 5.
A-146
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METHOD NUMBER: A-21
ANALYTICAL METHOD: Total Solids Measurement
ANALYTES: Total solids content
DESCRIPTION: Total solids in aqueous samples are determined gravi-
metrically.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples are kept cool (4°C) to minimize
biological decomposition of solids. Grab (S-ll) or composite
(S-10) samples may be analyzed using this method. Sample should
be mixed to ensure a representative aliquot is taken.
Method: Total solids are determined by evaporation of moisture using
a hot water bath and gravimetric determination of the solid residue
remaining after equilibration at 105°C. Total volatile solids are
determined by heating to 550°C.
LIMITATIONS: Inhomogeneity in the sample can cause major variations
in results.
SENSITIVITY: Usually 0.1 to 0.5 mg can be weighed with accuracy.
QA/QC: Blanks and matrix replicates should be analyzed with each
sample set. The precision of analysis should be reported.
EXTERNAL COST:
Per single analysis $5-$15
A-147
-------
METHOD NUMBER: A-21
INTERNAL COST:
Manhours/analysis Q.l-0.2
Capital Equipment:
Oven, balance $1,000-$3,QQO
REFERENCES: USEPA. Proposed Rules. Federal Rigister, 44(233),
December 3, 1979. [Amendment to 40 CFR 132]
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1981. [Method D-1888 -
Tests for Particulate and Dissolved Matter in Water]
USEPA, Office of Technology Transfer, Methods for Chemical
Analysis of Water andWastes, EPA-625/6-74-003, Washington, D.C.,
1974. [NTIS No. PB 297686/AS]. pp. 266.
American Public Health Association, American Water Works Associa-
tion, and Water Pollution Control Federation. Standard Methods
for the Examination of Water and Wastewater, 14th edition. APHA,
Washington, D.C., 1976. p. 89, [Method 208]
A-148
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METHOD NUMBER: A-22
ANALYTICAL METHOD: Total Dissolved Solids Measurement
ANALYTES: Dissolved solids.
DESCRIPTION: Dissolved solids in aqueous samples are determined
gravimetrically.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples are kept cool (4°C) to minimize
microbiological decomposition of solids. Grap (S-ll) or composite
(S-1Q) samples may be analyzed using this method. Mix sample well
to ensure a representative aliquot is removed.
Method: Solids are removed with a standard glass fiber filter, the
filtrate is evaporated, and the amount of filtrate solid residue
remaining after heating to 180°C is determined gravimetrically.
Total volatile dissolved solids are determined after heating to
550°C.
LIMITATIONS: Excessive residue mass may entrap water which is difficult
to remove by drying. Samples with high bicarbonate levels must be
carefully dried for extended periods at 180°C to convert to
carbonate. Volatile components such as HpS, NHU, and C02 are
lost in the determination.
SENSITIVITY: Sample should be weighted to nearest 0.1 rag.
QA/QC: Blanks and matrix replicates should be analyzed with each
sample set. The precision of analysis should be reported.
A-149
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METHOD NUMBER: A-22
EXTERNAL COST:
Per single analysis $5-$15
INTERNAL COST:
Manhours/analysis 0.1 - 0.2
Capital Equipment:
Oven, balance $1,000-$3,000
REFERENCES: USEPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1981. [Method D-1888 -
Tests for Particulate and Dissolved Matter in Water]
USEPA, Office of Technology Transfer, Methods for Chemical
Analysis of Water and Wastes, EPA-625/6-74-003, Washington, D.C.,
1974. [NTIS No. PB 297686/AS]. pp. 266.
American Public Health Association, American Water Works Associa-
tion, and Water Pollution Control Federation. Standard Methods •
for the Examination of Water and Wastewater, 14th edition. APHA,
Washington, D.C., 1976. p. 89, [Method 208]
A-150
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METHOD NUMBER: A-23
ANALYTICAL METHOD: Total Suspended Solids Measurement
ANALYTES: Suspended Solids
DESCRIPTION: Total suspended solids are determined gravimetrically.
APPLICATIONS: Aqueous samples
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples are kept cool (4°C) to minimize micro-
biological decomposition of solids. Grab (S-ll) or composite
(S-10) samples may be analyzed using this method. Samples should
be mixed well to ensure a representative aliquot is removed.
Method: Suspended solids are removed with a standard glass fiber
filter, and the filter residue after heating to 105°C is determined
gravimetrically. Volatile suspended solids are determined after
heating to 550°C.
LIMITATIONS: See A-22
SENSITIVITY: Sample residues should be weighed to nearest 0.1 mg
QA/QC: Blanks and matrix replicates should be analyzed with each
sample set. The precision of analysis should be reported.
EXTERNAL COST:
Per single analysis $5-$15
A-151
-------
METHOD NUMBER: A-23
INTERNAL COST:
Manhours/analysis 0.1-0.2
Capital Equipment:
Oven, balance $1,000-$3,000
REFERENCES: USEPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1981. [Method D-1888 -
Tests for Particulate and Dissolved Matter in Water]
USEPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
[NTIS No. PB 2976S6/AS], pp. 266.
American Public Health Association, American Water Works Associa-
tion, and Water Pollution Control Federation. Standard Methods
for the Examination of Water and Wastewater, 14th edition. APHA,
Washington, D.C., 1976. p. 89, [Method 208]
A-152
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METHOD NUMBER: A-24
ANALYTICAL METHOD: Determination of Chemical Oxygen Demand (COD)
ANALYTES: Chemical oxygen demand (COD)
DESCRIPTION: Chemical oxygen demand is determined by dichromate
oxidation followed by colorimetrie or titrimetric determination
of the excess dichromate.
APPLICATIONS: Aqueous sample.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples are preserved with H2SOt+ata pH <2
to prevent biological utilization of organic carbon. Grab (S-ll)
or composite (S-10) samples may be analyzed using this method.
Methods: An aliquot is placed in a reflux flask with HgS04. Concen-
trated sulfuric acid and 0.25N K2Cr207 and then sulfuric acid-
silver sulfate solution is added. (If volatiles are present in
the sample, use an allihn condenser and add the sulfuric acid-
silver sulfate solution through the condenser while cooling the
flask, in order to minimize loss by volatilization). The mixture
is refluxed, cooled and then rinsed with distilled water. The
mixture is transferred to an erlenmeyer flask and again washed
and diluted with distilled water. Perron indicator is added and
the excess dichromate titrated with 0.25N ferrous ammonium sulfate
solution to the endpoint. A color change from blue-green to a
reddish hue indicates the endpoint.
LIMITATIONS;. Chloride interference must be removed with mercuric
sulfate. For samples with high chloride levels, additional attention
to chloride removal is required. Traces of organic material from
glassware may cause gross positive error.
A-153
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METHOD NUMBER: A-24
SENSITIVITY: Depends upon specific analysis. For the 5-50 mg/L
range, sensitivity is 2 mg/L. With chloride levels above 1,000
mg/L, the minimum accepted value of sensitivity is 250 mg/L for COD.
QA/QC: A blank is simultaneous run to check on background contamination.
A matrix replicate should be analyzed with each sample. The pre-
cision of analysis should be reported.
EXTERNAL COST:
Per single analysis $15-$25
INTERNAL COST:
Manhours/analysis 0.2-0.4
Capital Equipment:
Oven, hot plate, condenser $100-$! ,000
Spectrophotometer $200-$2,500
REFERENCES: US EPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. (Amendment to 40 CFR 136)
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1981. (Method D-1252 -
Tests for Chemical Oxygen Demand (Dichromate Oxygen Demand) of
Waste Water
US EPA, Office of Tehcnology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
(NTIS No. PB 297686/AS.) pp. 20-25.
A-154
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METHOD NUMBER: A-24
American Public Health Association, American Water Works
Association, and Water Pollution Control Federation. Standard
Methods for the Examination of Water and Wastewater, 14th edition.
APHA, Washington, D.C., 1976. pp. 550 (Method 508•)
A-155
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METHOD NUMBER: A-25
ANALYTICAL METHOD: Determination of Biological Oxygen Demand (BOD)
ANALYTES: Dissolved oxygen
DESCRIPTION: The BOD test is an empirical procedure for measuring the
dissolved oxygen microbially consumed by the assimilation and
oxidation of organic material.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples are kept cool (4°C) and analyzed
within 24 hours. Otherwise, the time of test initiation, after
collection, should be referenced. Grab (S-ll) or composite (S-IOj
samples may be analyzed using this method.
Method: The sample is incubated for 5 days at 20°C in the dark. The
dissolved oxygen reduction during the period is a measure of bio-
logical oxygen demand.
LIMITATIONS: Toxic components in the wastewater may inhibit biological
oxidation.
SENSITIVITY: 5 mg/L
QA/QC: Blanks, matrix dilutions and matrix replicates are analyzed
with each sample set.
EXTERNAL COST:
Per single analysis $15-$35
A-156
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METHOD NUMBER: A-25
INTERNAL COST:
Manhours/analysis 0.2-0.4
Capital Equipment:
Dissolved oxygen meter and probe $300-$!,000
Incubation oven $500-$2,000
REFERENCES: US EPA. Proposed Rules. Federal Register, 44 (233),
December 3, 1979. (Amendment to 40 CFR 136 )
US EPA, Office of Technology Transfer, Methods for Chemical
Analysis of Water and Wastes, EPA-625/6-74-003, Washington, D.C.
1974. (NTIS No. PB 297686/AS.) pp. 11.
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APHA, Washington,
D.C., 1976. pp. 543. (Method 507 )
A-157
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METHOD NUMBER: A-26
ANALYTICAL METHOD: Distillation/Colorimetry (4-aminoantipyrine)
ANALYTES: Total Phenolics.
DESCRIPTION: Steam-distill able phenolic materials are reacted with
4-amino antipyrine (4-AAP) under select conditions to form a red-
dish-brown antipyrine dye. The amount-of color produced is a
function of the amount of phenolic material. The dye is concen-
trated by extraction into chloroform.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Preserve with HgPO^ to pH <4; add 1 g CuSOi,
per liter to limit biological degradation. Cool to 4°C and analyze
within 24 hours. Grab (S-ll) or composite (S-10) samples may be
analyzed for this method.
Method: An aliquot of the sample is distilled using a graham condenser.
NH^Cl is added to the distillate. The pH is adjusted with ammonium
hydroxide and the solution is transferred to a 1L separatory funnel.
Amino antipyrine solution is added, and mixed, followed by the
addition of potassium ferricyanide solution. The contents are
mixed well, and color allowed to develop. The solution is immediately
extracted with CHC13. The absorbance of the CHC13 extract is read
at 460 nm using a spectrophometer.
LIMITATIONS: For most samples a preliminary distillation is required
to remove interferences. Therefore, only steam-distillable phenols
are addressed in the analysis. Color response of phenolic materials
with 4-AAP is not the same for all compounds. For this reason,
A-158
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METHOD NUMBER: A-26
phenol has been selected as the standard and any color produced
by reaction of other phenolic compounds is reported as phenol.
The reported value will represent a minimum concentration of
phenolic compounds present in the sample. Sulfur compounds and
oil and grease are interferences.
SENSITIVITY: 50-200 yg/L; 1-20 yg/L with solvent extraction.
QA/QC: Calibration solutions are prepared and analyzed in order to
generate a calibration curve, blanks, calibration standards, blank
spikes, matrix spikes and matrix replicates should be analyzed with
each sample set. The precision and recovery of the analysis should
be reported.
EXTERNAL COST:
Per single analsis $20-$50
INTERNAL COST:
Manhours/analysis 0.2-1
Capital Equipment:
Distillation unit and spectrophotometer $600-$2,500
REFERENCES: US EPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. (Amendment to 40 CFR 136)
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadephia, PA, 1981. (Method D-1783 -
Tests for Phenolic Compounds in Water)
A-159
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METHOD NUMBER: A-26
US EPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
(NTIS No. PB 297686/AS) pp. 241.
American Public Health Assocaition, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APHA, Washington,
D.C., 1976. p. 574. ( Method 510)
A-160
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METHOD NUMBER: A-27
ANALYTICAL METHOD: Distillation/Titration
ANALYTES: Ammonia
DESCRIPTION: The sample is buffered with borate buffer after pH adjust-
ment with sodium hydroxide to pH of 9.5, and the ammonia is distilled
into a boric acid solution. The ammonia in the distillate is deter-
mined titrimetrically with standard sulfuric acid in the presence of a
mixed indicator.
APPLICATIONS: Aqueous samples and impinger solutions from gas sample
collection.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Preserve with H2S0lf to a pH <2, cool to 4°C.
Samples should be analyzed as soon after collection as possible.
Grab (S-ll) or composite (S-10) aqueous samples, or impinger sorbent
gaseous samples (S-07) may be analyzed using this method.
Method: The sample is first treated with a dechlorinating agent to
remove residual chlorine. The pH of the sample is adjusted to 9.5
with sodium hydroxide. The sample is transferred to a Kjeldhal
flask containing borate buffer, distilled into an Erlenmeyer
flask containing boric acid solution. The distillate is diluted
with distilled water.
The ammonia content is determined titrimetrically by adding a
mixed indicator (methyl red/methylene blue solution freshly
prepared) to the distillate, titrating the ammonia with 0.02N
H2S04, and matching the endpoint against a blank containing the
same volume of distilled water and H3B03solution (Pale lavender
color).
A-161
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METHOD NUMBER: A-27
To determine the concentration of ammonia present at <_ 1 mg/L
a colorimetric determination is used. An aliquot of the sample
is nesslerized and the absorbance read at 425 nm. The ammonia
content is determined from a prepared standard curve of absorbance
vs_ mg NH3.
LIMITATIONS: Cyanate if present may hydrolyze under test conditions.
Residual chlorine or oxidizing agents must be removed by pretreat-
ment before distillation as described in the method.
SENSITIVITY: Can range from 1.0 to 20 mg/L depending on the sample
volume analyzed.
QA/QC: Calibration solutions are prepared and analyzed in order to
generate a calibration curve. Blanks, calibration standards, blank
spikes, matrix spikes and matrix replicates should be analyzed
with each sample set.
EXTERNAL COST:
Per single analysis $15-$25
INTERNAL COST:
Manhours/analysis 0.5-1
Capital Equipment:
Distillation Unit $300-$! ,500
A-162
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METHOD NUMBER: A-27
REFERENCES: US EPA. Proposed Rules. Federal'Register, 44 (233),
December 3, 1979. (Amendment to 40 CFR 136 )
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1981. ('Method D-1426 -
Tests for Ammonia Nitrogen in Water)
US EPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
(NTIS No. PB 297686/AS) pp. 159.
American Public Health Association, Amerian Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APHA, Washington,
D.C., 1976. pp. 407. (Method 418)
A-163
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METHOD NUMBER: A-28
ANALYTICAL METHOD: Distillation/Colorimetry
ANALYTES: Cyanide, Total
DESCRIPTION: Cyanide as HCN is released from cyanide complexes by
reflux-distillation and absorbed in a scrubber containing NaOH.
The cyanide ion in the absorbing solution is determined by titration
or col orimetry.
APPLICATIONS: Aqueous samples and impinger solutions from gas sample
collection.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Preserve with NaOH to pH >12; cool, 4°C.
Samples should be analyzed within 24 hours of collection, or as
soon as possible, and the time from collection to analysis re-
ferenced. Grab (S-ll) or composite (S-10) aqueous samples or
impinger sorbed gaseous samples (S-07) may be analyzed using this
method.
The sample is prepared for analysis by first removing several in-
terferences. Oxidizing agents (indicated by Kl-starch test paper)
are removed with ascorbic acid. Sulfides (indicated by lead acetate
test paper) are removed with cadmium carbonate. Fatty acids are
removed by a single extraction with hexane at pH 6-7. Following
the extraction the pH is raised above pH 12.
Method: An aliquot of the sample is distilled in the presence of
sulfuric acid and Cu2Cl2or MgCl2 the gases trapped in sodium hydroxide.
A-164
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METHOD NUMBER: A-28
The total cyanide concentration is determined by adding Chlormine
T to the solution and mixing throughly. After 1-2 minutes a
pyridine-barbituric acid (or pyridine-pyrazolone) solution is added
and the absorbance read at 578 nm (630 nm when using pyridine-
pyrazolone) after the start of color development, 8-15 minutes,
(40 minutes for pyridine-pyrazolone). Alternatively, the solution
may be titrated with silver nitrate in the presence of benzylrhodamine
indicator to the first color change from yellow to brownish pink.
LIMITATIONS: The distillation step removes most interferences.
Sulfides must be removed prior to preservation by precipitation
with a lead or cadmium salt and filtration. Oxidizing agents
such as chlorine and other interferences must be removed to pre-
vent cyanide decomposition during reflux-distillation as described
in the method.
SENSITIVITY: Colorimetry - 0.02 to 0.2 mg/L; titration - >1 mq/L,
depending on sample volume and the complexity of the sample matrix.
QA/QC: Calibration solutions are prepared and analyzed in order to
generate a calibration curve. Blanks, calibration standards, blank
spikes, matrix spikes and matrix replicates should be analyzed
with each sample set. The precision and recovery of analysis
should be reported.
EXTERNAL COST:
Per single analysis $20-$40
INTERNAL COST:
Manhours/analysis 0.2-0.4
A-165
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METHOD NUMBER: A-28
Capital Equipment:
Distillation unit and spectrophotometer $600-$2,500
REFERENCES: US EPA. Proposed Rules. Federal Register, 44 (233),
December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1975. [Method D-2036 -
Tests for Cyanides in Water]
US EPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
[NTIS No. PB 297686/AS]/ pp. 40.
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APHA, Washington,
D.C., 1976. pp. 361 [Method 413]
ALTERNATES: Ingersoll, D., W.R. Harris, and D.C. Bomberger, "Ligand
Displacement Method for the Determination of Total Cyanide," Anal.
Chem. 53, 2254-2258, 1981.
Luthy, A. Manual of Methods: Preservation and Analysis of Coal
Gasification Wastewaters. Environmental Studies Institute,
Carnegie-Mellon University, Pittsburgh, PA, July, 1977.
A-166
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METHOD NUMBER: A-29
ANALYTICAL METHOD: Precipitation/Titration
ANALYTES: Sulfide
DESCRIPTION: Excess iodine is added to a sample previously treated
with zinc acetate to produce zinc sulfide. The iodine oxidizes the
sulfide to sulfur under acidic conditions. Excess iodine is back-
titrated with sodium thiosulfate. The iodine consumption is
proportional to sulfide concentration.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples may need to be filtered to remove
suspended solids prior to preservation of the filtrate by zinc
acetate addition. Samples should be analyzed for sulfide within
24 hours or as soon as possible and the time from collection to
analysis referenced. Grab (S-ll) or composite (S-10) sample
may be analyzed, however, compositing may cause loss of highly
volatile sulfides.
Method: A volume of standard iodine solution (estimated to be in
excess of the amount of sulfide present) is added to the sample.
If the iodine color disappears, more is added until the color
remains. The total volume added is recorded. To this sample is
also added 2 ml of 6N HC1.
The solution is titrated with 0.0250N sodium thiosulfate (reducing
solution) using a starch indicator until the blue color disappears.
The total volume titrated is recorded and sulfide concentrations
calculated.
A-167
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METHOD NUMBER: A-29
LIMITATIONS: Suspended solids may mask the end point if not removed
prior to the test. Reduced sulfur components may decompose and
yield erratic results. Therefore, the zinc sulfide precipitate may
be separated by filtration and saved for analysis. Samples must
be taken with minimum aeration to minimize volatile or oxidative
losses.
SENSITIVITY: 0.1 to 5 mg/L
QA/QC: Calibration standards are prepared and analyzed in order to
generate a calibration curve. Reagents should be standardized and
blanks, calibration standards, blank spikes, matrix spikes, and
matrix replicates should be analyzed with each sample set. The
precision and recovery of analysis should be reported.
EXTERNAL COST:
Per single analysis $10-$25
INTERNAL COST:
Manhours/analysis 0.1-0.2
Capital Equipment:
Miscellaneous laboratory$200
equipment
REFERENCES: US EPA. Proposed Rules. Federal Register,-44 (233),
December 3, 1979. (Amendment to 40 CFR 136)
US EPA, Office of Technology Transfer, Methods for Chemical
Analysis of Water and Wastes, EPA-625/6-74-003, Washington, D.C.
1974. (NTIS No. PB 297686/AS) pp. 284.
A-168
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METHOD NUMBER: A-29
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APHA, Washington,
D.C., 1976. pp. 499 [Method 428]
A-169
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METHOD NUMBER: A-30
ANALYTICAL METHOD: Colorimetry
ANALYTES: Thiocyanate ion
DESCRIPTION: Thiocyanate ion forms an intense red color in the pre-
sence of ferric ion at acidic pH.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Remove sulfides if present by cadmium, or
lead salt addition and filtration of the sulfide precipitate.
Cyanide interference must be removed by chlorination. Reducing
agents must be overcome with H202- Hexavalent chromium is reduced
by FeSO^ addition under acid conditions, raising the pH to 9
precipitates Fe (+3) and Cr(+3). Grabs (S-ll) or composite (S-10)
samples may be analyzed using this method.
Method: A sample aliquot is filtered. The pH is adjusted to pH 5
to 7 by the addition of nitric acid dropwise. Ferric nitrate
solution is added and the pH is adjusted to between pH 1 and 2.
The sample is diluted with distilled water and shaken well. The
absorbance is measured at 480 nm. Distilled water is used as a
reference blank.
LIMITATIONS: The method must be verified for samples which are either
highly colored or contain organic compounds. It is important that
sulfide, cyanide, hexavalent chromium and reducing agents are
removed from the samples prior to analysis as noted in the prepara-
tive requirements.
A-170
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METHOD NUMBER: A-30
SENSITIVITY: 1-4 mg/L
QA/QC: Calibration standards are prepared and analyzed in order to
generate a calibration curve. Blanks, calibration standards, blank
spikes, matrix spikes and matrix replicates should be analyzed with
each sample set. The precision and recovery of analysis should be
reported.
EXTERNAL COST:
Per single analysis $10-$30
INTERNAL COST:
Manhours/analysis 0.1-0.3
Capital Equipment:
Spectrophotometer $500-$2,000
PRIMARY REFERENCE: American Public Health Association, American
Water Works Association, and Water Pollution Control Federation.
Standard Methods for the Examination of Water and Wastewater,
14th edition. APAA, Washinton, D.C., 1976. pp. 383. [Method 413
Part K]
ALTERNATE REFERENCE: Luthy, Richard A., "Manual of Methods:
Preservation and Analysis of Coal Gasification Wastewaters,"
Environmental Studies Institute, Carnegie-Mellon University,
Pittsburgh, PA, July 1977
A-171
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METHOD NUMBER: A-31
ANALYTICAL METHOD: Specific Ion Electrode
ANALYTES: Fluroide ion
DESCRIPTION: Specific ion electrode determination of fluoride is
accomplished with a pH meter utilizing an expanded millivolt scale,
or a selective ion meter with direct concentration scale.
APPLICATIONS: Aqueous streams.
GENERAL METHOD PARAMETERS:
Preparative Requirements: This analytical technique is applicable
for grab (S-ll) or composite (S-10) samples, or impinger solutions
(S-07), if EPA Method 13 is not required.
Method: A aliquot of the sample and a buffer are added to a beaker.
The beaker is placed on a magnetic stirrer at a medium speed. The
electrodes are immersed in the solution and allowed to equilbrate
for 3 to 5 minutes. The fluoride level is read directly as mg/L
fluoride on the fluoride scale of the selective ion meter. When
a pH meter is used, the potential measurement is recorded for each
sample. This is converted to a fluoride ion concentration using
a standard curve of pH potential vs_ fluoride ion concentration.
LIMITATIONS: Si(+4), Fe(+3), and Al(+3) which can interfere by com-
plexing the fluoride ion are chelated. The effects of variable pH
and ionic strength on the analysis can be overcome by strong
i
buffering of the solution.
SENSITIVITY: 0.01 to 0.1 mg/L
A-172
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METHOD NUMBER: A-31
QA/QC: Calibration standards are prepared and analyzed in order to
generate a calibration curve. Blanks, calibration standards, blank
spikes, matrix spikes and matrix replicates should be analyzed with
each sample set. The precision of an analysis should be reported.
EXTERNAL COST:
Per single analysis $15-$30
INTERNAL COST:
Manhour/analysis 0.1-0.3
Capital Equipment:
pH meter, electrodes $500-$!,500
PRIMARY REFERENCES: US EPA Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31. Philadelphia, PA. 1981. [Method D-1179 - Tests
for Fluoride Ion in Water]
US EPA Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
[NTIS No. PB 297686/AS]. pp. 59.
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APAA, Washington,
D.C., 1976. pp. 387. [Method 414]
A-173
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METHOD NUMBER: A-32
ANALYTICAL METHOD: Cadmium Reduction/Spectrophotometry
ANALYTES: Nitrate, Nitrite
DESCRIPTION: A filtered sample is passed through a granulated copper-
cadmium column to reduce nitrate to nitrite. Nitrite is determined
spectrophotometrically after formation of a highly colored azo dye.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: The sample is kept cool (4°C) and should be
analyzed within 24 hours or as soon as possible. Samples requiring
longer storage prior to analysis should be preserved with H2SOtf
to a pH <2 , in addition to being kept cool. Tubridity is removed
by filtration and oil and grease by solvent extraction. Grab (S-ll)
of composite (S-10) samples may be analyzed using this method.
Method: The pH of the sample is adjusted to between 5 and 9 with
hydrochloric acid or ammonium hydroxide. The sample is passed
thorugh a reduction column (cadmium-copper granules). The
nitrite-nitrate nitrogen is determined by diazotizing the total
nitrite ion with sulfanilimide and cooling with N-(l-naphthyl)-
ethylene diamine dihydrochloride and the adsorbance read. Nitrate only
may be determed by omitting the cadmium reduction step. Nitrate is then
calculated as the difference between nitrate-nitrite and nitrite.
LIMITATIONS: The reduction column can be affected by suspended matter,
oil and grease. These interferences should be removed prior to
the column reduction step. Sulfide may also interfere with the
reduction column operation and/or efficiency. Excessive amounts of
chlorine will deactivate the reducing column.
A-174
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METHOD NUMBER: A-32
SENSITIVITY: 0.01 to 0.1 mg/L
QA/QC: Calibration standards are prepared and analyzed in order to
generate a calibration curve. Standards are analyzed in decreasing
order of concentration. Blanks, calibration standards, blank spikes,
matrix spikes, and matrix replicates (diluted samples) should be
analyzed with each sample set. The precision and recovery of
analysis should be reported.
EXTERNAL COST:
Per single analysis $15-$30
INTERNAL COST:
Manhours/analysis 0.1-0.4
Capital Equipment:
Column, spectrophotometer $600-$2,500
PRIMARY REFERENCES: US EPA. Proposed Rules. Federal Register, 44
(233), December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31, Philadelphia, PA, 1981. [Method D-3868-79-
Nitrite-Nitrate in Water]
US EPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
[NTIS No. PB 2976867AS], pp. 201.
A-175
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METHOD NUMBER: A-32
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APAA, Washington,
D.C., 1976. pp. 418. [Method 419]
A-176
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METHOD NUMBER: A-33
ANALYTICAL METHOD: Silver Nitrate Titration with Potentiometric
End-point Determination
ANALYTES: Chloride
DESCRIPTION: Chloride is determined by potentiometric titration.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Preservation not required. Sulfite, sulfide,
cyanide (Fe(+3))and organic interferences are removed by acidification
with H2S01+ and boiling, and finally, treatment with alkaline H202 and
further boiling.
Grab (S-ll), composite (S-10) or impinger (S-07) samples may be
analyzed using this method.
Method: The pH of the sample is adjusted to 8.3. Chloride is deter-
mined by potentiometric titration with silver nitrate solution
using a glass and Ag/AgCl electrode system. A millivolt meter is
used to detect changes in potential. The endpoint of the titra-
tion is that reading at which the greatest potential change per
titrant volume is observed.
LIMITATIONS: Organic compounds, S03, FE(+3), CN(-l) and S(-2)
interfere. Pretreatment requires boiling under acidic (H2S0lt)
conditions, then with H202, and finally alkaline (NaOH conditions.)
SENSITIVITY: 2-10 mg/L
A-177
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METHOD NUMBER: A-33
QA/QC: The potentiometer (pH - meter) and AgN03 titrant are standardized
using a standard NaCl solution. A differential titration curve is
plotted to determine the exact endpoint. Blanks, blank spikes*
matrix spikes and matrix replicates should be analyzed with each
sample set. The precision and recovery of analysis should be
reported.
EXTERNAL COST:
Per single analysis $10-$35
INTERNAL COST:
Manhours/analysis 0.2-0.4
Capital Equipment:
Millivoltmeter, electrodes, hot plate $600-$2,000
PRIMARY REFERENCES: US EPA. Proposed Rules. Federal Register, 44
(233), December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1981. [Method D-512 -
Chloride]
US EPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
[NTIS No. PB 297686/AS]. pp. 29.
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APAA, Washington,
D.C., 1976. pp. 302. [Method 408]
A-178
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METHOD NUMBER: A-33
ALTERNATE REFERENCE: Fritz, J.S., D.T. Gjerde, and C. Pohlandt. Ion
Chromatography. Huthig Verlag. Heidelberg, New York. 1982.
A-179
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METHOD NUMBER: A-34
ANALYTICAL METHOD: lodometric Titration
ANALYTES: Sulfite
DESCRIPTION: An acidified sample containing a starch indicator is
titrated with a standard KI/KIOs titrant to a faint permanent blue
end'-point which appears when the reducing power of the sample is
exhausted.
APPLICATIONS: Aqueous samples.
GENERATED METHOD PARAMETERS:
Preparative Requirements: The sample is kept cool (4°C) and aeration or
filtration is minimized. Sulfide if present must be removed by
precipitation with zinc acetate. (P-ll). Grab samples (S-ll) are
most appropriate for this analysis. Sample contact with air must
be kept to a minimum. A portion of an EDTA Solution (a preservative)
should be added to the sample prior to analysis.
Method: An aliquot of sample is placed in a titration vessel.
Sulfuric acid crystals, and the starch indicator is added. The
sample is titrated with a potassium iodide-iodate titrant until
a permanent faint blue color develops. It is important to keep
the pipet tip below the surface of the sample. The volume of
titrant is recorded and sulfite concentration calculated.
LIMITATIONS: Fe(+2) and S(-2) and other oxidizable components are
positive interferences and must be addressed (P-ll). Nitrate if
present will oxidize sulfite upon acidification. Heavy metals
will catalyze sulfite oxidation.
SENSITIVITY: 2-10 mg/L.
A-180
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METHOD NUMBER: A-34
QA/QC: Blanks, standard solutions, matrix spikes and matrix replicates
should be analyzed with each sample set. The precision of analysis
should be reported.
EXTERNAL COST:
Per single analysis $10-$25
INTERNAL COST:
Manhours/analysis 0.2-0.4
Capital Equipment:
Glassware $100
REFERENCES: US EPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1981. [Method D-1339 -
Tests for Sulfite Ion in Water]
US EPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
[NTIS No. PB 297686/AS]. pp. 285.
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APAA,
Washington, D.C., 1976. pp. 508. [Method 429]
A-181
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METHOD NUMBER: A-35
ANALYTICAL METHOD: Turbidimetric Analysis
ANALYTES: Sulfate
DESCRIPTION: Sulfate ions are converted to a barium sulfate sus-
pension under controlled conditions. The resulting turbidity is
determined spectrophotometrically and compared to a sulfate
standard calibration curve.
APPLICATIONS: Aqueous samples. -
GENERAL METHOD PARAMETERS:
Preparative Requirements: The sample is kept cool (4°C)- Grab (S-ll)
or composite (S-10) samples may be analyzed by this method.
Method: A portion of conditioning solution (solution containing
glycerol, Cone HC1, NaCl, isopropyl alcohol in distilled water),
is added to the sample and the solution is stirred. BaCl2 crystals
are added.
The turbidity is measured at regular intervals at 420 nm for 4
minutes; at which time a maximum reading is recorded. The sample
is run against a blank treated as stated above without the addition
of Bad2- Concentration of the samples are determined by com-
parison to a calibration curve.
LIMITATIONS: Suspended matter and color will interfere; this is
corrected by analysis of sample blanks (without barium).
SENSITIVITY: 1-5 mg/L
A-182
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METHOD NUMBER: A-35
QA/QC: Calibration standards are prepared and analyzed in order to
generate a calibration curve. Blanks, calibration standards,
matrix spikes and matrix replicates should be analyzed with each
sample set.
EXTERNAL COST:
Per single analysis $10-$20
INTERNAL COST:
Manhours/analysis 0.1-0.2
Capital Equipment:
Spectrophotometer $500-$2,500
REFERENCES: US EPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136].
American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1975. [Method D-516 -
Tests for Sulfate Ion in Water and Wastewater].
US EPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D.C., 1974.
[NTIS No. PB 297686/AS]. pp. 277.
American Publich Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APAA, Washington,
D.C., 1976. pp. 493 [Method 427].
A-183
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METHOD NUMBER: A-36
ANALYTICAL METHOD: Radioactivity
ANALYTES: Gross alpha, gross beta.
DESCRIPTION: An aliquot of the aqueous sample is evaporated and dried;
the residue analyzed. Alpha and beta emissions are counted by gas
proportional counter.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Preserve filtered (to determine dissolved
radioactivity) or unfiltered (to determine total radioactivity)
samples with HN03 to pH <2. Grab (S-ll) or composite samples
may be analyzed using this method.
Method: A sample aliquot containing not more than 200 mg of residue
for beta examination and not more than 100 mg residue for alpha
examination is taken for each 20 cm2 of counting per area. The
sample is evaporated slowly just below boiling. The sample is
placed in a 105°C oven to complete dryness, then allowed to cool
in a clean dry desiccator. The sample is weighed and placed in an
internal counter (or geiger counter) for alpha and beta activity
counts.
If the residue has airborne particles, a few drops of a Lucite
solution is added and allowed to set. This acts as a binder to
prevent counter contamination by such particles.
For determination of the activity of dissolved solids. The sample
is filtered through a Gooch crucible. The filtrate is treated in
the same manner as above.
A-184
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METHOD NUMBER: A-36
LIMITATIONS: Maximum of 200 mg residue/200 cm2 counting pan for
alpha analysis; 100 mg for beta.
SENSITIVITY: Dependent on counter.
QA/QC: Standards are used for instrument calibration. Blanks and
matrix replicates should be analyzed with each sample set. The
precision of analysis should be reported.
EXTERNAL COST:
Per single analysis $30-$50
INTERNAL COST:
Manhours/analysis 0.1-0.2
Capital Equipment:
Gas proportional counter $10,000-$30,000
REFERENCES: American Public Health Association, American Water Works
Association, and Water Pollution Control Federation. Standard Methods
for the Examination of Water and Wastewater, 14th edition. APAA,
Washington, D.C., 1976. pp. 633-679. [Method 703].
American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31. Philadlphia, PA, 1975. [Method D-3084 -
Alpha Spectrometry, D-1890 - Beta Particle Radioactivity, D-3085 -
Activity, Low Level].
US EPA. Proposed Rules. Federal Register, 44 (233), December 3,
1979. [Amendment to 40 CFR 136].
