United States
Environmental Protection
Agency
Office of
Reseach and
Development
Industrial Environmental Research EPA-600/7-77-009
Laboratory
Research Triangle Park. North Carolina 27/11 January 1977
PROCEDURES MANUAL FOR
ENVIRONMENTAL
ASSESSMENT OF
FLUIDIZED-BED
COMBUSTION PROCESSES
Interagency
Energy-Environment
Research and Development
Program Report
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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 seven series.
These seven broad categories 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 seven 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
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from
the effort funded under the 17-agency Federal Energy/Environment
Research and Development Program. 'These studies relate to EPA's
mission to protect the public health and welfare from adverse effects
of pollutants associated with energy systems. The goal of the Program
is to assure the rapid development of domestic energy supplies in an
environmentally—compatible manner by providing the necessary
environmental data and control technology. Investigations include
analyses of the transport of; energy-related pollutants and their health
and ecological effects; assessments of, and development of, control
technologies for energy systems; and integrated assessments of a wide
range of energy-related environmental issues.
RE VIEW NOTICE
This report has been reviewed by the participating Federal
Agencies, and approved for publication. Approval does riot
signify that the contents necessarily reflect the views and
policies of the Government, nor does mention of trade names
or commercial products constitute endorsement or recommen-
dation for use.
This document is available to the public through the National Technical
Information Service, Springfield, Virginia 22161.
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EPA-600/7-77-009
January 1977
PROCEDURES MANUAL FOR
ENVIRONMENTAL ASSESSMENT OF
FLUIDIZED-BED COMBUSTION PROCESSES
by
H.I. Abelson and W.A. Lowenbach
The Mitre Corporation
Metrek Division
McLean, Virginia 22101
Contract No. 68-02-1859, Task 7
Program Element No. EHB536
EPA Project Officer: W. B. Kuykendal
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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ABSTRACT
This documeri't describes recommended procedures for sampling and analysis,
for eventual use by source testing, contractors, in support of the environ-
mental assessment of fLuidiz'gd-bed cdmbustidn (FB'c) technology< A phased
strategy, involving two separate arid' distinct levels of sampling and analysis
is" empidye'd'. Proposed gene'ric units and corresponding case study units
fdr fche following process cdnf iguf atfidns are addressed:
I. Atmospheric FBC tff Goal.
II. Pressurized,- Combiried Cycle FBC of Coal.
III. Pressurized Combined Cycle FBC of Coal (Adiabatic Combu^to'f) .-
IV. Chemically Active Fluid Bed (CAFB) Gasification of Resi-d'u'a'i 0'il.-
in addition, a compendium of method options describing the sampling and
analytical state-6f-the aft is presented.
This report was submitted in fulfillment o'f Task Order No. 7 of Contract
No. 6v80'0'2-i8:59' by the MITRE Corporation, under the sponsorship of the U.S;
Ehviforimen'tal Protect ion Age'ncy. This report co'vefs a period from Se'ptembef
1975 to November 1976,- arid work was completed as of November 19'76;
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CONTENTS
Abstract ii
Figures vi
Tables viii
Acknowledgement xi
Introduction 1
Chapter 1 - FBC Background 4
Process Descriptions and Flow Sheets 4
General Information 4
Category I - Atmospheric FBC of Coal .... 6
Generic 6
Case study - PER (Alexandria) Unit .... 9
Category II - Pressurized, Combined Cycle
FBC of Coal 9
Generic 9
Case Study - Exxon Miniplant 12
Category III - Pressurized, Combined Cycle
FBC of Coal (adiabatic combustor) 12
Generic 12
Case study - Combustion Power Co. PDU-400 .15
Category IV - Chemically Active Fluid Bed
(CAFB) Gasification of Residual Oil ... .15
Generic 15
Case study - Esso, Ltd., CAF B UNIT
(Abingdon, U.K.) 15
Sorbent Regeneration and Sulfur Recovery . .19
Introduction 19
Atmospheric FBC Systems (Category I) . . .19
Pressurized FBC Systems (Categories II
and III) 21
CAFB Systems (Category IV) 21
FBC System Operating Characteristics . . . .24
Introduction 24
Fuel Types 24
Sorbent Types 24
Modes of Operation 25
Primary FBC System Variables 25
Combustor Steam Tube Arrangement 27
111
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Chapter 2 - Sampling and Analysis Program
Strategy 29
Introduction ..... 29
A Phased Approach to Sampling and Analysis . . 29
Process Development and Environmental
Assessment 30
Selection of FBC System Streams for Sampling . 36
Generic units 36
Case study units ; 40
Physical Characteristics of Sampled Streams . . 40
Areas of Analysis ; . -. . . 45
Introduction 45
Organic compounds 45
Inorganic gases . 50
Trace elements 51
Anions 51
Standard water analysis 51
Physical characterization of solids ..... 53
Bioassay 53
Chapter 3 - Recommended Sampling and Analysis
Procedures for FBC Processes 54
Introduction 54
General Sampling Considerations 54
Pre-test procedures 54
Sample size 55
Sample handling 55
Recommended Sampling Procedures for Generic
Units 56
Introduction 56
Particulate sampling . . . -. 56
Gassampling 60
Liquid sampling 61
Solid sampling 65
Air-borne fugitive sampling 67
Flow measurement 102
Recommended Sampling Procedures for Case
Study Units 103
Recommended Analytical Procedures 110
Introduction 110
Inorganic gas analysis Ill
Organic analysis 124
Elemental analysis 142
Anion analysis 168
Standard water analysis 180
Fuel analysis 190
Physical characterization of solids 198
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Chapter 4 - Procedures for Assessment of Water-
Borne Fugitives from FBC Processes • 202
Introduction . 202
Generation and Transport of Leachates in the
Environment 202
Sources of Water Borne Fugitives from Generic
FBC Processes 204
Leaching Mechanisms and Transport Modeling . .206
Survey of Leachate Testing Techniques 210
Recommended Procedures for Level 1 Assessment .244
Recommended Procedures for Level 2 Assessment .244
Chapter 5 - Sampling and Analysis Costs 246
Introduction 246
Sampling Cost Data 247
Analytical Cost Data 249
Additional Costs 255
Assessment Costs for Generic FBC Processes . .255
References 257
Appendix - Compendium of Sampling and Analytical
Method Options Al
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LIST OF FIGURES
Figure Number Page
1 Generic process flow sheet for Category I -
Atmospheric FBC of coal 7
2 Generic coal preparation and sorbent
preparation operations 8
3 Case study unit I - Pope, Evans and Robbins
(Alexandria, VA) test system schematic 10
4 Generic process flow sheet for Category II -
Pressurized, combined cycle FBC of coal 11
5 Case study unit II - EXXON Miniplant schematic 13
6 Generic process flow sheet for Category III -
Pressurized, combined cycle FBC of coal
(adiabatic combustor) 14
7 Case study unit III - Combustion Power Company
PDU-400 pilot plant schematic 16
8 Generic process flow sheet for Category IV -
CAFB gasification of residual oil 17
9 Case study unit IV - ESSO (Abindgon U.K.)
.CAFB pilot plant schematic 18
10 Generic sorbent regeneration and sulfur recovery
operations for atmospheric FBC systems 20
11 Generic sorbent regeneration and sulfur recovery
operations for pressurized FBC systems 22
12 Generic sorbent regeneration and sulfur recovery
operations for CAFB residual oil gasification systems . . 23
13 Sampling and analysis - Progression from pilot
to demonstration phase 37
VI
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LIST OF FIGURES (concluded)
Figure Number Page
14 Influents and effluents - generic FBC processes 42
15 Areas of analysis - solid samples 46
16 Areas of analysis - liquid samples 47
17 Areas of analysis - gas samples 48
18 Areas of analysis - particulate samples 49
19 Occurrence frequency of elements in 13 raw coals as
determined by spark-source mass spectrometry 52
20 Concentration range of elements in 13 raw coals
analyzed by spark-source mass spectrometry 52
21 Sample handling and transfer - SASS nozzle,
probe, cyclones, and filter 58
22 Sample handling and transfer - SASS nozzle,
probe, cyclones, and filter (continued) 59
23 Sample handling and transfer - SASS XAD-2 Module .... 63
24 Sample handling and transfer - SASS impingers 64
25 Overall analytical scheme - Level 1 114
26 Overall analytical scheme - Level 2 116
27 Level 1 organic analysis scheme 125
28 Level 1 inorganic analysis scheme 143
29 Sample preparation for Level 1 elemental analysis . . . .144
30 Sample preparation and analysis of Hg, Sb, and
As - Level 1 146
31 Inorganic compound characterization scheme -
Level 2 178
32 Schematic of infiltration/runoff problem 203
33 Analytical unit cost data - Level 1 250
34 Analytical unit cost data - Level 2 252
VII
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LIST OF TABLES
Table Number Page
1 Stream Designations for Generic Units
(Categories I through IV) 5
2 Example Values of Several Prime FBC System
Variables 28
3 Characteristics of Level 1 and Level 2
Sampling and Analysis 31
4 Phases of Process Evolution - Characteristics
and Sampling/Analysis Strategy 35
5 Stream Selection for Sampling and Analysis
(Process Categories I through IV) 39
6 Non-Selected Stream Summary 41
7 Physical Characteristics of Sampled Streams 43
8 Sample Size Requirements - Level 1 55
9 SASS Train Impinger System Reagents 62
10 Preservation of Liquid/Slurry Samples 66
11 Summary of Recommended Sampling Procedures for
Generic FBC Processes (Categories I through IV) .... 70
12 Summary of Recommended Sampling Procedures for Case
Study Unit I (PER-Alexandria, Va .) 104
13 Summary of Recommended Sampling Procedures for Case
Study Unit II (EXXON Miniplant) 106
14 Summary of Recommended Sampling Procedures for Case
Study Unit III (CPC-PDU-400) 108
Vlll
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LIST OF TABLES (continued)
Table Number Page
15 Summary of Recommended Procedures for Inorganic Gas
Analysis 118
16 Summary of Recommended Procedures for Organic
Analysis 130
17 Summary of Recommended Procedures for Elemental
Analysis 150
18 Summary of Recommended Procedures for Anion
Analysis 170
19 Summary of Recommended Procedures for Standard
Water Analysis 182
20 Summary of Recommended Procedures for Fuel Analysis . . 192
21 Summary of Recommended Procedures for Physical
Characterization of Solids 200
22 Summary of Generic FBC Streams with Potential
Leaching Impact 207
23 Summary of Shake Test Techniques 212
24 The Saturation Test 216
25 Summary of Column Test Techniques 218
26 Summary of Field Test Cell Techniques 226
27 Summary of Current and Past Efforts in Leachate.
Testing 232
28 Sampling Cost Data 248
29 Site Preparation Cost Data 249
30 Analytical Cost Data 254
31 Total Assessment Costs for Generic FBC Processes .... 256
IX
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LIST OF TABLES (concluded)
Table Number Page
A-l Method Options for Particulate Sampling A-2
A-2 Method Options for Gas Sampling A-24
A-3 Method Options for Liquid Sampling A-64
A-4 Method Options for Solid Sampling A-68
A-5 Method Options for Air-borne Fugitive Sampling A-76
A-6 Method Options for Inorganic Gas Analysis A-82
A-7 Method Options for Organic Analysis A-90
A-8 Method Options for Elemental Analysis - Spark
Source Mass Spectroraetry A-98
A-9 Method Options for Elemental Analysis - Isotope
Dilution Mass Spectroscopy A-100
A-10 Method Options for Elemental Analysis - Neutron
Activation Analysis A-102
A-ll Method Options for Elemental Analysis - Instru-
mental Photon Activation Analysis A-104
A-l2 Method Options for Elemental Analysis - X-ray
Fluorescence A-106
A-13 Method Options for Elemental Analysis - Proton
Induced X-ray Analysis A-l 10
A-14 Method Options for Elemental Analysis - Optical
Emission Spectroscopy A-116
A-15 Method Options for Elemental Analysis - Atomic
Absorbance, Atomic Fluorescence, Atomic Emission . . . .A-l18
A-16 Method Options for Anion Analysis A-130
A-17 Method Options for Standard Water Analysis A-134
A-18 Method Options for Fuel Analysis A-138
A-19 Method Options for Physical Characterization of
Solids A-142
A-20 Method Options for Flow Measurement A-148
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ACKNOWLEDGMENTS
This work was conducted under the technical direction of Mr. William
Kuykendal and administrative direction of Dr. L. Johnson, Project Officer at
EPA's Industrial Environmental Research Laboratory, Research Triangle Park,
North Carolina. The Environmental Planning and Engineering Department,
METREK Division of The MITRE Corporation, McLean, Virginia, was responsible
for the performance of this task. Dr. H. I. Abelson was the Project Manager.
Special credit is given to Mssrs. J. A. King, D. Martin, J. S. Gordon
and Dr. H. Mahar of MITRE as well as to Mr. R. Tussey of Kenvirons, Inc.,
Frankfort, Kentucky, for their valuable assistance in preparing this document.
Acknowledgement is also given to Mssrs. W. Kuykendal, D. B. Henschel, W.
Steen, J. A. Dorsey and Dr. R. M. Statnick of EPA-IERL-RTP for their many
helpful suggestions during the course of this effort as well as to Dr. J. M.
Allen of Battelle Columbus Laboratories and Dr. C. A. Flegal of TRW, Redondo
Beach, California, for their valuable comments and criticisms.
Finally, the many helpful suggestions from the following individuals
are greatly appreciated: Dr. N. Schomaker and Mr. D. Banning of EPA-MERL-
Cincinnati; Mr. R. Stone of Ralph Stone and Co., Inc., Los Angeles, California;
Dr. R. Hoke. and Mr. M. Nutkis of EXXON Research and Engineering, Linden, New
Jersey; Dr. J. Mahlock of USAGE, Vicksburg, Mississippi; Mr. R. Chapman of
EPA-IERL-Cincinnati, and, Drs. R. Rossi and J. Rossoff of The Aerospace
Corp., El Segundo, California.
XI
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INTRODUCTION
NATIONAL AND EPA FLUIDIZED-BED COMBUSTION PROGRAMS
Fluidized-bed combustion (FBC) is an available technology which, when
implemented on a commercial scale, can greatly increase the utility of
coal, including high-sulfur coals and low-rank or problem fuels, as an
environmentally acceptable source of energy. Therefore, a National FBC
Research, Development and Demonstration Program has in recent years been
instituted in the U.S. Energy Research and Development Administration. The
intent of this multi-agency government and industry co-sponsored program is
to advance FBC technology to a level of commercial acceptability such that
combustion equipment vendors can satisfy marketplace demand with equipment
that is capable of meeting user requirements and, at the same time, function
in an environmentally acceptable manner.
One of the roles of EPA in the National FBC Program involves the plan-
ning and management of a comprehensive program to environmentally character-
ize this developing energy technology through the acquisition of necessary
environmental data for all proposed FBC process configurations, over a full
range of feed parameters and operating/design variables. It is intended
that the data will be acquired on a suitable experimental scale such that
the environmental impact of future commercial units can be assessed, and on
a time schedule compatible with the hardware development schedule published
in the National FBC Plan (as well as with the plant construction schedules
on EPA's own oil gasification program). The need for a cost-and information-
effective sampling and analysis program for environmental data acquisition
has led to the generation of the present document.
OBJECTIVES AND SCOPE
The primary purpose of this document is to provide recommended proce-
dures for sampling and analysis, for eventual use by source testing con-
tractors, in support of the environmental assessment of FBC technology.
Four different process configurations or categories, each a candidate for
commercialization, are addressed in the present effort.
I. Atmospheric FBC of Coal
II. Pressurized, Combined Cycle FBC of Coal
III. Pressurized, Combined Cycle FBC of Coal (Adiabatic Combustor)
IV. Chemically Active Fluid Bed (CAFB) Gasification of Residual Oil
In each of these categories attention is focused on a proposed generic
process configuration which is intended to be representative of a future
-------
commercialized unit, (subject to our ability to forecast technological
developments). To enable the near term implementation of an environmental
assessment program for presently existing FBC facilities, procedures are, in
addition, specified for a selected case study unit in each category. Since
no commercial or demonstration units are presently in operation domestically
or abroad, case study selection is limited to pilot facilities.
To enable the recommendation of sampling and analysis procedures
appropriate to the environmental assessment of FBC technology, a comprehensive
survey and subsequent evaluation of applicable sampling and analytical
techniques, ranging from Federal Register methods through new techniques
presently under development, were performed. The data gathered during this
survey are included in the appendix of this document as a compendium of
applicable method options. This compendium serves to identify the current
sampling and analytical state-of-the-art.
To provide an environmental assessment program that is both cost-and
information-effective, a phased strategy involving two separate and distinct
levels of sampling and analysis is employed. A broad screening phase (Level
1) characterizes, in a semi-quantitative manner, the pollutant potential of
all influents and effluents of a process. The Level 1 effort is followed by
a second phase (Level 2), which is typified by the accurate, quantitative
identification of specific pollutant classes/species in specific streams and
designed on the basis of the Level 1 output. Two parallel sets of recommended
sampling and analytical procedures corresponding to both assessment phases
are therefore presented in this document. Estimates of assessment costs
for .each phase are also provided.
An "end^of-pipe" approach to sampling and analysis has been adopted
for the present effort; considerations relating to the transformation,
transport, and ultimate fate of pollutants discharged to the various media
are, in general, outside the scope of effort. As an exception, however,
coverage is given to methods for assessing the impact of leaching from FBC
solid residues.
ORGANIZATION OF DOCUMENT
This document has been divided into five chapters and an appendix.
The function of each document segment is discussed in the following para-
graphs .
The intent of Chapter 1 is twofold; to provide the reader with some
general background on fluidized-bed combustion technology and to describe
the four FBC process configurations under consideration. Flow sheets for
generic and case study units are presented and unit processes and streams
are identified. In addition, a discussion of the primary operating and
design variables associated with F?C systems, as well as the scope of this
document with respect to these variables, is provided.
Chapter 2 ds concerned with the overall strategy to be employed in
designing a sampling and analysis program for environmental assessment.
Specifically, the following topics are addressed: characteristics of
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the Level 1 - Level 2 phased approach; selection of FBC system streams
for sampling; physical conditions associated with selected streams (for case
study as well as generic units), and; areas of analysis to be addressed.
Chapter 3, comprising the "heart" of the document, presents recommended
procedures for multi-media sampling and analysis of the FBC processes under
consideration, for both the Level 1 and Level 2 efforts. The intent of this
chapter is to recommend and highlight procedures rather than to provide
detailed sets of instructions for sampling and analytical personnel to
follow. For convenient reference to the rather large volume of material
included, procedures have been summarized in tabular form.
Recommended analytical procedures are independent of process category
and, by in large, sample type (e.g., solid, liquid, etc.). Accordingly,
they are presented by analysis area (e.g., elemental analysis, organic
analysis, etc.).
Sampling procedures for generic units are identical in all process
categories (with some exceptions for the CAFB process) and are summarized
according to stream category. Analysis areas applicable to each of the
stream categories are listed so as to direct the reader to the appropriate
analytical procedures.
A separate summary of sampling procedures is provided on a stream-by-
stream basis for each case study unit. In many instances, procedures recom-
mended for the case study facilities are identical to their generic counter-
parts. Discussions of general sampling and analytical considerations are
also provided in this chapter.
Chapter 4 is concerned with methods to assess the impact of leaching
which can result from the subsurface disposal and outdoor storage of FBC
solid residues and feeds. A review of available methods for leachate
assessment, including shake, column, and field test cell techniques, as well
as a survey of current and past efforts in leachate/runoff testing are
provided. In addition, leachate testing procedures appropriate to the Level
1 and Level 2 efforts are recommended.
The intent of Chapter 5 is to provide a mechanism for estimating
assessment program implementation costs. Specifically, total cost estimates
for sampling and analysis of generic FBC processes are presented, both for
Level 1 and Level 2, using methodology and unit cost data developed previ-
ously by EPA contractors.
Finally, the appendix to the present document is a tabular compilation
of multi-media sampling and analytical method options, and their associated
characteristics, that may have application in the environmental assessment
of FBC and other technologies. The intent is to summarize pertinent charac-
teristics, advantages, and disadvantages of each method option. Key
references have, been included for each technique.
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CHAPTER 1
FBC BACKGROUND
INTRODUCTION
The intent of this chapter is to provide the reader with some general
background relating to fluidized-bed combustion technology as. well as to
describe the FBC process configurations under consideration, for which
sampling and' analytical procedures will be specified.
PROCESS: DESCRIPTIONS AND FLOW SHEETS
General Information
The generic process flow sheets presented here for the FBC configura-
tions under consideration represent projected commercialized processes.
Each flow sheet has; been divided into "operation blocks" and is- addressed
mainly to source assessment requirements. With few exceptions,. the opera-
tions are common to all four configurations. Differences i-n design and
operating conditions will be considered only insofar as they may affect
sampling and analysis procedures.
For convenience,, a common stream numbering system has been employed for
the four process configurations. A legend describing each numbered stream
is provided in Table 1. It should be noted that the generic process flow
sheets are not intended to be detailed. They depict only those streams and
operation blocks that are relevant to an environmental assessment or basic
to an overall process description. The same stream numbering system has
been employed; on the flow diagrams for the. case study units. There, however,
only those streams selected for sampling and analysis have been indicated by
number.
The selection of existing FBC facilities for case studies; was based on
sey.eral fac.tprs;;. representativeness of anticipated commercialized units,
size, accessibility,,, and; present operational status of the facilities. In
the case, of two, process categories (pressurized-adiabatic combustor and
GARB) ,a s,eilection-. was. Limited to a single facility. Brief discussions of the
four generic process configurations, a. comparison with the specific units
selected- for? case studies, and key references are provided in the following
sections:..
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TABLE 1. STREAM DESIGNATIONS FOR GENERIC UNITS (CATEGORIES I THRU IV)
STREAM NO.
DESIGNATION
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
Stack Gas
Particulate Removal Discard
Bed Solids Discard (not on CAFB unit)
Particulate Removal Discard—Regeneration Operations
Other Effluents from Regeneration and Sulfur Recovery Operations
Slowdowns from Steam Turbine Cycle
Slowdown from Water Treatment Operations
Product from Sulfur Recovery (Sulfur or Sulfuric Acid)
Raw Fuel to Preparation
Raw Sorbent to Preparation
Intake Water to Treatment
Air to Combustor/Gasifier
Air/Steam to Regenerator
Prepared Fuel Feed to Combustor/Gasifier
Prepared Fuel Feed to Regenerator (not present on CAFB unit)
Start-Up Fuel Feed
Prepared Sorbent Feed to Combustor/Gasifier
Bed Solids to Regenerator
Flue Gas to Particulate Removal (product fuel gas from CAFB gasifier)
Makeup Water to Steam Turbine Cycle
Recycle from Particulate Removal
Recycle from Regeneration and Sulfur Recovery
Gas to Gas Turbine Inlet (pressurized and pressurized-adiabatic
combustor units only)
Gas to Waste Heat Boiler (pressurized-adiabatic unit only)
Air to Steam Generator (CAFB unit only)
Fuel Gas Feed to Conventional Steam Generator (CAFB unit only)
Steam Generator Flue Gas to Particulate Removal (CAFB unit only)
Particulate Removal Discard (CAFB unit only)
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Category I - Atmospheric FBC of Coal
Generic—
A schematic flow sheet for a generic atmospheric FBC unit is presented
in Figure 1. Detailed process descriptions, developmental history, and
on-going as well as anticipated studies of atmospheric fluidized-bed combustion
are discussed in references 240 and 138.
Briefly, atmospheric fluidized-bed combustion occurs in the temperature
range of 788-843°C (1450-1550°F) with excess air values of 15-25 percent, at
normal atmospheric pressure. Steam produced in tube bundles and/or water
walls located within the fluidized region is converted to electrical energy
in a conventional steam turbine cycle.
Flue gas emissions of SC>2 are substantially reduced by having a lime-
stone sorbent serve as the non-combustible bed material. NO,, emissions
A.
are lower than EPA allowables due to the relatively low combustion temperatures.
Most of the ash present in the coal feed is normally elutriated from the bed
and must be removed (along with attrited limestone and other particulates)
prior to the release of flue gas to the atmosphere. Since this ash may be
high in carbon content, its direct disposal would result in a lowered
combustion efficiency. To remedy this problem, the atmospheric unit will
employ a carbon burnup cell (CBC), a separate high-temperature, high-excess-air
bed to which the collected ash is fed and combusted. Products from the CBC
would then undergo an additional particulate removal operation prior to flue
gas release to the atmosphere. Alternatively, reinjection of collected ash
back into the combustor may be adopted to improve combustion efficiency. It
should be noted that the "particulate removal operation" blocks indicated in
the generic flow sheets are general and may include combinations of cyclones,
filters, baghouses, precipitators, and other devices. Normally, a cyclone
or series of cyclones is employed initially to remove coarse particles from
the flue gas while final cleanup is accomplished by other methods.
The generic units under consideration are intended to be representa-
tive of anticipated commercialized systems and, as such, it is projected
that there will be on-site fuel preparation, sorbent preparation, and
sulfur recovery operations.
For the coal-fired systems (Categories I, II, and III), fuel prepara-
tion operations involve drying, size reduction,and size classification.
From an environmental point of view, these operations are similar to the
ones found in conventional combustion systems. Sorbent preparation for
the four process configurations consists of size reduction and classifica-
tion of raw. material and likewise poses no new problems.
Projected generic coal and sorbent preparation operations are shown
schematically in Figure 2. Raw coal undergoes a drying and size reduction
operation prior to injection into the combustor and regenerator. The over-
sized fraction from the coal size reduction operation is recycled back while
the undersized fraction and fines remain with the combustor/regenerator
-------
0
Figure 1. Generic process flow sheet for Category I—Atmospheric FBC of coal.
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oo
.0
C10/
CO;
DRY
AIR (CONTAINING COAL PARTICLES) COAL
\L
[NG
HEATED AIR
(HEAT RECOVERY]
'
COLLECTOR T0 MERGE WITH COMBUSTOR FLL
COLLECTED
COAL
DUST
COAL SIZE
^ REDUCTION AND
( 14 )
>r TO COMBUSTOR COAL FEEDER
SIZE X
CLASSIFICATION • ' \k /-^.
1
TO REGENERATOR COAL FEEDER
OVERSIZE UNDERSIZE FRACTION
FRACTION AND FINES
SORBENT
SIZE REDUCTION AND
SIZE
CLASSIFICATION
OVERSIZE UNDERSIZE
FRACTION FRACTION
^
TO COMBUSTOR (OR GASIFIER)
SORBENT FEEDER
Figure 2. Generic coal preparation and sorbent preparation operations.
-------
feed stream. An analogous situation occurs in the sorbent size reduction
operation, as shown in the figure. The air exiting the coal drier con-
tains entrained coal particles and is passed through a coal dust collector
prior to merging with the cotnbustor flue gas. The collected dust is
routed to the combustor/regenerator feed stream. For the CAFB process
(Category IV), maintaining the residual oil at a temperature suitable for
transport to the gasifier constitutes the only fuel preparation operation.
The coal and sorbent preparation operations as depicted in Figure 2 have
no effluent waste streams associated with them.
It is anticipated that natural gas, propane, and distillate fuels
will be employed for system start-up. No preparation operations are
associated with these fuels.
Sorbent regeneration and sulfur recovery operations will be discussed
in a later section.
Case Study - PER (Alexandria) Unit—
For FBC Category I, the Pope, Evans, and Robbins fluidized-bed module
(FBM) pilot test system at Alexandria, Virginia, has been chosen for a .
case study in accordance with the selection bases outlined earlier. A
schematic of this 0.5 MW unit is shown in Figure 3. Detailed descrip-
tions of the FBM along with test data are provided in references 1 and 3.
Major deviations from the Category I generic unit include the
absences of a sulfur recovery operation and steam turbine cycle (some
steam is fed to a water heater, condensed and recycled to the boiler;
the remainder is vented to the atmosphere). The regeneration operation
built in 1971 is presently decommissioned (a once-through system is used).
Coal size reduction is carried out at the facility while sorbent is pur-
chased pre-sized and stored on site.
Category II - Pressurized, Combined Cycle FBC of Coal
Generic—
A schematic flow sheet for a generic, pressurized, combined-cycle unit
is presented in Figure 4. Detailed process descriptions, developmental
history, and on-going as well as anticipated studies on pressurized FBC
units are discussed in references 108 and 177.
Combustion again occurs in a fluidized bed of sorbent, with excess air
ranges similar to those found in the atmospheric boiler and at temperatures
approximately 93°C (200°F) higher. Pressure within the combustor, however,
is maintained at a design value of 4 to 10 atmospheres, resulting in a
dramatic reduction in combustor size requirements and thus, combustor cost.
In addition to -the energy conversion achieved through a conventional steam
turbine cycle driven by steam produced in the bed tubes, the hot high-pressure
flue gas exiting from the combustor, after being cleansed of particulates,
-------
MULTI-CONE
DUST COLLECTOR
SALT WEIGH
HOPPER
"LARGE"DUST DROPS OUT
IN AIR HEATER
©
EXHAUST DUST SAMPLE POINT
EXIT GAS ••• i
<5
r \
I.D. FAN
REGENERATOR
(DECOMMISSIONED) ( 9
o O o o OO
oo o o oo
o o o o oo
o oo o oo
DUST TRANSPORT
SCREW
^=—>-TO WEIGHING
PREHEATED AIR
3 ) BED SOLIDS
LIMESTONE WEIGH
HOPPER
Figure 3. Case study unit I—Pope, Evans and Bobbins (Alexandria, VA) test system schematic.
-------
water
from various .
plant sources J
water
to various
plant locations
PRESSURIZED
. COMBUSTOR
PREPARATION
SORBENT REGENERATION
&
SULFUR RECOVERY
OPERATIONS
PREPARATION
0
Figure 4. Generic process flow sheet for Category II—Pressurized, combined cycle FBC of coal.
-------
is expanded through a gas turbine to generate additional power. The power
output of a typical combined-cycle unit is anticipated to be 80 percent
steam-turbine generated and 20 percent gas-turbine generated.
To maximize combustion efficiency, the larger ash particles removed by
the first stage cyclones are recycled to the combustor. Fuel and sorbent
preparation, the steam turbine cycle, and water treatment operations for the
pressurized unit are similar to corresponding operations for the atmospheric
FBC unit and require no further discussion. It is anticipated that dolomite
will be used as a sorbent in the pressurized FBC systems. Since fuel and
sorbent are injected into a pressurized combustion chamber (and regenerator),
feed operations must necessarily be more complex. Sorbent regeneration and
sulfur recovery operations will be considered in a later section.
Case Study - EXXON Miniplant—
For FBC Category II, the 630 kW Exxon R&E Miniplant, shown schematically
in Figure 5, has been selected for a case study. This continuous pilot
plant, which is based on Westinghouse specifications, is described in
reference 157.
Major deviations from the Category II generic unit include the absences
of a gas turbine (pressure reduction is accomplished in an orifice), a steam
turbine cycle (steam is condensed and recycled to boiler), and a sulfur
recovery operation. In addition, since feeds are purchased pre-sized and in
bags, no fuel and sorbent preparation operations are located on site. For
the generic unit, it is expected that coal will serve as both regenerator
fuel and main fuel. The Miniplant currently employs natural gas to fire the
regenerator.
Category III - Pressurized, Combined Cycle FBC of Coal (adiabatic combustor)
Generic—
A schematic flow sheet for a generic pressurized unit employing an
adiabatic combustor is presented in Figure 6. Detailed process descrip-
tions, developmental history, and on-going as well as anticipated studies of
this FBC configuration are discussed in references 68 and 69.
In contrast with the pressurized unit of Category II, there are no
steam generating tubes located within the combustor bed or walls. Tempera-
tures remain within the 816-982°C (1500-1800°F) range but are controlled by
means of high combustor air flows (around 300 percent excess air). A
commercial design operating pressure of 4 atmospheres is projected. The
higher air flow, lower pressure operation necessitates a combustor size
larger than that for Category II. Primary power is generated by a gas
turbine and secondary power by a low pressure steam turbine bottoming cycle.
In this case, however, steam is produced through gas turbine exhaust-heat
recovery in a waste heat boiler. Of the total power output, it is antici-
pated that 80 percent will be gas turbine-generated and 20 percent steam
turbine-generated, the reverse situation of Category II.
12
-------
COOLING
WATER
CITY
WATER
COAL&
LIMESTONE
FEED SUPPLY
COAL
LIMESTONE
& INJECTOR
AUXILIARY
AIR
COMPRESSOR
MAIN AIR
COMPRESSOR
LIQUID FUEL
STORAGE
Figure 5. Case study unit II—EXXON Miniplant schematic.
-------
PRESSURIZED
ADIABATIC
COMBUSTOR
0
01
f .
water from water to
various plant various plant
sources locations
SORBENT REGENERATION
&
SULFUR RECOVERY
OPERATIONS
©
Figure 6. Generic process flow sheet for Category Ill-Pressurized, combined cycle FBC of coal (adiabatic combustor).
-------
Other operations shown in the process flow sheet are similar to corre-
sponding ones for Categories I and II. Regeneration and sulfur recovery
operations will be discussed in a later section.
Case Study - Combustion Power Co. Process Development Unit (PDU-400)—
Combustion Power Company's PDU-400, the only presently existing facility
in Category III, has been, of necessity, selected for a case study. A
schematic of this 1 MW system is shown in Figure 7. Detailed descriptions
and test data may be found in references 68 and 69.
Major deviations from the Category III generic unit include the
absences of steam production (i.e., waste heat boiler and associated steam
turbine cycle) as well as regeneration and sulfur recovery operations. Coal
crushing is carried out at the facility while dolomite sorbent is purchased
pre-sized and stored on site.
Category IV - Chemically Active Fluid Bed (CAFB) Gasification of Residual
Oil
Generic—
The CAFB residual oil gasification process produces a clean, low-Btu
fuel gas for firing in a conventional boiler and is most applicable to the
electric utility industry as a retrofit to oil and gas-fired units. Energy
conversion occurs in a conventional steam turbine cycle. A schematic flow
sheet for a generic CAFB unit is shown in Figure 8. Detailed process
descriptions, developmental history, and on-going as well as anticipated
studies of CAFB systems are discussed in references 138 and 177.
Gasifier reactions occur in a fluidized bed of limestone sorbent at
atmospheric pressure, within a temperature range of 843-899°C (1550-1650°F) .
Air flow to the bed is 20 percent of the stoichiometric value. Prior to
firing in a conventional boiler, the low-sulfur product gas is cleansed of
particulates (with some particulate recycle to the gasifier). Additional
particulate removal operations are necessary on the flue gas exiting the
boiler. Residual oil must be maintained at a temperature (approximately
93°C) suitable for transport from storage to gasifier but requires no
additional preparation. Due to the high sulfide content of the bed solids,
discard of solids from the gasifier would be an environmentally unsound
practice and has been eliminated. The sorbent regeneration and sulfur
recovery operations will be discussed in a subsequent section.
Case Study - Esso, Ltd., CAFB Unit (Abingdon, U.K.)—
The Esso Abingdon unit, the only CAFB facility presently in existence,
has been, of necessity, selected for a case study. A process flow diagram
of this 0.29 MW-continuous pilot plant is shown in Figure 9. Descriptions
of the facility can be found in references 74 and 75.
15
-------
LOU PRESS.
BLOKER
OIL 0(
FUEL
1 00
PREHE
ECLIP
BUM
710
£
X
sJr^
FR ^1 1 '
^ ^S
Jr--*,
auio BCD'
COWUSTOR
CLEAN
MEDIA
LOM PRESS.
EXHAUST
-8
GRANULAR
FILTER
Za SAMPLED AT SAND BIN
SAMPLED AT BA6HOUSE
Figure 7. Case study unit III—Combustion Power Company PDU-400 pilot plant schematic.
-------
water water
from various to various
plant sources plant locations
STEAM GENERATOR
PARTICULATE
REMOVAL
OPERATIONS
TIONAL
STEAM
GENERATOR
. _^^. 30NVEN
CAFB
GASIFIER
SORBENT
REGENERATION
&
SULFUR RECOVERY
OPERATIONS
Figure 8. Generic process flow theet for category IV-CAFB gasification of residual oil
-------
oo
COMBUSTION AIR BLOWER
REGNERATOR AIR BLOWERS
OIL
METEB OTTFEED
PUMPS (3)
FUEL INJECTION
AIR (3)
PROPANE FOR
START-UP
GASIFIER AIR BLOWERS
Figure 9. Case study unit IV—Esso (Abingdon U.K.) CAFB pilot plant schematic.
-------
Major deviations from the Category IV generic unit include the absences
of a sulfur recovery operation (SOo-rich regenerator gas is released to the
atmosphere) and a steam turbine cycle. Gasifier product gas fires a
pressurized water boiler. The hot water is cooled by a secondary water
circuit and then returned to the boiler. Heat is rejected from the secondary
circuit by a cooling tower. Temperature control within the gasifier is
facilitated (independent of air/oil ratio) by the recycling of boiler flue
gas. Sorbent is purchased pre-sized, eliminating any preparatory operations.
SORBENT REGENERATION AND SULFUR RECOVERY
Introduction
Raw sorbent requirements and solids disposal difficulties can be
largely reduced by employing a regeneration process where sulfated sorbent
is withdrawn from the combustion bed, regenerated, and returned to the bed
for reuse. The S02 (or H2S)-rich gas produced in the regeneration process
is subsequently fed to a conventional sulfur recovery operation where liquid
sulfur or sulfuric acid is produced. Discussions of sorbent regeneration
processes and alternatives may be found in references 138 and 177. The "sorbent
regeneration and sulfur recovery operations" blocks shown in the generic
process flow sheets (Figures 1, 4, 6, 8) will be considered in more detail
in the following sections.
Atmospheric FBC Systems (Category I)
Employment of single-stage regeneration of limestone with subsequent
sulfur recovery in a commercial sulfuric acid plant is projected for commer-
cialized atmospheric FBC systems (i.e., Category I). A flow sheet of these
operations, again addressing mainly source assessment requirements, is shown
in Figure 10. Reference 275 provides descriptions and flow diagrams for the
commercialized contact type sulfuric acid process.
In brief, partially sulfated sorbent undergoes decomposition in reducing
gases at high temperature and atmospheric pressure:
CaSO. +
4
1900-2000°F
(1038-1093°C)
CaO
SO,
Reducing gases are produced by combustion of coal in the fluidized-bed
regenerator. The S02~rich regenerator off-gas is cleansed of particulates
prior to being fed to the acid plant. Tail gas from the acid production
process is recycled to the boiler combustion air supply.
As mentioned previously, the regeneration system on the PER Alexandria
unit is presently decommissioned and will not be considered further.
19
-------
TAIL GAS RECYCLE
REGENERATED SORBENT
1 (; ^
~l
CUMBUSTOK SORBENT*
CBC (^13^
REGENERATOR
S02RIC1
OFF-GAJ
(
i
•»
PARTICULATE
REMOVAL
OPERATIONS
Dl
SULFURIC
ACID
PLANT
IAIR & STEAM
1
DISCARD
©
COAL ASH DISCARD
FEED
PRODUCT
©
Figure 10. Generic sorbent regeneration and sulfur recovery operations for atmospheric FBC systems.
-------
Pressurized FBC Systems (Categories II and III)
Employment of the Westinghouse two-stage dolomite regeneration process
(see reference 177) with subsequent sulfur recovery in a conventional Claus
plant is projected for commercialized pressurized FBC systems (i.e.,
Categories II and III). A flow sheet of these operations is shown in
Figure 11. Reference 275 provides descriptions and flow diagrams for the
Claus sulfur production process.
Sulfated dolomite reacts with reducing gases at elevated pressure
0^8 atra) in the first stage fluid-bed regenerator to produce calcium sulfide:
CaS°4 + 4CO iTb^F CaS
r4H2o-i
4CO-
L. ^J
Reducing gases are produced by a conventional gasification of coal with
air and steam. The reduced solids are then fed to the second-stage fluid-
bed regenerator where they are reacted at high pressure (~12 atm) with steam
and CC>2 (obtained by stripping a flue gas side stream) to form calcium
carbonate.
CaS +
-co2 -|
_H20 J
CaC°3 + H2S
(593°C)
The l^S-rich off-gas is cleansed of particulates and fed to the Claus
plant. Tail gas from the sulfur recovery operation is recycled to the
combustor air supply.
CPC's pressurized-adiabatic CPU-400 unit, as noted earlier, does not
presently include a regeneration process. Exxon's Miniplant employs single-
stage, pressurized regeneration (fired by natural gas) with no subsequent
sulfur recovery. The SOo-rich off-gases are sent to a scrubber after
particulate removal and cooldown.
CAFB Systems (Category IV)
Employment of air-blown regeneration of limestone with subsequent
sulfur recovery in an Allied Chemical SC^ reduction plant is projected
for commercialized CAFB systems (i.e., Category IV). Figure 12 indicates
these operations. Reference 121 provides a description and flow diagram
of the Allied Chemical process.
Sulfided stone produced in the gasifier is fed to a fluid-bed regen-
erator where it is contacted with preheated air. Reactions at 1093°C (2000°F)
and atmospheric pressure result in the formation of calcium oxide, some calcium
sulfate, and a gas of about 8 to 10 percent (volume) SC^ which is cleansed
of particulates prior to entering the sulfur plant. The H2S-rich tail gas
21
-------
r>o
PRESSURIZED
COMBUSTOR
•»» TO GAS TURBINE
1st STAGE
REGENERATOR
2nd STAGE
REGENERATOR
COAL ASH DISCARD
FEED
C02 & STEAM
SORBENT RECYCLE
TAIL GAS RECYCLE
CLAUS
: SULFUR
PLANT
PRODUCT
Figure 11. Generic sorbent regeneration and sulfur recovery operations for pressurized FBC systems.
-------
LIMESTONE WATER
CAFB
GASIFIER
I , I
AIR
.(HEATED)
REGENERATOR
SORBEHT RECYCLE
GAS TO STACK
PRODUCT
SOLIDS DISCARD
Figure 12. Generic sorbent regeneration and sulfur recovery operations for CAFB residual oil gasification systems.
-------
from the sulfur recovery operation is sent to a scrubber before being
released to the atmosphere. Bed solids are discarded from the regenerator
since the sulfide content is relatively low at that point.
The Abingdon case study unit employs an air-blown limestone regeneration
system with no associated sulfur recovery operation. The sulfur-rich
regenerator off-gas, after being cleansed of particulates, is merged with
the boiler flue gas as shown in Figure 9. Solids are withdrawn from the
gasifier as well as from the regenerator.
FBC SYSTEM OPERATING CHARACTERISTICS
Introduction
This section presents a brief general discussion of the prime system
variables, modes of operation, fuel and sorbent types, and other character-
istics associated with FBC systems. In addition, the scope of the present
study in regard to certain of these characteristics is defined.
Fuel Types
The primary fuel of interest in atmospheric and pressurized FBC systems
is coal of all ranks and varieties including anthracite, bituminous, sub-
bituminous, and lignite. For the CAFB oil gasification process, petroleum
residual represents the primary fuel. In the coal-fired categories, secondary
fuels of interest are coke breeze, gasification char, and spent shale. In
certain plants, there is potential for use of supplemental fuels such as
combustible solid waste (municipal and industrial) as well as waste oil from
transportation and/or industrial sources. For purposes of the present
study, only coal and petroleum residual (for the CAFB process) will be
addressed as main fuels. It should also be noted that the sampling and
analytical procedures to be specified are insensitive to coal variety.
For those coal-fired plants employing sorbent regeneration, the potential
list of regenerator fuels includes coal, oil, and natural gas. Only coal
will be considered for the generic units addressed in this study.
For use in system startup, natural gas, propane, and distillate fuels
are expected to be employed for all process categories.
Sorbent Types
It is projected that commercialized atmospheric FBC systems will employ
calcitic limestone as a sorbent while dolomite (i.e., dolomitic limestone)
is planned for use in the pressurized FBC systems. Dolomite attrites more
rapidly than limestone but calcines readily to MgO CaC03 at temperatures
commonly found .in pressurized FBC. The use of limestone in pressurized
systems would require higher temperatures to achieve calcination and in
addition, limestone dust may erode gas turbine blades more rapidly.
24
-------
It is likely there will be considerable use of low quality limestone,
high in SiOo and other inert matter, since an economic incentive exists to
use stone local to a commercial plant site. Until a wider variety of stones
is systematically tested in FBC units, no statement can be made concerning
the impact of stone variety and quality on the effluents from an individual
plant.
Modes of Operation
Operating modes of FBC units will cover the range typical of existing
conventional boilers. These include:
1. Steady state;
2. Moderate increase in load;
3. Moderate decrease in load;
4. Rapid increase in load;
5. Rapid decrease in load;
6. .Startup from cold start; and
7. Shutdown sequence.
The scope of the present effort limits consideration to the steady-state
mode (within normal operating limits) and the moderate load increase/decrease
modes only. The latter are typical of utility systems where the boiler is
capable of rapid adjustments in steam delivery but turbine life considerations
limit load changes to _+! percent per minute. Under this rate of load change,
the system can be viewed as operating in a quasi-steady state. The rapid
increases/decrease modes are more typical of industrial process steam
generators or direct material heaters where a cyclic demand can occur in
certain industries.
Primary FBC System Variables
The following comprise the primary design/operating variables associated
with FBC systems:
Combustion temperature
Combustion pressure
Bed height
Fuel feed rate
Air flow rate
Sorbent feed rate
Superficial velocity
Ca/S mole ratio
During the sampling of FBC systems, values of the above items must be
recorded in order that the resulting environmental data may be related back
to the operating conditions of the process. Brief discussions of these
variables, including example values, are presented in the following paragraphs.
25
-------
Combustion Temperature—
The temperature in the combustor bed must meet the following requirements:
it must be sufficiently high to allow calcination of fresh sorbent in a flue
gas atmosphere and to allow sufficient coal burnup; it must be sufficiently
low to promote favorable SOV capture equilibria by lime. The- effect of
X
combustion pressure on bed temperature can be seen in the example values
that follow:
Atmospheric FBC - 788-843°C (1450 to 1550°F)
CAFB (Abingdon) - 1 atm: 849°C (1560°F)
Pressurized (Miniplant) - 10 atm : 954°C (1750°F)
Pressurized (BCURA) - 5 atm: 888-895°C (1630 to 1745°F)
Pressurized Adiabatic Combustor (CPC) - 4 atm: 781°C (1438°F)
Combustion Pressure—
Tests have indicated that increased combustion pressure enhances SO
X
absorption and burnup of reduced carbon species as well as reduction of NOX
emissions. These environmentally beneficial effects arise from chemical
equilibrium relationships and increased, gas reaction rates. The impacts of
pressurization on plant cost, component reliability, control requirements,
insurability, electricity cost and other factors of concern to- a power
company are controversial and must be resolved by demonstration plant
project operations.
Bed Height—
With commercially available fans and blowers for atmospheric systems,
static bed height is limited to about 3 feet (0.9 meters) (limestone) using
currently conceived air distribution grids. Two feet (.06 meters) is a
typical value. Excess bed depth, beyond actual requirements of coal combus-
tion and heat transfer, is to be avoided since this increases the fan power
drain with a resulting increase in boiler heat rate.
Bed expansion under load is a function of, among other things, the
design of the combustor internals (e.g., steam tube bundles). For the
generic pressurized FBC system, Westinghouse has specified expanded bed
depths of 12 feet (3.65 meters). At the Exxon Miniplant, expanded bed
depths of 3 to 7 meters have been used.
Fuel Feed Rate—
Fuel feed rate to the combustor correlates closely with heating value
of. the fuel and load on the unit. Rated and actual test values of fuel
feed rates are shown in Table 2.
Gombustor Air Flow Rate—
Air flow to the combustor correlates closely with load on the unit
and excess air level. Air used for pneumatic transport of solids usually
26
-------
comprises 6 to 7 percent of the total air flow. Rated and actual test
values of air flow rates are shown in Table 2.
Sorbent Feed Rate—
Sorbent feed rate to the combustor in the absence of sorbent regenera-
tion correlates closely with unit load, sorbent type (i.e., attrition rate),
and fuel sulfur content (i.e., Ca/S mole ratio). Rated and actual test
values of sorbent feed rates are shown in Table 2.
Superficial Velocity—
Design superficial velocity (U ) of gas in the fluid bed is a design
s
parameter impacting primarily on boiler size and cost, but also having
effects on bed sulfur retention and other environmental matters. Due to
elutriation, increasing the rated U generally increases the need for a
carbon burnup cell, but reduces the cost and floor space required by the
combustor. U is a major determinant of the smallest size particle that
can be retained in the bed, and the largest particle size capable of being
fluidized as bed material. Efficient burning of fine coal particles in the
feed is therefore related to Ug . Rated and actual test values of superficial
velocity are shown in Table 2.
Ca/S Mole Ratio—
Ca/S mole ratio correlates closely with sulfur capture performance of
the bed, especially at higher superficial velocities where in-bed residence
time is reduced and bubble phase transport is large. Excessively high Ca/S
ratios result in greater fresh sorbent requirements, increased solid waste
(i.e., spent sorbent), and a derating of the boiler (i.e., more heat required
for calcination). Reduction of the Ca/S ratio can be achieved by pressurized
operation and/or sorbent regeneration or additive utilization. Rated and
actual test values of Ca/S ratios are shown in Table 2.
Combustor Steam Tube Arrangement
The design of steam tube arrays for fluidized-bed combustors is presently
in a developmental stage. To date, atmospheric FBC units have been built
with water walls only and with horizontal staggered tube arrays. Pressurized
combined cycle units require more dense packing of tubes; horizontal and
vertical arrays have been used. Tubes in specialized cells or applications
may contain water, steam, boiling water/steam, air, or other fluids.
Staggered horizontal tube arrays have been shown to affect fluidization
favorably and bed mixing unfavorably. U.S. boiler practice favors 2" tubes;
the BCURA and Exxon Miniplant units use 1" tubes. The ultimate form of
final design practice in future commercial units is far from clear.
27
-------
TABLE 2. EXAMPLE VALUES OF SEVERAL PRIME FBC SYSTEM VARIABLES
FBC UNIT
PER (Alexandria, VA)
Exxon Miniplant
Combustion Power Co.
PDU
Esso, Ltd.
(Ablngdon, U.K.)
Rlvesvllle
BCURA (2'x3')
MERC
Generic
(Foster Wheeler)
Generic
(Westlnghouse)
Generic
(Combustion Power Co.)
TYPE
Atmospheric
Pressurized
Pressurized
CAFB
Atmospheric
Pressurized
Atmospheric
Atmospheric
Pressurized
Pressurized
Adlabatlc
POWER
(MW
EQUIVALENT)
0.5
0.63
1.0
0.29
30
0.5
6.0
200
300
50
FUEL FEED RATE
KG/SEC
(LB/HR)
0.1008
(800)
0.0417*
(331.01)
0 . 3024
(2400)
0.0493
(391)
4.158
(30,000)
0.0558-0.0583
(443-463)
0.5895
(4650)
27.72
(200,000)
27.177
(215,690)
7.068-7.6734
(56,100-60,900)
COMBUSTER
AIR FLOW RATE
KG/SEC
(LB/HR)
0.4032-0.9198
(3200-7300)
0.9084
(7210.87)
10.16
(80,640)
0.1579
(1253)
38.052
(302,000)
0.6213-06745
(4931-5353)
6.3
(50,000)
252
.(2,000,000)
294
(2,340,000)
230.4-382.3
(1,828,800-
3,034,800)
SORBENT FEED RATE
KG/SEC
(LB/HR)
0.0036-0.0252
(29-200)
.0088
(70)
0.0907
(720)
0,0042
(33)
0.9828
(7800)
0.0113-0.0173
(90-137)
0.1966
(1560)
8.316
(60,000)
6.006-18.018
(43,333-130,000)
3.153-3.425
(25,020-27,180)
SUPERFICIAL
VELOCITY
M/SEC
(FT/SEC)
2.103-4.48
(6.9-14.7)
2.3
(7.546)
2.042
(6.7)
1,219
(4)
3.658
(12)
0.6706-0.762
(2.2-2.5)
2.134-4.572
(7-15)
3.658
(12)
1.71-2.74
(5.6-9)
2.134
(7)
Ca/S
MOLE RATIO
2.2-2.7
1.5-2
1.5-2
1.0
(Regeneration)
2-2.7
1.5-2.2
0-7
Not Available
1.0-1.2
(Regeneration)
2
* = Partial Load
-------
CHAPTER 2
SAMPLING AND ANALYSIS PROGRAM STRATEGY
INTRODUCTION
This chapter is concerned with the overall strategy which will be
employed in developing a sampling and analysis program for the FBC tech-
nology under consideration.
A phased measurement strategy involving two separate and distinct
levels of sampling and analysis is introduced in the next section. Subse-
quent sections are concerned with: the selection of FBC system streams for
sampling; physical characteristics of sampled streams for generic and case
study units, and, areas of analysis.
A PHASED APPROACH TO SAMPLING AND ANALYSIS
Because of usual constraints on resource allocation, a sampling and
analysis program must be designed to fulfill the goals of being both cost-
effective and information-effective. A strategy in which each sample is
directly analyzed for an entire spectrum of possible components, individually,
is obviously information-effective, but prohibitively expensive. On the
other hand, direct analysis of a sample for a limited list of components
known to be harzardous is relatively inexpensive but not information-effective
since the risk of bypassing unsuspected hazardous materials is greatly
increased.
A program strategy representing a compromise between the above extremes
employs a phased approach (see references 147 and 317) where two separate
and distinct levels of sampling and analysis are utilized. A screening
phase (Level 1) characterizes the pollutant potential of all influent and
effluent streams of a process and has a broad range of applicability. In
this phase, sampling and analysis is designed to determine, within broad
general limits, the presence or absence, approximate concentrations, and
associated emission rates of inorganic and organic stream components.
Biotesting is limited to a determination of the cytotoxic and mutagenic
potential of a sample. Most importantly, no assumptions need be made, a
priori, regarding the nature of the constituents in any given stream.
Using the output of Level 1, priorities for additional testing can be
established among streams within a given process and components within given
streams, on the basis of pollution potential. In this manner, an optimized
29
-------
Level 2 program can be planned and the appropriate resource allocation
made. The goal of Level 2 analysis is the accurate-, quantitative identifi-
cation of specific components in selected streams (as dictated by the Level
1 output) and the determination of associated emission rates. Level 2 out-
put provides data needed for requisite control technology development,
health effect studies, and transport/fate analysis of pollutant emissions.
The sampling and analytical procedures specified in the present document
for Level 1 environmental assessment are based on material contained in refer-
ence 147. Strict adherence to these procedures will be required of source
testing contractors assigned to perform assessments on FBC facilities. In
certain cases where this may prove to be impractical, a modified plan should
be submitted by the contractor to the Project Office and the Process Measure-
ments Branch, IERL-RTP, for approval prior to initiating the sampling effort.
The general characteristics of Level 1 and Level 2 sampling and analysis
are summarized in Table 3. These characteristics are, of necessity, consistent
with the goals of each level, as restated in the table. The issues addressed
will be treated in more detail when procedures for Level 1 and Level 2
sampling and analysis of FBC processes are presented in the following
chapter.
PROCESS DEVELOPMENT AND ENVIRONMENTAL ASSESSMENT
Ideally, the environmental assessment of a process should proceed
in parallel with process development. This would allow for relative ease
in process modifications as well as development lead time for control
technology, should environmental factors warrant such action. The allocation
of resources for environmental assessment at the various phases of process
evolution should, again, reflect a balance between cost-effectiveness and
information-effectiveness. For example, the expenditure of a relatively
large fraction of the total allocated resources in the very early phases of
process development is unjustified due to the generally low probability of
commercial success. On the other hand, a delay in initiating environmental
assessment until commercialization is imminent poses the risk of delaying
plant operation (due to regulatory restraints, etc.) until suitable control
technology has been developed.
Table 4 summarizes the sampling and analytical strategies as well as the
process characteristics associated with each phase of the process evolutionary
cycle.
During the research (i.e., bench) phase, almost no funds are expended
for environmental assessment; general observations are made and some low
level testing is done.
In the development (i.e., pilot) phase, the Level 1 effort entails the
sampling of all influent and effluent streams and the subsequent screening
for all pollutant classes. Depending on the size of the unit and the complete-
ness of its process configuration, the sampling and analysis of fugitive
emissions may also be required.
30
-------
TABLE 3. CHARACTERISTICS OF LEVEL 1 AND 2 SAMPLING AND ANALYSIS
ISSUE
LEVEL 1
LEVEL 2
GENERAL
• Goal
• Streams
considered
• Pollutant
classes/species
considered
• Process oper-
ating condition
Characterization of the pollutant
potential of influent and effluent
streams of a process. Planning
basis for Level 2 effort
All process influents and effluents
including airborne and waterborne
fugitive emissions
Broad screening for elements,
organics, and selected anions
Steady-state representative
condition
Accurate quantitative identifica-
tion of selected components in
selected streams and determina-
tion of associated emission rates
Selected influents and effluents
based on Level 1 output
Selected pollutant classes/
species based on Level 1 output
Steady-state representative con-
dition
SAMPLING
Sampling
techniques
Particulates:
Particulates:
Single point, isokinetic at
cross-section point of average
velocity
Convenient location, not in
region of irregular flow
Full traverse of cross-sec-
tion, isokinetic at each
point
Specified distance from flow
disturbances, as per EPA
Method 1
-------
TABLE 3. (Continued)
ISSUE
LEVEL 1
LEVEL 2
SAMPLING
Sampling
techniques
Gases:
• Convenient sampling site in
unstratified location
• Single point, grab (e.g., dis-
placement bomb)
OJ
ho
.iquids:
• Homogeneous - single point
grab or tap
• Heterogeneous - full stream
cut grab at discharge or tap
in well-mixed region of line
Solids:
Pile or open holding container-
depth integrated grab
Stream discharge point - full
steam cut grab
Belt conveyor - stopped belt
(full stream cut)
Gases:
• Same sampling location as for
particulates
• Single point unless stratifica-
tion exists (then, traverse
required)
• Individual trains for specific
components (primarily Federal
Register methods)
Liquids:
• Homogeneous - single point grab
or tap
• Heterogeneous - automatic
sampler (full steam cut operation)
• Pneumatic transport line - auto-
matic sampler (e.g., Vezin type)
• Belt conveyer - stopped belt
(full stream cut)
-------
TABLE 3. (Continued)
ISSUE
LEVEL 1
LEVEL 2
Replications
None
Particulates: 3 minimum, separate
analysis for each sampling
Gas: compliance with Federal Register
specifications
Solids and liquids: 3 minimum,
separate analysis for each sampling
u>
ANALYTICAL
• Sensitivity
• Accuracy
• Specificity
• Physical char-
acterization of
solids and
particulates
Sufficient to insure detection of
all'class/species at trace levels
Target accuracy factor of +2 on
concentration
• Broad screening for inorganic
gaseous species
• Separation of organics into eight
fractions on the basis of polarity
• Elemental analysis
• Selected anions from standard
water analysis
Morphology, sizing
Sensitivity requirements will be
determined by Level 1 output
Target accuracy of +10%
• Selected inorganic gases based on
Level 1 output
• Identification of specific organic
compounds from selected fractions
• Selected species based on Level 1
output
• Selected anions from Level 1
elemental and standard water analyses
More refined morphological and sizing
determinations
-------
TABLE 3. (Concluded)
ISSUE
LEVEL 1
LEVEL 2
BIOASSAY
• Analyses performed
• Sample
Cytotoxicity, mutagenicity
Whole
Cytotoxicity, mutagenicity,
carcinogenicity
Fractionated; specific components
-------
TABLE 4. PHASES OF PROCESS EVOLUTION-CHARACTERISTICS AND SAMPLING/ANALYSIS STRATEGY
PROCESS PHASE
PROCESS CHARACTERISTICS
SAMPLING AND ANALYSIS - LEVEL 1 SAMPLING AND ANALYSIS - LEVEL 2
Research
(Bench Scale)
• Use of pure (Idealized) feeds.
• Exploratory operation solely of key
components of process configuration.
• Generally low probability of success-
ful commercialization.
• Nominal Instrumentation to provide
key process and product character-
istics.
• Intermittent operational mode.
General Observation, Low Level Testing
Development
(Pilot)
CO
Cn
• Larger scale, more complete process
configuration than in research phase.
• More representative feedstocks.
• Fair probability of eventual com-
mercialization.
• Instrumentation of feed, product,
and by-product streams,.and some in-
termediate streams.
• Semi-continuous operational mode
dependent on requisite process
changes.
• All system influents and
effluents.
• All pollutant classes.
Selected system Influents and
effluents (based on Level 1 pi-
lot output).
Selected pollutant classes/
species (based on Level 1 pilot
output).
Demonstration
• Complete process configuration.
• Representative feedstocks.
• Excellent probability of com-
mercial success.
• Process measurements for quali-
ty control and process stability.
• Operational mode consistent with
obtaining economic quantities of
products.
• All system influents and
effluents as well as fugi-
tive emissions.
• All pollutant classes.
• Selected system influents and
effluents (based on Level 1 demo
output) .
• Selected pollutant classes/
species (based on Level 1 demo.
output).
Commercial
• Same configuration as in demon-
station phase, but with poten-
tial further process improvements
and possible scale-up.
• Routine process stream monitoring.
• Same as for demonstration
phase.
• Same as for demonstration
phase.
-------
The Level 1 output is then used to establish stream-and stream component
priorities for the Level 2 program. The outputs of the Level 2 effort,
health effects studies, transport and fate analysis, and control technology
development are integrated with the results of process optimization studies
to ultimately produce a demonstration plant design.
The sampling and analysis strategy for the demonstration phase consists
of a Level 1 screening for all pollutant classes in every influent and
effluent stream (including fugitive emissions) followed by a Level 2 sampling
of selected streams and analysis of selected stream components. As in the
pilot phase, the Level 1 output is used to define the subsequent Level 2
effort. Figure 13 depicts the progression of sampling and analysis from the
pilot to the demonstration phase as well as the areas of interaction between
sampling and analysis, other environmental assessment areas, and process
studies. It should be emphasized that the results of the Level 1 and Level
2 efforts at the pilot phase contribute to the generation of the demonstra-
tion plant design but do not directly provide a basis for planning the
demonstration phase sampling and analysis effort.
If environmental assessment did, in fact, proceed in parallel with
process development from bench scale to demonstration phase, the requirement
for a comprehensive sampling and analysis program for commercialized units
would not exist. Prior assessment results from the demonstration phase
could be utilized and the monitoring of a few streams of key environmental
interest using Level 2 methods would probably suffice. This represents an
ideal situation however. For a variety of reasons, it is possible that
environmental assessment may, in some instances, be initiated after process
commercialization. In this case, a strategy identical to that employed for
the demonstration phase would be applied to commercial units, as indicated
in Table 3.
SELECTION OF FBC SYSTEM STREAMS FOR SAMPLING
Generic Units
As noted earlier, the generic units considered in this study are intended
to be representative of anticipated commercialized (or demonstration) units.
As such, sampling and analytical procedures for these units will be based on
the above mentioned' demonstration phase strategy.
Nbt having the benefit of Level 1 output to enable the prioritization
(and possible subsequent elimination) of streams and stream components, the
development of an: optimized Level 2 program as part of the present effort is
not feasible. Instead,, Level 2 sampling and analytical procedures will be
specified for every stream and; every analysis area addressed in the Level 1
effort (i.e., no elimination of streams' or stream components will be made).
Although^ Level 1 strategy requires that all influents to a process be
sampled1, cases can arise where certain influent streams may be eliminated
from cons-ideration- (-with prior approval by the Project Office) so that the
36
-------
PILOT
LEVEL 1
S & A
PLAN
PILOT STUDIES
PILOT
S & A
OUTPUT
LEVEL 2
STUDIES
DESIGN
DEMONSTRATION
PLANT
DEMO.
S & A
PLAN
LEVEL 2
DEMO .1 STUDIES
DEMO.
LEVEL 2
S & A
Figure 13. Sampling and analysis—progression from pilot to demonstration phase.
-------
cost- and information-effectiveness of the program is maximized. "Clean
intake air streams and "clean" intake water streams are such examples.
The contractor must, however, at the time of assessment, evaluate each
individual case before recommending that a stream be dropped from considera-
tion. Blanket rejection of specific stream types (e.g., any intake water
stream) should be avoided. For the generic FBC processes addressed in
this document, the assumption has been made that all air and water intake
streams originate from relatively clean sources and therefore do not require
sampling. Similarly, since the use of clean start-up fuels (e.g., natural
gas, propane, distillates) is anticipated for commercialized units, sampling
is not planned for influent stream No. 16.
The sampling of internal process streams is, in general, excluded
from the Level 1 and Level 2 strategies. Primary interest in these streams
relates to process and control device evaluations. (Accidental discharge
from within-process streams, while posing a hazard to the environment,
will not be addressed within the present scope.) An exception to the
internal stream exclusion is stream No. 26, the CAFB gasifier product.
This stream, comprising the fuel feed to a retrofitted conventional steam
power plant is of particular interest in environmental assessment.
The sampling of air-borne and water-borne fugitive emissions is an
integral part of the environmental assessment of a process. For the air-borne
category, the specific fugitive sources to be addressed in the present
effort are storage piles of feed materials and solid residues that may be
subjected to winds. Fugitives originating from vents, "loose" system
components (e.g. seals, connections), careless materials handling, and other
miscellaneous plant sources are site specific in nature and cannot be
addressed in a generic context. Fugitive sampling procedures that are
applicable to these sources will, however, be presented. In addition, it is
assumed that appropriate control techniques will be employed in process
operations such as coal and sorbent preparation to minimize or eliminate
air-borne fugitives.
For the water-borne fugitive category, leaching from outdoor storage
piles of feed and residual materials as well as from subsurface disposal
sites (e.g., land fills) will be considered. No projections, however, will
be made for the generic plants regarding disposal and storage methods to be
employed or potential disposal and storage sites. (Other contractors are
currently investigating these areas.) Emphasis will be focused on identifying
laboratory and field techniques for obtaining leachate/runoff samples
from solid residue and feed specimens. For purposes of the present document,
all generic solid feed and solid residue streams will be considered for
air-borne and water-borne fugitive sampling, as indicated in Table 5.
Table 5 provides a summary of generic streams selected for sampling
and analysis at- Level 1 and the environmental interest associated with
38
-------
TABLE 5. STREAM SELECTION FOR SAMPLING AND ANALYSIS (PROCESS CATEGORIES I THRU IV)
STREAM
NO.
STREAM DESIGNATION
ENVIRONMENTAL INTEREST
1*
2*
3*.
4*+
6*
7*
8
10
26
28'
Stack Gas
Particulate Removal Discard
Bed Solids Discard (not on CAFB unit)
Particulate Removal Discard—Regeneration Operations
Other Effluents from Regeneration and Sulfur Recovery Operations
Slowdowns from Steam Turbine Cycle
31owdov/n from Water Treatment Operations
Product from Sulfur Recovery (Sulfur or Sulfuric Acid)
Raw Fuel to Preparation
Raw Sorbent/Additive to Preparation
Fuel Gas Feed to Conventional Steam Generator (CAFB unit only)
Particulate Removal 1/iscard (CAFE unit only)
Key effluent
Key effluent, air-borne and
water-borne fugitives
Key effluent, air-borne and
water-borne fugitives
Key effluent, air-borne and
water-borne fugitives
Key effluent, air-borne and
water-borne fugitives
Secondary effluent
Secondary effluent
Process by-product
(possible contamination)
Key influent, air-borne and
water-borne fugitives
Key influent, air-borne and
water-borne fugitives
CAFB product (fuel feed to conventional
power plant)
Key effluent, air-borne and
water-borne fugitives
*Stream will undergo biological testing
+See Figures 10 thru 12.
-------
each. Also indicated are those streams which have been selected for
biological testing. (it should be noted that corresponding case study
unit streams will be similarly sampled and analyzed.) A summary of the
the "non-selected" generic streams and their primary sampling interest is
presented in Table 6.
Figure 14 shows all influent and effluent streams associated with
generic process categories I through IV and indicates those streams that
will undergo Level 1 sampling and analysis. Included in the figure are
fugitive sampling selections. It should again be emphasized that, for
purposes of presenting Level 2 assessment procedures, all streams considered
at Level 1 will have procedures specified for Level 2 as well. Actual
selection of streams for the Level 2 sampling effort cannot be made, however,
until the output of Level 1 assessment is available.
Case Study Units
The FBC units selected for case studies are pilot facilities. As
discussed earlier, and as is evident by comparison of flow sheets for generic
and case study units, certain operations associated with the generic (i.e.,
commercialized) processes are absent from the pilot process configurations.
As a result, some generic streams selected for sampling have no counterpart
in the case studies. From Table 7, a stream-by-stream comparison can be
made for each process category.
PHYSICAL CHARACTERISTICS OF SAMPLED STREAMS
Assessment of the physical conditions present in streams selected
for sampling is prerequisite to the development of sampling and analytical
procedures. Two important parameters influencing technique selection are
stream static pressure and temperature. For the range of system operating
conditions under which sampling is planned, typical values of these parameters
at proposed sampling sites are displayed in Table 7 for both the generic and
case study units of each process category. Values for the case study units
were derived from FBC literature, site visits, and contacts with principals
at the sites. For the generic units, values were based in part on the
literature and supplemented by engineering judgment.
For reasons of both thermal economy and personnel safety, it is antici-
pated that all high-temperature solid residue streams (e.g., particulate
removal, bed solids) associated with the generic units will undergo
cooldown to 93-149°C (200-300°F) prior to being discarded (and sampled).
The method forecasted for solids cooldown is indirect heat exchange with an
air or water coolant (not shown in the generic process flow sheets). Heat
recovery with subsequent use of the coolant somewhere else in the process
(e.g., preheated air to combustor) increases unit thermal efficiency.
Additional solids cooldown occurs through heat losses in pipes and other
system equipment. Solid residue transport is assumed to be accomplished
pneumatically.
40
-------
TABLE 6. NON-SELECTED STREAM SUMMARY
STREAM
no.
STREAK DESIGNATION
PRIMARY S&A INTEREST
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
27
Intake Water to Treatment
Air to Combustor/Gasifier
Air/Steam to Regenerator
Prepared Fuel Feed to Combustor/Gasifier
Prepared Fuel Feed to Regenerator (not on CAFB)
Start-Up Fuel Feed
Prepared Sorbent/Additive Feed to Combustor/Gasifier
Bed Solids to Regenerator
Flue Gas to Particulate Removal (Product fuel gas
from CAFB gasifier)
Makeup Water to Steam Turbine Cycle
Recycle from Particulate Removal
Recycle from Regeneration and Sulfur Recovery
Gas to Gas Turbine Inlet (pressurized and
pressurized-adiabatic units only)
Gas to Waste Heat Boiler (pressurized-adiabatic
unit only)
Air to Steam Generator (CAFB unit only)
Steam Generator Flue Gas to Particulate Removal
(CAFB unit only)
See pg. 36 discussion
See pg. 36 discussion
See pg. 36 discussion
Process evaluation
Regeneration evaluation
See pg. 36 discussion
Process evaluation
Regeneration evaluation
Process evaluation, particulate removal
evaluation
Water treatment assessment
Process evaluation
Regeneration evaluation
Gas turbine corrosion and erosion studies
Thermal economy evaluation
See pg.36 discussion
Particulate removal evaluation
-------
IS •
INTAKE
AIR
0MAIN FUEL i
**!
©SORBENT |
• i
©STARTUP FUEL B L
1 L
©INTAKE WATER ^ § GENERIC FBC SYSTEM \
!( CATEGORIES I THROUGH IV) 1
F
1 '
Vd/ B-
®(CAFB ONLY) ^^ X^\ GASIFIER pRODUCT GAS l_
"^-^ (CAFB ONLY) F
STACK GAS ^~~\
.^ r^\ - T .
"*"' ^ !
/7\ ^ SOLID
"™ ™r> V_|y ' " RESIDUES
..ni». (TW u •,
(CAFB ONLY) • x-x
•• O)
^^ v_y l LIQUID
x->. ( WASTE
SULFUR BY-PRODUCT ^_^
» W
iX Denotes sampling at Level 1
• Denotes air-borne and water-borne fugitive sampling
* Denotes biological testing.
Figure 14. Influents and effluents—generic FBC processes.
-------
TABLE 7. PHYSICAL CHARACTERISTICS OF SAMPLED STREAMS
CATEGORY I
CATEGORY II
STREAMS SELECTED FOR SAMPLING
STREAM
NO.
1
2
3
4
5
6
7
8
9
10
26
28
STREAM
DESIGNATION
Stack gas
Paniculate removal discard
Bed Jolids discard
(not on CAFB unit)
Paniculate removal discard
—regeneration operations
Other effluents from
regeneration and sulfur
recovery operations
Slowdowns from steam
turbine cycle
Slowdown from water
treatment operations
Product from sulfur
recovery (sulfur or
sulfuric acid)
Raw fuel to preparation
Raw sortaent to
preparation
Fuel gas feed to
conventional steam
generator (CAFB unit only)
Paniculate removal
discard (CAFB unit only)
PHYSICAL
COMPOSITION
gas,
particulars
solid
solid
solid
see individual
units
liquid
liquid
liquid
coal (1,11,111)
residual oil (IV)
solid
flas.
paniculate
solid
ATMOSPHERIC FBC OF COAL
GENERIC UNIT
TEMP.
240-300 F
200-300 F
200-300 F
200-300 F
200-300 F
100 F
ambient
100 F
ambient
ambient
PRESS.
atm
atm
atm
atm
atm
atm
atm
atm
atm
atm
REMARKS
Ash discard
from regenerator
Sulfuric acid
produced
POPE. EVANS &ROBBINS
ALEXANDRIA UNIT
TEMP.
400-600 F
200-300 F
1500 F
ambient
ambient
PRESS.
atm
atm
atm
atm
atm
REMARKS
Sample upstream
of 10 fan
Regenerator
not functional
Sampling
•not
recommended
No sulfur
recovery
operation
Pre -sized
sorfaent
purchased
PRESSURIZED COMBINED
CYCLE FBC OF COAL
GENERIC UNIT
TEMP.
275 F
200-300 F
200-300 F
200-300 F
200-300 f
100 F
ambient
230 F
ambient
ambient
III
PRESS.
atm
atm
atm
atm
atm
atm
atm
atm
atm
atm
REMARKS
Ash discard
from regenerator
Sulfur produced
-------
CATEGORY It
TABLE 7. PHYSICAL CHARACTERISTICS OF SAMPLED STREAMS (CONCLUDED)
CATEGORY III CATEGORY IV
PRESSURIZED COMBINED
CYCLE FBC OF COAL
EXXON MINIPLANT
TEMP.
1500 F
180-200 F
250 F
120-150 F
300400 F
ambient
atm
PRESS.
10 atm
atm
atm
atm
20-25
pig
ambient
atm
REMARKS
High pressure, higl
temp, sampling
required
Sample at lock
hopper outlet
Sample at lock
hopper outlet
No lock hopper
Off -gas to
scrubber
No blowdowns
• No sulfur re-
covery operation
Pre -sired
coal
purchased .
Pre-tizEd
so rtaent
purchased
PRESSURIZED COMBINED CYCLE FBC OF COALllADIABATIC COMBUSTOR)
GENERIC UNIT
TEMP.
300 F
200-300 F
200-300 F
200-300 F
200-300 F
100F
ambient
230 F
ambient
ambient
\
PRESS.
atrn
atm
atm
atm
atm
atm
atm
atm
atm
atm
REMARKS
Ash discard
from regenerator
Sulfur produced
COMBUSTION POWER CO. PDU-400
TEMP.
940 F
400 F~2a
300 F~2b
ambient
ambient
PRESS.
atm
atm
atm
atm
*
REMARKS
Turbine exhaust
2s 1st and 2nd
stage sep. discard
to sand bin
2b-grahular
filter discard at
baghouse'
No regenerator
on unit
No steam
production
No sulfur recovery
operation
Pro-sized
sprfaent
purchased
CAFB RESIDUAL OIL GASIFICATION
.GENERIC UNIT
TEMP.
300 F
200-300 F
200-300 F
ambient 5a
170 F 51
ZOO-300|F5c
100 F
ambient
230 F
ambient
.1550-
1650 f
200-300 F
PRESS.
atm
atm
atm
atm
atm
atm
atm
atm
atm
atm
REMARKS
Sa-slurry efflu-
ent from scrubber
Sb-scrubbad gas
to stack
Sc-regen. solids
discard
Sulfur produced
No preparation
; for residual
,oil
EXXON, LTD. ABINGDON UNIT
TEMP.
239 F
100 F
176 F
HOOF
ambient
ambient
1595F
875F~30a
248F~30b
PRESS.
atm
atm
atm
atm
atm
i atm
atm
. atm
REMARKS
Recycle to
gasifier and
regenerator
Samples taken
under nitrogen
-then cooled
• Regen. solids
discard sam-
ples taken as
in stream 3
No preparation
for residual
oil
Pre-jized1
sortaent
purchased
-------
The only generic stream requiring high-temperature sampling (around
871°C) is the CAFB product gas (No. 26). As indicated in Table 7, each
selected stream in every generic:process category will be sampled at approxi-
mately atmospheric pressure. For the case study units, several instances
are indicated where high-temperature and/or high pressure sampling will be
required. In general, the physical conditions associated with the selected
generic streams do not in themselves pose particular sampling difficulties.
AREAS OF ANALYSIS
Introduction
Figures 15 through 18 provide an overall view of the multi-media
chemical and biological analyses associated with Level 1 and Level 2 assess-
ment. Organic analyses, inorganic analyses, and bioassay are relevant to
samples from all media. Additionally, physical characterization studies are
performed on solid and particulate samples while aqueous liquid streams are
subjected to further analyses to determine pH, dissolved and suspended
solids, COD, BOD and other quantities. Leachates from solid samples also
demand analytical concern. The special fuel analyses (e.g., ultimate and
proximate) which are performed routinely during process operation have not
been indicated in the figures but do form a part of the Level 1-Level 2
strategy.
It is of interest to examine the FBC process and, using theoretical
principles, attempt to forecast the classes-species of pollutants which may
be released to the environment during its operation. This task has already
been performed by GCA Corporation (reference 123). In the paragraphs that
follow, a brief discussion of potential pollutants, based on the GCA study
and other information, is presented. The pollutants mentioned in this
discussion should not be construed as representing the entire list of
analytical concern in an environmental assessment. On the contrary, in the
present strategy, all classes and species of pollutants are treated as
potential stream constituents; only through the broad screening associated
with Level 1 can certain classes/species be eliminated from further
consideration.
Organic Compounds
Data on specific organic compounds emitted during fluidized-bed
combustion are extremely rare. Analysis of flue gas is often limited to
only CO, C02, 02, S02, and NOX. Occasionally total hydrocarbons (THC) are
measured, generally by a flame ionization technique. While THC values may
well be of use in measuring overall combustion efficiency, they are of
relatively little help in predicting species concentrations, even though
values for total hydrocarbons are typically reported in terms of methane.
Potentially, an extremely wide variety of organic compounds could form.
Detailed kinetic or thermodynamic calculations are of limited value; both
the identity of the true reacting species and the assumption of true equi-
librium between reacting species are often speculative.
45
-------
SOLIDS
OR
SOLIDS PORTION
OF SLURRY
H
INORGANIC
MATERIAL
ORGANIC
MATERIAL
LEACHABLES/
RUNOFF
PHYSICAL
CHARACTERIZATION
AREA OF INTEREST
LEV
ANIONS
(CALCULATED)
1
ELEMENTAL
ANALYSIS
VC12
ORGANIC
ANALYSIS
NON-VOLATILE
ORGANIC
ANALYSIS
SEE LEVEL 1
LIQUID
ANALYSIS
MORPHOLOGY
SIZING
TOXICITY
MUTAGENICITY
TX 1 ANALYSIS
1
LE
SELECTED
ANION
ANALYSIS
ELEMENTAL ANALYSIS;
SELECTED SPECIES
ORGANIC COMPOUNDS
FROM SELECTED
C,-C.. FRACTIONS
D 12
ORGANIC COMPOUNDS
FROM SELECTED
NON-VOLATILE
FRACTIONS
SEE
LEVEL 2
LIQUID ANALYSIS
MORPHOLOGY,
SIZING
TOXICITY
MUTAGENICITY
CARCINOGENICITY
VEL 2 ANALYSIS
Figure 15. Areas of analysis—solid samples.
-------
•u
VI
LIQUIDS,
LIQUID PORTION
OF SLURRY,
OR
LEACHATES
INORGANIC
MATERIAL
ORGANIC
MATERIAL
STANDARD WATER
ANALYSIS
(AQUEOUS STREAMS)
BIOASSAY
AREAS OF INTEREST
ELEMENTAL ANALYSIS;
SELECTED SPECIES
ORGANIC COMPOUNDS
FROM SELECTED
C,-C,. FRACTIONS
o 12
ORGANIC COMPOUNDS
FROM SELECTED
NON-VOLATILE FRACTIONS
ACIDITY, ALKALINITY,'
PH, BOD, COD, DO,
TDS, TSS, HARDNESS,
CONDUCTIVITY
TOXICITY
MUTAGENICITY
CARCINOGENICITY
LEVEL 2 ANALYSIS
Figure 16. Areas of analysis—liquid samples.
-------
INORGANIC
COMPONENTS
GASES
ORGANIC
COMPONENTS
ANALYSIS
OF
GASEOUS INORGANIC
SPECIES
Crc6
ORGANIC
ANALYSIS
SELECTED
INORGANIC
SPECIES
ORGANIC COMPOUNDS
FROM SELECTED
C -C, FRACTIONS
1 b
AREA OF INTEREST
LEVEL 1 ANALYSIS
LEVEL 2 ANALYSIS
Figure 17. Areas of analysis—gas samples.
-------
PARTICULATES
(FROM GAS STREAM
OR FUGITIVES)
INORGANIC
MATERIAL
ORGANIC
MATERIAL
PHYSICAL
CHARACTERIZATION
DTnACCAV
AREA OF INTEREST
-*•-
=»••
— »-
LEV
1
ANIONS
CCALCULATED)
I
ELEMENTAL
ANALYSIS
1 .
1 *
1
I .
1
SELECTED
ANION
ANALYSIS
ELEMENTAL ANALYSIS;
SELECTED SPECIES
i
VC12
ORGANIC
ANALYSIS
NON-VOLATILE
ORGANIC
ANALYSIS
MORPHOLOGY,
SIZING
TOXICITY
MHTAGENICITY
EL 1 ANALYSIS
!
1
8
1. »
LE
ORGANIC COMPOUNDS
FROM SELECTED
C,-C,, FRACTIONS
1 o l£
ORGANIC COMPOUNDS
FROM SELECTED
! NON-VOLATILE
' FRACTIONS
MORPHOLOGY,
SIZING
TOXICITY
MUTAGENICITY
CARCINOGENICITY
VEL 2 ANALYSIS
Figure 18. Areas of analysis—paniculate samples.
-------
Combustion is a combination of two competitive pathways: oxidative and
pyrolytic. The oxidative pathway leads to partially oxidized products
such as CO and fully oxidized products such as CG^. The pyrolytic pathway
leads to reduced species such as aromatics, and of greater concern, polycyclic
aromatics such as benzo (a) pyrene. Pyrolytic reactions are important for
an additional reason; the products of these reactions may play an important
role in the formation and growth of particulate matter.
In brief, little may be predicted a priori about specific compound
formation.
Inorganic Gases
Data on inorganic gaseous species is incomplete; typical stack gas
analysis often consists of measuring only S02, NOX (NO and Nt^-)',, CO, C02>
and 02 concentrations. Occasionally, S02 may be measured for compliance
testing. S©2 is regarded as the single most hazardous pollutant by health
authorities. Structural damage caused-- by S02~S03 corrosion is also well
known, S02 is also a process parameter. Both N02 and' NO are potential
health hazards. Moreover, these species play important roles in smog
formation' under adverse conditions. The problem of GO emissions from
combustion1 sources may be less significant than was originally thought
according to recent studies at Argonne National Laboratories (reference 5).
However, CO is s-till considered a potential health hazard. Neither carbon
dioxide nor oxygen, are considered to be pollutants, although steadily
increasing G02 levels do pose certain environmental hazards. Both C02 and 02
are, however, primary process control parameters. Another species of
interest which relates? to process control is ^0 in the stack g.as.
There are, aside from the previously mentioned species, a number of
other gaseous compounds which may be synthesized during the combustion
process. While detailed, calculations can be made, the numbers generated by
such methods represent only trends or perhaps concentration ratios (generally
the most common method: is to minimize the chemical system's free energy,
assuming equilibrium conditions—see reference 290).
The following list of inorganic gaseous species that may be present is
not intended to be exhaustive or exclusive, but rather a framework in which
analytical methods- and conditions may be1 discussed' later in the' document:
ammonia (NH^), carbon1 dioxide (C02), carbon monoxide (GO), halogens, the
hydrogen halides, hydrogen cyanide (HCN;), hydrogen sulfide (l^S), miscel-
laneous sulfur containing" species (e.g., carbonyl sulfide (COS)), mercury
(Hg), nitrogen oxides (NO ),. miscellaneous nitrogen containing species,
oxygen (0 ), sulfur oxides (SO ) and water vapor (HO).
50
-------
Trace Elements
Virtually all elements below atomic number 92 are contained in at
least trace amounts «100 ppm) in coal and oil. Typical ranges of con-
centrations of trace elements for coals and oils are shown in Figures
19 and 20.
Trace elements from combustion processes may be emitted via various
pathways. One primary mechanism of environmental release is via particu-
late emissions; recent investigations have shown that certain toxic elements
are volatilized and preferentially concentrated in submicron sized parti-
cles (reference 194). A number of elements, for example mercury, cadmium,
bromine, and iodine, are sufficiently volatile to be emitted in the gas
phases in their elemental form. Compounds of a number of trace elements may
react in the FBC process to form gaseous species of concern (an example is
the reaction of nickel and carbon monoxide under suitable conditions to form
nickel carbonyl, Ni(CO)^). Trace elements may also be leached from solid
residues and feeds and adversely impact water quality.
All areas of the ecological system are affected to varying extents by
trace elements. Metals, in particular, are the most insidious pollutants
because of their nonbiodegradable nature. Currently, only beryllium and
mercury emissions are regulated by Federal Emission Standards. In general,
however, only a few trace elements are completely nontoxic at any level
(references 98, 267).
Seventy-six elements are considered at Level 1. To present a comprehen-
sive treatment of level 2 analytical procedures these seventy-six elements
will again be addressed at Level 2.
Anions
A variety of anions will be found in particulates, solid residues, and
solid feeds as well as in leachates from these materials. In addition,
certain anions are associated with water treatment and steam cycle blowdowns.
The following list provides a framework in which Level 2 analytical methods
can be discussed later in the document: arsenate and arsenite, bromide,
carbonate and bicarbonate, chloride, cyanide, fluoride, iodide, nitrate,
nitrite, phosphate, sulfide, sulfite, and sulfate". Level 1, elemental
analysis will provide estimates of most anion concentrations. The estimation
procedure assumes .that each element capable of anion formation is present,
in toto, in a single anionic form. These calculations will yield upper
limits of anion concentrations but no information on specific species.
Anions which are not analyzed in the above procedure, are analyzed as part
of Standard Water Analysis.
Standard Water Analysis
These analyses are covered only as standard analytical procedures,
i.e., either EPA or ASTM recommended methods. Analysis areas include selected
51
-------
H
ND
Li
100
Na
100 :
K
100
Rb
100
Cs
100
Fr
NO
Be
100
Mg
100
Cal
100
Sr
100
Ba
100
Ra
ND
Sc;
100:
Y
100
La
.100
Ac
NO
Til
too:
Zr
100
Hf I
46
Ce
100
Th ;
92
V
100
Nb
100
Ta
62.
Pr
100
Pu
ND
Cr ;
'00
Mo
100
W
69
Nd
100
U
92
Mn
100
Tc
Nd
Re
0
Pm
ND
Fe
100
Ru
0
Os
0
Sm
100
Co
100
Rh
0
Ir
0
Eu
100
Nj
100
Pd
0
Pt
0
Gd
85
Cu
100
AS
92
Au
0
Tb
85
Zn
joo
Cd .
92
Hg
38
Dy
85
B
100
Al
jog
Ga
100
In
Stand-
ard
Tl
31
Ho
77
. C
NO
Si
100
Ge
100
Sn
100
.f!>
100
Er
77
N
NO
P
100
As
100
Sb
.92
Bi
31
Tm
0
0
ND
S
ipp
Se
100
Te
65
• Po
' ND
Yb
62
;F
100
Cl
100
Br
100
1
85
, At
1 ND
Lu
38
Figure 19. Occurrence frequency of elements in 13 raw coals as determined by spark-source mass spectrometry.
All quantities in %. ND = not determined. O = checked but not detected.
H
ND
Li
4-163
Na
100-
1000
K
300-
6500
Rb
1-150
Ct !
0.2-9
Fr
ND
Be
0.4-
3
Mg
500-
3500
Ca
800-
6100
Sr
17- L
1000'
Ba
20-
1600
Ra '
ND
Sc
3-30
Y :
3-25
La
0.3-
29
Ac I
ND
Ti
200-
1800
Zr
28-300
Hf
-------
anions and eight additional measures of water quality: acidity, alkalinity,
biochemical oxygen demand (BOD), conductivity, chemical oxygen demand (COD),
dissolved oxygen, pH, and total dissolved and suspended solids. The selected
species are: ammonia, carbonate, cyanide, nitrate, phosphate, sulfate and
sulfite.
Physical Characterization of Solids
For solid and particulate samples, Level 1 procedures for physical
characterization provide information on the following: size distribution,
classification into general morphological types, and possible compound
identification (by crystalline structure only). Level 2 physical charac-
terization is an expansion and refinement of techniques used in Level 1. Of
particular importance, however, is inorganic compound identification. Data
from all phases of an analysis program (e.g., elemental and anion analysis,
etc.) are combined to identify specific inorganic compounds, but methodology
for this area is ill-defined and thus a complete analytical scheme is not
presented in this document.
Bioassay
Biological testing, an integral part of phased environmental assessment,
is planned for both the Level 1 and Level 2 efforts. In the former case,
whole samples from selected generic FBC streams (see Table 5) will undergo
bioassay to determine cytotoxicity and mutagenicity within broad limits.
The results of the Level 1 testing, biological and chemical, will be
utilized in establishing priorities and plans for further bioassay work
at Level 2. The Level 2 effort will involve testing on fractionated
samples or on specific components of a given sample and will be extended
to include determinations of carcinogenic potential.
At present, specific biological test procedures have not been completely
identified and, therefore, cannot be incorporated into the present document.
Procedures for Level 1 bioassay will, however, be provided in a manual
scheduled for issue in January 1977. It should be noted that the sample
sizes specified in the next chapter may be modified when exact procedures
for. bioassay are defined.
53
-------
CHAPTER 3
RECOMMENDED SAMPLING AND ANALYTICAL PROCEDURES
FOR FBC PROCESSES
INTRODUCTION
This chapter presents recommended procedures for multi-media sampling
and analysis of the FBC processes .under consideration, using the phased
assessment strategy outlined in Chapter 2. Both generic and case study
units within each process category are addressed; emphasis, however, is
focused on the former. For convenient reference to the large volume of
material included, both sampling and analytical procedures for Level 1
and Level 2 have been summarized in tabular form.
The intent here is to recommend and highlight procedures rather than to
provide detailed sets of instructions for sampling and analytical personnel
to follow. Key references that provide detailed instructions have been
listed in the summary tables. Additional data and references can be found
in the compendium of sampling and analytical techniques presented in the
Appendix.
In the following section, some general aspects of a sampling test
plan are discussed.
GENERAL SAMPLING CONSIDERATIONS
Pre-Test Considerations
Before a detailed final sampling test plan can be devised and executed,
certain preliminary tasks must be performed by the source testing contractor.
A detailed discussion of these pre-test procedures is found in reference
147. Because of the typical complexity of an assessment sampling program
(particularly for a demonstration or commercialized unit), a preliminary
test plan should be prepared in advance of the pre-test site survey. To
prepare this plan, relevant data concerning the facility assigned for testing
should be gathered through contacts with plant personnel, literature, etc.
Items of particular interest include:
1. Process flow sheets and descriptions;
2. Plant layout drawings;
3. Specifications on plant equipment;
4. Operating procedures;
54
-------
5. Value ranges for operating parameters; and
6. Stream conditions (e,.g., pressures, temperatures, flow rates).
In addition, results of tests on similar units (if available) should be
studied to identify possible areas of commonality.
At the time of the pre-test site survey, suitability of the tenta-
tive sampling sites selected in the preliminary test plan, with regard to
accessibility, Level 1 (or Level 2) location criteria, and safety require-
ments, should be verified.: Appropriate modifications should be made if
necessary. On the basis of the preliminary test plan and the pre-test site
survey, a detailed final sampling plan can be formulated.
Prior to testing, sampling personnel should be briefed to acquaint
them with new procedures that will be employed and plans to be followed in
the event of test equipment failure or unexpected process variations during
sampling.
Sample Size
Table 8 lists the minimum sample sizes required for Level 1 analysis
according to sample type. Level 2 minimum sample sizes are dependent upon
the pollutant concentrations determined from the Level 1 effort and cannot
be specified a priori.
TABLE 8. SAMPLE SIZE REQUIREMENTS - LEVEL 1
Sample Sample
Type Quantity
3
Stack particulate 30m
Stack gas 3 liters
3
Fugitives (ambient air) 480m (STP)
Liquid 10 liters
Solid 1 kg
Sample Handling
Since environmental assessment is concerned with the detection and
quantification of pollutants which may be present in trace amounts, and
since bioassay is an integral part of environmental assessment, it becomes
extremely important that contamination and degradation of the sample does
not occur. To minimize this possibility; the following precautions should
be taken:
55
-------
1. Sampling apparatus and sample containers must be con-
structed of biologically inert materials and must not
appreciably alter the concentration of sample con-
stituents by erosion; adsorption, or any other mechanism;
2. Adequate sample preservation techniques- should be employed; and'
3. Sampling equipment .must be*, thoroughly cleaned .^before each
use. Transfer of' samples -frornn. sampling: apparatus to- conr-
tainers must be performed : in: a consistent and< careful manner
in a clean environment. Samp 1 ing, ;;cont'ainers "should ;be- air-
tight.
RECOMMENDED SAMPLING PROCEDURES FOR' GENE-RIG UNITS
Introduction
Recommended Level 1 and Level 2 .sampling procedures for generic
process Categories I through IV are summarized in Table 11. Included in
the table are site preparation requirements, rationale for method selection,
key references, and .other relevant data. Because of the similarity of
process configurations and the -commonality both ;of ^streams-selected for
sampling and associated stream' physical conditions; the*- procedures' specif ied
for Categories I through 'IV are , for the most part; identical. (Assessment
of the CAFB process requires the sampling of four additional1 streams
however) .
Sampling . procedures are summarized according to "stream category"
rather than on a stream-by-stream.-bas:is. Use of the stream category subdivision
enables the -specif icat ion1 of a single sampling procedure for any -group of
generic streams having similar -physical compositions, physical conditions,
and1. -site preparation requirements (e .g. , solid residue streams at 200-300°F
and atmospheric pressure). Certain FBC process streams, however, cannot be
grouped in this manner, as is evident in Table 11. In the case of the stack
gas stream, two separate categories (particulate and gaseous components) are
employed to specify the two drstinct types of sampling required.
To link generic sampling procedures with analytical procedures j and to
direct the reader to the appropriate analytical tables, the analysis areas
associated with each stream category are listed in the "Applicable Areas of
Analysis" column, of, Table 1 1 .
Particulate Sampling
Recommended Methods.r-
The sampling of particulates from stacks and other' ducted gas streams
represents one . of the most costly and complex aspects of an assessment
sampling ..program,. For both Level 1 and-Level 2 particulate sampling, use of
56
-------
the Source Assessment Sampling System (SASS) is recommended. Selection
rationale, site preparation requirements, and other considerations relating
to the SASS train are provided in Table 11 under Stream Category F. More
detailed discussions of the train can be found in Appendix Table A-l as well
as in the references listed there and in Table 11.
Sampling Location—
For Level 1 particulate sampling, a convenient, readily accessible
sampling site (preferably an existing port) should be selected to minimize
site preparation efforts and costs. For stack gas sampling, the selected
site may be located in the stack or in the breeching. Regions where irreg-
ular flow patterns exist should, however, be avoided.
For Level 2 sampling, EPA Method 1 specifications for port placement
and traverse point locations must be followed. Sampling sites should be
located at least eight equivalent diameters downstream of any flow dis-
turbance'. For stack gas sampling, the erection of scaffolding may be
required since sampling sites will be located up and on the stack.
The achievement of Level 2 accuracy goals requires that a full traverse
be performed at isokinetic conditions. The SASS train is designed to
operate at a pre-determined constant flow rate, which if changed, would alter
the cut size of particulate captured by the train's cyclones. To maintain
isokinetic conditions for a full traverse would entail a change of nozzles
at each traverse point (a rather impractical procedure). An alternative
involves locating the sampling site at a cross-section where the traverse
point velocities do not vary more than 10 percent from a mean value. The
SASS train would then provide conditions that are isokinetic within Level 2
accuracy limits. Another option is applicable to sampling locations where
some traverse points (i.e., outlier points) have a velocity variation
greater than 10 percent of a mean value. If the number of outlier points is
small compared to the total number to be sampled, then nozzles may be
changed at these points to maintain isokinetic conditions.
Sampling Procedure—
At Level 1, a velocity traverse is performed at the selected site
and the average velocity is calculated. The cross-section point most nearly
approximating the average velocity is selected as the sampling point and
the proper nozzle size for isokinetic sampling is then chosen. Sampling
extends for a time period required to obtain a specified sample quantity.
•At Level 2, the sampling site is chosen in accordance with the pre-
viously discussed criteria. One of the above mentioned techniques for
isokinetic sampling is selected and a traverse is then performed in accord-
ance with EPA Method 1.
Sample Handling—
Procedures for sample handling and transfer from the SASS train nozzle,
probe, cyclone, and filter are presented in Figures 21 and 22.
57
-------
PROBE AND
NOZZLE
t-M-^-U : V-rUUn
RINSE INTO AMBER
GLASS CONTAINER
ADD TO 10*
CYCLONE RINSE
i
10 »• CYCLONE
STEP 1: TAP AND BRUSH
CONTENTS FROM WALLS
AND VANE INTO LOWER
CUP RECEPTACLE
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL ON WALLS AND VANE
INTO CUP (CH2CI2 : CHjOH)
—
REMOVE LOWER CUP
RECEPTACLE AND
TRANSFER CONTENTS
INTO A TARED NALGENE
CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER (CHjClj : CH-OH)
INTO PROBE RINSE CONTAINER
(COM
1
Ln
00
3 * CYCLONE
STEP 1: TAP AND BRUSH CON-
TENTS FROM WALLS INTO
LOWER CUP RECEPTACLE
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL WITH CH,CI, : CH-OH
INTO CUP i l J
STEP 3: RINSE WITH CH2CI2:CH3OH
INTERCONNECT TUBING JOINING
10,, TO 3M INTO ABOVE CONTAINER
c
REMOVE LOWER CUP RECEP-
TACLE AND TRANSFER CON-
TENTS INTO A TARED NAL-
GENE CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
AN AMBER GLASS CONTAINER
HCOMBINE)
COMBINE
ALL RINSES
FOR SHIPPING
k AND ANALYSIS
Figure 21. Sample handling and transfer- SASS nozzle, probe, cyclones and filter
-------
CYCLONE
STEP 1: TAP AND BRUSH
CONTENTS FROM WALLS
INTO LOWER CUP RECEP-
TACLE
STEP 2: RECONNECT LOWER CUP
RECEPTACLE AND RINSE ADHERED
MATERIAL WITH CH,CI,:CH,OH
INTO CUP l l A
STEP 3: RINSE WITH CH2CI2:CH.jOH
INTERCONNECT TUBING JOINING
3*.TO 1M INTO ABOVE CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
A TARED NALGENE CONTAINER
REMOVE LOWER CUP RECEPTACLE
AND TRANSFER CONTENTS INTO
AN AMBER GLASS CONTAINER
FILTER
HOUSING
STEP1: REMOVE FILTER AND
SEAL IN TARED PETRI DISH
STEP 2: BRUSH PARTICULATE FROM
BOTH HOUSING HALVES INTO A
TARED NALGENE CONTAINER
STEP 3: WITH CH2CI2:CH3OH
RINSE ADHERED PARTICULATE
INTO AMBER GLASS CONTAINER
STEP 4: WITH CH2CI2:CH3OH
RINSE INTERCONNECT TUBE
JOINING IM TO HOUSING
INTO ABOVE CONTAINER
NOTES: ALLCH2CI2:CH3OH
MIXTURES ARE 1:1
ALL BRUSHES MUST HAVE
NYLON BRISTLES
ALL NALGENE CONTAINERS
MUST BE HIGH DENSITY
POLYETHYLENE
Figure 22. Sample handling and transfer- SASS nozzle, probe, cyclones and filter (continued)
-------
Gas Sampling
Recommended Methods--
Recommended techniques for the sampling of gaseous components from
stacks are specified in Table 11 under Stream Category E. (It should be
noted that these methods are applicable to ducted gas streams in general.)
Additional information on these techniques can be found in Appendix Table
A-2 and in the references listed in Tables 11 and A-2.
For Level 1 gas sampling, use of a simple displacement gas bomb (a single
point, manual method) is recommended.
For the Level 2 effort, two sampling options are recommended for most
gases. In each case, the first option is a manual technique while the
second option uses a continuous analyzing instrument and an extractive
sampling procedure. It is expected that the second option would be selected
if the equipment was already employed on site for monitoring purposes.
Techniques have been selected on the basis of proven field experience
as well as for compliance with the goals of each strategy level. (An
exception to the field experience criterion is the SASS train.)
Sampling Location—
For Level 1 gas sampling (as in the case of particulates), a convenient,
readily accessible sampling site, preferably an existing port, should be
selected. If stratification exists there, another location sufficiently
downstream of any air inleakage point and in a well-mixed flow region,
should be chosen. Stratification investigations at existing ports are
performed using a portable (^ analyzer. To locate new sampling ports,
however, engineering judgment is used to predict the presence of strati-
fication.
For cost-effectiveness, it is desirable that the Level 2 particulate
sampling site be used for Level 2 gas sampling. If -stratification does not
exist at this location, single point sampling is satisfactory. If, however,
an investigation indicates the .presence of stratification, a sampling
routine involving multi-point traversing must be designed. Techniques for
performing stratification investigations are described in Appendix Table
A-2. A detailed treatment.of the stratification problem is provided in
references 55, 77, 331, and 332.
Sampling Rrocedures--
A 3 liter simple displacement bomb is recommended for Level 1 gas
sampling. Samples are extracted at a single point using a teflon line as a
probe and a glass wool plug as a prefilter for particulates. Detailed
discussions of gas bomb sampling techniques are found in references 13.6, 211,
and 323.
60
-------
Detailed procedures for each of the recommended Level 2 methods can be
found in the references listed in Tables 11 and A-2.
SASS train impinger reagents are specified in Table 9 and apply to
both Levels 1 and 2.
Sample Handling—
Because of possible sample instability, gas bomb samples acquired at
Level 1 should be analyzed as soon as possible and must be stored away from
direct sunlight and heat. Handling and transfer procedures for the impingers
and XAD-2 modules of the SASS train are provided in Figures 23 and 24.
References listed in Table 11 and A-2 should be consulted for sampling
handling and transfer instructions for each of the recommended Level 2
techniques.
Liquid Sampling
Recommended Methods—
Recommended techniques for the sampling of liquids are specified
in Table 11 under Stream Categories C and D. Appendix Table A-3 as well as
the references listed there and in Table 11 offer more detailed discussions
of these techniques.
For the liquid sulfur or sulfuric acid by-product (stream No. 8),
tap sampling is recommended both for Level 1 and Level 2. Since these
liquids are homogeneous in nature, a tap sample should be representative.
Taps may be installed in either a discharge line or a holding tank, at any
convenient location.
For the blowdown streams (stream No. 6 and 7), the possibility of
high solids content (and thus, stratification) exists. If the discharge
point of a blowdown stream is accessible, a full-stream cut technique using
a dipper is recommended for Level 1 sampling. If this point is inaccessible,
a tap should be installed in a well-mixed region of the blowdown line.
Level 2 sampling requires the use of an automatic hi-volume sampler, also
installed in a well-mixed region of the line.
Sampling Location--
Sampling location has been addressed in the above discussion.
Sampling Procedure--
For tap sampling, the maximum sampling rate recommended in ASTM proce-
dures is 500 ml/minute. Tap installation specifications are also covered in
the ASTM procedures.
When using a dipper for full-stream cut sampling of line discharge
points, the dipper must not be allowed to overflow during sampling. If
overflow does occur, a larger container should be used.
61
-------
TABLE 9. SASS TRAIN IMPINGER SYSTEM REAGENTS
IMPINGER
REAGENT
QUANTITY
PURPOSE
#2
#3
6 M H202
0.2 M (NH4)2S208
+0.02 M AgN03
0.2 M (NH4)2 S20Q
+0.02 M AgN03
Drierite (Color Indicating)
750 ml
750 ml
750 ml
750 g
Trap reducing gases such as
S02 to prevent depletion of
oxi dative capability of trace
element collecting impingers
2 and 3.
Collection of volatile trace
elements by oxi dative
dissolution.
Collection of volatile trace
elements by oxi dative
dissolution.
Prevent moisture
reaching pumps.
from
-------
STEP NO. 1
COMPLETE XAD-2 MODULE
AFTER SAMPLING RUN
STEP NO. 2
RELEASE CLAMP JOINING XAD-2
CARTRIDGE SECTION TO THE UPPER
GAS CONDITIONING SECTION
REMOVE XAD-2 CARTRIDGE FROM
CARTRIDGE HOLDER. REMOVE FINE
MESH SCREEN FROM'TOP OF CART-
RIDGE. EMPTY RESIN INTO WIDE
MOUTH GLASS AMBER JAR
CLOSE CONDENSATE RESERVOIR VALVE
RELEASE UPPER CLAMP AND
LIFT OUT INNER WELL
WITH GOTH UNITIZED WASH BOTTLE
(CH2CI2:CH3OH) RINSE INNER WELL
SURFACE INTO AND ALONG CON-
DENSER WALL SO THAT RINSE RUNS
DOWN THROUGH THE MODULE AND
INTO CONDENSATE COLLECTOR
WHEN INNER WELL IS CLEAN,
PLACE TO ONE SIDE
REPLACE SCREEN ON CARTRIDGE, RE-
INSERT CARTRIDGE INTO MODULE. -.
JOIN MODULE BACK TOGETHER.
REPLACE CLAMP.
OPEN CONDENSATE RESERVOIR
VALVE AND DRAIN AQUEOUS
CONDENSATE INTO A 1 LITER
SEPARATORY FUNNEL. EXTRACT
WITH CH2CI2.
RINSE ENTRANCE TUBE INTO MODULE
INTERIOR. RINSE DOWN THE CONDEN-
SER WALL AND ALLOW SOLVENT TO
FLOW DOWN THROUGH THE SYSTEM
AND COLLECT IN CONDENSATE CUP
RELEASE CENTRAL CLAMP AND
SEPARATE THE LOWER SECTION
(XAD-2 AND CONDENSATE CUP)
FROM THE UPPER SECTION (CON-
DENSER)
THE ENTIRE UPPER SECTION IS NOW
CLEAN.
RINSE THE NOW EMPTY XAD-2 SEC-
TION INTO THE CONDENSATE CUP
RELEASE LOWER CLAMP. AND
REMOVE CARTRIDGE SECTION
FROM CONDENSATE CUP
THE CONDENSATE RESERVOIR NOW
CONTAINS ALL RINSES FROM THE
ENTIRE SYSTEM. DRAIN INTO AN
AMBER BOTTLE VIA DRAIN VALVE.
Figure 23. Sample handling and transfer— SASS XAD-2 module
63
-------
ADD RINSE FROM
CONNECTING LINE
LEADING FROM XAl>-2
MOD TO FIRST IMPINGER
IMPINGER NO. 1
TRANSFER TO
NALGENE
CONTAINER
RINSE WITH 1:1 IPA/
DIST. H20 AND ADD
IMPINGER NO. 2
TRANSFER TO
NALGENE
CONTAINER
RINSE WITH 1:1 IPA/
DIST. H2O AND ADD
2
z
IMPINGER NO. 3
TRANSFER TO
NALGENE
CONTAINER
RINSE WITH 1:1 IPA/
DIST. H2O AND ADD
COMBINE AND
MEASURE TOTAL
VOLUME FOR
SINGLE ANALYSIS
IMPINGER NO. 4
DRIERITE
DISCARD
Figure 24. Sample handling and transfer— SASS impingers
64
-------
The automatic high-volume sampler should be operated so that the intake
velocity matches or exceeds the velocity of the stream at the sampling point.
Sample Handling—
Preservation and handling considerations for liquid/slurry samples
are addressed in Table 10 and apply to Levels 1 and 2.
Organic samples should be placed in amber glass bottles for transfer.
Bottles should be thoroughly cleaned before use (by washing with solutions
of soap, tap water, and then distilled water) and then oven dried at a
temperature of 40°C. Polyethylene or polypropylene bottles should be used
for the aqueous portion of the liquid/slurry samples. Washing procedures
involve a detergent wash with a distilled water rinse, followed by a 1 to 1
sulfuric and .nitric acid wash..
Liquid samples (10 liters) are separated for subsequent analysis
by the following scheme: one liter of the liquid sample is retained for BOD
and COD analysis. (it is important this sample be transferred carefully to
avoid air entrainment). The remaining nine liters are filtered under
pressure; the solid portion is dried, weighed (total suspended solids) and
preserved for later analysis. The filtrate is separated into an aqueous and
organic fraction using a separatory funnel. The aqueous portion is extracted
with methylene chloride to complete the separation of aqueous from organic
material. These organic.fractions are preserved for organic analysis. The
remaining aqueous solution is divided into three portions; the first portion
is acidified to pH<2, the second portion is left as is, and the third is
adjusted to pH 8-12.