A-185
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METHOD NUMBER: A-37
ANALYTICAL METHOD: Extraction/Gravimetric Analysis
ANALYTES: Oil and grease,
DESCRIPTION: Oil and grease is serially extracted from the water
sample with Freon-113 in a separatory funnel. The solvent is
evaporated from the extract and the residue is weighed. For
samples containing extractable free sulfur, infrared detection
of oil and grease should be used.
APPLICATIONS: Aqueous samples
GENERAL METHOD PARAMETERS:
Preparative Requirements: The sample is preserved with HC1 to a pH
<2 and kept cool (4°C) if analysis cannot be performed within a few
hours of collection. Grab samples (S-ll) are preferred for analysis
using this method.
Method: The sample is extracted with Fluorocarbon-113 (Freon-113) and
transferred. The extract is filtered through moistened filter paper
into a clear, tared boiling flask (if any emulsion fails to break,
pass anhydrous emulsion through Na?SOi+). The extract is repeated
twice and all extracts combined in the collection flask.
The boiling flask is connected to a distilling head, and the
solvent evaporated slowly by immersing the flask in warm water
(70°C). As the flask appears to be dry, the distilling head is
removed and flask swept with air to remove all solvent vapor.
The flask is cooled in a desiccator and weighed for gravimetric
determination.
A-186
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METHOD NUMBER: A-37
LIMITATIONS: The method is applicable to relatively non-volatile
hydrocarbons, vegetable oils, animal fats, and waxes. Light
hydrocarbons that volatilize below 70°C are lost. Some crude
and heavier fuel oils are only partially recovered due to com-
ponents insoluble in Freon-113. Samples containing sulfide will
form free sulfur upon preparative acidification. This sulfur
is somewhat soluble in Freon-113 and may bias gravimetric results.
SENSITIVITY: 5-50 mg/L
QA/QC: Blanks, blank spikes, matrix spikes and matrix replicates
should be analyzed with each sample set. The precision and re-
covery of analysis should be reported.
EXTERNAL COST:
Per single analysis $15-$40
INTERNAL COST:
Manhours/analysis 0.2-1
Capital Equpment:
Special glassware, vacuum pump, balance $2,000-$5,000
REFERENCES: US EPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136].
American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31. Philadelphia, PA, 1981. [Method D-2778 -
Solvent Extraction of Organic Matter from Water].
A-187
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METHOD NUMBER: A-37
US EPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington D.C., 1974.
[NTIS No. PB 297686/AS]. pp. 226.
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APHA, Washington,
D.C., 1976. pp. 513. [Method 502].
A-188
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ANALYTICAL METHOD:
METHOD NUMBER: A-38
Ascorbic Acid Colorimetric Method for Dissolved,
Hydrolyzable, or Total Phosphorus
ANALYTES:
Phosphorus
DESCRIPTION: Phosphorus (phosphate) solutions react with ammonium
molybdenate and potassium tartrate in an acid medium to form a
complex which, when reduced with ascorbic acid, is intensely blue
colored. The color is proportional to the phosphorus concentration.
Other phosphorus forms can be converted to phosphate by acid
digestion with sulfuric acid or by persulfate digestion.
APPLICATIONS: Aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: The method of preparation depends on the
information required:
Analyte
P (POt, Dissolved)
P (Total, Hydrolyzable)
P (Total)
P (Total, Dissolved)
Preservation
Filter
Cool to 4°C
Cool to 4°C,
H2S04 to pH <2
Cool to 4°C,
H2S04 to pH <2
Filter
Cool to 4°C,
H2SO^ to pH <2
Preparation
None
H2SOl+ hydrolysis
Persulfate digestion
Persulfate digestion
Grab (S-ll) or composite (S-10) samples may be analyzed using this
method.
A-189
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METHOD NUMBER: A-38
Method: Phosphorus, hydrolyzable phosphorus, and other forms
are converted to the phosphate by sulfuric acid or persulfate
digestion. Once prepared, the pH of the sample is adjusted to
> +. 0.2 using a pH meter.
An aliquot of freshly prepared, combined reagent (ascorbic acid
solution, ammonium molybdate solution, potassium antimohyltartrate
solution and dilute sulfuric acid) is added to the sample. After
setting, the color absorbance is measured at 650 or 880 nm with
a spectrophotometer, using a reagent blank as a reference.
SENSITIVITY: 0.01 to 0.1 mg/L as phosphorus.
QA/QC: Calibration standards are prepared and analyzed in order to
generate a calibration curve. Blanks, calibration standards,
blank spikes, matrix spikes and matrix replicates should be
analyzed with each sample set. The precision and recovery of
analysis should be reported.
EXTERNAL COST:
Per single analysis $15-$40
INTERNAL COST:
Manhours/analysis 0.2-0.4
Capital Equipment:
Spectrophotometer $500-$2,500
A-190
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METHOD NUMBER: A-38
REFERENCES: USEPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials, Annual Book of
ASTM Standards, Part 31. Philadelphia, Pennsylvania, 1981.
[Method D-515 - Test for Phosphorus in Water]
USEPA, Office of Technology Transfer, Methods for Chemical
Analysis of Water and Wastes, EPA 625/6-74-003, Washington, D.C.,
1974, p. 249. [NTIS No. PB 297686/AS]
American Public Health Association, American Water Works Association
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th Edition. APHA,
Washington, D.C., 1976, p. 466. [Method 425]
A-191
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METHOD NUMBER: A-39
ANALYTICAL METHOD: Acid/Base Titration
ANALYTES: Acidity, alkalinity
DESCRIPTION: An unfiltered sample is titrated to an electromagnetic
endpoint of pH 4.5 for alkalinity determination. Acidity is
determined by titration to electrometric endpoints of pH 8.3
and 3.7. Standard indicators (phenolphthalein, methyl orange)
may be used.
APPLICATIONS: Aqueous samples
GENERAL METHOD PARAMETERS:
Preparati ve Requi rements: The sample is kept cool (4°C) and analyzed
as soon as possible. Grab (S-ll) or composite (S-10) samples are
analyzed using this method.
Method:
Acidity. An aliquot of the sample is pipeted into a beaker. The
pH is measured and lowered to pH 4 or less with a standard sulfuric
acid solution. Hydrogen peroxide is added and the sample boiled
for several minutes (to remove ferrous iron present).
The sample is cooled to room temperature and titrated electro-
metrically with a standard sodium hydroxide solution to a pH
of 8.3. (Solution may be titrated to phenolphthalein endpoint
as well.)
Alkalinity. An aliquot of the sample is pipeted into a beaker.
The pH is measured and recorded. The sample is titrated
A-192
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METHOD NUMBER: A- 39
electrometrically with standard acid (sulfuric or hydrochloric)
solution to a pH of 4.5. The volume is recorded and alkalinity
determined (low alkalinity requires slightly modified conditions).
LIMITATIONS: Samples with high concentrations of mineral acids may
undergo a shift in the titration endpoint pH. Calculations are
made on a stoichiometric basis; therefore, iron concentrations
are not rigorously represented in the results.
SENSITIVITY: Highly dependent on concentration of the titrant;
can vary from 1 to 100 mg/L
QA/QC: The normality of the titrant should be verified regularly
during analysis of samples. A check of titration endpoint,
verification of pH as a function of titrant volume, may be
necessary for unknown samples.
SAMPLING REQUIREMENTS: Analytical technique is applicable for
grab (S-ll) or composite (S-10) samples.
EXTERNAL COST:
Per single analysis $10-$25
INTERNAL COST:
Manhours/analysis 0.1-0.3
Capital Expenditure:
pH meter and electrodes $300-$! ,300
A-193
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METHOD NUMBER: A-39
REFERENCES: USEPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadelphia, Pennsylvania, 1981.
[Method D-1067 - Tests for Acidity or Alkalinity of Water]
USEPA, Office of Technology Transfer, Methods for Chemical
Analysis of Water and Wastes, EPA 625/6-74-003, Washington, D.C.,
1974, p. 1. [NTIS No. PB 297686/AS]
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th Edition. APHA,
Washington, D.C., 1976, p. 273. [Method 402, Method 403]
A-194
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METHOD NUMBER: A-40
ANALYTICAL METHOD; Elemental Analysis by Inductively Coupled Optical Emis-
sion Spectroscopy (ICP) or Atomic Absorption Spectroscopy (AA)
ANALYTES: Ag, Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo,
Na, N1, Pb, Sb, Se, S1, Te, T1, Tl, V, Zn.
PREPARATIVE REQUIREMENTS; Preservation of a filtered sample (to determine
dissolved metals) or an unflltered sample (to determine total metals)
with HNO to pH <2.
LIMITATIONS: No single sample preparation technique 1s applicable for com-
plete conversion of all element from solid to liquid phase. In many
cases the water sample matrix Interfer with the analysis. Viscosity dif-
ferences between samples and standards can result 1n different sample
aspiration rates and therefore bias results.
SENSITIVITY! Dependent on both element and method:
Sensitivity
(mg/L) Elements
0.001-0.01 Ag,Al,Ba,Be,Cd,Co,Cr,Cu,Mn,Mo,N1,V,Zn,Al,
0.01-0.1 As,B,Ca,Fe,Hg,K,Mg,Na,Pb,Sb,Se,S1,T1,
0.1-1.0 Te,Tl
.QAZQC: Good laboratory practice Including blanks and dally standard cali-
bration curves.
SAMPLING REQUIREMENTS; Analytical technique 1s applicable for grab (S-ll)
or composite (S-10) samples.
A-195
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METHOD NUMBER: A-40
EXTERNAL COST!
Per single analysis:
AA/element $8-$24
ICP/sample $50-$200
INTERNAL COST!
Manhours/analysls
AA/element 0.1-0.3
ICP/sample 0.1-0.2
Capital Equipment:
AA and lamps $10,000-$50,000 (depending on optical resolution)
ICP $50,000-$250,000 (depending on multielement capa-
bilities, resolution, data
systems)
PRIMARY REFERENCES; USEPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136].
American Society for Testing and Materials, Annual Book of ASTM Stan-
dards, Part 31. Philadelphia, PA, 1975. [Numerous methods, by element
of Interest],
A-196
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METHOD NUMBER; A-40
USEPA, Office of Technology Transfer, Methods for Chemical Analysis of
Water and Wastes, EPA-625/6-74-003, Washington, D. C., 1974. [NTIS No.
PB 297686/ASD. pp. 78-156.
American Public Health Association, American Water Works Association, and
Water Pollution Control Federation. Standard Methods for the Examination
of Water and Wastewater, 14th edition. APHA, Washington, D. C., 1976.
p. 143. [Part 300 - Determination of Metals],
A-197
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METHOD NUMBER: A-41
ANALYTICAL METHOD: Spectrophotometric Determination of Nitrogen
Oxides in Vapor Phase Samples
ANALYTES: Nitrogen dioxide
DESCRIPTION: Sorbent solutions are analyzed Spectrophotometrically
and the intensity related to sample concentration
APPLICATIONS: Spectrophotometry is applicable for the analysis of
Saltzman solutions, and the sulfuric acid/peroxide catch from EPA
Method 7 after the evaporation and phenoldisulfonic acid reaction.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Saltzman solutions stable for a week prior
to analysis if kept cool (<25°C), dark and in an 502-free atmosphere.
Method 7 solutions must be held 16 hours prior to analysis for
reaction completion. Vapor phase samples (S-02) are analyzed
using this method.
Method: A sample aliquot is taken to dryness on a steam bath. After
cooling, phenoldisulfonic acid solution is added to the residue
(ground to a fine powder). Distilled water and concentrated
sulfuric acid are added to the powdered residue, followed by
heating.
The solution is transferred to a volumetric flask and brought to
volume with distilled water. The absorbance is measured between
400 and 415 nm (maximum absorbance determined using standard
solutions). The absorbance of the sample is compared with those
of calibration standards run (dilutions may be required to bring
the sample into the range of the calibration curve).
A-198
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METHOD NUMBER: A-41
LIMITATIONS: Nitrous oxide (NO) is not measured using EPA Method 7
or the Saltzman technique. Chloride interferes with Method 7
analytical preparation. Ozone at 5:1 and SOp at 30:1 interfere
with Saltzman technique, addition of 1% acetone to Saltzman
reagent minimizes the SOo interference. Saltzman stoichiometric
factor is disputed.
SENSITIVITY: Saltzman method O.l-l yg N02/ml_, gas volume can be
increased to achieve low stream concentration. EPA Method 7
minimum detection level ^10 vppm.
QA/QC: Calibration standards are prepared and analyzed. Blanks,
matrix replicates, and matrix dilutions should be analyzed
with each sample set. The precision of analysis should be
reported.
EXTERNAL COST:
Per single analysis $20-$100
INTERNAL COST:
Manhours/analysis 0.2-4 (depending on
technique)
Capital Equipment:
UV Spectrophotometer $200-$2,500 (depending on
range and optical quality)
A-199
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METHOD NUMBER: A-41
PRIMARY REFERENCES: Title 40, CFR Part 60, Appendix A, December 5, 1980.
[Method 7 - Determination of Nitrogen Oxide Emissions from Stationary
Sources]
Texas Air Control Board, Laboratory Methods for Determination of
Air Pollutants, Laboratory Division, Austin, TX, 1978.
Purdue, L.J., J.E. Dudley, J.B. Clements, and R.J. Thompson.
Reinvestigation of the Jacobs-Hochheiser Products for Determining
Nitrogen Dioxide in Ambient Air, Environ. Sci. & Tech., 6_(2) :152-154,
February 1972.
ALTERNATE METHODS: Jacobs, M.B., and S. Hochheiser, Continuous
Sampling and Ultra-Microdetermination of Nitrogen Dioxide in Air.
Anal. Chem., 30_, 1958, p. 426.
Christie, A.A., R.G. Lidzey, and D.W.F. Radford, Field Methods of
the Determination of Nitrogen Dioxide in Air, The Analyst, 95,
May 1970, p. 519.
A-200
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METHOD NUMBER: A-42
ANALYTICAL METHOD: Instrumental Methods for Total Organic Carbon
ANALYTES: Organic carbon
DESCRIPTION: Organic carbon is determined by oxidation with infrared
detection (2-200 mg/L range) or reduction with flame ionization
detection (1-2000 mg/L range).
APPLICATIONS: Aqueous streams
GENERAL METHOD PARAMETERS:
Preparative Requirements: Preserve the H2S04 to pH <2 and refrigerate
to 4°C. Grab (S-ll) or composite (S-10) samples may be analyzed
using this method.
Method: Organic carbon in a sample is converted to carbon dioxide (C02)
by catalytic combustion or wet chemical oxidation. The COo formed
can be measured directly by infrared detector or converted to
methane (CH^) and measured by a flame ionization detector. The
amount of C02 or CH. is directly proportional to the concentration
of carbonaceous material in the sample.
LIMITATIONS: Results may be influenced by sample handling prior or
during the analysis. Organic carbon can be determined by difference
between the total and inorganic carbon or by analysis of an acidified
sparged sample. Sparging may result in a loss of volatile components.
Analysis of samples with a high inorganic carbon content for low
level TOC by difference may result in poor accuracy and precision.
Filtration of the sample prior to analysis will limit the determin-
ation to soluble or dissolved organic carbon.
A-201
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METHOD NUMBER: A-42
SENSITIVITY: 0.1 to 10 rng/L.
QA/QC: Calibration standards are prepared and analyzed in order
to generate a calibration curve. Blanks, calibration standards,
blank spikes, matrix spikes, and matrix replicates should be
analyzed with each sample set. The recovery and precision of
analysis should be reported.
EXTERNAL COST:
Per single analysis $15-$35
INTERNAL COST:
Manhours/analysis 0.1-0.2
Capital Equipment:
Total Organic Carbon Analyzer $10,000-$25,000
PRIMARY REFERENCES: USEPA. Proposed Rules. Federal Register,
44(233), December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31. Philadelphia, Pennsylvania, 1975.
[Method D-2579 - Tests for Total and Organic Carbon in Water]
A-202
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METHOD NUMBER: A-42
USEPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA 625/6-74-003, Washington, D.C., 1974, p. 236.
[NTIS No. PB 297686/AS]
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th Edition. APHA,
Washington, D.C., 1976, p. 532. [Method 505]
A-203
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METHOD NUMBER: A-43
ANALYTICAL METHOD: Infrared Analysis for Inorganic Carbon
ANALYTES: Total inorganic carbon
DESCRIPTION: Evolved C02 is measured by non-dispersive infrared.
APPLICATIONS: Samples with high levels of dissolved carbonate/bicarbonate
will require dilution. Grab (S-ll) or composite (S-10) samples may be
analyzed using this method.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Sample should be homogeneous, and stored
in glass at 4°C.
Method: Inorganic carbonates are decomposed with acid and sparged as
carbon dioxide. The carbon dioxide evolved is measured with a
non-dispersive infrared analyzer (NDIR). Filtration prior to
analysis limits the results to soluble inorganic carbon.
LIMITATIONS: Volatile organic carbon may be purged and interfere
with the determination.
SENSITIVITY: 0.1 - 100 mg/L.
QA/QC: Calibration standards are prepared and analyzed in order to
generate a calibration curve. Blanks and matrix replicates should
be analyzed with each sample set. The precision of analysis
should be reported.
A-204
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METHOD NUMBER; A-43
INTERNAL COST:
Manhours/analysis 0.1-0.3
Capital Equipment:
Total carbon analyzer $10,000-$25,000
REFERENCE: American Society for Testing and Materials. Annual Book
of ASTM Standards, Part 31, 1975. [Method 505 - Total and Organic
Carbon in Water].
A-205
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METHOD NUMBER: A-44
ANALYTICAL METHOD: Membrane Electrode Measurement
ANALYTES: Dissolved oxygen content
DESCRIPTION: An oxygen sensitive electrode is immersed in the sample.
The diffusion current measured is directly proportional to the
molecular oxygen concentration.
APPLICATIONS: Any aqueous sample. Highly colored or heavily polluted
waters may also be analyzed with this technique.
GENERAL METHOD PARAMETERS:
Method: The membrane electrode is calibrated against a water sample
of known dissolved oxygen concentration (as determined by the
iodometric method), and a blank with no dissolved oxygen (excess
sodium sulfite and trace CoCl^ will bring the dissolved oxygen
content to zero). The electrode is then calibrated for the type
of aqueous sample to be measured, i.e., fresh, salt, estuary, etc.,
water. The dissolved oxygen content of the sample is measured with
the calibrated membrane electrode and reported.
LIMITATIONS: Electrodes generally exhibit high temperature coefficients
due to membrane permeability changes.
SENSITIVITY: Usually to + 0.1 mg/L.
QA/QC: Calibration standards are prepared and analyzed in order to
generate a calibration curve. Blanks, calibration standards and
matrix replicates should be analyzed with each sample set. The
precision of analysis should be reported. Temperature correction
is required.
A-206
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METHOD NUMBER: A-44
EXTERNAL COST:
Per single analysis $10-$25
INTERNAL COST:
Manhours/analysis 0.1-0.2
Capital Equipment:
Dissolved oxygen electrode, meter $500-$! ,500
REFERENCES: American Public Health Association, American Water Works
Association, and Water Pollution Control Federation. Standard
Methods for the Examination of Water and Wastewater, 14th Edition.
Washington, D.C., 1976. [Method 422 - Oxygen Dissolved]
USEPA, Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA 625/6-74-003, Washington, D.C., 1974, p. 51
American Society for Testing and Materials, Annual Book of ASTM
Standards, Part 31. Philadelphia, Pennsylvania, 1975.
[Method D-1589]
A-207
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METHOD NUMBER: A-45
ANALYTICAL METHOD: Ion Chromatography
ANALYTES: Ionic Species, i.e., Sulfate, Chloride, Formate
DESCRIPTION: The aqueous sample is directly injected onto an ion
exchange column. The eluent, which may be varied in ionic strength
or composition for a specific analyte, flows through the column
and the ionic species eluted are quantified by a conductivity
detector. Chemical red-ox potential detection is also available.
Various exchange resins and suppressor column options are available
for specific analysis needs.
APPLICATIONS: Aqueous samples or aqueous extracts of solids may
be analyzed.
GENERAL METHOD PARAMETERS:
Method: 1C may be used for determination of F~, Cl~, NO^, NO^,
SO^, SO^, and PO^ in bulk aqueous liquids and also in the solution
resulting from the aqueous extraction of bulk solids.
A solution of distilled, deionized water containing 0.5 g each of
NaHC03 and Na2C03 per liter is used as the eluent. 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~, NO^.
NOg, PO^, SOf, 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
A-208
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METHOD NUMBER: A-45
interferences is suspected. These include polyvalent cations
such as Fe and Al , which interfere by forming complexes with
F~; and iron, which will interfere with PO^ and Cl~ through
complex formation.
LIMITATIONS: Species which are unstable or have low ionic strength
are difficult to analyze. Complex species do not elute well. Some
suppressor columns require regeneration after a period of usage.
SENSITIVITY: 0.1-10 mg/L depending on column and analyte.
QA/QC: Calibration standards are prepared and analyzed in order to
generate a calibration curve. Blanks, calibration standards,
blank spikes, matrix spikes and matrix replicates should be
analyzed with each sample set. The precision and recovery of
analysis should be reported. Columns must be regenerated
frequently.
EXTERNAL COST:
Per single analysis $10-$60 (depending on
analytes and sample matrix)
INTERNAL COST:
Manhours/analysis 0.1-1 (depending on analytes
and sample matrix)
Capital Equipment:
Ion Chromatograph $15,000-$25,000
A-209
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METHOD NUMBER: A-45
REFERENCES: Fritz, J.S., D.T. Gjerde, and C. Pohlandt. Ion
Chromatography. Huthig Verlag. Heidelberg, New York, 1982.
Small, H., T.S. Stevens, and W.C. Baumar, "Novel Ion Exchange
Chromatographic Method Using Conductirnetric Detection,"
Anal. Chern.. 47, 1801-1809, 1975.
Lentzen, D.E., D.E. Wagoner, E.D. Estes, and W.F. Gutknecht.
EPA/IERL-RTP Procedures Manual: Level 1 Environmental Assessment,
Second Edition. EPA Research Triangle Park, NC, 27709.
EPA-600/7-78-201, 1978.
A-210
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METHOD NUMBER: A-46
ANALYTICAL METHOD: Sedimentation
ANALYTES: Settleable Solids
DESCRIPTION: Solids are measured volumetrically in an Imhoff cone.
APPLICATIONS: All aqueous samples.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples cannot be altered or preserved
chemically. Grab samples (S-ll) may be more appropriate for
determination if sedimentation occurs over long compositing
periods.
Method: An Imhoff cone is filled to the liter mark with a thoroughly
mixed sample. The sample is allowed to settle for 45 minutes,
and gently stirred with a rod or by spinning and allowed to settle
15 minutes longer. The volume of seattleable material is recorded
as mi Hi liters per liter.
LIMITATIONS: Floatable material, if present, is not measured. For
some applications, suspended solids (A-2) which measures both
seattleable and floatable material, may be preferred.
SENSITIVITY: Practical lower level is ^1 mL/L/hr.
EXTERNAL COST:
Per single analysis $10-$30
A-211
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METHOD NUMBER: A-46
INTERNAL COST:
Manhours/analysis 0.2-1
Capital Equipment:
Imhoff cones $20-$50
REFERENCES: USEPA, Office of Technology Transfer, Methods for
Chemical Analysis of Water and Wastes, EPA-625/6-74-003,
Washington, D.C., 1974, p. 273.
American Public Health Association, American Water Works Association
and Water Pollution Control Federation. Standard Methods for
the Examination of Water and Wastewater, 14th edition.
Washington, D.C., 1976 [Method 213].
A-212
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METHOD NUMBER: T-01
TEST METHOD: Laboratory Corrosion Testing of Metals
DESCRIPTION: The corrosivity of wastes may be determined by pH
measurement (H20)or corrosion of steel. A waste is considered to
be corrosive, as defined by RCRA, 40 C.F.R. Part 261.22 if it is
aqueous and has a pH <2 or >_ 12.5; or it is liquid and corrodes
steel at a rate >6.35 mm per year at a test temperature of 55°C.
APPLICATIONS: This technique is applicable to solid streams that
contain a liquid fraction, including organic streams.
GENERAL METHOD PARAMETERS:
Preparative Requirements: The liquid fraction of the solid waste
stream must be separated from solids for use in this test. Cen-
trifugation, filtration, or settling may be used as the separatory
method.
Method:
Corrosivity Toward Steel - The weight loss of a circular coupon
of SAE type 1020 steel is determined after a designated time
period (200-2,000 hours). The waste must be agitated and main-
tained at 55°C throughout the duration of exposure. The coupon
must be carefully cleansed prior to each weighing.
LIMITATIONS: Large differences in corrosion rates occasionally occur
under conditions where the metal surface becomes passivated.
SENSITIVITY: Corrosion rates of duplicate coupons are reproducible
only to within 10%.
A-213
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METHOD NUMBER: T-01
QA/QC: Samples should be analyzed in duplicate. The precision of
analysis should be reported.
EXTERNAL COST:
Per single analysis $50-$200
INTERNAL COST:
Manhours/Analyses 4-8
Capital Equipment:
Reflux Condenser, Coupons $500-$!,500
Specimen Mounting Racks
REFERENCES: U.S. Environmental Protection Agency, Office of Solid
Waste and Emergency Response. "Test Methods for Evaluating Solid
Wastes"--Physical/Chemical Methods. SW-846, Washington, DC,
July 1982. (Method 1110 - Based on NACE Standard TM-01-69, 1972
Revision.)
A-214
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METHOD NUMBER: T-02
TEST METHOD: Reactivity (RCRA)
DESCRIPTION: The RCRA classification scheme for reactivity includes
six categories: (1) undergoes violent change without detonating,
(2) reacts violently with water, (3) forms explosive mixtures with
water, (4) generates toxic gases when mixed with water, (5) cyanide
and sulfide-bearing waste (pH 2-12.5) which generates fumes or gases,
and (6) wastes capable of detonation when heated or confined. If a
waste can be assigned to any of these categories on the basis of
qualitative or quantitative test results, it is classified as
hazardous. Although test methods are not specified by EPA in the
reference given, analytical methods for HCN (A-28) and ^S (A-29)
are available and a number of ASTM methods for explosivity and
detonation characteristics appear applicable (see references).
APPLICATIONS: This technique is applicable to streams expected to be
reactive in the exact manner(s) listed above (sublimating solids,
and CN-containing streams, tars containing volatile organics).
GENERAL METHOD PARAMETERS:
Preparative Requirements: The sample should be representative of the
waste and maintained without chemicals. Technique is applicable for
all types of random and composite samples (S-01).
SENSITIVITY: The reactivity classification is assigned on the basis
of qualitative judgements.
QA/QC: Does not apply unless specific tests for explosivity, CN~,
and \\$ are performed
A-215
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METHOD NUMBER: T-02
EXTERNAL COST:
Per single analysis $10-$250
INTERNAL COST:
Manhours/Analyses 0.5-8
Capital Equipment:
Explosion Tester $100-$250
CN" Distillation Equipment $100-$500
REFERENCES: U.S. Environmental Protection Agency, Office of Solid
Waste and Emergency Response. Test Methods for Evaluating Solid
Wastes-Physical/Chemical Methods. SW-846. July 1982. [Methods
9010 (CN") and 9030 (h^S) from same document]
USEPA. Rules and Regulations. Federal Register, 45(98), May 19, 1980.
[Hazardous Waste Management System]
American Society for Testing and Materials, Philadelphia,
Pennsylvania, Annual Book of ASTM Standards, Part 25 [Method D3115 -
Test for Explosive Reactivity of Lubricants with Aerospace Alloys
Under High Shear, Method D2389 - Test for Minimum Pressure for Vapor
Phase Ignition of Monopropellants, Method D2539 - Test for Shock
Sensitivity of Liquid Monoprooellants by the Card Gap Test], and
Part 41, [Method E680 - Test for Drop Weight Impact Sensitivity of
Solid-Phase Hazardous Materials].
A-216
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• METHOD NUMBER: T-03
TEST METHOD: Pensky-Martens Closed-Cup Method for Ignitability of
Solids
DESCRIPTION: Solid sample is heated at a slow constant rate with
continual stirring while a small flame is directed into cup at
regular intervals and the flash point is determined.
APPLICATIONS: This technique is applicable only to streams expected
to be ignitable (e.g., organic sludges, tars, and resins);it does
not apply to solids which have been exposed to high temperature or
combustion; i.e., ashes or slags.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples are stored in glass containers since
volatile materials may diffuse through the walls of plastics bottles.
This technique is applicable to random or composite samples (S-01).
Approximately 50 mL of sample is used per test.
Method: The sample is heated at a rate sufficient to achieve a constant
5-6°C/iminute increase in temperature. For samples with flash points
below 110°C the flame is directed into the cup at 1°C intervals
starting at a temperature 15 to 30°C less than anticipated
flash point. For samples with flash points over 110°C, the flame
is directed into the cup at 2°C intervals starting at a temperature
15 to 30°C less than the anticipated flash point.
LIMITATIONS: Ambient pressures, sample homogeneity, drafts, and
operator bias can affect flash point values.
A-217
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METHOD NUMBER: T-03
SENSITIVITY: Sensitivity will depend on thermometer accuracy,
barometer accuracy, purity of reference standards, and operator
precision.
QA/QC: Duplicates and standard reference materials should be routinely
analyzed. The flash point of the p-xylene standard must be determined
in duplicate at least once per sample batch; the average of the two
analyses should be 27° +_ 0.8°C.
EXTERNAL COST:
Per single analysis $10-$60
INTERNAL COST:
Manhours/Analyses 0.2-1
Capital Equipment:
Pensky-Martens Cup $700-$!200
REFERENCES: USEPA, Office of Solid Waste and Emergency Response.
Test Methods for Evaluating Solid Wastes Physical/Chemical Methods.
SW-846. July 1982. [Method 1010, (Based on ASTM D93-77)].
USEPA. Rules and Regulations. Federal Register, 45(98), May 19, 1980.
[Hazardous Waste Management System]
American Society for Testing and Materials, Philadelphia,
Pennsylvania, Annual Book of ASTM Standards, Parts 15, 22, 23, 27,
and 29 [Method D93 - Test for Flash Point by Pensky-Martens Closed
Tester]
A-218
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METHOD NUMBER: T-04
TEST METHOD: Permeability (Hydraulic Conductivity) of Solid Waste
Samples
DESCRIPTION: The waste is mixed with water at optimum moisture content
and compacted into the permeameter. The rate of leachate production
is monitored. Permeability coefficients are calculated from the
amount of leachate collected and the hydraulic gradient applied.
APPLICATIONS: This technique is applicable only to the solid fraction
of solid waste streams. It is inappropriate for water soluble solids.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Technique is applicable for all types of
random or composite samples (S-01). A minimum of 5 Ib of sample
is required. Sample should be representative of the waste, and
care should be taken to maintain the physical integrity of the
specimen. The sample should not be subjected to grinding or other
processes that could modify the particle size distribution.
Method: A portion of the sample is compacted in a permeameter. The
apparatus is evacuated for 15 minutes. Evacuation is followed by
slow saturation of the sample with water from the bottom upward,
then is slowly allowed to saturate with water from the bottom up
under full vacuum. The vacuum is disconnected and the quantity of
flow from the saturated sample is determined under various conditions
of applied hydraulic head. The permeability coefficient is calculated
from the resulting data.
LIMITATIONS: If material is either extremely permeable or extremely
impermeable, accurate measurements will be difficult to achieve. If
material reacts with water, or gases are formed, measurements will
be adversely affected.
A-219
-------
METHOD NUMBER: T-04
-3
SENSITIVITY: The applicable range of the method is between 10
and 10"8 cm/sec; method is imprecise outside these boundaries.
(JA/QC: A minimum of one column should be run in duplicate per batch
of measured mixtures. Gas regulators should be checked regularly.
EXTERNAL COST:
Per single analysis $50-$500
INTERNAL COST:
Manhours/Analyses 4-24
Capital Equipment:
Permeameter $50-$250
REFERENCES: Department of Army Office of Chief of Engineers.
Laboratory Soils Testing, Engineer Manual, EM 1110-2-1906,
Appendix VII. Headquarters, 1970.
American Society for Testing and Materials, Philadelphia,
Pennsylvania, Annual Book of ASTM Standards. Part 19 [Method D2434
Test for Permeability of Granular Soils (Constant Head)]
A-220
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METHOD NUMBER: T-05
TEST METHOD: Particle-Size Distribution of Solid Samples
DESCRIPTION: A quantitative distribution of sizes larger than 75
microns is determined by sieving, while particle sizes smaller than
75 microns can be determined by a sedimentation process using a
hydrometer.
APPLICATIONS: This technique is applicable to any solid waste stream
which has a soil-like consistency and does not react with water.
It can usually be applied successfully to ashes, slags, and some
sludges,but not to tars.
GENERAL METHOD PARAMETERS:
Preparative Requirements: The sample should be representative of the
waste, and it should not contain preservatives. Grab or composite
(S-01) samples may be analyzed using this technique.
Method:
Sedimentation - The sedimentation rate of a mixture, the sample,
a surfactant and distilled water, is determined at a constant
temperature with a hydrometer. The particle size is calculated
from the resulting data.
LIMITATIONS: Samples must be dried and free-flowing. If drying causes
particle-size abberation through aggregate formation, measurement
will be imprecise. Samples that react or are highly soluble with
water cannot be successfully subjected to this method.
SENSITIVITY: There is not an established standard limit of acceptable
sensitivity for this method.
A-221
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METHOD NUMBER: T-05
QA/QC;. At least one duplicate particle-size analysis per sample
batch should be performed.
EXTERNAL COST:
Per single analysis $50-$200
INTERNAL COST:
Manhours/Analyses 2-4
Capital Equipment:
Sieve Set $1,000-$2,000
Rotovap $500-$2,000
Hydrometer $50-$200
REFERENCES: American Society for Testing and Materials, Philadelphia,
Pennsylvania, Annual Book of ASTM Standards. Part 19 [Method D422 -
Particle-Size Analysis of Soils] and Part 26 [Method D410 - Sieve
Analysis of Coal, and Method D431 - Designating the Size of Coal
from its Sieve Analysis]
A-222
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TEST NUMBER: T-06
TEST METHOD: Specific Gravity of Solid Samples
DESCRIPTION: Several methods may be used to determine the volume,3
specific (unit) mass of waste will occupy when voids are excluded.
APPLICATIONS: The specific gravity of every solid waste stream can be
determined, but the method will be different for streams with
different physical/chemical properties. The references listed
should be consulted to select a procedure for a specific waste stream.
GENERAL METHOD PARAMETERS;
Preparative Requirements: Samples should be as representative and as
homogeneous as possible. No preservatives should be added unless
required by the procedure.
Method: In some cases, a sample can simply be dried, weighed, and
submerged under a liquid to determine volume displacement; in
other instances it will be necessary to coat the solids with paraffin,
or use a pycnometer with special procedures.
LIMITATIONS: For certain wastes with mixed character no single method
will be perfect for specific gravity determination. Waste
inhomogeneity can cause results to vary.
SENSITIVITY: The sensitivity for each method is specified in the
references.
QA/QC: Matrix replicates should be analyzed with each sample set.
The precision of analysis should be reported.