Solid Sampling
Recommended Methods—
Recommended techniques for the sampling of solid materials are specified
in Table 11 under Stream Categories A and B. Appendix Table A-4 as well as
the references listed there and in Table 11 provide more detailed discussions
of these techniques.
Level 1 sampling of FBC solid residue streams should be performed
by a simple grab technique where one shovelful of material is taken from the
discharge point of a hopper or line. If a discharge point is not readily
accessible, then the residue should be sampled from a pile or a container
used for material storage or transport (e.g. railroad car). Depending on
the density of the residual material, a pipeborer or an auger is employed.
For Level 2 sampling of solid residues, use of an automatic Vezin-type
sampler, installed in a vertical section of a pneumatic transport line, is
recommended (residues are assumed to be transported pneumatically in generic
systems). If installation in a line is not practical, residues must be
sampled from a pile or a container using a pipeborer or auger.
65
-------
TABLE 10. PRESERVATION OF LIQUID/SLURRY SAMPLES
Ana-lysis
Acidity
Alkalinity
Conductivity
BOD
COD
Suspended Solids
Total Dissolved Solids
Hardness
Water & HC1 Leachable Anions
Trace Cations
pH
Organic Material
Meth.ylene Chloride Extracts
Cyanides
Ammonia Nitrogen
Fraction
Untreated
Untreated
Untreated
Untreated
Ac id i f y
Untreated
Untreated
Untreated
Basify
Acidify
Untreated
Untreated
Untreated
Untreated
Untreated
Preservation
Cool 4°C
Cool 4°C
Cool 4°C
Cool 4°C
H SO to pH<2
None Required
None Required
Cool 4°C
NaOH to pH12
HNO <2
-
None Required
None Required
Cool 4°C
Cool 4°C
Holding
24 hr's ,
24 hr.s .
24 hr-s .
6 hrs.
7 days
-
-
7 days
Depends on
An ion
38 days
Run immediately
7 days
7 days
Run immediately
24 hrs.
66
-------
For Level 1 and Level 2 sampling of the coal and sorbent feeds, a
stopped-belt technique is recommended: (in generic units, solid feed
materials are assumed to be transported from storage to.size reduction
operations by belt conveyor).
Sampling Location--
Sampling location has been addressed in the above discussion.
Sampling Procedures--
Level 1 sampling requires that only one increment be taken per sample
except in the case where the simple grab technique is used for sampling
piles of large aggregate material such as a coal. In.this instance, four
shovelfuls of material are collected from different portions of the pile.
In using a pipeborer or auger, care must be taken that the entire depth
of the pile is sampled. If the pile is of such depth that this is not
feasible, then an alternate technique must be used.
Level 2 stopped belt.sampling entails the stopping of a belt conveyor
every 10 to 15 minutes during the course, of the test period. A full cross-
sectional cut is taken from the belt by drawing a flat-edged shovel across
it. For Level 1 sampling, the belt is stopped only once.
Sampling procedures for each Level 2 technique involve collecting a number
of increments which are then subject to a size reduction operation such as
riffling to produce a representative sample. ASTM procedures for determining
the weight and number of increments should be followed (where applicable).
Sampling Handling-
Samples should be placed in polyethylene containers or bags for shipment.
Containers must be air-tight.
Air-borne Fugitive Sampling
Recommended Methods—
Air-borne fugitive emission sources can be divided into three categories:
diffuse wide-area sources, diffuse area sources, and specific point sources.
For the first category (also called site sources), emissions are specific to
a plant location but are due to the combination of many sources which produce
a diffuse emission cloud over the entire plant area. The second-category is
characterized by a diffuse cloud over an area which can be related to a
single specific source such as a coal pile. Specific point sources, the
third category, are associated with a distinct plume (such as that from a
vent) and normally can be enclosed (i.e., ducted) for sampling purposes.
For commercialized FBC units, it is anticipated that the total number
of specific point sources will be small as a result of (projected) proper
67
-------
design, maintenance, and operating practices. As discussed in Chapter 2,
the only specific air-borne fugitive sources that are addressed in the
present study are stockpiles of feed materials and solid residues that may
be subjected to winds. (These sources belong to the diffuse area category.)
Recommended techniques for air-borne fugitive sampling are presented
in Table 11 under Stream Category M. Additional information on these
techniques may be found in Appendix Table A-5 as well as in the references
listed there and in Table 11. The methods employed for 'sampling fugitive
gases are essentially the same as those recommended for ducted gas streams
(e.g., simple displacement bomb, gas specific trains, etc.).
A downwind technique employing a high-volume sampl-er is recommended
for Level 1 (particulate) sampling of diffuse area sources (e.g., piles).
Presently, a possible .method which may be employed for Level 2 diffuse area
sampling is an upwind-downwind technique developed by Midwest Research
Institute, also employing a high-volume sampler. An XAD-2 absorber which
is attached to the high-volume sampler is used to sample nonvolatile
organics (>C7).
If, during the pre-test site survey, specific point sources are
identified, then plume sampling employing a SASS train and gas bomb is
recommended for the Level 1 effort while quasi-stack sampling using the SASS
and gas-specific trains is suggested for Level 2.
Finally, if the number of fugitive sources (diffuse area and specific
point sources) at a particular site is large, the most cost-effective
approach would be to sample the entire plant area as a diffuse wide-area
source. At Level 1, an upwind-downwind technique using high-volume samplers
and gas bombs is recommended. The Level 2 effort would involve a comparison
of ambient background data with operating plant data gathered at the same
sampling sites. If background data is unavailable, an upwind-downwind
method should be employed.
Sampling Location—
For diffuse wide-area sampling, the number and placement of samplers
is, in general, site specific. In the upwind-downwind method specified for
Level 1, one sampler placed upwind and two or three samplers placed downwind
of the site and removed from any specific sources should be sufficient.
For downwind sampling of diffuse area sources at Level 1, one high-
volume sampler is placed directly in the emission cloud. In the Midwest
Research upwind-downwind method for Level 2, samplers are mounted on a
vertical towe-r in a grid arrangement. Tower placement is site specific.
For Level 1 sampling of specific point sources, sampling probes are placed
directly in the plume;, while in the Level 2 quasi-stack method, a duct is
constructed around the source which is then sampled as a normal ducted stream.
68
-------
Sampling Procedures—
Detailed sampling procedures; for each of the recommended methods
specified in Table 11 can be found: in the references listed there and-in
Appendix Table A-5.
Samplie Hand'ling--
The filter of a high-volume sampler should be handled carefully during
transfer to a Petri dish. The Petri dish should be sealed for shipment.
Handling and transfer considerations for gas samples are the same as those
discussed earlier under "Gas Sampling".
69
-------
TABLE 11. SUMMARY OF RECOMMENDED SAMPLING PROCEDURES FOR GENERIC FBC PROCESSES
(CATEGORIES I THROUGH IV)
STREAM
CATEGORY
A.
Solid -
Residues
B.
Raw
Solid
Feeds
(Coal
and
Sorbent )
APPLI-
CABLE
STREAM
NUMBERS
2, 3,
4, 5
28
(CAFB)
9, 10
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
Simple
grab
Pipeborer
Auger
Stopped
belt
sampling
SELECTION
RATIONALE
Simple,
inexpensive
technique
This tech-
nique will
eliminate
bias caused
by size
segregation
which may
occur in the
pile.
Solids pile
should be
sampled if
discharge
point is
not access-
ible.
If material
is too dense
to permit the
use of a
pipeborer, an
auger should
be employed.
Most repre-
sentative
sampling
bechnlque.
Simple and
inexpensive
technique .
SITE
PREPARATION
REQUIREMENTS
None
None
None
None
REFER-
ENCES
297
8.33
297
297
REMARKS
For sampling site
at discharge point
of line or hopper.
One shovelful is
taken from the
idischarge point of <
a hopper or line.
One kilogram Is re-
quired for analy- \
'sis.
For sampling site
at a pile or con-
tainer. One sam-
ple, at least one
kilogram in
weight, is taken.
For sampling site
at a pile or con-
tainer. One sam-
ple, at least one
kilogram in
weight, is taken.
Selection assumes
that raw feeds are
transported' by belt
conveyor to size :
reduction operr
tions. A single
sample, at least
1 kg in weight, is
taken. A flat-
edged shovel is
drawn straight
across the belt to
produce a full
stream cut.
70
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Automatic,
full
stream cut,
Vezin-type
sampler.
Pipeborer,
auger '
Stopped
belt
sampling.
SELECTION
RATIONALE
Sampling
device was
selected due
to its applic-
ability of use
in pneumatic
transport
lines.
Cutter vari-
ables are
determined by
particle size
and mass flow
rates.
If sampling
device cannot
be installed
in line, then
pipeborer or
auger • should
be used. See
Level 1.
See Level 1.
Human bias can ;
be minimized
by systematic
sampling .
SITE
PREPARATION
REQUIREMENTS
Installation of
sampling
equipment
necessary in
vertical
section of
pneumatic trans-
port line..
Installation of
the devices "
should be eight
pipe diameters
downstream and
two pipe dia-
meters upstream
of any flow
disturbance.
None
None
REFER-
ENCES
297
8.33
J
297
-
REMARKS
For pneumatic transport
line sampling. (As-
sumes that materials
in question are con-
veyed by pneumatic
transport j .
For sampling site at a
pile or container. The
number of increments is
to be in accordance
with ASTM specifica-
tions .
Usually a minimum of
35 increments of 3 kg
weight is required .
The sample is then
riffled to size re-
quired •for""Hnalysis. '
See Level 1.
If transport is pneu- ,
matic, a Vezin sampler '•
should be used. (See i
stream category A,
Level 2).
A minimum of 35 incre-
ments should be taken
with a minimum weight
«
APPLICABLE
AREAS OF
ANALYSIS
Elemental
analysis,
Organic
analysis,
Anion
analysis.
Physical
character-
izations,
Leachate
testing
Elemental
analysis,
Organic
analysis,
(sorb. nt A
only)
Fuel /
analysis ^
(
-------
TABLE.11 (continued).
STREAM
CATEGORY
B.
(cont. )
C.
Slow-
downs
APPLI-
CABLE
STREAM
NUMBERS
9,10
6, 7
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
Auger'
Simple
grab
Dipper
(full
stream
cut)
'
SELECTION
RATIONALE
If conveyor
Is not acces-
sible then
the storage
hopper shoulc
be sampled
using an
auger.
An auger is
used rather
than a pipe-
borer because
of the den-
sity of the
material.
Simple and
inexpensive
technique.
If the
storage hop-
per is not
accessible,
then the
coal or
sorbent pile
must be
sampled
directly.
Simple and
inexpensive
technique.
This method
will elim-
inate poss-
ibility of
sample bias
which could
be caused by
stratifica-
tion.
SITE
PREPARATION
REQUIREMENTS
None
None
None
REFER-
ENCES
297
297
O •*!'••»
8.33
13.1
13.2
13.3
13.5
REMARKS
For sampling site
at a storage hop-
per or silo. One
sample, at least
one kilogram in
weight, is taken.
For sampling site
at a pile. Four
shovelfuls from
different sides of
the pile are taken
For sampling site
at discharge point
of blowdown. Care
must be taken that
the dipper does
not overflow while
the sample is be-
ing taken. A 10
liter sample vol-
ume is required
for analysis.
72
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Automatic
Hi-Volume
Sampler.
SELECTION
RATIONALE
i This method
has been shown
to produce rep-
sentative sam-
ples from high
solids content
; streams .
SITE
PREPARATION
REQUIREMENTS
Installation of
sampling device
in line is
necessary.
Sampler should
be placed in a
highly turbulent
region of the .
transport line.
REFER-
ENCES
REMARKS
of 3 kg for each
increment. A samp-
ling scheme (repli-
cation, sample size)
can be determined
.from previous test
;runs. Access to the
: conveyor must be
unhampered .
For sampling site in
blowdown line. Sam-
pling lines should be
purged prior to the j
taking of each sample."
Materials of construe-'
. tion should conform tq
ASTM standards. ASTM
procedure for sampling
water from boilers
should be followed .
The sampling velocity
, should match or exceed
the stream velocity at
i the sampling point.
Samples should be
APPLICABLE
AREAS OF
ANALYSIS '
Physical
character-
ization,
Leachate
testing
Elemental
analysis
Organic
analysis
Anion
analysis
Standard
Iwater
analysis
73
-------
TABLE 11 (continued) .
STREAM
CATEGORY
c.
(cont . )
D.
Liquid
Sulfur/
Sulfurlc
Acid
Product
APPLI-
CABLE
STREAM
NUMBERS
6,7
8
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
Tap
Tap
SELECTION
RATIONALE
If access to
the discharge
point Is re-
stricted
then this
method must
be employed.
Since these
streams are
homogeneous
in nature, a
tap sample
should be
representa-
tive.
SITE
PREPARATION
REQUIREMENTS
Tap Installed
In well-mixed
region (e.g.,
after pump,
transition
piece, elbow,
etc. ) of blow-
down line.
Tap installed
in product
discharge
line or in
holding tank.
REFER-
ENCES
13.1
13.2
13.3
13.5,
13.1
13.2
13.3
13.5
REMARKS
For sampling site
in blowdown line.
Sample rate should
be less than 500
ml/min . Apparatus
should conform witl
requirements in
AS'TM 510.
A 10 liter sample
volume is required ,
for analysis.
For sampling site
in discharge line
or tank. Tap
materials of con-
struction must be
acid resistant and
be able to with-
stand the tempera-
ture of the liquid
sulfur. Sample
rate should be lest
than 500 ml/min.
A 10 liter sample
volume is required
for analysis.'
74
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Tap
SELECTION
RATIONALE
Same as Level
1.
SITE
PREPARATION
REQUIREMENTS
Same as Level
1.
REFER-
ENCES
13.1
13.2
13.3
13.5
REMARKS
taken on a time pro-
portional basis.
ASTM procedures for
water sampling should
be used to determine
sampling rate based
on Level 1 results.
APPLICABLE
AREAS OF
ANALYSIS
-------
TABLE 11 (continued).
STREAM
'CATEGORY
E.
Stack Gas
(Gaseous
Compo-
nents)
SOo
c.
APPLI-
CABLE
STREAM
.NUMBERS
1
1
LEVEL 1
RECOMMENDED
SAMPLING
iMETHOD
Simple Dia:
placement :
Bomb
SELECTION
.RATIONALE
Reasonable
cost.
Available
trained
operators .
Allows for
analysis of
other gases.
Uses stand-
ard appara-
tus . 'Ref-
erence
method for
CO, 002, °2»
H2, N2, CH4.
Can be used
to sample
high pres-
sure, high
temperature
streams 'by
means of
side- split
bleed strean
and water
cooled heat
exchanger.
SITE
PREPARATION
REQUIREMENTS
REFER-
ENCES
13.6
211
323
REMARKS
See text under "Gas
Sampling" for
sampling . location
and technique
ispec-ifications for
Level 1.
Gas displacement,
liquid displace-
ment or evacuated
:bbmb techniques
can be -used.
Requires rapid
analysis.
Glass-wool pre-
.f lit e"r; used.
Distance from
stack wall to
bomb should be
minimized to pre-
vent condensation
in sampling line.
,Gas displacement
bombs should be
purged with 10
'liters of stack
gas before the
sample is taken.
76
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Option 1
(Manual) :
EPA
Metho^ 6
Option 2
(Contin-
uous ) :
Perform-
ance Speci-
fication
No. 2
SELECTION
RATIONALE
Commonly rec-
ognized as a
standard ref-
erence method
that other
mettiods are
compared to.
A method for
continuous
measurement of
SOg will prob-
ably be re-
quired as a
part of EPA's
New Source
Performance
Standards for
PBC, if adopt?
ed. It is al-
so desirable
from the stand-
point of not-
ing S02 levels
versus process
changes . .S02
is Just one
of several
gases that will
probably be
measured on a
continuous ba-
sis.
A continuous
system is less
expensive over
a long period
if numerous
measurements
will be made.
SITE
PREPARATION
REQUIREMENTS
Erection of
scaffolding
.will normally
be required.
Multiple stack
(or duct) ports
may be re- , .
quired for
stratification
investigations.
REFER-
ENCES
116
114
(120,
107,
77)
REMARKS
See text under "Gas
sampling" for sampling,
location and technique
specifications for
Level 2.
A combined S02-S0.o
train is recommended
for this option.
A stratification In-
vestigation using any
one of the concepts
presented in the
Gas Sampling Options
Table In the Appendix
should be conducted to
design the extractive
sample system. .
An extractive rather
than an In-situ sys-
tem is recommended for
generic units. This
allows the potential
of continuous instru-
mental analysis for
more gaseous pollut-
ants that the in-situ
devices will currently
measure. The system
can either be split-
stream or on-line.
Both should be evalu-
ated for sample repre-
sentativeness .
APPLICABLE
AREAS OF
ANALYSIS
Inorganic
gases,
Organic
analysis
Inorgani c
gases
77
-------
TABLE 11 (continued).
STREAM
CATEGORY
( cont . )
SO,
3
NOX
H2S
APPLI-
CABLE
STREAM
NUMBERS
1
1
1
RECOMMENDED
SAMPLING
METHOD
SASS train
Simple
Displace-
ment Bomb
Simple
Displace-
ment Bomb
SELECTION
RATIONALE
Order of
.magnitude
determina-
tion can be
made by
•analyzing
iihpinger
solutions,,
cohdensate
trap, porous
polymer
adsorber and
partic'ulate.
LEVEL 1
SITE
PREPARATION
.REQUIREMENTS . ,
REFER-
ENCES
321
(37,
95,
302.
279)
13.6
211
323
13.6
211
323
REMARKS
See discussion of
SASS train under
Steam Category F.
See Simple Dis-
placement Bomb
discussion under
Se'e Simple Dis-
placement Bomb
discussion under
78
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Controlled
Conden-
sation
( Goksoyr-
Ross)
Option 1
(Manual):
EPA-
Method 7
Option 2
(Contin-
uous) :
Perform-
ance Spec-
ification
No. 2
EPA
Method 3
SELECTION
RATIONALE
803 specific.
Short sample
period .
Simple
analysis.
Low concen- '
tratlon detec-
tion.
Extensive
application
on combustion
sources.
Standard
reference
method .
Sufficient
accuracy for
Level 2
requirements
using simple,
Inexpensive
equipment .
Multi-gas
sampling.
Ease of Inte-
gration with
analytical
procedure.
SITE
PREPARATION
REQUIREMENTS
Only one port .
Routine 15 amp
power required.
Small space
requirement
(one man plus
equipment ) .
See Level 1.
One port.
Routine 15 amp
power require-
ment .
Small space
requirement
(one man plus
equipment ; .
REFER-
ENCES
321
(37,
95,
302.
279)
116
114
(120.
107)
116
REMARKS
NOTE: This Is a "wet"
technique.
A continuous monitoring
procedure Is not avail-
able at this time for
803.
Requires constant
temperature water
bath.
See S02 Level 2
remarks .
Sample Is drawn Into
evacuated flask con-
taining an oxidizing
absorbent which con-
sists of hydrogen
peroxide in dilute
sulfuric acid.
See Performance
Specification No. 2
discussion under SOg.
For H_S: G/C flame
photometric detection
with adaptions for
analysis.
APPLICABLE
AREAS OF
ANALYSIS
Inorganic
gases
Inorganic
gases
Inorganic
gases
79
-------
TABLE 11 (continued).
'STREAM
CATEGORY
E.
( corit . )
CQ2
APPLI-
CABLE
STREAM
NUMBERS
1
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
Simple
Dliapi'ace-
Tiierit Bomb
SELECTION
RATIONALE
SITE
PREPARATION
REQUIREMENTS
REFER-
ENCES
13.6
211 :
323 •
REMARKS
See Simple Dis-
.p'racefherit Bomb
aiscus'aibn under
sbg
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Option 1
(Manual):
EPA
Method 3
Option' 2
( Contin-
uous) :
Perform-
ance Spec-
ification
No. 3
SELECTION
RATIONALE
OUrrent EPA
Reference
Specification
that is re-
lated back to
Method 3.
Allows use of
either ex-
tractive or
non- ex-
tractive con-
tinuous sys-
tems.
SITE
PREPARATION
REQUIREMENTS
REFER-
ENCES
116
114
(107)
REMARKS
See EPA Method 3. dis-
cussion under HpS.
For COg: OC or NDIR
analysis.
Conduct a stratifica-
tion investigation to
design system.
Recommend using ex-
tractive sampling sys-
tem which allows multi-
gas instrumental
analysis.
APPLICABLE
AREAS OF
ANALYSIS
Inorganic
gases
81
-------
TABLE 11 (continued).
STREAM
CATEGORY
E. (cont. )
HC1
HCN
HF & F
CO
APPLI-
CABLE
STREAM
NUMBERS
1
1
1
1
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
SASS
Train
Simple
Displace-
ment Bomb
SASS
Simple
Displace-
ment Bomb
SELECTION
RATIONALE
Particulate
fluoride
will be
routinely
determined
" from the
particulate
SITE
PREPARATION
'REQUIREMENTS
-
REFER-
ENCES
218
173
2
13.6
211
323
13.6
211
323
REMARKS
See SASS Train
discussion under
SO
3
See Simple Dis-
placement Bomb
under SOg.
A specific
method has not
been written up.
See Simple Dis-
placement Bomb
under SOg.
82
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Impinger
Train
Impinger
Train
Impinger
Train
Option 1
(Manual):
EPA
Method 10
SELECTION
RATIONALE
Most accurate
sampling and
. analysis
technique.
Rapid .
Routine sam*
pling train.
Same train
may be used
for different
gases by.
changing
reagent .
Commercially
available.'
Gaseous HP
and P are
obtained .
Partlculate,
HP and P
determined
from partlc-
ulate train.
See Selection
Rationale
for HC1,
Level 2.
Manual, metho.d
for Level 2;'
Acceptable
accuracy,' low
cost,1 simple
multi-gas
sampling
system.
SITE
PREPARATION
REQUIREMENTS
One port.
One man train
operation.
Routine 15 amp
requirements.
•
Single port
sampling.
Small space
requirements .
for one man
operation.
Normal 15 amp
power required .
REFER-
ENCES
311
13.8
196
^
166
261
152
166
311
261
204
112
(99)
REMARKS
Single point, manual
method.
Midget impingers
operated In a fashion
similar to EPA Method
6 for S02 (probe,
heated impingers,
pump, test meter, etc.]
A specific method
has not been written
up. ' The train will
have to be developed
from reference Infor-
mation.
For HC1 use distilled
HgO in impingers for
collection.
See Impinger train
dlcussion under HC1.
Por'HCN: use either
KOH or NaOH in' impin-
gers for collection.
See implnger train
discussion under HC1.
For HF and P: use
distilled water in
impingers for collec-
tion.
This ._ is a grab, Btngle
point method that is
acceptable for Level
.2 sampling.
Essentially an EPA
Method 3 sampling
system.
Use stainless bellows
pump if sample passes
thru pump -to bag.
APPLICABLE
AREAS OF
ANALYSIS
Inorganic
gases
Inorganic
gases
Inorganic
gases
Inorganic
gases
83
-------
TABLE 11 (continued).
STREAM
CATEGORY
E. (cont)
CO (cont)
°2
APPLI-
CABLE
STREAM
NUMBERS
1
1
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
Simple
Displace-
ment Bomb
SELECTION
RATIONALE
SITE
PREPARATION
REQUIREMENTS
REFER-
ENCES
13.6
211
323
REMARKS
See Simple Dis-
placement Bomb
discussion under
SCL.
2
84
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Option 2
(Contin-
uous) :
EPA
Method 10
Option 1
(Manual):
EPA
Method 3
Option 2
(Contin-
uous) :
Perform- :
anne
Specifi-
cation No.
3
i . I
SELECTION
RATIONALE
Reference
method . Con-
tinuous method
for Level 2.
Accurate, con-
venient system.
Reasonable
cost.
SITE
.PREPARATION
REQUIREMENTS
Same as
above.
The number of
ports required
depends on
results .of a
stratification
investigation.
The recommend-
ed location up
the stack .
should only
require single
point sampling.
REFER-
ENCES
112
(94)
116
114,
(101)
REMARKS
This is the continu-
• ous monitoring option
; for CO. The sampling
j and instrument set-upv
operation and specif 1?-.
• cation are well de-
fined . A stratifi-
cation investigation
should be conducted to
verify single point
probe sampling.
: Otherwise, multi-
: point sampling may be
'. required .
For generic units,
• sampling at least 8
diameters up the
stack will be speci-
. fled as a minimum.
All particulate and
gaseous sampling
should be conducted
at that same location.
Extractive system
recommended to facili-
tate multi-gas
analysis.
See EPA Method 3 dis-
cussion under H2S.
For .02 : GC thermal
Conductivity analysis.
An 'accurate calibra-
tion standard is
required .
See Performance
Specification No. 3
discussion under COo.
For 02: polarograpnlp
or paramagnetic in-
struments will meet
specifications.
APPLICABLE
AREAS OF
ANALYSIS
Inorganic
gases
Inorganic
gases
85
-------
TABLE 11 (continued).
STREAM
CATEGORY
E. (;cont..)
NH-,
J
H20
COS
APPLI-
CABLE
STREAM
NUMBERS
1
1
1
LEVEL 1
RECOMMENDED
' SAMPLING"
METHOD
Simple
Displace-
ment Bomb
EPA
Method 4
Simple
Displace-
ment Bomb
; SELECTION
RATIONALE
A commonly
used tech-
nique incor-
porated in
a reference
toethod .
Simple,
inexpensive,
rapid ,
accurate,
and applic-
able to
wide range
of concen-
trations.
SITE
PREPARATION
REQUIREMENTS
Single port
sampling.
Small space
requirements
for one-man
operation.
Normal 15 amp
power require-
ments.
REFER-
ENCES
13.6
211
323
116
70
50
281
13.6
211
323
REMARKS
See Simple Dis-
placement Bomb
discussion under
so2
Ice bath (approx-
imately 0°C) con-
denses most mois-
ture and dessl-
cant collects
remaining moisture
down to relatively
insignificant
levels.
See Simple Dis-
placement Bomb
Discussion under
S02
Analyze immedi-
ately
86
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
KJeldahl
(Nessler-
ization)
EPA
Method 4
EPA
Method 3
SELECTION
RATIONALE
A reference
method for
NH3 in stack
gas has not
been adopted
by EPA or
ASTM. This
EPA method for
NHo in waste-
water is sug-
gested as an
interim method .
The sampling
procedure is
an impinger
wet-chemical
method . Ap-
plies a com-
monly used an-
alytical pro-
cedure. Accu-
rate, inexpen-
sive sampling
procedure.
SITE
PREPARATION
REQUIREMENTS
Single port
sampling.
Small space
requirements
for one-man
operation.
Normal 15 amp
power require-
ments .
REFER-
ENCES
216
278
287
116
70
50
281
116
REMARKS
Impingers contain
0.1N H2S04.
Same as Level 1 .
An NDIR may be used
for low concentration
moisture as an adapted
continuous monitor.
In general, a contin-
uous instrument is
not available for
higher (10$) concen-
trations of moisture.
A commercially avail-
able monitor la re-
ported to handle up to
5$ moisture (105) .
If Installed and cali-
brated with Method 4
for the anticipated
range, it could be
used for Level 2.
See EPA Method 3 dls- -
cussion under HoS.
For COS: G/C flame
photometric detection
with adaptations for
analysis.
i .
Analyze immediately
APPLICABLE
AREAS OF
ANALYSIS
Inorganic
Gases
Inorganic
Oases
Inorganic
Gases
87
-------
TABLE 11 (continued).
STREAM
CATEGORY
E. (cont. )
CS2
Hff
£
Volatile .
Organ! cs
(Cl-C6)
APPLI-
CABLE
STREAM
NUMBERS
1
1
1
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
Simple
Displace-
ment bomb
SASS Train
Simple
Displace-
ment'Bqmb
SELECTION
RATIONALE
SITE
PREPARATION
REQUIREMENTS
REFER-
ENCES
13.6
211
323
218
173
2
13.6
211
323
REMARKS
See Simple Dis-
placement Bomb
discussion under
S02.
See SASS Train
discussion under
so3.
See Simple Dis-
placement Bomb
discussion under
S02.
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
EPA
Method 3
Gold
Amalga-
mation
EPA
Method 3
SELECTION
RATIONALE
Defacto refer-'
ence method.
Accurate for
obtaining both
gaseous and
particulate
Hg . Commonly
applied and
available sam-
ple train with
special Hg
adaption.
SITE
PREPARATION
REQUIREMENTS
See Level 1.
Traversing
facilites re-
quired . Power
required for
pump and heat-
ing elements.
See Level 1.
REFER-
ENCES
lib
175
115
116
1
116
REMARKS
See EPA Method 3 dis-
cussion under HoS.
For CS2: G/C flame
photometric detection
with adaptions for
analysis.
Reference (83) pre-
sents a technique of
adapting EPA Method 5
(partlculates) to
collect Hg (gas and
particulatesj. Refer-
ences (67) and (l)
should be used for
operational and in-
structions and refer-
ence (83) should be.
used for train setup
and sample removal
and analysis. A sat-
isfactory, single
write-up method does
not exist for Hg at
this time since
Method 105 (67) is un-
acceptable in higher
concentration SOg
streams .
Operations of the full
Method 5 traverse
train is specified
here to obtain total
(gaseous plus particu-
late) Hg emission rate
information.
NOTE: This parti cu*
late emission rate da-
ta may be compared
with the SASS train
for correlation.
See KPA Method 3 dis-
cussion under H2S.
For volatile organics:
G/C flame ionization
detection with adap-
tions for analysis.
APPLICABLE
AREAS OF
ANALYSIS
Inorganic
Gases
Inorganic
Gases
Organic
Analysis
-------
TABLE 11 (continued).
STREAM
CATEGORY
.Organic B'
Non-
volatile
Hydro-
carbons
(>C6>
\J
APPLI-
CABLE
STREAM'
'NUMBERSI
1
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
SASS'
SELECTION
-- RATIONALE
The predom-
inate sfea-
: son for se-
lecting this
system for
non-volatile
hydrocarbons
is that'(l)
it is a par-
ticulate
-train (much
of these
hydrocarbons
•Will exist
as particu-
lates at
stack con-
ditions).
(2) it is
specially
designed to
cool the
gases for
additional
condensa-
tion of
these
species for
collection,
and. (3) it
will collect
those more
volatile
species on
the XAD-2
adsorber.
It is a
multi-
pollutant
sampling
system.
See Stream
Category P.
SITE
PREPARATION
; REQUIREMENTS
fSee Particu-
late Stream
Category for
.site prepara-
tion requlre-
iments.
REFER-
ENCES
2
218
175
REMARKS
The SASS train
(system) is. dis-
cussed In. more de-
tail under1 Stream
• Category P:i This
recommended Level
1 particulate
: sampling: system
will also collect
the non-volatile
hydrocarbons .
The species will
be found con-
densed , with par-
ticulates, on the
porous polymer ad-
sorber and in the
impingers .
This is a state-
of-the-art system
that needs
additional field
testing to clarify
performance and
operating
characteristics .
90
-------
TABLE 11 (continued).
LEVEL 2
'RECOMMENDED
SAMPLING
METHOD
SASS
SELECTION
RATIONALE
See Level 1
discussion.
This system
provides the
one- train
capability of
obtaining a
representative
sample of a
wide range of
organic mater-
ial that 'can be
analyzed using
a promising1'
combination
of reference
and. recognized.
'techniques
with state-of-
the-art'
adaptions .
SITE
PREPARATION
REQUIREMENTS
See Level 1.
REFER-
ENCES
2
211
173
REMARKS
See Level 1.
For sampling location
and recommended tech-
nique, see text. This
'system Is versatile in
collecting simultane-
ously many organic ma-
terials that exist in
various forms from
solid to liquid to
gas. It should be
noted that other samp-
ling methods are per-
haps more efficient
for some specific or-
ganics of interest.
Prior to sampling the
future generic facili-
ties, the Level' 1 eval-
uation should be con-
sulted to identify
those organics of in-
terest and then a de-
termination made as to
the SASS. in obtaining
these select organics
in the desirable man-
ner. Other more com-
plex techniques, in-
cluding a Kaiser Tube
for cryogenic collec-
tion of low molecular
weight materials, may
be required, separate-
ly or as an add-on to
the SASS.
APPLICABLE
AREAS OF
ANALYSIS
Organic
Analysis
91
-------
TABLE 11 (continued).
STREAM
CATEGORY
F.
Stack
Gas (Par-
ticulates;
i
APPLI-
CABLE
STREAM
NUMBERS
1
.
LEVEL 1
RECOMMENDED
'SAMPLING
METHOD
SASS
SELECTION
RATIONALE
This system
will simul-
taneously
collect arid
classify^
in a previ-
ously un-
available
mariner, par-
tlculate and
gaseous
samples .
The system
can obtain
a necessary ;
quantity
of sample
for physi-
cal, chemi-
cal, and
biological
analysis in
a reasonable
period of
time and is
commercially
available.
SITE
PREPARATION
REQUIREMENTS
One port re-
quired . Power
required for
:two pumps and
heatliig ele-
ments'. Over-
sized port or
associated el-
ements may be
required !tb
support train.
More than nor- ;
mal space re-
.quirements for '
men and train.
.Field lab re-
quired for •
train cleanup.
REFER-
ENCES
2
218
173
REMARKS
See text under
"Particulate
Sampling for
sampling location
and technique
specifications
for -Level 1 .
The. SASS train is
expected to pro-
vide the follow-
.;irig information:
. -I. Parti c.ulate
-concentration .
2;; . Parti/cle
• size, distribu^-
tlon>.
. . ::3<£' Npn-vola-
• tile organic
and inorganic
concentrations .
4. Particulate
for morpholog-
ical; analysis .
A velocity -profile
must be deter-
mined 'at sampling
location in
accordance with
EPA Methods 1 and
2 to convert con-
centrations to
emission rates .
92
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
SASS
SELECTION
RATIONALE
See Level 1.
The current
equipment sys-
tem can be com-
bined with a
location speci-
fication to
provide mass
emission rates
that reflect
representative
sampling.
SITE
PREPARATION
REQUIREMENTS
Erection of
scaffolding
will normally
be required.
More than one
port required.
Traversing
facilities
required .
Power required
for two-" pumps
and heating
elements
More than
normal space
requirements
for men and
train.
Field lab
required for
cleanup.
-
REFER-
ENCES
2
218
173
REMARKS
See text under '"Partic-
ulate Sampling" for
sampling location and
technique specifica-
tions for Level 2.
Velocity. profile is de-
termined by EPA Method
1 and 2. A standard
pitot should be used
in place of the "S1
type tube.
Level 1 results will
dictate specific
pollutants of interest
for Level 2. Depend-
ing on the applicabil-
ity of the SASS train
as it evolves, some of
these pollutants
should, for specifi-
city and accuracy, be
sampled using a pollu-
tant specific train
rather than SASS.
See Level 1.
APPLICABLE
AREAS OF
ANALYSIS
Elemental
analysis,
Organic
analysis,
Anion
analysis,
Physical
character'
ization.
93
-------
TABLE 11 (continued).
STREAM
CATEGORY
G.
CAFB
Residual
Oil
Peed
H.
Scrubber
Slurry
Effluent
APPLI-
CABLE
STREAM
NUMBERS
9
5a
(CAFB
only)
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
Tap
Grab,
full
stream cut
Tap
SELECTION
RATIONALE
Due to the
homogeneous
nature of
the stream,
a tap sample
should be
represen-
tative.
Due to the
hetero-
geneous
nature of a
slurry, a
full stream
cut of the
discharge
, should be
made to
obtain a
represen-
tative
sample .
When the
discharge
point is
inaccessible
tap sampling
can be used.
Due to the
hetero- _ -
geneous
nature of
the slurry,
the tap must
be Installed
in a well-
mixed region
of the line,.
SITE
PREPARATION
REQUIREMENTS
Tap must be
installed in
tank or trans-
port line .
None
Tap must be
Installed in
slurry line.
REFER-
ENCES
13.1
13.2
13.3
13.5
13.1
13.2
13.3
13.5
REMARKS
; For sampling site
at tank or trans-
port line.
A sample size of
1'' liter is suf-
ficient.
. For sampling site
at discharge
point of slurry
line.
A sample size of
10 liters is re-
quired .
When the discharge
point is not
accessible a tap
method should be
used.
For sampling site
in slurry line.
A sample size of
10 liters is re-
quired .
94
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Tap
Grab,
full
stream cut
Automatic
High-
Volume
sampler
SELECTION
RATIONALE
Same as for
Level 1.
Same as for
Level 1.
When the dis- '
charge point :
Is Inaccess- '
ible this !
method has. !
been proven
to provide
representative
samples for
liquids with
high solids
contents. i
i
SITE
PREPARATION
REQUIREMENTS
Same as for
Level 1.
None
Sampling line
Is Installed
in the slurry
line.
REFER-
ENCES
13.1.
13.2
13.3
13.5
REMARKS
For sampling site at
tank or transport
line.
Sample size and the
number of sample in-
crements are deter-
mined from Level 1
results and ASTM
reference.
ifor sampling site at
'discharge point of
slurry line.
Sample size and the
number of sample in-
crements are deter-
mined from Level 1 re-
sults and ASTM
references.
For sampling site in
the slurry line (at a
well mixed region).
Sample line intake
velocity oust match
or exceed the stream
velocity at the
sampling point.
Sample size and the
number of sample In-
crements are deter-
mined from Level 1
results and ASTM
references.
APPLICABLE
AREAS OF
ANALYSIS
Elemental
analysis
Fuel
analysis
Anion
analysis
Elemental
analysis,
Organic
analysis,
Anion
analysis,
Standard
water
analysis,
Leachate
testing^
95
-------
TABLE 11 (continued).
STREAM
CATEGORY
APPLI-
CABLE
STREAM
NUMBERS
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
SELECTION
RATIONALE
SITE
PREPARATION
REQUIREMENTS
REFER-
ENCES
REMARKS
I.
CAPE
Gasifier
Product
Gas
'Ogaseoua
compo-:
;nents,)
26
(GAFB
only^)
J.
CAFB
Gasifier
Product
Gas
(Partic-
ulates)
K.
Tail Gas
from
Sulfur
Recovery
(gaseous
compo-
nents)
L.
Tail Gas
from
Sulfur
Recovery
(partic-
ulates)
26
(CAPS
only)
5b
5b
The temperature of Stream 26 is between 1550 P and 1650 F, which
is high enough to require special sampling equipment. The atr''
tempt is to rely upon the same sampling methods that were speci-
fied for Stream Category E, but to employ, in addition, a high-
temperature -interface system. The particulates should be pre-
fil'tered at a .point in the train that is as cool as possible,
yet above the moisture :dew point. A commercial liquid-cooled
probe '(without an In-stack filter.) could be used to Initiate
the cooling and should >be followed by a filter. A 316 stainless
steel, heated cyclone pre-fliter should be used in heavy dust
loading and followed by a quartz or glass wool plug. 'Automatic
blow back is probably too complex an installment for filter
cleaning. An alternate to this system would consist of• an ex-
tra long stainless coll acting as an air cooler prior 'to the
filters. Regardless of the selected system, the temperature
should be monitored prior to the routine wet, ;grab., or continu-
ous train. Carpenter. 20 stainless steel Is also preferred due
to its chemical resistence. Reference ('51).
A high-temperature, liquid-cooled probe is commercially avail-
able '(58) to fit the SASS particulate monitoring system and its
use is recommended for Level 1 and Level '2 sampling of Stream
28. 'The 'cooling component of the HTHP system'may also be
utilized.
The same sampling methods proposed for Stream Categories E and
P should be used for Stream 5b. The stream Characteristics
(temperature, pressure, dust, loading, gas composition,) will be
very similar. One difference relative to sampling'procedures
should be noted. The moisture content and its form (droplets vs.
vapor) downstream of the scrubber may require using multiple
sampling procedures to insure that moisture In droplet form is
not measured as vapor. Several test runs using both hot and
cold pre-filters for the•cbndenser method should verify the
actual vapor content.
96
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
SELECTION
RATIONALE
SITE
PREPARATION
REQUIREMENTS
-
REFER-
ENCES
REMARKS
See Level 1.
See Level 1.
See Level 1.
See Level 1.
APPLICABLE
AREAS OF
ANALYSIS
Same as
for
Stream
Category
E.
Same as
for
Stream
Category
P.
Same as
Stream
Category
E.
Same as
Stream
Category
97
-------
TABLE 11 (continued).
STREAM
CATEGORY
M.
Air-
borne
Fugi-
tives
Diffuse
Wide
Area
Sources
APPLI-
CABLE
STREAM
NUMBERS
LEVEL 1
'RECOMMENDED
SAMPLING
METHOD
Upwind-
Downwind
SELECTION
RATIONALE
This method
is used when
the number
of point
sources at
a particular
site are too
numerous
to sample
individually ,
SITE
PREPARATION
REQUIREMENTS
None required
REFER-
ENCES
73
176
REMARKS
The number of
high-volume samp-
lers necessary for
sampling is plant-
specific, but
should be kept to
a minimum. Gas
bomb sampling is
used to determine
concentrations of
volatile organics
and inorganic
gases.
An Anderson single
stage head will
separate the par-
ticulates into
two size fractions
(cutoff point at
3.5W.
An XAD-2 adsorber
which is attached
to the high-volume
sampler is used to
sample non-vola-
tile organics.
98
-------
TABLE 11 (continued).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Back-
ground vs.
Operating
Plant
SELECTION
RATIONALE
This method
will indicate
the total
contribution
of a plant
to ambient
background
' levels and
can be used
when the
number of
point sources
at a particu-
lar site are
too numerous
to sample in-
dividually.
SITE
PREPARATION
REQUIREMENTS
None required.
REFER-
ENCES
REMARKS
Ambient data gathered
for an environmental
impack statement can
be used as back-
ground data. When
the plant is in oper-
ation, the same samp-
ling sites are used
to measure the in-
crease in partlculates
and gases over back-
ground levels. High-
volume samplers with
fractionating Ander-
son heads are used
for particulate samp-
ling. .;
Volatile organics are
sampled by means of
gas bombs: less vola-
tile hydrocarbons are
measured with an XAD-
2 adsorber which is
attached to the high-
volume sampler. In-
organic gases can be
sampled either manu-
ally or oontinuously
according to tech-
niques outlined
earlier (see Stream
Category E).
If ambient background
date is not available,
an upwind-downwind
technique should be
used. The sampling
sites for such a
technique are plant-
specific.
APPLICABLE
AREAS OF
ANALYSIS
Particu-
lates:
Elemental
analysis,
Organic
analysis,
Anion
analysis,
Physical
character-
ization
Gases:
Inorganic
gases,
Organic
analysis
99
-------
TABLE 11 (continued),
STREAM
CATEGORY
M.
( cont.)
• Diffuse
Area
Sources
• (Aggre-
gate
piles)
Specific
Point
Sources
N.
Water-
borne
. Fugi-
tives
APPLI-
CABLE
STREAM
NUMBERS
i 2, 3,
4, 5,
9> 10,
28
. (CAFB)
LEVEL 1
RECOMMENDED
SAMPLING
METHOD
Downwind
Sampling
Plume
Sampling
SELECTION
RATIONALE
This method
is used for
sampling
specific
sources
which emit
a diffuse
emission
cloud.
Simpler and
less expen-
; slve than
', plume
sampling.
This method
is applic-
' able to
sampling
• specific
' point
1 sources
(e.g.,
•• vents)
; where the
• downwind
sampling
1 method Is
not applic-
able.
(i.e., when
, a sampler
•'can not be
': placed in
! emission
I cloud-)<'.
i
SITE
PREPARATION
REQUIREMENTS
None required.
Scaffolding
may be neces-
sary.
Power required
for two pumps
and heating
elements.
Field lab
required for
train cleanup.
REFER-
ENCES
14?
147
REMARKS
One sampler is
placed downwind
of the source and
in the emission
cloud .
A high volume
sampler with an
attached Anderson
head is used.
, An XAD-2 adsorber
is attached to the
high-volume
sampler to obtain
concentrations of
nonr volatile
organic s.
Gas bombs are
used to sample for
volatile organics.
and inorganic
gases.
The sampling tech-
niques employed
are an SASS train
and gas bomb.
Sampling probes
must be placed in
the plume.
See Chapter 4
for discussion.
100
-------
TABLE 11 (concluded).
LEVEL 2
RECOMMENDED
SAMPLING
METHOD
Upwind -
Downwind :
Midwest
Research
Method
Quasi-
stack
SELECTION
RATIONALE
Method can be
used to accur-
ately deter-
mine emission
rates from
piles and can
determine the
effects of
loading and
unloading
operations on
emissions.
. This method
will produce
accurate
emission rate
data.
SITE
PREPARATION
REQUIREMENTS
Samplers
mounted on
vertical tower
in grid arrange
jnent .
Traversing
facilities may
be required .
Same as for
Level 1.
REFER-
ENCES
73
176
REMARKS
High-volume samplers
with fractionating
Anderson heads are
used.
An XAD-2 adsorber
attached to the
sampler is used to
sample for non-
volatile organlce.
Volatile orgaiics.
are sampled .by means
of gas bomb.
Inorganic gases can
be sampled either
manually or contin-
uously according to
techniques outlined
earlier. (See
Stream Category E).
The point source is
hooded and a duct
constructed .
Sampling techniques
include the SASS
train and the gas
specific trains out-
lined earlier (See
Stream Category E).
See Chapter 4 for
discussion.
APPLICABLE
AREAS OF
ANALYSIS
101
-------
Flow Measurements
Introduction—
Appendix Table A-20 presents a compilation of multi-media flow measure-
ment techniques and their associated characteristics. This compilation
includes devices which do not require .permanent installation and that would
normally be brought to the site by the sampling team, as well as permanently
installed flow measurement devices that are employed primarily for process
monitoring. Also included a-re methods to calculate or estimate flow rates.
The techniques which 'have .been recommended in the following paragraphs for
Levels 1 and 2 asse'S'srae.nt have been selected from the -Table .20 compilation.
Gas Streams—
For Level 1 .application, the "S"-type pitot tube is recommended for gas
flow measurement while at Level 2, use of an ellipsoidal-nosed standard
pitot tube is recommended because of its high accuracy-and lower sensitivity
to yaw. Traverse .points for both Level 1 and Level 2 velocity determina-
tions are selected in accordance with EPA Method 1. Pitot tubes are inserted
into ports employed for sample acquisition.
In situations where a flow measurement device has already been installed
in a gas duct or stack, in conjunction with a continuous pollutant monitoring
system or for purposes of -obtaining process data, the device may be employed
for Level 1 flow determinations. .At Level 2, however, where multi-point
traversing is required to sample >particulates (and also 'Stratified gases), a
device already installed may be ^employed only if it is designed for point
velocity 'determinations (rather than for total flow measurement) and if, in
addition, it meets Level 2 accuracy requirements.
To measure flow rates in conjunction with the quasi-stack method
of sampling air-borne fugitives from specific point sources, use of a
hot-wire anemometer may toe required due to the normally low flow velocities
encountered.
Liquid Streams—
'For Level 1 determinations of flow rates in liquid streams, it is
recommended that one of the following options be employed:
1) Estimation using pump characteristics and (where applicable)
operating data, or any other estimation technique.
2) Flow measurement devices already installed
At Level 2, the selection of a suitable flow measurement technique
is site specific. Previously installed equipment that meets the accuracy
requirement's of Level 2 may be utilized.
102
-------
Solid Streams—
.Flow rates in solids streams can be determined by equipment specifi-
cations and'operating data or by solids weighing devices. For the former
category, "some measurable quantity such as the RPM of a screw feeder can be
related to mass flow rate using calibration curves supplied by the manufac-
turer;
RECOMMENDED SAMPLING PROCEDURES FOR CASE STUDY UNITS
Recommended Level 1 and Level 2 sampling procedures for case study units
I, II, and III are summarized on a stream-by-stream basis in Tables 12, 13,
and 14, respectively. Recommendations are based, in part, on site inspection
of the facilities and reflect the unit .configurations at the time of inspec-
tion.
Since inspection of the ESSO CAFB pilot facility in Abingdon, U.K. (case
study unit IV) was not made and unit data was limited, specific sampling
procedures have not been recommended within this document. Streams selected
for sampling, however, have been identified in Figure 9 and associated stream
conditions are defined in Table 7. Until further data on this facility
becomes available, the generic sampling procedures of Table 11 should serve
as a guide.
To enable convenient comparison of sampling procedures for case study
and generic units, a "Generic Stream Category" column has been included in
Tables 12, 13, and 14 which serves to direct the reader to the appropriate
sections of Table 11.
Since periodic .modifications of equipment, process configuration, etc.,
are made at each case study facility, the source testing contractor, at the
time of assessment, should review the sampling procedures recommended herein
and submit procedure modifications., if required, to the EPA Project Office
for approval.
103
-------
TABLE 12. SUMMARY OF RECOMMENDED SAMPLING PROCEDURES FOR CASE STUDY UNIT I
(PER-ALEXANDRIA, VA.)
STREAM NUMBER
AND
DESIGNATION
2
Particulate Removal
Discard
; 3
Bed Solids Discard
9
Raw Coal Peed
10
Raw Sorbent Peed
1
•Stack Qas
(gaseous components
and partlculates)
GENERIC
STREAM
CATEGORY
A
A
B
B
ErF
LEVEL 1
SAMPLING
Drum contents, after
mixing, should be sam-
pled with a plpeborer
or auger. A single In-
crement of at least one
kilogram Is taken.
Same procedure as for
Stream No. 2 above.
A sampling port has
been cut Into the feed
line. A sample can be
taken by opening the
port and collecting at
least one kilogram while
coal is being fed. Sam-
ple represents "as-fired"
rather than raw coal.
A sample is obtained
from the in-plant hopper
with a pipeborer or
auger. A single incre-
ment of at least one
kilogram is taken.
The gas sampling methods
recommended for generic
units should be applied
here.
SITE PREPARATION
None required.
None required.
None required.
Gas is exhausted to at-
mosphere by I.D. fan
through a long duct.
Existing ports (located
. on roof) meet Level 1
and Level 2 sampling
location requirements.
104
-------
TABLE 12 (concluded).
LEVEL 2
SAMPLING
SITE PREPARATION
REMARKS
Entire residue genera-
ted during test period
may be collected in
drums and transported
to a clean environment
where the contents are
then riffled to appro-
priate size. Alterna-
tively, the drums may
be sampled directly
using a pipeborer or
auger, with the number
and size of increments
chosen in accordance
with ASTM procedures.
Stream No. 2 above.
Sampling is performed
in the same manner as
in Level 1. Number and
size of increments (min-
imum 3 kg) are deter-
mined on basis of Level
1 results. In no case
should sample weight ex-
ceed more than a few
percent of the feed
rate in order to avoid
process upset.
The pneumatic lines
cannot be sampled due
to their small diameter.
Since the sorbent is
transported from stor-
age to the in-plant
hopper by bucket, one
of every ten buckets
should be taken' as an
Increment. The sample
can then be riffled to
required size.
Gas .sampling methods
recommended for generic
units should be applied
here. For Level 2 as-
sessment, existing con-
tinuous monitoring
equipment may be employ-
ed if accuracy goals of
Level 2 are.met.
None required.
None required,
See Level
paration.
1 site pre-
Particulates are pneumatically
conveyed from the hopper to
drums.
The bed solids are gravity fed
from the bed through a valve
and short piece of tubing into
a drum. The solids temperature
is approximately 1500°F.
The coal is pneumatically trans-
ported from an outdoor crushing
operation to an in-plant hopper,
The coal is then transported by
a screw conveyor to a second
pneumatic line which feeds into
the combustor.
Sorbent is purchased pre-sized
and stored in an outdoor shed
from where it is bulk trans-
ported to an in-plant hopper.
From the hopper, the material
is pneumatically conveyed into
the unit.
Stack gas monitoring primarily
employing continuous analyzers
is included as a part of case
study unit operating .procedure.
The gaseous components normally
monitored include
NOX, and CO.
C00, SOr
105
-------
TABLE 13. SUMMARY OF RECOMMENDED SAMPLING PROCEDURES FOR CASE STUDY UNIT II
(EXXON MINIPLANT)
STREAM NUMBER
AND
DESIGNATION
2
Particulate Removal
Discard
3
Bed Solid Discard
4
Particlate Removal
Discard - Regeneration
9
Raw Coal Peed
10
Raw Sorbent Peed
1
Stack Gas
(gaseous components
and particulates)
:
GENERIC
STREAM
CATEGORY
A
A
A
B
B
E,P
1
LEVEL 1
SAMPLING
Drum contents, after
mixing, should be sam-
pled with a pipeborer
or auger. Alterna-
tively, the carting
vehicle may be sampled
directly, again employ-
ing a pipeborer or
auger. A single incre-
ment of at least one
kilogram is taken.
Same alternatives as
for Stream No. 2 above.
Same alternatives as
for Stream No. 2 above.
Coal should be trans-
ferred from sacks to a
drum, mixed well, and
sampled with a pipe-
borer or auger. A
single increment of at
least one kilogram is
taken.
Same procedure as for
Stream No. 9 above.
The Aerotherm HTHP train
should be employed for
particulate sampling.
Gas samples are with-
drawn through a gas sam-
pling line to a dis-
placement bomb. A
water-cooled heat ex- .
changer Is used for gas
temperature reduction.
Pressure reduction is
accomplished by partial
bleeding of the gas sam-
pling line. Non- vola-
tile organics are sam-
pled by porous polymer
adsorber attached to
the gas sampling .line.
SITE PREPARATION
None required .
None required.
Existing port locations
can be used but port
modifications will be
required. A side-split
bleed stream gas sam-
pling line. and a water-
cooled heat .exchanger
must be installed. •
I06
-------
TABLE 13 (concluded).
LEVEL 2
SAMPLING
SITE PREPARATION
REMARKS
Entire residue genera-
ted during test period
may be collected in
drums and transported
to a clean environment
where the contents are
then riffled to appro-
priate size. Alterna-
tively, the drums or
carting vehicle may be
sampled directly using
a pipeborer or auger,
with the number and size
of increments chosen in
accordance with ASTM
procedures.
Same alternatives as
.for Stream No. 2 above.
Same alternatives as
for Stream No. 2 above.
Same as Level 1, but
number and size of In-
crements chosen in
accordance with ASTM
procedures.
Same procedure as for
Stream No. 9 above.
Same as Level 1 for par-
ticulates and non-vola-
tile organics. For
gases, Level 2 tech-
niques recommended in
Table 11 should be em-
ployed after pressure
and temperature reduc-
tion. Existing contin-
uous monitoring equip-
ment may be employed if
accuracy goals of Level
2 are met.
None ^required.
Residue is gravity fed through
pipe from second stage cyclone
to a lock hopper. Periodically,
the contents of hopper are disr
charged into drums or a carting
vehicle (e.g. open truck).
None required.
Solids are discharged from a
lock hopper into drums or cart-
Ing container as above.
Periodically, residues are dis-
charged directly from cyclone
separator (through a valve) into
drums or carting container.
Coal is purchased pre-sized and
delivered in sacks.
Sorberrt is purchased pre-sized
and delivered in sacks.
The Miniplant process configura-
tion does not include a gas tur-
bine. Pressure reduction for
the combustor effluent gas
stream is accomplished by an
orifice or valve. Existing
ports for gas and particulate
sampling are located upstream of
the pressure reduction device,
requiring sampling at ~10 atm
,and 1500°P. The Aerotherm HTHP,
presently undergoing field test-
ing at the Miniplant, Is the
only unit applicable for parti-
culate sampling at these condi-
tions .
107
-------
TABLE 14. SUMMARY OF RECOMMENDED SAMPLING PROCEDURES FOR CASE STUDY UNIT III
(CPC-rPDU-400)
STREAM NUMBER
AND
DESIGNATION
2a
Particulate
Removal Discard -
at Sand Bin
2b
Particulate
Remoyai Discard T
at Baghpuse
9
Raw Coal Peed
10
Raw Sorbent Peed
1
Stack Gas
(gaseous compon-
ents and part IT
culates ) ' "'
GENERIC
STREAM
.CATEGORY
A
A
B
B
E,F
LEVEL 1
SAMPLING
Residue may be collec-
ted in drums and sam-
pled with a pipeborer
or auger after contents
are well-mixed. Alter-
natively, the carting
vehicle may be sampled
directly, again employ-
Ing a pipeborer or
auger. A single incre-
ment of at least one
kilogram is taken.
Drum contents, after
mixing, should be sam-
pled with a pipeborer
or auger. A single in-
crement of at least one
kilogram is taken.
Stopped-b.elt sampling
(of the belt conveyor)
is recommended. A full-
stream cut is taken by
drawing a flat- edged
shovel straight across
the belt. A single in-
crement of at least one
kilogram is taken.
Samples should be taken
from the hopper using a
pipeborer or auger.
SITE PREPARATION
None required .
None required.
None required .
-
None required.
Existing ports located
in one of the two tur- ;
bine exhaust stacks are
acceptable for Level 1
sampling. Scaffolding
has already been erec-
ted.
108
-------
TABLE 14 (concluded).
LEVEL 2
SAMPLING
SITE PREPARATION
REMARKS
Entire residue generated
during test period may
be collected in drums
and transported to a
clean environment where
the contents are then
riffled to appropriate
size. Alternatively,
the drums or carting
vehicle may be sampled
directly using a pipe-
borer or auger, with the
number and size of in-
crements chosen in
accordance with ASTM
procedures.
Same alternatives as
recommended from Stream
2a above.
Stopped-belt sampling as
in Level 1. A gross
sample of 35 increments
of 3 kilograms each
should be sufficient.
A pipeborer or auger
can be employed to sam- .
pie the hopper as in
Level 1. The number
and size of increments
should be in.accordance
with ASTM procedures.
Alternatively, an auto-
matic Vezin,sampler may
be installed in a pneu-
matic sorbent transport
line. This device pro-
duces a full stream cut.
None required.
None required.
None required,
None required for
pipeborer or auger.
Installation in line
required if Vezin
option is used.
Suitability of existing
ports for Level 2 sam-
pling can only be de-
termined from Level 1
results.
Residues removed by the first
and second stage cyclone sepa-
rators are transported pneumat-
ically to a sand bin. Period-
ically, the contents of the sand
bin are discharged (through a
valve) directly into an open
truck and carted away. The sand
bin is equipped with a cyclone.
Venting is to the atmosphere (or
to the baghouse).
Residues removed by the granular
filter are transported pneumat-
ically to a baghouse. The cap-
tured residue is discharged to a
drum periodically. The baghouse
is vented to the atmosphere.
Raw coal is bulk transported
from an outdoor storage pile to
a bin and then discharged
through a control valve to an
open belt conveyor for transport
to a crushing operation. To
minimize fugitive coal dust, the
bin and crushing operation are
maintained under negative pres-
sure. A Micro-Pul unit is used
for filtration.
Sorbent is purchased pre-sized
and stored in a shed from where
it is bulk transported to an
open hopper. Sampling accessi-
bility downstream of the hopper
is limited (i.e. installation
of a Vezin-type sampler in a
pneumatic transport line would
be required).
See remarks and Level 1 and 2
sampling recommendations under
Stream No. 1, Case Study Unit I
(PER).
109
-------
RECOMMENDED ANALYTICAL PROCEDURES
Introduction
Multi-media overviews of the recommended analytical schemes for Levels
1 and 2 are presented in Figures 25 and 26, respectively. Analytical
procedures are independent of process category or whether a generic or case
study unit is being considered. Furthermore, procedures for a particular
analysis area (e.g., elemental analysis) are, by in large, independent of
sample type (e.g., solid, liquid, etc.). Accordingly, analytical procedures
are presented by major analysis area only, rather than on a- process category
and/or stream-by-stream basis. Any special considerations (e.g., sample
handling and preparation) that relate to sample type or stream conditions
are, however, addressed.
The Level 1 analytical scheme has broad screening capability and is
designed to detect the following:
•.. Organic species in all influent and effluent streams;
• Inorganic elements in all influent and effluent streams;
• S02, NOX, CO, 02, C02, N2> H2S, COS, NH3, HCN, and (CN)2
in gaseous streams;
•• pH, acidity, alkalinity, conductivity, BOD, COD, dissolved
oxygen, dissolved solids, and suspended solids in aqueous
streams in addition to inorganic elements; and
• Leachable cations and anions from samples which are solids
(particulate matter from SASS, slurry solids, etc.).
The precision and accuracy goals for a Level 1 assessment are a factor of
two to three for emission rates. To achieve this goal, analytical results
must have an accuracy of -50 to +100 percent, assuming equal sampling accuracy,
The goal, of Level 2 analysis is to provide a more accurate, quantitative
identification of specific components in selected streams based on Level 1
output. As such, methods are chosen on an individual basis; in general,
procedures are selected from standard EPA, ASTM, API, etc., methods which
have an- accuracy and/or precision or _+ 10 percent or better. No> general
statement of: Level 2 analytical accuracy can be made here as these require-
ments are dependent on overall Level 2 program goals.
Tables 15 through 2-1 provide summaries of recommended analytical pro-
cedures for Levels- 1 and 2 according to the following major analysis areas:
1. Inorganic gas analysis (Table 15);
2. Organic analysis (Table 16);
110
-------
3. Elemental analysis (Table 17);
4. Anion analysis (Table 18);
5. Standard water analysis (Table 19);
6. Fuel analysis (Table 20); and
7. Physical characterization of solids (Table 21).
Included in these tables are special sampling and analytical requirements,
rationale for method selection, key references, and other pertinent data.
Inorganic Gas Analysis
Recommended procedures for inorganic gas analysis are presented in
Table 15. Sample concentrations will range from ppb levels for sulfur
compounds to several percent for carbon dioxide, oxygen and water in the
stack gas. Because the stability of many samples, particularly those
containing hydrogen sulfide and other sulfur species, is unknown (due to
wall absorption or possible chemical reaction), GC analysis should be
performed on site. At Level 1, this eliminates the shipping of a potentially
large number of bulky sample containers and permits additional sampling if
problems should arise.
Recent advances in gas chromatography have led to the development of
sensitive and compact instruments that are practical for field applications.
In addition, multidetector units such as those manufactured by Meloy,
Beckman, Tracer and others expand the scope of analysis to include virtually
all gaseous species without having a van full of different gas chromato-
graphic units.
While a specific list of inorganic species and proposed conditions are
shown in Table 15, this list does not exclude additional species which may be
found. Indeed, it is not expected that the proposed set of conditions will
be suitable for all mixtures and concentration ranges. When unique situations
arise, appropriate analytical conditions should be selected and submitted to
the project officer and PMB-IERL-EPA for approval.
Level 2 analytical methods are generally chosen from ASTM, EPA, API,
etc. methods where possible. As such, these methods are designed for
specific species analysis and often require the use of special sampling
trains. Under certain circumstances, it is possible that Level 1 methods
may be used for Level 2 analysis. If this is done, aside from meeting Level
2 accuracy requirements, the proposed GC procedure must be shown to be free
from interferences (i.e., identical retention times) from other species.
Additionally, continuous analytical methods (e.g., NDIR, UV, etc.) are also
presented as Level 2 options as this equipment may be available at the site.
If continuous monitoring equipment is used, calibration procedures should be
consistent with Level 2 goals.
Ill
-------
On-site sampling at Level 1 is done with an evacuated or a flow-through
(for pressurized systems) three liter glass bomb. This vessel is returned
to the mobile laboratory and attached to the gas chromatograph via an
automatic gas sampling valve.
Two gases of environmental interest (NO and NC^) are not measured
routinely on a gas chromatograph. The Level 1 analysis:of NO/NOo concen-
trations will be performed using the chemiluminescence method. Although
this is a state-of-the-art analysis technique, it is substantially less
labor-intensive than EPA Method 7. This method as adapted to Level 1
analysis involves admitting .gas samples into a 3-liter evacuated flask. The
sample is then transported .to .the instrument and analyzed. Because a major
portion of the analysis time on .the instrument involves calibration, it is
recommended that only sufficient calibration to maintain a minimum accuracy
of a factor of *_ 2 ( + 100 percent, -50 .percent) be performed. The Level 2
analysis of NO is performed by the phenol disulphuric acid procedure (EPA
Method 7). X
112
-------
INORGANICS
ON-SITE GC
ANALYSIS
N°x
CHEMILUMINESCENT
ANALYSIS
ON-SITE GC
ANALYSIS
COLUMN CHROMATOGRAPHY
SEPARATION INTO
8 FRACTIONS
(a) Implnger solutions excluded
(b) Hg, Sb, Aa are analyzed by
wet techniques
(c) An aliquot from the extract
is used 'for these analyses
Figure'25. Overall analytical scheme-Level 1
114
-------
p
PHYSICAL
CHARACTERIZATION
*•
LEACHATE
GENERATION
»
SOXHLET
EXTRACTION
WITH CH2C12
SEE ANALYTICAL
SCHEME FOR
•LIQUIDS
-
WET ASHING
COLUMN .
CHROMATOGRAPHY
SEPARATION INTO 8
FRACTIONS
-*
SIZING:
SIEVING, AIR
ELUTRIATION,
OPTICAL MICROSCOPE
MORPHOLOGY:
POLARIZING
LIGHT
MICROSCOPE
(b)
ELEMENTAL ANALYSIS
SSMS
ORGANIC ANALYSIS
IR, MS
STANDARD WATER ANALYSIS
(AQUEOUS STREAMS ONLY)
INCLUDES SELECTED ANIONS
ELEMENTAL ANALYSIS
SSMS
(a) Implnger solutions excluded
(b) Hg, Sb, As are analyzed by
wet techniques
(c) An aliquot from the extract.
is used for these analyses
COLUMN CHROMATOGRAPHY
SEPARATION INTO 8
FRACTIONS
(b)
ORGANICS < C12(
GC ANALYSIS '
ORGANIC ANALYSIS
' IR, MS
Figure 25. Overall analytical scheme-Level 1 (concluded)
115
-------
WET METHODS (E.G., SPECTROMETRIC,
TITRIMETRIC), GC, NDIR, UV
UV,
IR, GCMS, NMR
>10u
3-10u
*Anion analysis
includes compound
identification
ANION ANALYSIS
(VARIOUS
TECHNIQUES)
ORGANIC ANALYSIS
UV, IR,
GCMS,'NMR
MORPHOLOGY: POLARIZING
LIGHT AND SCANNING
ELECTRON MICROSCOPE
SIZING: OPTICAL
AND SCANNING
ELECTRON MICROSCOPE
Figure 26. Overall analytical scheme-Level 2
116
-------
SIZING: SIEVING,
COULTER COUNTER,
OPTICAL AND
SCANNING MICROSCOPES
MORPHOLOGY:
POLARIZING
LIGHT AND SCANNING
ELECTRON MICROSCOPES
ELEMENTAL ANALYSIS
AAS
ANION ANALYSIS
(VARIOUS TECHNIQUES)
ORGANIC ANALYSIS
UV, IR, GCMS, NMR
STANDARD WATER
ANALYSIS (AQUEOUS
STREAMS ONLY)
ANION ANALYSIS
(VARIOUS TECHNIQUES)
ELEMENTAL ANALYSIS
AAS
COLUMN
CHROMATOGRAPHY
PRELIMINARY
SEPARATION"
ORGANIC ANALYSIS
UV, IR, GCMS, NMR
Figure 26. Overall analytical scheme-Level 2 (concluded)
117
-------
TABLE 15. SUMMARY OF RECOMMENDED PROCEDURES FOR INORGANIC GAS ANALYSIS
ANALYSIS
AREA
Ammonia
Carbon Dioxide
Carbon Monox-
ide
Halogens and
Volatile
Halides
Hydrogen
Chloride
Hydrogen
Cyanide
( Cyandgen )
* Detection
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
QC Thermal
Conductiv-
ity Detect-
or (TCD)
GO*
(TCD)
QC
(TCD)
SSMS
See Halo-
gems and
Volatile
Halides
QC
(TCD)
limit for TC
SELECTION
RATIONALE
This method Is rapid,
accurate, simple, low
cost and has multi-
component capabilities .
This method is rapid,
accurate, simple, low
cost and has multi- com-
ponent capabilities.
This method is rapid,
accurate, simple, low
cost and has multi- com-
ponent capabilities.
This method is suitable
for the rapid routine
measurement of Halogens
and Volatile Halides.
This method Is rapid,
accurate, simple, low
cost and has multi- com-
ponent capabilities.
is ~ 25 ppm
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Collection in a 3L gas
bomb and analyzed on
site. Column: 6'SS,
Poropak Q, isothermal at
40°C.
Collection in a 3L gas
bomb and analyzed on
site. Column: 6'SS,
Molecular Sieve 5A, iso-
thermal .at 40°C.
Collection in a 3L gas
bomb and analyzed on
site. Column: 6'SS,
Molecular Sieve 5A, iso-
thermal at 40°C.
These species may appear
in particulates, XAD-2
trap and impingers.
Collection in a 3L gas
bomb and analyzed on
site. Column: 6'SS,
Poropak Q, Isothermal at
40°C.
REFER-
ENCES
13.4
94
94
8.32
118
-------
TABLE IS (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Absorption/
Titration-
(>lppm).
Colorimet-
ric
(0.05-lppm)
GC
Non-Dls-
penslve
Infra- Red
(NDIR)
GC
NDIR
Absorption/
Titriraetric
Absorption/
Colorimet-
ric/
Titrimetric
GC
SELECTION
RATIONALE
Accurate, reasonably
rapid technique.
As in Level 1.
As in Level 1.
EPA Reference Method.
Accurate, reasonably
rapid technique.
This method is suit-
able for the determ-
ination of soluble
and Insoluble cya-
nides in aqueous
solution.
- SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Sample is buffered at
pH 9.5 and distilled
into a solution of
boric acid. The am-
monia in the distil-
late can be deter-
mined colorimetri-
cally by nessleriza-
tion(MgI2,KI,NaOH) or
tltrimetrically with
H2S04 using a .mixed
indicator (Methyl
Red/Methylene Blue).
As in Level 1.
Water and particu-
lates must be re-
moved .
An He ionlzation de-
tector is required
for concentrations
below 25 ppm. Water
and partlculates
must be removed.
Chlorides cannot be
accurately measured
, at Level 1 in partl-
culates or XAD-2
trap because of sam-
ple dissolution pro-
cedure.
Titration with Hg
(N03)2. Indicator;
d Ipnenyl carpazone
and bromophenol blue.
Absorption in IN KOH;
sample is acidified
arid distilled into
1/25 N NaOH. Color 1-
metric : reaction
with chloramlne T;
color development
with pyridine; pyra-
zolone reagent, mea-
sure at 629 'nm.
Titration: AgNC>3
with an appro-
priate indicator.
See Level 1.
REFER-
ENCES
94
112,
94
8.9
b.21
REMARKS
(LEVELS 1& 21
Certain amines may
interfere.
Concentration will
determine analytical
method. GC may also
be used.
NDIR detector limit
is 10 ppm.
Bromide and iodide
interfere with SIE
measurement .
Titrlmentric method
is applicable to oy-
anide concentration
of Ippm; Colorimet-
ric 0.05-lppm. Fatty
acids make endpolnt
determination diffi-
cult. Acidify with
HOAC to pH 6 and ex-
tract with Heyane.
Sulfldes interfere
but may be removed
with Cd COo as pre-
cipitate.
119
-------
TABLE 15 (continued).
ANALYSIS
AREA
Hydrogen
Fluoride
(Fluorlces)
Hydrogen
Sulfide
•Mercaptans ;
Mercury
Nitrogen
Oxides
^Detection lii
ffi -special i'te:
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
See /Halo-
gens and
Volatile ;
•Halides
.*
GC
.(TCD/FPD) :
•
GC
(TCD/FPD) .
'Flameless
Atomic
Absorption :
.Spectrosco-
py
IEAAS )
Chemilu-
minescence
lit (for ,FPD i
lon-,coated ,:a
SELECTION
RATIONALE
This method is rapid,
accurate, simple and
has multi-component
capabilities .
As above
.GC and SSMS are not
suitable techniques for
Hg analysis, ?FAAS Meth-
od provides accurate
analysis of Hg.
This method provides a
reliable and rapid
technique for £he .mea-
surement of -nitrogen
oxides.
B 10 ,ppb .
nd -glass -system is recess
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Collection in 3L gas
bomb and analyzed on
site. Column: acetone-
.washed teflon -18 in. x
1/8 in. O.-D. column
packed with 80/100 mesh
acetone-washed .Poropak '.
QS; Column temperature
prggrammed, -start at
30 C, post-injection0de-
lay of 1 mln. to 210 C
at 40°/min. Alternate
column: 6' glass, J$>
OV-1 on chromosorb W,
100/120 mesh, isothermal
at 60.
Hg is absorbed in SASS
train impingers. Hg may
also be absorbed by the
XAD-2 trap and on parti-
culates. See Table 18:
Mercury
Sample is collected in
3L Bomb and analyzed on
.site. Calibration
standard .is required .
ary for these analyses .
REFER-
ENCES
87
87
175,
307
148
120
-------
TABLE 15 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Absorp-
tion/Spe- -
cifio ION
Electrode
(SIE)
GC
Flame
Photo-
metric
Detector
(FPD)
GC
(FPD)
FAAS -
Gold
Amalga-
mation
Technique
Phenol
Di-Sul-
phonlc
Acid
Method
Chemilu-
minescent
Measure-
ment
SELECTION
RATIONALE
This method offers
better accuracy and
precision and ease .of
analysis than does
the SPADNS Colori-
metric Method.
As is in Level 1.
As In Level 1 .
As in Level 1";
This method provides
an accurate measure
of nitrogen oxid;es .
Federal Register
Method .
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Absorption in dis-
tilled water; pH
buffered to 5.2-5-5;
standard addition
technique for analy-
sis.
As in Level 1; Flame
Photometric Detec-
tion.
As above .
Absorption on lOg
gold chips; chips
are transferred to
furnace and measured
by standard FAAS
techniques .
Absorption in 2L
flask with 25ml of
0.1N H2S04 in 0.1#
IfeOg • Spectrometric
measurement at 430nm.
An accurate callbra-.
tion standard is re-,
quired .
REFER-
ENCES
87-
87
175,
307
14
44
REMARKS
(LEVELS 1 &2) ,
A third column 1/8"
x 11' teflon with
expanded silica gel
has been described
by D.: P. Manka, In-
strumentation
Technology 22, 45-9
(1975).
Method uses EPA
isokinetic sampling
train; mercury may
also be collected
on filter prior to
implngers; these
particulates are nor
mally combined with
impingers for anal-
ysis.
Total oxides of ni-
trogen are measured .
Chemllumlnescent
measurement is pre-
ferred for continu-
ous measurement.
121
-------
TABLE 15 (continued).
ANALYSIS
AREA
Oxygen
Sulfur Com-
pounds
Sulfur Diox-
ide
Sulfur
Trloxlde
Water
(as vapor)
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
GO
(TCD)
GC
(TCD/FPD)
GC
(TCD/FPD)
SSMS
GC
(TCD)
SELECTION
RATIONALE
GC provides a rapid,
accurate, simple tech-
nique for oxygen meas-
urement .
See Hydrogen Sulflde.
Gas chromatography Is a
rapid, accurate, simple
technique for SOg
measurement .
This method Is suitable
for the rapid routine
measurement of elemen-
tal sulfur
GC provides a rapid and
simple technique for
measurement of water
vapor .
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Sample is collected In
a 3L Bomb and analyzed
on site. Column: 6'SS,
molecular sieve 5A, Iso-
thermal at 40 C.
See Hydrogen Sulfide.
*
See Hydrogen Sulfide .
803 may be found in XAD-
2 trap, implngers, and
with paftlculates.
Sample is collected in
a 3L bomb and analyzed
on site.
Column: 6SS, molecular
siqve 5A, isothermal at
40°C.
REFER-
ENCES
94
87
281
122
-------
TABLE 15 (concluded).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
GC
Polaro-
graphic
Paramag-
netic
QC
(TC/PPD)
Absorp-
tion/
Titrimet-
ric
Control-
led Con-
densation
/Titrimet'
ric
Condensa-
tion
NDIR
SELECTION
RATIONALE
As in Level 1 .
See Hydrogen Sulfide.
These methods are all
recognized as suit-
able techniques for
SOg measurement .
This method provides
an accurate measure
of S03. Other meth- ,
ods are subject to
S02 being measured
as SO-,-
j
As in Level 1.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Sample from gas bomb.
An accurate calibra-
tion standard is re-
quired .
See Hydrogen Sulfide.
As is Level 1.
Absorption in 3#
H20g titration with
barium perchlorate
and thorln indicator
Condensation of flue
fag isocontrolled at
0. -90 C and collected
on a. glass frit;
titration with barium
perchlorate; thorin
indicator.
Sample must be main-
tained above dewpolnt.
REFER-
ENCES
M rovo
VJlVO-fc"
covo*
<•
87,
93
93
281,
1 /"4O
102
REMARKS
(LEVELS 1 &2)
Polarographic or
paramagnetic meth-
ods may be used for
continuous monitor-
ing.
NDIR and UV methods
may be used for oon-
.tinuous monitoring-.
SO^ may be ab-
sorbed in 80J? iso-
propanol - 20$
water; however SOg
may be oxidized to
SOo under these
conditions .
123
-------
.Organic Analysis
The obj.ect of Level 1 procedures for organic analysis, is to provide an
..estimate of the predominant classes .of organic compounds present in a
given sample. From these results, environmentally .significant fractions can
'b.e .selected for Level 2 analysis and individual species identified and
^measured within the program goals.
Organic sample .preparation techniques, as shown in Figure 27, .vary .with
sample type. These techniques, for Level 1, consist of preliminary separa-
tions by gas and column chromatography prior to analysis. At level 2, the
sample procedures are used to provide a cr.ude separation of .classes prior to
sophisticated HPLC separations.
The low molecular weight -Ci--Cg hydrocarbons are determined by gas
chromatography on site and require no preparation. Organic liquids, such as
fuel oils, will not need pretreatment and are placed directly into the
analysis scheme. However, the majority of the samples, including the SASS
train components, aqueous solutions, and solids, require extraction with
solvent prior to analysis. This is done to separate the organic .portion of
the sample from ijiprganic species and allow analysis to proceed .without
complication. Aliquots are taken from the organic extract or liquid .for a
direct GC and ;IR analy,sis of the Cy^-C^ hydrocarbons. The IR analysis
identifies functional groups in the sample. All functional groups identified
in the "total sample" must ,be accounted for in subsequent analysis.
The sample extract or organic liquid is separated by column chromato-
g-raphy on silica gel, using a solvent ..gradient series, into eight fractions.
Each fraction is weighed and analyzed by infrared spectroscope so that a
distribution by class type can be determined. A low resolution mass
spectrum (LRMS) is also obtained on all fractions which exceed the concentra-
tion threshold criteria in order to determine the principal compound types
present in each fraction. For the sample streams identified in the Level 1
scheme (Figure 26), these concentrations, computed back to the source,
are:
3
• Gas (particulate, sorbent trap, etc.) 0.5 mg/m
;,« Solids 1 mg/kg
• Solutions 0.1 mg/1
Care must b.e taken In this computation to correct for those Cy-Cio
compounds that were analyzed :by GC and not lost in concentration
steps.
It should :be .emphasized that sample contamination and solvent impurities
3Te common problems in .organic, analysis. The best pos.sible laboratory
procedures -must b.e ,used along ?with verified pure solvents. -Blanks and
controls sho.uld.be run at each stage of the analysis scheme.
124
-------
ALIQUOT FQR
C7-.C12
ORGANICS BY
GC .
IR ANALYSIS .
ORGANIC
LIQUIDS
„
SASS
.TRAIN
'RINSES
'.,
ALIQUOT FOR
.c7-c12.
ORGANICS BY
GC
<
•
' CONCENTRATE
AND
WEIGH
IR ANALYSIS
ON
TOTAL SAMPLE
COLUMN CHRO-
'MATOGRAPHY
(Si02) .
COLUMN CHRO--
- MATOGRAPHY
sio2
AS. BELOW AS BELOW
• (1) Impinger solutions
•are not analyzed for
. AQUEOUS ^
SOLUTIONS
EXTRACTION^
WITH CH2C12
(SEP. FUNNEL
3x-500ml)
ALIQUOT FOR
ORGANICS BY
GC
, I
CONCENTRATE
AND
WEIGH
IR ANALYSIS
ON
TOTAL SAMPLE
SOLIDS (2)
SOXHLET
EXTRACTION
WITH CH2C12
(24 HOURS)
ALIQUOT FOR
ORGANICS BY
GC
CONCENTRATE
AND
WEIGH
IR ANALYSIS
ON
.TOTAL SAMPLE
,
COLUMN CHRO-
MATOGRAPHY
Si02
COLUMN CHRO-
MATOGRAPHY
510,
1
AS BELOW
SORBENT
TRAP
SOXHLET
EXTRACTION
WITH C5H12
(2L FOR 24
HOURS)
ALIQUOT FOR
C7-C12
ORGANICS BY
GC .
CONCENTRATE
AND
WEIGH
IR ANALYSIS
ON
TOTAL SAMPLE
COLUMN CHRO-
MATOGRAPHY
Si02
1
AS BELOW
SEPARATION INTO 8 FRACTIONS ;
WEIGHT DETERMINATION OF
INDIVIDUAL FRACTIONS
|
T t f
(2)
Coal Is not analyzed
by this scheme
(3) Aqueous solutions are
extracted at pH 7;
HCL/NH^OH is used for
neutralization
» t » t
ON-SITE GC
ANALYSIS FOR
ORGANICS
Figure 27. Level 1 organic analysis scheme
125
-------
The following discussion presents procedures that are appropriate for
most samples. The specific solvents indicated should be used where possible.
In the case of unusual sample requirements, an alternate procedure should be
selected and presented to the project officer and the Process Measurements
Branch, IERL-RTP, for approval.
When possible, it is recommended to have at least 10 mg of sample for
the gravimetric analysis. Prior to column chromatography, it is recommended
that the solvent solutions be concentrated to 1 to 10 ml. The Kuderna-Danish
apparatus is recommended for sample concentration of volumes less than one
liter, and a rotary evaporator is recommended for volumes which exceed
this amount.
Extraction of aqueous solutions should be carried out with methylene
chloride using a standard separatory funnel fitted with a Teflon stopcock.
If necessary, ammonium hydroxide or hydrochloric acid should, be used to
adjust the pH of the sample to pH 7 before extraction. Normally, three
500-ml methylene chloride extractions of 10-liter samples should be suffix
cient to extract.
All solid material with the exception of coal but including raw materials,
cyclone, probe and filter particulate, and ash should be extracted for 24
hours with methylene chloride in a Soxhlet apparatus. The Soxhlet cup must
be previously extracted in order to avoid contamination. The sample is
covered with a.plug of glass wool during the extraction to avoid carry-over
of the sample.
A large Soxhlet extraction apparatus (dumping volume of approximately
1,500 ml) is used to extract the XAD-2 resin (-400 ml) after homogenization
and removal of a 2 g portion for inorganic analysis, the resin is<'transferred
to a previously cleaned extraction thimble and secured with a glass wool plug.
Approximately 2 liters of n-pentane is added to the 3-liter reflux flask arid
the resin extracted for 24 hours. The reflux flask should be examined;
periodically to determine whether additional solvent is needed to replace
that lost by volatilization.
The XAD-2 resin should not be extracted with methylene chloride^
because the compatibility of this resin with methylene chloride has not been
fully evaluated.
If large quantities of .polar materials are extracted, they may precipitate
in the reflux flask near the completion of the extraction. Addition of
cool methylene chloride to the flask, after extraction is complete, will
simplify the subsequent transfer and analysis steps.
126
-------
The chromatbgraphy/IR/LRMS procedure will provide reliable data on
the compound types present in the samples for the relatively high boiling
compounds. Unfortunately, the SASS train will not capture (and retain
for analysis) the organic compounds with boiling points in the Pj-Cg
range (up to 70°C); the volatile materials in the C7~C12 range (100-200°C)
are lost to varying degrees in the sample concentration steps required for
analysis. Consequently, separate gas chromatography procedures are used for
the analysis of these two ranges of materials.
The on-site gas chromatographic requirements for analysis of the Ci-Cg
and volatile Cy-C^ Sases is presented in detail in Table 16. For organic
analysis the GC system should be calibrated for retention time and quantity
with Cj-Cjo n-paraffins. The GC system will simply be separating and
analyzing mixtures of materials within a given boiling point range (and
polarity in some cases). Since the chromatogram peaks will represent
mixtures of materials present in a certain boiling range, rather than pure,
individual compounds, it is recommended that material observed in the
chromatogram be reported as present in boiling point ranges. If, from other
information, the identity of specific chromotographic peaks can b'e as-
certained, individual organic compounds may be assigned to these peaks
provided the basis of assignment is clearly stated.
For extracted samples and neat organic liquids, additional problems
occur from solvent interference and GC requirements. Even for the dilute
sorbent trap extracts, a flame ionization detector is sufficiently ."sensitive
to require only a one~microliter sample. The initial isothermal portion of
the temperature program allows the solvent to elute prior to C-j hydrocarbons.
It will probably be necessary to prepare solutions of neat organic liquids
to prevent overloading and degradation of the column.
A detailed procedure for the column chromatographic separation is
given in Table 16 and in reference 147. All sample extracts and neat
organic liquids are subjected to this procedure if the sample quantity is
adequate. A sample of 100 mg is preferred but smaller quantities (> 15 mg)
can be used. This separation procedure is not a high resolution technique
and consequently there is overlap in class type between many of the fractions
Fraction 1 contains alkanes and possibly some olefins. Fractions 2 through
4 contain predominantly aromatic species. The smaller aromatics (e.g.,
benzene, naphthalene) will tend to elute in the early fraction (2) while the
larger aromatics (e.g., benzpyrene, etc.) will tend to elute in fractions 3
and 4. Some low polarity oxygen and sulfur containing species may also
elute in Fraction 4 but most of these will not elute until addition of
methanol.
127
-------
Fractions 5 through 7 will contain polar species including phenols,
alcohols, phthalates, amines, ketones, aldehydes, amides, etc. The distribu-
tion of. class type between Fractions 5 through 7 will be a function of
their polarity and affinity for the silica gel. Some weak acids may elute
in Fraction 7.
Very polar species, primarily carboxylic acids and sulfonic acids, will
elute in Fraction 8.
After each fraction is collected, it should be transferred to a tared
aluminum micro weighing dish for evaporation and gravimetric analysis.
Fraction 8 should be dried in a glass container because of its hydrochloric
acid content. Each fraction is subsequently analyzed by IR and, when the
quantify is sufficient, LRMS (Table 16).
The total sample extract, neat organic liquids, and the eight fractions
obtained from the column chromatographic separation are analyzed by infrared
(IR) spectrophotometry. IR spectra are obtained on KBr salt plates using
methylene chloride to transfer the sample to the plates. A grating spec-
trophotometer should be used. Sample quantity is adjusted so that the
spectra maxima and minima lie between about 10 and 90 percent transmission,
respectively. These spectra are interpreted in terms of functional group
types present in the samples.
Low resolution mass spectra (LRMS) are obtained on each of the eight
fractions,, deemed to have sufficient quantity, in terms of source emissions.
For the various samples these quantities are.:
3
Gas - SASS train samples 0.5 mg/m
- Ambient air - particulate 1 ug/m
- Ambient air - sorbent trap 0.5 mg/m
Solids 1 mg/kg
Aqueous solutions 0.1 mg/1
The mass spectrometer should preferably have a resolution (m/Am) of 1,0.00,
a batch and direct probe inlet, a variable ionizing voltage source and
electron multiplier detection. Volatile samples are analyzed by insertion
in the batch inlet. It is, anticipated, however, that most samples will be
introduced via the direct insertion probe. A small quantity of sample is
placed in the probe capillary and inserted into the cool source. The
temperature is then programmed to vaporize the sample. Spectra are recorded
periodically throughout this period. Spectra will normally be obtained at
70 ev ionizing voltage, but low voltage (~15 eV) or CIMS spectra, may yield
more useful data in some cases.
128
-------
Interpretation of the spectra is guided by knowledge of the separation
scheme, the IR spectra, and other information about the source. Data are
grouped by homologous series based on a most probable structure assignment.
Molecular ion series and fragment ions help to identify compound classes
(e.g., polynuclear aromatic hydrocarbons are characterized by intense double
ionization). Compilations of reference spectra will be useful in spectra
interpretation.
Without the benefit of Level 1, analysis (i.e., knowledge of stream
composition) it is impossible to specify exact analytical conditions for
Level 2 analysis. In general, Level 2 analysis is an extension of Level 1
separation techniques using GC and HPLC methods. A greater variety of methods
are used for compound identification and quantification and include UV-visible
spec troscopy , infrared spec troscopy , NMR spectroscopy , GC-mass spectroscopy ,
high resolution mass spectrometry , and gas chromatography .
Since Level 1 Cy-C^ GC procedures for volatile organic compounds are
designed only to separate components by boiling point range, a high resolution
SCOT column is used for initial compound identification; if specific classes
of compounds are suspected, appropriate supports may be chosen from the
listing in Table 16.
For non-volatile organic species, HPLC is used for initial separation;
HPLC techniques include gel permeation chromatography (separation primarily
by molecular weight) and subsequent separation of these fractions by bonded
phase liquid chromatography (separation by chemical class). Where very
polar organic species (e.g., ionic) have been identified from a Level 1
analysis, ion exchange chromatography can be used as a supplementary technique
to bonded phase chromatography.
Once the species of interest have been separated, the aforementioned
analytical techniques are used for specific compound identification either
separately or in combination.
129
-------
TABLE 16. SUMMARY OF RECOMMENDED PROCEDURES FOR ORGANIC ANALYSIS
ANALYSIS
AREA
Volatile
Organic
Compounds :
Ci-Cg Range
Range B.P.°C
1 -160/-100
2 -100/- 50
3 - 50/ 0
4 O/ 30
5 30/ 60
6 60/. 90
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
QC/Flame
lonizatlon
Detector
(FID)
SELECTION
RATIONALE
Gas chromatography pro-
vides a broad, rapid,
relatively simple, and
accurate method for the
determination of vola-
tile organics . The
method is amenable to
on- site analyses and Is
designed to separate
and analyze mixtures of
organic materials with-
in a given boiling
point range (polarity
in some cases) rather
than separate pure
compounds .
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
For 0^-06 volatile or-
ganics, the sample is
collected in a 3L glass
vessel with a pyrex wool
plug to remove particu-
lates.
Recommended Analysis
Parameters :
Column: Poropak Q, 100/
120 mesh, 6' x 0.125" SS.
Detector: Flame ibnlza-
tion. o
Temperature: 50 ,
isothermal .
A temperature calibration
curve is prepared from
pure samples of Ci-Cg n-
paraf ins . Peaks ob-
served in the chromato-
gram will generally rep-
resent mixtures of com-
pounds within a given
B.P. range rather than
individual compounds .
Unless additional evi-
dence can be presented
as to the specific Ident-
ity or given peak, ma-
terial and quantity
should be reported as
being present within a
given range.
Peak areas may be cal-
culated by a variety of
methods: peak height,
trlangulation, integra-
tion, etc.
REFER-
ENCES
14?
(173)
130
-------
TABLE 16 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
GO
(FID)
SELECTION
RATIONALE
A rapid-relatlvely
simple, accurate
method of. separation ;
and analysis ,of or-
ganiQ. compounds.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
For P-i-Cp volatile
organlcsy the sample
IB. collected in a
3L glass vessel with
a pyrex wool plug to
remoE particulates.
Many types of col- '
umns'may be used for
analysis; for C^-C^
hydrocarbons only.
the following analy-
sis scheme is recom-
mended: column:
8' x 1/8" o.d., s.s.»
Yl% by weight p, p'
oxydlproponitrlle on
100-150 mesh activa-
ted alumina. Tem-
perature: isother-
mal at 0°C.
Automatic integra-
tion techniques
should be used for
quantification (disc
type or electronic);
for accurate quanti-
fication, detector
response .calibra-
tion is essential.
REFER-
ENCES
8. 31
lb
173
224
.248
830
9
32
53
71
110
111
169
180
187
195
198
210
222
278
288)
REMARKS
(LEVELS 1 &2)
§as chromatography
is susceptable to
interferences, i.e.
identical retention
times; e.g. 2, 2-
dimethl propane and
trans 2-butane have
identical retention
times under the
; conditions given.
:
I3I
-------
TABtE 16 (continued).
ANALYSIS
AREA
Organic
Compounds:
G7~C12 RanSe
Range B.P.°C
7 90/110
8 110/140
9 140/160 •
10 160/180
11 180/200
12 200/220
.'
RECOMMENDED
ANALYTICAL !
METHOD
oc
(FID)
[
LEVEL 1
SELECTION
•RATIONALE
As above. .
This GC system is de- ;
signed to separate and
analyze mixtures with-
in given boiling point
ranges (polarity In
some cases) rather than
separate pure compounds.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
The C7-C12 organic com-
pounds may be found in
the following areas:
CH2Cl2/CHoOH washes,
CH2C12 extracts, Op-H, «
extract of the XAD^1^
sorbent trap, and neat
organic liquids.
All samples are analyzed
BEFORE concentration.
No preparation is needed
for the neat organic
liquids and washes .
Aqueous solutions (10 L
sample) are extracted 3X
with 500 ml of CH2C12.
Solids are extracted for
24 hours with CH2C12 in
a soxhlet apparatus.
The XAD-2 resin (after
homogenization and re-
moval of a 2g sample for
inorganic analysis) is
extracted for 24 hours
with pentane in a large
soxhlet extraction appar-
atus (dumping volume
1500 ml).
Recommended analysis con-
ditions:
Column: 1..5# OV-101 (or
SE-30) on gas chrom Q
100/120 mesh, 0.125" x
6'SS.
Detector: FID
Temperature : Programmed
50° isothermal for 5 min.
then 10°C/min to 150°C.
A temperature calibration
curve is prepared from
pure sample of C7-C12 n-
paraffins. As the number
of possible compounds in
these ranges is very
large, material and
quantity should be re-
ported as being present
within a given b.p.
range. Specific com-
pound identification
should be supported by
additional data.
REFER-
ENCES
14?
(173)
132
-------
TABLE 16 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
QC
(FID)
SELECTION
RATIONALE
Gas chromatography
provides a rapid and
relatively simple,
accurate method for
the separation and
quantification of
organic compounds.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
See Level 1 for sam-
pling considerations
and requirements.
While no single col-
umn may be suitable
for all organic com-
pounds In this range,
the following column
and conditions are
recommended for Iden-
tification screening
purposes:
Column: SCOT 0V 101
or 0V 17, 100m, 0.4
mm I.D.
Detector: FID
Temperature: Pro-
grammed 2 C/Mln, am-
bient to 300°C.
Other columns of use for Particular Com-
pounds are listed below:
Class of Compounds
Acids ci-C9
crcl8
Alcohols GI-C
5
0-,-C-iQ
Polyalcohols
Aldehydes C, -Cj-
-*• j
c5-cl8
*Amines
Amides
Esters
Ethers
Preons
Glycols
Halides
Hydrocarbons Cc-C,0
Aromatic
Column Type
Chromosorb 101
FFAP
Poropack Q, Chrom-
sorb 101
Silar 5CP, Carbowax
20M, FFAP
FFAP
Poropak N, DC-550
Ethofat
Carbowax 20M, Silar
5CP
Poropak Q/PEI, Poro-
pak R
* Chromosorb 103,
Penwalt 223
Versamid 900, Igepal
CO-630
Poropak Q, Dinonyl-
phthalate
Chromosorb 101 or 102
Carbowax 20M, Silar
5CP
Poropak Q, Chromosorb
103
Chromosorb 107
OV-210, FFAP
OV-101, SE-30
Silar $CP, Carbowax
20M
REFER-
ENCES
(15
10.1
10.2
63
91
139
172
212
224
236
264
278
286)
REMARKS
(LEVELS 1 & 2)
Supplemental analy-
ses (IR, MS) may be
necessary for com- .
po.und identifi^
cation; for a tab-
ular presentation of
these techniques
see non-volatile
organics - Level 2.
I33
-------
TABLE 16 (continued).
ANALYSIS
AREA
Non-Volatile
Organic
Compounds
(B.P.>220°C)
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Extraction
and frac-
tionation
by column
chroma-
tography;
class iden-
tification
within
each frac-
tion using
Infrared
spectro-
scopy (IR)
and low
resolution
mass
spectro-
metry
(LRMS)*
*LRMS is
defined as
a mass
spectra
with a
resolution
(M/ M) of
1000
SELECTION
RATIONALE
Column chromatography
is a low resolution
technique intended to
yield 8 fractions on
the basis of class
polarity; overlap of
class type between
many of the fractions
is inevitable. IR
analysis is used to
identify functional
groups present in each
sample and fraction.
When sample quantity is
sufficient (referenced
back to the source in
terms of emission rates);,
LRMS is utilized in
conjunction with IR
analysis to aid in
class identification.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Non-volatile organic
compounds may be found
in the following areas:
Organic liquids (inclu-
ding washes), aqueous
solutions, solids, and
the XAD-2 sorbent trap.
Organic liquid sepa.-
ration and analysis may
be run neat . Washes
(CHpCl2/CHoOH) are evap-
orated before separation
and analysis . Aqueous
solutio'ns (10 L sample)
are extracted 3X with
500 ml of CHpClg,
evaporated and weighed
before separation and
analysis. Solids are
extracted for 24 hours
with CHpClp in a soxhlet
apparatus. The extract
is concentrated and
weighed before separatior
and analysis . The XAD-2
resin (after homogenl-
zation and removal of a
2g sample for inorganic
analysis) is extracted
with pentane in a large
soxhlet extraction appa-
ratus (dumping volume
1500 ml). The extract
is evaporated and
weighed before sepa-
ration and analysis.
REFER-
ENCES
14?
(173)
134
-------
TABLE 16 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
REFER-
ENCES
REMARKS
(LEVELS 1& 2)
Olefins Cg and
greater
POM
Ketones
Halogenated
Aromatics
Phenols
DC-550, DC-703
Dexsil 300, OV-101,
SE-30
Poropak Q, Chromo-
sorb 102, FFAP
OV-101, OV-225,
OV-1, OV-17, SE-30
OV-17, Silar 5CP,
Carbowax 20M
Complete coverage of all contemplated techniques Is not possible. The following
Is a summary of applicable techniques taken from "Technical Manual for Analysis
of Organic Materials in Process Streams" Batelle, Columbus Laboratories, March,
1976. , This report should be consulted for further details of analysis.
(HPLG)
High Per-
formance
Liquid
Chromato-
graphy
Gel Permea-
tion Chro-
matography
Bonded
Phase
Liquid
Chromoto-
graphy
{Reverse)
See Level 1 for dis-
cussion of sample con-
siderations and re-
quirements . Frac-
tions from silica
gel column may be
analyzed individually
if required.
20mg of sample/100 ml
of column volume.
Preparative columns
can handle up to-
Ig samples.
181)
181)
Volatile and non-
volatile organic
separation of wide
variety of com-
pounds; especially
applicable to high
molecular weight
compounds and ther-
mally sensitive
compounds; small
sample size
requirement.
Separation by molec-
ular weight. A
common column
packing is a sty-
renedivinyl benzene
polymer; mobile
phase must be com-
patible with support
and detection
system - low refrac-
tive index allows
more sensitive de-
tection with RI
detector.
Separation by
chemical class;
class separation is
achieved by per-
forming gradient
elutioh on a ;
reversed phase
column; solvents
chosen for gradient
elution must be com-
patible with detec- ;
tion system; micro- ;
particle (5-10).
135
-------
TABLE 16 (continued).
ANALYSIS
AREA
Non-Volatile
Organic
Compound so
(B.P.>220 C)
(continued)
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS '
REFER-
ENCES
14?
(173)
136
-------
TABLE 16 (continued).
LEVEL 2^
RECOMMENDED
ANALYTICAL
METHOD
Thin- layer
Chroma-
tography
(TLC)
Liquid-
solid
Chroma-
tography
Ion-
Exchange
Chroma-
tography
J
Dispersive
IR
.1
SELECTION
RATIONALE
.SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
PS quantities of
sample required for
analysis. TLC sup-
port (SlOg & A1203)
n&y need activitation
by heating' at 110°C
for 1 hour.
mg quantities of
samples are necessary;
for analysis.
Preparative columns
can handle up to Ig
samples .
Thin film on crystal.
For micro determin-
ation, •micro-pressed
disk or microfilm
technique Is used.
REFER-
ENCES
(262)
(140)
(172)
(173)
(271)
(140)
REMARKS
(LEVELS 1 & 2)
reverse phase
packing preferred;
gradient elution is
difficult with RI'
detection system.
TLC data may give
data which is
directly applicable
to HPLC. Color
reagents may be
used on plate
directly for
class identification
A useful technique
for screening
studies; elution
from non-polar
to polar order is
solvents; a prepra-
tive method for
rough class separa-
tion.
Separation of polar
organic compounds .
Used for separation
of very polar
organlcs; supple-
mentary to reverse
phase. liquid
chromatography; used
after sequential
analysis has iden-
tified an ionic
fraction.
Class identification
by functional group;
also useful for
compound identi-
fication. Disper-
sive IR systems are
widely available;
average resolution
should be 4 cm"1
over the spectral
range of (3800 em"1-
600 cm"1).; wave-
length accuracy of
±10 cm"1 above
200 cm"1 and less
than that below
2000 cm"1. Wave-
length readability
should be better
than 10 cm"1 at
wavenumbers above.
137
-------
TABLE 16 (continued).
ANALYSIS
AREA
'. Non-Volat.ifle
. Organic
Compound s'0
(B.P.>220 C.).
('Continued)
LEVEL 1
RECOMMENDED
:. ANALYTICAL
•; METHOD-
\
i
;
SELECTION
RATIONALE
i'
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Samples are prepared for
separation by evapor-
ation on a Kuderna-
Danish apparatus such
that 20-500 mg of
sample is obtained
(100 mg is optimum).
Samples are separated on
a 200x10 . 5 mm glass
column (teflon stoplock)
packed with 6.0g of
freshly activated (2HR at
110°C) silica gel {60/10C
mesh, grade 950 - Pisher
scientific).
The evaporated sample
is weighed in a glass
weighing funnel and
transferred quantita-
tively by mixing with
Ig of activated silica
gel and placing this
onto the column via the
weighing funnel. The
funnel is rinsed with
5 ml of pentanei to
complete the transfer.
The column is now eluted
at 1 ml/min with the following eluants:
Fraction Eluant Volume
• Number Composition Collected
1 Pentane 25 ml
2 20$: CH2C12 in pentane 10 ml
3 50# CHpClp in pentane 10 ml
4 Cm el'* 10 ml
5 5#2CHfOH in CH-Clp 10 ml
6 20#. CH'OH in CH-CI, 10 ml
7 5P#CH|OH in CH^Cl? 10 ml
8 Cone. Hdj/CH_OHfCH2Cl
(5:70:30) 3 2 2
After each fraction is collected, it Is trans-
ferred to a tared" aluminum weighing dish (a glass
container is used for • evaporation of fraction 8)
evaporated and? weighed. The total sample and 8
fractions' are 'analyzed by IR spectroscopy for
functional groups present.
Mass spectra are taken on each fraction which is
deemed' significant in terms of emissions; the
criteria are:
REFER-
ENCES
147
(173)
1
138
-------
TABLE 16 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
•ME'THOD
Fourier
Transform
IR
OOt IR
NMR
CW
H1
With CAT*
NMR
FT
Hi
NMR
C^3
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Thin film on crystal/
KBr Pellet.
Gas cell .
Dissolution in suit-
able solvent.
~ 10 mg sample is
required .
Dissolution in suit-
able s'olvent.
Dissolution in suit-
able solvent .
CAT = Computer Averaged Transients
REFER-
ENCES
(140)
173
(271)
(140)
173
(271)
(140)
,173x
(271)
(140)
193
(291)
REMARKS
(LEVELS 1 81 2)
2000 cm~1_and better
than 5 cm" below
2000 -cm"1-.
Greater sensitivity
obviates need for
micro techniques;
accuracy and reso-
lution as above;
dedicated computer
necessary but
considered an ad-
vantage; a very
useful screening
technique.
Class identifica-
tion/Compound iden-
tification - Micro
techniques may
extend range
to 10-100 ng range;
useful for func-
tional group class-
ification after
"rough" separation
has been made.
Sensitivity ex-
tended by a factor
of 100.
Fourier transform
NMR is 100-100 X
more sensitive
than CW.NMR; micro
techniques may
extend range 10-
100 X lower; ded-
icated computer
required .
Large chemical shift
range (600 ppm) as
compared to H1 NMR
(20 ppm) which en-
hances effective
resolution.
Ability to identify
functional carbons;
most useful where IR
and MS give rela-
tively little Infor-
mation .
139
-------
TABLE 16 (continued).
ANALYSIS
AREA
?
Won- Volatile
Organic
Compounds
(;B.P.>220°C)
(continued)
LEVEL 1
[RECOMMENDED
^ANALYTICAL
METHOD
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Gas - (SASS Train) - 0.5 mg/m,
('Ambient Air) - 1 g/n£
Aqueous Solutions - 10 g/m5
Solids 100 .g/nr*
Volatile samples may be inserted into the gas
inlet; less volatile samples are placed in the
solid inlet probe.. The probe is programmed up
to vaporize the sample; spectra are recorded
periodically. Spectra are obtained at 70eV
ionizing voltage, but a lower ionizing voltage
(~15eV) or a .CI source, if available, may yield
much useful information
REFER-
ENCES '
147
(173)
140
-------
TABLE 16 (concluded).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
uv-
Visible
Spectro-
scopy
Mass
Spectro-
scopy El*
Mass
Spectro-
scopy
Chemical
lonization
(CI)
GC-MS
El and CI
El = Elect]
SELECTION
RATIONALE
ron Impact
SPECIAL SAMPLING
AND ANALYTICAL
• 'REQUIREMENTS
Sample Is dissolved
in a suitable
solvent (UV/VTS;
inactive . in wave-
length region .of
interest).
Several injection
methods possible
(probe Insertion
preferred ) ; temper-
ature programming of
probe may give add-
itional ' separation .
Several injection
. methods possible
(probe insertion pre-
ferred); temperature
programming of probe
may give additional
separation.
As In GC analysis.
•
REFER-
ENCES
173
( 271 J
(140.)
193.
fas)
(Tl
(140)
ii lin\
140)
271)
REMARKS
(LEVELS 1& 2)
Class Identifi-
cation-Useful in
identifying func-
tional groups and
certain types of
compounds; sensi-
tivities are gen-
erally higher in UV
region. Used in
conjunction with
IR, NMR, and MS.
Class Identifi-
cation-Not a useful
screening technique;
computer access to
a large data base
is essential.
Compound Identi-
fication/Molecular
Weight Determina-
tion ;CH4 and NH3
are commonly used
as ionizing gases;
suitable" standards
are unavailable at
this time for CIMS;
of limited use as a
screening technique.
Compound Identi-
fication/Molecular
Weight Determina-
tion- - Dedicated
mini- computer is
essential for best
results; quantifi-
cation may be
achieved by
specific Ion
. current integration
or by total ion
current comparison.
I4I
-------
Elemental Analysis
Figure 28 provides an overview of the Level 1 inorganic analysis scheme,
Recommended procedures for elemental analysis are presented in Table 17.
Spark Source Mass Spectroscopy (SSMS) is recommended for screening purposes
at Level 1, while a variety of techniques are used at Level 2.
Four specific groups of samples for inorganic element analysis result
from a Level 1 sampling survey:
(1) XAD-2 trap;
(2) Aqueous samples;
(3) Organic samples (liquid or solid); and
(4) Particulate matter, including probe and cyclone washes and ash
s amp1e s.
To analyze these samples by SSMS, two general conditions must be met:
(1) The sample, if it is not a conductor, must be placed into a con-
ducting medium (graphite); and
(2) The sample must be as free as possible from organic matter which
can complicate spectra interpretation.
In Figure 29, preparation procedures for each of the abovementioned
sample types are indicated.
Aqueous samp.les are prepared by adding a small amount of the sample
to powdered graphite and evaporating to dryness. (One ml of solution is
needed to obtain a 1 u,g/j0 sensitivity assuming a basic SSMS sensitivity
of 10~9g.) The graphite is then pressed into an electrode. Particulate
matter, ash, and fuel samples require reduction of organic matter by wet
ashing in a Parr bomb over nitric acid; an aliquot of this sample is added
to graphite, evaporated, and pressed into an electrode.
An analysis of the XAD-2 sorbent trap for trace elements is a unique
problem because little is known about volatile element retention of the
sorbent trap. Since absorption is not uniform throughout the length of the
trap, the XAD-2 sorbent is first thoroughly mixed to ensure homogeneity, and
then a 2 g portion of the sorbent is used for Parr bomb combustion over HNO-j.
An aliquot of this s-ample is then formed into an electrode in the same
manner as above.
\
Sample homogeneity is of the utmost importance for solid inorganic
samples which are not dissolved prior to analysis. These samples should be
reduced to less than 200 mesh in a micro-mill equipped with stellite blades.
(Alternatively the sample may be ground with a boron carbide mortar and
pestle.) The ground sample is blended with graphite (equal parts) and
pressed into electrodes.
There are two general types of SSMS detection systems; photographic
plate, and electrical detection. For Level 1 elemental analysis, the
142
-------
LEVEL 1
INORGANIC ANALYSIS
GASES
CO
SSMS
ELEMENTAL
ANALYSIS
OF SORBENT
TRAP
GC FOR:
CO, Cp2,
N2, H2S,cOS
HCN, (CN)
NO^BY
CHEMILUMINESCENCE
SSMS ELEMENTAL
ANALYSIS
WET CHEMICAL
ANALYSIS FOR
Hg, Sb, As
WET CHEMICAL
ANALYSIS FOR
Hg, Sb, As
STANDARD .