A-223
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METHOD NUMBER: T-06
EXTERNAL COST:
Per single analysis $25-$500
(depending on specific
procedure required)
INTERNAL COST:
Manhours/Analysis 2-8
(depending on specific
procedure required)
Capital Equipment:
Hogarth Specific Gravity Bottle $50-$100
Pycnometer $50-$500
REFERENCES: American Society for Testing and Materials, Philadelphia,
Pennsylvania, Annual Book of ASTM Standards. Parts 15 and 19
[Method D70 - Test for Specific Gravity of Semi-Solid Bituminous
Materials, Method D1188 - Test for Bulk Specific Gravity of Comparted
Bituminous Mixtures Using Paraffin-Coated Specimens] and Part 19
[Method C97 - Tests for Absorption and Bulk Specific Gravity of
Natural Building Stone, Method 854 - Test for Specific Gravity of
Soils]
A-224
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METHOD NUMBER: T-07
TEST METHOD: In-Place Bulk Density of Solids
DESCRIPTION: A sand cone method and/or balloon densitometer are used
to obtain a known weight of damp solid sample from a representative
irregular hole in the solid waste pile. The volume of the hole and
the percent moisture of the wastes are determined. The volume
occupied by a given mass of waste under normal in-place conditions
is calculated.
APPLICATIONS: This technique is applicable to solid waste streams
having a soil-like consistency (ashes, slags, and dewatered sludges)
that are placed in piles before final disposal.
GENERAL METHOD PARAMETERS:
Sand Cone Method: This method is restricted to tests in soils
containing particles not larger than 2 inches in diameter.
Rubber Balloon Method: This method covers the determination of the
density in-place of compacted or firmly bonded soil. It is not
suitable for very soft material which will deform under slight
pressure. For such materials the sand cone method may be used.
LIMITATIONS: In-place bulk density measurements can vary due to waste
pile inhomogeneity. Representative samples must be taken from
several areas of the pile.
SENSITIVITY: With careful instrument calibration, the method can be
both precise and accurate.
QA/QC: Field-density test apparatus should be calibrated regularly
and duplicate measurements performed in similar site areas.
A-225
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METHOD NUMBER: T-07
EXTERNAL COST:
Per single analysis $10-$100
INTERNAL COST:
Manhours/Analysis 1-2
Capital Equipment:
Sand Cone Apparatus $25-$300
Balloon-Density Apparatus $100-$500
REFERENCES: American Society for Testing and Materials, Philadelphia,
Pennsylvania, Annual Book of ASTM Standards, Part 19, [Methods D1556 -
Test for Density of Soil in Place by the Sand-Cone Method, Method 2167
Test for Density of Soil in Place by the Rubber-Balloon Method]
American Association of State Highway Officials. Standard Specifi-
cations for Transportation Materials and Methods of Sampling and
Testing, llth Edition, Washington, D. C,, 1974.
A-226
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METHOD NUMBER: T-08
TEST METHOD: Moisture-Density Relations of Solids (Optimum Moisture
at Maximum Dry Bulk Density)
DESCRIPTION: At least four representative samples of waste are
prepared by adding increasing amounts of water to each sample and
compacting into a standard compaction mold. A plot of moisture
versus density usually forms a parabola in which the optimum moisture
content corresponds to the maximum dry density.
APPLICATIONS: This technique is applicable to any solid waste stream
having a soil-like consistency. While it is appropriate for ashes,
slags, and dewatered sludges, it cannot be used effectively with
tars and resins.
GENERAL METHOD PARAMETERS:
Preparative Requirements: The sample should be representative of the
waste, and should not have preservatives added to it. The original
moisture content should be maintained as practicable. Grab or
composite samples (SOI) may be analyzed using this technique.
Approximately 2kg is required.
Method: A portion of the sample is sieved to a uniform particle size
and mixed with water. The sample is then uniformly compacted to a
known volume and the weight of the sample determined. A represen-
tative portion is weighed, dried,and reweighed and the weight of
water determined. This procedure is repeated until a constant
weight is obtained. The resulting data is used to determine the
moisture density relation.
LIMITATIONS: For free-draining aggregate mixtures, a well-defined
moisture-density relationship cannot be produced.
A-227
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METHOD NUMBER: T-08
SENSITIVITY: The acceptable range of relative standard deviation
(ASTM) for maximum density and optimum moisture content for soil-
like materials are +1.66 and +0.86, respectively.
QA/QC: At least one point per compaction curve near the maximum
should be duplicated.
EXTERNAL COST:
Per single analysis $60-$250
INTERNAL COST:
Manhours/Analyses 4-8
Capital Equipment:
Compaction Mold $100-$300
Rammer $100-$200 (Manual)
$5,000-$!0,000 (Automated)
Extruder $50-$100
REFERENCES: American Society for Testing and Materials, Philadelphia,
Pennsylvania, Annual Book of ASTM Standards, Parts 14, 15 and 19,
[Methods D698-78, C127, D854, D2168, D2216, D2487, 02488, Ell, and
D1557-78] Parts 13, 14, 15, 18, 20, 30 and 41 [Method Ell -
Specifications for Wire-Cloth Sieves for Testing Purposes], Parts
14 and 15 [Method C127 - Test for Specific Gravity and Absorption
of Coarse Aggregate], and Part 19 [Method D558 - Test for Moisture -
Density Relation of Soil-Cement Mixtures, Method D698 - Tests for
Moisture-Density Relations of Soils and Soil-Aggregate Mixtures,
Method D854-Test for Specific Gravity of Soils, Method D1557 -
A-228
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METHOD NUMBER: T-08
Tests for Moisture Density Relations of Soils and Soil-Aggregate
Mixtures, Method D2168 - Calibration of Laboratory Mechanical-
Panimer Soil Compactors, Method D2216 - Laboratory Determination
of Uater (Moisture) Content of Soil-Rock and Soil Aggregate
Mixtures, Method D2487 - Classification of Soils for Engineering
Purposes]
A-229
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METHOD NUMBER: T-09
TEST METHOD: Specific Conductance (Conductivity) of Aqueous Samples
DESCRIPTION: Specific conductance is measured using a conductivity
meter.
APPLICATIONS: All wastewater streams including those from organic
and organic-free sources.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Samples are kept cool (4°C) if analysis
cannot be performed within 24 hours. Grab (Sll) or composite
(S10) samples may be analyzed using this technique.
Method: The specific conductance of a sample is measured with a
self-contained conductivity meter (Wheatstone bridge-type or
equivalent.) Samples are analyzed at 25°C or temperature
corrections are made and results are reported at 25°C.
SENSITIVITY: 10-50 ymhos/cm at 25°C.
QA/QC: KC1 standard solution analyses are performed daily for
instrument calibration.
EXTERNAL COST:
Per single analysis $5-$15
INTERNAL COST:
Manhours/Analysis MD.l
A-230
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METHOD NUMBER: T-09
Capital Equipment:
Conductivity Meter $300-$!,500
REFERENCES: USEPA. Proposed Rules. Federal Register, 44(233),
December 3, 1979. [Amendment to 40 CFR 136]
American Society for Testing and Materials, Philadelphia,
Pennsylvania, Annual Book of ASTM Standards. Part 31 [Method D1125 -
Tests for Electrical Conductivity and Resistivity of Water]
USEPA. Office of Technology Transfer, Methods for Chemical Analysis
of Water and Wastes, EPA-625/6-74-003, Washington, D. C., 1974.
NTIS No. PB 297686/AS p. 275.
American Public Health Assoc., American Water Works Assoc., and
Water Pollution Control Federation. Standard Methods for the
Examination of Water and Wastewater, 14th edition. APHA,
Washington, D. C., 1976. pp. 75. [Method 205]
A-231
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METHOD NUMBER: T-10
TEST METHOD: Viscosity (Fluid Friction) Determination in Liquids,
Tars, and Sludges
DESCRIPTION: Fluid friction is measured by different methods for
liquids, tars, and sludges.
APPLICATIONS: Viscosity measurements are applicable only to fluid
solids streams which contain a liquid fraction.
GENERAL METHOD PARAMETERS:
Preparative Requirements: Technique will vary with method. Special
attention must be given to stratified streams.
Method: For liquids, the resistive flow of a fluid under gravity
can be measured through a capillary of a calibrated viscometer
under a reproducible driving head at controlled temperature. For
asphalt and tar-like samples, a sliding plate microviscometer is
used to measure the ratio between the applied shear stress and the
rate of shear. An insertable Brookfield viscometer is used for
high-solids sludges.
LIMITATIONS: Limitations for given methods are discussed in
references. The major limitation is providing a representative
sample.
SENSITIVITY: Sensitivity of measurement is procedure- and waste-
dependent.
QA/QC: Equipment is calibrated and matrix replicates analyzed as
given in the references.
A-232
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METHOD NUMBER: T-10
EXTERNAL COST:
Per single analysis $20-$300
(depending on procedure
required)
INTERNAL COST:
Manhours/Analysis 1-10
(depending on procedure
required)
Capital Equipment:
Brookfield Viscometer $300-$!,000
Capillary Viscometers $100-$500
Capillary Viscometer Bath $1,500-$2,500
Sliding Plate Microviscometers $100-$500
REFERENCES: American Society for Testing and Materials, Philadelphia
Pennsylvania, Annual Book of ASTM Standards, Parts 10, 14, 32, 35,
and 51 [Method E4], Part 15 [Methods D5, D2170, D2171, D3205, and
D3570], Parts 15, 22, 23, 27, and 29 [Method D93], Parts 15, 23,
and 40 [Method D92], Parts 23 and 40 [Method D445], Part 23
[Method D446], and Parts 25 and 44 [Method Cl]
Brookfield Viscometer Manual for Operators
A-233
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METHOD NUMBER: T-ll
TEST METHOD: Determination of Specific Surface Area of Sol Ids
DESCRIPTION: The specific surface refers to the area per unit weight of
waste usually 1n m /g. There are a number of absolute and relative meth-
ods which yield total surface area (Including the area associated with
pores): the Hark1ns-Jura absolute method, gas adsorption (BET), liquid
adsorption, and mercury poroslmetry. See Table 1 for discussion of prin-
ciples.
APPLICATION^; Surface area can be determined only on solid, dry samples
(e.g., ash, slag, dewatered sludge).
LIMITATIONS; Each type of surface area method has certain limits, e.g., ab-
solute methods must have a firm theoretical basis for application and
experimental conditions must be precisely controlled for relative meth-
ods. All methods require a representative homogeneous sample. See Table
1 for further discussion about specific methods.
SENSITIVITY; Most absolute methods for surface area determination are high-
ly precise, but not always accurate. Relative methods may be Imprecise.
(See Table 1.)
.QA/£C: Control measures should Include those normally used with a specific
method.
SAMPLING/SAMPLE HANDLING REQUIREMENTS; A representative, dry solid sample
should be taken for this analysis. Care should be taken to avoid surface
manipulation (I.e., no breaking or grinding should be performed).
EXTERNAL COST;
Per single analysis $200-$!,000 (depending on procedure)
A-234
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TABLE 1. METHODS FOR DETERMINATION OF SPECIFIC SURFACE AREA
He thod
Principle
Equipment
Limitations
Precision and Accuracy
Harkins-Jura Calorimetric determination of
Absolute Method energy change when impended
particles are dropped from
saturated vapor into bulk liquid.
Gas Adsorption Measures volume of adsorbed inert
(BET) gas required to form a monolayer.
Precision calorimeter.
analytical balance
BET apparatus (vacuum
degassing, pressure,
and temperature measure-
ments)
Too Involved for routine
work.
Tedious, time consuming.
Absolute method used as standard
for evaluating other methods.
Can be used to measure specific
surface area down to 100 cm'/g.
Conventional technique gives 2-4%
reprodncibility. Simplified
methods give 10-20%.
I
ro
CO
en
Liquid Adsorption
Measures amount of liquid compo-
nent (sorbate) adsorbed from a
solvent on solid surface.
Flask, shaker, equipment
for analysis of sorbate
concentration
Applicability of a speci-
fic solid/liqnid/sorbent
system must be determined
experimentally. Time
required to reach equili-
brium varies.
Accuracy is determined by compar-
ison with other methods (BET).
Keproducibillty is within 3%.
m
—I
n:
o
o
oo
m
-------
METHOD NUMBER: T-ll
INTERNAL COST:
Manhours/analyses 2-8 (depending on procedure)
Capital Equipment:
BET analyzer $10,000-520,000
REFERENCES; Mortland, M. M., and W. D. Kemper, Specific Surface, Methods of
Soil Analysis, American Society of Agronomy, 1965, pp. 532-546.
Schwltzgebel, K., Meserole, F. M., Thompson, C. M., Skloss, J. L., and
N.P. Phillips, "Development of Sampling and Analytical Methods of L1me/
Limestone Wet Scrubbing Tests," Vol. I and II, Final Report, GAP Contract
No. CPA 70-143, Radian Project No. 200-006.
A-236
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METHOD NUMBER: T-12
TEST METHOD: Bioassay for Health Effects
DESCRIPTION: A variety of test organisms are exposed to a prepared
sample. After exposure, organisms are assayed for symptoms of adverse
effects. Common screening organisms are given in Table 1.
APPLICATIONS: Liquids, solids, condensed gases and extracts of all three
media may be assayed for mutagenicity, cytotoxicity or acute toxicity.
LIMITATIONS: Screening test results may be difficult to interpret or
assign to a specific component of the sample. Interpretation must be
performed by an experienced professional.
SENSITIVITY: Test species are selected for their sensitivity to respond.
Response quantifiable in most cases.
QA/QC: Dose response and multiple trials should be conducted. Good
biological laboratory practices are mandatory.
EXTERNAL COST:
Per single analysis $400-$2,000
INTERNAL COST:
Manhours/analysis 1-40
Capital Equipment:
Cell culture assembly $1,000-$6,000
Animal housing $3,000-$10,000
A-237
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TABLE 1. GENERAL HEALTH EFFECTS BIOASSAY TESTS
Test Designation/
Assay Type
Activity
Measured
Test Organism
Appropriate
Sample Type
Ames/in-vitro
RAM/in-vitro
CHO/in-vitro
CHO/Kl/in-vitro
CHO/SCE/in-vitro
ro
CO
CO
Mutagenesis
(point mutation)
Cytotoxicity, EC5o
Cytotoxicity, EC5o
Mutagenesis
(point mutation)
Mutagenesis
(gross genetic
change)
Salmonella Typhimurium
Rabbit Alveolar Macrophage
Chinese Hamster Ovary
Chinese Hamster Ovary
Chinese Hamster Ovary
Liquids, extracts of solids
particles
Particles
Liquids, extracts
Liquids, extracts
Liquids, extracts
-------
METHOD NUMBER: T-12
REFERENCES: D.J. Brusick and R.R. Young, IERL-RTP Procedures Manual:
Level 1 Environmental Assessment Biological Tests, EPA 600/8-81-024.
D.J. Brusick and R.R. Young, Level 1 Bioassay Sensitivity, EPA
600/7-81-135.
Ames, B., J. McCann, and E. Yamasaki, Methods for Detecting Carcino-
gens and Mutagens with the Salmonella/Mammalian-Microsome Mutagenicity
Test, Mutation Res., Vol. 31, 1975, pp. 347-364.
Waters, M.D., et al., Metal Toxicity for Rabbit Aveolar Macrophage
in vitro, Environ. Res., Vol. 9, 1975, p. 32-47.
Mahar, H., Evaluation of Selected Methods for Chemical and Biological
Testing of Industrial Particulate Emissions, EPA-600/2-76-137 B.P. 257
912/AS, U.S. Government Printing Office, Washington, D.C., 1976.
i
Gardner, D.E., et al., Technique for Differentiating Particles that Are
Cell Associated or Ingested by Macrophages, Appl. Microbiol., Vol. 25,
1974, p. 471.
Sontag, H., N. Page, and U. Saffiotti, Guidelines for Carcinogen Bio-
assay in Small Rodents, NCI Technical Report Series No. 1, DHEW Pub.
No. (NIH) 76-801, NCI-CG-TR-1, 1976, p. 64.
Balazs, T., Measurement of Acute Toxicity, in Methods in Toxicology,
G. Paget, Ed., F.A. Davis Co., Philadelphia, PA, 1970, pp. 49-81.
N.G. Sexton, Biological Screening of Complex Samples from Industrial/
Energy Processes, EPA 600/8-79-021.
A-239
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METHOD NUMBER: T-13
TEST METHOD: Bioassay Testing for Ecological Effects
DESCRIPTION: A variety of test organisms are exposed to a sample or
aqueous leachate of a sample. The test organisms are then assayed for
signs or symptoms of ecological effects. Some generally used test
species and the activities measured are given in Table 1.
APPLICATIONS: Numerous emission streams or extracts (leachates) of
emission streams may be assayed. A variety of test species can be used.
LIMITATIONS: Test results are often difficult to associate with specific
causes. Must be performed by an experienced professional.
SENSITIVITY: The test organisms commonly used are selected for their
sensitivity to change within their environment and subsequent response.
QA/QC: Good biological laboratory practices are essential. Dose response
and multiple assays are necessary to produce quality data.
EXTERNAL COST:
Per single analysis $300-$6,000 (depending on test)
INTERNAL COST:
Manhours/analysis 20-120 (depending on test)
Capital Equipment:
Tanks, test species, incubators $15,000-$50,000 (depending
on laboratory facilities)
A-240
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TABLE 1. GENERAL ECOLOGICAL EFFECTS BIOASSAY TESTS
Test Designation/
Assay Type
Activity
Measured
Test Organism
Appropriate
Sample Type
>
ro
Acute Static Bio-
assay/Vertebrate
Acute Static Bio-
assay/ Invertebrate
Algae Growth/Algae
Lethality, LC50
Lethality, LC50
Growth Inhibition, EC50
or Growth Stimulation,
SC2o
Fresh water or marine
minnow
Daphnia (fresh water)
or mysid (marine)
Selenasium capricornutum,
Skeletonemer costatum
Aqueous leaches of
solids or particulates
-------
METHOD NUMBER: T-13
REFERENCES: D.J. Brusick and R.R. Young, IERL-RTP Procedures Manual:
Level 1 Environmental Assessment Biological Tests, EPA 600/8-81-024.
Lentzen, D.D., D.E. Wagoner, E.D. Estes and W.F. Gutknecht, EPA/IERL-
RTP Procedures Manual: Level 1 Environmental Assessment, Second Edition,
EPA-600/7-78-201 (January 1979), NTIS No. PB 293795/AS.
USEPA, Committee on Methods for Toxicity Tests with Aquatic Organisms,
National Water Quality Labs., Methods for Acute Toxicity Tests with
Fish, Macroinvertebrates, and Amphibians, Duluth, MN, EPA 660/3-75-009,
P.B.-242 105/AS, 1975.
Finney, D.J., Statistical Method in Biological Assay, 2nd Edition,
Hafner Publishing Company, New York, 1964, p. 668.
Brungs, W.A. and D.I. Mount, A Device for Continuous Treatment of Fish
in Holding Chambers, Trans. Amer. Fish Soc., Vol. 96, 1967, pp. 55-57.
Sprague, J.B., Measurement of Pollutant Toxicity to Fish. I. Bioassay
Methods for Acute Toxicity, Water Res., Vol. 3, 1969, pp. 793-821.
Sprague, J.B., The ABC's of Pollutant Bioassay Using Fish, In:
Biological Methods for the Assessment of Water Quality (J. Cairns, Jr.
and K. L. Dickson, editors), ASTM Spec. Tech. Publ. 528, American
Society for Testing and Materials, Philadelphia, 1973, pp. 6-30.
A-242
-------
METHOD NUMBER: T-14
TEST METHOD: Opacity Measurement
DESCRIPTION: The opacity of a plume may be estimated by a qualified
observer or determined as a function of the change in attenuation
of a light projected through the emission.
APPLICATIONS: Visual opacity determinations may be made of plumes
from almost any source. Instrumental (transmissometer) determinations
require a stack or duct geometry for implementation.
LIMITATIONS: Visual determinations can only be made under favorable
ambient conditions. Poor visual contrast to the plume generally
causes some positive error. Instrumental determinations must be
performed across a representative portion of the emission.
SENSITIVITY: Visual determinations have been verified against
standardized transmissometer readings to +5%. Allowable instrumental
error is <3%.
EXTERNAL COST:
Per single visual determination $3Q-$80
(excluding any travel or
associated expenses for
certified personnel)
INTERNAL COST:
Manhours/Deterrnination -0.1 (excluding
personnel certification)
Capital Equipment:
Opacity Monitor $3,000-$5,000
A-243
-------
METHOD NUMBER: T-14
REFERENCES: USEPA. Title 40, Code of Federal Regulations, Part 60,
Appendix A. December 5, 1980 [Method 9 - Visual Determination of
the Opacity of Emissions from Stationary Sources]
USEPA. Title 40, Code of Federal Regulations, Part 60, Appendix B.
December 5, 1980 [Performance Specification 1 - Performance
specifications and specification test procedures for transmissometer
systems for continuous measurement of the opacity of stack emissions].
USEPA. Proposed Rules. Federal Register, 45(224), November 18, 1980.
[Method 22 - Visual Determination of Fugitive Emissions from Material
Processing Sources]
A-244
-ft--
-------
APPENDIX B
STATISTICAL ISSUES
Statistical procedures and theory have been used 1n the approaches given
1n this manual for monitoring plan development. This Appendix presents some
background and additional discussions of these statistical procedures.
B.I DATA DISTRIBUTIONS
A common statistical approach Involves modeling a set of data with a dis-
tribution function. The set of data here refers to the measurements made for
a specific parameter at a specific plant location. Statistical distributions
often used for environmental and operating data Include the normal distribu-
tion (for symmetrically distributed measurements), the lognormal distribution
(for skewed measurements), and the binomial distribution for qualitative data
(e.g,, parameters classified as present/not present). When these distribu-
tions are adequate for modeling a set of measurements, properties of the dis-
tributions can be used to evaluate alternative monitoring strategies and
develop decision rules.
The normal distribution 1s the most widely used statistical distribu-
tion model for measurement data. The properties of the normal distribution
have been extensively developed. The model results 1n a symmetric distribu-
tion of measurements about a mean value, u. About two-thirds of the measure-
ments are within one standard deviation (o) of the mean, 95 percent of the
measurements are within two standard deviations of the mean, and 99.7 percent
of the measured values are within three standard deviations of the mean.
The mean (u) of a normal distribution can be estimated using the sample
average:
n
x =
B-l
-------
where a sample of n measurements (x) of the parameter 1s available. The
standard deviation (a) 1s estimated using the sample standard deviation:
n - 1
The lognormal distribution Is one of the most commonly used distribu-
tion models for environmental data. The model Includes only positive values
and 1s skewed toward smaller values. A measurement (x) can be modeled by the
lognormal distribution 1f the transformed value y = ln(x) can be modeled with
a normal distribution.
For the two-parameter lognormal distribution, the mean of the distribu-
tion 1s:
u + l/2a 2
mean = e
and the standard deviation of the distribution 1s:
standard deviation = eu [e^Ce02 - 1)]1/2
where u and a are the mean and standard deviation of the lognormal of the
data.
Flnney (Reference B-l) has developed efficient estimators of the mean (M)
1/2
and standard deviation (V) for a sample from a lognormal distribution:
M = eyg(S2/2)
V = e2y{g(2S2) - g[(n-2)S2/(n-l)]}
B-2
-------
where y = the average of y = ln(x), for the sample of n measurements,
S = standard deviation of the y values, and
g(t) = specific series 1n t (see Reference B-l).
The binomial distribution can be used to model data 1n which a
parameter 1s classified as either present or not present, but no measured
value 1s determined. This situation may occur when a multl-component
analytical method used to analyze a sample 1s capable of Identifying which
compounds are present, but not quantifying the compounds. Therefore the data
for each parameter states whether the compound 1s present or not present 1n
each sample analyzed. The statistic usually evaluated with the binomial model
1s the percent occurrence rate:
p = number of times parameter was found present x 100
number of samples analyzed for parameter
The standard deviation of p can be estimated using:
5 p (100-p)
^ n-1
where n 1s the number of samples analyzed.
The normal, lognormal, and binomial distributions are used as models 1n
this document. The normal model 1s applicable 1f the parameter of Interest
has measurements which are symmetrically distributed about a mean value. The
concentration of the parameter should be such that non-detected values are not
common. The lognormal distribution should be considered as a model when mea-
surements are skewed toward positive values. The binomial model 1s applicable
when data 1s not quantified (e.g., detect, nondetect).
If sufficient data are available to support alternative distribution
models for a particular parameter, the alternative model can be used within
B-3
-------
the framework of this document. The various properties and decision criteria
presented here for the normal and lognormal models should be developed for the
alternative models of measurement data. The Polsson, multlnormal, and nega-
tive-binomial distribution can be used as alternative models for qualitative
data. A statistician should be consulted 1f these alternative models are
used.
Another situation occurs with environmental measurements when some of the
data are quantitative and some of the data are qualitative (e.g., less than
detection limit). Data bases of this type can be modeled using mixed-
distributions; I.e., mixtures of discrete and continuous distribution models.
An example 1s the use of a mixture of a binomial and lognormal distribution to
model fugitive hydrocarbon emission data from process sources (Reference B-2).
A statistician should be consulted to develop decision rules for statistics of
this type.
An alternative approach to the use of distribution models would be non-
parametric (or distribution-free) statistics. When using nonparametrlc
statistics, no assumptions about the precise form of the distribution of the
parameters measurements are made. Decision rules can be based on criteria
that do not depend on the exact form of the distribution. The focus 1s on
order statistics (minimum, maximum, etc.) and percentHes (median, 95th per-
centlle, etc.). Estimation problems, such as estimating the mean concentra-
tion of a parameter, are usually more difficult when using nonparametrlc
statistics; but under certain conditions, estimation can be accomplished.
B.2 CONFIDENCE INTERVALS
A confidence Interval 1s a set of end points about a sample statistic
that 1s believed, with a specified degree of confidence, to Include the
population parameter. The width of the confidence Interval gives an
Indication of how precisely a parameter mean (or other statistic) can be
estimated from the sample data. Commonly used confidence levels are 90
B-4
-------
percent, 95 percent, and 99 percent. The expected width of a confidence
Interval for the parameter of Interest can be used as a guide to evaluating
alternative sampling and testing strategies.
The confidence Interval for the population mean can be computed as fol-
lows:
1) N|ormal Distribution Model; x + t (n_i) SX/rT
where x 1s the sample mean,
t , .. 1s the tabulated t-stat1st1c with confidence level (1-a),
a» (n-D
S 1s the sample standard deviation, and
n 1s the sample size (number of measurements).
2) Loanormal Distribution Model;
y ± t , ,, S//n"l 9
0»^\n™*l/ t / r»^ / o\
e I g(S /2)
where y 1s the mean of y = ln(x) for the n
sample measurements x,
S 1s the standard deviation of the y values,
t , ,^ 1s the tabulated t-stat1st1c, and
a, (D-D
g(S2/2) 1s the series described 1n Section B.I.
The standard deviation expressed as a percentage of the mean 1s called
the coefficient of variation (CV):
CV (%) = (S/x) x 100.
The CV can be used as a substitute for S 1n the confidence Interval formula
for the normal distribution. The confidence limits would then be expressed as
percentages of the mean.
B-5
-------
For the lognormal model
CV (%) = 100(e°2 -
where a 1s the standard deviation of y = ln(x).
Given the CV for a parameter, the standard deviation 1n the lognormal distri-
bution can be estimated by:
S =/ln[l - (CV/100)2] .
The confidence limits can then be expressed as percentages of the mean:
t , ,.
upper Hm1t = Ce a'(n~l> ]
lower I1m1t = Cl -
t . ,,.
ct»(n-l)
6
These formulas were used to develop the confidence Intervals for the lognormal
model 1n Table 4-18.
For qualitative data* the binomial distribution model can be used to
develop confidence Intervals for the percentage, p (I.e., how often the
parameter 1s detected 1n the sample). For large sample sizes and percentages
(I.e., n > 50, p > 0.10) the following can be used to approximate the
confidence Interval for the population percentage, p:
P -
where p, and a are as defined 1n Section B.I., and Za 1s the appropriate
value from a standard normal table. Table B-l gives Confidence Intervals for
p for some of the sample sizes expected from Phase 1 testing.
B-6
-------
TABLE B-l. 95% CONFIDENCE INTERVAL FOR p = PERCENTAGE OF SAMPLES WITH DETECTED
LEVEL OF THE PARAMETER FOR SMALL VALUES OF p AND n
No. of Detected Number of Samples Tested for Parameter (n)
Values 46 12 24 52 365
0 (0, 60) (0, 46) (0, 27) (0, 14) (0, 7) (0, 1)
1 (0, 80) (0, 64) (0, 39) (0, 21) (0, 10) (0, 2)
2 (7, 93) (4, 78) (2, 49) (1, 27) (0, 13) (0, 2)
3 (20, 99) (12, 88) (5, 58) (2, 33) (1, 16) (0, 3)
4 (40, 100) (22, 96) (10, 65) (4, 38) (2, 19) (0, 3)
5 (36, 100) (15, 72) (7, 42) (3, 21) (0, 4)
6 (54, 100) (21, 79) (10, 47) (4, 23) (0, 4)
8 (35, 90) (15, 55) (7, 28) (1, 4)
10 (52, 98) (22, 64) (10, 33) (1, 5)
12 (73, 100) (29, 71) (12, 37) (2, 6)
14 (36, 78) (16, 41) (2, 7)
16 (44, 85) (19, 45) (2, 7)
20 (62, 96) (25, 53) (3, 9)
24 (85, 100) (32, 61) (4, 10)
30 (43, 71) (6, 12)
40 (63, 87) (8, 15)
50 (87, 100) (10,17)
B-7
-------
Confidence Intervals can also be calculated for other statistics such as
the standard deviation. A statistician should be consulted for these calcu-
lations. Also, 1f distributed models other than those discussed here are
used* a statistician should be consulted to develop the appropriate estimating
formulas and confidence Interval procedures.
The confidence Intervals discussed 1n this section do not consider In-
accuracies (biases) 1n the measurement data. If the data 1s 50% low (e.g., a
method with only a 50% average recovery was used), then the estimated mean and
the confidence limits will be 50% low. Procedures to compensate for analyt-
ical bias (systematic errors) 1n developing the confidence Intervals can be
developed with the aid of a statistician. Biases 1n the measured methods do
not directly Impact the decision on sample size selection which 1s the primary
use of the confidence Interval 1n this document.
B.3 UPDATING PARAMETER ESTIMATES
The measurement data obtained 1n Phase 2 can be used to update the Phase
1 data base for each parameter measured 1n Phase 2. Note that 1f only
Indicator parameters are measured during Phase 2 testing, these will be the
only parameters updated. Data obtained during periods when no shift 1n the
baseline levels were Indicated can be used to update the Phase 1 mean and
standard deviation for the parameters.
For the normal distribution model the updated mean (X ) and standard
deviation (S ) would be:
x = — •"•— -
u n +
Su =
(n-1)
n
— t-
m
2 2 "
C _L / _ T \ p*-
O •, TV n— I ) O fy
+ m - 2
1/2
B-8
-------
where X. and S.. are the Phase 1 mean and standard deviation (based on n tests)
and X9 and S_ are the Phase 2 mean and standard deviation (based on m tests).
For a lognormal distribution model* the transformed statistics y and S
would be updated using the above formulas for the normal distribution model,
and then the updated values could be used 1n the 1ognormal distribution
formula (Section B.I).
B.4 CORRELATION COEFFICIENT
The correlation coefficient, r, 1s a measure of the strength of a linear
relationship between two variables (X and Y). The correlation coefficient 1s
defined as
r = covarlance (X,Y)
xy
[(Variance of X) (Variance of Y)
From a sample of data (pairs of measurements) the correlation coefficient can
be estimated using:
r
Xy
, 1/2 n „ 1/2
']
If the correlation coefficient Is near zero, the variables are said to be
uncorrelated, that 1s, unassodated with each other. If the correlation
coefficient 1s near 1 (positive or minus) then the variables are considered
highly correlated.
The statistical significance of various values of r 1s dependent on the
sample size, n. The following table gives critical values for testing
B-9
-------
the correlation between two variables to see 1f 1t 1s statistically signifi-
cant (different from zero) for typical sample sizes from Phase 1 testing:
Statistical Significance of Sample Correlation Coefficient
Sample
Size (n) 95% Level 99% Level
4 0.95 0.98
6 0.73 0.88
12 0.50 0.66
24 0.35 0.47
52 0.23 0.32
365 0.10 0.15
If the calculated value of r 1s greater than the tabulated value* the proba-
bility 1s 9556 (or 99%) that there 1s some association between the two
variables.
B.5 REFERENCES
B-l. Flnney, D.J. On the Distribution of a Varlate Whose Logarithm 1s Nor-
mally Distributed. Journal of-the Royal Statistical Soc1ety» Series B,
7:155-161, 1941.
B-2. Wetherold, R.G. and L.P Provost. Emission Factors and Frequency of Leak
Occurrence for Fittings 1n Refinery Process Units. EPA-600/2-79-044,
EPA Industrial Environmental Research Laboratory, Research Triangle
Park, NC. 1979.
B-10
-------
APPENDIX C
DISCUSSION OF AMBIENT POLLUTANTS
C.I INTRODUCTION
This section presents information on the chemicals that can be associated
with a particular synthetic fuel facility and which also are of concur- v, •••;•
respect to the possible impairment of human health and the environment. Escn
of the groups of chemicals should be addressed by means of the protocols for
sampling and analysis presented in Appendices D-F.
Since oil shale and coal (the basic resources for synthetic fuels) arise
from sedimentation of biological matter, they largely are organic substances
rich in nitrogen, oxygen, and sulfur heterocyclic compounds, polycyclic
aromatic compounds, and inorganic mineral impurities. Within gee logic cime,
many of these compounds have combined to form complex organo-metallic
substances. From site-to-site, oil shale and coal contain varying amounts of
these materials depending on meteorological, biological, and physical forces
affecting bed formation. Consequently, each particular synfuel facility can
have its own chemical "signature" in terms of the ratios of these resource
constituents and the types and amounts of organic and inorganic water
effluents and airborne emissions. Of particular importance is that all
pathways for the movement of water and airborne contaminants be monitored for
compounds representative of the classes of compounds of concern.
The groupings of chemicals of concern and exemplary compounds and
substances presented in this section reflect the subjective judgments of
scientists participating in an ongoing program of risk analysis for adverse
health and environmental effects of synfuels sponsored by the U.S. Environmen-
tal Protection Agency (C-l). Once each substance (a group of compounds, a
single element or compound or a mixture) has been found to be of little or
C-l
-------
no significance, it may be dropped from further consideration. Others may
be added or certain groups subdivided for further study.
The following is a brief discussion of each of the groups of the com-
pounds of concern. Examples are provided, together with guidance to sampling
and measurement protocols. For a more complete listing of the kinds
of compounds emitted from synfuel facilities, the reader is referred to
references C*-2, C-3, and C-4.
C.2 GENERIC EMPHASIS
The following groups of compounds should be the subject of monitoring
at each facility. Observed absence of certain groups over time can warrant
deletion of the group (or certain constituent compounds of a group) from
further monitoring.