WATER ANALYSIS
pH, ACIDITY,
ALKALINITY, BOD,
COD,^DISSOLVED
OXYGEN,
CONDUCTIVITY,
DISSOLVED AND
SUSPENDED SOLIDS,
SELECTED ANIONS,
HARDNESS
SSMS
ELEMENTAL
ANALYSIS
LEACHABLE MATERIAL SSMS-
ELEMENTAL ANALYSIS
REAGENT ANALYSIS, KITS-
SPECIES ANALYSIS
' WET CHEMICAL
ANALYSIS FOR
Hg, Sb, As
Figure 28. Level 1 inorganic analysis scheme
-------
BIS
SAMPLE FOR
ELEMENTAL
ANALYSIS
1
WATER AND
NON-ORGANIC
SOLUTIONS
BC3SBCT
XAD-2
SORBENT
ORGANICS :
LIQUID
OR SOLID
pnt^gi^^ragCTBMi^agMggii^egaaaji QG9GB^9^H^Q^3^BI3(O^3^B^&^BEEI^Q^BC3'
SLURRY ALIQUOT
WITH GRAPHITE
AND EVAPORATE
FORM ELECTRODE
•c
HOMOGENIZE
AND DIVIDE
2g.
1
PARR BOMB
COMBUSTION
OVER HNO-
EXTRACT
FOR
ORGANICS
SLURRY ALIQUOT
WITH GRAPHITE
AND EVAPORATE
„____
PARR BOMB
COMBUSTION
OVER HNO
PARTICULATE
MATTER, ASH
OR NON-ORGANIC
SOLIDS
PARR BOMB
COMBUSTION
OVER HNO
SLURRY SOLUTION
AND RESIDUE WITH
GRAPHITE AND
EVAPORATE
FORM ELECTRODE
SLURRY SOLUTION
AND RESIDUE WITH
GRAPHITE AND
EVAPORATE
FORM ELECTRODE
FORM ELECTRODE
.^^^^^^^^^^^^^^^^^^^^^^
SSMS'
SSMS
SSMS
S E3 03 EBBS
SSMS
SAMPLE
PREPARATION
ANALYSIS
Figure 29. Sample preparation for Level 1 elemental analysis
-------
photographic system using the "just disappearing line" technique is employed.
To achieve the highest sensitivity j'-a series'of exposures of the photoplate i's
made with the sample, and is compared to a series of exposures made with a
reference sample. Precision and accuracy are highly dependent on spectral
line widths and shapes. These parameters define optical densities which are
converted to ion densities by means of calibration curves. A number of
computer-oriented systems for the derivation and integration of ion intensity
profiles have been developed for use in accurate and precise determinations.
While SSMS can, in theory, analyze any element, arsenic, antimony, and
mercury are not determined.reliably by SSMS; in addition, carbon, hydrogen,
nitrogen, and oxygen are not commonly determined by SSMS. ThuSj the former
are determined by atomic absorption spectroscopy or wet techniques while
the latter group is determined by combustion methods. Figure 30 summarizes
the analytical scheme for arsenic, antimony and mercury. Since several
additional sample preparation steps are included in this scheme, care must
be taken to avoid contamination; blanks on all solutions, acids, and
reagents must be run to insure accurate and reproducible results.
At Level 2, the analytical methods employed are more varied. While
atomic absorption spectroscopy (either flameless or conventional) has been
chosen for a majority of elements, it is not unreasonable that, depending on
the total number of elements to be analyzed,.; SSMS might be used at Level 2.
To achieve the high accuracy and precision which is required at Level 2, a
spark source mass spectrometer employing ion sensitive multiplier phototubes
as detectors, is required; with electrical detection, precision rivals
that obtainable by any other analytical method.
If a small number of elements are to be .determined, AAS is a more
economical choice than SSMS; not only is AAS equipment commonly available
in most laboratories; but, in general, the method combines high specification
with high sensitivity. The use of a graphite furnace (flameless atomic
absorption, spectroscopy)can improve detection limits a thousand fold. (Other
methods such as NAA, XRF, etc. can also be used where appropriate and if the
required equipment is available.)
Another modification to AAS which has been found useful for arsenic,
antimony, bismuth, germanium, tellurium, and tin is the hydride evolution
technique. In this technique, volatile hydrides are generated and analyzed
with a conventional AAS system. The advantages of the Hydride Evolution
Technique are as follows: (1) practically all matrix effects are eliminated
since matrix materials are left behind; (2) very efficient use is made of
the sample as. the .entire amount of the element of interest present reaches
the flame in a form very suitable for efficient atomization; (3) the method
improves sensitivity by factors of 50 to 200.
Either specific procedures or relevant analytical conditions are given
in Table 17; where specific procedures have not been given, they can be
found in the references cited. (For general AAS procedures, see references
42 and 82.)
145
-------
SAMPLE TYPE
SAMPLE PREPARATION
SAMPLE ANALYSIS
WATER AND
NON-ORGANIC
LIQUIDS
PARTICULATE MATTER,
ASH, AND NON-ORGANI
SOLIDS
XAD-2
SORBENT
ORGANICS-
LIQUID
OR SOLID
;ARSINEi EVOLUTION
USING Ag-DIETHYL-
DITHIOCARBAMATE
IMETHOD .
Figure 30. Sample preparation and analysis of Hg, Sb and As- Level 1
-------
A variety of dissolution arid ashing procedures are used and referred to
within Table 17. These procedures are discussed below.
Dry ashing is the simplest prior treatment for samples containing
organic material and may be used where high temperature ashing is suitable
(as noted in Table 17). The general procedure is as follows:
An appropriate amount of sample (1-2 g, - 200 mesh) is weighed into
a porcelain crucible and placed in a cold vented, furnace. The furnace is
brought to a temperature of 300°C for 0.5 hour, to 550°C for 0.5 hour, and
to 850°C for 1.0 hour. The crucible is removed from the furnace, stirred,
and returned to the furnace at 850°C for 1.0 hour with no venting.
The resultant ash is placed in a 100 ml teflon beaker containing
5 ml of HF (cone.) and 15 ml of HNO-v (cone.), dissolved by gentle warming,
and evaporated until just- dry. Distilled water and 1 ml of HNO-j (cone.)
are added to dissolve the salts, and this solution is transferred to a
100 ml volumetric flask. Distilled water is added to adjust the volume
to 100 ml. This solution is transferred to a polyethylene bottle and
preserved as a- stock solution.
The oxygen bomb combustion method, used for organic matrix reduction in
Level 1 procedures, is as follows:
Approximately 1 g of -200 mesh sample is transferred to a clean
combustion crucible and weighed to the nearest 0.1 mg. Ten railliliters of
10 percent HNO-j is tranferred to a Parr bomb, the crucible placed in the
electrode support of the bomb, and the fuse wire attached. The bomb is
assembled and oxygen added to a pressure of 24 atm. (gage). The bomb is
placed in the calorimeter (cold water in a large stainless steel beaker
is also satisfactory) and the sample ignited using appropriate safety
precautions ordinarily employed in bomb calorimetry work. After combustion,
the bomb should be left undisturbed for 10 minutes to allow temperature
equilibration and the absorption of soluble vapors. The pressure is released
slowly and the contents transferred to a beaker. Any residue remaining can
be brought into solution by fusion techiques.
Siliceous materials (e.g., coal ash) may be solubilized by a lithium
tetraborate acid dissolution technique. The following method may be used:
One tenth g of sample is added to a plastic vial containing 1 g
of preweighed lithium tetraborate. The vial is hand shaken to mix the
material, and the contents are poured into a graphite crucible. The
material is fused at 950°C for 15 min in a muffle furnace. The resulting
bead is removed from the furnace and can either be stored in the original
vial or immediately solubilized. The bead is transferred to a teflon beaker
containing 5 ml of 3N-HC1, 2 ml of 2N HN03 and 10 ml of water. (Teflon is
used to eliminate sodium contamination.) The material is then boiled until
completely dissolved and immediately filtered into a 50 ml volumetric flask.
Hot filtration is required to prevent solid materials from crystallizing
out of solution before dilution and to remove carbon particles that result
147
-------
from fusion in graphite crucibles. The sample is then diluted to volume,
shaken, and then further diluted as required to bring the element concentra-
tion to within range of the working curve of interest.
A final method which has been found to be very effective for the
dissolution of silicate minerals is described by Bernas (reference 36).
Fifty mg of a representative -150 mesh size sample portion is transferred
into a Teflon decomposition vessel. Aqua regia (0.5 ml) is added and the
sample swirled to insure thorough wetting. Hydrofluoric acid (3 ml-
48 percent) is added and the vessel sealed. The crucible is placed in a
drying oven for 30 to 40 minutes at 110°C. After cooling to ambient
temperature, the decomposed sample solution is transferred to a polystyrene
Spex vial (50 ml). Care should be taken to quantitatively transfer any
precipitated metal fluorides which may have formed. The final volume should
not exceed 10 ml. Boric acid (1.8 g) is added and stirred with a Teflon
stirring bar to hasten the reaction. Upon addition of 5 to 10 ml of distilled
water, any precipitated metal fluorides will dissolve. The solution is
transferred to a 100-ml volumetric flask, adjusted to volume, and stored in
a polyethylene container. The sample solution should not remain in contact
with glass for longer than 2 hours.
A large number of abbreviations and notations are used within Table 17
for brevity. Those abbreviations, by columns, are:
o Recommended Analytical Method - Level 1
SSMS - Spark Source Mass Spectrometry
o Recommended Analytical Method - Level 2
AAS - Atomic Absorption Spectroscopy
FAAS - Flamel'ess Atomic Absorption Spectroscopy
HE - Hydride evolution technique
SIE - Specific Ion Electrode
o Special Sampling and Analytical Requirements - Level 2
The format used for AAS entries is - sample dissolution method,
oxidant and fuel type, analytical wavelength, and recommended slit
setting.
0 Remarks
Detection limits (intended to be representative, not "world's
records") are reported within parentheses and are in g ml . Where
FAAS and HE methods are appropriate, their detection limits are also
listed.
NRL-Non-Resonance Lines which are suitable for background inter-
ference correction with a deuterium lamp.
148
-------
TABLE 17. SUMMARY OF RECOMMENDED PROCEDURES FOR ELEMENTAL ANALYSIS
ANALYSIS
AREA
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Spark
Source
Mass
Spectrp-
metry
(SSMS)
Rhodamine
B
Silver
Diethyl-
Dithio-
carbamate-
Arsine
Evolution
Method
SSMS
SSMS
SSMS
SSMS
SELECTION
RATIONALE
See introduction for
SSMS selection
rationale (applies to
all elements listed
below where SSMS has
been selected) .
SSMS does not provide
reliable data within
the accuracy limits of
Level 1.
SSMS does not provide
reliable data with the
accuracy limits of
Level 1.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Additional general
SSMS references:
(129, 145, 149,
213, 229, 249).
Organic samples and
XAD-2 sorbent (2g) are
wet ashed by QQ combus-
tion in a Parr bomb over
HNOo. Particulates, ash
and inorganics are di-
gested with aqua regia,
the residue fused with
Na2C03 and then digested
with HC1. Liquid sam--
ples are analyzed as
received. All samples,
prior to SSMS analysis,
are siurried with gra-
phite, evaporated, and
briquetted to form the
electrode.
REFER-
ENCES
147
(325):
325
O"3T
337
3
147
(325)
147
325)
3
147
325)
3
147
325)
.150
-------
TABLE 17 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Atomic
Absorption
Spectro-
scopy
(AAS)
AAS
Hydride
Evoluti. on
Technique
(HE)
AAS
Hydride
Evolution
Technique
AAS
AAS
AAS
AAS
SELECTION
RATIONALE
See introduction for
AAS selection
rationale (applies
to ;al'l elements ' , "'••<
listed below where
AAS has been
selected).
Relatively matrix-
independent as com-
pared to conventional
AAS.
Relatively matrix-
independent as com-
pared to conventional
AAS .
•>
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Wet ashing; N20-
C2H2 flame, 3093 A,
Slit 2 A
02 bomb combustion;
HF/HNOo. dissolution.
Hydride is generated
.by TiClo-Mg method;
iilr-Cp)J2 flame,
J2175 A, Slit-7 A.
©2 bomb combustion;
HF/HN03 dissolution.
Hydride is generated
by TiCl^-Mg method;
alr-C2H2 flame, !
1937 A", Slit-7 A.
i
1-
Wet ashing; HF/HN03
dissolution. N20-
;C2H2 flame, 5536 A
Slit- 40 A. ;
Wet ashing; N20- '
C2H2 flame, 2349 A, :
Slit- 20 A. i
Wet ashing; air-
C2H2ftflame, 2231 A,
Slit-7 A.
Wet ashing; N20-C2H2 '•
flame, 2497 A, Slit-
2 A.
REFER-
ENCES
42
82
280
(239)
26
(124)
26
(124)
42
82
280
(239)
42.82
280
(239)
42
82
280
[239)
42
82
280
239)
REMARKS
(LEVELS 1 & 2)
(0.1-AAS, IxlO'6-
FAAS)» Zn, Ca, Cu,
Fe, alkalai and
alkaline earth metal
interferences are
reported .
Rhodamine B spectro-
metric method is
suitable 'for Level
2. Flameless HE
technique is
essentially matrix-
independent. (0.03-
AAS, Q.004-HE,
5xlO-6-FAAS).
Silver diethyl-
dithio carbamate
method is suitable
'for Level 2. Flame-
less HE technique is
.essentially matrix-
Independent.
•(0.03-AAS, 0.004-HE,
;8xl6-6-FAAS).
1 (•
'(0.02-AAS, 6x10 -
FAAS) Dry ashing is
acceptable. Al, Si,
'alkalai and alkaline
[earth metal inter-
ferences are repor-
ited.
i
i(0.002-AAS, 3xlO"8-
:FAAS).
i(0.04-AAS, 4xlO"6-
;FAAS) Dry ashing is
acceptable. Ca, Mg,
;Na, K molecular
.interferences are
reported.
-4
(3- AAS, 2x10 -FAAS)
The.carminic acid
method- is also an
acceptable method
for Level 2 (-0.005).
* Detection limits
in ppm.
151
-------
TABLE 17 (continued).
ANALYSIS
AREA
Bromine
Cadmium
Calcium
Carbon
Cesium
Chlorine
Chromium
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
•SSMS
SSMS
SSMS
Combustion
Gravi-
metric
SSMS
SSMS
SSMS
SELECTION
RATIONALE
Carbon is generally
not analyzed by SSMS.
Combustion is a
rapid, low cost tech-
nique which is in wide
use.
.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
See Level 2
Chlorine is not
measured in particulate,
ash, and inorganic
samples because of
dissolution procedure.
REFER-
ENCES
3
147
(325)
3
147
(325)
3
147
(325)
8.4
3
147
(325)
3
147
(325)
3
147
(325')
152
-------
TABLE 17 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Spectro-
metric
AAS
AAS
Combustion
Gravi-
metric
AAS
Combustion
Titri-
metrlc
AAS
SELECTION
RATIONALE
This method is an
accurate reprodu-
cible and fairly
rapid technique
which is in common
use In organic
analysis.
This method is an
accurate rapid and
reproducible tech-
nique. ASTM method.
- •
This method is an
accurate, rapid, and
reproducible
technique. ASTM
method .
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Combustion with Og
bomb/ Eschka mixture
and (Nlty) COg.
Spectrometric measure
ment at 515 nm.
Wet ashing; alr-CpHp
flame, 2288 A. Slft-
7 A.
Wet ashing; alr-C2H
flame, 4227 A, 2
Slit-20 A.
Absorbent may be
sodium or potassium
hydroxide Impreg-
nated in an Inert
carrier of 8-20 mesh.
Soda lime may also
be used.
High temperature
ashing; HF/HNOg dis-
solution; alr-CpHo
flame, 8521 A
Slit-40 A. -
02 bomb combustion
with (NHi|)2 CO^ or
Eschka mixture.
Wet ashing; air-CpHp
flame, 3579 A,
Slit-2 A.
-•
REFER-
ENCES
8.19
42,82,
280
(239)
42,82,
280
(239)
8.4
42,82,
280
(239)
8.9
42.82,
280
(239)
. REMARKS
(LEVELS 1 & 2)
See Table 19:
Bromide
(0.001-AAS, 8xlO"8-
FAAS) Fe molecular
Interference is
reported (2321 A
NHL).
(0.002-AAS, 4xlO~2-
FA'AS) Dry ashing is
acceptable. SO^"2,
P04T3, Al, Si, Na,
K Interferences
are reported . Sr
buffer reduces
interferenc.e.8^
0.05-AAS, 4xlO'7-
FAAS) Dry ashing is
acceptable alkalai
metal ionizatlon
interferences are
reported .
Potentiometric tl-
tration may dis-
tinguish between
Cl",'Br~, I". See
Table 19: Chloride
(0.002-AAS, 2xlO"6-
FAAS) Fe chemical
interference is
reported . NH^Cl
buffer is used to
eliminate Interfer-
ence.
153
-------
TABLE 17 (continued).
ANALYSIS
AREA
Cobalt
Copper
Dysprosium
Erbium
Europium
Fluorine
Gallium
Gadolinium
Germanium
Gold
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD-
SSMS ''
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
REFER-
ENCES
3
147
(325)
3
147
(325)
3,147
(325)
3,147
3,147
(325)
147
(325)
3,147
(325)
3,147
(325)
3,147
(325)
3,147
(325)
154
-------
TABLE 17 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
AAS
AAS
AAS
AAS
AAS
Combustion
/SIE
AAS
AAS
AAS
AAS
SELECTION
RATIONALE
This method is an
accurate, reproduci-
ble, fairly rapid,
and simple technique
for the measurement
of fluorine.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Wet ashing; air-C0H9
flame, 2407 A, d
Sllt-2 A.
Wet ashing; air-CpH2
flame, 3248 A, Slft-
7 A.
Wet ashing; NP0-C9H2
flame, 4212 AT Slit-
2 A.
Wet ashing; N00-C9H9
flame, 4008 A? Slit-
2 A.
Wet ashing; N.O-C2H2
flame, 4594 Af-Slit-
2 A.
Quartz sample holder;
absorption by IN
NaOH in bomb; plastic
ware is used through-
out analysis.
High temperature
ashing; HF/HNO, dis-
solution air-CpH9
flame, 2874 A.^SIlt-
20 A.
Wet ashing NgO-C2H2
flame, 3684 A, Slit-
2 A.
p2 bomb combustion
over HN03 ; wet ash-: ;
ing; N20-C2H2 flame,
2652 A, Slit-2 A.
Wet ashing; NpO-CpHo
flame, 2428 A, Sllt-
20 A.
REFER-
ENCES
42
82
280
(239)
42,82,
280
(239)
42,82,
280
(239)
42.82,
280
(239)
42.82,
2SO
(239)
303
26
42,82,
280
(239)
42.82,
280
(239)
42,82,
280
(239)
42,82,
280
(239)
REMARKS
(LEVELS 1 & 2)
(0.002-AAS, 2xlO~6-
FAAS) Dry ashing is
acceptable. Ca, Mg, ".
K, Na molecular
Interferences are
reported (2384 A,
2389 A-NRL).
(0.004-AAS) 6xlO"7-
FAAS) Ca, Na, K
molecular inter-
ferences are
reported (2961 A-
NRL).
(0.4- AAS; 0.007-
FAAS)
(0.1-AAS)
(0.2-AAS, 0.02-FAAS)
SIE procedure is
more accurate than
distillation- color-
imetric procedure.
(0.05-AAS, 4x10"^-
FAAS) Al molecular
interference is
reported .
(4-AAS)
(0.1-AAS, 3xlO~6-
FAAS) Presence of
excess chloride
tends to increase
losses.
(0.02- AAS, 1x10" 6-
FAAS) Fe and Ca
molecular Inter-
ferences are repor-
ted.
155
-------
TABLE 17 (continued).
ANALYSIS
AREA
Hafnium
Holmium
Hydrogen
Indium
Iodine
Iridium
Iron
Lanthanum
Lead
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
SSMS
SSMS
Combustion
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SELECTION
RATIONALE
Hydrogen is not
commonly analyzed by
SSMS. ASTM method.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
See Level 2
REFER-
ENCES
3
147
(325)
3,147,
(325)
8.4
3,147
(325)
3,147
(325)
3,147
(325)
3,147,
(325)
3,147,
(325)
3,147.
(325)
156
-------
TABLE 17 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
AAS
AAS
Combustion
AAS
Combustion
Spectro-
metric
AAS
AAS
AAS
AAS
SELECTION
RATIONALE
This method is an
accurate, rapid, and
reproducible tech-
nique. ASTM method.
This method is an
accurate repro-
ducible and fairly
rapid technique
which is in common
use in organic
analysis.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
LlnBjjOy fusion; HC1
UNO, dissolution;
&p02c2H2 flame 3073 A,
SIit-2 A.
Wet ashing; air-C H
flame, 4104 A, Slft^
2 A.
Absorbent is anhydrous
Mg(C10O2 of 8-45
mesh size.
LigB^Oy fusion; HC1
HNOo dissolution; air-
CoHp flame, 3039 A,
Stiff- 7A.
Combustion with 02
bomb. Spectrometric
method; measure at
45 nm.
Wet ashing; NoO-CoHo
flame, 2640 A, -Slit-
2 "A-:
Wet ashing; air-CpHp
flame; 2483 A;-Slft-
2 A.
Wet ashing; N-O-CoHp
flame, 5501 A? Sllt-
4 A.
Wet ashing; air-CoHp
flame, 2833 A, Slit-
20 A.
REFER-
ENCES
42
82
208
(239)
42,82
208
(239)
42,82,
208
(239)
8.19
42,82
208
(239)
42,82,
208
(239)
42,82
208
(239)
42,82,
208
(239)
REMARKS
(LEVELS 1 & 2)
(15-AAS) Wet ashing
is acceptable.
(0.3-AAS)
Sample should be
dried at 104-110°C
or moisture will be
included in
hydrogen value.
This method will
include water of
hydratlon of inor-
ganic compounds in
the value of
hydrogen reported .
(O.OVAAS, 4x10-7-
FAAS) Dry ashing is
acceptable.
See Table 19:
Iodide
(1-AAS)
(0.004-AAS, lxlO'5-
PAAS)oCa (molecular)
and Si (chemical)
interferences are
reported. (2511 A-
NRL).
(2-AAS)
(0.01-AAS, 2xlO~6-
FAAS) Al, Th, Zr
(chemical) and Ca,
Mg, K, Na (molec-
ular) interferences
are reported (2203-
NKL).
157
-------
TABLE 17 (continued).
ANALYSIS
AREA
.Lithium
Lutetium
Magnesium
Manganese
Mercury
Molyboenum
Neodymium
Nlck&l
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
SSMS
SSMS
SSMS
SSMS
FAAS
(Cold
Vapor tech-
nique)
SSMS
SSMS
SSMS
SELECTION
RATIONALE
SSMS does not provide
reliable data within
the accuracy limits
Level 1.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Organic samples and XAD-
2 sorbent (2g) are wet
ashed by Og combustion
in a Parr bomb over HNOo.
Particulates, ash, and
inorganics are digested
with aqua regia, the
residue fused with Na2C03
and then digested witn
HC1. Liquids are
analyzed as received.
REFER-
ENCES
ffl'
?325J
3,147,
(325)
3,147
(325)
175
307
3,147
(325)
3,147;
(325)
3,147.
(325)
158
-------
TABLE 17 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
AAS
AAS
AAS
AAS
FAAS
AAS
AAS
AAS
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Wet ashing; air-CoH-
flame, 6708 A, Slit-
40 A.
Wet ashing; NoO-C9H2
flame, 3312 A, Sllt-
7 A.
Wet ashing; air-CoHo
flame, 2852 A, Sllt-
20 A.
Wet ashing; air-CPHp
flame, 2795 A, Sllt-
7 A.
As in Level 1. 2795 A
Argon carrier.
LipBhO- fusion;
HCI-HNfio dissolution;
NgO-CoHp flame, 3133 A
Slit^l A.
Wet ashing; N 0-C-Hp
flame, 4634 Af Slft-
2 A.
Wet ashing; air-CpHp
flame, 2320 A, Sllt-
2 A.
REFER-
ENCES
42.82,
280
(239)
42,82,
280
(239)
42,82,
280
(239)
42,82,
280
(239)
175
307
42,82,
280
(239)
42.82,
280
(239)
42.82,
280
(239)
REMARKS
(LEVELS 1 & 2)
(0.001-AAS, 3xlO~6-
FAAS) Sr chemical
interference is
reported.
(3-AAS)
(0.003-AAS, 4xlO'8-
PAAS) Dry ashing
acceptable Al, Si,
P, SO,.-2 chemical
interferences are
reported; La, Sc,
or Ni buffer reduces
interference.
(0.0008-AAS, 2xlO'7-
FAAS) Cr (molecular)
and Si (chemical)
Interferences are
reported. Chemical
interference reduced
w'th Ca buffer.
(0.5-AAS, 2x10-5-
PAAS)
(0.03-AAS, 3xlO~6-
PAAS) Wet ashing is
acceptable.
Fe, Sr. Mn, Ca, and
Al(NOj)o chemical
interferences are
reported. Fe and
Mh interferences
may be eliminated
with NH^Cl buffer.
(l-AAS) Pr spectral
Interference
reported at 4925 A.
(0.005-AAS, 9xlO~6-
PAAS) Dry ashing is
acceptable. Ca molec-
ular interference
is reported (2328 A
NRLK
159
-------
TABLE 17 (continued).
ANALYSIS
AREA
Niobium
Nitrogen
Osmium
Oxygen
Palladium
Phosphorus
Platinum
Potassium
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
SSMS
Combustion
Titrimetric
/Spectro-
metric
SSMS
Combustion
SSMS
SSMS
SSMS
SSMS
SELECTION
RATIONALE
•Nitrogen is not
commonly analyzed by
SSMS; combustion is
a rapid, low cost
technique in wide use.
Oxygen is not
commonly analyzed by
SSMS; combustion is a
rapid, low cost tech-
nique in wide use.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
See Level 2
See Level 2
REFER-
ENCES
3,14?
(325)
3,147
(325)
186
3,147
(325)
3,147
(325)
3,147
(325)
3,147.
(325)
160
-------
TABLE 17 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
AAS
KJeldahl
digestion
followed
by Spectro-
metric or
Titri-
metric
procedure
AAS
Combustion
AAS
Combustion
Spectro-
metric/
Titri-
metric
AAS
AAS
SELECTION
RATIONALE
This method is an
accurate and repro-
ducible technique
which is in common
use. ASTM method.
This method is an
accurate and repro-
ducible technique
which is used in
organic analysis.
This method is an
accurate and repro-
ducible technique
which is in common
use. ASTM method.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Wet ashing; NoO-C2H2
flame, 3344 A, Sllt-
2 A.
Digestion with Hg
(catalyst) and H2S04.
CrO^ is useful also
in digestion proce-
dure. NHo is genera-
ted by zinc addition
and is distilled into
fl2SOi|. The HgStty is
back titrated.
Dry ashing; air-C2H2
flame, 2909 A, Slit-
2 A.
Combustion and con-
version to CO.
Wet ashing; air-C2H2
flame, 24y6 A, Slit-
2 A.
Wet ashing with HP and
HN03followed by fusioi
with Na2C03. PO^'J
is precipitated with
molybdate solution;
the ppt is dissolved
in excess NaOH and
back titrated. Color-
imetric technique is
based on formation of
ammonium phospho-
molybdate-vanadate
and is measured at
400 nm.
Ll2B407fusion; iHCl
HNOo dissolution, air
C H flame, 2659 A,
Slit-.2 A.
Wet ashing; air-.C2H2
flame, ?655 A, Slit-
13 A.
REFER-
ENCES
ui rocot
ro CDKK
Ul O
84
42
82
. 280
(325)
186
42
82
280
(325)
8.38
42
82
280
(325)
42
82
280
(325)
REMARKS
(LEVELS 1 & 2)
(5-AAS)
Other digestion
catalysts are
suggested in the
reference. See
reference for
spectrometric
method .
(1-AAS)
(0.01-AAS, 4xlO'6-
PAAS)
(0.05-AAS, lxlO~5-
PAAS) wet ashing is
acceptable. Pd, Rh,
Au, Ir, Ru, Os, and
Na chemical inter-
ferences are
reported. Inter-
ferences may be
reduced with Cu
buffer.
(0.003-AAS, 4xlO'5-
PAAS) Dry ashing is
acceptable . Na
ionization inter-
ference is reported.
161
-------
TABLE 17 (continued).
ANALYSIS
AREA
Praseodynium
Rhenium
Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
REFER-
ENCES
?'14T'
(325)
3,147,
(325)
3,147,
(325)
3,147,
(325)
3,147,
(325)
3,147,
(325)
3,147,
(325)
3,147,
(325)
3,147,
(325)
3,147,
(325)
162
-------
TABLE 17 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
Hydride
Evolution
Technique
AAS
AAS
SELECTION
RATIONALE
Relatively matrix-
independent as com-
pared to conventional
AAS.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Wet ashing; NpO-C?Hp
flame, 4951 A; Slft-
2 .A.
Wet ashing; N90-CpH9
flame, 3460 AT Slft-
2 A.
Wet ashing; air-C HP
flame, 3435 A, Slft-
2 A.
Wet ashing; -air- C2H2
flame, 7800 A, Slit-
40 A.
Dry ashing; air-C2H2
flame, 3499 A, Slit-
7 A.
Dry ashing; N20-C2H2
flame, 4297 A, Slit- .
2 A.
Dry ashing; ^0-02^
flame, 3912 A, Slit-
7 A
A.
Parr oxygen bomb
combustion at 4 atm.
by HC1/HN03. Hydride
is generated by
T1C13 - Mg method.
Ar-H2 entrained air-
flame, I960 A, Slit-
20 A.
Wet ashing ; N20- C^R?
flame, 2516 A, Slit-
2 A.
Wet ashing; air-C2H2
flame, 3281 A, Sllt-
7 A.
REFER-
ENCES
42
82
280
(239)
42
82
280
(239)
42
82
280
(239)
42
82
— O —
280
(239)
42
82
280
(239)
42
82
280
(239)
42
82
280
(239)
26
(124)
42
82
280
(239)
42
82
280
(239)
REMARKS
(LEVELS 1 &2)
(10- AAS).
(1-AAS).
(0.02-AAS, 8xlO'6-
FAAS). Na, Pt, Pd,
Au, IT, Ru, and Os
Interferences are
reported .
(0.005-AAS, IxlO'6-
FAAS). Dry ashing
Is acceptable. Na
and K lonization
interferences are
reported .
(0.3-AAS).
(5-AAS).
(0.2-AAS)
(0. 1-AAS, 0.002-HE,
9xlO~b-PAAS). Cu
chemical inter-
ference is reported .
(0. 1-AAS, 5xlO"8-
PAAS).
(0.001-AAS, IxlO"7-
PAAS). Dry ashing
is acceptable. Th
chemical inter-
ference is reported .
163
-------
TABLE 17 (continued).
ANALYSIS
AREA
Sodium
Strontium
Sulfur
Tantalum
Tellurium
Terbium
Thallium
Thulium
Tin
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
! Sodium is not 'measured
.in particulate, ash,
;and inorganic solid sam-
jpltes because of- fusion
jprocedure.
REFER-
ENCES
3,147
(325)
3,147
(325)
3
147
(325)
14?
(325)
147
(325)
3,147
(325)
3,147
(325)
3,147.
(325)
3
147
(325)
164
-------
TABLE 17 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL,
METHOD
AAS
AAS
Combustion
Gravi-
metric
AAS
Hydride
Evolution
Technique
AAS
Hydride
Evolution
Technique
SELECTION
RATIONALE
Sulfur is determined
indirectly by AAS.
This method is an
accurate and repro-
ducible technique
which is in common
use.
Relatively matrix-
independent as com-
pared to conven-
tional AAS .
Relatively matrix-
independent as com-
pared to conven-
tional AAS.
SPECIAL SAMPLING
; AND ANALYTICAL
REQUIREMENTS
Wet ashing; air-CpHp
flame, 5890 A, Sllt-
4 A.
Wet ashing; air-C2H2
flame, 4607 A, Slit-
13 A.
Sample is combusted
under 20-30 atm. 0-;
Sulfur is determined
as BaSO/i gravimetric-
ally.
Wet ashing; N20-CpHp
flame, 2715 A, Sllt-
2 A.
Wet ashing; Hydride
is generated by NaBH^
method. Air-C2H2
flame, I960 A, Slit-
20 A.
Wet ashing; air-C2H2
flame, 4326 A, Slit-
2 A.
Wet ashing; air-C2H2
flame, 2768 A, Slit- .
20 A.
Wet ashing; air-C2H2
flame, 4106 A.
Wet ashing; Hydride
is generated by
T1C13-- Mg method;
air-C2H2 flame,
2246 A, Slit-7 A.
REFER-
ENCES
42
82
280
(239)
42
82
280
(239)
26
(124)
26
(124)
REMARKS
(LEVELS 1 & 2)
(0.0008-AAS, IxlO"7-
FAAS). Dry ashing
is acceptable.
(0.005-AAS, IxlO"6-
FAAS). Dry ashing
is acceptable. Al
and P (chemical) and
Na and K (ionization)
interferences are
reported. Chemical
Interferences may be
reduced with a La
buffer. Ionization
interferences level
off above 100 ppm
Na or K.
Eshka Fusion method
is alsp acceptable.
Bomb washing may
come directly from
calorific value
determination.
(3- AAS). Dry
ashing is accept-
able.
(0.05-AAS, 0.004-HE,
0.003-FAAS) Cu
chemical inter-
ference is reported .
(0.05-AAS, IxlO"6^
FAAS ) .
(0.02-AAS, IxlO-6-
FAAS).
(1-AAS).
(0.05-AAS, 0.004-HE,
0.0003-FAAS). Dry
ashing is accept-^
able. Na and P0^~
chemical interfer-
ences are reported .
165
-------
TABLE 17 (continued) .
ANALYSIS
AREA
Titanium
Tungsten
Uranium
Vanadium
Ytterbium
Yttrium
Zinc
Zirconium
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SSMS
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS -
REFER-
ENCES
3,147
(325)
3,147,
(325)
3,147
(325)
3,147
te)
3,147
(325)
3,147,
(325)
3,147
(325)
3,147
(325)
166
-------
TABLE 17 (concluded).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Wet ashing; N.O-CoHp
flame, 3643 A? Sllt-
2 A.
Wet ashing; N20-OjH9
flame, 4009 k, Sllt-
2 A.
Wet ashing; NoO-C-H,,
flame, 3514 A? Slft-
21 A.
Wet ashing: N^O-CoH,,
flame, 3184 A? Sllt-
2 A.
Wet ashing; N00-C_H.
flame, 3988 A? Slft^
2 A.
Wet ashing; N 0-C0Hrt
flame, 4077 Af Sifts
2 A.
Wet ashing; Air-CpH2
flame, 2138 A, Sllt-
20 A.
Dry aBhing; LioB^Oy
fusion; HCL HNO, dis-
solution, NoO-CpHo
flame, 3601 A, Slit-
2 A.
REFER-
ENCES
42,82
280
(239)
42.82
280
(239)
42,82,
280
(239)
42,82,
280
(239)
42.82,
280
(239)
42,82,
280
(239)
42,82,
280
(239)
42.82,
280
(239)
REMARKS
(LEVELS 1 &2)
(0.1-AAS, 4x10-5-
PAAS)
(3-AAS). Li BO
fusion is accept-^
able.
(30- AAS).
(0.02-AAS, 3xlO-6-
FAAS).
(0.04- AAS).
(0. 3-AAS).
(0.001-AAS, 3xlO"8-
PAAS). Pe, Al, Na,
K, Mg, Ca molecular
interferences are
reported . No suit-
able NRL for com-
pensation has been
found .
'(5- KRSfy.'
167
-------
Anion Analysis
Recommended procedures for anion analysis are presented in Table 18.
The list within this table does not pretend to cover all possible anions
but, rather, is intended to present a survey of analytical methods for
the more common anions.
At Level 1, anion analysis is accomplished by SSMS with the exception
of those species which are analyzed within the Standard Water Analysis
procedures (Table 19). The former procedure presupposes that each element
capable of anion formation is present, in toto, in a single anionic form;
thus this can yield only upper limits on anion concentrations.
Analysis at Level 2, in addition to anions, includes inorganic compound
identification. As such, these analyses provide information needed for
Level 2 characterization. A proposed scheme for inorganic compound character-
ization is presented in Figure 31 and includes analysis by X-ray diffrac-
tion, electron microscopy, differential scanning colorimetry, ESCA, etc.
Because methodology for inorganic component identification is still
somewhat ill-defined, specific methodology is not presented within this
document.
At Level 2, analytical methods for specific anions are chosen from
either Standard Methods, ASTM, or EPA approved procedures.
168
-------
TABLE 18. SUMMARY OF RECOMMENDED PROCEDURES FOR ANION ANALYSIS
ANALYSIS
AREA
Ammonia
Arsenate/
Arsenite
Bromide
Carbonate
(Bicarbonate)
LEVEL1
RECOMMENDED
ANALYTICAL
METHOD
Color-
imetric
SSMS
SSMS
Titri-
metrlc
r
SELECTION
RATIONALE
Rapid and simple
method.
Elemental analysis
provides upper con-
centration limit for
anions. SSMS has
multicomponent
capability.
As for arsenate
Method provides a
rapid, and simple
analysis technique.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
As specified by reagent
test kit.
Aqueous samples: slurry
with graphite and
briquette. Solid
samples: see elemental
analysis .
As for arsenate
As specified by reagent
test kit.
REFER-
ENCES
I70
-------
TABLE 18 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Color-
imetric
(0.05-1
ppm)
Titri-
metric
1.0-25
ppm)
Spectro-
metrlc
Titri-
metric
Titrl-
metric
SELECTION
RATIONALE
Method provides an
accurate technique
for analysis of
ammonia in water.
EPA method .
Method provides an
accurate, fairly
rapid technique for
measuring arsenic.
ASTM method .
Method provides an
accurate, fairly
rapid technique for
measuring bromide.
ASTM method.
Method provides an
accurate technique
for measuring total
carbonate present:.
ASTM method.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Sample Is buffered at
p'H 9.5 -and distilled
Into a solution of
boric acid. The
ammonia in the
distillate can be
determined colori-
metrically by
nesslerlzatlon (Hgl_,
KI, NaOH) or titri-
metrically with H S(X
using' a mixed
indicator (methyl red/
methylene blue).
25 ml of sample is
acidified with =HC1,
mixed with KI arid
ShClg. 3 g of zinc
are added and the
arslne generated is
bubbled thru a
silver diethyldithlo-
carbamate-pyridlne
solution. Absorbance
is measured at 540 nm
within 30 minutes .
Sufficient NaCl is
added to 100ml of the
sample to produce a
3g -chloride content.
KC10 is added to ox-
idize bromide to bro-
mine (excess is des-
troyed with NaCH02).
KI is added and lib-
erated 12 is titrated
with 0.01N Na2S203.
Apparatus is described
in reference. C02 is
liberated by acidify-
ing and heating the
sample In a closed
system. C02 is ab-
sorbed in a -barium
hydroxide 'Solution.
Excess barium hydrox-
ide is titrated with
0.04 N HC1.
REFER-
ENCES
8.43
8.40
8.19
8.10
REMARKS
(LEVELS 1 & 2)
Volatile organic
alkaline compounds
may cause an off
color in the
nesslerization
procedure.
Measurement of ars-
enic by AAS is also
an acceptable tech-
nique and may be
; subject to fewer
interferences.
_
This method measures
bromide and iodide:
thus, this method is
;to be used in con-
Junction with iodide
"determination. Fe*2,
Mn+2 interfere, but
may be removed by
treatment with CaO.
Sulfides,. (H2S) in-
terfered but are re-
moved by scrubbing
with an iodine solu-
tion; other inter-
ferences are removed
by scrubbing with
chromic acid.
Prom pH measurement
H2C03, HCOo~, COg-2
concentrations may
be estimated.
171
-------
TABLE 18 (conttnued).
ANALYSIS
AREA
Chloride
Cyanide
Fluoride
Iodide
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
SSMS
Color-
imetric
SSMS
SSMS
SELECTION
RATIONALE
As for arsenate.
Method provides a
rapid, .simple analysis
technique.
As for arsenate
As for arsenate.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
As for arsenate.
As specified by reagent
test kit.
As for arsenate.
As for arsenate.
REFER-
ENCES
172
-------
TABLE 18 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Titri-
metric
Titri-
metric/
Spectro-
metric
Specific
Ion
Electrode
(SIE)
Spectro-
metric
SELECTION
RATIONALE
Method provides an
accurate technique
for measuring
chloride content
of industrial waste
water. ASTM method.
Method provides an
accurate technique
for measuring
cyanide. ASTM
method.
Method provides an
accurate, rapid,
simple technique
for analysis or
fluoride.
Method provides an
accurate technique
for analysis of
iodide". ASTM method.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
50 ml sample is titra-
ted with 0.025 N sil-
ver nitrate to a po-
tassium chromate end-
point.. Suifites.are
oxidized to sulfates
by H000 addition.
c. c.
500 ml of sample is
refluxed under acidic
conditions with CuClo.
HCN liberated is ab-
sorbed in NaOH.
Titration: titration
with AgNOo to rhoda-
nine endpoint.
Spectrometric :
neutralize absorption
solution with acetic
acid to pH 6.5 - 8.0
0.2 ml of chloramine •
T solution is added.
Absorbance measured
at 620 nm after 20
minutes .
pH is adjusted to
5.2 - 5.5 with 0.5 N
H2S04. C02 is re-
moved by heating on
a hot water bath.
Buffer is added (pH
6.3, 1M sodium citrate
- citric acid - 0.2 M
KNOg) and fluoride is
measured by known
addition method.
Iodide is determined
by oxidation to iodate
by oxidation with satr
urated bromine water
in acid solution. Ex-
cess bromine .-is des- :
troyed by addition of '
solium formate. Sam-
Die is titrated with
b.Ol N sodium thio-
sulfate solution.
REFER-
ENCES
8.9
8.32
303
260
8.19
REMARKS
(LEVELS 1 & 2)
[Phosphates (>250ppm)
interfere. Iodine
;and bromide may also
(interfere with visu-
ial 'endpoint; poten-
itiometric titration
'may solve this
problem.
Titration method
applies when cyanide
'concentration >lppm;
.spectrometric method
for
-------
TABLE 18 (continued).
ANALYSIS
AREA
Nitrate
Nitrite
Ortho-
Phosphate
Sulflde
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Color-
imetrlc
Color-
metric
Color-
Imetrlc
SSMS
SELECTION
RATIONALE
Method provides 'a rapid
and simple analysis
technique.
Method provides a
rapid, simple analysis
technique . '
Method provides a
rapid, simple analysis
technique.
As for arsenate.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
As specified by
.reagent test kit.
As specified by
reagent test kit.
As specified by reagent
test kit.
As for arsenate.
REFER-
ENCES
174
-------
TABLE 18 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Spectro-
metrlc.
Spectro-
metric
Spectro-
metrlc
Tltrl-
metric
SELECTION
RATIONALE
Method provides an
accurate technique
for analysis of
nitrate. ASTM
method .
Method provides an
accurate technique
for analysis of
nitrite. ASTM
method .
Method provides an
accurate technique
for analysis of
phosphate.
Method provides a
rapid and accurate
technique for
measurement of
sulflde.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
5 ml of sample is
mixed with brucine-
sulfanilic acid solu-
tion then mixed with
10 ml of 15.6 M
H2S04. Color is
developed for 10 ± 1
minutes in a dark
area; absorbance is
measured at 410 nm.
pH is adjusted to 7
,with CHoCOOH. If
isample nas appreci-
able color, filter
:with Al(on)o gel.
EDTA is added to com-
plex cations. 2 ml
of sulfanllic acid
solution and 2 ml of
a naphthylamine hy-
drochloride-are added
to the sample, solu-
tion is buffered at .
ph 2.0 - 2. 5 -with
NapC^oOp solution,
allowed to stand 30
minutes, and absor-
bance measured at
515 nm.
If pH >7, sample is
neutralized with
H2SO/j. Molybdate
reagent and stannous
chloride reagent are
added. Absorption
is measured at 690
nm between 10-12 min-
utes after reagent
addition.
Sample is acidified
and stripped with an
inert gas and collec-
ted in a zinc acetate
solution. Iodine
solution is added to
collection vessels,
acidified with HC1
and back titrated
With 0.025 N sodium
thiosulfate solution.
REFER-
ENCES
8.14
8.22
8.12
8.37
REMARKS
(LEVELS 1 & 2)
Color does not
follow Beer-Lambert
relation; however,
plotting absorbance
vs. concentration
yields a smooth
curve. Turbid or
colored samples
interfere, but may
be removed by fil-
tration and treat-
ment with A1203
and activated
carbon.
Mercury (ll) causes
high results while
copper (II) cata-
lyzes the decom-
position of the
diazonium salt and
thus leads to low
results. Certain
bacteria utilize
nitrites in their
metabolism.
Storage at low
temperature
minimizes this
effect.
Color intensity is
time and tempera-
ture dependent.
Solution may be
extracted with
benzene-lsobutanol
solvent to remove
interferences and
increase sensivity.
I75
-------
TABLE 18 (continued).
ANALYSIS
AREA
Sulfite
Sulfate
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Color-
Imetric
Turbid-
imetric/
Color-
Iraetric
SELECTION
RATIONALE
Method provides a
rapid, simple analysis
technique .
Method provides a
rapid, simple analysis
technique.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
As specified by
reagent test kit.
As specified by regeant
test kit.
REFER-
ENCES
176
-------
TABLE 18 (concluded).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Titrl-
metric
Gravi-
metric
SELECTION
RATIONALE
Method provides a
rapid and accurate
technique for
measurement of
sulfite. ASTM
method .
Method provides an
accurate technique
for measurement of
sulfate. ASTM
method .
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Air Is excluded
while sample is being
taken by use of
apparatus described
in reference. HC1,
KI and KIOo are added.
Excess" iodine chloride
formed is titrated
with 0.01 N NagS203
using a dead stop
end-point -indicating
apparatus .
Sample is filtered,
pH adjusted to 4.5
with HC1, hot BaCl2
added, allowed to
stand for 2 hours,
filtered and ignited
at 800°C.
REFER-
ENCES
8.23
8.13
REMARKS
(LEVELS 1 & 2)
Starch indicator
may be used.
A titrimetric
method may also be
used using BaCl2,
titrating in an
alcoholic solution
to a thorin end-
point.
177
-------
Figure 31. Inorganic compound characterization scheme-Level 2
178
-------
THERMOGRAMS
INDICATE COM-
POUNDS PRESENT
BY CHARACTERISTIC
DEGRADATION
TEMPERATURES
DIRECT IDENTIFICA-
TION CO WOUND
BY CRYSTAL MORPH-
OLOGY AND
MICROSfOT TEST
PROCEDURES
DIRECT ANALYSIS
OF COMPOUND
PRESENT BY
CHARACTER I SI 1C
CHEMICAL SHIFT
OF PHOTOEIECTRON
SPECTRA
COMPOUND
IDENTIFICATION BY
RATIO OF KNOWN
ELEMENTS
COMPOUND
IDENTIFICATION BY
RATIO OF KNOWN
ELEMENTS
COMPOUND
IDENTIFICATION
OF CRYSTALINE MATERIAL
BY DIFFRACTION PATTERN
DIRECT ANALYSIS OF
COMPOUND PMSINT
BY CHARACTERISTIC
CHEMICAL SHIFT OF
PHOTOELECTRON
SPECTKA
IN STACK INFORMA-
TION ABOUT ANIONIC
STRUCTURE OF
PARTICULATE
Figure 31 (Concluded)
I79
-------
Standard Water Analysis
In addition to organic analysis (Table 16) and elemental analysis
(Table 17) all aqueous samples are analyzed for the following parameters or
species by the procedures given in Table 19:
• Acidity/Alkalinity
• Ammonia
• BOD
» Carbonate
0 COD
• Conductivity
• Cyanides
• DO
9 Nitrate/Nitrite
• pH
• Phosphate
• Sulfate
• Sulfite
• Total dissolved and suspended solids
For Level 1 analysis, determinations can be performed in the field or
laboratory using reagent test kits, although practical considerations will
usually dictate that all analyses except BOD, COD, and suspended solids be
done in the field. These kits, manufactured by Hach or Bausch and Lomb, use
procedures that usually follow a modified and simplified version of standard
methods. The reagents are encapsulated and stored in small plastic pillows
in pre-measured quantities. Upon addition of the reagent or reagents to the
sample, component concentrations are determined colorimetrically or turbidi-
metrically using reference color discs or portable photometers. In some
cases endpoint titrations are used. Although they are not as accurate as
the standard laboratory procedures, they have sufficient accuracy to satisfy
Level 1 objectives.
At Level 2, all analysis are performed in a laboratory using either
Standard Methods, ASTM or EPA procedures to provide increased reliability
and accuracy consistent with Level 2 goals.
180
-------
TABLE 19. SUMMARY OF RECOMMENDED PROCEDURES FOR STANDARD WATER ANALYSIS
ANALYSIS
AREA
Acidity
Alkalinity
Ammonia
Biological
Oxygen
Demand (BOD)
Carbonate
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Titration/
Visual
Endpoint
Titri-
metric
Visual
Endpoint
Color-
imetric
Titrl-
metric
Tltri-
metric
SELECTION
RATIONALE
Rapid and simple
method .
Rapid, simple method.
Rapid and simple
method .
EPA method.
Rapid and simple method
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Analysis within 24
hours. As specified
by reagent test kit.
As specified by reagent
test kit.
As specified by reagent
test kit.
Incubation of sample
for 5 days in darkness
at 20°C. Reduction
of dissolved oxygen
content gives BOD.
As specified by reagent
test kit.
REFER-
ENCES
337
I82
-------
TABLE 19 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD;
Titration/
Electro-
• metric
.. Endpoint
Titri-
metric
Visual
Endpoint
Color-
imetric/
(0.05-1
ppm.) Tit-
rlmetric
(1.0-25
PPm)
Titration
Titri- .
metric
SELECTION
RATIONALE
Accurate method .
ASTM method.
' f
Rapid, .accurate,
simple method.
ASTM method .
Method provides an'1
accurate technique
for analysis of
ammonia in water.
EPA method.
-
As in Level 1.
Method provides an
accurate technique
for measuring total
carbonate.
SPECIAL SAMPLING
AND ANALYTICAL
'REQUIREMENTS
100 ml sample is
titrated with 0.02N
NaOH and endpoint
is determined
potentiometrically.
A 100 ml solution is
titrated with 0.02N
HC1 (HgSO^) to
phenolphthalein end-
point. Strontium
chloride is added
to precipitate carbo-
nates.
Sample is buffered
at pH 9.5 and dis-
tilled into a.
solution of boric
acid . The ammonia
in the distillate
can be determined
color imetrically by
nesslerlzation
(Hglp, KI, NaOH) or
titrimetrically with
HgSO^ using a mixed
indicator (methyl
red/methylene blue).
As in Level 1.
Apparatus is
described in
reference. COg is
liberated (by
acidifying and
heating the sample
in a closed system)
and absorbed in a
barium hydroxide
solution. Excess
.barium hydroxide is
titrated -with 0.04 N
HC1.
REFER-
ENCES
8.15
8.15
13."
337
8.12
REMARKS
(LEVELS 18. 2)
Organic matter.
aluminates, and
silicates which
are not precip-
itated by strontium
chloride, inter-
fere.
Volatile organic
alkaline compounds
may cause an off
color in the
nesslerization
procedure.
Sulfides (H2S)
interfere but are
removed by
scrubbing with an
iodine solution;
other interferences
are removed by
scrubbing with
chromic acid .
TJ f*r\f* vr*f\ ~
ripvUXj riwUQ j
CO-"* may be esti-
mated from pH
measurement .
I83
-------
TABLE 19 (continued).
ANALYSIS
AREA
Chemical
Oxygen
Demand (COD)
Conductivity")
Cyanides
Dissolved
Oxygen
Hydrazine
(in water)
Nitrate
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Titration
Electro-
metric
Color-
imetric
Electro-
metric
Colori-
metric
SELECTION
RATIONALE
Rapid and simple
method. EPA method.
Rapid and simple method
Rapid and simple method
Rapid and simple method
Rapid and simple method
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
A 50 ml sample is
oxidized with 0.25QN
KgCrpOy under acidic
conditions. The sample
is titrated with 0.250 N
ferrous ammonium
sulfate with phenan-
throline ferrous sulfate
indicator.
Analyze within 24 hours
As specified by reagent
test kit.
Sample should be
analyzed within 6 hours.
As specified by reagent
test kit.
REFER-
ENCES
8.20
337
13.12
13.13
184
-------
TABLE 19 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Titratlon
Electro-
metric
Colorl-
metrlc
(0.05-1
ppm)
Titri-
metrlc
( 1 ppm)
Electro-
metric
Spectro-
metrlc
Spectro-
metrlc
SELECTION
RATIONALE
As in Level 1.
As In Level 1.
Method provides an
accurate technique
for analysis of
cyanides In water.
EPA method.
As In Level 1.
Rapid and accurate
method .
Method provides an
accurate technique
for analysis of
nitrate. ASTM
method .
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
As in Level 1
As in Level 1.
Sample is distilled
into 1.25 N NaOH.
Colorimetrlc:
reaction with
chloramine T. Color
development with
pyrldine. Pyrazolone
reagent; measurement
620 nm.
Tltration: AgNOo
with an appropriate
Indicator.
As in Level 1.
A sample (containing
0.2-5.0 g NoH^) is
acidified with IN HC1;
p-d imethyl- amlno
benzaldehyde is added
and absorbance is
measured at 458 nm.
5 ml of sample is
mixed with bruclne-
sulfanilic acid
solution and mixed
with 10 ml of 15.6 M
H2SO/J. Color is
developed for 10 ±1
minutes in a dark
area; absorbance is
measured at 410 nm.
REFER-
ENCES
8.20
337
8.32
13.12
13.13
8.24
8.14
REMARKS
(LEVELS 1& 2)
Fe+2, NOp", SOo-2,
S-2 and halldes
are measured by thie
technique in
addition to organic
compounds.
Fatty acids maKe
endpoint determi-
nation difficult.
Acidify with HOAc
to pH 6 and extract
with hexane.
Sulfides interfere
but may be removed
with CdCOgas ppt.
Sample should be
analyzed as quickly
as possible as Np^ty
undergoes auto-
oxidation. Method
is used for boiler
blowdown analysis.
Absorbance does not
follow Beer-Lambert
relation; however,
plotting absorbance
vs. concentration
yields a smooth
curve. Turbid or
colored samples
interfere, but may
be removed by
filtration and
treatment with
AlgOg and activated
carbon .
185
-------
TABLE 19 (continued).
ANALYSIS
AREA
Nitrite
Total
Dissolved
and
Suspended
Solids
pH
Ortho-
phosphate
(Total)
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Colori-
metric
Filtra-
tion/
Drying
Colori-
raetric
Colori-
metric
SELECTION
RATIONALE
Rapid and simple method
Rapid and simple
method . ASTM method .
Rapid and simple
method .
Rapid and simple
method .
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Analyze as quickly as
possible. As specified
by reagent test kit.
Sample is filtered
thru a filtering
crucible. Extractable
material is removed
by washing with
solvent. Filtered
material is dried at
180°C and weighed.
Dissolved matter is
determined by evapor-
ation of filtrate
(100°C), drying at l80°C
and weighing.
Analyze immediately.
As specified by reagent
test kit.
REFER-
ENCES
8.16
8.29
186
-------
TABLE 19 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Spectro-
metric
Filtra-
tion/
Drying
Electro-
metric
Gravi-
metric
SELECTION
RATIONALE
Method provides an
accurate technique
for analysis of
nitrite. ASTM
method .
As in Level 1.
Rapid and simple
method .
Accurate method for
determination of
total phosphate.
ASTM referee method .
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
pH is adjusted to 7
with CH3COOH. If
sample Has appreci-
able color, filter
with Al(OH), gel.
EDTA is added to
complex cations. 2
ml of sulfanilic
acid solution and
2 ml of a- naphylamine
hydrochloride are
added to the sample,
solution is buffered
at pH 2.0-2.5 with
Na2c2K?.Q2 solution,
allowea to stand 30
minutes, and absor-
bance measured at
515 run.
As in Level 1.
pH is measured with
glass electrode
system.
Sample is pretreated
with KNO,, boiled
for 1 minute and
flit ered . Po 1 ypho s -
phates are converted
to orthophosphates
by boiling sample
with HNO, for 30
minutes. Phosphate
is first precip-
itated as ammonium
molybdophosphate,
redissolved in
NH^OH, precipitated
as magnesium
ammonium phosphate
and ignited.
REFER-
ENCES
8.22
8.12
REMARKS
(LEVELS 1& 2)
Mercury (ll) causes
high results while
copper (II) cata-
lyzes the decom-
position of the
diazonium salt and
thus leads to low
results. Certain
bacteria utilize
nitrites in their
metabolism.
Storage at low
temperature mini-
mizes this effect.
Extractable
material should be
analyzed for
organics. See
Organic Analysis,
Table 17.
Principally applied
to boiler blowdown
analysis.
187
-------
TABLE 19 (continued).
ANALYSIS
AREA
Sulfate
Sulfite
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Turbi-
metric
Colori-
metric
SELECTION
RATIONALE
Rapid and simple
method .
Rapid and simple method
where sulfite concen-
tration is above 3ppm.
SPECIAL SAMPLING
: AND ANALYTICAL
REQUIREMENTS
As specified by reagent
test kit.
Analyze as quickly as
possible. As specified"
by reagent test kit.
REFER-
ENCES
-------
TABLE 19 (concluded).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Gravi-
metric
Titration/
Potentio-
metric
Endpoint
SELECTION
RATIONALE
Method provides an
accurate technique
for measurement of
sulfate. ASTM
method .
Accurate method for
determination of
sulfite. ASTM
referee method .
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Sample is filtered,
pH adjusted to 4.5
with HC1, hot BaCl2
added, allowed to
stand for 2 hours,
filtered and ignited
at 800°C.
Air is excluded
while sample is being
taken. To 500 ml of
sample, 5 ml HCL,
5 ml KI solution and
5 ml of KIOo solution
are added. Excess
iodine chloride is
titrated with 0.01N
Na_S2Oo using a dead-
stop titrator.
REFER-
ENCES
8.13
8.23
REMARKS
(LEVELS 1 & 2)
A titrimetric method
may also be used
using BaClg, tit-
rating in an
alcoholic solution,
to a thorin end-
point.
Principally applied
to bioler blow-
down analysis.
I89
-------
Fuel Analysis
Table 20 summarizes recommended procedures for the analysis of fuels.
These procedures are taken directly from ASTM methods.
Proximate and ultimate coal analysis data will normally be obtained as
part of process operating practice, and thus, an additional determination is
unnecessary at Level 1 or Level 2.
190
-------
TABLE 20. SUMMARY OF RECOMMENDED PROCEDURES FOR FUEL ANALYSIS
ANALYSIS
AREA
I. Coal:
Moisture
Ash
Volatile
Matter
Fixed
Carbon
Sulfur
Heating
Value
Carbon
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Gravi-
metric
Combustion
Combustion
(Controlled)
By
difference
Combustion
Combustion
Combustion
SELECTION
RATIONALE
Rapid, accurate,
simple method. ASTM
method .
Rapid, accurate, simple
method. ASTM method.
Rapid, accurate, simple
method. ASTM method.
Rapid, accurate, simple
method . ASTM method .
Rapid, accurate, simple
method . ASTM method .
Rapid, accurate, simple
method. ASTM method.
Method is accurate,
rapid, and simple.
ASTM method.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Ig of sample is dried
at 104-110°C for 1
hour and weighed.
Dried coal sample heated
at 750°C to a constant
weight .
Ig of sample is placed
in Ft crucible with
cover in oven at 950°
+20°C. After rapid
initial discharge of
volatiles has subsided,
crucible is heated for
7 more minutes, cooled
and weighed.
Fixed carbon, % = 100 -
(moisture % + ash % +
volatile matter #) .
Sulfur is determined
from bomb washings from
oxygen bomb calorimeter
following calorimetric
determination. NH^OH is
added, and solution
boiled and filtered.
Saturated bromine water
is added, solution is
acidified with HC1;
BaCl2 is added and pt
ignited at 925°C to a
constant weight.
Ig of coal is combusted
in a bomb under 20-30
atm of oxygen-. Bomb
washings are titrated
with standard base to
determine correction
factor.
0.2g of coal is combusted
in stream of oxygen at
850°-900°C in a combus-
tion train. 002 formed
is absorbed in soda lime
and weighed.
REFER-
ENCES
8.4
8.4
8.4
8.4
8.4
8.4
8.4
192
-------
TABLE 20 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Gravi-
metric
Combustion
Combustion
Combustion
Combustion
Combustion
Combustion
SELECTION
RATIONALE
As in Level 1.
As in Level 1.
As in Level 1 .
As in Level 1.
As in Level 1 .
As in Level 1.
As in Level 1.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
As in Level 1.
As in Level 1.
As in Level 1.
As in Level 1.
As in Level 1 .
As in Level 1 .
As in Level 1.
REFER-
ENCES
REMARKS
(LEVELS 1& 2)
Moisture, ash,
volatile matter,
fixed carbon,
heating value, and
sulfur comprise a
proximate analysis .
Crucible cover
should fit tightly.
Bomb washing method.
Washings are used
for sulfur analysis.
Corrections are
made for nitrogen
and sulfur contents.
Carbon, hydrogen,
nitrogen and oxygen
comprise an ultimate
analysis. S02
which is formed is
absorbed on CuO,
PbCrO/j or silver.
I93
-------
TABLE 20 (continued).
ANALYSIS
AREA
Hydrogen
Nitrogen
Oxygen
Trace
Elements
II. Residual
Oil
HpO and
Bituminous
Material
Ash
Heating
Value
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Combustion
KJeldahl-
Gunning
Method
Difference
SSMS
Distill-
ation
Combustion
Combustion
SELECTION
RATIONALE
Method is accurate,
rapid, and simple.
ASTM method.
Accurate method for
determination of
nitrogen . ASTM method .
See Elemental Analysis
Table.
This method provides a
rapid, and simple
technique for .deter-
mination of HpO and
bituminous material in
residual oil. ASTM
method .
This method provides an
accurate, rapid, and
simple technique for
measurement of ash.
content of residual
oil. ASTM method.
Method provides a
rapid and simple method
for determination of
heating value of
residual oil.
SPECIAL SAMPLING •
AND ANALYTICAL
'; REQUIREMENTS
0.2g of coal is
combusted in stream of
oxygen at 850?i900°C in
a combustion train. HgO
formed .is adsorbed on
Mg(.Cib^)2 and weighed.
• Nitrogen in converted
to ammonium salts ,'by
' digestion with' hot H^S.Q/i
I (and a catalytic amount
of Hg) for several hours
Zinc is added and a
solution of KgS in NaOH
is added. The mixture
is distilled .into 6."2
s (NH4)2S04 and back ti-
trated 'to a. methyl red
end point with 0-.02 NaOR
Oxygen,. # = 100 -'.( %
Hydrogen, % carbon, %
• nitrogen, % sulfur, %
moisture, % ash). ,
See Elemental Analysis,
Table 18.
A sample is weighed to
± 1% and transferred to
a Dean-Stark apparatus.
Sample is distilled and
water is measured -. in
trap.
lOOg of sample is
combusted in an' open
crucible or evaporating
dish. . Carbonaceous
residue Is Cashed at
775°C, cooled, 'and
weighed .
Sample Is combusted in
09 bomb with 1 ml' of
H20 and under 30 a tin.
Contents of bomb are
titrated to determine
a correction factor.
REFER-
ENCES
8.4
8.4.
8.4
8.19
8.8
8.5
194
-------
TABLE 20 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Combustion
KJeldahl-
Gunning
Method
Difference
FAAS/AAS
Distill-
ation
Combustion
Combustion
SELECTION
RATIONALE
As in Level 1.
As in Level 1.
As in Level 1. .
See Elemental
Analysis, Table 18., .
As in Level 1.
As in Level 1.
As in Level 1.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
As in Level -1 .
As in Level 1 .
As in Level 1.
See Elemental
Analysis, Table 18.
As in Level 1 .
As in Level 1.
As in Level 1.
REFER-
ENCES
REMARKS
(LEVELS 1 & 2)
Ash sample may be
analyzed for trace
elements.
195
-------
TABLE 20 (continued).
ANALYSIS
AREA
Sulfur
Trace
Elements
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Bomb
Washing
Method
SSMS
SELECTION
RATIONALE
Method provides a
rapid and accurate
method for determi-
nation of sulfur
content of residual
oil
See Elemental Analysis
Table.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
Bomb washings from
heating value determi-
nation are acidified
with HC1; saturated
bromine water is added
and the solution is
boiled. BaCl2 is added,
solution is filtered,
precipitate ignited at
925°C.
See Elemental Analysis,
Table 18.
REFER-
ENCES
8.5
8.20
196
-------
TABLE 20 (continued).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
Bomb
Washing
Method
PAAS/AAS
SELECTION
RATIONALE
As in Level 1.
See Elemental
Analysis, Table 18.
SPECIAL SAMPLING
AND.ANALYTICAL
REQUIREMENTS
' L " ' ' >
As in Level 1.
See Elemental
Analysis, Table 18.
REFER-
ENCES
REMARKS
(LEVELS 1& 2)
I97
-------
Physical Characterization of Solids
Recommended procedures for physical characterization of solids are
given in Table 21. Both Level 1 and Level 2 analysis consist of particulate
sizing and morphological studies. At Level 1 sizing is accomplished by dry
sieving, centrifugal elutriation, or optical microscopy; morphological
analysis is performed using a polarizing light microscope. Level 2 proce-
dures rely on wet sieving, the Coulter Counter, and scanning electron
microscopy for size analysis. Both polarized light and scanning electron
microscopy are used in combination for particulate morphology determination
at Level 2.
198
-------
TABLE 21. SUMMARY OF RECOMMENDED PROCEDURES FOR PHYSICAL CHARACTERIZATION OF SOLIDS
ANALYSIS
AREA
Sizing
Morphology
LEVEL 1
RECOMMENDED
ANALYTICAL
METHOD
Dry sieving,
centrifugal
elutriation
(e.g. Bahoo]
Optical
micro-
scope
Polarizing
light
micro-
scope
SELECTION
RATIONALE
Relatively simple and'
inexpensive .
Most applicable device
for sizing of fine
particles.
Standard tool for
particle identifi-
cation.
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
During and after samp-
ling, care must be
taken that agglomeration
and attrition are mini-
mized. In reducing a
gross sample for -
analysis, special con-
cern should be given to
the representativeness
of the sample to be
analyzed .
Particles must be dis-
persed on the slide in
a random manner without
causing shattering of
the particles. Agglom-
erated particles should
be deflocculated.
Same as for optical
microscope.
REFER-
ENCES
8.3
287
338
50
287
338
50
147
200
-------
TABLE 21 (concluded).
LEVEL 2
RECOMMENDED
ANALYTICAL
METHOD
SELECTION
RATIONALE
SPECIAL SAMPLING
AND ANALYTICAL
REQUIREMENTS
REFER-
ENCES
REMARKS
(LEVELS 1 & 2)
Wet
sieving
and
Coulter
Counter
The two analysis
methods used in
series can be per-
formed relatively
quickly and will
give results
accurate to 0.3^.
Same as for Level 1.
28
33
50
Scanning
electron
micro-
scope
Has a greater range
than an optical
microscope and more
depth than a normal
electron microscope.
Methods of collection
usually employed to
minimize handling are
membrane filters, and
thermal and electri-
cal precipitators.
Other collection
techniques can be
used with a subse-
quent decrease in
particle representa-
tiveness.
287
338
50
Scanning
electron
micro-
scope.
287
33t
50
General: . The
devices chosen are
applicable to solids
ranging in size from
raw coal to powders.
If the material is
composed entirely of
fine particles, how-
ever, the optical
microscope should be
used.
Level 2: An orien-
tation correction
factor must be
applied to the
Coulter Counter
when fibrous part-
icles are present.
Also, the length
to diameter ratio
for other particles
must be near unity.
If a Coulter
Counter or other
accurate automatic
devices are not
available, then an
optical microscope
can be used.
Level 1: Photo-
micron should be
taken in the field.
Level 2: This
method can also be
used for morphology
See discussion of
scanning electron
microscope above.
The scanning elec-
tron microscope
should be used in
conjunction with
the polarizing
light microscope
for particle iden-
tification.
201
-------
CHAPTER 4
PROCEDURES FOR ASSESSMENT OF WATER-BORNE FUGITIVES
FROM FBC PROCESSES
INTRODUCTION
The intent of this chapter is to provide a mechanism for the environ-
mental assessment of water-borne fugitives from FBC processes. Specifically,
the impact on ground and surface water quality of leachate generated as a
result of subsurface disposal and outdoor storage of FBC solid residues (and
feeds) is of concern here. Other fugitives from miscellaneous plant sources
(e.g. leaks, spills, etc.), that ultimately become water-borne, are site
specific and cannot be addressed in a generic context. Because of (projec-
ted) proper plant design, maintenance, and operating practices, these
sources are expected to have a minimal impact on water quality.
GENERATION AND TRANSPORT OF LEACHATES IN THE ENVIRONMENT
Leachate is liquid which has contacted solid material and has extracted
and/or suspended constituents from it. (Whenever water comes into direct
contact with solid materials, the potential for leaching exists.) Many
species exist in solid materials which may be readily soluble in water.
Still others may be solubilized by the action of leachate upon them.
Transport of leachate occurs via two primary mechanisms—runoff (i.e.,
overland flow), and percolation (e.g. through soils). These mechanisms, as
they relate to the burial of solid residues (e.g., landfill) and the
outdoor storage of solid feeds and/or residues, are illustrated in Figure
32. Runoff, typically characterized by relatively high flow rates (as
governed by site topography) and short contact times (hours or, at most, a
few days), is the principal transport mode for suspended solids. Percolation,
on the other hand, is characterized by significantly lower flow rates
(governed by material permeability) and much longer contact times with solid
material. Species transport by this mode occurs primarily in solution.
Interflow, as shown in Figure 32, occurs when water first infiltrates and
percolates through a solid material and later re-emerges to become surface
runoff. This phenomenon is principally associated with storage piles, but
under certain geological and hydrological conditions may be associated
subsurface disposal.
Precipitation is the principal contributor to leachate generation,
whatever the transport mechanism. Other potential contributors include the
infiltration of ground and/or surface waters into the site, as well as the
initial moisture content of the solid material. For properly sited and
designed disposal and storage areas (e.g., with drainage away from the
202
-------
PRECIPITATION
PRECIPITATION
INTERFLOW
LINER FOR CONTROL
OF INFILTRATION
POSSIBLE ATTENUATION
1
1
1
(
1 1 1 1 1
WATER TABLE f t f t f
Figure 32. Schematic of infiltration/runoff problem
-------
site), the former factor should be negligible. (In addition, judicious site
design should minimize or eliminate percolation of leachate into surrounding
soils.) Although the total quantity (and rate) of leachate transported into
the surrounding environment will be minimized through proper site selection
and design, higher concentrations of pollutants are expected in the leachate.
The lower transport rates, however, should allow for greater attenuation and
possibly total degradation by natural mechanisms.
Since the generation and transport of leachate is site specific, any
procedure to estimate leachate quantity and quality requires knowledge of
topographical, geological, hydrological, climatological, and meteorological
data (see reference 54). Various methods have been employed to estimate
quantity of leachate generated. One such procedure, a calculation technique
which has been used with some success in field studies, is the water balance
method (see reference 122). (An alternative experimental procedure is the
construction of lined field test cells-^see Tables 26 and 27).
Briefly, the water balance method is based upon a one-dimensional flow
model and conservation of mass relationships between precipitation, evapo-
transpiration (i.e., the transport of water from the earth back to the
atmosphere), surface runoff, and field moisture storage. The influent to
the field is assumed to originate totally from precipitation. Of the total
incident precipitation, a portion will evaporate back to the atmosphere (or
be transpired by vegetative cover, if any), some may be transported away from
the site as runoff, a part will infiltrate and recharge the site to field
capacity*, or, for a site which has already attained field capacity, will
become downward percolation. Once field capacity is attained and downward
percolation begins, the amount of leachate produced can be calculated by the
following relationship:
Mass flow of leachate produced = Mass flow of incident
precipitation
Mass flow of water - Mass flow of water "lost"
runoff from site through evapotranspiration.
Knowledge of the total amount of leachate generated, together with
experimental data from leachate quality tests, can be used to assess the
impact of raw material storage and solid residue disposal on ground and
surface water quality.
SOURCES OF WATER-BORNE FUGITIVES FROM GENERIC FBC PROCESSES
In terms of potential leachate sources, coal-fired FBC systems are
somewhat similar to conventional coal-fired power plants. Sources asso-
ciated with FBC power generation include:
*"Field capacity is defined as the maximum moisture content which a soil
(or solid material) can retain in a gravitational field without producing
continuous downward percolation.
204
-------
(1) Coal storage piles;
(2) Sorbent storage piles;
(3) Spent sorbent;
(4) Fly ash;
(5) Deposited drift from cooling towers; and
(6) Deposited blowdown from steam vents.
Only points (2) and (3) are unique to FBC technology; points (5) and (6),
while potential contributors to water-borne fugitives, are site specific and
will not be considered further. (For a further discussion of these points,
see reference 54).
Coal-fired plants usually keep several months supply of coal in outdoor
storage. Storage piles and handling facilities are quite large and may cover
several acres, particularly where a plant is located near a coal mine.
(A 100-day supply of coal for a 635 MW FBC plant is equivalent to 500,000
tons.)
A major impact of coal storage piles is the generation of "acid mine
drainage". This condition develops in coal* from the oxidation of metallic
sulfides (MS) to sulfuric acid by the following mechanism:
MS M?" N + S7 x
(aq) (aq)
S + H20 r: HS~ + OH~
HS~ + 2 00 -> S0.~2 + H+
2 4
Sulfuric acid leaches heavy metals which then are transported to the environ-
ment in a biologically active state. Runoff from coal piles can also
contain large quantities of iron and magnesium, both as dissolved species or
suspended solids; aluminum, sodium, and manganese are also present, although
in somewhat lower concentrations. Runoff problems have been minimized,
in some cases, by isolating the coal on special vinyl liners and channeling
the runoff to one area where it can be treated before discharge to the
environment.
*The susceptibility of coal to this reaction depends upon the physical
form 'in which pyrite crystals occur in the coal. If the pyrite is highly
crystallized (with crystals or 5 microns or larger), it is less susceptible
to producing an acid leachate than if the pyrite crystals are small (less
than 1 micron) and disseminated through the coal (reference 259).
205
-------
Runoff and percolation associated with sorbent storage piles is similar
to that occurring naturally in geological formations of limestone and dolomite.
As such, relatively little adverse impact on water quality (aside from increased
hardness) may be expected. •'
Spent sorbent will be a major by-product of electric power generation
by FBC technology and, as such, has potential for a large environmental
impact. If a sorbent regeneration process is used, spent sorbent disposal
problems and fresh sorbent requirements may be reduced substantially. The
gross composition and quantity of solid waste produced by a typical FBC
power plant may be calculated from the stoichiometry of the SC>2 sorption
reaction. As an example, for a once-through system (i.e., without regenerar
t-ion) using dolomite, with 90 percent removal of SOo and a feed rate of
two moles of calcium per mole of sulfur, the reaction is:
MgCO CaCO- + 0.5 SO + 0.225 C>2 = 0.45 CaSC>4 +
MgO + 0.55 CaCO + 1.45 CO + 0.05 S02
i
From the above equation, for every pound of sulfur fed, 11.53 pounds of
dolomite are required and 3.38 pounds of calcium sulfate and 5.96 pounds of
magnesium oxide plus calcium carbonate are produced. Using the above example,
the annual quantity of spent sorbent for a 635 MW FBC plant burning 3 percent
sulfur coal at a Ca/S ratio of 2.0 (with no regeneration) is calculated to be
475,000 tons. In addition, the spent sorbent will contain some ash from the
coal and, more importantly, contain significant quantities of trace elements,
many of which could adversely impact water quality.
Fly ash is another major by-product of the FBC process; a 635 MW FBC plant
buring 12 percent ash coal will produce 165,000 tons of fly ash annually. In
addition to significant quantities of trace elements, both from the coal and
attrited bed material, fly ash may contain absorbed high molecular weight
organic compounds.
The potential leaching impacts associated with generic FBC process
streams are summarized in Table 22. (it should be noted that FBC solid
residues may be disposed of or utilized directly, or may undergo further
treatment prior to disposition to render them environmentally acceptable.)
LEACHING MECHANISMS AND TRANSPORT MODELING
All solid materials, both residues and feeds, associated with FBC processes
may be characterized as an insoluble matrix interspersed with soluble and semi-
soluble compounds and voids filled with either air or a liquid. After an
initial wash which removes loose particles from the surface, these materials
are regarded as being both chemically and physically stable. Semi-soluble
compounds would include inorganic species such as CaSO, , CaSOo, Ca(OHK, and
MgCO-j, as well as other species whose solubility products dictate that a solid
phase will exist when the sample is water-saturated. Soluble species will
206
-------
TABLE 22. SUMMARY OF GENERIC FBC STREAMS WITH POTENTIAL LEACHING IMPACT
Stream
Number
3
4
10
28
Stream
Designation
Particulate removal
discard
Bed solids discard
Particulate removal
discard—regener-
ation operations
Other effluents
from regeneration
and sulfur re-
covery operations
Raw coal
Raw sorbent
Particulate
removal discard
(CAFB unit only)
Potential
Environmental Impact
Trace element release; organic
compounds
Trace element release
Trace element release; organic
compounds
Trace element release
Trace element release ("acid
mine drainage")
Trace element, release
Trace element release
207
-------
include Na2C03, MgSO^, NaCl, CaClo, etc.; the solubility limits of these
species and their concentrations in the sample allow for complete solubili-
zation in the liquid-filled interstitial volume under saturation conditions.
Clearly the semi-soluble species will behave differently than the
highly soluble components under different .experimental conditions. Due to
common ion effects, the highly soluble species will control the initial
solubilization process. Furthermore, the problem cannot be discussed
solely from a total dissolved solid's standpoint; individual species must be
considered separately.
The principal concern of leachate assessment is not simply which
pollutants are released to the environment but, rather, the rate at which
these pollutants are released. Because the kinetic rate expression for
leaching is extremely difficult to write from ;purely theoretical considera-
tions, this data is best obtained experimentally (see Tables 23-26 for
experimental design). Once a leaching rate is known, various modeling
techniques may be used to describe the transport of this leachate into the
surrounding media.
Modeling techniques generally consist of solving a mass transport equa-
tion using different initial conditions (see reference 202). For mass
transport where diffusion is rate limiting, the .general form (for one-
dimensional flow) is:
dc = D 92c + K (c - c) (1)
8T S 72
8x
Where: c = Concentration of species leached
t = Time
D = Effective diffusivity
K = Dissolution rate constant
c = Concentration of species at saturation
S
x = Space coordinate
This equation has been examined for use in leachate tests for radio-
active materials and shows promise for application.
An alternative model, used to describe solute movement through perme-
able media, may be employed. This model (in one dimension) is:
208
-------
c = Concentration of species leached
t = Time
D = Diffusion constant
V = Advective velocity
x = Space coordinate
P = Bulk density
6 = Pore ratio
dq/dt = Rate of leaching of the species from the
material
The difference between this and the previous model is that advective flow
is assumed to be significant. This will be true if the permeability of the
medium surrounding the leached material is high.
The various parameters which affect shake test and column test design
are described in Tables 23, 24, 25. Tests to determine the physical
properties of solid materials subject to leaching must also be performed.
These properties include:
(1) Size analysis;
(2) Specific gravity of the solids;
(3) Bulk density;
(4) Dry density;
(5) Water content;
(6) Porosity/void ratio; and
(7) Permeability.
Appropriate methods for determination of these properties may be found in
reference 313.
209
-------
SURVEY OF LEACHATE TESTING TECHNIQUES
In Tables 23 through 26, a summary of laboratory and field techniques
applicable to leachate assessment are presented. Shake and column tests
as well as field cell techniques are addressed. Variations within each of
these methods are delineated. In Table 27, a summary of current and past
efforts in leachate testing by various governmental agencies and private
firms is presented.
210
-------
TABLE 23. SUMMARY OF SHAKE TEST TECHNIQUES
METHOD
Shake Test
VARIABLES
Eluant
1) PH
2) Dielectric Con-
stant
3) Eh
(Aerobic/ Anaerobic
Conditions)
4) Organic Constituents
4) Total Acidity/
Alkalinity
DESCRIPTION
A solid from which a leachate is to
be generated is agitated with an e-
luant under specific conditions
which relate to site specific
parameters.
Solid materials are leached in the
environment either by direct pre-
eipltation or by surface runoff
generated from precipitation. Elu-
ant composition will, in part, de-
termine the leachate mechanism.
The sample can be shaken at vari-
ous pH's to simulate a range of
possible natural eluants.
The dielectric constant is related
to the solvating power of the elu-
ant. The dielectric constant In-
creases with addition of ionic spe-
cies. Polar substances become more
soluble with increasing dielectric
constant, while non-polar sub-
stances become less soluble.
Eh is the oxldative or reductive
capacity of the eluant and provides
a frame of reference within which
redox and hydrolysis reactions of
different metals maybe compared.
Organic constituents will affect
the complex ing ability of the elu-
ant. Furthermore, these compounds
may react with the waste to pro-
duce new pollutants.
Total acidity/alkalinity together
with pH define the buffering capac-
ity of the eluant.
REFERENCES
131
178
193
202
203
259
334
336
212
-------
TABLE 23. (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
This teat is comparatively rap-
id and simple to perform. E-
quipment requirements are-min-
imized and are commonly'avail-
able. This test is relatively
inexpensive and may provide a
mechanism for a worst-case
analysis.
Simulation of natural condi-
tions.
A range of possible field con-
ditions as well as extremes
can be .simulated.
Natural eluants contain dis-
solved species which determine
the eluants solvating ability.
Eh (related to dissolved oxygen
concentration) in part deter-
mines the aerobic and anaerobic
.condition under which a materi-
al is leached. Aerobic or ana-
erobic conditions may dictate
the reaction mechanism.
Natural eluants will contain a
variety of organic compounds.
Natural eluants are likely to
be buffered.
This procedure does not furnish
results which can be readily
interpreted as steady state or
rate related data. Data is
provided only in terms of the
concentration of species in the
leachate. The relationship be-
tween environmental factors
which control leaching in the
field and variables within the
shake test is difficult to de-
fine.
Actual eluant may be difficult
to access and reproduce under
shake test conditions.
Reaction mechanism may change
with pH.
Estimation and determination of
the dielectric constant of
natural leachate may be
difficult.
Eh of the eluant in a natural
environment maybe difficult to
assess accurately and will
change with eluant concentra-
t ions.
Individual organic compounds
within the eluant maybe diffi-
cult to identify and measure
quantitatively.
A worst case analysis is defined
here as the maximum concentra-
tions at which pollutants are
likely to be released to the en-
vironment. No estimation of
made of either dilution or at-
tenuation effects.
Level 1 tests are designed to
screen and semi-quantitatively
measure all potential pollutants.
The shake test, as a worst case
analysis, is suitable as a Level
1 assessment procedure.
Eluant composition is the most
important factor controlling the
leaching mechanism. The follow-
ing parameters define eluant
characteristics.
The pH of the natural eluant is
controlled primarily by dissolved
CO,
2'
Acids and bases, buffered
suitably, may be used to control
pH of laboratory eluant:
Dielectric constant and thus the
solvating ability of the system
is determined by the choice of
eluant composition, (e.g. organic
vs inorganic acids, etc.)
Eh is a function of pH. The Eh
of rainwater is typically 0.4-
0.6 volts. Air must be excluded
from reaction vessel to maintain
negative Eh values (anaerobic
conditions).
Organic constituents in the elu-
ant principally from surface run-
off, infiltration thru soils, and
the leaching of organic constitu-
ents within the residue itself.
A wide variety of buffers is
possible. A particular buffering
system must be selected with care
213
-------
TABLE 23 (continued).
METHOD
Shake Test (cont.)
VARIABLES
Eluant (cont.)
6) Temperature
7) Total Volume
8) Cycles
Test Duration
Particle Size
Agitation Methods
1) Shaking Methc
2) Stirring
3) Compressed Ga
Agitation
d
3
DESCRIPTION
The temperature at which the test
is conducted will affect the solu-
bility of potentially leached ma-
terials. Temperature may change
the overall leaching mechanism.
Total volume will determine, in
part, amounts of species which
will be leached.
The saturated eluant may be fil-
tered from the solid and fresh e-
luant added to the system.
A test maybe conducted for varying
periods of time. A single test
duration maybe up to 96 hours.
A sample maybe finely ground prior
to a test, thereby increasing the
surface area exposed to the eluant.
A wrist action shaker is commonly
used for agitation.
Magnetic stirrers have been used to
effect mixing.
Compressed gas maybe used to agi-
tate a mixture.
REFERENCES
214
-------
TABLE 23. (concluded).
ADVANTAGES
DISADVANTAGES
REMARKS
.Temperature control is desira-
.ble to approximate natural con-
ditions and to insure reproduc-
ibility within a series of
tests.
By increasing eluant volume,
saturation equilibria maybe a-
voided. Species which would
normally appear in the leachate
only after long periods of time
maybe detected (and measured)
relatively quickly.
Eluant changes are designed to
represent the time dependent re
lease of pollutants until a
steady-state condition is
reached.
Establishment of chemical equi-
libria within a system is a
function of time.
Dissolution of a solid is limi-
ted in part by the surface area
of the solid. By increasing
the surface area of a sample,
the dissolution rate is in-
creased, thus equilibration
within the system is reached
sooner and test duration is
accordingly shortened.
Shaking rate is easily controll
ed. This equipment is common
to most laboratories.
Stirring rate is easily con-
trolled. This equipment is com
mbn to most laboratories.
Useful for control of aerobic
or anaerobic conditions . No
power requirement.
Temperatures significantly a-
bove or below ambient field
conditions will affect labor-
atory leachate quality. Ambi-
ent temperatures may vary wide-
ly within a waste disposal
site.
This process may lead to a
large overestimation of actual
pollutant concentrations.
The conditions reached in this
test may never be realized un-
der natural conditions.
System equilibrium represents a
worst case.
Increasing the dissolution rate
may seriously overestimate po-
tential pollutant release to the
environment.
The temperature at which a test
is conducted may affect reaction
rates significantly; temperature
during a test should be approxi-
mately the same as expected at
field conditions. Temperature
maybe controlled by placement
of the test vessel in a constant
temperature environment (e.g. an
incubator).
Minimum test duration is deter-
mined by experimental evaluation
of species concentration versus
time by periodic withdrawal of
sample aliquots.
Particle size reduction is a phys
leal process and thus cannot af-
fect the overall leaching mecha-
nism.
More expensive than other
methods.
Stirring is a somewhat less ef-
ficient method of agitation
than is shaking.
Aerobic conditions maybe simula-
ted by 02 or air agitation; anae-
robic conditions maybe simulated
by using an inert gas.
215
-------
TABLE 24. THE SATURATION TEST
METHOD
i Saturation Test
L
VARIABLES
Eluant
Eluant Volume
DESCRIPTION
A saturated paste is made by mix-
ing the test media with an eluant.
The paste is filtered and the fil-
trate analyzed.
Distilled water is commonly used.
Natural eluants (i.e. rainwater
or surface runoff water) and
synthetic eluants can also be used.
Eluant volume is variable. The
eluant is added to the media with
continual mixing until a saturated
paste is obtained.
REFERENCES
43
i
216
-------
TABLE 24 (concluded).
ADVANTAGES
DISADVANTAGES
REMARKS
The inherent water retention
characteristics of. the media
are considered in this test.
Natural eluants will represent
actual leaching process more
accurately.
It is difficult to obtain an
extract at field water content;
procedures using higher liquid/
solid ratios depart from
actual field conditions.
Distilled water is not repre-
sentative of natural eluant.
The quantity of eluant re-
quired to mix a media to a
paste is related to field
water content.
The inherent reproducibility of
this volume is less than for
other tests. By minimizing
eluant volume, saturation
effects are maximized.
This method has been used to
estimate the available salt con-
tent of soils but may be appli-
cable to other media. An esti-
mate of disposal site field ca-
pacity can be made with method.
The primary difference between
shake and saturation tests is
the high solid to eluant ratio
of the latter. Thus, only the
most soluble species will con-
trol the saturation test equilib-
rium. Test results may represent
the initial leachate composition.
The absolute and relative amounts
of species are influenced by the
water content of which the ex-
tract is made. Clearly, not all
species may be leached under
these condition.
217
-------
TABLE 25. SUMMARY OF COLUMN TEST TECHNIQUES
METHOD
VARIABLES
DESCRIPTION
REFERENCES
Column Test
Eluant
1) pH
2) Dielectric
Constant
3) Eh
(Aerobic/Anaerobic
Conditions)
4) Organic Constituents
5)
Total Acidity/
Alkalinity
A material to be leached Is placed
In a column and eluted with an ap-
propriate solvent under specific
conditions which relate to site
specific parameters.
Wastes are leached in the environ-
ment either by direct precipitation
or by surface runoff generated
from precipitation. Eluant compo-
sition will, in part, determine the
leachate mechanism.
The sample maybe leached at a num-
ber of different pH's to simulate
possible field conditions.
The dielectric constant is related
to the solvating power of the elu-
ant. The dielectric constant in-
creases with addition of ionic spe-
cies. Polar substances become more
soluble with increasing dielectric
constant, while non-polar sub-
stances become less soluble.
Eh is the oxldative or reductive
capacity of the eluant and provides
a frame of reference within which
redox and hydrolysis reactions of
different metals may be compared.
Organic constituents will affect
the complexIng ability of the elu-
ant. Furthermore, these compounds
may react with the waste to pro-
duce aaw pollutants.
Total acidity/alkalinity together
with pH define the buffering ca-
pacity of the eluant.
131
178
202
203
257
259
218
-------
TABLE 25 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
This test may, if carefully de-
signed, provide data which can
be related to the rate of pol-
lutant release to the environ-
ment. The test may also be
used to measure the ion ex-
change capabilities of soils
for attenuation studies. The
test is inexpensive in its sim-
pler forms and utilizes common-
ly available equipment.
Simulation of natural condi-
tions. Composition of actual
eluant at specific site should
be determined.
A range of possible field con-
ditions as well as extremes
can be simulated.
Natural, eluants contain dis-
solved species which determine
the eluants solvating ability.
Eh (related to dissolved oxygen
concentration) determines in
part the aerobic or anaerobic
condition under which a materi-
al is leached. Aerobic or ana-
erobic conditions may dictate
the reaction mechanism.
Organic composition of the elu-
ant will affect the reaction
mechanism and thus the trans-
port mechanism.
Natural eluants are likely to
be buffered.
Test durations tend to be ra-
ther long (months-years) be-
cause of flow rates through the
column, in simulation of natu-
ral infiltration rates, are
very small. Relationships be-
tween environmental factors
which control leaching in the
field and variables of a column
test are difficult to define;
results concerning rate data
must be interpreted with ex-
treme caution.
Actual eluant maybe difficult
to assess and reproduce under
column test conditions.
Reaction mechanism may change
with pH.
Estimation and determination of
the dielectric constant of nat-
ural leachate maybe difficult.
Eh of the eluant in a natural
environment maybe difficult to
assess accurately and will
change with eluant concentra-
tions.
Individual organic compounds
within the eluant may be diffi-
cult to identify and measure
quantitatively.
Column tests are the most widely
used methods for leachate genera-
tion. With proper design, column
tests are suitable methods of
leachate generation for a Level
2 assessment.
Eluant composition is the most
important factor controlling the
leachate mechanism. The follow-
ing parameters define leachate
characteristics.
The pH of the natural eluant is
controlled primarily by dissolved
co2.
Dielectric constant, and thus the
solvating ability of the system,
is determined by the choice of
eluant (e.g. organic vs inorganic
acids).
Eh is a function of pH. The Eh
of rainwater is typically 0.4-
0.6 volts. Air must be excluded
from reaction vessel to maintain
negative Eh values (anaerobic
conditions) .
Organic constituents in the elu-
ant originate principally from
surface runoff, infiltration
through soils, and the leaching
of organic constituents within
the residue itself.
A wide variety of buffers is pos-
sible. A particular buffering
system must be selected with
care.
219
-------
TABLE 25 (continued).
METHOD
Column Test
(cont.)
VARIABLES
Eluant (cont.)
6) Temperature
7) Total Volume
Compaction of Sample
Particle/Column
Diameter Ratio
Flow Rate
1) Constant Head
2) Falling Head .
DESCRIPTION
The temperature at which the test
is conducted will affect the solu-
bilities of leached materials.
Temperature may change overall
leachate mechanism.
Total eluant volume is related to
the total influx of precipitation
and/or surface runoff at a particu-
lar site. Total volume will deter-
mine, in part, amounts of species
which will be leached.
Flow rate through a porous medium
is dependent on permeability. A-
mount of sample compaction will
affect the permeability.
The largest particle size will de-
termine the minimum volume element
which is representative of the
field site.
Residence time within a medium
will be controlled by flow rate.
Flow rate is proportional to head.
Hydraulic head is the potential
energy per unit weight of a fluid
and includes pressure head and ele-
vation head (head due to gravity).
Only elevation head is relevant to
free flow systems. A constant
head system requires a constant e-
luant level above the column.
In a falling head system, no ef-
fort if made to maintain a constant
eluant level. Flow rate will de-
crease with falling head (other
variables kept constant) .
REFERENCES
220
-------
TABLE 25 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
Temperature control is desir-
able to approximate natural
conditions and to insure re-
producibility within a series
of tests.
Approach to equilibrium, or the
attainment of a steady-state
condition is time dependent.
Species, concentrations are nor-
mally measured as a function of
total eluant volume.
The simulation of the permea-
bility of the natural medium
will help approximate natural
conditions and flow rates.
Proper selection will minimize
scale effects.
Simulation of infiltration
rates under field conditions
by control of flow rate within
a column provides a method to
control the mean residence
time of the eluant. Careful
control of flow rates are
necessary to insure test and
reproducibillty.
Under saturated flow conditions,
a constant head system implies
a constant flow rate (assuming
hydraulic conductivity is con-
stant).
A falling head system may rep-
resent actual field conditions
more closely than a constant
head system. Rapid infiltra-
tion of precipitation and/or
runoff with subsequent attain-
ment of field capacity is sim-
ulated. A falling head sys-
tem is easily constructed.
Temperatures significantly a-
bove or below ambient field
conditions will affect leachate
quality. Ambient temperatures
may vary widely within the
-disposal site.
Reproducing field conditions
(i.e. compaction and permeabil-
ity values) within a laboratory
column is difficult.
A small column diameter with
respect to particle size, will
not in general, be representa-
tive of flow through a larger
volume.
Estimation of flow rates under
field conditions is difficult.
Low flow rates imply long time
periods for leachate collect!
from a column test.
Leaching is more effective un-
der saturated flow conditions
and leads to overestimation of
species concentrations. Con-
stant flow rates will rarely
be realized under field con-
ditions. Construction of a
constant head system is more
complex than a falling head
system.
Re'producibility of falling
head tests is inherently less
than that for constant head
tests.
The temperature at which a test
is conducted may affect reaction
rates significantly; temperature
during a test should be approxi-
mately the same as expected at
field conditions.
This variable is difficult to re-
late to laboratory tests. D/d
ratios are most Important where
the media is inhomogeneous (e.g.
municipal landfills, etc.). The
quantitative relationship between
flow rate and leachate quality
is difficult to define.
Flow rates along with eluant com-
position are the two factors
which have the greatest influence
on the generation of leachates
from a column test. Diffusion,
for a chemically fixed sample,
maybe simulated by packing a
more permeable media, such as
glass beads, around the test
media.
The theory of saturated flow
leaching is better understood
than that for unsaturated leach-
ing.
221
-------
TABLE 25 (continued).
METHOD
VARIABLES
DESCRIPTION
REFERENCES
Column Test:
Attenuation Studies
Soil Characteristics
1) PH
2) Chemical Exchange
Capability
3) Conductivity
4) Surface Area
5) Permeability
Soil Composition
6) Total Acidity/
Alkalinity
Attenuation studies attempt to des-
cribe the interaction of leachates
with surrounding soils. Soil at-
tenuation, as It occurs in the real
world, is a complex phenomenon in-
volving at least three major ele-
ments:
1) Soil adsorption and desorptlon
which determines the underlying
pattern.
2) Porous flow and diffusion which
produce a dispersion of the
pollutants.
3) Water infiltration and evapora-
tion, which determines the amount
of movement of a chemical.
Soils characteristics will define
the sorption mechanism.
Soil systems have varying buffer-
Ing capacities.
Soils have differing Ion exchange
capabilities.
Soil conductivity will depend on
moisture content and dissolved
solids concentrations.
Surface areas of soils depend on
Individual soil types and compo-
sition.
Flow condition at the system
boundary is controlled by soil
permeability.
Different soil types have different
attenuation capacities which vary
with composition.
Total acidity/alkalinity 'together
with pH define the buffering capaci
ty of the eluant.
131
143
335
336
222
-------
TABLE 25 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
The eventual disposal site for
most solid wastes is the soil.
Interaction of leachate and
evaluation of pollutant release
rates to the ground water after
passing through soils is the
major goal of water-borne fug-
itive assessment. Data from
column-methods which measure •
the relative rates of ion mi-
gration through soils, i.e.,
attenuation studies, can be
used in computer simulation of
leachate impact from waste
sites.
Characterization allows evalu-
ation of pollutant attenuation
versus an Individual soil
properties.
pH of the soil will effect the
sorption mechanism, e.g., the
chemical exchange capacity.
Exchange capabilities define
the total system capacity for
sorption.
Conductivity is related to the
moisture capacity of the soil
and thus to transport proper-
ties.
Surface areas relate to absorp-
tion capacity, exchange sites,
and permeability of soils.
By measurement of soil permea-
bility, Intermittent effects
such as ponding, may be evalu-
ated. The .least permeable med-
ia will control steady state
'flow.
Composition will define soil
chemistry.
Soils are buffered systems.
Attenuation studies are sub-
ject to the same limitations as
discussed for leachate genera-
tion by column tests. In par-
ticular, quantitative interpre-
tation of extraction data must
be made cautiously.
Exchange capabilities should be
measured for all ions to be
considered. Individual ex-
change capabilities may be dif-
ficult to directly relate to
overall attenuation.
Leachate generation and attenua-
tion studies maybe performed
within the same test. This is
done by putting the soil to be
studied at the bottom of the col-
umn and placing a suitable amount
of material to be leached above
the soil layer. Standard column
procedures may then be used to
evaluate leachate attenuation.
Attenuation studies may also be
conducted with only soils placed
in a column using either a syn-
thetic or natural leachate.
For a complete discussion of
eleven soils and their properties
with regard to attenuation stud-
ies (see Reference ).
•Exchange capabilities may be
measured using 1 M ammonium ace-
.tate.
Surface areas are commonly
measured by gas (usually N )
absorption techniques.
Complete analysis of a soil is
expensive.
223
-------
TABLE 25 (continued).
METHOD
Column Test
Attenuation Studies
(cont.)
VARIABLES
Soil Composition
(cont.)
1) Composition by
Mineral Type
2) Elemental Analysis
3) Total Organic
Content
Eluant
1) Natural Eluant
2) Synthetic Eluant
3) Temperature
4) Flow Rate
DESCRIPTION
Individual minerals have differing
attenuation capabilities.
Elemental analysis will, In part,
define soil chemistry and characo.
terlstics.
Organic compounds In soils may
complex or react with leachate
constituents.
For column tests leachates maybe
generated In the laboratory or
natural leachate maybe used.
Soil sorptlon studies maybe con-
ducted with or without In situ
generation of leachate; a"natural"
leachate Is used in either case.
Soil sorptlon studies may be con-
ducted using a synthetic leachate;
I.e., a material which has been
spiked with pollutants of Interest.
The temperature at which attenua-
tion studies are conducted will
affect sorptlon mechanism and
thus sorption and desorption rates.
Residence time within a medium is
controlled by flow rate. Flow
rate is dependent on driving
force (e.g., head) and system re-
sistances (e.g., permeability,
drain valve opening, etc.).
REFERENCES
224:
-------
TABLE 25 (concluded).
ADVANTAGES
DISADVANTAGES
REMARKS
Classification of soils by
mineral content is useful for
comparison of gross attenuation
characteristics.
Chemical analysis can identify
ion exchanging species.
The actual amount of leaching
in soils is a function of the
total organic content of the
soil.
If properly designed, in situ
generation of a leachate may
represent field conditions.
Determination of natural leach-
ate attenuation is a major en-
vironmental assessment goal.
Synthetic leachates may be
made easily and inexpensively.
Leachate analysis is greatly
simplified.
Temperature control is desira-
ble to approximate natural con-
ditions and Insure test repro-
ducibility.
Attenuation is an equilibrium
process. Pollutant migration
thru- a column is a function
of flow rate. Column flow
rates should approximate natu-
ral flow conditions.
Complete chemical analysis, may
be quite expensive and unneces-
sary.
Classification should include per-
centage of sand, silt and clay.
Predominate clay minerals should
be identified.
See Elemental Analysis Tables in
Chapter 3 for applicable analyti-
cal techniques. Iron and manga-
nese oxides are important parame-
ters for defining attenuation
capabilities of soils.
Total simulation of all field
conditions are difficult in a
laboratory environment.
Collection of a natural leach-
ate in sufficient quantity
maybe difficult and expensive.
Preservation of natural leach-
ate may present special
problems.
Synthetic leachates may not re-
produce actual sorption phe-
nomena accurately.
Temperatures at sorption sites
may be difficult to measure.
Flow rates at disposal sites
may be difficult to measure.
A "natural" leachate is,by defini-
tion, site specific.
Such studies may be used to pre-
dict relative ion mobilities' on
different soils.
Either a constant or variable head
system may be used. (See the
previous discussion under column
tests). Sorption/desorption e-
quilibria, i.e., ion migration
rates, will probably be overesti-
mated under saturated flow con-
ditions.
22$
-------
TABLE 26. SUMMARY OF FIELD TEST CELL TECHNIQUES
METHOD
Field Test Cells
VARIABLES
Lined Test Cell
DESCRIPTION
Field test cells are scale models
of waste disposal sites employed
to evaluate leachate generation
from solid wastes and the impact
of such leachates on ground water
quality. Alternatively field
test cells may be large columns or
other devices (lined with an inert
material) which are Installed at
the disposal site and exposed to
actual field conditions for the e- .
.valuation of liners as control de- •
vices as well as leachate genera-
tion.
A wide range of materials are po-
tentially useful as barriers for
the Impoundment and the subsequent
collection of. leachates. Only
those liners which are impermeable
and non-reactive are useful for
leachate collection.
Test cells are modeled to reproduce
actual site conditions (i.e. com-
paction of the waste depth of the
waste, composition of the waste,
etc.).
REFERENCES
257
257.1
335
226
-------
TABLE 26 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
The leachate generated from
such cells is done under natu-
ral conditions (temperature,
rainfall, etc.)- Scale effects
of leachate generation (in
theory at least) are minimal
for field test data.
The leachate generated under
"natural conditions" is attenu-
ated under actual conditions.
Field test cells are -ve*y ex-
pensive to construct and moni-
tor. Continuous in situ samp-
ling capability is required.
Placement and. maintenance of
such sampling devices is incon-
venient.
Field test cell evaluation
studies are lengthy (i.e.,
months to years).
Since the total leachate sample
Is collected, an empirical re-
lationship may be derived be-
tween total precipitation, run-
off, and infiltration and
leachate generation.
Interaction between leachate
and the surrounding environ-
ment is limited.
Impoundment of leachate may in-
crease residence time and thus
affect species concentrations.
Liner defects will develop with
time and allow interaction with
the surrounding environment and
lead to unknown sample losses.
Improper leachate collection
(e.g. allowing an anaerobic
leachate to become aerobic)
may change leachate properties.
Field test cell, design is d.epen-
dent on a variety of factors:
media homogeneity, media size,
media availability, etc.
Sample collection devices are of
several general types: liners
which collect the total leachate,
lysimeters which collect a por-
tion of the leachate at a speci-
fic point, and wells which are
designed to assess infiltration
of leachate into ground water.
Each method has definite advan-
tages and limitations and Is
discussed below.
Under certain circumstances (e.g.
where the test cell is being e-
valuated in a dry climate) water
may be added to simulate disposal
in areas with higher precipita-
tion rates or accelerated leach-
ate generation.
Liners which are potentially use-
ful.for total collection studies,
are usually synthetic polymeric
membranes. These liners may be
either reinforced or unreinforced
Typical liners are as follows
(reference ):
Butyl rubber
Ethylene propylene rubber (EPDM)
Chlorosulfonated polyethylene
(Hypalon)
Chlorinated polyethylene (CPE)
Elasticized polyolefln (3110)
Polybutylene (PB)
Polychloroprene (Neoprene)
Polyester elastomers
Polyethylene (PE)
Polyvinyl chloride (PVC)
Liners may be protected from
physical damage by a protective
layer of an inert material such
as sand.
227
-------
TABLE 26 (continued).
METHOD
Field Test Cells
(cont.)
VARIABLES
Unlined Test Cell
Collection Devices
1) Deep wells
2) Shallow obser-
vation wells
3) Auger
4) Soil sampling
5) Inflltrometers
DESCRIPTION
Unlined test cells are cells in
which the leachate is allowed to
Interact with surrounding media.
While this definition precludes
Impermeable liners, clay and/ or
soil liners may be used for attenu-
ation studies under field condi-
tions.
Test cells are designed to repro-
duce actual site condition (i.e.
compaction of the waste, depth of
the waste, composition of the
waste, etc.).
A variety of methods may be used
for collecting leachate and moni-
toring seepage from a disposal
site. The following is a short
summary of -the procedures.
Ground water wells—domestic or
agricultural.. Equipment: electri-
cal conductivity meter.
Shallow wells with perforated
casings, gravel backfilled. Possi-
ble equipment: electrical conduc-
tivity meter.
Hand or power augered holes (usu-
ally following soil sampling).
Equipment: auger.
Soil sampling to incremental depths
pending textural changes. Equip-
ment : auger .
Plastic covered ring infiltrometers
22.0 - 61 cm (9 - 24 in.) diameter,
double or single, manometer equipp-
ed. Equipment: special driving
hammer.
REFERENCES
228
-------
TABLE 26 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
Interaction between waste resi-
due and the environment is not
limited. Unllned cells permit
monitoring of horizontal pollu-
tant gradients (i.e.' diffusion
studies).
If large cells are constructed
(e.g. 30 m x 30 m x 10 m )
in the vicinity of the plant,
not only is a partial disposal
site provided but actual dis-
posal site impact may be evalu-
ated in the areas where resi-
dues are likely to be ultimate-
ly disposed.
Records easily available, his-
tory may be traced.
Quantity and quality can be
monitored, fairly inexpensive,
low maintenance, permanent
installation.
Quantity and quality can be
monitored, Inexpensive.
Minimum equipment required,
offers wide range of quality
and moisture monitoring.
Fairly easy to monitor, inex-
pensive, no special maintenance
required, permanent.
Collection of.leachate is diffi
cult; an underdrain leachate
collection system is not
feasible within unlined cell
and lyslmeters must be used.
Total leachate generation is
difficult to evaluate.
Once a unlined cell is in oper-
ation, control of pollutant re-
lease is extremely difficult
and the effects may be long
term.
After-the-fact method. Wells
too far away or absent.
Suitable for monitoring water
table conditions only--unsat-
urated flow cannot be detected.
Difficult to maintain, unsatu-
rated flow cannot be detected.
Expensive laboratory analyses,
requires repetitive and back-
ground sampling.
Requires some expertise for in-
stallations; chance of errors—
short circuiting, evaporation
losses, and erroneous measure-
ment .
Lyslmeters are installed at dif-
ferent depths to collect leachate
and determine the velocity of
pollutant migration to the ground
water table.
Wells may be installed upstream
and downstream of ground water
flow and additionally thru the
test cell to determine the effect
on ground water quality.
For either lined or unlined cells
meteorological phenomenon (e.g.
temperature, total precipitation,
etc.) and conditions within the
test cell (temperature, moisture
content, gas production, etc.)
should be monitored so that
leachate generation may be re-
lated to environmental conditions
These methods have been applied
to pond seepage detection, but
are applicable for monitoring
liquid infiltration or seepage
studies in general.
Monitoring quality for back-up
data and possible changes in
quality for nearby areas.
Detection of lateral water move-
ment from areas over restricting
substrata.
Preliminary soil investigation of
all sites; determination of seep-
age in and adjacent to sites.
Measurement of soil profile
moisture and its quality in all
sites when necessary.
Measurement of Infiltration both
inside and outside sites.
229
-------
TABLE 26 (continued).
METHOD
Field Test Cells
(cont . )
VARIABLES
Collection Devices
(cont.)
6) Piezometers
7) Gypsum blocks
(Bouyoucos
blocks)
8) Lysimeter
9) Neutron probe
10) Remote sensing
11) Salinity
sensors
DESCRIPTION
6.35 - 9.52 mm (1/4 - 3/8 In.)
metal pipe, perforated at end.
Equipment: driving hammers, riv-
ets, rods, pump, tubing, soundbell.
Unit: gypsum, nylon, or fiber-
glass blocks; plate electrode.
Other equipment: resistance
meter.
Porous ceramic device. Equipment:
vacuum pumps, lines, etc.
Neutron scattering moisture meter:
Includes radioactive source, trans-
mission lines, counter. Other e-
qulpment: dummy probe, access
tubes, etc.
Infrared photographic detection
of changes in the radient energy
status of a discharge area.
Salinity sensing device to detect
dynamic changes in salt concentra-
tion In the soil profile.
REFERENCES
230
-------
TABLE 26 (concluded).
ADVANTAGES
DISADVANTAGES
REMARKS
Very inexpensive, simple to in-
stall, easy to read, no special
maintenance or calibration re-
quired, both quality and quant-
ity of special zones can be
determined.
Easy to install, easy to moni-
tor, very little maintenance
required.
Samples can be obtained easily,
rather inexpensive, low main-
tenance, permanent installation
High reliability, access tubes
permanent, good for frequent
checking.
Monitor at anytime without
prior notice, permanent record,
Interpretation easily delinea-
ted. . ':
Simple to set up and operate.
Quick response to new equilib-
rium conditions.
Measures only saturated zones,
relies on impervious subsoil
conditions, cannot determine
unsaturated flow.