C.2.1. Aliphatic Hydrocarbons
These are the simplest of organic compounds, containing only hydrogen
and carbon. The alkanes and cyclic alkanes do not have double bonds and are
relatively unreactive. The alkenes, cyclic alkenes, and dienes contain one
or more double bonds and are more reactive. The alkynes have triple bonds,
may be reduced to alkenes by the addition of hydrogen, or can form aldehydes
or ketones upon the addition of water (C-5).
At the ambient concentrations of these hydrocarbons expected outside of
the synfuel plant boundaries, no direct toxicity is expected. Volatile
aliphatic hydrocarbons are not considered to be carcinogenic, mutagenic, or
teratogenic, but some alkanes may be co-carcinogens or tumor-promoters (C-3).
Also, they are important indicators of emissions and are precursors of other
more harmful pollutants.
The following are examples of aliphatic hydrocarbons expected to be
emitted from synfuel facilities:
A. Alkanes:
Methane Pentene
Ethane Alkanes (more than five carbon atoms)
Propane Cycloalkanes
Butane Polycycloalkanes
C-2
-------
B. Alkenes:
Ethylene Pentene
Propylene Cycloalkenes
Butylene Polycycloalkenes
C. Dienes:
Butadiene Hexadiene
Pentadiene Cyclohexadiene
Cyclopentadi ene Polycyclodi enes
D. Alkynes:
Acetylene
Propyne
C.2.2 Benzene and Related Compounds
This group contains simple aromatic hydrocarbon compounds such as
benzene and compounds with simple substitutions at one or more positions on
the benzene ring. Benzene is a suspected carcinogen and some of the long-
chain alkylated benzene derivatives are weak tumor promoters (C-6, C-l).
The following are examples of simple aromatic hydrocarbon compounds
expected to be emitted from synfuel facilities:
A. Benzene and Alkylbenzenes:
Benzene Alkylbenzene (greater than three
Toluene carbon atom substitution)
Xylene Ethyl benzene
Propylbenzene Styrene
B. Naphthalene and Alkylnaphthalenes:
Naphthalene Acenaphthalene
Methyl naphtha!ene Alkylnaphthalenes (greater than two
Ethyl naphtha!ene carbon atom substitution)
Dimethyl naphthalene
C. Biphenyls and Diphenyls:
Biphenyl
Diphenylmethane
Oiphenylethane
C-3
-------
C.2.3 Polynuclg_a_r Aromatic Hydrocarbons
Compounds in this category have two or more fused benzene rings. This
group contains numerous known and suspected carcinogens (C-l). Minor changes
in structure among the compounds can drastically affect respective carcinogenic
properties. Thus, detailed fractionation of this group is important in
analysis, as a high concentration of a weak carcinogen can "dilute" the
observed effects of a potent carcinogen existent at a lower concentration in
an Ames test applied to a mixture of compounds contained in this group.
The following are examples of the kinds of polynuclear aromatic hydrocar-
bons expected to be emitted from synfuel facilities:
Anthracenes Benzopyrenes
Phenanthrenes Benzochrysenes
Benzanthracenes Benzoperylenes
Pyrenes Fluorenes
Benzophenanthrenes Fluoranthenes
Chrysenes Benzofluoranthene
Triphenylenes Binaphthyl
Perylenes Picene
C.2.4 Heterocyclic Nitrogen Compounds
Compounds within this group contain a nitrogen atom as a member of an
aromatic carbon ring. Many compounds within this group are presumed to be
carcinogenic to some degree. As is the case for polynuclear aromatic
hydrocarbons, minor changes in chemical structure can drastically affect
oncogenic properties of these compounds (C-5).
The following are examples of the kinds of heterocyclic nitrogen com-
pounds expected to be emitted from synfuel facilities:
Pyridines Pyrroles
Quinclines Indoles
Benzoquinolines Carbazoles
Acridines Dibenzocarbazoles
C-4
-------
C.2.5 Heterocyclic Sulfur Compounds
Compounds within this group contain a sulfur atom as a member of an
aromatic carbon ring. Since these are derived from the five-membered ring
called thiophene, this group is also termed the "thiophenes" (C-5).
Many members of this group are considered to be carcinogens or co-
carcinogens (C-7). Only recently has this group been rigorously studied with
respect to toxicity and measurement techniques.
The following are examples of the kinds of heterocyclic sulfur compounds
expected to be emitted from synfuel facilities:
Thiophenes
Benzthiophenes
Dibenzthiophenes
Naphthiophenes
Benzonaphthi ophenes
C.2.6 Heterocyclic Oxygen Compounds
These compounds contain an oxygen atom as a member of aromatic or non-
aromatic carbon rings. The aromatic compounds are derived from a five-membered
heterocyclic ring called a furan or from xanthene which contains a six-membered
heterocyclic ring (C-5).
Furan is considered highly toxic if inhaled or absorbed through the
skin. Other members of this group also may be toxic, but have not been
thoroughly studied (C-8).
The following are examples of the kinds of heterocyclic oxygen compounds
expected to be emitted from synfuel facilities.
Furans Xanthene
Benzofurans Tetrahydrofuran
Dibenzofurans Dioxane
Naphthofurans
C.2.7 Phenolic Compounds
These compounds contain one or more hydroxyl groups (-OH) attached directly
to an aromatic ring. Simple phenols readily degrade under biological activity;
however, complex phenols tend to be highly toxic and many have co-carcinogenic
properties. They are a major component of aqueous wastes from synthetic
C-5
-------
fuel facilities. Complex phenols can be found in the particulate phase of
airborne pollutants (C-l, C-9, C-10).
The following are examples of the kinds of phenolic compounds expected
to be emitted from synfuel facilities:
Phenols Catechol
Cresols Indanol
Naphthol Phenylphenol
Resourcinol Hydroxyfluorene
Alkylphenols (greater than one carbon atom substitution)
C.2.8 Alcohols
Alcoholic compounds contain one or more hydroxyl groups (-OH) attached to
one or more carbons of an alkyl group. These compounds can be found in aqueous
airborne aerosols or in wastewaters. They can contaminate potable water and
impair aquatic biota by interfering with membrane permeability.
The following are examples of the kinds of alcohols expected to be
emitted from synfuel facilities:
Methanol
Ethanol
Propanol
Alcohols (with more than three carbon atoms)
C.2.9 Aldehydes. Ketones, and Quinones
These compounds contain a carbonyl group (C=0). Because of the tendency
of the oxygen atom to acquire electrons, they react readily. In aldehydes
the carbonyl group is attached to a simple aliphatic or aryl hydrocarbon
group. Quinones are cyclic and contain two carbonyl groups (cyclic ketones
contain one carbonyl group). These substances are known to be toxic; for
example, certain quinones of benzo(a)pyrene may be co-carcinogens (C-l).
The following are examples of the kinds of compounds within this group
expected to be emitted from synfuel facilities:
Formaldehyde
Benzoquinone
Naphthoquinone
Anthraquinone
Phenanthraqui none
C-6
-------
C.2.10 Carboxylic Acids and Derivatives
Carboxylic acids contain one or more carboxyl groups (a hydroxyl ion
attached to the carbon or a carbonyl group) attached to an alky! or an aryl
group. They readily react with bases to form salts and, by means of replace-
ment reactions, form amides and esters as derivatives.
These diverse substances may account for 10-26 percent of the benzene-
soluble organic matter associated with urban pollution. A few are known to
be toxic in high concentrations; but only limited information is available
regarding their biological activity at the low levels at which they normally
exist in the ambient environment (C-l).
This group can be characterized using a gas chromatograph coupled with
a mass spectrometer for simple acids (to C5). The identification of dicar-
boxylic acids, aromatic acids, aliphatic acid (greater than C5), and acids
with additional functional groups may require the use of reverse phase high
performance liquid chromatography (C-6).
The following are examples of the kinds of these substances expected to
be emitted from synfuel facilities:
Formic Acid Methylbutanoic Acid
Acetic Acid Hexanoic Acid
Propanoic Acid Acetates (esters)
Butanoic Acid Phthalates (esters)
Methylpropanoic Acid Amides
Pentanoic Acid
C.2.11 Amines and Nitrosamines
These compounds are generally volatile and considered a major health
concern with respect to synthetic fuel facilities. Aromatic amines in
particular are highly toxic. Many, together with numerous nitrosamines,
are considered to be carcinogenic. They can be absorbed through the skin
or inhaled.
The following are examples of the kinds of compounds within these
groups that are expected to be emitted from synfuel facilities:
Primary Aromatic Amines (having more than two rings)
Aliphatic Nitrosamines
Aromatic Nitrosamines
C-7
-------
C.2.12 Cyanide Derivatives
These substances, termed "nitriles", contain a carbon atom joined to a
nitrogen atom by a triple covalent bond (C-11). They hydrolyze in water to
form carboxylic acids. With heat they can decompose into toxic cyanide vapors.
They also can act as catalysts in the formation of toxic nitrosamines.
The following are examples of the kinds of these substances expected to
be emitted from synfuel facilities:
Thiocyanates
Nitriles
C.2.13 Trace Elements
In above-normal concentrations, many trace elements are toxic. They
can accumulate in food chains, and exist primarily in combination as particles
or adsorbed on other particles in air and water media.
The primary tool for the analysis of most (i.e., metals) trace elements
is the atomic absorption spectrophotometer. It provides a high degree of
selectivity, simplicity, sensitivity, and reproducibility for air and water
samples (C-12, C-13). Other techniques used for trace element analysis
include inductively-coupled, argon-plasma emission spectrometry, X-ray
fluorescence, and neutron activation analysis.
The following are examples of trace elements expected to be emitted
from synfuel facilities:
Aluminum Nickel
Antimony Potassium
Arsenic Rubidium**
Bari urn Samari urn**
Beryl 1i urn Scandi urn**
Bromine* Selenium
Cadmium Silicon
Cerium** Silver
Cesium Sodium
Chlorine* Strontium**
C-8
-------
Chromium Tantalum**
Cobalt Terbium**
Fluorine* Thallium
Gallium** Thorium**
Germanium** Tin
Iridium Titanium
Iron Tungsten**
Lead Vanadium
Magnesium Ytterbium**
Manganese Zinc
Mercury Zirconium**
Molybdenum
C.2.14 Hazardous Gaseous Substances
A number of hazardous gases can be emitted from synthetic fuel facilities.
These gases (e.g., hydrogen sulfide, carbonyl-sulfide, carbon disulfide,
hydrogen cyanide, and gaseous vapors of metal carbonyls) can be highly toxic
in concentrations possible within the workplace environment. Extremely
toxic metal carbonyls persist only for five seconds, unless a high concentra-
tion of carbon monoxide exists (C-14). Highly odoriferous and persistent
mercaptans are considered harmless at normal ambient levels detectable to the
olfactory organs.
Examples of potentially hazardous gaseous substances expected to be
emitted from synfuel facilities are:
Hydrogen Sulfide Ammonia
Carbonyl Sulfide Metal Carbonyls
Carbon Disulfide Mercaptans (thiols)
Hydrogen Cyanide
C.2.15 Radioactive Materials
Due to the sedimentary origin of coal and oil shale, many radioactive
elements (e.g., uranium and thorium and their decay products) have become
concentrated (by a factor of ten) within the strata. Further concentration
*Halogens (see Reference C-15).
**Metals requiring special spectrophotometric equipment.
C-9
-------
can occur during cleaning, processing, and waste concentration. Various
routes can lead to both water and airborne transmission through the ambient
environment. These radioactive materials can be inhaled or passed along the
food chain and ingested (C-16).
Those radioactive compounds which potentially could be released into
the ambient environment from synthetic fuel facilities include (C-17, C-18):
Uranium-238 and daughter products
Uranium-235 and daughter products
Thorium-232 and daughter products
Radon 220 and 222
C.2.16 Conventional Pollutants
A number of air and water pollutants are typical components of air and
water monitoring programs associated with large fossil fuel facilities.
Those expected to be an integral part of a synfuels site ambient monitor-
ing program include:
Air
Sulfur Dioxide Suspended Particles
Nitrogen Dioxide Hydrocarbons
Carbon Monoxide Ozone
Water
Acidity Organic Carbon
Chemical Oxygen Demand pH
Dissolved Oxygen Temperature
Specific Conductance (dissolved solids)
C-10
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C.3 REFERENCES FOR APPENDIX C
C-l. Hoffman, D., and E. Wynder. Organic Particulate Pollutants-Chemical
Analysis and Bioassays for Carcinogenicity. In: A.C. Stern, ed., Air
Pollution, Third Edition. Volume II. Academic Press, NY, 1977.
C-2. Pellizzari, E. D., 1978. Identification of Components of Energy-Related
Wastes and Effluents. EPA-600/7-78-004, Environmental Research
Laboratory, U. S. Environmental Protection Agency, Athens, GA, 1978.
C-3. Hushon, J., et al. An Assessment of Potententially Carcinogenic,
Energy-Related Contaminants in Water. MTR-79W171. The MITRE Corporation
McLean, VA, 1980.
C-4. Research Triangle Institute. Environmental Hazard Rankings of
Pollutants Generated in Coal Gasification Processes. Available from
NTIS or from the Industrial Environmental Research Laboratory, U.S.
Environmental Protection, Research Triangle Park, North Carolina, 1981.
C-5 Kingsbury, G. L., J. B. White, and J.S. Watson. Multimedia
Environmental Goals for Environmental Assessment. Volume 1, Supplement
A. EPA-600/7-80-041, Industrial Environmental Research Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC, 1980.
C-6. Environmental Protection Agency. Procedures for Level 2 Sampling and
Analysis of Organic Materials. EPA-600/7-79-033 (NTIS PB 293 800),
Industrial Environmental Research Laboratory, Research Triangle Park,
NC, 1979.
C-7. Bingham, E., R. P. Trosset, and D. Warshawsky. Carcinogenic Potential
of Petroleum Hydrocarbons. A Critical Review of the Literature.
Journal of Environment. Pathology and Toxicology, 3: 483-563, 1980.
C-8. Kingsbury, G., R. Sims, and J. W. White. Multimedia Environmental Goals
for Environmental Assessment, Volume IV. EPA-600/7-79-176b, Industrial
Environmental Research Laboratory, U. S. Environmental Protection
Agency, Research Triangle Park, NC, 1979.
C-9. Kornreich, M. R. Coal Conversion Processes: Potential Carcinogenic
Risk. MTR-7155 (Rev. 2). The MITRE Corporation, McLean, VA, 1976.
C-10. DeGraeve, G., D. Geiger, and H. Bergman. Acute and Embryo-Larval
Toxicity of Phenolic Compounds to Aquatic Biota. Arch. Environmental
Contamination and Toxicol, 9: 557-568, 1980.
C-ll. Fasset, D. W. Cyanides and Nitriles, Industrial Hygiene and Toxicology
Second Edition, Vol. 2, F. A. Patty, ed., Interscience Publishers, New
York, NY, 1963.
C-12. West, P. W. Analysis of Inorganic Particulates. In: A. C. Stern, ed,
Air Pollution, Third Edition, Volume III. Academic Press, NY, 1976.
C-ll
-------
C-13. American Public Health Association. Standard Methods for the
Examination of Water and Wastewater, Fifteenth Edition, APHA,
Washington, DC 1981.
C-14. Christensen, H. E., E. J. Fairchild. Registry of Toxic Effects of
Chemical Substances: 1976 Edition, HEW Publication No.(NIOSH) 76-191
1976.
C-15. Nader, J. S. Source Monitoring. In: A. C. Stern, ed., Air Pollution,
Third Edition, Volume III. Academic Press, NY, 1976.
C-16. Brown, R. Environmental Effects of Coal Technologies: Research Needs.
MTR-79W159-03 (NTIS No. 81-220824). The MITRE Corporation, McLean, Va.,
1981.
C-17. Office of Radiation Programs. Radiological Impact Caused by Emission of
Radionuclides into Air in the United States. Preliminary Report. EPA
520/7-79-006, (NTIS NO. PB 80-122336), U. S. Environmental Protection
Agency, Washington, DC, 1980.
C-18. Wilson, R., et al. Health Effects of Fossil Fuel Burning. Ballinger
Publishing Company, Cambridge, MA, 1980.
C-12
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APPENDIX D
AMBIENT AIR MONITORING TECHNIQUES
D.I CRITERIA POLLUTANTS
The principal critera pollutants are ozone, carbon monoxide, the
nitrogen oxides, sulfur dioxide and total particulates. Methods for their
determination are as follows:
D.I.I Ozone
The EPA reference method for determination of ozone (03) is a
photometric method (D-l). Ambient air and ethylene are delivered
simultaneously to a mixing chamber in which the ozone reacts with the
ethylene to emit light which in turn is detected by a photomultiplier at 430
nm. The resulting photocurrent is amplified and is either read directly or
displayed on a recorder. The calibration procedure, which is complex, is
based on the dynamic generation and standardization of ozone. This
standardization involves measurement of ozone concentration using
spectrophotometry (D-l). That is, absorption by ozone in a
spectrophotometric cell is measured at 254 nm and 03 concentration is
calculated using Beer's Law. This method of calibration is the basis of an
EPA equivalent method'for ozone analysis (D-2). Another equivalent method
is based on the chemiluminescent reaction which occurs between ozone and
rhodamine B (D-2).
The detection limit for the photometric method is about 0.01 ppm. The
typical range of the method is 0.05 to 1.0 ppm with the precision of the
measurement method about 0.01 ppm at 20 percent of the upper range limit.
The analysis is typically performed using commercially available
apparatus which must be EPA approved (D-3).
D.I.2 Carbon Monoxide
The EPA reference method for determination of carbon monoxide (CO) is
based on the absorption of infrared (IR) radiation by CO in a non-dispersive
D-l
-------
photometer (D-4). The photometer contains two cells and two detectors. The
beam of radiation from the source is split into two parallel beams. One
beam passes through the reference cell and the other through the sample
cell. Each detector, in this arrangement, is filled with the pure CO. When
some of the latter is present in the sample beam, the sample detector re-
ceives less radiant energy by the amount absorbed by the sample component at
its characteristic wavelength. The difference in signal from the two detec-
tors is related to CO concentration. Both C02 and water vapor interfere
in the analysis and thus standards and test samples should be matrix
matched.
The detection limit of the method is about 0.05 ppm. The typical range
of the method is 0.10 - 50 ppm and the precision of the method is about 0.05
ppm at 20 percent of the upper range limit.
This analysis is typically performed using commercially available
apparatus which must be EPA approved (D-3).
D.I.3 Nitrogen Oxides
The EPA reference method for determination of nitrogen dioxide (N02)
is a photometric method (D-5, D-6). The N02 is measured indirectly by
photometrically measuring the light intensity, at wavelengths greater than
600 nm, resulting from the chemiluminescent reaction of nitric oxide (NO)
with ozone (03). N02 is first quantitatively reduced to NO by means of a
converter. NO, which commonly exists in ambient air together with N02
passes through the converter unchanged causing a resultant NOX
concentration equal to NO + N02- A sample of the input air is also
measured without having passed through the converter. This latter NO
measurement result is subtracted from the NOX value to yield the N02
value. Calibration is performed with cylinders containing 50 to 100 ppm NO
in N2 with less than 1 ppm N02- These cylinders must be traceable to a
National Bureau of Standards NO or N02 in nitrogen Standard Reference
Material.
Interferences are limited. Unsaturated hydrocarbons react with 03 to
luminesce in the visible region of the spectrum; an optical filter is used to
control this interference. Compounds such as ammonia, peroxyacetyl nitrate
and some amines and organic nitrites can be converted to NO by the same
D-2
-------
system that converts N02 to NO and thus yield a positive interference.
Other useful information regarding NOX determination is contained in
references D-7 and D-8.
The detection limit of the method is about 0.01 ppm and the typical
range of the method is 0.05 to 0.5 ppm. The relative standard deviation of
the measurement method is about ten (10) percent.
This analysis is typically performed using commercially available
apparatus. The apparatus must be EPA approved (D-3).
D.I.4 Sulfur Dioxide
The EPA reference method for determination of sulfur dioxide (S02) is
a wet, colorimetric method (D-9). $03 is collected by passing a known
volume of air through a solution of potassium tetrachloromercurate. A di-
chlorosulfitomercurate complex is formed which is then reacted with pararo-
saniline and formaldehyde to form intensely colored pararosaniline methyl
sulfonic acid. The absorbance of the solution is measured spectrophoto-
metrically at 548 nm. Other useful information regarding S02 determina-
tion is contained in references D-7 and D-8.
The detection limit of the method in 10 ml of absorbing reagent is 0.75
lag which represents a concentration of 25 pg/m3 S02 (0.01 ppm). The
typical range of the method is 25 to 1000 ug/m3 (0.01 to 0.40 ppm). The
relative standard devastion of the measurement method (exclusive of sam-
pling) is about 5 percent.
The effects of the principal known interferences, including oxides of
nitrogen, ozone, and heavy metals, have been minimized or eliminated.
Samples should be stored at 4°C for maximum stability.
Equivalent instrumental methods are available for S02 analysis (D-10,
D-ll). One is based on photometric detection of the chemiluminescence from
sulfur atoms in a hydrogen-rich flame. This flame photometric detector
(FPD) is sensitive to all sulfur-containing molecules, and gases such as
H2S must be removed prior to measurement. Species other than H2S, such
as methyl mercaptan are difficult to remove. Also the FPD signal is subject
to quenching by oxygen and carbon monoxide and thus standards and test
samples must be matrix matched. A typical lower detection limit for the
FPD-based S02 analyzer is 0.005 ppm, with the range being 0.05 to 0.5 ppm
D-3
-------
and the precision at 20 percent of the upper range limit being 0.01 ppm.
Any instrument used for S02 analysis must be EPA-approved.
D.I.5 Suspended Particulates
The EPA reference method for determination of suspended particulates in
the atmosphere is based on the measurement of the parti cul ate mass collected
on a filter (D-12). In the method, air is drawn into a covered housing and
through a pre-weighed glass fiber filter by means of a high-flowrate blower
at a rate of 40 to 60 ft^/min. The system design in combination with the
flow rate results in particles within the size range of 100 to 0.1 ym
diameter being collected on the glass fiber filter. The mass concentration
of suspended particulates in the ambient air (yg/nP) is computed by
measuring the mass of collected particulates and the volume of air sampled.
Concentrations as low as 1 yg/m^ can be measured by sampling at 60
ft3/min for a period of 24 hours. The reproducibility of the method is
about 4 percent. The error in the measured concentration may, however, be
in excess of +50 percent. This inaccuracy is due in large part to changes
occurring in the airflow rate which, in turn, is affected by the
concentration and nature of the particulate material being collected.
Equipment needed for sampling includes the sampler, a sampler shelter,
a rotameter, an orifice calibration unit, a differential manometer, a
barometer, and a positive displacement meter. Analysis requires a chamber
for conditioning the filters, an analytical balance capable of weighing 8 by
10 in. filters to 0.1 mg, and a light source for checking for holes in the
filters. Glass fiber filters should have a collection efficiency of at
least 99 percent for particles 0.3 ym diameter. All this equipment may be
purchased.
D.2 HAZARDOUS GASES
The principal hazardous gases of concern are ammonia, hydrogen,
cyanide, hydrogen fluoride, total hydrocarbons, and sulfur gases (HgS,
COS, C$2). Methods for their determination are as follows:
D.2.1 Ammonia
Ammonia is collected by passing a known volume of air through a diluted
solution of sulfuric acid in an impinger. Several different methods are
D-4
-------
available for measurement of the ammonium sulfate produced during sampling.
In one method, the ammonium sulfate is mixed with Nessler reagent to produce
a yellow-brown complex. Ammonia concentration is then determined by measur-
ing the absorbance of the solution at 440 nm (D-13, D-14). The range of the
method is 20 - 135 ppm. The only interferent reported is that of ammonium
salts, which can be removed by filtration of the air before entry into the
impinger The method does not distinguish between free and combined ammonia. A
more sensitive method involves reaction of the ammonium sulfate with phenol and
alkaline sodium hypochlorite to produce indophenol, a blue dye which is measured
colorimetrically (D-7). Analyses in the 1 to 30 ppb range with a relative
standard deviation of 30 percent are possible with this method, though it is
prone to interferences. Certain metal ions and particulate material must be
removed from the air before being passed through the impinger. The only
instrument required is a spectrophotometer operating in the visible range.
Finally ammonia can be determined using the ammonia-selective electrode (D-15);
metals which complex ammonia will interfere with this method and the method of
standard additions should be used as a quality control measure.
D.2.2 Cyanide Compounds
Cyanide is collected by passing a known volume of air through an impinger
containing 0.1 P{ sodium hydroxide (D-16, D-17). The cyanide collected is mea-
sured using a cyanide ion specific electrode. This ion specific electrode in
conjunction with a reference electrode gives rise to a potential which is re-
lated to the logarithm of the cyanide concentration. The range for the method
is 0.013 to 13 mg/m3 in air. The only significant interferent is sulfide,
which must be removed through precipitation as cadmium sulfide if present. The
equipment needed for this determination includes a cyanide ion specific elec-
trode, a reference electrode and an expandable scale, mV/pH meter.
Colorimetric and titrametric procedures for measurement of the collected
cyanide are also available (D-18) and should be performed to verify the applic-
ability of the electrode method when the latter is preferred.
D.2.3 Fluorides
Fluorides are collected by passing a known volume of air through impingers
containing 0.1 Nl sodium hydroxide (D-19, D-20). The fluoride
D-5
-------
collected is measured using a fluoride ion specific electrode. This ion
specific electrode, in conjunction with a reference electrode, gives rise to
a voltage signal which is related to the logarithm of the fluoride
concentration. A special buffer prepared with glacial acetic, sodium
hydroxide, sodium chloride and cyclohexane diamine tetraacetic acid
monohydrate (CDTA) must be added to the collected sample prior to
measurement to prevent interference by hydroxide ion and ions of silicon,
iron and aluminum. The range for the method with a 40-liter sample is 0.05
to 475 mg/m^ of air and the relative standard deviation for sampling and
analysis of 100 ug HF is about 7 percent.
The equipment needed for this determination includes a fluoride ion
specific electrode, a reference electrode and an expandable scale mV/pH
meter.
D.2.4 Total Hydrocarbons
Total and non-methane hydrocarbons in ambient air are measured using a
flame ionization detector (FID) (D-21, D-22). This device consists of a
hydrogen/air burner and two electrodes; hydrocarbons entering and decompos-
ing in the flame give rise to ions which conduct current between the elec-
trodes. This current is measured and is proportional to the number or con-
centration of carbon atoms in the flame. Thus one molecule of butane would
give twice the signal of one molecule of ethane. Methane concentration,
which is usually significant, is not of particular interest as it is con-
sidered photochemically unreactive. Various schemes are used to separate
methane from the rest of the hydrocarbons. Some of the commercially avail-
able instruments use gas chromatographic columns to separate the methane
from the other hydrocarbons. The total organic concentration (TOC) and the
methane are measured separately and the non-methane organic concentration is
calculated by difference. In other systems TOC is measured and then all
organic compounds except methane are catalytically oxidized and the methane
is measured alone. Again MMOC is calculated by difference. In still other
systems the oxidized compounds are reduced to methane and measured as NMOC
directly using the FID. NMOC can be measured directly using FID after col-
lection in a cryogenic trap which does not collect methane. The TOC mea-
surement is depressed by moisture, often producing negative NMOC values.
D-6
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Also inaccuracies are inherent with the subtraction of large numbers
(methane) from slightly larger numbers (TOC)(D-23). The minimum detection
limit for the method is about 0.05 ppm as carbon The typical range for the
method is 0.5 to 10 ppm C and the precision is about 0.10 ppm C for TOC.
D.2.5 Hydrogen Sulfide, Carbon Disulfide and Carbonyl Sulfide
A variety of methods are available for analysis of the individual
sulfur compounds (D-8, D-24). It is most cost effective however to use a
single method for determination of all three compounds (D-25, D-26). This
method is based on measurement using a gas chromatograph fitted with a flame
photometric detector. In the method an aliquot of air is loaded onto a
column suitable for separation of the sulfur gases. The separated gases are
then measured. Compounds eluting after the sulfur compounds are usually
vented without passing through the FPD.
The lower detection limit for the FPD-based analyzer is about 0.005
ppm. The relative standard deviation is typically about ten (10) percent.
D-7
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D.3 ORGANIC COMPOUNDS
D.3.1 Sampling Vapor Phase Organic Compounds
Sampling methods for vapor phase organics generally involve the passage
of a measured amount of air through a device containing a solid sorbent.
Organics are removed by adsorption to the solid, and are thus transported to
laboratory facilities for later analysis. Prior to the adsorption process,
the air is usually filtered to remove particulate matter. The chief benefit
of this approach is that it allows for significant concentration of the
sample component prior to analysis. Since ambient air levels are almost
always low for most organics (
-------
lack thermal stability, and are solvent rinsed for compound desorption.
Tenax is useful for collection of compounds boiling between ca. 60° and
300°C, while XAD-2 and PUF are useful for compounds with boiling points
above ca. 150°C.
Carbon adsorbents have relatively low affinity for water, and strong
affinity for unsaturated organic molecules, particularly aromatics. This
allows for the collection of certain low boilers that are not efficiently
trapped by polymeric sorbents. Carbon adsorbents consist of activated
charcoals, carbon molecular sieves and carbonaceous polymeric sorbents.
D.3.1.1.1 Procedure—The chosen sorbent is prepared for sample collec-
tion using rigorous and well defined procedures. In the case of Tenax GC,
the polymer is solvent extracted, dried, sieved to a specified mesh size
range, packed into sampling cartridges, and thermally desorbed under ultra-
clean helium purge (D-28, D-29). The high affinity of Tenax for organics
requires extremely tight control over the entire preparation process. Other
resins are similarly prepared, with omission of the thermal desorption step
if the resin (e.
-------
For resins such as XAD-2 or PDF, with no thermal desorption step, ca.
16 person-hours are ^required for preparation of up to 1 kg of XAD-2.
Carbon sorbents generally require only packing in sampling tubes followed
by thermal desorption. Total effort required is ca. 8 person-hours for the
preparation of up to 50 cartridges.
D.3.1.2 Impinger Collection--
Collection of ambient organics from air via the use of impingers (bub-
blers) involves the passage of a measured volume of air through a liquid in
which the target organics are trapped. The impinger usually consists of a
tubular glass reservoir with a gas inlet tube fitted so that the incoming
gas stream is introduced into the liquid near the bottom of the reservoir.
To increase the contact between the air stream and the liquid trapping
medium, the air is dispersed by the use of fitted diffusers or capillary
jets. Generally a number of impingers are connected in series to ensure
quantitative collection of analytes. To prevent evaporation of reservoir
liquid during collection, the impingers can be cooled (e.cj. , ice water
bath). The reader is referred to Stern (D-8) for details on impinger design.
Impingers are commonly used to collect organics in solutions containing
derivatizing reagents. The formation of derivatives of target compounds is
usually carried out to enhance the detectability of certain species.
Aldehydes for example can be collected in solutions of dinitrophenylhy-
drazine which convert them to stable non-volatile highly chromophoric hydra-
zones. Analysis can be conducted later using chromatographic/spectroscopic
techniques (D-30, D-31).
D.3.1.3 Cryogenic Collection--
Ambient air organics can be collected by the passage of a measured air
sample through a cold trap. Depending on the refrigerant used, various com-
ponents will be condensed and thus collected for subsequent analysis. The
method has the advantage of providing a concentrated sample of air vapors in
a form that is immediately available for analysis. Stern (D-8) provides
details of the methodology; Rasmussen (D-32) has reported on a portable
cryocondensing sampler.
D-10
-------
Commonly used refrigerants include liquid nitrogen or argon, and dry-
ice/solvent mixtures. The trap, usually consisting of a metal tube (stain-
less steel, nickel), is arranged such that the trap contents can be valved
directly to the analytical device (e.g., GC). Sample transfer is accomplished
by flash heating with gas purge. The method requires that the entire sam-
pling/analysis system be used in the field, or that a whole air sample is
collected for transport to the cryogenic collection device. An important
factor in the consideration of the use of this approach is the concentration
of relatively large amounts of water, which can block the trap (as ice), and
serves to create a potentially high acid solution by dissolution of NO
/\
and/or SO-.
D.3.1.4 Whole Air Collection-
Whole air samples can be collected for transport to the analytical
laboratory for subsequent analysis. Evacuated containers are most commonly
used for sample collection, although samples can be taken by pumping air
through a bulb or other device, and sealing inlet and outlet after passage
of a suitable volume of air. Specific collection methods are dealt with in
some detail by a National Academy of Sciences monograph (D-33).
Rigid containers (glass, metal bulbs, gas-tight syringes) are advanta-
geous in that sample loss due to permeation and/or leakage is generally
minimal. However, losses of certain species through adsorption or reaction
with container surfaces may be a problem. The use of non-rigid containers
(e.g., Teflon, Tedlar bags) minimize adsorption problems, but limit the time
between sampling and analysis due to permeation of collected materials out
of the bag and contaminants into the bag.
Whole air collection is not readily useful for ambient air monitoring
unless some form of sample concentration (e.g., cryofocussing) is employed
prior to analysis.
D.3.2 Sampling Semi- and Non-Volatile Airborne Organic Compounds
Non-vapor phase organics are present in ambient air in a particle-
bound state by virtue of adsorption to airborne particles. Semi- and non-
volatile compounds include, generally, those with boiling points greater
than 150°C. Many types of sampling devices are available for the collection
0-11
-------
of air aerosol. These devices utilize principles of filtration, centrifuga-
tion, impaction or electrostatic precipitation. Filtration is by far the
most important for organics collection, due to the relatively large amount
of particulate trapped. Cyclones and impactors are most commonly used for
particulate characterization (size, weight, inorganic content, etc.), and
generally collect too little material for analysis of adsorbed organics
(such organics usually comprise ca. 1-10% by weight of ambient air aerosol).
Thus for monitoring for semi- and non-volatile organics at synfuels facilities,
only filtration will be addressed as the most practical collection procedure.
D.3.2.1 Filtration—
A typical level of ambient air particulate is ca. 50 ug/m3. In order
to obtain a sufficient quantity of particulate for organic analysis (c_a. 50
mg) some 1000 m of air would need to be sampled. To collect the requisite
amount of particulate in less than 24 h, sampling rates of ca. 1 m /min are
required. These rates are available through the use of the Hi-Vol sampler,
a commercially available device that has been used extensively for many
years. Warner (D-35) provides a thorough description of the sampler.
The filter media used with the Hi-Vol sampler consist of glass or
quartz fiber mats. Glass fiber filters can be obtained that are Teflon®
coated to reduce surface activity. Cellulose and membrane filters are not
amenable to high volume air sampling, and thus would have limited application
to synfuels organics monitoring programs. Mitchell (D-36) provides a complete
discussion of filter media.
Collected particulate mass (from the Hi-Vol) is determined by weighing
tared filters under controlled humidity conditions. The entire filter, with
particulate, is then extracted for organics analysis.
D.3.3 Analytical Techniques for Determination of Organic Compounds
A relatively small number of basic analytical techniques are currently
successfully used for ambient level monitoring of air, water and soil. Most
involve well-developed chromatographic methods, and utilization of a variety
of detection systems to achieve requisite sensitivity and selectivity.
The Massive Air Volume Sampler (D-34) utilizes principles of impaction and
electrostatic precipitation, and is capable of collecting very large quan-
tities of particulate. This capability and the sampler's expense render the
device not useful for routine monitoring for synfuels facilities.