Not capable of measuring quali-
ty or quantity of seepage, cal-
ibration required—low sensi-
tivity in moist and wet range.
Subject to deterioration.
Measures best under saturated
conditions—normally measures
in the "available moisture"
range, depth limited.
Very elaborate and expensive,
requires special expertise,
frequent calibration, special
access holes, high maintenance,
does not detect quality, re-
quires special storage and li-
censing by AEC.
Expense not well established
subject to weather interferen-
ces, does not give quantity or
quality of drainage water.
Initial expense is high. Does.
not measure quantity and indi-
vidual ions.
Detection and measurement of
moisture movement under ponds
overlying restricting layers.
Detection of changes in soil
moisture under sites.
Detection of seepage quality .
over a wide moisture range.
Detection of vertical moving
moisture fronts under and sur-
rounding sites.
Detection of changes In the
growth rate of plants In and a-
round a discharge area as com-
pared to native areas.
Quick detection method of changes
in salt concentration in the soil
profile.
231
-------
TABLE 27. SUMMARY OF CURRENT AND PAST EFFORTS IN LEACHATE TESTING
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
The Aerospace
Corporation
(257)
Column
EPA
(IERL-RTP)
Field Test
Cells
Shake Test
One hundred gram samples are
packed Into 4cm glass columns
through which 3.6 liters of dls
tilled delonlzed water Is elu-
ted. A set of three columns
Is prepared for each material
to be leached.
Unbuffered leach eluants are
adjusted to pH 4, 7 and 9 with
either HC1 or NaOH. Eluant and
leachate were allowed to Inter-
act with air so as to simulate
aerobic conditions.
A similar procedure is used for
leaching experiments which sim-
ulate anaerobic conditions.
The eluant and leachate are
protected from interaction
with the atmosphere; only an
eluant of pH 7 is used.
Leachate so generated is ana-
lyzed periodically (750ml In-
crements) .
Samples were ground to a uni-
form size in an attempt to
maximize surface area.
No specific test method has
been recommended; however, a
complete analysis of test cell
design, liners and monitoring
equipment is presented.
A slurry Is prepared using
from 2 to 4 parts distllled-de-
lonized water to 1 part solid.
This slurry is shaken continu-
ously for 72 hours at room
temperature. The slurry is fil
tered. The above steps are re-
peated ten times and the leach-
ate from the filtration is
analyzed for each repetition.
This test has been used for the
testing of raw FGD sludges.
For FGD sludges (and perhaps for
other media) it is convenient to
perform analyses as a function
of pore volume displacements.
(Analysis is performed at first,
second, third pore volume dis-
placements and then-on the 15th,
30th and 60th pore volume dis-
placement.) Pore volume may be
calculated from the mass and vol-
ume of each packed column.
Elements and species monitored
were: As, Be, Cd, Cr, Cu, Pb,
Hg, Se, Zn, Cl', f, SO ~2,
SO -2, pH and TDS.
No mention of flow rate and/or
control Is made (FGD sludges are
rather impermeable and presuma-
bly this controls flow rate -
a constant head of about 72" W.C.
is used.)
Differences are noted between
aerobic and anaerobic columns.
Aerobic leachate is always found
to be acidic while anaerobic
leachates are basic. Lead con-
centration (50th pore volume) is
is significicantly higher under
anaerobic conditions.
Field test cells are in the form
of lined and unlined ponds. See
table 26 for field test cell de-
sign, liner materials and moni-
toring equipment.
Mention of this test does not im-
ply current endorsement of this
method by EPA.
Experience has shown that some
species are released immediately
from the waste while others are
released in the later leachings.
The effect of pH on teachability
may be determined by adjusting
the pH of the slurry to the de-
sired range and following the
aforementioned procedures for
each pH
232
-------
TABLE 27 (continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
EPA
(IERL-RTP)
(cont.)
Shake Test
(cont.)
EPA
(MERL-
Department
of the
Army)
(131)
Column Test
(Attenuation)
EPA
(MERL)
Shake Test
Columns are prepared from 37
mm I.D. glass tubing with a 8
mm diameter tip on the bottom.
Glass .wool is placed over the
bottom hole and covered with
washed quartz sand. One hun-
dred grams of waste is packed
into the column (-10-13 cm
depth). The waste is covered
with sand and a thin layer of
glass wool and then fitted with
a stopper containing a 3 way
stopcock which allows either
sampling the leachate or di-
recting the leachate on an up-
flow path into a soil column.
The soil column may be pre-
pared (typically) by packing
160g of -20 mesh soil to a
density of 1.5 g/cc (-10cm
depth).
Leachate is analyzed at incre-
ments of 2 pore volume dis-
placements.
A liquid to solid ratio of
~5 to 1 (50-100g sample) is.
used initially. The sample Is
shaken continuously until sat-
uration (equilibrium) is
reached and then analyzed. A
fresh sample is extracted at
higher liquid to solid ratios
(e.g. 10:1, 15:1, 20:1 etc.)
until saturation phenomena
does not control leachate
composition. Eluant may be
condition which is considered.
A similar test has been used by
lERL-New Jersey. A liquid to
solid ratio of 2.5 is used and
samples are agitated for 24
hours using a Burrell Shaker.
The Department of Army uses a
similar test; liquid to solid
ratios of from 4:1 to 1:1 are
used. Shake time is 72 hours.
The above steps are repeated 7
times.
An upflow arrangement is used to
maintain saturation flow, to
minimize channeling, and permit
better flow control at low flow
rates ( 0.5-1.5 pore volumes per
day). A 84" W.C. head pressure
was used.
Leachate and attenuation studies
from four industrial wastes
(Ni-Cd battery, electroplating,
water base paint, and Inorganic
pigment wastes) were evaluated
using this technique. After com-
pletion of each leaching experi-
ment, the soil column was divided
Into four equal sections and Ig
samples of each section analyzed.
An attempt was made to maintain
equal flow rates in all columns.
This test has evolved from a
series of informal discussions
with MERL personnel.
See Table 24 for a more complete
discussion of eluant composition
and general test considerations.
Leached solid (from which leach-
ate has been generated) should
also be analyzed for the same
elements and species (where ap-
plicable) as the leachate.
233
-------
TABLE 27 (continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
EPA
(MERL)
(cont.)
Shake Test
(cont.)
EPRI
(334)
Shake Test
(Solubility
Test)
Chemfix
(131)
Column
Method
distilled deionized water but
better is an eluant which re-
sembles natural rainwater (i.e.
deionized water saturated with
C02 and 0 at STP).
Temperature should be con-
trolled to approximate natural
environment.
Sample may be finely ground
to shorten test period.
A sample is stirred for 24
hours with deionized water in
a closed container. A 5 to 1
liquid/solid ratio is used.
After filtering with a porous
membrane filter, the leachate
may be analyzed.
The effect of pH is evaluated
by varying pH between 7.5 and
13 using a carbonate buffering
system.
The kinetics of leachate gen-
eration may be evaluated using
procedures similar to the a-
bove. Ninety-six hours of
contact time were used to in-
sure equilibrium and the mix-
tures were sampled at 2, 5, 10,
60, 480, 1445 and 2880 minutes.
One hundred grams of material
to be leached are placed in a
glass chromatography column
(40mm x 600 mm) containing
one inch of glass wool at the
bottom. The material to be
leached is compacted in the
column. Distilled water is
used as the eluant (for ease
of reproductiblllty). The re-
maining eluant fills the upper
portion of the column. Eluant
flow is approximately 1 ml/min.
Leachate is normally collected
in 100 ml portions and subse-
quently analyzed. Eight por-
tions (i.e. 800ml) simulates
roughly 25 inches of ground
water passing thru the materi-
al in the field.
Mention of this test does not
imply current endorsement of this
method by EPA.
This test has been used for the
evaluation of leachate from
bottom and precipltator ash.
Column sorption tests are per-
formed using these leachates.
Relatively small soil columns
are used (height 4cm, width 3.5
cm). The columns are attached
to a vacuum system which is
used to regulate flow.
This test was developed to eval-
uate leachate from chemically
fixed wastes.
This test has been well tested
and successfully correlated
with actual samples taken from
materials tested in the field.
While only distilled water was
used as an eluant, other eluants
could easily be used (e.g. rain-
water) .
234
-------
TABLE 27 (continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
IUCS
Shake Test
Princeton
Aqua
Science
(336)
Column Test
(Attenuation
Studies)
(336)
Shake Test
A sample ( 5olOg) to be
leached Is shaken for varying
times. An Initial liquid to
solid ratio of approximately
4 to 1 is used and subse-
quently increased until the
solution is no longer satura-
ted. Using this liquid to sol-
id ratio (at which saturation
does not occur), a fresh sample
is shaken for 48 hours and the
leachate filtered and analyzed
This sequence is repeated five
times.
Two column sizes have been
used, a small column (2.25" x
36") and a large column (18" x
72"). Each column is treated
with silica grease to minimize
seepage of eluant along the
walls (i.e. minimize wall
effects).
A soil column is obtained by
driving the column into the
ground to the required depth
(~2-3"). Soil columns are
typically loaded with 6" and
12" waste layers (equivalent
to loadings of 700 and 1400
tons/acre). A soil column
without waste is used as a
control.
Distllled-deionized water is
added over a period of four
weeks during which leachate
is collected. (For the small
column 3.2 liters roughly
represent 49" of rainfall.)
Fifty grams of ash is placed
into each of 3 Erlenmeyer
flasks with 500 ml of die- .
tllled-delonized water. The
pH of each flask is adjusted
to pH 5,.7 and 8.5 respective-
ly. The flasks are placed on
a shaker for ten days and the
pH is adjusted daily with
either HSO or NaOH.
Kinetic data may be obtained by
more frequent analysis (e.g. 1,
2, 4, 8, etc. hours) of the un-
saturated leachate.
The first value obtained from
the "unsaturation leachate test"
has been suggested as represent-
ative of runoff liquors: the
fifth test Is suggested as repre
sentative of steady state leach-
ing. Sample is rinsed prior to
analysis. Rinse Is not analyzed
These tests were designed to
evaluate leachate and runoff
from incinerator ash residue.
This test generates a raw leach-
ate in situ and measures leach-
ate output after attenuation by
a soil.
Use of the small column is pre-
ferred from a convenience stand-
point.
The leachate was analyzed for
38 chemical constituents.
Aerobic and/or anaerobic condi-
tions were not specifically
maintained.
This test is designed to simu-
late worst probable runoff con-
ditions.
A worst case analysis is obtain'*
ed by using a lower liquid to
solid ratio (i.e. 500g of solid
to 500ml of water).
Other pH's used in the .study
are pH 3, 5, 7 and 9.
235
-------
TABLE 27 (continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
Princeton
Aqua Science
(cont.)
Ralph Stone.
Inc.
(335)
Shake Test
(cont.)
Column Test
(335)
Field Test
Cells
After 10 days, the flasks are
removed from the shaker and
ithe ash allowed to settleji
Both supernatant and
residue are analyzed.
Five hundred of each residue
and stratographic materials
are placed in FVC columns
(20cm x 3.0m). Distilled
water Is passed through these
samples at the rate of 100ml
per day. Water Is added at
the rate of 7.5 liter every
other day. Lyslmeters are
placed at various levels in
the columns; lyslmeter and
drain samples are collected
every other day. No attempt
was made to control the head
or the specific temperature
at which the leachate is
generated.
Prior to the loading of the
residue on the column, water
was added to the columns at
the rate of several liters per
day for several weeks. This
establishes column background
value for all constituents.
Wells are installed upstream
and downstream of the ground-
water flow and an additional
well sunk in the test cell to
determine the effects on
ground water quality. Three
lysimeters at different depths
are also installed to collect
leachate. A series of gas and
temperature probes are in-
stalled within the test cell.
Provisions are also made to
evaluate media settling rates.
These studies are designed to e-
valuate leachate and runoff en-
vironmental impact from disposi-
tion of fly ash and spent bed
material from FBC processes in a
variety of situations.
Residues from the PER, EXXON
miniplant, ESSO-England, and
CPU-400 units are in the process
of being evaluated.
A variety of stratographic mater-
ials (bituminous coal, dolomite,
limestone, claystone, #16 sand-
stone, #60 sandstone, granite
material, p-gravel were used to
simulate disposal sites. Resi-
dues were tested with pyritic
tailings to evaluate the effect
of the residue on the production
of acid mine drainage. Analyti-
cal values generally reach a
constant value by the fifteenth
week of continuous leaching. At
this point the more soluble com-
ponents have been leached, leav-
ing slowly leaching compounds be-
hind.
Residues are analyzed for acid,
base and water soluble constitu-
ents by shaking each with dis-
tilled water, 0.1N HC1 and 0.1N
NaOH.
For test cell construction de-
tails, see reference. If, from
hydrologlcal studies conducted
at the test site, ground water
contamination is not possible,
only lysimeters are used to mon-
itor and collect leachates.
The design of the test cell is
determined by several factors,
including residue availability.
Initial plans are to use small
test cells (0.9m x 0.9m x 0.3m).
Large cells (30m x 30m x 10m)
provide a test of actual disposal
imoacts In the area where resi-
dues are likely to be disposed.
236
-------
TABLE 27 (continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
TRC
Runoff
Sampling
(54)
(54)
Runoff
Sampling-
Field Test
Method
Waterway
Experimental
Station
(WES)
(202)
(203).
Shake Test
A weighed portion of the materi
al to. be tested is placed in a
container with a known volume
of distilled water. The resul-
ting mixture is allowed to
stand for three days and is
then filtered thru a membrane
filter (0.3u). The filtrate is
analyzed for species of Inter-
est.
The media is reweighed and
mixed with the same volume of
water and the process repeated
a number of times. A high
liquid to solid ratio (-10 to
1) is used.
Samples are collected by a
series of plug collectors (see
reference for design. These
samplers are driven into the
ground at selected locations
where runoff will occur (e.g.
the base of piles, gullies,
etc.). Samplers are changed
at regular intervals during a
storm. The volume collected in
each sampler is recorded and
relevant analyses are per-
formed. A .gross estimate of
flow is made from a knowledge
of the total rainfall and soil
permeability.
A 1:4 mixture of material and
water is prepared. The water
used should be saturated prior
to the test with CO, (pH 4.7).
This slurry is then shaken on
a wrist action shaker for 1
hour. The sample is centri-
fuged for 30 minutes at 2500
rpm then filtered using a
0.45(i filter. The leachate is
subsequently analyzed for de-
sired constituents.
Runoff is presumed to be the
primary mechanism of waterborne
pollutant transport. This test
is designed to evaluate leachate
potential from material storage
piles (e.g. coal, fly ash, etc.)
Test data cannot be directly
correlated with actual precipi-
tation data, quantity of runoff,
and the transport of runoff.
This method is proposed by TRC
as a Level 1 method for runoff
assessment. This method in-
cludes estimating the quantity
and measuring the quality of
runoff by collection of repre-
sentative samples.
During storms, rainfall intensi-
ty and duration should be
monitored.
This test was utilized as a
rapid leach test for fixed and
raw FGD sludges.
237
-------
TABLE 27 (continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
Waterway
Experimental
Station
(WES)
(cont.)
(173)
Shake Test
(Modified
Elutriate
Test)
(202)
(203)
Column Test
A representative sample from
the disposal site water Column
should be collected and ana-
lyzed.
Sediment samples are taken with
a grab sampler or corer and
should be representative of the
sediment.
A mixture of sediment (150ml)
and disposal site water (2850
ml) is placed in a 6 liter Er-
lenmeyer flask (20:1 liquid to
solid ratio).
A porous diffusion tube Is in-
serted almost to the bottom of
the flask such that the mix-
ture Is agitated vigorously by
a compressed gas for 30 minutes
The flasks are swirled manually
at 10 minute intervals to In-
sure complete mixing. After
agitation, the mixture is
allowed to sit for 60 minutes
and Is then filtered (0.45u).
This elutriate Is analyzed for
desired constituents.
The leaching columns are four
inches in diameter (I.D.) and
designed to contain a sample
volume of ~0.35 cubic feet.
The inlet port is ~1" above
the top of the sample to
maintain a fluid head of that
height.
Columns are capped with Para-
film to minimize air contami-
nation. Leachate is collected
at the bottom of the column
and regulated by a stop cock
to maintain a fluid velocity
of roughly 1x10 cm/sec. A
three inch layer of polypro-
pylene pellets is placed at
the bottom of the column to
retard movement of suspended
solids from the columns.
Prior to loading the columns,
all materials were washed with
detergent followed by a rinse
with dilute HC1. The entire
apparatus was pre-leached with
deionized water for one week
This test was designed as a
rapid elutriate test for
dredged sediments. The test pro
vides information on the chemi-
cal compounds released to the
water column during disposal of
hydraullcally dredged material.
This test is normally run In
triplicate.
Aerobic and anaerobic condi-
tions may be simulated by using
either oxygen (aerobic) or an
Inert gas (anaerobic) to mix
the samples.
This leaching test is designed
to measure the rate of pollutant
migration (from fixed or raw
FGD sludges) into an aqueous
medium, and is intended to rep-
resent field conditions as
closely as possible.
Concepts for the initial design
of this system were extracted
in part from a proposed standard
method for leachate testing of
immobilized radioactive waste
solids developed by the Inter-
national Atomic Energy Agency.
A velocity of 1x10 cm/sec cor-
responds approximately to the
permeability thru a very fine
sand.
Boric acid is used to buffer
the leaching fluid at a pH of
7.5 - 8.0; boric, acid was
chosen because of its relative
inertness and is used in low
concentration so as not to
affect the leaching properties
of the samples.
238
-------
TABLE 27 (continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
Waterways
Experimental
Station
(WES)
(cont.)
(202)
Column Test
(cont.)
Westlnghouse
(178)
Shake Test
at the design flow rate. The
samples are weighed, loaded In-
to the columns and Initially
filled from the bottom with
leaching fluid to minimize air
entrapment. Two buffered
leaching solutions are used —
pH 4.5-5.0 and pH 7.5-8.0.
Columns are fed from a constant
head reservoir. Columns are
run in triplicate.
Sampling for leachates Is con-
ducted over a one year period.
Twelve samples are analyzed at
total elapsed times of 7, 14,
21, 28, 42, 56, 86, 116, 146,
,206, 266 and 356 days. Weekly
measurement of temperature,
pH, conductivity, and volume
of leachate collected, Is per-
formed. At the conclusion of
the test, the leached media
may be analyzed.
Columns were packed according
to recommendations of chemical
fixation processors. No
attempt was made to maximize
surface area.
Deionlzed water (250ml) is
mixed with the 'spent stone
(25g) in a 500 ml flask. The
mixture is agitated for 24
' hours using an automatic sha-
' ker (Eberbach) at 70 excur-
sions per minute at room temp-
erature. This supernatant is
filtered (Whatman No. 42
paper) and the filtrate
analyzed.
This test has been conducted
with samples as received and
with samples which are finely
ground. Shaking may be con-
ducted under aerobic (air
atmosphere) or anaerobic con-
ditions (inert atmosphere).
Shaking versus non shaking
Carbon dioxide Is used to buffer
the leaching fluid to..a; pH of
.4.5-5.0. This should be repre-
sentative of rainwater which
assumes an acidic pH due to its
reaction with carbon dioxide.
The two leaching fluids represent
both sides of the pH scale and
should provide some concept of
the pH effect on leaching. All
materials used for leach fluid
distribution are polypropylene
or teflon.
Mass transport theory specifies
a diffusion mechanism between
the material surface and the
leaching solution. While other
reactions may occur (I.e. at-
tenuation) , the data as evalu-
ated by laboratory procedures,
represent an "effective" dlf-
fusivlty for a given pollutant.
Behavior of these systems are
characterized by a stable, mono-
tonically decreasing leach rate
which approaches some limiting
value. In this sense, the In-
itial leaching period Is more
critical than the later stages
of leaching and is best followed
by a logarithmic sampling pro-
cedure.
This test has been used as a
rapid test for the evaluation
of waterborne pollutant release
from FBC spent aorbent.
This test has been applied to
residues from pressurized and
atmospheric FBC units (PER,
Westinghouse and Esso Mlmiplant
units).
Similar test results were ob-
tained despite variations in
media surface area (i.e. grind-
ing of the sample prior to shake
test) and reaction conditions
(aerobic and anaerobic atmos-
pheres). Leachates are analy-
zed for 31 trace elements,pH,
specific conductance,and sul-
fate.
239
-------
TABLE 27 (continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
Meetinghouse
(cont.)
(178)
Shake Test
(cont.)
Runoff Test
Roy R.
Weston, Inc.
(259)
Shake Test
(259)
Column Test
procedures have been evaluated.
Deionized water was dripped
onto 25 g of spent stone which
was manually packed Into a
cylindrical column (1.1mm x
213mm).
Successive 250ml leachates were
collected and analyzed. Flow
was controlled by media
permeability.
The coal sample Is shaken with
three solutions - an acidic
solution (pH 3,9), a neutral
solution (pH 7,1), and a basic
solution (pH 10).
The procedure is as follows:
(1) Samples are dried to a
constant weight at 105°C.
(2) Twenty grams af the
sample are placed in 100ml of
water and the pH adjusted to
the desired value (HC1 and
NaOH are used).
(3) The mixture is then
transferred to a shaker table,
which is set at the maximum
shake rate for 30 minutes.
(4) The supernatant is
filtered and the filtrate
analyzed for the desired
constituents.
A column (4" I.D. x 36") was
packed with coal In 6" layers,
ten tamps per layer, yielding
a total packed depth of 2.5
feet. A small air pump was
connected to the bottom of
the test column and air was
slowly pumped through the
column. 500ml of distilled
water was then poured onto the
column.
The following was determined from
leach tests on spent FBC residue:
(1) Calcium and sulfate dis-
solution plateaued at concen-
trations limited by calcium
sulfate solubility; (2) The
equilibrium calcium and sulfate
concentrations were high and
exceed current water quality
criteria; (3) There was negli-
gible dissolution of magnesium
ions; (4) Insignificant amounts
of heavy metal ions were leached;
(5) The leachates were alkaline
(pH 10.6-12.1). Runoff leachates
(similar to a column test) show
gradual decrease in pH with the
amount of eluant.
This test has been used to assess
the environmental impact of
leachate generation from coal
piles. The results from the
test are suggested to represent
worst case levels of leachate
quality.
The-results of these shake tests
for coal from the Decker Coal
Mine are as follows: (1) Acidic
conditions - Initial pH 3.9
final pH 9. Heavy metal concen-
trations were negligible (well
below proposed EPA standards in
1973).
(2) Neutral conditions - initial
pH 7.1 final pH 8.5. Again
heavy metal concentrations were
negligible.
(3) Basic conditions: initial
pH 10.0, final pU 9.4. Heavy
metal concentrations were
negligible.
This test Is designed to model
coal stock pile conditions and
possible sulfuric acid production
(acid mine drainage) under
oxidatlve conditions. Only
leachate pH and volume were
measured. Initial leachate pH
was determined to be pH 8.5; pH
decreased to a final value of
pH 8.0.
240
-------
TABLE 27 (continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
Roy R. Western,
Inc. (cont.)
(259)
Column Test
(cont.)
Illinois State
Geological
Survey
(143)
Attenuation
Studies
The water percolated through th
coal column and collected In a
flask, and after measuring the
volume pH, the leachate was
poured onto the column again
(volume was made up to 500ml by
adding distilled water). This
procedure was repeated a total
of 8 times.
To evaluate the potential of
clay materials for attenuating
the various chemical constitu-
ents of landfill leachate,
leachate was passed through
laboratory columns that con-
tained various mixtures of
calcium saturated clays and
washed quartz sand.
Clays used in this study were:
kaolinite, montmorillonite,
and illlte. These clays were
purified and the .clay minerals
present identified by X-ray.
diffraction techniques. In
addition to chemical analysis,
exchangeable cations, cation
exchange capacity, carbon
content, and surface areas
were determined for all clays.
Leachate used in this study
was collected- from a sanitary
landfill; the collected
leachate was stored at 3-5°C
and maintained under anaerobic
conditions. The leachate was
analyzed for chemical constitu-
ents.
Columns were constructed of
2-lnch acrylic tubing. To
simulate field conditions,
the leachate containers and
columns were protected from
light. The sand-grams were
coated with various percent-
ages of clays and uniformly
packed in columns (30-40cm
depth). The columns were
packed to bulk densities
approximating natural con-
ditions (~1.8g/cc).
The susceptability of coal to
oxidation of pyrites to sulfuric
acid appears to be a function of
the physical form in which pyrite
crystals occur in coal.
Clay minerals were chosen for
study because earth materials
containing one or more of these
minerals can generally be
obtained locally for landfill
liners. In addition to clay
columns, a column of 100% sand
was used as a control.
The leachate used in this study
was compared to 20 other
leachates and found to be
reasonably representative, with
the exception of phosphate and
sulfate which were abnormally
low. Chloride, sodium, and
water-soluble organic compounds
(COD) were poorly attenuated;
K, NH4, Mg, Si, and Fe were
moderately attenuated. Heavy
metals, such as Pb, Hg, and Zn
were strongly attenuated by even
small amounts of clay.
Of the three clays used in the
study, montmorillonite had the
highest attenuation capability,
followed by illite and then
kaolinite. Attenuation was a
function of the CEC of the clay
mineral, the initial exchange-
able cations on the clay, the
chemical composition of the
leachate, and the pH of the
leachate.
In this study, precipitation
and/or a filtration mechanism
appears to be the cause of
complete attenuation of heavy
metals. This Is consistent
with analysis of the sectioned
columns and the fact that no
difference in attenuation was
found among the three clays.
241
-------
TABLE 27 .(continued).
AGENCY/FIRM
(REFERENCES)
METHOD
DESCRIPTION
REMARKS
Illinois State
Geological
Survey (cont.)
Attenuation
Studies
(cont.)
University of
Ottawa
(131)
Attenuation
Studies
Flow rates were designed to
simulate the slow (2 pore
volumes per month), saturated,
anaerobic flow of leachate.
Leachate was passed through
the columns for periods of
between 6 and 10 months. After
leaching of approximately 15
pore volumes was completed, the
clay mineral columns were
sectioned and the contents
analyzed to determine the
vertical distribution of
chemical constituents in each
column.
For each waste, five reactors
are placed in series and each
prepared by loading with 200g
of air-dry soil, bringing the
soil to "field capacity"
through the addition of ground
water, purging the reactor with
nitrogen, and sealing from the
environment.
In the sequence of five
reactors per soil, 200ml of
liquid waste was added to the
first reactor and mixed. The
liquid,after chemical equili-
bration in the reactor had been
reached, was then drained from
the soil and was passed on
to the next of the five
reactor in series. An aliquot
of the filtrate was taken for
chemical analysis following
drainage from the first, third,
and last reactor.
Subsequently, a total of five
portions, each of 200ml volume,
of groundwater was passed
through the five reactor series
to evaluate the desorption of
contaminants attenuated.
The chemical data describing
the changes in contaminant
concentration during the
migration of the liquid waste
and desorption water through
the dispersed.soil reactors
were used to calculate:
(1) The net attenuation of
each contaminant by all
processes, including dilution.
The traditional approach to
contaminant attenuation with
soils has involved soil column
experimentation.
This method was used to evaluate
the attenuation of two liquid
industrial wastes in soils using
a dispersed soil methodology.
Three soils were used in this
study.
The liquid waste and desorption
water, upon being mixed with the
moist sample, is diluted
Initially by the soil moisture.
In a field situation, diffusion
and dispersion would result in a
similar effect; however, the
magnitude of the effect would be
less. Dispersed soil data Is
corrected to account for this
difference by an empirical
factor, FE(0.71 for this study).
The following contaminants were
studied: V, TOC, 8203, CNS, Na,
.Pb, Cd, and Fe.
Conclusions reached by this
study are:
(1) Dilution is an important
mechanism for all contaminants.
(2) Desorption was exhibited by
all contaminants studied and was
most prominent for those
attenuated primarily by a di-
lution mechanism.
(3) Attenuation data collected
from dispersed soil experi-
mentation can be used to project
242
-------
TABLE 27 (concluded)..
i AGENCY/FIRM
'/ (REFERENCES)
METHOD
DESCRIPTION
REMARKS
'.University of
Ottawa (cont.)
Attenuation
Studies
• (cont.)
.'University of
Arizona
131
Attenuation
Studies
(2) The net attenuation, minus
the effect of dilution, and
(3) The net desorption for
each contaminant.
Ten sorbed trace elements
(As, Cd, Cf, Cu, Hg, Ni, Pb,
Se, -V, Zn) were- extracted from
soil columns which had been
leached with a natural''
leachate individually' spiked'
with each element. Trace
element concentrations were
from 70 to 120 ppm. A leaching
rate of 1/2 to 1 pore volume
per day was continued for -30
days. Eleven soi-ls represent-
ing the seven most prominent
orders were used. -At the
conclusion of! the- leaching, the
soil columns (-SxlOcm) were
segmented- into T cms sections.
Each- section was- dr-i'ed; and-
extfacted' with'sO'. V. N- HC1! and
water., Two grams; of; the dried
soil were shaken with-1 20 ml of
extractant, centrlfuged, and
filtered1.. Both, the filtrate
and^ residue'were analyzed and-
a material balance calculated.
The effect-of solution flux* was
studied^ by 'addi'rig: the1 leachates
at various; constant flow rates
using peristaltic pumps.
soil water concentrations in a
field situation by the use of a
correction factor, Fg.
(4) The zone of influence of the
disposal operations is closely
related to the waste-loading. It
is postulated that the past
practice of waste disposal in
small sites may account for the
limited environmental impact
measured to date.
Actual mechanisms of 3orption and
desorption of trace elements on
soils have not been identified.
This fact, coupled with' demon-
strations' that soils- can release
pollutants when leached with
various solutions, indicates the
permanence of land disposal is
unknown. A method' to evaluate
the permanence of ion atten-
uation is.to relate it to
extraction efficiency. Natural
leaching is best simulated by a
mild extractant (e.g., water).
Extraction with a harsher reagent
provides information as to ionic
movement in the soil.
Relatively large quantities of
sorbed material were extracted
with 0.1'N HC1. Furthermore,
the more coarse-textured the soil
(e.g., sandy soils), the greater
the extraction efficiency. The
order of extractabilitv with
water was;: V>Se>As>Cr>Zn>Ni>Cd>
Hg>Cu>Pb.
Total amounts of the sorbed ion
extracted by'water, were low,
usually less than 3% of the total
absorbed'. Most of the ion was
absorbed on the top 107. of the
soil column; thus, the percent
extracted does not represent the
potential for ion migration
because the ions would be re-
adsorbed as they move down the
column.
243;
-------
RECOMMENDED PROCEDURES FOR LEVEL 1 ASSESSMENT
For Level leachate assessment, use of the shake test is recommended.
This method is inexpensive, rapid and will provide a leachate of "worst
case" quality. To estimate the quantity of leachate generated the water
balance method should be employed. (Note that the water balance method
requires a site survey of topographical, geological, hydrological,
climatological, and meteorological conditions.) The following general
procedure is proposed:
A 10 gm sample (ground to 100/200 mesh) is shaken with 250 ml of
eluant at a constant temperature using a wrist-action shaker set at the
maximum rate for 48 hours. The mixture is filtered and both the filtrate and
residue are analyzed by Level 1 procedures (see Figure 25 and relevant tables
in Chapter 3.)
The eluant should simulate natural conditions. This may be done by
saturating distilled, deionized water with carbon dioxide under ambient
conditions. (An alternative is the use of plain distilled-deiohized water.)
The solid to liquid ratio has been arbitrarily set at 25:1; what is important,
however, is that species saturation not be reached. Thus, this ratio should
be confirmed experimentally and adjusted accordingly, if necessary.
The temperature at which this test is conducted should be selected.to
represent the mean temperature to which the leached material would be exposed.
It should be cautioned that wide variations in test temperature may have an
unpredictable effect on leachate quality; certain species (e.g., CaSO^, CaCO^,
etc.) are more soluble while others (e.g., MgC03, MgSO^) are less soluble
as temperature decreases. As part of a Level 1 leachate assessment, the
physical properties of test media should be defined. These properties
include particle size analysis, specific gravity, bulk density, dry density,
water content, porosity/void ratio, and permeability. Suitable methods are
found in reference 313.
Level 1 runoff assessment may be made in the field by collecting runoff
in plug collectors. (Plug collector design is discussed in reference 54.)
Collectors are driven into the ground at selected locations where runoff
will occur, such as at the base of material storage piles, and in natural
gullies and channels. During a storm, the collectors are changed at regular
intervals (dependent on storm intensity). The volume collected in each plug
is recorded and a Level 1 analysis performed on each sample. A gross
estimate of flow is made from the amount of total precipitation and the soil
permeability in the area between the sampling plug and the receiving water.
At this time, a suitable laboratory procedure for runoff assessment cannot be
recommended here.
RECOMMENDED PROCEDURES FOR LEVEL 2 ASSESSMENT
Field test cell techniques and column tests are suggested as options for
Level 2 assessment. The former, being exposed to actual rather than a
simulated field environments, represent leachate quantity and quality more
244
-------
accurately. Major disadvantages associated with field test cells, however,
are the lengthy test periods required, and the expense of construction and
monitoring. Column tests, while suffering from the disadvantage of having
to. simulate field conditions, have the significant advantages of relatively
short test periods (typically 1-2 years) and relatively low construction
costs. (Advantages and disadvantages of both methods are discussed at greater
length in Tables 25 and 26.)
The specific objectives of each particular Level 2 assessment of
leaching will determine the design parameters and procedures for either
test. Issues germane to Level 2 assessment include:
• Attenuation of the leachate (including attenuation as a
control method, e.g., clay liners);
• Disposal site selection;
• Disposal method selection (e.g., landfill, ocean dumping, etc.); and
• Necessity for further treatment prior to disposal/utilization.
Because each issue will dictate the ultimate assessment procedure,
and each use may be different, only general guidelines for Level 2 test design
can be presented within this document. With proper selection of test variations
within Tables 25 and 26, a procedure to assess water-borne fugitive impact
for each site can be designed.
Leachate generation and monitoring for either field test cells or column
tests should not be terminated until steady-state conditions are reached.
For column tests, past experience with FGD sludges indicates that test durations
of one to two years may be expected; field test cells, depending on local
site conditions, will require longer (order of magnitude) test periods.
For column tests, eluant composition should simulate natural conditions.
A satisfactory synthetic eluant may be prepared by saturating distilled-
deionized water with carbon dioxide and oxygen under ambient conditions.
The temperature at which leaching is conducted should be held constant and
should reproduce expected field conditions. Sample compaction and permeability
should also be representative of field conditions. Flow rate through the
column, which is a function of these parameters, should be maintained constant.
As actual field flow is difficult to assess, an arbitrary flow rate of 1 x 10~5
cm/sec, corresponding to the flow through very fine sand, may be used.
To estimate total leachate production, the water balance method may be
used. All leachate, whether generated from field test cells or column tests,
should be analyzed by Level 2 analytical techniques (see Figure 26 and relevant
tables). All solid materials to be tested will be physically characterized
by Level 2 procedures and, in addition, the physical properties listed in
the preceding Level 1 discussion will be determined. Plug collectors may
again be used for runoff collection for Level 2 assessment.
245
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CHAPTER 5
SAMPLING AND ANALYSIS COSTS
INTRODUCTION
The intent of this chapter is to provide a mechanism for estimating
assessment program implementation costs. Specifically, estimates of the
total costs for sampling and analysis of the four generic FBC systems under
consideration are presented, both for Level 1 and Level 2, using methodology
developed previously by EPA contractors (references 148 and 317).
Costs associated with the following areas have been excluded from
the overall sampling and analytical cost estimates:
1) Biological testing;
2) Sampling of air-borne fugitives;
3) Sampling of water-borne fugitives; and
4) Standard fuel analysis (i.e., ultimate, proximate).
As noted in Chapter 2, biological testing procedures have not been completely
identified at this time and thus, costs associated with bioassay cannot be
defined. Because of the site specific (and plant design specific) nature of
air-borne fugitive emissions, no rational cost estimate for fugitive sampling
could be developed for the generic FBC systems. Methodology for the sampling
of water-borne fugitives has not been finalized at this time (see Chapter 4
discussion), which precludes the presentation of meaningful cost data.
Finally, results of standard fuel analyses are assumed to be available as
part of the process operating data.
The primary sources of unit cost data presented in this chapter are refer-
ences 148 and 317. It should be noted that the costs provided in these
references were generated in 1975 and may not represent costs prevailing at
the time of publication of the present document. Specific costs for sampling
rely principally on data obtained from commercial organizations routinely engaged
in source sampling. Analytical costs are based on commercial quotes whenever
possible. Estimates for semi- and non-routine analyses were provided by various
sources including EPA (various branches), EPA contractors (SRI, BMI, MRI, RADIAN),
academic sources, and various commercial testing laboratories. Capital costs
are not considered in the development of overall estimates, based on the
assumption that all required sampling and analytical equipment is available.
The differences that are evident in the Level 1 and Level 2 unit cost
data reflect the different goals associated with each assessment phase. Level
1 is a survey phase in which all system influents and effluents are screened
under the following general guidelines:
246
-------
1) Sampling is done from a conveniently available location such
that a reasonably characteristic sample may be obtained;
2) No replications are planned for either sampling or analysis;
and
3) Chemical analysis is semi-quantitative and limited to elemental
analysis, class identification for organic compounds, identifica-
tion of inorganic gases, and field tests for various water quality
parameters.
The goal of the Level 2 effort is a more accurate, quantitative identifi-
cation of specific components in selected streams and the determination of
associated emission rates. Sampling procedures are, in general, refinements
of those used in Level 1. Chemical analysis is expanded to include identifi-
cation of specific inorganic and organic compounds and a more complete physical
characterization of solids. Finally, replication in both sampling and analysis
is done.
As discussed in Chapter 2, the design of an optimized Level 2 program
is based on results obtained from the Level 1 effort. Not having the benefit
of Level 1 output, the following assumptions have been made to enable the
development of an overall sampling and analysis cost estimate for Level 2.
1) Each stream addressed in Level 1 would again be considered
at Level 2 (i.e., no stream elimination); and
2) A complete analysis will be made at Level 2 for each stream
considered (i.e., no elimination of stream components).
Obviously, since this represents a "worst case" situation, the figure
derived should be regarded as an upper bound rather than an actual total cost
for Level 2.
SAMPLING COST DATA
The basic sampling strategy, for costing purposes, has been organized
around four* general sampling categories that are associated with FBC and
other technologies. Of these four categories, the sampling of particulates
from ducted gas streams (e.g., stacks) requires the greatest effort, estimated
at 12 man-hours and 64 man-hours, respectively, for Levels 1 and 2. For
each of the remaining three categories (liquid, solid, and ducted gas
sampling), sample acquisition time is estimated at one or two man-hours at
Level 1 and one and one-half man-days at Level 2. The estimates include
equipment preparation at the site, equipment operation, dissassembly, and
clean up time. Level 2 values include an allowance for sample replication
time. At Level 1, samples are taken without replication or compositing. To
*As mentioned previously, sampling of air-borne and water-borne fugitives
has not be costed.
247
-------
assign a cost to these procedures, it has been assumed that one man-day of
fully burdened labor, including $70 per diem and other general direct costs,
is equal to $250.
A summary of sample acquisition times and associated costs is presented
below, according to sample type.
TABLE 28. SAMPLE ACQUISITION COST DATA
3
Sample Type Man-hours Cost (10 $).
Level 1 Level 2 Level"!Level 2
Particulate 12 64 .375 2.0
Gas 2 12 .063 .375
Liquid or Slurry 1 12 .032 .375
Solid 1 12 .032 .375
The costs associated with sampling site preparation are a function
of specific plant design. Therefore, for generic systems, rough estimates,
at best, can be assigned to these costs. For Level 1, it is assumed that
sampling access is available at convenient stream locations. An overall
charge of $250 per stream (for all stream types) is assessed to account for
nominal site preparation such as cutting sampling ports, installation of
taps for liquid sampling, providing electricity, etc.
Level 2 site preparation charges become a function of stream type
and are higher than their Level 1 counterparts due to the added costs of
installing generally more sophisticated sampling equipment in an optimum
location. For example, Level 2 site preparation costs may involve erection
of complex scaffolding, cutting additional ports for traversing, installation
of mechanical samplers for solids, and the use of automatic liquid stream
samplers, etc.
Implicit in the site preparation cost figures for Level 1 and Level 2
is that no special provisions for sampling (e.g., ports) have been incorporated
into the overall design. As such, the site preparation cost figures should
be regarded as upper bound values.
Level 1 and Level 2 site preparation costs are summarized below according
to sample type:
248
-------
Level 1
.25
.25
.25
.25
Level 2
25.0
8.0
2.5
10.0
TABLE 29. SITE PREPARATION COST DATA
3
Sample Type Cost (10 $)
Particulate
Gas
Liquid or Slurry
Solid
ANALYTICAL COST DATA
The multi-media overall analytical schemes for Levels 1 and 2, introduced
in Chapter 3, are repeated here in Figures 33 and 34 with unit costs for
each analysis area superimposed. It should be re-emphasized that a complete
analysis on all stream samples is assumed at Level 2. "Complete analysis"
implies that each analytical area indicated in Figure 34 for a given media
is addressed and, where applicable, that all components screened within
a given analysis area at Level 1 are again investigated, individually, at
Level 2. In terms of analytical costs per stream at Level 2, this of course
represents a "worst case" or upper bound.
Each analysis area shown in Figures 33 and 34 has been assigned
a unit cost and is discussed briefly in the following paragraphs.
At iLevel 1, Spark Source Mass Spectroscopy with photo-plate detection
is employed for elemental analysis. Seventy-six elements are scanned at a
cost of $125 per sample. A number of elements (antimony, arsenic, carbon,
hydrogen, mercury, nitrogen, and oxygen) are not satisfactorily measured by
SSMS and are analyzed by wet chemical procedures at a cost of $100 per
sample. Atomic Absorption Spectroscopy is the recommended technique for
elemental analysis at Level 2. Since "complete analysis" has been assumed for
Level 2 costing purposes, however, this corresponds to the analysis of 76
elements. The use of AAS for each element in this case would be prohibitively
expensive. SSMS with an ion-PMT detector would- be a more economical choice
which would still satisfy Level 2 requirements. The cost per sample for
elemental analysis using this technique is $400.
Organic analysis at Level 1 consists of physical separation of organic
samples into eight fractions on the basis of polarity, followed by characteri-
zation by functional group analysis using IR Spectroscopy at a cost of $250
per sample. Organic analysis at Level 2 may entail separation of each of
the initial eight fractions into as many as 50 fractions using High-Performance
Liquid Chromatography, with subsequent determination of specific compounds
within each fraction by suitable techniques (e.g., GC, GCMS, NMR, etc.).
The total cost for Level 2 organic analysis based on eight initial fractions,
each of which is then separated into approximately 50 additional fractions,
is $4000 per sample (i.e., $500 per fraction).
249
-------
INORGANICS
ON-SITE GC
ANALYSIS
CHEMILUMINESCENT
ANALYSIS
ON-SITE GC
ANALYSIS
ORGANICS C?-C
GC ANALYSIS
(c)
COLUMN CHROMATOGRAPHY
SEPARATION INTO
8 FRACTIONS
ORGANIC > C12
IR, MS ANALYSIS
ELEMENTAL
ANALYJJS
SSMS
(b)
ELEMENTAL
ANALYSES
SSMS
(b)
SELECTED
ANION ANALYSIS
FIELD TEST KITS
WET ASHING
COLUMN
CHROMATOGRAPHY
SEPARATION INTO
8 FRACTIONS
ELEMENTAL
ANALYS/S
SSMS (b)
ORGANIC
ANALYSIS
IR, MS
$100
$25
$100
$100
$250
$225
$225
$95.
$225
'$250
MORPHOLOGY:
POLARIZING
LIGHT
MICROSCOPE
$275
SAME AS ABOVE
(a) Implnger solutions excluded
(b) Hg, Sb, As are analyzed by
wet techniques
(c) An aliquot from the extract
is used for these analyses
Figure 33. Analytical unit cost data-Level 1
250
-------
*.
PHYSICAL
CHARACTERIZATION
*.
LEACHATE
GENERATION
SOXHLET
EXTRACTION.
WITH CHjClj
SEE ANALYTICAL
SCHEME FOR
LIQUIDS
-
WET ASHING
COLUMN '
CHROMATOGRAP'HY
SEPARATION INTO 8
FRACTIONS
-
-
SIZING:
SIEVING, AIR
ELUTRIATION,
OPTICAL MICROSCOPE
MORPHOLOGY:
POLARIZING
LIGHT
MICROSCOPE
(b)
ELEMENTAL ANALYSIS'
SSMS
ORGANIC ANALYSIS
, IR, MS "
LS275
$225
$250
STANDARD WATER ANALYSIS
(AQUEOUS ^STREAMS ONLY)
INCLUDES SELECTED ANIONS
$95
ELEMENTAL ANALYSIS
SSMS
(a) Impinger eolations excluded
(b) Kg, Sb, As are analyzed by
.vet techniques • • ••
(c) An aliquot from the extract.
Is used for these analyses
COLUMN CHROMATOGRAPHY
SEPARATION INTO 8
FRACTIONS
(b)
ORGANICS < Cn(c)
GC ANALYSIS
ORGANIC ANALYSIS
IR, MS
$100
$250
Figure 33. Analytical unit cost data-Level 1 (concluded)
251
-------
WET METHODS (E.G., SPECTROMETRIC,
TITRIMETRIC), GC, NDIR, UV
COLUMN
CHROMATOGRAPHY
PRELIMINARY
SEPARATION
HPLC
UV,
IR, GCMS, NMR
•$4000
*Anton analysis
Includes compound
Identification
'$300
$400
$400
$1500
$400
$4000'
MORPHOLOGY: POLARIZING
LIGHT AND SCANNING
ELECTRON MICROSCOPE
SIZING: OPTICAL
AND SCANNING
ELECTRON MICROSCOPE
$400
Figure 34. Analytical unit cost data-Level 2
252
-------
SIZING: SIEVING,
COULTER COUNTER,
OPTICAL AND
SCANNING MICROSCOPES
MORPHOLOGY:
POLARIZING
LIGHT AND SCANNING
ELECTRON MICROSCOPES
ELEMENTAL 'ANALYSIS
AAS
ANION ANALYSIS
(VARIOUS TECHNIQUES)
ORGANIC ANALYSIS
UV, IR, GCMS, NMR
$400
$400
$1500
.$4000
STANDARD WATER
ANALYSIS (AQUEOUS
STREAMS ONLY)
'$450
COLUMN
CHROMATOGRAPHY
PRELIMINARY
SEPARATION
ANION ANALYSIS
(VARIOUS-TECHNIQUES)
ELEMENTAL ANALYSIS
ORGANIC ANALYSIS
UV, IR, GCMS, NMR
;$150
I $400
1$4000
Figure 34. Analytical unit cost data-Level 2 (concluded)
253
-------
Gaseous samples are analyzed for inorganic components (except NO ) and
organic components «Cg) using on-site gas chromatography. The cost per
sample for each type of analysis (i.e., inorganic and organic) is estimated
at $100. Level 1 NO analysis by chemiluminescence is estimated to cost
$25 per sample. At Level 2, analysis for the inorganic and organic
components considered at Level 1 would be accomplished by a variety of
techniques, including gas chromatography. The estimated cost for each type
of analysis (i.e., inorganic and organic) is $300 per sample.
At Level 1, anions are analyzed (indirectly) using output from the SSMS
elemental analysis which was previously costed. Anion analysis at Level 2
is accomplished by various techniques at an estimated cost of $150 per
sample.
As indicated in Figures 33 and 34, aqueous liquid samples under-
go a standard water quality analysis at Levels 1 and 2. The Level 1 analysis
is performed on-site using field equipment while at Level 2 the analysis is
performed in a commercial laboratory to achieve increased reliability and
accuracy. The Level 1 and Level 2 costs are estimated at $95 and $450
per sample, respectively.
Level 1 morphological examination of collected particulate will
include microscopic examination of shape, size distribution, and surface
features at a cost of $275 per sample. Level 2 physical characterization,
is expanded and refined to include sizing by sieve analysis and air elutria-
tion techniques (e.g., Coulter Counter). Morphological data are obtained
using optical and scanning electron microscope methods as well as polarizing
light microscopy. Level 2 physical characterization costs are estimated at
$400 per sample.
A summary of analytical costs by sample type, for Levels 1 and 2,
is presented below. These costs are based on the overall analytical schemes
of Figures 33 and 34 and the aforementioned unit cost data.
TABLE 30. ANALYTICAL COST DATA
3
Sample Type Cost (10 $)
Level 1 Level 2*
Particulate 2.045 26.000
Gas 0.575 4.600
Liquid (or liquid portion
of slurry) 0.670 5.000
Solid (or solid portion
of slurry) 0.750 6.300
^assumes "complete analysis" at Level 2
254
-------
ADDITIONAL COSTS
In addition to the costs incurred for sample acquisition, sampling
site preparation and analysis, the following costs must also be included in an
overall estimate:
1) Travel expenses for the sampling crew;
2) Equipment preparation and freight charges; and
3) Report preparation.
Travel expenses for each sampling crew member are based on a $300
round trip airfare (1500 miles one-way) and 16 hours travel time at $250 per
man-day. It is assumed that the crew required for the Level 1 and Level 2
efforts consists of 6 men and 11 men, respectively, bringing the total
travel expense to $4800 for Level 1 and $8800 for Level 2.
Equipment preparation and freight charges are estimated at $200 and
$1000, respectively, for Levels 1 and 2.
The cost of reporting results is estimated at $250 for each level,
assuming that 40 man-hours of senior professional time are required (the
equivalent of $1500) along with an additional $1000 of computation time.
A summation of the three aforementioned costs for each assessment phase
yields total additional costs of $7500 for Level 1 and $12,300 for Level 2.
ASSESSMENT COSTS FOR GENERIC FBC PROCESSES
The total costs of Level 1 and Level 2 assessment are presented in
Table 32 for each generic process category. These values have been
calculated by multiplying the sampling plus analysis unit cost for each
stream (or sample) type by the number of streams sampled of that type,
summing the resulting products, and adding on the additional costs described
earlier.
It should be noted that the total cost estimates reflect the exclusions
and the Level 2 assumptions discussed in the introduction to this chapter.
The Level 1 and Level 2 assessment costs for process categories
I through III are $21.6 K and $212.6 K, respectively, while for Category IV
values of $43.1 K and $377.4 K have been estimated.
255
-------
TABLE 31. TOTAL ASSESSMENT COSTS FOR GENERIC FBC PROCESSES
STREAM
TYPE
Ducted Gas
(particulates)
Ducted Gas
(gaseous
components)
Liquid
Liquid (high
solids content)
or '"Slurry"
Solid
NUMBER OF SAMPLED
STREAMS
CATEGORIES
I-III
1
1
1
2
6
CATEGORY
IV
3
3
1
3
7
UNIT COST* PER STREAM
(103$)
LEVEL 1
2.670
.888
.952
1.702
1.032
LEVEL 2
53.000
12.975
7.875
14.175
16.675
TOTAL COSTS
CATEGORIES I-III (103$)
LEVEL 1
2.670
.888
.952
3.404
6.192
LEVEL 2
53.000
12.975
7.875
28.350
100.050
TOTAL COSTS
CATEGORY IV (103$)
LEVEL 1
8.010
2.664
.952
5.106
7.224
LEVEL 2
159.000
38.925
7.875
42.525
116.725
rss
*unit cost is sum of site preparation,
sampling and analysis costs.
Sums
Additional Costs
TOTALS
14.106
7.5
21.606
200.250
12.3
212.550
35.582
7.5
43.082
360.050
12.3
377.350
-------
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275
-------
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APPENDIX
,COMPENDIUM OF SAMPLING AND ANALYTICAL METHOD OPTIONS
This appendix is a compilation of multi-media sampling and analytical
method,, options, and their .associated characteristics, that may have applica-
tion in the environmental assessment of FBC and other technologies. The
options considered range from Federal Register methods through new techniques
presently under" development., To .conveniently display the large volume of
material included and to simplify comparison of the various techniques, a
tabular presentation is used.
The intent here is to summarize pertinent characteristics, advantages,
and disadvantages of each method rather'than to present detailed procedures.
(Additional data may be found, in the references provided). Each option is,
in addition, classified as being suitable for" Level 1 and/or Level 2
application. ...*',-•
•f,
It should-be noted that the methods recommended in Chapter 3 for the
Level 1 and Level 2 assessment of EEC systems have been seTected from the pre-
sent compilation.
In the following tables, method options for sampling are presented accord-
ing to sample type, as indicated below:
Particulates (Table A-l)
Gases, (table A-2)
Liquids (Table A-3)
Solids ; (Table A-4)'
Air-borne Fugitives (Table A-5)
Analytical method options are delineated by major analysis area as follows:
Inorganic gas analysis (Table A-6)
Organic analysis .(Table A-7)
Elemental' analysis (Tables A-8 through A-15)
Anion ana-lysis (Table A-16)
Standard water analysis (Table A-17)
Fuel analysis (Table A-18)
Physical characterization
:of solids (Table A-19)
In addition, multi-media flow measurement options are presented in
Table A-20. .
A-l
-------
TABLE A-l. METHOD OPTIONS FOR PARTICULATE SAMPLING
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
I.
Total concen- '
tratlon and mass
emission. Low'
sample rate.
EPA
Method 5
116, 281,
32
ASTM
D2928-71
13.8,
12
(a) More or less recognized nationally as the
standard method for testing.-
(b) Utilizes reasonably defendable sampling
point traverse system based on flow disturbance
(EPA Methods 1," 2) .• ,.::
(c) Simultaneous measurement of moisture
(EPA Method "4) to give on-line isokinetic
sampling, conditions". '
(d) Utilization-of cyclone as a pre-fliter
allows sampling in high dust loading and
moisture laden, streams. . '
(e) An in-stack impactor. can be added to the
probe for particle size measurement.
(f) The method attempts to control the
temperature of the dust laden gas sample
and employs in-line glass condensers; thus
slight adaptations would allow the collection
of"volatile organics and Inorganics without
contamination.
(a) Less cumbersome due to fewer simultane-
ous operating systems than EPA Method 5.
(b) Simpler probe and support system since
nonheated and no simultaneous measurement of
velocity.
(c) See (a) in EPA Method 5 above.
(d) Allows discretion relative to sample
collectors and-number of sampling points.
A-2
-------
TABLE A-l (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Fails to measure participate mass in
the stack that can be directly compared with
ambient High-Volume mass. Other chemical
reactions, condensation and evaporation
(sulfate) can change the physical state of
particulate prior to ambient measurement.
(b) The captured particulate is maintained
at an elevated temperature (320°F) for the
duration of the test. This allows re-
evaporation of some volatile constituents.
(c) A manual method requiring field
handling of fragile equipment precisely
positioned and maintained in a hostile
environment.
(d) Under high SO. concentration conditions
(3 percent sulfur fuel), filterable aerosols
may be forced from gaseous SOj, thus intro-
ducing a potential error in measurement (32)
(e) Requires a glass probe up .to a specific
temperature and a probe length which
requires excessive care to prevent breakage.
(a) Separate measurement of sample rate and
velocity under the assumption of Insignifi-
cant change in gas flow rate can produce
error in isokinetic sampling rate.