D-12
-------
Spectroscopic techniques are used either in conjunction with chromatography
systems, or as stand-alone devices for specific analyses.
A brief, general description of those techniques most commonly employed
in ambient level monitoring programs is provided prior to a discussion of
specific methodologies. These descriptions were taken, in part, from a
draft EPA report ("Technical Assistance Document for Sampling and Analysis
of Organic Compounds in Air", by R. W. Rigging, Battelle Columbus Laboratories,
November, 1982).
Gas chromatography (GC) is by far the most widely used technique for
environmental monitoring. It is applicable to all compounds that possess
sufficient thermal stability and volatility, and can utilize a wide variety
of detection modes.
GC basically is a separation technique wherein components of a sample
are separated by differential distribution between a gaseous mobile phase
(usually helium, nitrogen, or hydrogen carrier gas) and a solid or liquid
stationary phase held in a glass or metal column. Sample is injected into
the carrier gas as a sharp plug and individual components are detected as
they elute from the column at characteristic "retention times" after injection.
Many basic texts are available for a detailed description of GC principles
and applications; Katz (D-27) represents one of many examples.
Analysis by GC is conducted using either packed columns or capillary
columns. The former consists of a relatively wide bore (typically 2-6 mm)
column filled with an inert support material coated with a liquid film of
stationary phase. Capillary columns have very small bores (<500 u), with
the walls of the tubing coated with liquid stationary phase. For a number
of reasons, capillary columns are superior to packed columns in terms of
resolution, and have found wide application for environmental analysis.
A complete discussion of capillary column technology is provided by
Jennings (D-37) and Bertsch et al_. (D-38). A wide variety of GC detectors are
useful for pollutant monitoring. The flame ionization detector (FID) is the
most popular detector, and the one with the most universal response. Virtually
any carbon-containing molecule can be detected with the FID. The electron
capture detector (ECD) is useful for detection of electron deficient molecules
and can provide high selectivity and sensitivity for such molecules. The
D-13
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photoionization detector (PID) is selective for photoionizable molecules and
is especially suitable for the highly sensitive detection of aromatic com-
pounds. The Hall electrolytic conductivity detector (HECC) can be operated
specifically for detection of halogen, sulfur, or nitrogen-containing species.
Other less commonly used detectors include the flame photometric detector
(FPO), which is useful for sulfur or phosphorus-containing compounds, and the
alkali flame (AFD), and thermoionic specific (TSD) or nitrogen-phosphorus (NPD)
detectors; these detectors are selective for nitrogen or phosphorus and are
more sensitive than either FPD or FID. Specific GC application usually
determines the mode of detection.
Another general analytical technique that has found widespread applica-
tion for environmental analysis is gas chromatography/mass spectrometry
(GC/MS). In simple terms the technique can be viewed as gas chromatography
with a mass spectrometer as a detector. The benefits of this approach
include high analytical sensitivity and specificity, the latter sometimes
minimizing the sample purification effort required. In the mass spectrometer,
the sample components are ionized and fragmented into characteristic spectral
patterns by continuously scanning GC effluent as it is introduced into the
mass spectrometer. Complete mass spectral scans (40-600 amu) can be produced
as often as I/second. It is also possible to operate the spectrometer in a
selected ion monitoring mode or multiple ion detection mode wherein only a
few selected ions are monitored rather than scanning a broad mass region.
These approaches provide increased sensitivity for monitoring for specific
compounds. The data output from a GC/MS system can be prodigious, and
various mass storage devices (usually magnetic tape) and sophisticated
software are employed for data archiving and reduction. Several textbooks
are available for more comprehensive discussions of the technique of GC/MS
(e.cj., D-39); environmental applications using GC/MS have been addressed by
Burlingame (D-40).
For those compounds not amenable to gas chromatographic separation,
either by virtue of being nonvolatile or thermally labile, the technique of
high performance liquid chromatography (HPLC) is used. This methodology
employs closed chromatographic columns consisting of small diameter particles,
either uncoated or coated with liquid phase, over which mobile phase can be
D-14
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passed. Because of the size of the column packing particles high pressures
are required to obtain optimum solvent flow for which various types of
sophisticated solvent delivery systems are utilized. Currently available
instrumentation allows for the selection of a wide variety of flow rates and
adjustable mobile phase compositions. Several authors (e.c[. , Parris, D-41) have
written detailed texts describing methodology, instrumentation and application.
HPLC is most commonly utilized in ambient air monitoring programs for semi-
volatile compounds such as polycyclic aromatic hydrocarbons and for compounds
such as aldehydes which are usually determined as nonvolatile derivatives.
Most HPLC systems utilize UV absorbance and/or fluorescence emission detection
systems. Recent advances have shown the feasibility of interfacing a mass
spectrometer to an HPLC thus bringing the same advantages to this technique
as are currently enjoyed by gas chromatography (D-42, D-43).
Other chromatographic techniques such as column chromatography and
thin-layer chromatography are used primarily for sample purification or
"clean-up" prior to determination by more sophisticated separations methods.
Stern (D-44) discusses thin-layer chromatography.
D.3.4 Measurement of Organic Vapors
With generally few exceptions, ambient levels of organic vapors are
low, and the procedures and techniques required for analysis must therefore
embody high performance capability. This entails the use of research grade
equipment, some of it very sophisticated and expensive, and highly skilled
chemists well trained in trace analysis.
This section addresses the general analytical approaches most effectively
utilized for the determination of organic vapors following collection.
D.3.4.1 Solid Sorbent/Thermal Desorption Analysis—
For those compounds collected on certain heat-stable sorbents (e.cj. ,
Tenax GC®, charcoal, Chromsorb®), analysis is conducted by gas chromatography
(GC) or gas chromatography/mass spectrometry (GC/MS). The selectivity of
GC/MS renders that technique more useful for the complex mixtures likely to
be found in air samples. For the same reasons high resolution capillary
columns are usually a necessary component of the GC system, although in
certain cases, for example the monitoring of single, selected compounds,
packed columns can provide sufficient resolution for analysis (D-33).
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0.3.4.1.1 Procedure—Sorbent cartridges containing tne collected vapor
phase components are analyzed either directly, or, for quantitative analysis,
after loading with measured quantities of reference standards. Such loading,
for reference standards or for the preparation of control cartridges, is
accomplished most expeditiously via a permeation system (D-45).
The sample cartridge is placed in a unit suitable for heat desorption
with a purge gas and collection of the desorbed components in a cryogenic
trap. A commercial version of such a device has been described (D-46).
Following desorption and collection of the condensed vapor-phase components,
the cryotrap is rapidly heated and purged, thereby transferring the sample to
the GC column as a discrete low-volume injection. Analysis thus proceeds
using either GC with a variety of detectors (e.cj. , flame ionization, electron
capture, flame photometric, photoionization, etc.), or GC/MS using a variety
of operational modes (e.cj. , selected ion monitoring, multiple ion detection,
full scan, etc.). The use of GC/MS in environmental research has been
reviewed (e.g., D-47). A typical example of the use of solid sorbent/thermal
desorption analysis for organic vapors in ambient air is provided by Pelliz-
zari et al_. (D-45, D-48).
D.3.4.1.2 Performance Parameters—Detection limits for most vapor phase
compounds, when analyzed by GC using flame ionization detection, range from c_a.
1-100 ppb; the volume of air sampled directly affects this figure. For certain
classes of compounds (e.g., amines, halogenated species), specific detectors
(e.£., nitrogen-phosphorous detector, electron capture detector) can provide
lower limits of detection and enhanced selectivity. Detection limits for
thermal desorption analysis using GC/MS range from ca. 100 ppt-100 ppb
depending on compound, volume of air sampled and MS operating mode. Precision
and accuracy for both GC and GC/MS methods are limited by sample collection
procedures, sample storage time, performance of the desorption unit and GC
or GC/MS, and on the physical/chemical properties of the target compounds.
Accuracies of +10-40% have been reported for GC/MS analyses (D-45).
Interferences can be a problem in the analyses of some compounds with
certain sample collection procedures. Proper use of blanks and controls is
essential to minimize the magnitude of the problem. For sorbent trapped
material, sampling in caustic or high level halogen-containing atmospheres
should be conducted with caution.
D-16
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0.3.4.2 Solid Sorbent/Solvent Desorption—
Higher boiling (i_.e. , > ca. 150°C) vapor-phase air pollutants are usually
collected via sorbents such as Amber!ite XAD-2 (styrene-divinyl benzene
copolymer), or polyurethane foam (PUF). These materials are not thermally
stable, and the trapped sample components are removed by solvent rinsing.
Amber!ite XAD-2 resin is specified as the vapor-phase trap component of the
EPA promulgated stationary source sampler (SASS train). A description of
the analytical methods used for the XAD-2 trapped materials is provided in
an EPA report (D-49). A detailed description of the solvent desorption
procedures and analytical methods for PUF samplers is provided by Lewis
et al_. (D-50).
D.3.4.2.1 Procedure--The removal of relatively nonvolatile vapor-phase
substances from polymeric sorbents is accomplished via the use of Soxhlet (or
Soxhlet-type) extraction. The sorbent is placed in the receiver of a Soxhlet
apparatus, and extracted for a prolonged period (ca. 4-24 h) with an appro-
priate solvent. Following extraction the sample solution (usually ca.
100-1000 mL) is concentrated using solvent removal techniques that minimize
evaporative or adsorptive sample loss. Careful rotary evaporation, Kuderna-
Danish techniques and/or nitrogen blow-down are commonly used procedures.
The concentrated sample (ca. 0.1-10 ml) may be analyzed directly, or may
require chromatographic purification. In the latter case alumina or silica
gel column chromatography has been used to obtain fractions containing the
analyte(s) in a form amenable to direct analysis (D-28, D-29).
Gas chromatography has been used most often for the analysis of the
solvent desorbed compounds, although any of a variety of instruments (e.c[. ,
HPLC, AA, etc.) may be used. Any chromatographic procedure will utilize
direct liquid injection for sample introduction; this means that only approxi-
mately 1-10% of the sample is available for direct analysis. Replicate
analysis can be conducted, a feature not possible with thermal desorption
processes. As noted earlier, the use of capillary vs. packed columns, and
certain specific detectors can enhance analytical performance. The choice
of column and detector are dictated by the specific site-monitoring require-
ments, and by the analytes monitored.
D-17
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D.3.4.2.2 Performance Parameters—Overall method sensitivity for solvent
desorption of sorbed compounds is generally less than for thermal desorption.
This is primarily due to the inability to analyze for more than a fraction of
the sample at a time (vide supra). In addition there is more sample handling
(extraction, concentration, purification) associated with the solvent desorp-
tion procedure, and hence greater potential for sample loss. These factors
are somewhat offset by the ability to sample larger volumes of air using
XAD-2® or PUF, than, say, Tenax GC®.
Precision and accuracy are highly dependent on the specific analytical
procedure adopted; both suffer because of the greater degree of sample
manipulation inherent to this method, particularly if chromatographic clean-up
is required. The working range of compound quantitation is defined by the
analytical instrumentation, since the sample concentration can be adjusted
to ensure compatibility.
D.3.4.3 Cryocollection Analysis--
The analysis of cryocollected samples depends to some extent on the
particular method of sample collection. For some cryosamplers (D-32), selec-
tive distillation and recovery of fractions is possible. Most samplers provide
for syringe removal of gas samples for analysis. Some constraint is imposed
on the sampling and analysis system since cryogenic temperatures must be
maintained on the sample between time of collection and time of analysis.
D.3.4.3.1 Procedure--Cryocol1ected samples are analyzed by GC. Virtu-
ally any detector, including MS, can be used. Sample aliquots are withdrawn
from the cryocondensor vessel with a gas-tight syringe and injected into the
GC. Alternatively, the cryotrapping system can be interfaced directly to the
GC via a multi-port valve (D-51). This approach requires that the sampling
and analysis system be transported to the monitoring site.
D.3.4.3.2 Performance Parameters—The overall system performance for
the analysis of cryogenically collected samples is dependent on the volume
of air collected, and on the specific performance characteristics of the GC
or GC/MS. The concentration of air contaminants during collection usually
allows for the analysis of compounds in the ppb range. The use of selective
detectors such as electron capture or photoionization can significantly
enhance detectability over the flame ionization detector.
D-18
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Rasmussen (D-32) has reported extremely good precision (ca. 1-3%) for
the repeated collection of air samples under laboratory conditions. The effi-
ciency of collection is normally very high particularly for those samplers
that employ low temperature coolants (liquid nitrogen, oxygen, etc.).
D.3.4.4 Impinger Collection Analysis--
Samples collected by impingement in a liquid are concentrated to some
degree, depending on the efficiency of collection and volume of trapping
medium. Further concentration of the liquid solution is possible if the
sample components (or derivatives thereof) are nonvolatile. By far the
most common use of impingers is for collection and simultaneous derivatization
of certain air pollutants. The prime benefit to the analyst of converting
samples to derivatives is the enhanced detectability of the sample. For
example carbonyl compounds such as formaldehyde and acetone, which have no
significant UV absorption, are quantitatively converted to
2,4-dinitrophenylhydrazone (DNP) in impingers. The hydrazones possess
generally intense chromophoric properties, and thus render the carbonyl
components at once nonvolatile and readily amenable to HPLC analysis using
UV absorption detection. Other derivatization procedures are possible for
compounds such as phenols, amines and phosgene. The procedure presented
below describes the analysis of impinger-collected aldehydes (as DNP), and
is representative of such methods generally (D-30).
D.3.4.4.1 Procedure--Impinger solutions of acidic 2,4-dinitrophenyl-
hydrazine are used to convert airborne aldehydes to the stable, nonvolatile,
UV-absorbing hydrazone. Five to thirty liters of air are bubbled through two
serial impingers at 0.5-1.5 L/min. The impinger solutions are combined and
extracted with chloroform. The extracts, after washing with acid and distilled
water, are concentrated to dryness under mild vacuum. The residue is then
dissolved in 2 ml of acetonitrile and analyzed by HPLC. Isocratic mobile phase
compositions of ca. 70:30 acetonitrile:water are employed with a reverse phase
column. Column eluant is monitored by UV detection (254 nm); quantisation
is accomplished by comparison of detector response to calibration curve
values.
D-19
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D.3.4.4.2 Performance Parameters—The method is applicable to virtually
all simple aldehydes and ketones, from formaldehyde to tolualdehyde and acetone
to methyl-n-amylketone. Detection limits were reported as 0.1 ng for formal-
dehyde; 0.2 ng for C-2 and C-3 aldehydes; and 0.5 ng for higher alkane and
aromatic aldehydes.^ These values correspond to air levels of ca. 1.5-2.6
ppb. Recoveries of test compounds prepared by spiking impinger solutions
ranged from 81-103%. Analytical precision for recovery studies ranged from
ca. 2-8% relative standard deviation. Determinations of levels of vapor phase
aldehydes prepared as a test mixture showed precision for 5 replicates, of ca.
1-7% RSD. The method has been used for the determination of vapor phase
aldehydes in urban air, industrial emissions, automobile exhaust and tobacco
smoke.
D.3.5 Measurement of Aerosol Organics
The analysis of air aerosol for adsorbed semi- and non-volatile organics
has been conducted, at least for certain compounds, for many years. Although
a number of different specific procedures have been developed and utilized,
most are similar in one respect or another. General analytical approaches
for aerosol organics are available from a number of sources such as
Stern (D-44) and the National Academy of Sciences (D-52).
The basic analytical methodology involves extraction of collected
particulate with organic solvent, purification of the extracted material,
and analysis by any of several methods depending on target materials. A
vast body of literature is available for the analysis of polycyclic aromatic
compounds (PAC), and the methods used for these compounds are generally
representative of procedures for aerosol organics. Methods for PAC analysis
are deemed most pertinent for synfuel processes monitoring. The methods are
usually based on particulate collection using Hi-Vol samplers, although
particulate collected by any means can be incorporated into the methods
described below.
D.3.5.1 Procedure [Method 1, polycyclic aromatic hydrocarbons (D-53)]--
Filter material (glass fiber, Teflon, etc.) containing collected particu-
late is placed in cyclohexane and sonicated for 1 h. The solution is filtered
(0.5 H Teflon), and the filtrate passed through a silica gel cartridge
D-20
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(Waters Assoc. Sep-Pak, or equivalent). The silica cartridge is washed with
ca. 5 ml of hexane:methylene chloride (9:1). The wash solution is concen-
trated to ca. 2 ml_, mixed with ca. 1 ml acetonitrile, and concentrated to
ca. 0.1 ml. The concentrated extract is then streaked onto a cellulose TLC
plate. After developing the plate in the specified solvent system, the band
corresponding to the PACs is scraped, and the collected cellulose is sonicated
with acetonitrile. This solution is centrifuged, and an aliquot of super-
natant is injected onto a reverse phase HPLC column. The eluant is monitored
using a fluorescence detector (340 ex; >425 em). Quantisation of selected
target PACs is accomplished by comparison of detector response with calibra-
tion curve values.
D. 3. 5.1.1 Performance Parameters—The lower limit of detection for most
3
PACs corresponds to ca. 100 ng/m . Precision and accuracy are not specified
in the NIOSH protocol. The TLC clean-up step can be problematic, giving non-
reproducible elution times. The number and similarity of many PACs prevent
complete resolution by HPLC; confirmatory techniques for certain target
compounds may need to be employed.
D.3.5.2 Procedure [Method 2, polycyclic aromatic compounds (D-54)] —
Filter media (glass fiber, Teflon-coated glass fiber) containing collec-
ted particulate is Soxhlet extracted with methylene chloride, and the extract
is concentrated via rotary evaporation and nitrogen blow-down. The extract
is subjected to an aqueous acid/base wash sequence to separate bases, acids
and neutrals. The neutral fraction is then separated into 4 fractions by
open column silica gel chromatography. The polycyclic aromatic hydrocarbons
elute in a single fraction, and are free of less polar materials (alkanes),
as well as more polar compounds (oxygenated species, heterocyclis, etc.).
The fraction is concentrated and analyzed by fused silica capillary column
GC/MS. Compounds are identified by their mass spectra and retention time;
quantisation is achieved by reference to a sample standard using pre-calcula-
ted response factors. For certain compounds negative ion chemical ionization
can be used to achieve lower limits of detection and quantisation.
D-3.5.2.1 Performance Parameters—The method is applicable to particulate
samples containing up to 1 g of organic extractables. Overall method sensitivity
D-21
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depends on sample size; ambient levels of most PACs are easily within reach
of the method. Recoveries of organics through the procedure range from
75-104%.
D.4 INORGANIC SPECIES
The inorganic species of concern in air are metals and anions. These
usually will be associated with particulate material. A few metals such as
selenium and mercury can be found in the vapor state in air. Background
information on the toxicity of trace elements and their presence in emis-
sion from synthetic fuel plants is contained in references (D-55 - D-60).
The high volume sampler described under CRITERIA POLLUTANTS can be
used to collect samples for analysis. Samples also can be collected with
smaller systems using smaller filters, e.g., 47 mm (D-7, D-8, D-12, D-58).
Metals in their vapor state such as mercury and selenium are collected by
drawing a known volume of air through an oxidizing medium such as potassium
permanganate or potassium persulfate solution in an impinger (D-61).
D.4.1 Metals
The metals collected on filters can be analyzed in several different
ways. The filters can be analyzed directly, without treatment, using x-ray
fluorescence (XRF) (D-62, D-63). The filters are placed in the x-ray
system in a multifilter cassette and are automatically analyzed. About 30
elements can be measured simultaneously this way ranging from aluminum
(atomic number = 13) to barium (atomic number = 56). Minimum detectable
limits range from 20 ngm/cm2 of filter for aluminum to 3 ngm/on2 of
filter for selenium. The x-ray apparatus for air filter analysis may be
purchased and used in-house. Commercial laboratories also are available to
perform x-ray analysis.
The filters can also be analyzed directly using neutron activation
analysis (NAA) (D-64). This technique can be used to measure most of the
elements of concern, but when many different elements are present together
on a filter, interferences occur and detection limits are high, usually in
the range of micrograms per filter. However, with sufficient sample
material, elemental levels in air at the ngm/m3 level can be measured.
Neutron activation analysis instrumentation is expensive and this type of
analysis is best performed by a commercial laboratory.
D-22
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The metals also may be measured using spark source mass spectrometry,
atomic absorption spectrophotometry or inductively-coupled, argon plasma
emission spectrometry. All three techniques require that the metals be
dissolved from the filter; this is best done by extraction with dilute acid.
Organometallic compounds present must be decomposed using the Parr bomb
combustion technique. Combustion must also be performed if the organic level
in the particulate material is high, as it will interfere in the measurement
process, especially for spark source mass spectrometry.
Spark source mass spectrometry (SSMS) is a very useful technique as it
permits simultaneous measurement of essentially all the elements (D-65 - D-67).
Assuming 50 mgm of particulate are collected, minimum detection limits range
from about 0.05 pg/m3 for manganese to about 5 yg/m^ for cadmium. The
method is fairly imprecise, usually about +_ 30 percent. This poor precision
and the fact that the technique can be used to measure essentially all the ele-
ments make this a good screening technique. Finally the equipment is very ex-
pensive and analyses are best performed by an outside, commercial laboratory.
Atomic absorption spectrophotometry (AAS) with electrothermal atomization
provides the lowest detection limits of the various methods available (D-68,
D-69). These detection limits range from 0.5 to 100 ngm/mL of metal extract
solution. As many as 67 elements can be measured by atomic absorption spec-
trometry and the precision of the technique is about ± 2 percent for most ele-
ments at mid-range (D-70). The linear response range usually spans two orders
of magnitude. The principal limitation of the technique is that only one
element at a time can be measured. However, the newest computer-controlled
atomic absorption spectrometers can be programmed to change light sources,
wavelength settings, etc., so that about ten (10) elements can be determined in
each of 30 to 50 samples without operator attention.
The final method to be discussed is inductively coupled, argon-plasma
atomic emission spectrometry (ICP-ES) (D-71, D-72). One form of this instru-
ment permits the simultaneous measurement of up to 50 elements; the other and
much less expensive form measures the elements sequentially under computer con-
trol. The minimum detection limits for ICP-ES are about ten (10) times those
D-23
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of AAS. An advantage of the technique is its wide linear response range,
which for many elements extends over five (5) orders of magnitude with a
precision of several percent. ICP-ES is not as selective as AAS, with
emission lines from certain elements in the sample overlapping emission lines
of other elements. The sequential analysis instrument does allow one to
select alternate emission lines if the primary lines have interferences.
D.4.2 Ions
The extractable ionic species chloride, nitrite, nitrate, sulfate, phos-
phate and ammonium are best measured using ion chromatography (D-73, D-74).
This method involves injection of the aqueous filter extract onto an ion ex-
change column. Eluent is forced through the column resulting in separation of
the ions. The effluent of the first column passes into a second column which
neutralizes the elution medium. The ions emerge from the second column in
this neutral medium which then is passed through a conductivity cell. The
ions passing through this cell give rise to a measurable signal. One type of
column and eluent is used for determination of anions and another for deter-
mination of cations. The ion chromatograph is commercially available. The
minimum detection limit for the method is about 0.1 ppm for ions, in the
aqueous extract, with the normal response range being 0.1 to 100 ppm. The
relative precision above the 1 ppm level is about 5 percent.
The ionic species fluoride, sulfide, and cyanide are best measured using
ion selective electrodes. The ion selective electrode in conjunction with a
reference electrode is placed in a quantity of aqueous filter extract. The
voltage measured is related directly to the logarithm of the ion concentra-
tion. The minimum detection limit for this method of analysis is about 0.1
ppm for ions in the aqueous extract, with the normal linear response range
being 0.1 to 100 ppm. The relative precision above 1 ppm is about 5 percent.
D-24
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D.5 BIOLOGICAL TESTS (MUTAGENICITY)
D.5.1 Laboratory Screening
The Ames screening bioassay test is a method of detecting the presence
of mutagenic substances in the ambient atmosphere adjacent to synthetic fuel
plants. It is a highly sensitive, reliable, and relatively simple point
mutation test with consistent results.
Samples are collected much the same as for particulate organic pollutants
and then subjected to an Ames screening bioassay test using the bacteria
Salmonella typhimurium as the standard test organism. Detailed information
on the sampling and analytical protocols of this method may be found in
references D-75 - D-87.
Other possible laboratory screening tests for mutagenicity (employing
mammalian cells rather than bacteria) include: a Chinese hamster ovary muta-
genesis test using the Kl cell line (which measures point mutation, as does
the Ames); and a related Chinese hamster ovary test evaluating sister chromatid
exchange, a measure of gross genetic change. More detailed tests for mutagenic
activity (e.g., measures of cell transformation) are considered to be beyond
the screening bioassay procedures envisioned in this manual.
D-5.2 Possible Field Screening
Since it is not possible to assure that all potentially mutagenic sub-
stances emitted from synfuels facilities will be chemically identified, there
is a need for an ambient monitoring technique to be used to detect the presence
of such substances. The plant Transdescantia paludosa (Spiderwort) in the family
Commelinaceae, can be used to detect the presence of mutagens under field con-
ditions. The test is a simple, rapid, inexpensive, and a reliable bioassay
technique (D-88 - D-90).
Although the test also can be used in a laboratory to detect mutagens in
liquid discharges or ambient water, it is described here within the context of
its use in the field to monitor airborne pollutants. Cuttings of the plant can
be maintained in tapwater or nutrient solution for year-round growth and repro-
duction by giving supplemental light during the short-day season of the year.
Inflorescences of the plant cuttings can be carried to monitoring sites on and
off the synthetic fuel plant site for exposure to the atmosphere for a standard
period of time (e.g., 6 hours) prior to fixation in acetoalcohol and storage
in ethanol for future preparation of microslides for observation of micronuclei
(MCN) development during the early tetrad stage of meiotic development. Field
D-25
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and laboratory controls can be established. Repeated monitoring under dif-
ferent weather and wind conditions can give reference data for a particular
site. The appropriateness and effectiveness of this technique for ambient air
monitoring has been demonstrated in its use at industrial complexes, public
parking garages, truck stops, a bus stop, and an office where smoking occurs
(D-88, D-90).
D.6 RADIOACTIVE SUBSTANCES
Because of their sedimentary origin, shales and coals contain trace
amounts of radioactivity, notably radionuclides of the Uranium-238, Uranium-
235, and Thorium-232 decay chains. Important decay products are Radium-226
found in solid and gaseous samples. Liquid samples should be analyzed for
Radium-226 and Radium-228. It is known that some of the radio-nuclides be-
come enriched in coal and shale plant production streams and wastes relative
to raw resources. Considerable concern has been expressed that when these
wastes are released into the ambient environment (in the atmosphere—mostly
associated with airborne particles) there is a potential for radiological
impact on humans (D-91 - D-94).
Concentrations of Radium-226 on particulate filters can be determined
by Ge(Li) spectroscopy. Along with Radium-226, the important radionuclides
of Lead-212, Lead-214, Bismuth-214, Potassium-40 and other elements can be
quantitatively measured by this method (D-92, D-95, D-96).
Proportional counters have been used widely for counting filter papers
for alpha and beta radiation. Counting of gamma activity usually is per-
formed with a crystal as a scintillation source. If a high reading is ob-
served, the material on the filter can be dissolved and chemically sepa-
rated to identify particular elements of concern. A good discussion of the
use of radiological surveillance as a tool in ambient air pollution moni-
toring is presented in reference D-95.
D-26
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D.7 REFERENCES FOR APPENDIX D
D-l. Code of Federal Regulations, Title 40, Part 50, Appendix D. Measurement
Principle and Calibration Procedure for the Measurement of Ozone in the
Atmosphere. General Services Administration, Washington, DC, 1981.
D-2. Sexton, F. W., R. M. Michie, Jr., F. F. McElroy, V. L. Thompson and J. A.
Bowen. Performance Test Results and Comparative Data for Designated
Reference and Equivalent Methods for Ozone. Contract Nos. 68-02-2714,
68-02-3222, QAD/EMSL/USEPA, Research Triangle Park, NC, 1981.
D-3. Code of Federal Regulations, Title 40, Part 53. Ambient Air Monitoring
Reference and Equivalent Methods. General Services Administration,
Washington, DC, 1980.
D-4. Code of Federal Regulations, Title 40, Part 50, Appendix C. Measurement
Principle and Calibration Procedure for the Continuous Measurement of
Carbon Monoxide in the Atmosphere (Non-Dispersive Infrared
Spectrometry). General Services Administration, Washington, DC, 1981.
D-5. Ellis, E. C. Technical Assistance Document for the Chemiluminescence
Measurement of Nitrogen Dioxide. EPA-600/4-75-003, EMSL/USEPA, Research
Triangle Park, NC, 1975.
D-6. Code of Federal Regulations, Title 40, Part 50, Appendix F. Measurement
Principle for the Measurement of Nitrogen Dioxide in the Atmosphere (Gas
Phase Luminescence). General Services Administration, Washington, DC,
1981.
D-7. APHA Intersociety Committee. Methods of Air Sampling and Analysis,
Second Edition. American Public Health Association, Washington, DC
1977.
D-8.
Stern, A. C. Air Pollution, Third Edition, Vol. Ill, Measuring
Monitoring and Surveillance of Air Pollution. Academic Press, NY, 1976.
D-9. Code of Federal Regulations, Title 40, Part 50, Appendix A. Reference
Method for the Determination of Sulfur Dioxide in the Atmosphere
(Pararosanaline Method). General Services Administration, Washington,
DC, 1981.
D-10. Eaton, W. Cary. Use of a Flame Photometric Detector Method for
Measurement of Sulfur Dioxide in Ambient Air. EPA-600/4-78-024,
EMSL/USEPA, Research Triangle Park, NC, 1978.
D-ll. U. S. Environmental Protection Agency. Summary of Performance Test
Results and Comparative Data for Designated Equivalent Methods for 503.
Document No. QAD/M-79.12, QAD/EMSL/USEPA, Research Triangle Park, NC,
1979.
D-12. Code of Federal Regulations, Title 40, Part 50, Appendix B. Reference
Method for Determination of Suspended Particulates in the Atmosphere
(High Volume Method). General Services Administration, Washington, DC,
1981.
D-27
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D-13. National Institute for Occupational Safety and Health. Criteria for a
Recommended Standard Occupational Exposure to Ammonia. Pub. 74-136,
U.S. Department of Health Education and Welfare, Washington, DC, 1974.
D-14. National Institute for Occupational Safety and Health. Ammonia in Air,
NIOSH Manual of Analytical Methods, Pub. 77-157-A, U. S. Department of
Health, Education, and Welfare, 1977. p. 205-1.
D-15. U.S. Environmental Protection Agecny, Methods for Chemical Analysis of
Water and Wastes, EPA-600/4-79-20, 1979, Method 350.3.
D-16. National Institute for Occupational Safety and Health. Criteria for a
Recommended Standard Occupational Exposure to Hydrogen Cyanide and
Cyanide Salts. Pub. 77-108, U. S. Department of Health, Education, and
Welfare, Washington, DC, 1976.
D-17. National Institute for Occupational Safety and Health. Cyanide in Air,
NIOSH Manual of Analytical Methods. Pub. 75-121, U.S. Department of
Health, Education, and Welfare, Washington, DC, 1974, p. 116-1.
D-18. U. S. Environmental Protection Agency. Methods for Chemical Analysis of
Water and Wastes. Method 335.1-.3, EPA-600/4-79-020, EMSL/USEPA,
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D-34
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APPENDIX E
AMBIENT WATER MONITORING TECHNIQUES
E.I SAMPLE COLLECTION AND PREPRATION FOR ORGANIC ANALYSIS
The importance of procedures for collection and preservation of aqueous
samples for organic analysis cannot be overemphasized. The sample must be
collected so that it is representative of the process or body of water being
sampled, and the sample must be presented to preparation and analysis proce-
dures without loss of any of the compounds of interest and without contamina-
tion. The choice of methodologies to be employed in collection and preserva-
tion of samples must take into consideration the system that is being sampled,
the compounds of interest in the sample, and the analytical techniques which
will be used to determine these compounds.
E. 1.1 Sampling
There are two basic procedures used for aqueous sampling: discontinuous
or batch sampling and continuous sampling.
E.I. 1.1 Batch sampling--
Batch sampling is probably the most commonly used procedure because it
is simple, fast, and requires no specialized apparatus. Usually, the sample
container, a glass bottle or jar, preferably amber, is filled with the aqueous
sample and capped. If a sample collected by the batch method is to be
analyzed for very volatile organic compounds, the bottle must be filled and
capped so that there are no air pockets into which the compounds of interest
can vaporize (E-l). If headspace analysis is to be used in determining
highly volatile compounds, a fixed volume of headspace should remain in the
bottles after the samples have been collected. A combined sample collection/
storage/purge vessel has been designed for the analysis of volatile organics
in sediments (E-2, E-3). Using this approach, losses of volatile components
due to sample transfer are eliminated.
E-l
-------
Storage conditions can significantly affect analyte recovery during
®
volatile analysis. For samples sealed using Teflon septa, losses of compo-
nents were lowest for samples stored without headspace. If headspace is
present, losses are minimized by storing the sample inverted. Apparently
volatile organics partition into the headspace and then can permeate through
®
the Teflon septum over time.
Batch sampling for the analysis of moderately volatile compounds is
generally carried out by simply filling the sample bottles and sealing with
®
Teflon lined screw caps. Volatility losses have been reported for C-^ to
C,g alkanes during storage using this technique (E-4). A hexane keeper
solvent has been used to minimize these losses (E-4, E-5).
There are significant problems associated with the use of batch extrac-
tion techniques. Batch sampling increases the probability of obtaining
nonrepresentative samples. Analysis of a sample obtained by batch methods
provides information about the system only at the point and time at which
the sample is taken. Statements made about the system as a whole based on
this information may be inaccurate. Pooling, blending, and dividing a
number of grab samples or using depth-integrated batch samplers to obtain a
sample which is truly representative requires a detailed knowledge of the
flow and transport characteristics of the system. For volatile compounds,
pooling or blending are unacceptable since significant losses of volatile
components may occur during transfer.
E.I.1.2 Continuous sampling—
An alternative to batch sampling is continuous sampling. With this
method, a large volume of water is pumped into a sample reservoir or through
a column packed with a sorbent material. The sorbent material is commonly
activated carbon, resin, or polyurethane foam. Continuous methods allow
sampling of larger volumes of water over extended periods of time. Thus,
samples collected by this technique are more representative of the system
under investigation, and results of the analyses of these samples are not
affected by spurious changes in the character of the system under investiga-
tion. Additionally, a single time-integrated sample can often be collected
and analyzed in lieu of several batch samples to significantly reduce
analysis costs (E-6 - E-9). Commercial units, e.g., ISCO, are available for
time-integrated, grab sampling.
E-2
-------
Disadvantages associated with continuous sampling techniques are that
it is time-consuming; it requires specialized (and somewhat costly) equipment,
and it is difficult to use if there are space limitations at the sampling
site. There is also a greater chance of contamination during a continuous
sampling procedure since the sample is exposed for longer periods of time
and since there are more equipment surfaces which the sample must contact.
Samples collected by continuous methods are subject to losses, degradation,
and contamination just as those collected batchwise. Losses are particularly
significant for more volatile compounds, and it is difficult to add any type
of preservative to a sample which has been collected on a sorbent column.
E.I.1.3 Sample Contamination—
A problem which affects both batch and continuous sampled waters is
contamination. Cleanliness of the sample containers and cap is very important
if contamination of the sample is to be avoided (E-l, E-10). To check contamina-
tion levels, field blanks and laboratory blanks should be run with each set
of samples (E-5, E-ll). A lab blank is water of known purity which is collected
under controlled laboratory conditions and stored in the laboratory. Field
blanks are prepared in a similar manner and then subjected to the environment
of exposure, handling, shipping, and storing along with the samples. In
this way, it is possible to identify and quantify compounds in the sample
which are due to contamination.
E.I.2 Sample Preparation
E.I.2.1 Phase Separations-
Environmental waters are not a one-phase system, and, in most cases,
aqueous organic contaminants do not exhibit true solution behavior. Rather,
the behavior is governed by competitive interactions between phases. In
order to adequately sample and analyze water matrices, it is necessary to
know the identity of competing phases, their nature, their effect on organics
in aquatic ecosystems, and their experimental behavior during analysis.
Where possible, all phases of the sample should be extracted. This is
possible for solvent extraction techniques. Unfortunately, sorbent columns
accumulate only dissolved organics which may introduce an experimental bias.
E.I. 2.2 Internal Standard—
In order to assess the degradation of a sample or the loss of compounds
E-3
-------
of interest, an internal standard or group of standards should be
added (E-5, E-ll). These are best added to the sample in the field at the
time of collection (E-5), but are usually added in the laboratory. The
marker compounds should be different from any compounds expected to be in
the sample but should be chemically similar to the species of interest so
that the fate of the standards mimics the fate of the sample analytes during
handling, preservation, transportation, and storage procedures.
E.I.2.3 Preservation—
The immediate analysis of an aqueous sample at the collection site
would preclude the need for sample preservation; however, this is impractical
for most situations. Preservation of organic samples is a very difficult
problem with a limited number of techniques available. Additionally, the
requirements of many analytical methodologies impose severe restrictions on
the preservation techniques which can be used.
Ideally, preservative would be present in the sample container prior to
collection and would disperse immediately, stabilizing all parameters (ana-
lytes) for an indefinite period of time. Samples are protected from photode-
composition by using amber glass bottles as sample containers.
Chlorination has been one of the most extensively used techniques for
the inhibition of biochemical degradation. Unfortunately, free chlorine is
also an active oxidizing agent and readily reacts with substituted aromatics.
Thus, the use of chlorine as a preservative is not appropriate when trace
levels of aromatic species are to be analyzed (E-12, E-13).
Alternate sterilization techniques and biocides reported for environ-
mental matrices include: (1) mercuric chloride (E-14); (2) formalin or hexa-
chlorophene (E-15); and (3) sodium hydroxide, sulfuric acid or copper sulfate-
phosphoric acid (E-16). An alternative to chemical preservation is to seal
the sample container and store the sample at as low a temperature as possible.
Another process which can compromise the integrity of an aqueous sample
is adsorption of the organic components onto the glass walls of the sample
container. This problem is minimized by the addition of a nonpolar solvent
such as isooctane, methylcyclohexane, or methylene chloride to the sample
container before it is sealed in the field (E-17).
E-4
-------
E.2 DETERMINATION OF VOLATILE ORGANIC COMPOUNDS
E.2.1 Static Headspace Analysis
Static headspace analysis is a method for determining volatile compounds
in liquids by measuring vapor phase components which are in thermodynamic
equilibrium with the sample of interest in a closed system. For aqueous
systems, the distribution of sample components between water and gaseous
phases depends upon their water solubility and vapor pressure at the equili-
bration temperature. For example, compounds with a high vapor pressure and
low solubility will preferentially partition into the vapor phase.
In static headspace analysis, equilibration is performed in a sealed
glass container at a constant temperature. Equilibration time depends upon
the sample volume and equilibration temperature and, in most cases, even
with large samples does not exceed 60 minutes.
After equilibration, a volume of headspace is injected onto the chro-
matographic column using a gas tight syringe or a gas sampling loop (E-18,
E-19). Since the sample is a gas, a heated injection port is unnecessary
making this technique well suited for heat labile compounds. Usually packed
column gas chromatography has been used for analysis; however, adaptation to
high resolution capillary columns with no loss in quantitative precision and
a significant improvement in retention time accuracy and chromatographic
separation has been reported (E-20).
Accurate quantitative analysis for the static headspace technique depends
upon the calibration procedure. Since the partition coefficient of the solute
in the equilibrated gas-liquid system is a function of its activity coefficient,
calibration solutions should closely approximate the sample matrix. A standard
addition method was developed to calibrate unknown samples (E-20, E-21). As
an alternative, hydrocarbons in water were quantitated using multiple equili-
brations of the sample with equal volumes of gas (E-22, E-23). Each gaseous
extract was analyzed by GC and analyte concentrations calculated by
extrapolating the relationship between the peak areas and the number of
equilibrations.
E-5
-------
Quantitative headspace analysis can be a very accurate procedure.
However, good reproducibility depends upon two factors; namely, exact temper-
ature control during equilibration, and a reproducible method for transport-
ing and injecting the headspace sample into the gas chromatograph. Results
with a commercial headspace sample accessory have given precisions of 0.8%
as a coefficient of variation (E-24). A precision of ±5% was reported for the
analysis of halocarbons in drinking, surface, and wastewater samples (E-18).
Detection limits for static headspace analysis depend upon: compound
type, GC detector, and conditions for equilibration. The following table
summarizes reported detection limits under a variety of test conditions.
Any compound which will give a vapor pressure over its aqueous matrix
can be analyzed via static headspace analysis. Obviously, the higher the
vapor pressure, the more suitable the technique. Low molecular weight, low
boiling point, hydrophobic compounds are best suited. Vapor phase partition-
ing for the following chemical classes followed the order: alkanes >
olefins > cycloalkanes > aromatics. Within each chemical class, an
increased vapor partition was observed as the molecular weight decreased.
With salting-out and sufficiently high equilibration temperatures, water
soluble compounds including methanol, ethanol, acetone, and methyl ethyl
ketone are also amenable to analysis (E-25). However, use of elevated tempera-
tures during equilibration may prevent the analyses of heat-sensitive com-
pounds.
1.2.2 Purge and Trap
The most widely used method for isolating volatile organic materials
(boiling point <200°C) from water is to purge the sample with prepurified
gas, collect the stripped materials on a sorbent trap, and analyze the
trapped compounds by thermal desorption followed by gas chromatography or
gas chromatography/mass spectrometry. Alternatively, for samples which tend
to foam, the sample headspace may be purged instead of the sample itself.
Removal of organic compounds from water by sparging with an inert gas
is frequently referred to as volatile organic analysis (VOA) or purge and
trap. The technique depends upon partitioning of the compounds between the
aqueous and gaseous phases. This partitioning is a function of water
E-6
-------
Table 1. DETECTION LIMITS FOR STATIC HEADSPACE ANALYSIS
Compound or
Compound Class
Chloroform
Sulfides, carbonyls,
esters
Halogenated
aliphatics
Methanol
Methanol, ethanol,
acetone
Methyl ethyl ketone
Halogenated
aliphatics
Hydrocarbons
Hydrocarbons
Benzene
Chloroform
Vinyl chloride
Hexachloroacetone ,
hexafluoroacetone
Equilibration Pre-
condition Concentration
90°C, 45 min no salt None
Na0SO. None
3.35M Na2S04, 50°C None
Na SO. None
70°C, Na S04 Distillation
70°C, Na S04 Distillation
80°C, no salt None
None
40°C, no salt None
40°C, no salt None
0.1N Na2S203, 50°C None
None
KOH hydrolysis
Detector
BCD
FID
ECD
FID
FID
FID
FID
FID
FID
FID
FID
FID
FID
Detection
Limit
1 ppb
10 ppb
1 ppb
1 ppm
4 ppb
8 ppb
1-5 ppb
100 ppm
2 ppb
100 ppb
1.5 ppb
5 ppb
10 ppb
Reference
E-26
E-25
E-27
E-25
E-26
E-26
E-28
E-22
E-21
E-20
E-29
E-30
E-31
Exact conditions unknown.
-------
temperature, gas-water interfacial area, and the water solubilities (<2%),
volatilities (<200°C), and aqueous activity coefficients of the test com-
pounds. In addition, the partition rate depends on the flow rate and total
volume of the purge gas.
The assembled purge apparatus consists of a container with a purge gas
inlet, a device for regulating sample temperature, and a purge gas outlet
through a sorbent cartridge (E-32 - E-34).
The cartridge is composed of material with a high affinity for organic
®
compounds, and preferably, a low affinity for water. Tenax GC is the most
commonly used trapping material. It is thermally stable, contains few
background contaminants, provides few sites for irreversible adsorption, is
chemically inert, and has a low affinity for water. Its major drawback is
its low affinity for a number of very volatile organic compounds including
the lower alkanes and methanol (E-35). Alternate sorbents have also been
employed. EPA Method 624 for the analysis of volatile organics currently
uses a silica gel/Tenax trap (E-36).
Sample volumes vary from 0.5-1000 ml depending upon the type of sample
and concentration of the substances to be determined. Gas flow rates range
from 20-200 mL/min and purge times from a few minutes to several hours
depending, again, upon the sample concentration and the appropriate break-
through volume for the target analyte on the sorbent cartridge.
There are a number of considerations involved in determining purge
temperature. Even though maximum stripping occurs at 90-98°C, these elevated
temperatures may cause problems with condensation on the trap material,
artifact formation, and thermal decomposition. Furthermore, samples which
tend to foam do so to a greater degree at higher temperatures. For these
reasons, analysis of low molecular weight, hydrophobic compounds is performed
at ambient temperatures. Compounds with boiling point less than 200°C and
aqueous solubilities less than 2% are amenable to this type of analysis.
Elevated temperature purge and trap techniques have been reported for a
number of volatile polar organic compounds (E-5, E-37 - E-39). Recoveries
of many of these compounds improved significantly with the addition of salt
to the aqueous solution prior to analysis (E-37).
E-8
-------
Analytes trapped on the sorbent cartridge are introduced into the
chromatographic system using thermal desorption. At this point test compo-
nents may be either focused in a cryogenic trap (E~39) or transferred directly
to the GC column (E-36). For packed column analysis the latter approach is
generally used. The purge and trap technique can be performed with the
cartridge directly on-line to the gas chromatograph and detector system.
For the separation of volatile organics, both capillary (E-39) and
packed (E-36) columns have been used. Chromosorb 101, Carbowax 1500 and 20M,
SE-30 and OV-101 are the most frequently used liquid phases for GC analysis.
Fused silica capillary columns with bonded phases have become popular for
all GC analysis including the analysis of volatile compounds. However, the
use of an on-line purge and trap system interfaced to a capillary column
causes several difficult problems. During capillary column chromatography
the sample components must be introduced onto the column as a sharp band to
avoid deteriorating chromatographic resolution. This may be achieved by
cryotrapping using either a cryofocusing unit (E-39) or by cooling a small
portion of the capillary column to liquid nitrogen temperatures (E-40).
Unfortunately, the volume of water collected on the trapping material is
often large enough to cause freezing during the focusing procedure. The use
of a water cooled condenser or a condenser tube to remove water from the gas
stream prior to the sorbent cartridge has been reported (E-41). A dry purge
of the sample cartridge to remove water after the load operation has also
been reported (E-39, E-42). Other researchers have split the gas stream after
desorption to minimize the amount of water entering the chromatographic
system (E-43). However, this significantly decreases method sensitivity.
E.2.3 Closed-Loop Gas Stripping
The closed-loop gas stripping technique involves continuous gas stripping
of water samples followed by trapping on a small activated carbon filter.
This can be done by either stripping at 30°C using the headspace gas to
purge the sample, or stripping with water vapor by boiling the sample in a
closed-loop system (E-44, E-45). A modified version purges the aqueous sample
rather than the sample headspace (E-46, E-47). The continuous purge and trap
apparatus is constructed entirely of glass or glass and stainless steel to
minimize surface contamination.
E-9
-------
For ambient stripping, a water sample of 0.5-2.0 L is carefully intro-
duced into a 1 or 5 L glass bottle equilibrated at 30°C, and connected to
the closed-loop system. An adsorbent filter constructed of 1.5-5.0 mg heat-
activated wood charcoal collects organics in the stripping loop. Stripping
is initiated at 1.0-2.5 L/min for 1-3 hours by activation of a stainless
steel bellows pump. During the process, stripping gas is warmed to approxi-
mately 40°C just prior to the carbon filter to minimize adsorption of water
vapor and hence restriction of flow through the filter.
Extraction of the exposed carbon filter can be effected in two ways:
If only volatiles are desired, the filter can be analyzed by thermal desorp-
tion directly onto the gas chromatographic column (E-48). Extraction of less
volatile compounds from the filter involves careful elution with 5-15 uL of
purified and redistilled carbon disulfide (E-49, E-45). In cases where heavily
contaminated water has been purged, 10-100 uL methylene chloride has been
used (E-50). Component identification as well as quantitative analysis are
performed by gas chromatography/mass spectrometry (GC/MS) without further
concentration.
Due to the number and diversity of compounds which may be collected on
the charcoal filter, glass or fused silica capillary GC columns are recommended,
although packed columns should provide sufficient resolution for clean water
samples.
No inherent difficulties are associated with mass spectrometric detection
in conjunction with closed-loop gas stripping analysis. In every reported
instance a mass spectrometer was employed as a detector, presumably because
of its utility in identifying components of complex mixtures.
E.3 DETERMINATION OF EXTRACTABLE ORGANIC COMPOUNDS
E.3.1 Li quid-Li quid Extraction
Liquid-liquid extraction (LLE) is a widely employed method for concen-
trating semi volatile nonpolar organic compounds from water samples. If the
analyte of interest has a higher affinity for the extracting solvent than
the sample matrix, then it will partition into the solvent. The affinity of
an analyte for the solvent is defined by the distribution coefficient (KQ)
using this parameter, the percent of analyte extracted into the solvent
phase (%E) can be calculated by (E-5]):
E-10
-------
100 Kn
%E = *Hk
U Vo
where Vw and Vo are the volume of water and organic solvent used during
extraction. From this equation it is obvious that high analyte recoveries
during LLE depend upon either a large distribution coefficient or a small
water:solvent ratio.
The choice of solvent is critical to LLE procedures. As discussed
above, the solvent must have a large distribution coefficient for the com-
pounds of interest. Extensive listings of partition coefficients are avail-
able for various solvent systems (E-51). Partition coefficients for all
organic compounds are higher for neutral species than for compounds with an
electrostatic charge. To achieve electrostatic neutrality, acids are ex-
tracted at a low pH. Conversely, bases are extracted at an alkaline pH.
Along with having a high extraction efficiency for the analytes of
interest, the extracting solvent should be immiscible with the sample, not
contain contaminants which might compromise subsequent analysis, be chem-
ically inert, be specific for the compounds of interest, and be amenable to
the analytical method of choice. Since solvent evaporation is usually
employed to further concentrate sample extracts, solvents with low boiling
points are preferred. Benzene (E-52, E-53), toluene (E-54), pentane (E-55),
hexane (E-56, E-57), and methylene chloride (E-54) are routinely used to
extract hydrophobic compounds from water. Chloroform (E-58, E-59), ethyl
acetate (E-60, E-54), diethyl ether (E-61), methyl t-butyl ether (E-62, E-63),
and isopropyl ether (E-64) have been used to extract more polar analytes.
The addition of salt to the aqueous matrix will increase the activity
coefficients of organic analytes to effectively increase the partition
coefficient into the organic solvent. Sodium sulfate (E-65, E-66) and sodium
chloride (E-62, E-63, E-65) are most commonly used to achieve salting-out.
Unfortunately, the addition of salt increases the density of aqueous solutions
which may promote emulsion formation when heavier-than-water solvents are
used for extraction. This is significant since methylene chloride is com-
monly used as an extracting solvent.
E-ll
-------
In practice, LLE procedures are of two types, batch and continuous.
Batch extractions are generally carried out by thoroughly mixing the sample
and extracting solvent in a separatory funnel. The two phases are allowed
to separate and the organic layer is removed. For separatory funnel tech-
niques two minutes of vigorous shaking is usually sufficient to obtain
equilibrium partition between the phases. Samples which tend to emulsify
are often extracted using gentle mixing over a longer time period. For
separatory funnel techniques, heavier-than-water solvents are preferred for
easy handling. Exhaustive extraction procedures can involve extracting 1 L
aqueous sample as many as three times with 200 to 250 ml of organic solvent
each time (E-63). The use of large solvent volumes is essential for polar
compounds with low affinity for organic solvents; i.e., amines, alcohols,
hydroquinone, phenols, and nitro compounds. But the use of large solvent
volumes has several disadvantages (E-66): a concentration step is required to
remove most of the solvent to improve sensitivity; impurities in the solvent
are also concentrated during the concentration step; the more volatile
compounds may be lost during evaporation; contamination and sample losses
are more probable because of handling and transfers; and the cost of analysis
increases because more solvent is used and the concentration step adds to
the time per analysis. For compounds which partition readily into organic
solvents these problems can be circumvented using microextraction techniques.
Typically, sample to solvent ratios of 100 to 500 with total organic solvent
volumes of 100 to 1000 uL have been used. This technique should be applicable
to analyzing hydrophobic compounds in water samples. However, special
vessels are required, more aggressive shaking is necessary to establish
equilibrium, only lighter than water solvents can be used and problems with
phase separations may be more severe for small solvent volumes (E-66).
The Environmental Protection Agency has developed a series of extrac-
tion procedures which use gas chromatography with specific detectors or HPLC
for the measurement of specific organic materials. Test organics were
divided into several classes based on chemical structure and specific methods
were then developed for extraction, cleanup, and detection of these analytes.
Of these methods, only Method 610 for polynuclear aromatic hydrocarbons is
applicable for the range of compounds expected to be found in synfuel
wastes (E-67).
E-12
-------
EPA Method 625 (E-68) uses extraction with methylene chloride and analysis
by GC/MS to quantitate priority pollutants in wastewater samples. Recoveries
for these compounds are generally greater than 70% with a limit of detection
of 10 ppb. Although the method has not been tested for many of the compounds
expected in synfuel waste (j_.e. , aldehydes, thiophene, basic nitrogen con-
taining compounds, nitrogen heterocycles, and weakly acidic phenols), preci-
sion and accuracy of the method should be acceptable. Poor recoveries can
be expected for the carboxylic acids, alcohols, and the dihydrophenols due
to poor partitioning into the extracting solvent. Poor recoveries for the
alkanes and alkenes will probably result from volatility losses during
storage and transfer. In addition, weak acids such as phenol and cresol
tend to partition into both fractions, to give low recoveries in any single
fraction. The use of mass spectrometry verifies compound identification and
may reduce interferences during quantisation. However, for complex water
sample, packed column chromatography may not provide sufficient resolution
for either quantitative or qualitative analysis. No cleanup procedures have
been given for use with very complex samples.
Using the Master Analytical Scheme for the analysis of organics in
water, two separate water samples are extracted and analyzed. One sample
which is extracted at pH 8 with methylene chloride will contain basic,
neutral, and weakly acidic compounds (E-5). The second sample which is
extracted at low pH with methyl-t-butyl ether will contain strong acids.
This method has been tested and used for the analysis of a range of ex-
tractable organic compounds, including alkanes, PNAs, alcohols (>C,Q),
ketones, phenols, thiophenes, basic N-containing compounds, nitrogen
heterocycles, and carboxylic acids. Recoveries for most compounds are
greater than 60% with a limit of detection of approximately 10 ppm. The use
of a keeper solvent prevents volatility losses for the alkanes and alkenes.
Use of methyl-t-butyl ether as the extracting solvent improves extraction
efficiency for the carboxylic acids. The use of capillary column chromatog-
raphy, and sample cleanup procedures help to minimize interference during
analysis.
E.3.2 Sorbent Columns
The use of sorbent columns in determining organic compounds in water is
an application of liquid-solid chromatographic techniques (LSC). Compounds
E-13
-------
are isolated from the aqueous matrix cv adsorption onto a solid phase which
is composed of small particles of co^c,re:al"!y available materials, including
carbons, resins, and foams.
Sorbed analytes are eluted from the solid phase with a solvent or
solvent mixture for which they have a hlgn affinity. Solvents such as
methanol (E-62, E-69) ethanol (E-70): acetone (E-71, E-72), diethyl
ether (E-71, E-73), acetonitrile (E-74), chloroform (E-72, E-75), and
methylene chloride (E-62) have been used either alone or as solvent mixtures.
Water at an alkaline pH (E-76) or weak organic bases (E-77) have been used
to recover organic acids from resin coiumns. Alternately, thermal desorption
has been used to recovery analytes from a number of sorbent materials. This
(R)
technique is most commonly applied tc Tenax GC , but has also been reported
for XAD resins (E-78, E-79).
A method using 12 L water sample concentrated on XAD-4 resin has been
tested and used for the analyses of phenols, PNAs, alcohols (>C,Q), ketones,
thiophenes, basic N-containing compounds and nitrogen heterocycles (E-5).
Recoveries for most compounds are greater than 60% with a limit of detection
of approximately 0.5 ppm. Recoveries of alkanes and some PNAs is low due to
volatility losses during storage and column accumulation procedures. This
method should only be used for sample waters containing low levels of parti -
culates to prevent clogging the resin crs".u!r,r< during sample processing.
E.4 DETERMINATION OF INTRACTABLE ORGANIC COMPOUNDS
Intractable organics are defined as those compounds which are polar and
water soluble and, therefore, are not easily concentrated from water using
either purging or extraction techniques.
E.4.1 Direct Aqueous Injection
The easiest approach for measuring intractable organics is simply to
analyze them in the water sample without preconcentration. Analysis of
organic compounds in water by direct aqueous injection (DAI) involves analysis
in an aqueous medium, by gas-liquid or gas-solid chromatography. Injection
volumes, which are typically 1-50 uL, have been used for the determination
of volatile organics in various waters.
E-14
-------
Chromatographic separation is achieved using a variety of solid sup-
ports such as Tenax GC®, Chromosorb 101 (E-80, E-81) or Porapak Q (E-81 - E-84).
Separations involving compounds with ami no functional groups have been done
on columns containing Carbowax 1500 (E-85) or Pennwalt 223 plus 4-7% KOH (E-86)
to minimize peak tailing. Similarly, Apiezon L has been used to determine
N-nitrosamines (E-87). Manufacturers' literature for some fused silica capil-
lary columns indicate good performance using the DAI technique. However,
some initial work has reported problems with poor peak shape and poor repro-
ducibility for both peak area and retention time for a number of low molecular
weight polar compounds (E-88).
The lack of sample preconcentration in DAI necessitates that optimal
sensitivity be achieved during detection. Flame ionization detectors are
useful only when the component concentrations are quite high (~0.1 ppm), as
is the case with most energy effluents and wastewaters. Electron capture or
Hall electrolytic conductivity detection does possess sufficient sensitivity
to detect halogenated hydrocarbons at levels found in drinking waters. Mass
spectrometry affords sensitive and selective detection for DAI only when
operated in the selected ion monitoring mode. Compatibility of DAI with MS
is facile, requiring only that the elution of water from the Chromatographic
column not coincide with the elution of other sample constituents.
For nonvolatile organics, detection limits may be decreased by concen-
trating the water sample (E-89). Recoveries of ~70% were achieved for
acrylamide spiked into water samples using this procedure. Limits of detec-
tion are approximately 50 ppb for GC/MS, and 10 ppb for GC/FID, and 1 ppb
for GC/NPD. Other amides likely to be found in synfuel waste could also be
analyzed by this procedure.
E.4.2 Ion Exchange
Ion exchange is an adsorption process involving the displacement of
resin ions by solute ions of similar charge. Functional groups on the
surface of a solid sorbent provide sites for electrostatic exchange (E-90).
Theoretically, ion exchange processes should remove any ionic species from
an aqueous solution making ion exchange a valuable technique for concentrat-
ing charged polar organics or removing inorganic ion interferences from
environmental water samples.
E-15
-------
Generally, an ion exchange resin consists of a hydrocarbon backbone
with soluble ionic functional groups attached. The concentration of ionic
groups within the resin determines exchange capacity, while the chemical
nature of the groups effects both ion exchange equilibrium and general ion
selectivity (E-91).
During concentration, an aqueous solution is passed through the resin
column, allowing exchange to take place. Adsorbed ions are then eluted
either by neutralizing the charge on the solute or by rinsing the column
with a highly concentrated solution of counterions (E-9Q). Eluting solutions
for organic acids have included HC1 in methanol (E-92, E-93) HC1 in diethyl
ether (E-94), and NaHSO. in a mixture of water/acetone or acetom'trile/ace-
tone (E-93, E-95, E-95). Organic bases have been eluted with KOH in acetonitrile.
In highly saline solutions, resin capacity may be quickly saturated
with inorganic ions to give low and variable recoveries for the organics of
interest (E-97).
An anion exchange procedure was developed for the analysis of low
molecular weight carboxylic acids (E-5). Recoveries greater than 60% have
been reported for the C- to Cg acids with a limit of detection of approxi-
mately 1 ppm using a 3 L sample. The use of capillary column chromatography
and ion exchange concentration helps to minimize interferences during analy-
sis.
E.5 DETERMINATION OF INORGANIC SPECIES
The metals and ions found in surface and ground waters can be determined
by those same methods used to analyze extracts of particulate material (E-98,
E-99 - E-102) . Spark source mass spectrometry is a suitable technique for ele-
mental screening (E-103 - E-105) while atomic absorption spectrometry (E-106 -
E-108) or inductively-coupled argon plasma emission spectrometry (E-109, E-110)
are best for accurate and precise monitoring of metals.
Ion chromatography (E-lll, E-112) and ion-specific electrodes (E-113) are
the best methods for measurement of ions in the water samples.
E-16
-------
E.6 REFERENCES FOR APPENDIX E
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28:739, 1974.
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E-18
-------
E-36. "Purgeables - Method 624," Federal Register, 44, No. 233, 69532, Monday,
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E-19
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E-52. Kulekova, G. S. , V. E. Kiricnenko, and K. I. Pashkevich. Zh. Anal.
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E-23
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APPENDIX F
AMBIENT SOIL MONITORING TECHNIQUES
F.I SAMPLE COLLECTION AND PREPARATION FOR ORGANIC ANALYSIS
The aim of any sampling procedure is to ensure that the sample is
entirely representative of the environment from which it was taken and that
the sample maintains its integrity until extraction and analysis. Procedures
for sampling should address sample collection, sample preservation, and
preparation of sampling devices and containers to avoid contamination.
F.I.I Sample Collection
Because soils, sediments and sludges are poorly mixed matrices and
because collection is restricted to discrete grab samples, special attention
must be given to obtaining a representative sample. The generally accepted
method for accomplishing this is the sample compositing method. The exact
design of such a method depends on many factors such as sample material,
source and rate of natural and anthropogenic inputs, and the information
desired. Guidance in the design of the sampling protocol can be obtained
from the Handbook for Sampling and Sample Preservation of Water Wastewater
(1976) and the NPDES Compliance Sampling Inspection Manual (1977). The aid
of statisticians may be required to effectively apply these principles to a
given sampling situation. In general, multiple grab samples are taken from
regular locations on a sampling grid, and composited. If information about
recent deposition in the soil is desired, then the sample is scraped from
the top few cm of the surface. On the other hand, if a history of the
substrate is desired, then core sampling is used. This can be accomplished
by a simple bulb-planter or by a more elaborate drilling device depending on
the depth of sample desired (F-l).
F.I.2 Sample Handling and Preservation
Losses of organic compounds during handling and storage of soil samples
may occur due to volatilization, adsorption, or chemical, bacterial or
photodecomposition.
F-l
-------
Samples can be protected from photodecomposition by using amber glass
bottles as sample containers or alternatively by wrapping the container
carefully with aluminum foil.
Musterman and Morand report the effective preservation of sludge from
bacterial decomposition with formaldehyde (F-2). Bacterial decomposition may
also be prevented by the addition of mercuric chloride (F-3), formalin (F-4),
or hexachlorophene (F-4). A more prevalent method for avoidance of bacterial
degradation is sample storage at 0° or 4°C until analysis (F-5). Maienthal
and Becker report the storage of samples at -70° to -80°C to prevent the
biological breakdown of certain pesticides (F-6). Adsorption of organic
components onto the glass walls of the sample container may be minimized by
the addition of a nonpolar solvent to the sample container before it is
sealed in the field (F-7). The addition of certain quenching agents to the
sample inhibit further formation or organochlorine compounds by reducing
free chlorine. Sodium thiosulfate (F-8), sodium sulfite (F-9), potassium
ferrocyanide (F-10), and ascorbic acid (F-ll) are commonly used in this applica-
tion. Drying of samples prior to analysis should be approached with caution
as losses of pesticides have been reported via this process (F-12).
In general, the use of preservation methods has been reported for
individual compounds or compound classes. Their applicability to compounds
of interest to the synfuel industry must be evaluated prior to use.
F.I.3 Materials, Purity and Cleanliness of Sampling Equipment
Careful selection and cleaning of sampling equipment and containers is
necessary to prevent contamination, degradation or adsorption of the sample
and its components. The choice of construction materials for equipment is
further dictated by the need for ruggedness and ease of cleaning in the
field.
Rubber, neoprene, vycor, polyvinyl chloride, polystyrene, glass, poly-
propylene, linear polyethylene, platinum, etc., have been found to cause
contamination of samples for organic analysis. Stainless steel, glass, FEP
Teflon and aluminum foil are recommended for sampling (F-6). Contamination
of all types of samples for trace organic analysis by plastics and plasticiz-
ers has been well documented (F-13). Persons involved in sampling, sample
F-2
-------
handling and analysis should be constantly alert for possible contamination
from this source.
Much diversity exists in methods used for cleaning glass containers and
equipment (F-14, F-15). Nonglass sampling equipment should be vigorously
scrubbed and thoroughly rinsed with water between uses. While a thorough
scrubbing with hot detergent solution followed by rinsing with deionized water
and solvent might seem a prudent choice, the probable need for repeated use of
samplers in the field may well make this impractical. Whatever the method
chosen, its effectiveness should be demonstrated by the regular analysis of
field blanks.
F.2 DETERMINATION OF EXTRACTABLE ORGANIC COMPOUNDS
Analytical methods for the determination of organics in soil are
basically three-step procedures: (1) extraction and isolation from the
sample matrix (both aqueous and solid); (2) fractionation or cleanup of the
sample extracts; and (3) analysis of sample fractions. Currently, there are
no standardized methods for analyzing organics in soils. Further, since
soils are complex matrices which can undergo multiple interactions with
organic compounds, the "best" method for analysis may vary from sample to
sample. Comparisons of methods has been made by assessing recoveries for
organic analytes spiked into solid matrices. Unfortunately, this approach
does not always provide meaningful information, since samples spiked with
test compounds will not necessarily reflect extraction behavior of soils.
Alternately, recoveries of standards from spiked sample extracts, and inter-
and intralaboratory comparisons of test methods applied to reference samples
have also been used. The majority of this research has been applied to the
analysis of hydrocarbons and polynuclear aromatics (PNAs) in sediments.
With only a few exceptions, soils should behave in a manner similar to
sediments, and although the nitrogen- and oxygen-substituted aromatic hydro-
carbons of interest to the synfuels industry are more polar compounds, many
of the procedures should also be applicable directly or with slight modifica-
tions to their analysis. A brief description of the analytical procedures
follows.
F-3
-------
F.2.1 Extraction/Isolation Procedures
For the analyses of soils or sediments, it is necessary to isolate the
organic compounds from both the solid matrix and the water associated with
that matrix.
Water removal procedures are extremely important for sediment samples
which always have a high water content, and are also important for soils
which may contain significant amounts of water when fully saturated. Using
the most common procedures, water is removed either before extraction, i.e. ,
air drying (F-16), freeze drying (F-16, F-17), or rinsing with a water miscible
solvent (F-18, F-19), during extraction, i.e., adding a desiccant to the sample
matrix (F-20), or after extraction, i.e., partitioning the extracts with a
water immiscible solvent (F-21, F-22). Air drying or 1iophilization may cause
losses of volatile organics (F-16). However, with the exception of the pyri-
dines, most of the target compounds should be sufficiently nonvolatile for
adequate recoveries. Dewatering with a water miscible solvent may extract
the more polar organics. For example, significant losses (>30%) were
reported for nitrobenzene, phenol, and decanol during rinses with methanol
and acetonitrile (F-23). Many of the target compounds should be sufficiently
hydrophobic to minimize this type of loss. Solvent partitioning of the
sample extract with a nonpolar solvent also may result in losses for polar
organics.
Extraction of organics from the solid matrix occurs when the solvent is
brought in contact with the soil sample. If the analyte of interest has a
higher affinity for the extracting solvent than the sample matrix, then it
will partition into the solvent. The percent of analyte extracted into the
solvent phase (%E) can be calculated by:
100 KQ
/wC ™" \t . i i
W0
where 1C. is the distribution coefficient of an analyte between the solvent
or solvent mixture and the solid matrix and W<. and Wn are weights of the
matrix and solvent, respectively. Operationally, there are a number of ways
F-4
-------
in which solvents may be physically brought into contact with the solid
matrix including mechanical shaking or stirring, Soxhlet extraction, reflux-
ing, and ultrasonication. If equilibrium is achieved during extraction,
then KD should be the same for all method and differences in extraction
efficiency would then be a function of the volume of solvent used during
extraction. However, for complex soil samples, it may be difficult to reach
an equilibrium state and difference between methods, for the same solvent
systems is then a function of how rapidly the partitioning may proceed.
F.2.2 Soxhlet Extraction
The most common method for extraction soils and sediments is Soxhlet
extraction. During extraction the sample is placed in a thimble in the
Soxhlet tube, solvent evaporates from a boiling flask, condenses, and
passes through the sample. This sample extract then returns to the solvent
pot. When operated over an extended time period (4-48 h), Soxhlet extraction
provides a large volume of solvent for extraction. Soxhlet extraction has
the dual advantage of leaving the sample cool and providing multiple extrac-
tions over an extended period of time. However, some sediments and clay
soils are difficult to extract especially when wet because they agglomerate
into a single mass and the solvent does not penetrate. This effect may be
reduced by adding inert amendments such as sand, sodium sulfate, or Celite
to the sample.
Soxhlet extraction with benzene and methanol has generally been consid-
ered the most efficient technique for extracting hydrocarbons (F-23 - F-26).
Recently, toluene has been substituted for benzene to avoid contact with a
carcinogenic solvent. Solvent systems using methylene chloride/benzene (F-18),
methylene chloride (F-17, F-27, F-14), hexane/acetone (F-28, F-29), and diethyl
ether/petroleum ether (F-28, F-30) have also been used to extract both soils and
sediments with good recoveries for a range of nonpolar and semipolar compounds.
Several different methods of extraction have been compared to Soxhlet extrac-
tion, including ultrasonic treatment with acetone as the solvent and extrac-
tive steam distillation (F-29). All of the methods were quantitative for the
spiked sediment. The recoveries were different when a weathered sediment
was used with Soxhlet extraction being superior to the other methods.
F-5
-------
Careful choice of solvents and extraction conditions are necessary to
prevent artifact formation. In situ methylation of acids occurred during '
Soxhlet extraction of sediment samples using methanol/toluene, whereas
Soxhlet extraction with diethyl ether caused formation of benzyl ethers (F-27).
F.2.3 Shaking or Tumbling
Methods which use shaking or tumbling as an extraction procedure are
performed by adding the solid matrix and the extracting solvent to a closed
vessel, mixing for a specified time period and decanting the solvent.
Sequential extractions are usually performed to increase both solvent recovery
and extraction efficiency.
Mechanical shaking or stirring at room temperature adds little energy
to the sample during extraction and, therefore, minimizes the potential for
artifact formation. However, shaking sediment samples with various solvents
can produce stable emulsions (F-18). As an alternative, tumbling procedures
have been employed which provide gentler mixing. Shaking or tumbling proce-
dures can reduce the time and space required for analyzing multiple samples
compared to solvent extraction techniques.
According to some reports tumblings provide extraction efficiencies as
high as Soxhlet techniques (F-24). Conversely, significantly reduced recoveries
(17-33%) have also been reported (F-21). In a comparison of extracting solvent,
hydrocarbon extraction efficiencies were 2-3 times better when methanol was
used as a cosolvent for wet sediment (F-18, F-19). Apparently, methanol helps
to remove water from the soil or sediment which then promotes better extract
efficiency for water immiscible solvent. A number of nonpolar neutral
compounds have extracted from soil with a variety of solvent systems:
ethanol/acetone (F-31), hexane/acetone (F-32), toluene/acetone (F-32), and
toluene/ethyl acetate (F-32).
F.2.4 U1trasoni c Extracti on/Homogeni zati on
These techniques rely upon ultrasonic energy to break the solvent-sample
interface into the smallest droplets/particles possible, such that contact
between the sample and solvent is maximized. During extraction the solid
matrix plus desiccant is added to an open extracting vessel with the solvent.
Sonication is then performed for a very short period of time (less than 1 h).
F-6
-------
Depending on the solvent system, separation of the sample and solvent
after treatment is accomplished by centrifugation or filtration. Some
solvents, such as dichloromethane do not mix well with the solid matrix and
will separate without aid. A variety of polar and nonpolar solvents have
been used with this technique with good extraction efficiency (F-26, F-33,
F-34).
F.2.5 Fractionation/Cleanup Procedures
Soil samples may contain complex mixtures of both naturally-occurring
and anthropogenic compounds which make it difficult to identify, and quan-
tify individual compounds. Even with the use of high resolution capillary
chromatography, interferences still occur which require some form of
prefractionation in order to reduce the number of compounds which must be
resolved during the final analytical step and to remove extraneous background
interferences.
Solvent partitioning and open column chromatography are the two most
common procedures used and will be discussed briefly.
F.2.6 Solvent Partitioning
Solvent partition depends upon the preferential distribution of solute
into one of two intermittently contacted but immiscible liquid phases with
compound polarity providing the basis for separation. For ionic species,
solute solubilities may be altered by controlling the pH of the aqueous
phase as in the familiar acid/base wash sequence. Although solvent partition
provides some sample fractionation, additional clean-up methods are usually
required prior to final analysis.
The simplest form of solvent extraction fractionation is used when a
sample has been extracted with a polar or semipolar solvent. Under these
conditions, the addition of water plus a nonpolar solvent to the sample
extract will separate nonpolar neutrals from polar neutrals and ionic
organics. A number of solvent fractionation schemes have been applied to
isolated polynuclear aromatics (PNAs) and aliphatic hydrocarbons from soil,
and sediments extracts (F-22, F-34, F-35). In most cases, the extract is first
cleaned up using open column chromatography, then the fraction is partitioned
between two immiscible solvents to separate the more polar PNAs from the
F-7
-------
hydrocarbons. The most commonly used solvent systems include: cyclohexane/
m'tromethane; pentane or hexane/dimethyl sulfoxide; and isooctane/dimethyl
sulfoxide.
F.2.7 Column Chromatography
Some form of open tubular column Chromatography has been incorporated
in most fractionation procedures for soils and sediments. Normal phase
Chromatography is currently the most common separation mode in general use
and is characterized by a polar stationary phase and a relatively nonpolar
mobile phase. Where the solid support functions as the stationary phase,
the technique is termed adsorption Chromatography. Retention and selectivity
result from the degree and types of interactions which occur between the
polar functional groups of eluting components and the active sites (hydroxy,
Lewis acid, ether) on the surface of the support. These factors are easily
controlled by proper adjustment of such mobile phase characteristics as
dielectic constant, polarizability, hydrogen bonding and fl-bond interactions.
Only a few supports have shown much utility for fractionation of the broad
range of organic compounds found in environmental matrices: (1) silica;
(2) alumina (acidic, neutral, basic); and (3) Florisil (magnesium silicate).
Table 1 compiles a representative listing of applications reported in
the literature. Information on sample matrices, compounds, chromatographic
adsorbents, elution patterns and compound recoveries has been included where
available. Data in the table demonstrate the applicability of column
Chromatography to sample fractionation techniques. In addition, an extrap-
olation to generalized operating parameters may be made using information on
elution patterns and solvent systems.
Gel permeation Chromatography (also referred to as GPC, size-exclusion,
or molecular sieve Chromatography) differs from other chromatographic modes
in that retention is controlled solely by the molecular size of the eluting
species relative to the size of the pores in the support and interaction
between the eluting sample components and the support is undesirable.
Open-column GPC has been extremely useful in removing high molecular
weight interferences (e.g., humic acids, lipids) from environmental samples
prior to analysis by GC, GC/MS or HPLC (F-22, F-34).
F-8
-------
Table 1.
OPEN COLUMN CHROMATOGRAPHIC SYSTEMS USED FOR FRACTIONATING ENVIRONMENTAL SAMPLES
Matrix
Distillation
axtract from
crop malarial
Sol
Sadimantt
Sediment!
Muoal tissue
•dimantf
taawead
Sadimanti
Sadimantt
AdfMtNNt
FlorWI
Floriii
(3% H20 deactivated)
Silica tal
Alumina-neutral
(9% H20 daactivatad)
Silka gal
13% H20 daactivatad)
Floriiil
(5% H20 daactivatadl
Silica gal
Alumina: silica
gal (3: 1)
Alumina: silica
gal (1:11
Alumina: silica
gal (1:2)
ElvtMn f atttm
1) Hexene.-diefhyl ether (9:1)
2) Hexane: ethyl acetate (19:1)
1) Pantana
2) 6X Ether In pentane
3) Ethar
11-
1) Haxana
1) Haxana
2) Ban/ana
1) ToluaM
1) Petrolaum athar
2) Mathylena chlorida in
patrolaum ather
1) Hexana
2) Benzene
3) Methanol
1| Haptana
2) Benzene
1) Haxana
2) Ben/ana
1) Isooctana
2) liooctane: benzene (1:1)
3) Benzene: tlhyl acetate (1:1)
4) Beniena: methanol (1:1)
Campoundt Recoveries
1) Chlorinated hydrocarbon pasticidas f) -
2) 2,40.2.4.51 2) 70-90%*
2)
1) - 90Xb
2) Lindana
Si-
ll Saturated hydrocarbons. PAHs -
1) Chlorinated pasticidas -
1) Aldrin. PCBs. PCNs f 85 • 100Xb
2) Chlordana. ODD. DOE. DOT. /
heptachlor. lindana. toxtphana *
1) Hydrocarbons and PAHs 1) 90%b
1) Hydrocarbons -
2) PAHs
1) Hydrocarbons -
2) PAHs
3) Polar neutrals
1) Hydrocarbons -
2) PAHs
1) Hydrocarbons -
2) PAHs
1) -
2) PAHs.BHC
3) Acetophanone derivatives, phthalatas,
sterols
4) Polyethylene glycol compounds
References
F-36
F-37
F-19
F-38
F-39
F-40
See footnotes at and of tabla.
(Continued)
-------
Table 1
(continued)
Matrix
SoHand
toybaani
Soil and
ttdimant
Soil and
•tdimant
Sediment
~n
i
° Soil
Sediment
Soil
Sewage
tludgt
Sewage
iludgt
AdMrbant
Silica gel
Alumina: silica
».M1:1)
FlorisR
Alumina
Silica gel
Florid!
Silica mkro-column
Flomil
(3% H20 deactivated)
Silica gel
Silica gel
Elulieii Pattern
1) IX methyl acalala in
mathylana chloride
1) Methylene chloride in
pentana (4 to 100%)
1) Ethyl ether in petroleum
ether 15. 15. and 50%)
1) 20mLhexane
2) 20 35 ml haxana
3) 35 50 ml hexane
1) Hexane
2) Beniena
1) Acetone In diethyl ether (4%)
2) Acetone in dielhyl ether (50%)
1) Hexane
2) Methylene chloride
3) Melhylene chloride: methane)
11:7)
1) liooctane
2) Benzene
f) Hexene
2) Toluene
1) Hexane
2) Methylene chloride In
hexane (2:8)
Compounds Recoveries
1) Oioxin D 25 to 100%°
1) PAHs fractionated 1) 97Sb
I) Neutral priority pollutants
1) PCBs,PCNs.aldrin.chlordane.DDD.
DDT, heptachlor, lindane, toxaphene
2) Oieldrin, endrin, heptachlor epoxida -
3) Ethion, malaihion. methyl parathion, -
parathion
1) PCN, PCBl, atdrin
2) Chlordine. ODD, ODE, DDT,
heptachlor, lindane, toxaphene
1) Aldicarb sullonitrile. aldtearb tultona >90%b
oxime
2) Aldicarb sullona
1) Hydrocarbons, pristana, phy tana -
2) Atkylated benzenes, PAHs
3) Ketones, alcohols, phenols, fatty acids
1) Lindana
2) PAHs
1) Chlorinated hydrocarbons -
2) Pesticides -
1) Hydrocarbons j 76to92%b
2) Aromatics >
Raferencei
F-41
F-22
F-42
F-43
F-44
F-45
F-37
F-32
F-46
See footnotes at and of table.
(Continued)
-------
Table 1 (continued)
Recovery for column chromatography alone.
Recovery for entire analytical procedure including column cleanup.
-------
F.2.8 Analysis
Analysis of soils sample extracts is usually performed using gas
chromatography with either a mass spectrometer or a selective detector. Due
to the complexity of the sample extracts, high resolution capillary columns
are preferred for compound separation. All of the organics of interest to
the synfuels industry should be amenable to GC analysis without chemical
derivatization or special column treatments.
Since there are currently no standardized methods for the analysis of
soils for the organics of interest and since the matrix effects on any
analytical operation will be significant, it is essential that any method
selected should be validated prior to use and stringent QA/QC procedures
including blank, controls, and surrogate samples be used throughout the
analysis program.
F.3 DETERMINATION OF INORGANIC SPECIES
Inorganic species originating from synfuels production find their way
into the soil by deposition of airborne particulate material and/or movement
by wind and surface water from storage/dump sites. The inorganic species of
principal concern in the soil are those which can be released in soluble
form. Thus soils are extracted with water adjusted to pH of 5 with acetic
acid (F-47). This extract is then analyzed using the same techniques used
for water analysis.
F-12
-------
F.4 REFERENCES FOR APPENDIX F
F-l. Dunlap, W. J., J. F. McNibb, M. R. Scalf, and R. L. Cosby. Sampling
for Organic Chemicals and Microorganisms in the Subsurface. EPA
600/2-77-176, U. S. Environmental Protection Agency, Ada, OK, 1977.
22 p.
F-2. Musterman, J. L., and J. M. Morand. J. Water Pollut. Control Fed.,
49:45, 1977.
F-3. Sutton, C. J., and A. Calder. Environ. Sci. Techno!., 8:654, 1974.
F-4. Shultz, D. J., J. F. Pankow, D. Y. Tai, D. W. Stephans, and R. E.
Rahtbun. J. Res. U. S. Geol. Survey, 4:247, 1976.
F-5. Zweidinger, R. A Comprehensive Method for Analysis of Volatile
Organics on Solids, Sediment and Sludges, EPA Contract No. 68-03-2994,
1982.
F-6. Marenthal, E. J., and D. A. Becker. A Survey of Current Literature on
Sampling, Sample Handling and Long Term Storage for Environmental
Material. U.S. Department of Commerce and National Bureau of Standards,
Washington, DC. 24 pp.
F-7. Mieuve, J. A. J. Amer. Water Works Assoc., 69:60, 1977.
F-8. Brass, H. J., M. A. Fuge, T. Holloran, J. W. Mellow, D. Munch, and
C. F. Thomas. Presented at ACS National Meeting, New Orleans, LA,
April 1977.
F-9. Henderson, J. E., G. R. Peyton, and W. H. Glaze. In: Identification
and Analysis of Organic Pollutants in Water. L. H. Keith, ed., Ann
Arbor Science, Ann Arbor, MI, 1976. p. 105.
F-10. Kopfler, F. C., R. G. Melton, F. D. Lingg, and W. E. Coleman. Ibid,
84, 1976.
F-ll. Kissinger, L. D. , and J. S. Fritz. J. of the Am. Water Works Assoc.,
69:435, 1976.
F-12. Tan, Y. L. J. Chromatogr., 176:319, 1979.
F-13. Bauman, A. J., R. E. Cameron, G. Kritchevsky, and G. Rouse. Lipids,
2:85, 1967.
F-14. Sherman, J. Manual of Analytical Quality Control for Pesticides and
Related Compounds in Human and Environmental Samples. EPA-600/1-79-008,
U.S. Environmental Protection Agency, Research Triangle Park, NC, 1979.
402 p.
F-13
-------
F-15. Oswald, E. 0., R. G. Lewis, R. F, f^s'/msn, ana K. R. Watts. Analysis
of Pesticide Residues in Human and Environmental Samples. U.S. Environ-
mental Protection Agency, Health Effects Research Laboratory, Research
Triangle Park, NC, 1977.
F-16. Tan, Y. L. J. Chromatogr., 176:319, 1979.
F-17. Bates, T. S. Anal. Chem., 51:551, 1979.
F-18. Brown, D. W., L. S. Ramos, M. Y. Uyeda, A. J. Friedman and W. D. Macleod,
Jr. In: Petroleum in the Marine Environment, L. Petrakis and F. T.
Weiss, eds. Advances in Chemistry Series 185, American Chemical
Society, Washington, DC, 1980. p.313.
F-19. Brown, D. W., L. S. Ramos, A. J. Friedman and W. 0. Macleoug. MBS
Special Publication 519, Proceedings of the 8th Materials Symposium,
Gaithersburg, MD, 1978. p. 161.
F-20. Zweidinger, R. A., and P. A. Hyldburg. Extraction of Volatile Organic
Compounds from Sludge: A New Approach. ACS National Meeting, Las
Vegas, NV, 1982.
F-21. Lake, J. S. , C. W. Demock, and C. B. Norwood. Op. cit., L. Petrakis and
F. T. Weiss, eds., 1980. p. 345.
F-22. Giger, W. and M. Blumer. Anal. Chem., 46:1663, 1974.
F-23. Solvent Selection in the Extraction of Volatile Organic Compounds from
Soils and Sediments. ACS National Meeting, Las Vegas, NV, 1983.
F-24. Rohrback, B. G., and W. E. Reed. Evaluation of Extraction Techniques
for Hydrocarbons in Marine Sediments. Institute of Geophysics and
Planetary Physics. University of California, Los Angeles, CA. No.
1537, 1975.
F-25. Farrington, J. W., and B. W. Tripp. In: Marine Chemistry in the
Coastal Environment. ACS Symposium Series, 18:267, 1975.
F-26. Clark, R. C., Jr., and J. S. Finley. Techniques for the Analysis of
Paraffin Hydrocarbons and For Interpretation of Data To Assess Oil Spill
Effects in Aquatic Organisms. Proc. Int. Conf. Prev. Control Oil Spill,
197:161, 1973.
F-27. Biere, R. H., M. K. Aieman, R. J. Huggett, W. Maclntyre, P. Shou, C. L.
Smith, C. W. Su, and G. Ho. Toxic Organic Compounds in the Chesapeake
Bay. Grant No. R806012010. U.S. Environmental Protection Agency,
1980.
F-28. Lyons, E. F. , and H. A. Salmon. Development of Analytical Procedures
for Determining Chlorinated Hydrocarbon Residues in Waters and Sediments
from Storage Reservoirs. Engineering and Research Center, Bureau of
Reclamation, Denver, CO, 1972. 13 p.
F-14
-------
f-2r.', Bellar, T. A., J. J. lichtenberg, and S. C. Lonneman. Recovery of
Organic Compounds in Environmentally Contaminated Bottom Kate rials.
In, Contaminants and Sediments, Volume 2, R. A. Baker, ed, Ann Arbor
Science, Ann Arbor, MI, 1980. p. 57.
i-iunqet, Robert J. , M. M. Nichols, and M. E. Bender. Ibid. , Volunria "i,
1980. p. 33. •
Amore, F. Analysis of Soil and Sediment to Determine Potential Pesti-
cide Contamination of a Water Supply Impoundment. Op. cit. NBS Special
Publication 519.
Erickson, M. 0., R, A. Zweidinger, L. C. Micha.1 and E. D, Pellizza^i.
Environmental Monitoring Near Industrial Sites: Pol vchl oronaphthalf-nes.
EPA Contract No. EPA-560/6-77-019, 1977. 266 p.
Smith, A. D. J. Agr. Food Chem., 25:893, 1977.
Slumer, M., W. Blumer, and T. Reich. Environ. Sci. and Techno!.,
11:1083, 1977.
Helpert, L. R., W. E. May, S. A. Wise, S. N. Chesler, and H. S, Hertz.
Anal. Chem., 50:458, 1978.
Munro, H. E. Pestic. Sci., 8:157, 1977.
Mathur, S. P., and J. G. Saka. Bull. Environ. Contam. Toxicol., 17:4
-------
F-46. Reley, R. G., and R. M. Bean. Application of Liquid and Gas Chromato-
graphic Techniques to a Study of the Persistence of Petroleum in Marine
Sediments. Op. cit. NBS Spec. Publ. 519, 1978. p. 33.
F-47. Code of Federal Regulations, 40 Part 260, Subpart C, Section 261.24.
Characteristic of Extraction Procedure (EP) Toxicity, 1976.
F-16
-------
APPENDIX G
GROUNDWATER MONITORING TECHNIQUES
Groundwater supplies the domestic water needs of 80 percent
of all public water supply systems and 96 percent of rural America.
Overall, about one-half of all U.S. residents rely u«. groundwater as
their primary source of drinxing water. Groundwater has tradition-
ally been and continues to oe a major source for industrial process
water. Moreover, it has come into rapidly increasing use for live-
stock production and agriculture. Intercepting migrating pollutants
before they reach a groundwater supply and detecting their presence
and pattern of movement is essential for preventing, reducing, and
eliminating deterioration of water supplies.
In identifying the constituents of groundwater which should be
monitored, consideration should oe given to the groupings of chem-
icals defined in Appendix C. In making the determination of which
chemicals should be monitored, close coordination should be made with
the monitoring planned in connection with the source monitoring data
base (Section 4.0).
G.I COLLECTION OF INFORMATION
Shallow aquifers that drain laterally into streams should be
monitored for horizontal variations in water quality. Because
aquifers generally are not well mixed, more than one well should be
placed in a line perpendicular to water flow, and toward the center
of the drainage pattern. If vertical variations are suspected, test
wells should be constructed at different depths. Sample collection,
by pump or other metnods, should be preceded by water removal equal
G-l
-------
to three times the estimated volume of the well to ensure represen-
tative sampling. Parameters analyzed should oe oased on the nature
of the potential pollution, and the hydrological and geochemical
characteristics of the aquifer. Specific sampling methods will
depend on the parameter of concern (e.g., organic compounds require
sampling with a peristaltic pump and teflon tubing) (G-l, G-2, and
G-3 through G-8).
Existing information and wells could be used, when availaole,
for ambient monitoring. Baseline analysis should include identifi-
cation and characterization of deep aquifers and interrelationships
between different aquifer zones. The ability of soils and the vadose
zone to remove pollutants from downward percolating water should be
considered. In cases where there is rapid movement through the
vadose zone or pollutant potential is high, deep well monitoring is
extremely important. At minimum, a single up-gradient well and a
series of down-gradient wells should be monitored (G-l, G-2, G-6,
G-9, and G-10).
If in-situ gasification is planned for the site, special atten-
tion must oe given to isolating process waters and treating or re-
moving potential leachates. A series of wells around the zone of
activity will be necessary. Monitoring for process-specific pollut-
ants will be necessary. At the present time, options available for
treating in-situ wastes are not well known (G-9, and G-ll through
G-15).
During the operational phase, suspected pollutant species from
plant wastes should be monitored in deep aquifers. This technique
is a last line of defense (following surface water and vadose zone
interception) in detecting pollutant presence and groundwater con-
tamination from synthetic fuel activities (G-10, G-16).
G-2
-------
G.2 FREQUENCY
Monthly samples should be analyzed to estaolish baseline condi-
tions for all parameters at least one year prior to site activities.
During construction and operation, more frequent monitoring may be
required if significant changes occur in relative concentrations of
existing water quality parameters or if new pollutes are suspected.
The monitoring of groundwater should oe considered a long term com-
mitment (G-l, G-2, and G-16).
G-3
-------
G.3 REFERENCES FOR APPENDIX G
G-l. U.S. Environmental Protection Agency. Environmental Per-
spective on the Emerging Oil Shale Industry, E.R. Bates and
T.L. Thoem, eds. (EPA-600/2-80-205a). Industrial Environ-
mental Research Laboratory, U.S. Environmental Protection
Agency, Cincinnati, OH, 1981.
G-2. Everett, L.G. Groundwater Monitoring Guidelines and Method-
ology for Developing and Implementing a Groundwater Quality
Monitoring Program. General Electric Company, Schenectady,
NY, 1980.
G-3. U.S. Environmental Protection Agency. Monitoring Groundwater
Quality: Monitoring Methodology. (EPA-600/4-76-026). En-
vironmental Monitoring and Support Laboratory, Las Vegas, NV,
G-4. U.S. Environmental Protection Agency. Groundwater Quality
Monitoring of Western Oil Shale Development: Monitoring
Program Development. G.C. Slawson, ed. Contract No. 68-
03-2449, Environmental Monitoring Systems Laboratory, Las
Vegas, NV, 1980.
G-5. U.S. Environmental Protection Agency. Effects of Coal-Ash
Leachate on Ground Water Quality. (EPA-600/7-80-066). In-
dustrial Environmental Research Laboratory, Research Triangle
Park, NC, 1980.
G-6. U.S. Environmental Protection Agency. Monitoring Groundwater
Quality: Illustrative Examples (EPA-600/4-76- 036). Environ-
mental Monitoring and Support Laooratory, Las Vegas, NV, 1979.
G-7. U.S. Environmental Protection Agency. Monitoring Ground-
water Quality: Methods and Costs (EPA-600/4-76-023; NTIS No.
PB 257-133). Environmental Monitoring and Support Laboratory,
Las Vegas, NV, 1976.
G-8. Tomson, M.B., S. Hutchins, J.M. King, and C.H. Ward. A Ni-
trogen Powered Continuous Delivery, All-Glass-Teflon Pumping
System for Groundwater Sampling from Below 10 Meters. Source
unknown. Research sponsored by U.S. Environmental Protection
Agency. Grant No. R805292 and National Center for Groundwater
Research Grant No. CR806931, 1981.
G-4
-------
G-9. U.S. Environmental Protection Agency. Monitoring Ground-
ater Quality: The Impact of In Situ Oil Shale Retorting
(EPA 600/7-80-132). Interagency Energy/Environment Research
and Development Program Report. Washington, D.C., 1980.
G-10. National Water Well Association. Manual of Ground Water
Quality Sampling Procedures. Worthington, OH, 1981.
G-ll. Campbell, J.H., E. Pellizzari, and S. Santoe. Results of
a Groundwater Quality Study Near an underground Coal Gasi-
fication Experiment (Hoe CreeK I). (UCRL-524U5). Lawrence
Livermore Laboratory, Livermore, CA, 1978.
G-12. U.S. Environmental Protection Agency. Lysemeter Study on
the Disposal of Paraho Retorted Oil Shale (EPA-600/7-79-188).
Interagency Energy/Environment Research and Development Pro-
gram Report. Washington, D.C., 1979.
G-13. Bergman, H.L. Aquatic Ecosystem Hazard Assessment of Under-
ground Coal Gasification Process Waters. Proceedings, 20th
Hanford Life Sciences Symposium on Coal Conversion and the
Environment, Richland, WA, Octooer 19-23, 1980.
G-14. Walters, E.A. and T.M. Niemczyk. The Effect of Underground
Coal Gasification on Groundwater. Research Grant No. R806303,
University of New Mexico, Alouquerque, N.M. prepared for In-
dustrial Environmental Research Laooratory, U.S. Environmental
Protection Agency, Cincinnati, OH, 1981.
G-15. U.S. Environmental Protection Agency. Groundwater Quality
Monitoring Recommendations for In-Situ Oil Shale Development.
Contact Les McMillion (Project Officer), Environmental Moni-
toring and Support Laboratory, Las Vegas, NV, In Preparation.
G-16. U.S. Environmental Protection Agency. Procedures Manual for
Groundwater Monitoring at Solid Waste Disposal Facilities.
Office of Solid Waste, Washington, D.C., 1980.
G-5
-------
APPENDIX H
SPECIAL BIOLOGICAL MONITORING TECHNIQUES
H.I TERRESTRIAL EFFECTS MONITORING
The purpose of terrestrial effects monitoring is to detect po-
tential adverse effects associated with the operation of a synthetic
fuel facility. It is not the intent to inventory, measure, enarae-
terize, or model the entire ecosystem, including its dynamics, within
the local and regional setting of a facility. The emphasis of such
monitoring is to observe key species in order to determine if process
and emission control systems are effectively controlling the release
of pollutants.
H.I.I Sampling and Analysis
The species selected for observation are routinely examined for
residuals of interest and for visible signs of adverse effects at
tne individual or population level. Examination for ooth residuals
and adverse effects is necessary oecause several groups of pollut-
ants, although accumulated in the tissues of plants and animals, do
not induce visiole symptoms. Conversely, several pollutants that
cause extensive diotic damage are not accumulated to any appreciable
extent. Representative(s) of the first group are metals and hydro-
carbons and of the second group is ozone. A third group may accumu-
late as well as produce visiole symptoms (e.g., halogens).
The specific species or biotic groups for study may vary with
site specific requirements. Those monitored have included soil de-
composers (retarded oy chronic exposure to airborne toxic pollutants,
H-l
-------
e.g., S02), fruit flies, earthworms, isopods/millipedes, ants,
honeyoees, flies, beetles, spiders, starlings, sparrows, house mice,
shrews, lichens, mosses, grasses, and various higher plant species
(including crops).
There are many important considerations in the establishment of
terrestrial monitoring programs focusing on oioacenmulation. These
include (in order of priority), importance to the health of man,
position of the species in the food chain, importance as an economic
resource, species aoundance and distribution on and near the site,
and collection costs and maintenance. Emphasis should be on the
gathering of oioaccumulation data without mortality, especially with
respect to important verteorate organisms (e.g., sampling of blood,
hair, feathers).
The general vitality of populations and communities can be
monitored by focusing on the observation of changes in numbers of
species, species abundance, distribution patterns, diet, longevity,
reproductive patterns, and overall diversity. For considerations in
the establishment of a site-specific terrestrial monitoring program,
the reader is referred to the long-term studies on the bioenvironmen-
tal impact of the coal-fired power plant at Colstrip, Montana and to
recent documents on terrestrial monitoring protocols (site-specific
monitoring: H-l through H-4; generic observations: H-5, H-6; moni-
toring protocols and their application: H-7 tnrough H-13).
H.I.2 Frequency
Terrestrial effects monitoring requires a long-term commitment.
Continuous monitoring is required, although not dedicated to every
species at every point in time. Studies at Colstrip have indicated
H-2
-------
that certain insects, meadowlarks (pulmonary damage), and Ponderosa
pines express symptomatic responses to coal derived pollutants. Such
changes, although subtle, are an observable result of long-term moni-
toring (5 years).
H.2 PERIPHYTON MONITORING
Degradation of water in natural habitats can oe detected oy
monitoring natural communities, especially, with regard to changes 1°
community structure. In the absence of a pollution load, many spe-
cies are present and most are in relatively moderate abundance. A
few species are rare and a few are highly aoundant. in the presence
of pollution, fewer species are present, they do not occur in the
same relative abundances, and a few species are represented oy very
large numbers.
Data of tnis nature can be used to indicate stress in an aquatic
system, in conjunction with more routine measurements of the physical
and chemical parameters. When an aonormal community is observed,
chemical testing can oe initiated to identify the source and the
particular contaminant (H-14 through H-17).
H.2.1 Sampling and Analysis
In-situ monitors such as the Catherwood Diatometer or other
artificial substrates can oe used to detect the presence of toxic
substances, including heavy metals and organic compounds (H-14).
Exposure for two weeks or more allows for colonization of the sur-
face. Duplicate surfaces can oe analyzed for speciation and for
bioaccumulation. Organic compounds may be extracted and analyzed
by gas chromatography. A series of suostrate colonizations and
H-3
-------
analyses can indicate fluctuations of pollutant concentrations over
time. Placement aoove and below discharge sites will provide pollut-
ant concentration profiles relative to the facility site. Baseline
monitoring can characterize tne normal community structure for a
particular site. Operational monitoring should consist of at least
two stations (above and downstream of the facility) sampled monthly
(H-18 through H-21).
H.2.2 Frequency
Monthly samples should be obtained after placing the artificial
substrate in tne water for a period of at least two weeks in summer
to four weeks in winter. Under relatively unpolluted conditions,
the kinds of species change from season to season, yet the numoer of
species and community structure are relatively constant. If monthly
samples indicate stress in the natural community, then more frequent
biological monitoring and monitoring at strategically located sites
should be conducted along with chemical analyses to determine the
source and extent of contamination (H-14 and H-18).
H.3 AQUATIC BIOACCUMULATION MONITORING
Heavy metals, organic pollutants and radioactive materials tend
to accumulate in certain biota at greater levels than in the water
column. Potentially hazardous substances may oe detected sooner
in resident fish, for example, than in ambient water. Because such
bioconcentration is Known to affect humans, it is important to test
for oioaccumulation in the ambient environment around synthetic fuel
sites.
H-4
-------
H.3.1 Sampling and Analysis
Although bioaccumulation also can be tested in the laooratory
through uptake tests, it is presented here as a static measure of
ambient water pollutants. Fish may oe ootained oy active or passive
sampling methods, and native species of the same size and age should
be collected. In addition, several specimens of representative spe-
cies should be preserved for future reference and possible analysis.
Whole oody analysis should be performed oy homogenizing several fish
within eight hours, and by analyzing tissue and water samples within
48 hours (at least two samples of water should be analyzed for the
materials of interest and conventional water parameters) (H-22 and
H-23).
Sample analyses should follow standard procedures as descrioed
in other sections of this document (in general, atomic absorption
spectrophotometric methods for metal, and gas chromatographic methods
for organic compounds). No standard method has oeen developed for
this procedure using field samples. However, it is currently used
as a fast, efficient method of detecting toxic materials of concern
in field monitoring activities (H-24 and H-25).
If the pollutant is Deing concentrated in fish tissues, tissue
measurements should exceed ambient water concentrations (H-26).
H.3.2 Frequency
Annual analyses should be sufficient to detect the presence of
toxic materials in the organisms. If significantly high levels are
found, then further study of the water body will be necessary to
determine the source and extent of contamination and to eliminate
hazards to the environment.
H-5
-------
H.4 REFERENCES FOR APPENDIX H
H-l. U.S. Environmental Protection Agency. The Bioenvironmental
Impact of a Coal-Fired Power Plant. Sixth Interim Report,
Colstrip, Montana. EPA-600/3-81-007. Available from the
Center for Environmental Research Information, U.S. Envi-
ronmental Protection Agency, Cincinnati, OH, 1981.
H-2. U.S. Environmental Protection Agency. The Bioenvironmental
Impact of a Coal-Fired Power Plant. Fifth Interim Report,
Colstrip, Montana. EPA-600/3-80-044. Available from the
National Technical Information Service (NTIS;, Springfield,
VA, 1980.
H-3. U.S. Environmental Protection Agency. The Bioenvironmental
Impact of a Coal-Fired Power Plant. Fourth Interim Report,
Colstrip, Montana. EPA-600/3-79-044. Available from the
National Technical Information Service (NTIS), Springfield,
VA, 1979.
H-4. U.S. Environmental Protection Agency. The Bioenvironmental
Impact of a Coal-Fired Power Plant. Third Interim Report,
Colstrip, Montana. EPA-600/3-78-021. Available from the
National Technical Information Service (NTIS), Springfield,
VA, 1978.
H-5. U.S. Fish and Wildlife Service. Impacts of Coal-Fired Power
Plants on Fish, Wildlife and Their Habitats. Biological
Services Program, FWS/OSS-78/79. U.S. Department of the
Interior, Washington, D.C., 1978.
H-6. Jones, H.C., and J.C. Noggle. Ecological Effects of Atmos-
pheric Emissions from Coal-Fired Power Plants. Presented at
Air Quality Management in the Electric Power Industry, January
22-25, 1980, Austin, Texas. This paper may be obtained from
the Office of Natural Resources, Air Quality Branch, Air
Quality Research Section, Tennessee Valley Authority, Muscle
Shoals, AL, 1980.
H-7. Borman, F.H. and G.E. Likens. Pattern and Process in a
Forested Ecosystem. Springer-Verlag, NY, 1979.
H-8. Holling, C.S. Adaptive Environmental Assessment and Man-
agement. John Wiley and Sons, NY, 1978.
H-9. Likens, G.E. et al. Bio-geo-chemistry of a Forested Eco-
system. Springer-Verlag, NY, 1977.
H-6
-------
H-10. Metcalf, R.L. A Laboratory Model Ecosystem to tvaluate Com-
pounds Producing Biological Magnification. In, Hayes, W.J.
(ed). Essays in Toxicology, Volume 5. Academic Press, NY,
1974.
H-ll. Brown, R. Environmental Effects of Coal Technologies: Re-
earch Needs. A Report to the Federal Interagency Committee on
the Health and Environmental Effects of Energy Technologies.
Available as PB81-220824 from the National Technical Informa-
tion Service (NTIS) or as MTR-79W15903 from The MITRE Corpora-
tion, McLean, VA, 1981.
H-12. Science Advisory Board, Ecology Committee. Goal of and
Criteria for Design of a Biological Monitoring System. U.S.
Environmental Protection Agency, Washington, D.C., 1979.
H-13. Heck, W. and C. Brandt. Effects on Vegetation: Native,
Crops, Forests. In, Air Pollution. Third Edition. Volume
II. The Effects oT~Air Pollution (A.C. Stern, ed.) Academic
Press, NY, 1977.
H-14. American Public Health Association. Standard Methods
for the Examination of Water and Wastewater. 15th Edition.
American Public Health Association, Washington, D.C., 1981.
H-15. American Society for Testing and Materials. Biological Moni-
toring of Water and Effluent Quality. ASTM Special Technical
Publication 607. Philadelphia, PA, 1977.
H-16. Cairns, J., G.P. Patil, and W.E. Waters. Environmental Bio-
monitoring, Assessment, Prediction, and Management - Certain
Case Studies and Related Quantitative Issues. International
Co-operative Publishing House, Burtonsville, MD, 1979.
H-17. Cairns, J. and W.H. Van Schalie. Biological Monitoring Part 1.
California Warning Systems. Water Research 14:1179- 1196,
1980.
H-18. Friant, L. and J.W. Sherman. The Use of Algae as Biological
Accumulators for Monitoring Aquatic Pollutants. _In_ 2nd Inter-
agency Workshop on In-Situ Water Quality Sensing: Biological
Sensors: Pensacola Beach, Florida; April 28-30. 1980. EPA/
NOAA/USACE/USGS. Washington, D.C., 1980.
H-19. Brown, R.D. The Use of Biological Analyses as Indicators of
Water Quality. 3. Envir. Health 34(1); 62-66, 1971.
H-7
-------
H-20. Patrick, R., M.H. Hohn, and J.H. Wallace. A New Method
for Determining tne Pattern of the Diatom Flora. No. 259
Academy of Natural Sciences, Philadelphia, PA, 1954.
H-21. Friant, S.L. and H. Koeiner. use of an in Situ Artificial
Suostrate for Biological Accumulation and Monitoring of
Aqueous Trace Metals - A Preliminary Field Investigation.
Water Research 15(1):161-167, 1981.
H-22. U.S. Environmental Protection Agency. Environmental Perspec-
tive of the Emerging Oil Shale Industry, E.R. Bates and T.L.
Thoem, eds. (EPA-600/2-80-205a). Industrial Environmental
Research Laooratory, U.S. Environmental Protection Agency,
Cincinnati, OH, 1981.
H-23. Hamelink, J.L., and J.G. Eaton. Proposed Standard Practice
for Conducting Bioconcentration Tests witn Fishes and Salt-
water Bivalve Molluscs. ASTM Committee F-47. American
Society for Testing and Materials, Philadelphia, PA, 1981.
H-24. Eaton, J.G. U.S. Environmental Protection Agency, Environ-
mental Research Laboratory, Duluth, Minn. 55804. Personal
Communication. September 4, 1981.
H-25. Osata, M. and Y. Miyake. Gas Chromatography Combined with
Mass Spectrometry for the Identification of Organic Sulfur
Compounds in Shellfish and Fisn. J. Chromatogr. Sci.
18(11):594-605, 1980.
H-26. U.S. Environmental Protection Agency. The Precision of the
ASTM Bioconcentration Test. (EPA-600/3-81-022). Environ-
mental Research Laooratory, Duluth, MN, 1981.
H-8
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APPENDIX I
SFC INTERIM GUIDELINES
The U.S. Synthetic Fuels Corporation (SFC) has prepared Interim Environ-
mental Monitoring Plan Guidelines. These Interim guidelines were published 1n
the Federal Register on April 1, 1983, with an Invitation for public comments.
A copy of the published Interim guidelines 1s attached. Where this Environ-
mental Monitoring Reference Manual refers to the SFC guidelines, 1t 1s
referring to the published Interim guidelines.
In response to public comments received on the Interim guidelines, the
SFC will be preparing final Environmental Monitoring Plan Guidelines, which
will supercede the Interim guidelines. The final guidelines will be addressed
1n any future revision of this Monitoring Manual.
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APPENDIX I
SFC GUIDELINES
14108
Federal Register / Vol. 48. No. 64 / Friday, April 1. 1983 / Notices
SYNTHETIC FUELS CORPORATION
Interim Environmental Monitoring Plan
Guidelines
AGENCY: U.S. Synthetic Fuels
Corporation
ACTION: Publication of interim
Environmental Monitoring Guidelines.
SUMMARY: This notice publishes, and
invites written public comment on.
Environmental Monitoring Plan
Guidelines which have been adopted in
interim final form by the Board cf
Directors of the U.S. Synthetic Fuels
Corporation to carry out the
requirements of Section 131(e) of the
Energy Security Act, Pub. L. 96-294,
relating to environmental monitoring
plans. Written comments will be
accepted through May 23,1983, and
should be directed to the Corporation's,
Director of Environment at the address
indicated below. Copies of the
Environmental Monitoring Plan
Guidelines and all comments thereon
will be available in the Corporation's
Public Reading Room at the address
indicated below. After receipt of
comments, the Environmental
Mon:toring Plan Guidelines will be
presented to the Corporation's Board of
Directors, with such changes as may be
recommended by the Chairman, for
adoption in final form.
FOB FURTHER INFORMATION CONTACT:
Steven M. Gottlieb, Director of Environment,
U.S. Synthetic Fuels Corporation. 2121 K
Street! NW.. Washington. D.C. 20580,
(202) 822-6316.
For copies of the guidelines and public
comments: Catherine McMillan. Director
of Public Disclosure. U.S. Synthetic
Fuels Corporation. 2121 K Street. NW..
Washington. D.C. 20586. (202) 822-6460.
United States Synthetic Fuels Corporation,
Interim Environmental Monitoring Plan
Guidelines
Table of Contents
1. Purpose
II. Statutory Basis
III. General Approach to Implementing
Section 131(e)
IV. Procedures for Developing Outlines and
Plans
A. General Considerations
B. Development of Outlines
C. Development of Plans
D. Determination of Acceptability
V. Substantive Areas of Outlines and Plans
A. Overview
B. Supplemental Monitoring
C. Substantive Monitoring Areas
1. General
2. Source Monitoring
3. Ambient Monitoring
4. Health and Safety Monitoring
5. Other Monitoring
D. Quality Assurance/Quality Control
E. Data Management; Reporting
Requirements
VI. Confidentiality of Data
VII. Monitoring Review Committees
A. Membership; Meetings
B. Functions
1. Data Review
2. Modification of Monitoring Requirements
VUI. Amending the Guidelines
I. Purpose
Section 131(e) of the Energy Security
Act specifies that project sponsors
receiving financial assistance from the
United States Synthetic Fuels
Corporation (the "Corporation") shall
develop, in consultation with the
Environmental Protection Agency
("EPA"), the Department of Energy
("DOE") and appropriate state agencies
an environmental monitoring plan
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Federal Register / Vol. 48, No. 64 / Fr.aay, April 1, 1983 / Notices
14109
acceptable to the Corporation's Board of
Directors. In implementing this statutory
mandate, the Corporation is utilizing a
two-stage approach under which the
sponsors (1) develop an Outline of their
monitoring plans, which will be
incorporated into financial assistance
contracts, and (2) develop a monitoring
plan (based on the outline) after
financial assistance contracts are
executed.
The purpose of these Guidelines is to
set forth the procedural steps to be
taken and the broad substantive areas
to be addressed in developing outlines
and plans. The Guidelines provide the
general basis on which the Corporation
will determine the "acceptability" of
outlines and plans. However, the
Guidelines do not specify the
substantive details required for an
acceptable outline or plan since the
actual development of an outline and
plan is the responsibility of sponsors, in
consultation with the appropriate
agencies.
II. Statutory Basis
Section 131(e) of the Energy Security
Act ("ESA") requires that:
Any contract for financial assistance shall
require the development of a plan, acceptable
to the Board of Directors, for the monitoring
of environmental and health-related
emissions from the construction and
operation of the synthetic fuels project. Such
plan shall be developed by the recipient of
financial assistance after consultation with
the Administrator of the Environmental
Protection Agency, the Secretary of Energy,
and appropriate state agencies.
The Conference Committee's Joint
Explanatory Statement relating to this
provision states, in pertinent part:
The monitoring of emissions—gaseous.
liquid or solid—and the examination of waste
problems, worker health issues and other
research efforts associated with any
synthetic fuels project * * * will help to
characterize and identify areas of concern
and develop an information base for the
mitigation of problems associated with the
replication of synthetic fuels proiects. The
Corporation is not expected to involve itself
in tht! (ii'u-lupment or execution of such
pi.ins except l'ir the necessary approval. The
' onierees intend that development of the
plans and actual data collection be reserved
to the applicants fcr financial assistance after
consultation with appropriate federal and
s,tate agencies. (Joint Exolanatory Statement,
of 'he Committee of CoTterence: pp 20B-209
<>i Compilation of the Energy Security Act of
I ')«<)]
III. General Approach To Implementing
Section 131(e)
The Corporation views the
• h.iractorization and identification of
t'r.is of concern and the development of
.1,1 information base for the mitigation of
problems associated with the replication
of synthetic fuels projects to be the
fundamental purposes of environmental
monitoring pursuant to monitoring plans
under Section 131(e). Toward this end,
the Corproation requires that sponsors
perform a broad range of monitoring
activities, during the entire life-cycle of
their project.1 (Socioeconomic and water
consumption monitoring will not be
considered to be part of monitoring
under Section 131 (e); however, it is
anticipated that some socioeconomic
and water consumption monitoring will
be required by separate terms of the
financial assistance contract.)
Monitoring pursuant to section 131(e)
shall include that which is required by
federal, state, and local permits,
approvals," and other regulatory
obligations ("compliance monitoring")
and, as appropriate, additional
requirements ("supplemental
monitoring"), such as the monitoring of
unregulated substances which may be
present at concentrations of significant
environmental or health concern.3
The Corporation requires that the
environmental monitoring plan be
developed in two stages. In the first
stage, sponsors are required to develop
an outline of the environmental
monitoring plan ("outline"), in
consultation with the federal and state
agencies referred to in section 131(e)
(the "consulting agencies"). This outline,
which will contain a general description
of the sponsors' monitoring tasks, will
be incorporated into the financial.
assistance contracts. Under the second
stage, sponsors are required, by a date
fixed in the contract, to develop an
environmental monitoring plan ("plan")
which provides a detailed description,
based upon the general terms of the
outline, of the specific monitoring tasks
to be undertaken. Both the outline and
plan shall address the methods by
which data will be acquired, managed.
' "Project" applies to those facilities to be covered
by the financial assistance agreement, as well as
any dedicated mining operation at the proiect site
winch is controlled by the sponsors. "Sponsors"
applies to the sponsor or sponsors of a project
before the Corporation.
-Monitoring reauired by "approvals" shall
include monitoring specified in anv federal or state
environmental impact statement (EIS) or agency
record of decision relating thereto. This in no way
implies that the award of financial assistance by the
Corporation is a major federal action under Section
102(2)(C) of tne National Environmental Policy Act
|.\EPA) Section 175(b) of the ESA spenficailv
provides that ail actions of the Corporation, except
for construction and operation of Corporation
construction projects, are exempt from the EIS
requirements of NEPA.
'The Corporation has previously notified
sponsors that they must consider the monitoring of
unregulated substances. (See. e.g., the Corporation's
Si/cond Solicitation Section. Section IV.C.d.l, and
Third Solicitation. Section. Section III B.6.b 2).
and analyzed. The plan should be
viewed by sponsors and consulting
agencies as a dynamic document which
can be modified as conditions warrant.
In determining the "acceptability" of
the outline and plan under Section
131(e), the Corporation will decide
whether the sponsors have addressed
both the broad monitoring areas referred
to in the Guidelines and the specific
recommendations of the consulting
agencies. The Corporation will consider
the costs of monitoring relative to the
potential usefulness of this information.
Where the sponsors do not include in
their outlines or plans monitoring which
is indicated in these Guidelines or
-ecommended by the consulting
agt.icus, a specific explanation shall be
provided which will be evaluated by the
Corporation as part of the process of
making acceptability determinations.
IV. Procedures for Developing Outlines
and Plans
A. General Considerations
To promote the timely development of
sound monitoring outlines and plans,
with meaningful input from the
consulting agencies, the procedural
approach set forth below should be used
in developing and reviewing monitoring
outlines and plans. In implementing
these procedures, several general points
are relevant:
• Section 131(e) formally designates
EPA, DOE and appropriate state
agencies 4 as consulting agencies for
purposes of developing monitoring
plans. While the Corporation has the
ultimate statutory responsibility for
making acceptability determinations,
the Corporation regards the consulting
agencies' opinions and comments as
fundamental to the development of the
outline and plan.5
• Early meetings between sponsors
and consulting agencies and informal
communications between them
throughout the process of developing an
outline and plan are inherent to the
Section 131(e) consultation process. (The
Corporation will notify sponsors which
consulting agency officials to contact.)
Sponsors should bear in mind that they
have the responsibility for developing
their outline and plan and they should
'The Governor in whose state a project is located
designates an "appropnaie s'ate agency off:ci Jl" to
work with the sponsors to develop the outline and
plan.
SEPA has prepared a monitoring reference
manual for synthetic fuels processes (presently in
draft form) which the agency will make available to
sponsors to indicate EPA's areas of interest. This
manuals contains no requirements; rather, it is a
general reference tool which may be used by
drafters and reviewers of monitoring plana.
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Federal Register / Vol. 48, No, 84 / Friday. April 1, 1983 / Notices
not unduly burden the consulting
agencies in this effort.
* A number of sponsors have already
begun to develop their monitoring
outlines in consultation with the
appropriate agencies. In these cases, the
Corporation will not require repetition
of the procedural steps set forth herein
to the extent they have already been
effectively performed.
• To maximize coordination among
the parties to the process—sponsors.
federal and state consulting agencies,
and the Corporation—courtesty copies
of all formal communications (draft and
revised outlines and plans and all
correspondence, including consulting
agency comments and sponsors'
responses) from any party should be
provided simultaneously to all other
parties.
B. Development of Outlines
The following is the sequence which
shall be followed in developing
monitoring outlines in consultation with
the appropriate agencies:
• For projects submitted under the
Corporation's first three general
solicitations, sponsors shall initiate
preparation of their monitoring outline
no later than immediately after passing
the Corporation's strength review. For
those sponsors submitting proposals
under the Corporation's "Competitive
Solicitation for Oil Shale Projects" (or
comparable solicitations developed in
the future), sponsors' technical
proposals shall include a schedule for
preparing an acceptable monitoring plan
outline; the schedule should provide that
if the technical proposal is found
acceptable by the Corporation, sponsors
will immediately initiate preparation of
their outline.
• The sponsors' draft outline shall be
submitted to the consulting agencies for
their review and comment. The sponsors
should confer with the Corporation
regarding the timing of submission of the
draft outline (as well as the revised
outline) so that an acceptable outline
can be prepared on a schedule
consistent with the anticipated financial
assistance agreement signing date.
• Consulting agencies should provide
written comments to the sponsors on the
draft outline expeditiously. It is
expected that absent special
circumstances, comments will be
provided within five weeks of receiving
the draft.
• Upon receiving comments from the
consulting agencies, the sponsors shall
prepare a revised outline which
responds to the comments, either by
modifying the outline or by explaining
(in a cover letter) the specific reasons
for not accepting any specific monitoring
task suggested by the consulting
agencies and for excluding any general
monitoring area covered in the
Guidelines.
• The revised outline shall be
submitted to the consulting agencies for
final review.
• Absent special circumstances, the
consulting agencies should submit to the
Corporation their comments on the
revised outline1 within four weeks of
receiving it.
• The Corporation will evaluate the
revised outline and the consulting
agency comments and determine the
outline's acceptability.
C. Development of Plans
Each financial assistance contract will
establish a date by which sponsors shall
submit their draft and revised plans. It is
anticipated that the revised plan will be
required approximately four to six
months after contract signing, depending
on the complexity of the plan and other
project-specific circumstances.6
Following the revised plan's submittal, it
must be found acceptable by the
Corporation within a time fixed in the
contract (approximately two months
from the submission deadline).
The sequence for developing a plan,
including the time periods for consulting
agency comments, is 'analogous to that
for an outline set forth above. In brief,
the sponsors develop a draft p'an; it will
be reviewed and commented on by the
consulting agencies; a revised plan will
be developed; final comments will be
provided by the consulting agencies; and
the revised plan and comments thereon
will be evaluated by the Corporation
and a determination of acceptability is
made. Absent unusual circumstances,
the plan must be consistent with the
terms of the outline. (With respect to
modifying the plan during the period in
which it is being implemented, see
Section VII.3.2.)
D. Determination of Acceptability
The Corporation will determine the
acceptability of all monitoring outlines
and plans based on whether the
sponsors' specific treatment of the broad
substantive areas set forth in these
Guidelines meets the Corporation's
environmental monitoring goals of
characterizing and identifying areas of
concern and developing an information
base for the mitigation of problems
associated with the replication of
synthetic fuels projects. In making
acceptability determinations, the
Corporation will evaluate the consulting
agencies' comments and monitoring
recommendations and the sponsors'
responses to the agencies' comments
and recommendations.
If the Corporation determines that a
monitoring outline is acceptable, it will
then be incorporated into the financial
assistance contract. As a general rule, if
a sponsor's outline is not found to be
acceptable, the Corporation will not
enter into an agreement for financial
assistance until the outline is made
acceptable. With respect to monitoring
plans, failure to submit an acceptable
plan as required by the statute, and
failure to properly implement plans
determined to be acceptable by the
Corporation, will be addressed under
ule default and remedy provisions of the
financial assistance agreement.
V. Substantive Areas of Outlines and
Plans
A, Overview
A monitoring outline should be a
general description of the environmental
monitoring tasks which the sponsors
will perform, including a summary of
compliance monitoring obligations and a
brief description of supplemental
monitoring tasks. (Where a permit has
not yet been obtained, sponsors should
include in the outline and plan
anticipated requirements based on the
terms of comparable permits.) TUB
outline should state what substances
will be monitored (both regulated and
unregulated), where the monitoring will
take place (such as ambient or
workplace), how the monitoring would
be performed (such as high volume
sampler or personal dosimeter), and the
duration. The monitoring plan shall
include all of the specific terms and
conditions of permits and other
approvals and the specific monitoring
tasks relating to supplemental
monitoring. The plan should be a
detailed description of the monitoring
tasks set forth in the outline, including
sampling protocols, monitoring site
locations, monitoring frequency.
monitoring equipment, analytical
methods, etc.7 The plan shall also state
what substances will be monitored; if a
more detailed list is available at this
stage than when the outline was
prepared, such additional detail shall be
provided.
When sponors have not identified the
specific unregulated substances which
•Where monitoring activities, e g . baseline or
construction monitoring, should be initiated prior to
completion of the plan, the outline should indicate
when this monitoring should begin.
7 Sponsors may provide in their outlines details
on any or all aspects of environmental monitoring
that are at a level of specificity not reoutred in an
outline but appropriate for a plan. This is solely at
the sponsors' discretion and will not affect the
Corporation's acceptability determination regarding
the outline.
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Federal Register / Vol. 48, No. 64 / Friday, April 1, 1983 / Notices
14111
may be of significant environmental or
health concern, the sponsors shall
provide in the outline and plan
qualitative assessments of the classes of
substances (e.g., phenols, polynuclear
aromatic hydrocarbons, organic sulfur
compounds), likely to be present and the
method(s) by which the specific
substances will be identified.
In both the outline and plan, sponsors
shall provide (as appendices or by
separate submission) sufficient
background information on their project
to enable the consulting agencies to
meaningfully evaluate the outline and
the plan. This information should
include an overall process description, a
process block flow diagram, design
performance of environmental control
systems, plot plans and layouts and a
detailed site description; it shall also
include studies, reports, data, etc., which
are used to support statements and
decisions by sponsors in the outline and
plan.
Neither an outline nor a plan need be
in any particular format. Sponsors can
tailor the format of their outline and
plan according to their own specific
project reporting systems, but
consideration should be given to the
comments of the consulting agencies
regarding format.
B. Supplemental Monitoring
"Supplemental monitoring," as used
herein, refers to any monitoring that is
not required by the terms and conditions
of permits and approvals or other
regulatory obligations, i.e., compliance
monitoring. Supplemental monitoring
should be performed by sponsors when
it nan produce environmental and health
data which are relevant to project
replication, i.e., data which are relevant
to comparable facilites which may be
built in the future. The need for, and
duration of, supplemental monitoring
will be detm-mined on a project-by-
projer.t basis, with consideration being
given lo meeting the following broad
^oals:
• Characterizing and identifying
unregulated substances, such as those
trace metals and polynuclear aramatic
hydrocarbons (PAHs) which are
suspected of causing carcinogenesis,
mutagenesis, teratogenesis. reproductive
effects, other systemic disorders and
environmental effects. 8In developing
'Th? Corporation views unregulated substances
.is including those substance!) not presently
I'^'ulateil under any law and those which may be
r>'^ulatud under one law but not another. For
••t.imple. a substance may be regulated under the
Occupational Safety and Health Act but not
»".;uliited under the Clean Water Act; monitoring for
'i.i.h a substance in the water would be a
supplrmrntiil monitoring requirement, but in th«
their outline a:)d plan, sponsors are
encouraged to consider a two-phased
approach to identify tnd characieri2e
unregulated substances. The psurpose of
the first phase is to monitor until
sufficient data have been collected to
statistically establish an emissions
baseline. The purpose of the second
phase is to limit ths scope of monitoring
in a manner which will provide data on
those substances which are of
significant environmental or health
concern, while reducing monitoring
costs.
8 Identifying and characterizing
regulated substances or performing
baseline monitoring when not required
pursuant to permits. 9
• Assessing the health risks
associated with occupational exposure
by conducting comprehensive medical
surveillance programs of workers and
establishing worker registries.
In addition, sponsors should consider
the following points in developing the
supplemental monitoring tasks in their
outline and plan:
• The Corporation does not expect
supplemental monitoring to include
monitoring which is relevant essentially
to a specific project as a specific site
(e.g., monitoring project impact on the
local wildlife population) unless such
monitoring has broader applicability to
project replication. However, such site-
specific monitoring if required by permit
would be included as compliance
monitoring in the monitoring outline and
plan.
• The Corporation does not expect
sponsors to perform off-site
supplemental monitoring with regard to
solid and hazardous wastes shipped to
facilities owned by others because the
receiver is subject to its own monitoring
obligations.
• The Corporation does not expect
sponsors to perform supplemental
monitoring with regard to wastewater
after its discharge to publicly owned
treatment facilities (POTWs) because
these facilities are subject to the
monitoring requirements of their own
National Pollutant Discharge
Elimination System (NPDES) permits.
workplace would be a "compliance monitoring"
requirement.
" When modeling of emissions indicates that
concentrations may fall below those levels for
triggering permit-mandated monitoring (notably for
prei ention of significant detenoratio (PSD) review),
monitoring to determine the actual level of
emissions (vis-a-vis calculated levelsl of regulated
substances should be performed where necessary to
develop a data base relevant to project reolication.
It 13 expected that such monitoring would be of
short duration.
C. Substantive Monitoring Areas
1. General. Sponsors shall monitor
during all stages of a project's life-
cycle—pre-construction (baseline),
construction, operation and post-
operation (shutdown of facility and
reclamation of site).10 In monitoring
during each of these stages, three
generic areas of environmental
monitoring—source, ambient, and health
and safety monitoring—shall be
performed as appropriate to that stage.
Other monitoring, such as ecological
monitoring, as well as lexicological
testing may also be required on a case-
by-case basis. In general, monitoring
must be conducted during start-up,
„.' . ;Jown, and upset conditions, as well
as during steady-state operati^a of the
project.
2. Source Monitoring. Source
monitoring refers to the moiiuoririg of air
emissions (including fugitive emissions),
water effluents and solid wastes as they
are released from a project's vent.
stacks, pipes, etc., as well as to the
efficiency of environmental control
systems.11
• For air emission source monitoring,
sponsors shall monitor for regulated
substances, including those under
applicable New Source Performance
Standards, National Emission Standards
for Hazardous Air Pollutants
(NESHAPs), etc., as well for unregulated
substances (including those adsorbed on
particulates) which may be present at
concentrations of significant
environmental or health concern.
• For water effluent source
monitoring, including underground
releases and releases into POTVVs,
sponsors shall monitor for regulated
substances including those in NPDES
permits or specified by EPA "consent
decrees", etc., as well as for unregulated
substances which may be present at
concentrations of significant
environmental or health concern.
• For solid waste monitoring,
sponsors shall monitor these wastes -
pursuant to the requirements of the
Resource Conservation and Recovery
Act as well as monitor for unregulated
substances which may be present at
concentrations of significant
environmental or health concern. (See
Section V.B regarding monitoring of
solid and hazardous wastes once they
are shipped off-site).
'"While compliance monitoring occurs throui^hout
a project's life-cycle, supplemental monitoring is
pimr.ipally applicable during the operation stage.
" It is expected that sponsors will monitor the
efficiency of environmental control systems for all
source monitoring activities: however, sponsors are
not expected to provide proprietary operation
condition information pursuant to the plan.
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Federal Register / Vol. 48. No. 64 / Friday. April 1. 1983 / Notices
3. Ambient Monitoring. Ambient
monitoring refers to monitoring the
unconfined environment—the air, water,
and land—in the vicinity of a project.
Sponsors shall monitor in the
unconfined environment the level of
substances found in the facility's
emissions and discharges.
• For ambient air monitoring,
sponsors shall monitor, as applicable by
permit, those regulated pollutants
identified in EPA's PSD Regulations and
NESHAPs, etc.. as well as for
unregulated substances which may be
present at concentrations of significant
environmental or health concern.
Monitoring of possible public nuisances,
such as odor, should also be considered.
• Where the project will be
discharging into surface waters,
sponsors shall monitor for regulated
water quality parameters (chemical and
biological orygen demand, total
suspended solids, etc.), as well as for
unregulated substances which may be
present at concentrations of significant
environmental or health concern.
• Where substances have the
potential to impact groundwater,
groundwater monitoring shall be
conducted to identify contamination
from leachates, discharges, or .
underground injection and shall include
monitoring for regulated substances
listed under the Safe Drinking Water
Act, etc., as well as for unregulated
substances which may be present at
concentrations of environmental or
health concern. —
• Where substances have the
potential to contaminate the soil, soils
shall be monitored for regulated and
unregulated substances.
4. Health and Safety Monitoring.
Health and safety monitoring 12 refers
both to monitoring workers' exposure to
potentially hazardous in-plant emissions
and/or conditions associated with the
project and to the development of
worker registries. The sponsor shall
characterize and identify work-related
exposures to specific substances or
conditions in the facility during routine
work, maintenance, repair and sampling
activities throughout construction,
operation and decommissioning of the
facility.
Ail sponsors shall develop and
maintain worker registries, to
encompass collecting and storing
information on medical and work
histories, physical examinations, and
industrial hygiene exposure records.
Registries should provide information to
be used to determine if impacts
identified in groups of workers are
related to various substances or
conditions with which workers had been
in contact at synthetic fuels facilities.
What the registries cover will be
determined on a case-by-case basis
depending on the health concerns
associated with the facility. Sponsors
shall develop, in consultation with' the
consulting agencies, formats and
protocols for the registries which are
acceptable to the Corporation, which
shall include the method by which the
confidentiality of workers' identity will
be protected.
5. Other Monitoring. It may be
appropriate for sponsors to perform
ecological or other monitoring as well as
toxicological testing (including
biomonitoring) in some situations.
Ecological monitoring should be
performed where substances from the
facility have the potential for impacting
terrestrial and aquatic species: however,
for the purposes of Section 131(e), such
monitoring should be included only if
the collection of such data would be
needed to characterize and identify
areas of concern and develop an
information base for the mitigation of
problems associated with the replication
of synthetic fuels plants.
Although not generally considered as
a part of monitoring (since it determines
dose-response relationships and relative
toxicities of substances rather than
measuring concentrations), toxicological
testing should be performed where there
is potential for significant human
exposure to unregulated substances of
concern with unknown or uncertain
toxicities.IJ
D. Quality Assurance/Quality Control
The outline and plan shall indicate
what quality assurance/quality control
(QA/QC) measures will be taksn to
assure that environmental monitoring
data produced will be sound. The
outline should briefly indicate the
sponsors proposed QA/QC program
while the plan should establish specific
requirements of a comprehensive QA/
QC program."
"Health and safety monitoring as used herein
includes industrial mgiene monitoring and medical
survpillance monitoring.
13 Sponsors should be aware that EPA could
specify toxicologic testing as part of its
Premanufacrure Notification reQuirement under the
Toxic Substances Control Act (TSCA). and are
urged to contact EPA early reg=
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Federal Register / Vol. 48, No. 6-.- / Friday, April 1, 1983 / Notices
14113
data for the three immediately preceding
months, include a characterization of
the unregulated substances of
environmental and health concern.
—Assess the project's permit
compliance status.
—Identify and characterize the
presence of significant levels of
unregulated substances and correlate it
to the operating conditions of the facility
and environmental control performance.
—Discuss the performance of
environmental control systems.
—Identify potential problem areas
encountered throughout the quarter, e.g.,
problems with monitoring techniques/
procedures, sampling, quality control,
etc. and propose preliminary solutions.
—Recommend modification or
deletion of monitoring tasks not yielding
useful data, including the basis for the
sponsors' recommendation.
• Annual Reports.
Annual reports shall:
—Summarize and analyze the
monitoring data previously collected
and the monthly, quarterly, and annual
reports previously submitted. The
summary and analysis shall include
characterizations of unregulated
substances which have been found in
concentrations of significant
environmental and health concern, and
the identification of trends and patterns
in the data, including data available in
worker registries.
—Based upon monitoring data and the
reports which have been submitted,
indicate if there are any actual or
potential environmental or health
impacts.
—Recommend modification, deletion
or addition of monitoring tasks,
including the basis for the sponsors'
recommendation.
—Indicate whether any of the problem
areas identified in the monthly or
quarterly reports have been resolved
and, if not, what additional measures
should be taken. Copies of all annual
compliance reports or analyses
submitted to regulatory agencies should
also be included in the annual report.
VI. Confidential Information
The contents of all monitoring outlines
and plans (including drafts and
revisions) submitted by sponsors will be
publicly available as will all formal
written comments of the consulting
agencies on the outlines and plans.16
"Copies of all Initial and revised monitoring
outlines and plans as well as written consulting
agency comments thereon will be available for
review in the Corporation's Public Reading Room.
Consulting agencies may also wish to make these
documents available to the public as they deem
appropriate
It is expected that all monitoring data,
data summares, data analyses, reports,
etc., provided to the Corporation by the
sponsors will not be proprietary or
otherwise confidential business
information. Any information which is
properly designated by the sponsors as
confidential fin accordance with the
Corporation's Guidelines on Disclosure
and Confidentiality) will not be
provided to federal or state agencies
except as authorized by law and unless
its confidentiality is protected.
Public information requests will be
handled in accordance with the
Corporation's Guidelines on Disclosure
and Confidentiality.
VII. Monitoring Review Committee
A. Membership; Meetings
Each financial assistance contract will
establish a Monitoring Review
Committee (the "Committee") consisting
of representatives of the sponsors, the
consulting agencies, and the
Corporation. The Corporation
representative will act as chairperson
for the Committee. The Corporation will
convene meetings of each Committee at
least once per year.
B, Functions
1. Data Review. Each Monitoring
Review Committee will assess the
sponsors' environmental monitoring
data, including the monthly, quarterly
and annual reports. The main purpose of
data review is to determine if there are
any significant findings among the data,
e.g., data points of excessively high
readings or if there are significant trends
or patterns in pollutant releases from the
project which could result in significant
health or environmental impacts in the
future.
2. Modification of Monitoring
Requirements. Based on the
Committee's ongoing review of the
monitoring data and the monthly,
quarterly, and annual reports, members
of the Committee can recommend to the
Corporation representative that the
sponsors discontinue, modify or add
monitoring tasks, substitute new
analytical techniques or instrumentation
as they are developed, or change the
format of the above reports. The
Corporation, after consultation with the
sponsors, will authorize such changes if
appropriate. (Modification of sponsors'
monitoring plans by the Corporation
shall have no effect on the sponsors'
responsibility to monitor under federal,
state, and local requirements.) Absent
unusual circumstances, the Corporation
will not require additional monitoring
beyond that supplemental monitoring
specified in the plan unless the costs of
the additional requirements have been,
or are being, offset by the elimination of
comparable costs.
Monitoring plans should have
flexibility so that when sufficient data
have been obtained to establish a
definitive baseline or when the
monitoring data indicate that certain
monitoring tasks are found to be
relatively unimportant, they can be
reduced or eliminated, and, conversely,
when monitoring data suggest that
certain tasks take on incresasing
importance monitoring can be
expanded. Thus, if an unregulated
substance in the work environment is
consistently absent from monitoring
Gait., monitoring for it should be reduced
in scope or terminated; conversely,
where new data in the scientific
literature indicating that a particular
substance may be of increased health or
environmental concern, monitoring shall
be expanded under the limitation set
forth above."
VIII. Amendments to Guidelines
Amendments to these Guidelines may
be authorized in writing by the
Corporation. All sponsors with projects.
before the Corporation at the time any
amendment is made will be notified
immediately of such amendment. Copies
of these Guidelines, as amended, will be
available in the Corporation's Public
Reading Room.
Dated: March 29,1983.
Jimmie R. Bowden,
Executive Vice President, U.S. Synthetic
Fuels Corporation,
[FR Doc. 83-8505 Filed 3-31-83: 8:45 am)
BILLING CODE OOOO~00-M
17 Where production, process or pollution control
or feedstock changes occur that may reasonably be
expected to contribute to affecting the emission of
unregulated substances of environmental and health
concern, monitoring tasks should be renewed or
extended accordingly.
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TECHNICAL REPORT DATA
(Please read /HUructiuns on the reverse before completing)
1 REPORT NO. 2
EPA-600/8-83-027
4 TITLE AND SUBTITLE
Environmental Monitoring Reference Manual for
Synthetic Fuels Facilities
7 AUTMOR(S)
D. Bruce Henschel (IERL-RTP) and James T.
Stemmle {OEPERj {Project Officers)
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Industrial Environmental Research Laboratory (EPA),
Research Triangle Park, NC 27711; and Office of
Environmental Processes and Effects Research
(EPA), Washington, DC 20460
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
3. RECIPIENT'S ACCESSION- NO.
6. REPORT DATE
Julv 1983
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT N
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
NA
13. TYPE OF REPORT AND PERIOD COVEREI
Users Manual; 9/82-5/83
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES Tnis document supersedes and cancels, "Interim Source Monitor-
ing Reference Manual for the Synthetic Fuels Industry, " IERL-RTP- 1359a. IERL-
RTP support bv Radian Corp. under contract 68-02-3171. Tasks 69 and 77.
Fuels Corporation (SFC), and environmental reviewers in developing and reviewing
plans covering source and ambient monitoring around coal-, oil shale-, and tar
sand-based synfuels plants, consistent with the Energy Security Act. The Act, which
established the SFC, specifies that applicants for SFC financial assistance must
develop an acceptable plan for environmental monitoring of the construction and
operation of the proposed synthetic fuels facilities, following consultation with the
EPA and other agencies. The manual does not provide rigorous specifications for an
acceptable monitoring plan. Rather, it describes approaches to consider and issues
to address in developing a monitoring plan (or an outline of a plan). The exact con-
tent of the plan or outline for a specific facility would depend on conditions associatec
with that plant.
17. KEY WORDS AND DOCUMENT ANALYSIS
a DESCRIPTORS
Pollution
Fossil Fuels
Monitors
Coal
Oil Shale
Bituminous Sands
13. DISTRIBUTION STATEMENT
Release to Public
b. IDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Synthetic Fuels
19 SECURITY CLASS fThis Report)
Unclassified
20 SECURITY CLASS (This page}
Unclassified
c. COSATI 1 icId/Group
13 B
21D
14G
08G
21. NO. OF PAGES
582
22. PRICE
EPA Form 2220-1 (t-73)
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