(b) Allows different collectors (filter
media) depending on sampling conditions,
resulting in a varying collection efficiency,
particularly with fine particles (<3um).
(c) Allows considerable discretion relative
to number of sample points in larger ducts.
(d) Care required to prevent condensate
(unheated. probe) from flowing back into
filter during handling.
(e) Generally allows more discretion to
the user of the method than EPA Method 5,
which could result in variability in emis-
sion measurements depending on user.
(f) See (c) In EPA Method 5 above.
1 and 2
1 and 2
'The following methods allow the
measurement of both concentration
and mass emission rate using a
sampling rate of less than 2.5 cpm.
Particulate defined as material
collected prior to and on a fiber-
glass filter media at 320°F.
Isokinetic sampling.
Sampling rate is approximately 1.0
scfm.
Method 5 trains are commercially avail-
able from several companies.
Method involves simultaneous determi-
nation of stack gas volumetric flow
rate and particulate mass concen-
tration, which allows calculating
particulate mass emission rate.
Particulate defined as material (dry
plus aerosol) collected in-the-stack
at stack temperature and pressure
after oven drying overnight at 102°C.
Fundamental difference between EPA
Method 5 and ASTM is that the latter
train collects the particulate using
an in-stack thimble and filter while
the EPA train collects the particulate
using an out-of-stack cyclone and
filter.
Isokinetic sampling.
Sampling rate is approximately
1-2 cfm.
Trains are commercially available.
A-3
-------
TABLE A-1 (continued).
INTEREST
AREA
I. (cont.)
METHOD
OPTION
ASTM
D2928-71 (cont.)
ASME
PTC-27
Western
Precipitation
WP-50
Los Angeles
County
San Francisco Bay
Area
B.C.U.R.A.
REFERENCES
17
70, 164
70, 164
70, 164
70, 164
METHOD
ADVANTAGES
(a) See, a, c, d, and e in ASTM D2928-71.
(b) Offers comments and observations on many
questions from experience; however, does not
specify exact procedures to be followed under
different circumstances.
A-4
-------
TABLE A-l (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(g) The captured particulate is maintained
at stack conditions longer than would occur
naturally, thus potentially allowing a
change in characteristics as Indicated in
EPA Method 5 (a) above.
(a) See (a), Method 5
(b) Allows considerable discretion relative
to the number of sample points in large
ducts. Number of points depends on range
of velocity at that location with up to 20
points needed in large ducts.
(c) Allows different collectors (cloth
bags, paper or alundum thimbles) which re-
sults in a varying collection efficiency
depending on particle size.
(d) Farticlessmaller than 1 micron are not
sampled by definition.
1 and 2
Farticulate defined as "dust". Gas-
borne solid matter larger than l(im
(micron) mean diameter collected in
or out of the stack.
Minimum tip diameter of 1/4 inch.
Isokinetic sampling.
10 minute sampling at each point and
2 circuits of the points.
The collection efficiency is stated to
be 99.0 percent for size of dust en-
countered.
A-5
-------
TABLE A-l (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
II.
Size distri-
bution.
Low sampling
rate; in-sltu
impactors.
Anderson Models II
and III
207, 284
283, 285,
22
University
Washington
Mark III
Monsanto Brink
207, 284,
283, 285,
237
207, 284,
283, 285,
52
Environmental
Research
Corporation
TAG-
207
(a) Extensive data collected by users on many
source types allows relative comparison of
data.
(b) Fits standard particulate sampling
equipment.
(c) Allows isokinetic sampling by changing
inlet nozzle diameter.
(d) Stainless steel construction allows in-
sertion into high temperature gas streams.
(e) Since EPA has not adopted a size distri-
bution method (not a part of existing emission
or ambient standards), this impactor, and the
following ones have more or less been adopted
by the testing community.
(f) Commercially available.
(g) Options Include pre-separator glass fiber
substrates. (13) A backup filter can be
added.
(h) A calibrated, modified pre-separator is
available for unit. (13)
A-6
-------
TABLE A-l (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
v LEVEL
REMARKS
(a) Reported particle bounce off and re-
entrainment. Upper limit to approximately
10 m/sec to prevent this (285).
(b) Tends to overload when used in higher^;.
particulate loading situations (e.g.,
control device inlet).
(c) Electrostatic effects on bare plates
may be substantial (285).
(d) Collection plates are massive relative
to material collected, resulting in slight
loss of sensitivity. Substrates are avail-
able, but sulfate uptake on substrate may
cause error (207, 285).
(e) Cannot be used for isokinetic total
mass measurement at different duct cross-
section velocity points since it must be
maintained at constant velocity.
(f) Lacks good calibration under conditions
appropriate for field sampling (202).
(g) Requires "immediate" weighing after
24 hours dessication to prevent loss (283).
(h) Due to size, frequently cannot be
located in gas flow.
(a) Sec (a), (b), (c), (d), (e), and (h)
for Anderson.
(b) Built-in filter holder.
(a) Cannot be easily added to a mass
sampling train.
(b) Requires modification for in-stack use.
(c) Low sample rate requires very long
periods to obtain a sample in low loading
situations.
(d) Due to low flow rate and minimum
.sample tip diameter, often cannot sample
isokinetlcally.
(e) See (b), (c), (e), (f), and (h) for
Anderson.
1 and 2
1 and 2
1 and 2
The following presents a discussion of
impactors. They are devices rather
than methods per se. Their use in
conjunction with mass sampling equip-
ment allows determination of particle
size distribution by mass, or aero-
dynamic size distribution.
Samples at less than 1.0 cfm.
Separates 0.3 to 20 microns with 9
collection plates with multi-jets.
Wall losses may explain part of the
difference between EPA Method 5 mass
emission and impactor measurements
(284).
Generally, impactors are very sensi-
tive to overloading. The sample
duration must be carefully determined
depending on mass loading in the gas
stream.
Impactors, when mounted outside the
stack, may be inaccurate due to probe
wall losses (207)..
Generally, impactors rely on theory
of impaction developed by Rantz and
Wong (246).
Samples at less than 1.2 cfm.
Separates 0.2 to 20 microns with 8
stages with multi-jets.
Samples at approximately 0.1 to 0.25
cfm.
Separates 0.3 to 3 microns with
5 stages.
A sillcone grease substrate has been
used expensively with this unit to
prevent re-entrainment. Grease
blowoff, however, can occur at
velocities greater than 65 m/sec (284).
Very similar to Anderson unit with
appropriate advantages and dis-
advantages .
A-7
-------
TABLE A-l (continued).
INTEREST
AREA
II. (cont.)
III.
Size distri-
bution.
Low sample rate
cyclones.
IV.
Size distri-
bution.
High sample rate
cyclones.
METHOD
OPTION
MRI
Model 1502
Impactor
SRI
Chang T2A
SRI 5-1
SRI
Aerotherm
H.V.S.S.
REFERENCES
305
285
285, 308,
306
METHOD
ADVANTAGES
(a) A cyclone system allows the collection of
significantly more mass for analysis by the
appropriate size fraction.
(b) Cyclone performance is independent of
orientation.
(c) An in-stack system that can be used In
6- inch ports.
(d) Can be added to a typical, commercially
available test train to obtain the sample.
(e) Cyclones have been calibrated using
laboratory aerosols.
(f) Stainless steel construction allows high
temperature sampling.
(a) A 3 cyclone sizing system that is added
to the probe of a commercially available
isoklnetic "Method 5 Type" particulate sampler.
(b) A high flow rate sampling system that take:
less time per run to obtain sufficient mass of
sample for physical, chemical, and biological
characterization.
A-8
-------
TABLE A-l (continued):
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) ,A cyclone ""cut" point is directly
dependent on sample flow rate. Thus, a
constant rate is. required to maintain
calibration. Isokinetic sampling requires
.changing train characteristics to maintain"
constant flow rate (i.ei ,'iprobe tip dia-
meter or stack sample points for, each
significant change in velocity).
;(b) Extreme care required' in cleaning
cyclones^ and totally removing'the sample.
Difficult to visually determine whether
'all the sample has been removed from
hidden corners.of cyclones.
(c) , Not, commercially available yet.
(d) Due to practical handling problems in
changing probe tips at each traverse point
in a stack with .varying .velocity profile,
it is difficult to^obtain"total mass
emission rate and size distribution with
this system.
(a) In its current configuration, the.
first cyclone (<10um) is rather large and
cumbersome' for typical stack testing.
(b) This state-of-the-art experimental
system looks promising;, however, it
requires additional-calibration and
refinement to avoid excessive wall losses.
1 and 2
1 and 2
Three cyclone arrangement with cut
points of approximately 0.5um, 0.9pm,
and 2.6fim and a flow rate of 1 acfm
with particle density of 1.35 gm/cm3.
A backup filter is also used.
Uses 10 different nozzles to allow
isokinetic sampling for stack
velocities between 10 and 100 feet
per second.
This sampling system is not a method
per se; rather, it is an experimental
assembly of particulate sizing
components (cyclones) designed to
provide data of interest.
The system has not been adopted by
EPA.
Three cyclone arrangement with cuts
to provide (1) <10jim, (2) 3-10^tm,
and (3) l-3um, at 5.0 scfm, with
capacity for collection of large
quantities.
This is a state-of-the-art experi-
mentally developed system that is
not a method per se.
The 3 cyclones are being developed
by IERL-EPA as a part of a combined
high sample rate particulate system
("High Volume Sampling System") (306).
A-9
-------
TABLE A-l (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
V.
Particulate .
sulfate
concentration,
mass emissions,
and size distri-
bution.
EPA
Method 8
305, 116
EPA
Aerotherm
H.V.S.S.
305
MRI
Model 1502
Impactor
305
(a) This is one of the 'reference methods for
mist sampling.
(b) Utilizes reasonably defendable sampling
point traverse system based on flow dis-
turbance. (EPA Methods 1 and 2.)
(c) Simultaneous measurement of moisture (EPA
Method 4) and- velocity -(EPA Methods 1 and 2) to
give data validation of ispkinetic sampling.
(d) Proved to be the "most efficient in the
pilot studies in the field" (305). '
(e) Probably, the best method for adaptation
and ultimate application as sulfate • sampling
system.
(f) When used to traverse the stack, will
provide both concentration .and emission data.
(a) A high volume sampling system (5 acfm)
very similar to the EPA Method 5 train.
(b) Stainless steel and lexan construction
with inside of filter housing coated >with
teflon.
(c) Since the filter is operated hot,
moisture does not plug the filter.
(d) See (b), (c) , and (f) above.
(a) Provides particle size distribution data
in addition to sulfate concentration data
simultaneously.
(b) This unit, during the study, "provided
excellent results on sulfate particle size
distribution" (305).
A-IO
-------
TABLE A-l (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY ''
LEVEL
REMARKS
(a) • Probably fails to measure sulfate in
the stack that can ibe directly compared to
ambient sulfate measurements due to
evaporation/condensation processes.
(b) -'JThe -impinger solution (isopropanol)
was found to absorb'SC^, thus rendering
sulfate data as suspect.
(c) Inadequate for ammonium compounds.
(d) New filter material needed with low
sulfate blank.,
(e) The-ambient temperature filter allows
blowthro'ugh of participate (305).
(a) See (a), (c), and (d) above.
(b) The "pre-cooler" scrubs S02-
'1 and 2
1 and 2
.Characteristic of impactore in that they
•are calibrated for,only one flow rate.
A traverse cannot be done isokinetically.
1 and 2
Other particulate sampling trains like
those identified in this table can be
used to obtain a sample'for sulfate •••. •
analysis.
Three "particulate type" sampling
trains were investigated in a study
(305) to determine the utility of each
for sampling sulfate particulate
matter emissions from flue gas de-
sulfurization control systems.
This method is specifically for
mist sampling. As with any selective
method, its use for other purposes,
such as sulfate sampling, will require
adaptation. The. disadvantages cited
should be viewed as recommended
adaptations as opposed to weaknesses
of the method.
the train was essentially set up in a
particulate collection operating mode,
that is, with water in the impingers
for ultimate collection of sulfates.
The Meteorology Research, Inc. (MRI)
device is a cascade impactor designed
for particulate size distribution. It
is used here to determine ability to
size particulate and aerosol sulfates.
The train consisted of the Aerotherm
probe, the MRI impactor in the heated
cyclone-filter oven and then the
Aerotherm coolers, etc.
The MRI unit was maintained at stack
temperature.
A-ll
-------
TABLE A-l (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
VI.
Trace inorganic
material
concentration and
'mass emissions.
EPA
Aerotherm
H.V.S.S.
307
EPA
Method 5
116, 100
238
(a) Basically relies on components of a
commercially available sampling system.
(b) The unit Is very similar to EPA
Method 5. Thus, it may be accepted as a
reference In the future.
(c) See advantages ,(bJ > (c)', (d), and ~(e)" ' v
under EPA Method 5. (Section I o'f .'the table.')
(d) High sampling rate (to 6 scfm).
(e) Impingers are- rugged lexam construction.
(f) Capable of horizontal and vertical
sampling.
(g) Well-packaged unit for shipment.
(h) Appears to offer an effective ['sampling
system relatively free of contaminating
components and capable of collecting both
vaporous (or fine participate As, Hg, Sc, Sb,
F, Cl), and non-volative trace materials (Ba,
B, Be, Ca, Cd, Cn, Cr, Cu, Mn, Ni, N03, Pb,
P04, S, S04, Sr, V, Zn).
(i) Since it relies on a basic commercial
system, it can be adapted to provide samples
by size fraction.
(a) Relies on an established method of
measuring mass concentration and emissions.
(b) Could be adapted to provide samples by
size fraction.
(c) Extensive data have: been collected using
this method. The number and type of Inorganic
materials varys.
(d) Unofficial procedures of sample removed
and cleanup have been drafted for inhouse and
contractor use that require nitric .acid clean-
Ing of portions of ,the sample train and storage
bottles. (35)
A-12
-------
TABLE A-l (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Stainless steel connectors are possible
source of Hi and Cr sample contamination.
(b) Heated teflon (filter housing coating)
may cause particulate sample alteration.
(c) Time consuming to clean gas cooling
coils between runs. -•
(d) Larger and heavier than standard
particulate testing equipment.
(e) Due to size and weight, difficult for
traversing.
({) The Kapton probe liner film appears to
require extreme care and patience in insert-
ing into the probe.
(g) Ammonium persulfate impinger solution
must be prepared Immediately prior to a
test run.
(a) Potential sample contamination from
being exposed to stainless steel probe tip
and probe.
(b) High and variable background con-
centration in filter media (typically
fiberglass), depending on Inorganic material
(c) Fine particulate and vaporous inorganic
material collection efficiency is variable
and generally unknown.
The following presents results of a
study to "present procedures and
methods for sampling and analysis--
for trace Inorganic materials" (307).
The basic train consists of an Aero-
therm high-volume sampler with a poly-
mer film probe liner, ultraclean
filter material and a special se-
quential exidative scrubbing solution
for the inpingers.
NOTE: Other non-contaminating
sampling systems, including an
adopted.version of EPA Method 5,
may be employed for trace material
sampling, in addition to this unit.
Not a method of sampling trace
Inorganic material per se. Just
the application of best available
tools.
NOTE: Other Method 5 type sampling
trains can be used. The materials
of construction govern the type and
amount of potential contamination.
A-13
-------
TABLE A-l (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
VI. (cont.)
EPA
Method 104
(Beryllium)
115
EPA
Method 105
(Mercury)
SRI MA #6
(Mercury)
115
Gold
Amalgamation
(Mercury)
175
SRI MA #5
(Selenium)
72
SRI MA #3
(Lead)
72
(a) Essentially the same train as Method 5.
(b) Isokinetic sampling.
(c) Has been extensively tested by EPA.
(d) Allows some flexibility for filter
location in train to account for higher
temperature sources.
(a) Essentially the same train as Method 5.
(b) Isokinetic sampling for accuracy.
(a) Essentially uses the Method 5 type train
to isokinetically collect particulates and
gaseous Hg.
(b) Accurate for concentrations up to 0.05
0.05 (ig/ft3.
(c) Excellent method writeup addressing
accuracy, precision, stability, etc.
(d) Precision at 5% for 100 ft3 sample.
(a) Associated accuracy of Method 5 train to
measure total pollutant emissions isokinetical-
iy-
(b) More or less has replaced EPA Mthood 105
for high SO- concentration streams.
(a) Well defined and specified procedures.
(b) Analytical accuracy at ±14% up to
2Kg/ft.
(c) Associated accuracy and acceptance of
Method 3 type train.
(a) Well defined and specified procedures
(b) Associated accuracy and acceptance of
Method 5 type train.
(c) Routine sampling period of approximately
2 hours.
A-14
-------
TABLE A-l (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Required using millipore filter which
is relatively more 'difficult to handle.
(b) Requires .extensive acid washing of
train components prior to sampling.
(c) See EPA Method 5 for other dis-
advantages .
(a) Serious interference in high con-
centration SC>2 gas streams (loss 0 IC1).
(a) Designed for chlpralkali plants and
non-ferrous metal smelters.
(b) The sample ..volume should be limited to
10 ft3 when sampling high concentration
(7%) S02 sources.
(c) Needs additional field testing.
(a) Maximum sampling period of 5-10
minutes (method too .sensitive).
(b) Procedure requires 'further refinement.
(c) Requires several tests to first find
the range of Hg concentration and then the
actual concentration. '
(d) Can not ship samples back to lab for
ana lysis .-
(a) Method requires further field testing.
(b) Interference from hypochloride or
Sn (II) and possibly nitrate ion in excess.
(c) Unused filter should be saved for
blank determination.
(d) Leaching of filter may be required
prior to use.
(a) Organic matter can interfere with Pb
analysis—can be removed with low'temperature
activated oxgen ashing.
(b) Analyze blank filters for Pb.
(c) Requires further field testing.
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
EPA Methods 103 (not Included in this
table) and 104 are specific methods
for Beryllium sampling and analysis
to determine compliance with EPA
hazardous emission standards.
Method 103 is a screening method that
does require full duct traverse
sampling. Method 104 is a full duct
traverse method.
This method is not recommended for Hg
sampling and analysis.
An adapted version of EPA Method 105
consisting of a probe, pyrolysis
furnace, solid scrubber, and impingers
containing Id.
Applicable for particulate and
gaseous Hg.
A modified version of EPA Method 5
designed to collect particulate and
gaseous Hg by utilizing two impingers
containing 10 grams of gold chips to
collect Mg vapor as an amalgam.
The second amalgamator is a backup
to the first.
A modified version of EPA Method 5
designed to collect particulate and
gaseous selenium (excluding H.Se).
A modified version of EPA Method 5
designed to collect particulate and
gaseous lead.
AA analysis.
Use glass fiber filter for nitric acid
extraction.
Nitric acid in impingers.
A-.I5
-------
TABLE A-l (continued).
INTEREST
AREA
VI. (cont.)
METHOD
OPTION
SRI MA #4
(Cadmium)
SRI MA #1
(Asbestos)
REFERENCES
72
72
METHOD
ADVANTAGES
(a) Well defined and specified procedures.
(b) Associated accuracy and. .acceptance of
Method 5 type train.
(c) Routine sampling period of approximately
2 hours.
(a) Well defined and specified procedures
with backup references.
(b) Can use low temperature oxidation of some
interfering (i.e., visual confusion) fibers
and then recollect on another nuclepore filter.
(c) Allows preparation of photomicrograph for
visual characterization of genrral particulate
sample.
A-16
-------
TABLE A-l (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Several interferences overcome by
adding EDTA.
(b) Potential important interference from
NaCl.
(c) Requires further field testing.
(d) Leaching of filter required.
(a) At least 10% of collected material
must be chrsotile asbestos.
(b) Very difficult to identify specific
fibers and is a very tedious and time
consuming task to manually-visually perform
the work.
(c) Major errors arise from particulate
counting—experienced counter should keep
errors <10%.
(d) Very difficult to transfer particles
to microscope grid for counting.
(e) Trial and error in obtaining optimum
amount of sample.
1 and 2
A modified version of EPA Method 5
designed to collect particulate and
gaseous cadmium.
1 and 2
Particulate collected on a nuclepore
membrane filter at rate of 0.1 cfm.
Collected materials transferred to
electron microscope grid for visual
identification, sizing and counting.
Use standard reference samples of
asbestos from the International Union
Against Cancer (IUAC).
A-17
-------
TABLE A-l (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
VII.
Total
concentration
and mass
emission.
High sample rate.
EPA
Aerotherm
H.V.S.S.
190, 1
Rader
244, 114,
48
(a) Commercially available.
(b) Developed under funding from EPA and
used as a starting system to further develop
refined sampling systems for sulfates,
organics, particle size distribution, and
trace inorganics, as previously discussed
in this table. It has also been adapted to
simultaneously collect particulate mass
samples by three cut sizes (cyclones)
followed by total adsorption of volatile
organics, and a collector for trace elements;
thus encompassing in one sampling system, a
refined method of collecting bast amounts of
data during one isokinetic measurement. (It
should be noted that, mass emissions based on
traversing is still a limitation when the
3 cyclones are used.)
(c) Highly researched and tested unit is well
constructed.
(d) Wide range of optional equipment avail-
able.
(a) Samples at a very high flow rate (10-
20 cfm).
(b) Can be hand held.
(c) Uses the same filter as Is used in ambient
high-volume samplers which is the reference
EPA ambient method.
(d) Has been adopted as a standard method for
sampling cyclones in Oregon (49).
(e) Due to the higher sample rate, requires
significantly less time to obtain a sample.
This may be Important in very low concen-
tration sources.
(f) Has been automated to electronically total
the sample flow and maintain the unit at
isokinetic conditions. Thus, it is the only
commercially available automatic isokinetic
sampler.
A-18
-------
TABLE A-l (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY"
LEVEL
REMARKS
(a) Relatively expensive compared to
routine Method 5 type equipment (approxi-
mately $9000 versus $4000).
(b) the equipment is much heavier and
harder to handle.
(c) Stainless steel construction can be
a source of contamination for some tests.
(d) Uses Lexan tmpingers Instead of glass
(glass is available as an option).•
(e) Time .consuming' to clean cooling coils
(prior, .to Implngers for condensation
efficiency) if impinger wash is desired.
'This unit essentially meets the
specification of EPA Method 5 with
the exception that the probe and
filter holder are constructed of
stainless steel instead of glass
and the flow rate is much higher.
The unit is currently being
evaluated by EPA for approximate
equivalency and a statement is
expected by mid-1976.
(a) Can only be used in ambient temper-
ature sources.
(b) Saturated gas streams can easily plug
the filter.
(c) Oversized ports are required for
in-stack use.
(d) The unit is not directly comparable
to EPA Method 5.
This unit was recently improved and
is now automatic. It is primarily
designed to sample ambient temperature
sources since it does not contain
impingers for moisture measurement.
This is not a method per se. It is
a tool to sample gas streams for
partlculates.
A-19
-------
TABLE A-l (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
VIII.
Simultaneous
organic and
trace Inorganic
materials,
total concen-
tration,
size distribution
SASS
(a) In one sampling system an Isokinetic
particulate sample is classified into three
calibrated size fractions in which each can '
be analyzed for organics and trace inorganic
materials; non-condensed organics, including
POM pollutants, are collected on porous poly-
mer adsorbent, and; fine particulates and
volatile inorganic specias (e.g., Hg) are
collected In a glass implnger train.
(b) Most, If not all-, of the system components
are commercial available (1, 2).
(c) Highly researched and extensively funded
to develop a unit approaching "best available,"
utilizing space age technology.
(d) The three sizing cyclones will handle
inlet and outlet particulate size from
normally encountered control equipment.
(e) High-volume sample rate will allow sample
collection in shorter period.
A-20
-------
TABLE A-l (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) The system is very expensive
($15,000-$25,000).
(b) This constant flow rate system is not
designed to allow.continuous isokinetic
traversing of a duct or stack.
(c) Due to (b) above, selection of a
single point in the stack for a repre-
sentative sample is required.
(d) The system may still require refine-
ments to condense moisture without
excessive pressure drop.
(e) Currently two pumps due to pressure
drop.through the many components are
required.
(f) More complex temperature and moisture
regulation due to high flow rate (up to
6 cfm) is required.
(g) This new system has not been
extensively field tested. EPA is in
the process of awarding a contract to
have it tested.
1 and 2
This system is a state-of-the-art,
highly sophisticated, manual-type
particulate sampling train essentially
based on the HVSS system.
It is expected to be commercially
available in mid-1976.
An Isokinetic traverse can be perform-
ed by changing nozzles at each
traverse point.
Another technique involves locating a
sampling site where traverse point
velocities do not vary more than 10%
from a mean volume (i.e., flat profile)
This eliminates the need for nozzle
changing and still provides essential-
ly isokinetic conditions.
A third option combines aspects of the
above two options (see text).
A-21
-------
TABLE A-l (continued).
INTEREST
AREA
IX.
Total
Concentration and
size distri-
bution.
High temperature,
high pressure
systems
(HTHP) .
METHOD
OPTION
HTHP
(Aerotherm)
REFERENCES
METHOD
ADVANTAGES
'
(a) Satisfies safety concerns.
(b) Will traverse 50 Inches mechanically
against high pressure In 2-1/2 minutes, and
has an automatic brake.
(c) Utilizes a "scalping" cyclone In-situ.
(d) Secondary participate collection is by
a Mark III University of Washington Impactor
which also provides size distribution data.
(See earlier discussion of Mark III.)
(e) Utilizes complex temperature — controlling
coolant system that appears to be well designed
and allows for thermal expansion yet properly
colls the sample.
A-22
-------
TABLE A-l (concluded).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Just a design at this stage that needs
extensive field testing.
(b) Not commercially available.
(c) Extremely expensive.
A new class of particulate and gaseous
sampling instrumentation is being
developed to handle measurement
problems associated with new energy
related processes, including coal
gasification, combined cycle power
plants, and fluidlzed bed combustion.
High temperature—high pressure
involves'temperatures up to 2000°F
and pressures up to 100 atmospheres.
This write-up presents preliminary
information from a project funded
by EPA to develop HTHP sampling
instrumentation.
This system is scheduled to be field
demonstrated at the Exxon "Mini-plant"
at Linden, N.J.
A-23
-------
TABLE A-2. METHOD OPTIONS FOR GAS SAMPLING
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
I.
Sample
Acquisition and
Conditioning
Systems for
Continuous
Instrumental
Analysis
Acquisition:
Probe Location
Performance
Specification
No. 2
114, 120,
107, 77
Stratification
Investigation.
Pollutant Ratio
Concept
331, 332,
55, 77
(a) Written to provide guidance for both
extractive and non-extractive (in-situ)
sampling.
(b) The number of sample points and location
is dependent on the upstream distance to an
air in-leakage device or measured stratifi-
cation profile.
(c) Represents the first regulatory agency
attempt to define sampling techniques for
potentially stratified gases.
(d) The total sampling and analysis system
has been demonstrated in place to be
comparable with reference methods.
(e) Based on extensive field testing.
(a) Preferred over multi-point sample
extraction.(331).
(b) Simple system relying on a single probe;
proportional sampling is now required.
(c) Since spatial average concentrations
agree with flow-proportional average con-
centrations, then concentration and flow data
can be taken independently and still be used
to accurately determine species mass emissions
(55).
(d) Can be applied to both circular and
rectangular ducts.
A-24
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Tends to specify desirable character-
istics of results rather than provide clear
cut examples and procedures of obtaining
those results. . ,
(b) Primarily designed for S02 and NOx from
power plant combustion sources with known
stratification causing processes (e.g.,
pre-heater).
(c) Does not address merging of two or •
more different gas streams.
(d) Specifies sampling at "average" con-
centration yet does not'fully'define term.
(e) Requires "multi-point" probe in one
instance yet fails to-specify number of
points. , • •
(a) Consists of a simplified field tested
concept, that is incomplete as a method
which can,, be applied to other general
situations. ... , ,
Acquisition and conditioning of stack
gases by removing partlculate and ..
moisture and controlling sample temper'
ature is a necessary step prior to
sample sensing (analysis) using most
continuous monitoring Instruments that
require sample extraction and trans-
port to the instrument. Instruments
have been developed to monitor
selected gases in-situ, in the stack
(non-extractive). However, they do
not monitor the wide range of gases of
interest in fluidized bed combustion.
They are discussed herein by specific
gas monitored. Manual sampling
methods Incorporate conditioning as an
integral part of the sample train.
Proper, non-interfering sample acqui-
sition and conditioning appears to be
the weakest link in the system to
continuously monitor many pollutant
gases of interst (106).
Continuous stack gas monitoring sys-
tems have traditionally consisted of
a single in-stack 'filter (single point
sampling): for sample extraction and
transport to an analytical instru-
ment. If the one sample point in the
duct cross-section is sufficiently
downstream from a gas mixing device
such as a fan, the single point will
be representative. If gas stratifi-
cation exists, several sample points
in the cross-section may be sampled
simultaneously or a different location
in the ductwork may be selected.
Performance Specification No. 2 (PS2)
allows single point, multi-point,
cross-stack, etc., depending on
distance downstream from a distur-
bance and existence of stratification.
Emissions of the tracer gas selected
should be theoretically predictable
to enable comparison with measured
emissions (i.e., C02 for combustion
processes)..
Several recent extensive studies have
been conducted to determine the extent
of gas stratification and the effect
on measurement techniques (331, 332,
55, 77).
Some of the measurement techniques In-
clude static pressure null probes,
thermal null probes, several contlnu-
ous-automatic sample rate adjustment
A-25
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
Acquisition:
Probe Location
(cont.)
Pollutant Ratio
Concept, (cont.)
Stratification
Investigation
Row Average
Concept
55, 77,
331, 332,
309
Stratification
Investigation.
"Inner 507."
Concept
77
[a) Has been field tested and results look
promising (55).
[b) Local duct geometry can usually be examined
to select a row that will be In the direction of
highest stratification (for which the technique
works best). .
[c) Presents a specific description of the
nethod, thus eliminating different inter- i,
retations of the techniques and subsequently,
non-comparable results (55).
[d) Reported .higher accuracy, and hardware
simplicity (55).
(e) The row sample points can easily.-be In-
corporated In a single multi-port probe. •. •
'f) An Ellison Annubar, which Is a commercial-
.y available multi-port probe,can be used-(309).
[a) Based on extensive .field testing of a broad
representative group of boilers with characteris'
tic duct-stack configurations.
[b) Considerably advances, the 'State of knowl-
edge of actual stratification conditions.
Narrows the cross-sectional area of concern to
the inner 507..
A-26
-------
TABLEI; A-2 (continued).
METHOD
DISADVANTAGES
'APPLICABLE
STRATEGY
LEVEL
REMARKS
.(a) Main problem is a lack of predictability
(b) Requires preliminary survey tra'versing
to select optimum system.
(c) System hardware is not commercially
available.
(d) , Requires additional field testing.
(e) Care"requlred in probe (multi-point)
port sizing to insure desired flow into
probe.
(a) Still does hot provide a clear method
of conducting a stratification investigation
and subsequent selection of a valid number
of representative sample points.
devices, multi-point probe arrays, ann-
ubars, and constantly traversing probes
(332). An extensive review of these
techniques is beyond the scope of this
study.
Monitoring at the stack rather than in
a duct is preferred for uniform
conditioning (77).
One investigator (331) recommended the
discussed pollutant ratio technique.
It should be noted that extensive test-
ing and development is 'still required
to present commercially marketable
reference method type samplers for
application in a stratified gas stream.
Each system must be designed for a
specific location due to site condition
variability.
See above for general comments on
stratification investigations.
The row average technique was initially
developed as a velocity (flow rate)
ne asurement technique. It consists of
extracting continuous samples from
several selected points (ports) on a
particular traverse or "row" across
the cross-section.
Primarily for rectangular ducts.
This writeup discusses findings of an
entensive field evaluation of gas
stratification (77). Conclusions inclu-
ded: (1) sampling confined to travers-
ing the inner 50% of the duct will al-
low a determination of the flue gas
composition which is very close to the
actual composition; (2) single point
sampling is inappropriate for obtaining
representative gas samples; (3) recom-
mended multi-point sampling within the
A-27
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
Acquisition:
Probe Location
(cont.)
"Inner 507."
Concept
(cont.)
Stratification
Investigation.
"Tangential"
Concept
309
Acquisition:
Partlculate
Separation
In-Stack, On-Line
Filtering
106, 215,
77, 231,
211
(a) Follows directly from accepted (Method 5)
procedures used for manual sampling.
(b) Flow-proportional sampling Is not
required; same sample rate at each selected.
point.
(a) Most commonly applied method of removing
particulate using a filter in the stack.
(b) Extensive experience for process monitor-
ing in the larger process industries.
(c) Typically ^stainless steel or .ceramic
construction; thus, resistant and reasonably
inert relative to sample contamination.
(d) Structurally strong to withstand vacuum
sampling and high pressure blowback at high
temperature.
(e) Commercially available with varying
porosity to provide necessary particulate
removel without high pressure drop.
(f) Can be installed in a heated chamber
outside the stack to provide access (less
desirable due to particulate buildup in
probe).
(g) Multiple in-stack units can be designed-.
to provide simulated traverse sampling.
A-28
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Still requires traversing Investi-
gation and then design and selection of a
representative number of sample points.
(a) The sample Is exposed to a more
concentrated partlculate cake on the
filter surface that could result In
Increased losses by adsorption.
(b) Requires additional plumbing and
controls to provide blowback gases.
(c) Care required to prevent breaking
ceramic filters.
(d) Requires backup instrument air
compressors with associated cleaners
for secured continuous operation.
1 and 2
inner 50% of the duct; each point
representing an equal area (a minimum
of 3 points).
Seven different fossil fuel-fired
utility boilers were tested.
Results of "in-stack" tests as opposed
to "in-duct" tests indicate that stack
conditions are extremely uniform and
are preferred (77).
S02, NO, CC>2, 02 concentration
profiles as well as velocity and
temperature profiles were obtained.
Primarily for multi-point gas sampling
in a circular duct or stack.
Consists of a technique of properly
selecting a number of points and the
associated location from which
continuous gas samples may be
extracted.
Basically consists of a simple probe
with an attached sintered filter and
a compressed gas (dry plant instru-
ment air) system for timed blowback
to periodically clean the filter of
particulate buildup. The entire gas
sample flow is delivered to the
analysis instrument, thus making it
"on-line" filter.
This system is essentially the
"external" filtering system described
in (211).
Associated with extractive sampling
systems.
May be applied in the stack to remove
larger partlculate and is frequently
followed with additional filters
(before the instruments) to remove
finer particulate.
A different type of in-stack filter re-
ferred to as the "Internal" system has
been tested (211). This system consists
of a sintered type filter that may be
packed with glass wool, and is es-
sentially the old Alundum Thimble
System, used traditionally to obtain
particulate emission data. This sys-
tem, however, requires manual filter
cleaning since blowback systems would
destroy the glass wool packing and may
not properly "clean" the filter. The
performance period, however, may
approach that of the external filter
A-29
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
Acquisitions:
Partlculate
Separation
(cont.)
Acquisition
Diverted Stream
In-Stack, On-Line
Filtering (cont.)
Large Volume
Subsequent
Splitting
106, 241
Conditioning
Moisture
Control
Dilution
251, 223
Condensation
151, 211,
231
(a) Convenient to install, check, and main-
tain several connected sample lines.
(b) Allows short sample lines to analysis in-
strument and direct access to the filter for
checkout.
(c) The high velocity fan required to deliver
the diverted stream provides excellent mixing
and a uniform sample In the manifold.
(d) Has been extensively used in the process
industry evaluation; thus, various filters,
conditioners, etc., are commercially available
to build the system.
(a) Immediately prevents sulfur oxides from
being exposed to moisture which could result
In losses of sample
(b) Usually results in simultaneous tempera-
ture control of sample gases.
(c) Commercially available probes.
(a) Commercially available and is typically
part of a total system for stack-gas monitor-
ing (100).
(b) A knock out trap condenser is very simple
and inexpensive.
(c) Usually results in simultaneous tempera-
ture control.
A-30
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) An efficient high horse power blower
is required to insure that velocity in pipes
and manifold is high enough to prevent
particulate buildup.
(b) The transfer pipe is reasonably large
( 3 inches plus), thus requiring external
structural support and additional heating
capability. \
(c) Subject to single point (cross-section)
sampling errors due to stratification in
the stack.
(a) Requires large volumes of dry instru-
ment gas which is relatively expensive.
(b) Requires monitoring of the dilution
flow rate for concentration correction.
(c) Generally, a more complicated system
than condensation.
(a) Care and maintenance is required to in-
stall and operate a condenser to prevent
uncontrolled condensation. The condenser
must be tuned relative to the specific stack
moisture conditions to Insure adequate sam-
ple line heating and insulation prior to
condensation. Wintertime wind chill factors
should be considered in designing heating
requirements.
In some applications. The elimi-
nation of backflushing saves cost
and maintenance problems, a definite
plus for this system. .
Basically consists of a piping system
for drawing a high flow, high tempera-
ture, diverted portion of the stack
gas down to a manifold which can in
turn be sampled in a more convenient
manner. The high flow rate prevents
particulate settling and a return line
redeposits the gas stream downstream
from the diverted sample point.
A filtering system similar to that des-
cribed above is still required.
Basically consists of'.adding, under
controlled conditions, dry instrument
gas that mixes with the sample stream
resulting in a lower dew point and
typically lower gas temperature.
The temperature limitations of the
analytical instrument governs the type
of condensation system selected. Like-
wise, the amount of moisture in the
gas stream and the gas dewpoint influ-
ence selection. The simplest conden-
sation option consists of a knockout
trap that is temperature controlled
(between stack temperature and AOO°F
if sample lines are Teflon). The
trap is preferably located outside but
near the stack. The other system in-
volves a refrigeration type unit that
that removes all moisture down to or
below approximately ambient tempera-
ture. The gases are then slightly re-
heated for analysis.
A-31
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
Conditioning
Moisture Control
(cont.)
Permeation
Distillation
234, 77,
211
Desslcatlon
278, 231
211
(a) Commercially available. '
(b) No moving parts or electrical connections;
thus, explosion proof.
(c) Can be mounted horizontally or vertical-
ly when purchased as a coll.
(d) Has been extensively 'applied to sampling
systems associated with auto emissions moni-
toring.
(e) Can be operated under high pressure con-
ditions (to 100 pslg sample pressure).
(f) Reasonable efficiency and capacity to han-
dle high moisture conditions for typical 'samp-
ling systems (up to 6 scfh).
(g) No possibility of sample loss by solution
in liquid condensate.
(a) Commercially available
(b) "Indicators" available to illustrate sat-
uration, thus necessary disposal.
(c) Highly efficient.
A-32
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Requires a continous purge of dry
plant instrument air or N..
(b) Participates and condensable oil va-
pors must be removed prior to drying (oil
mist and vapors degrade the drying ability).
(c) Performance as a function of tempera-
ture has not been fully evaluated. (Norm-
ally operates at ambient.)
(d) May require additional heating of sam-
ple gas to prevent condensation.
(e) Permeation, or sample loss by other
very low concentration gases of interest,
may occur - extensive test information not
available.
(f) Particulate plugging seems to be the
biggest problem (106).
(a) Saturates easily, thus requiring fre-
quent maintenance.
(b) SO. loss on some dessicant materials
has been reported (106).
Consists of a bundle of tubes that are
permeable to water vapor and are en-
closed in a shell. A continuous
purge of either recycled dried gas
product or other dry instrument air
(or N ) removes the permeated water
vapor. The tubes are constructed of
a proprietory material.
Vacuum purge used when sample gas has
5% or more water vapor by volume.
1 and 2
Essentially a granular material that
adsorbs moisture.
A-33
-------
TABLE A-2 (continued) .
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
II.
Acid Gas
Sampling
SO.
EPA
Method 6.
116
EPA
Performance
Specification
No. 2
114,
120, 107
EPA
Method 3
(Integrated Grab)
116
(a) More or less recognized nationally as a
standard method for testing.
(b) Adaptable to different types of sources
with a reasonably wide range of gas concen-
trations, even with high partlculate concen-
trations.
(c) The method Is reasonably explicit regard-
ing exactly where in the process stream or
duct cross-section that sample-will be
collected, the volume required for a sample,
the exact train configuration, and how the
sample will be recovered and stored.
(d) Units are commercially available from
several manufacturers.
(a) The measurement system described (a set
of criteria as opposed to a specific vendor
product) has been field tested on several
processes and has been satisfactorily
xemonstrated.
(b) The system (sampling interface analyzer,
and data recorder) is directly compared in the
stack with the EPA Reference Method (MeChod 6)
prior to acceptance. Thus continuous data can
be compared with batch reference data.
(c) Performance Specifications are provided; .
thus, varying and innovative Instrument
procedure can be used instead of specifying
any one manufacturer's type of instrument.
Both extrative and non-extractive procedures
are allowed.
(d) The system analyzer could be Installed to
service more than one stack source.
(e) The non-extractive system can operate at
relatively high stack temperatures since the
sample does not have to be conditioned for
transport and analysis.
(a) The simplest, most convenient, least time
consuming form of sampling is the grab sample.
In this case the grab is an Integrated sample
over a controlled period of time. The con-
tainer is a flexible inert bag which can be
easily transported to a field location for
Orsat analysis, or, In this case, SC>2 analysis.
A-34
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) A manual method requiring field
handling of fragile equipment (glassware,
motors, pumps, etc.) precisely positioned
and maintained in a frequently hostile
environment.
(b) The method specifies a single point
(in the duct cross-section) sampling
approach. This could result in errors If
gas stratification exists (due to air leak-
age, etc.) even though'sample location
criteria have been satisfied pursuant to
Method 1.
(c) The short test time of the method
(20 minutes for each sample) could result
in inaccurate measurements for processes
that have short term or erratic changes in
SO. concentration.
(a) Frequently relies on manufacturer's
instructions which are too vague.
(b) The weakest part of the extraction
sampling system is the sampling interface.
Theoretically, the zero and span cali-
bration gas should be Inserted Into the
system at the probe tip to determine the
performance of the total system. How-
ever, for practicality it is inserted at •
•a convenient point as close to the
sampling Interface as possible. This can
result in reduced sample (i.e.,'wall)
losses and an inaccurate calibration.
(c) Typically a single point (in the cross-
section) sampling system that could be
seriously Influenced by stratification and
erratic profiles.
1 and 2
(a) Method 3 pulls the sample through the
pump and then discharges Into a bag. In
order to use the system to extract samples
for analysis of gases like S02 which are
not specified in the method, the train
should be evaluated to determine the effect
of the condenser.
The minimum sample time Is 20 minutes
and a minimum volume Is 0.75 standard
ft. . Two samples will constitute one
run, to be collected at 1-hour inter-
vals.
Method yields SO2 concentration which
must be combined with stack gas flow
rate (Method 2) to obtain S02 mass
emission rate.
This continuous measurement system
was developed to allow more or less
continuous observations of the com-
pliance of emissions with applicable
New Source Performance Standards.
This system may well become, with the
corresponding monitoring of gas flow,
a source of data for "Principal
Evidence" regarding compliance with
standards.
Basically requires a sampling system
capable of monitoring emission levels
within 20% with a confidence level of
95%.(116).
This EPA Reference Method for extract-
ing an Integrated or grab sample Is
primarily designated to obtain a
sample for analysis of CC>2, excess air,
and dry molecular weight. In this
case an Orsat analyzer is employed for
concentration measurement good to the
nearest 0.1 percent. It Is identified
here for Level 1 sampling of SC>2 and
other reactive gases-and is a refer-
ence method of "grabbing" a sample.
A-35
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
S02 (cent.)
EPA
Method 3 (cont.)
Detection Tube
196, 198
Hays-Republic
Orsat
Simple
Displacement
Bomb
(ASTM 1605-60)
214
13.6,
323
211.
(b) The sample period can be anywhere from
30 seconds to several hours, depending on
bag size and sample rate.
(c) The system can be easily adapted to
obtain a sufficiently large sample of gas
for analysis of many species (for detection
level work)
(a) This gas sampling and analysis tool Is
probably the simplest, most Inexpensive, and
most convenient system for obtaining approxi-
mate concentration of many gases Including
S02.
(b) A direct reading of the gas concentration
Is obtained.
(c) The sampling Instrument Is light-weight
and easily hand-held.
(a) Contained In a basic Orsat package, thus
providing one Instrument for multiple gases.
(b) Inexpensive.sampling system.
(a) Very simple, inexpensive technique for
obtaining a sample up to 3 liters in size.
(b) Little site preparation necessary.
(c) Reference method for carbon dioxide,
carbon monoxide, methane, oxygen, hydrogen
and nitrogen.
A-36
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(b) Wall losses on the sampling lines and
bag may be significant; however, for
detection as opposed to quantification,
this method is probably the best.
(c) Depending on the gas of interest,
sample loss due to reaction condensation
can occur in the condenser.
(a) By its inherent nature of being quick
(a sample can be obtained in a matter of
minutes), direct reading, etc., the method
is not particularly accurate in repre-
senting an average concentration of the gas
in the stack.
(b) The tool is short and hand-held,
making it difficult ID obtain readings
at large ports with negative pressure
and to get stack gas as opposed to
dilution air.
(c) Many of the tubes for specific gases
have been developed for the mid-
concentration range (for use with person-
nel monitors). Stack concentrations may
exceed the limit of the tubes.
(d) Many of the detection tubes are
subject to interference; thus, judgment
is required in selecting tubes and
evaluating results.
Limited accuracy.
(a) Small sample size.
(b) Sample loss on walls of container.
(c) Analysis for reactive gases must be
performed quickly.
(d) Should not be stored in direct
sunlight.
A typical instrument consists of a
hand pump to obtain a sample of
approximately 100 ml which is drawn
through a small glass tube filled
with an indicating reaction chemical.
The physical length of a discolo-
ration indicates the specific gas
concentration. Specific tubes are
available for 80 or more pollutants.
Shelf life can be extended up to
one or two years by storage at or
below 25°C (198).
Essentially consists of a tube
(similar to detection tubes) where
a sample is drawn through and the
length of a stain indicates the
gas concentration. Can read to
nearest 100 ppm.
Bomb techniques Include air
displacement and evacuated
flask technique.
Can be used to sample high-pressure,
high temperature lines by use of a
water-cooled heat exchanger.
A-37
-------
TABLE A-2 (continued).
INTEREST
AREA
SO- (cont.)
2
METHOD
OPTION
Other
Continuous
Systems
EPA
Method 12
Cross-Stack
In-situ
(Type I)
REFERENCES
117
288, 132
METHOD
ADVANTAGES
(a) Does not require extracting, conditioning,
and transporting the sample.
(b) Involves a unit placed on opposite sides
of stack or duct cross-section path that
measures the Integrated average gas concen-
tration over that "path."
(c) Also measures Co, C02, NO.
(d) Overcomes gas stratification problems
associated with single-point sampling systems
by measuring over a "path" in the stack or
duct cross-section.
(e) The response time is very short and
almost instantaneous (132).
(f) Will probably meet or exceed EPA
continuous monitoring specifications (114).
(g) Insensitive to alignment.
A-38
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Relatively expensive; approximately
$30,000 to $50,000 Installed for multi-gas.
(b) The system Is located entirely on the
stack, requiring service and maintenance on
the stack.
(c) Stack gas temperature limitation of
600°F (132).
(d) Ambient temperature limitation of
105°F (132).
(e) Gas stratification problems are not
entirely .eliminated—they are minimized
relative to single point sampling.
Adequate mixing Is still necessary up-
stream of the path to Insure a repre-
sentative sample at the path.
(f) The.stack-Instrument Interface
"window" must be maintained clean.
(g) See (e) below.
Part I of this table presents
techniques of extracting and
transferring a continuous sample
to a selected Instrument. Once a
stack gas has been extracted and
conditioned, It may be analyzed for
any number of specific constituent
gases by selecting the proper
Instrument. The appropriate instru- .-.
ment for each pollutant gas of
interest is presented in the
"Inorganic Gas Analysis" table
in the appendix.
See Performance Specification No. 2
above for advantages and disadvantages.
Method 12 is not a method per se but
is a specification of measurement and
instrument characteristics that are
determined by comparing continuous
measurements with manual (Method 8)
results. (Probe tips are side-by-
side In the stack.) The zero and
calibration drift Is based on a
percent of the "emission standard"
Instead of "span" as In Performance
Specification No. 2.
Two types of cross-stack In-situ
systems are available. Type I is
a non-dispersive infrared instru-
ment often called a correlation
spectrometer (132).
A-39
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
SO (cont.)
Cross-Stack
In-Situ
(Type II)
105, 59,
288, 58,
160
In-situ
Non-Extractive
192
SO,
Controlled Conden-
sation (Goksoyr-
Ross)
37, 95,
136, 32,
96
(a) Same as (a) and (b) for Type I.
(b) Also measures CO, CO., NO, hydrocarbons
and opacity. Expect applicability in near
future for N02> H^S, SO.^ HC1, C12 (288).
(c) Very short response time, as In Type I.
(d) Will probably meet EPA specifications,
as in Type I.
(e) Overcomes gas stratification problems, as
in Type I.
(1) Very high reliability - up to 98% (160).
(g) Has been compared favorably with EPA
Method 7 (288).
(h) Excellent discrimination against other
stack gases (58).
(a) Commercially available (192).
(b) Meets EPA specifications for monitoring
specifications for S02 and NO (114, 120).
(c) Well constructed for permanent Instal:.. : .
latlon.
(d) Reported high degree of interference re-
jection, exceptionally long operational period,
and high reliability (192).
(e) Simultaneous temperature measurement for
automatic adjustment. '
(f) Partlculate interference problems appar-
ently negligible using, non-reactive ceramic
filter with aerodynamic deflector. Reported
3 to 19 months maintenance-free probes.
(g) Can be used as a portable instrument.
(h) Integral data system available.
(a) Well researched, applied, and evaluated
technique of collecting SO..
(b) Reasonably accurate with few Interferences.
(c) Flow rates of up to 20 liters per minute
still result in good collection efficiency.
A-40
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Also relatively expensive.
(b) Also located on the stack, requiring
effort to service in a frequently cold,
windy environment.
(c) Requires an in-stack alignment tube.
(d) Moisture interference when measuring NO
(62).
(e) The system must be committed to only
one source and cannot be time-shared between
several sources at same location.
(f) More complex calibration equipment re-
quired than for extractive analyzers (160).
(a) Single point In-stack sampling; thus,
concerned with stratification.
(b) On-the-stack mounting requires on-the-
stack service and maintenance.
(c) A different probe utilizing an air-
purge blowback is required for "wet, sticky,
partlculates" from sources like a scrubber
outlet (192).
(d) Extensive performance data unavailable
at thin time.
(e) Response time could be a problem since
diffusion through a filter Is required and a
rapid driving force, compared to the extr-
active system, is not utilized.
(a) Care required In handling glassware and
maintaining water bath temperature; other-
wise SO, Is oxidized, leading to high SO,
values. J
(b) Not a method per Be, just a writeup of
a technique that can be used.
(c) Requires complex plumbing for field
work.
(d) Not commercially available.
Type II is an absorption spec-
troscopy system . (105, 288). The
Type II absorption spectroacopy tech-
nique is Implemented by dispersive
gas cell correlation and derivative
spectroscopy (288).
This Is a specific commercially
available unit. It is not a method
per se. a
An in-situ single point system for SO.
and NO using second derivative spectro-
scoplc technique. A porous filter Is
exposed to stack gases. The sample
gases diffuse through the filter for
sensing. The sample Is not extracted
through the filter. The sensor (light
absorption) is located in the filter
cavity.
Primarily designed to meet EPA specifi-
cations to monitor NO/SO only. A
different unit will monitor 00.
The method consists of drawing a hot
stack gas sample through a glass spiral
in a controlled temperature water bath
SO. but con-
denses SO, on a glass frit.
that selectively passes
3
An EPA method has not been adopted for
SO
'3'
EPA Method 8 for H.SO^ mist
measures free mist and converts SO,
a mist to be combined with the free
mist.
to
A-41
-------
TABLE A-2 (continued).
INTEREST
AREA
S03 (cont.)
NO
X
METHOD
OPTION
Los Angeles
County
Shell-Thornton
Cell
EPA
Method 7
EPA
Specification
No. 2
Other
Continuous
Systems
Detection Tube
Simple
Displacement Bomb
REFERENCES
60
220, 32,
271
116
114, 120,
102
196, 198
13.6, 211,
323
METHOD
ADVANTAGES
(a) More or less recognized nationally as a
standard method.
(b) Commercially available unit that Is
reasonably Inexpensive.
(c) The method Is reasonably explicit
regarding exactly where in the process
stream (Method 1) and duct cross-section
samples will be collected, the exact train
configuration, and how the sample will be
recovered and stored.
(a) See discussion under S02. Same
advantages (a through f). In (f) the
comparable EPA method is Method 7.
A-42
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
1 and 2
1 and 2
(a) A manual method requiring field
handling of fragile equipment (glassware,
meters, pumps, etc.) precisely positioned
and maintained in a frequently hostile
environment.
(b) The method specifies a single point
(in the duct cross-section) sampling
approach. This could result in errors if
gas stratification exists.
(c) The batch nature of this method and
the short sample period (less than a few
seconds) could be heavily influenced by
erratic processes or stratification leaks.
(d) The precision and reproducibillty are
constant down to about 100 ppm NOX. The
method begins to yield low results below
this concentration.
1 and 2
(a) See discussion under SC>2.
disadvantages (a through c).
Same
(a) NC>2 very soluble in water.
(b) Wall losses can be considerable
(possible total loss of sample) (211).
(c) To reduce losses, nylon, EVA, and PVC
tubing or containers should not be used
(323).
The controlled condensation method
above was first described In this
Shell report (271). The advantages
and disadvantages are thus described
under that method discussion.
This method consists of grabbing a
sample in an evacuated 2 liter flask
containing an absorbing solution.
The sampling location shall be the
same as for S02 (Method 6) sampling.
Four samples shall be taken at
30 minute intervals. Method 7 is
also applied to nitric acid plants.
See discussion under SO..
Part I of this table presents tech-
niques of extracting and transferring
a continuous sample to a selected
instrument. Once a stack gas has been
extracted and conditioned, it may be
analyzed for any number of specific
constituent gases by selecting the
proper instrument. The appropriate
instrument for each pollutant gas of
interest is presented in the "Inorganic
Gas Analysis Options" table in the
appendix.
See Detection Tubes discussion under
so2.
See Simple Displacement Bomb
discussion under SO
'2'
A-43
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
NO (cont.)
CO,
ASTM
D1608-60
Cross-Stack
In-Sltu
In-Sltu
Non-Extract ive
EPA Method 11
Detection Tube
EPA Method 3
ASTM
D2725-70
Simple Displace-
ment Bomb
EPA Method 3
EPA Performance
Specification
No. 3
14
105, 59,
288, 132,
160
192
112
196, 198
116
311, 270
13.6, 211,
323
116
114, 107
(a) Wide applicable concentration range
(up to several thousand ppm).
(b) Very similar to EPA Method 7 (evacuated
flask).
(c) Supported by extensive field testing.
(d) Reasonably simple sampling train that does
not require extensively trained operators.
(a) Reasonably simple sampling train con-
sisting of midget Implngers.
(b) Can be used on pressurioed ducts.
(c) Based on techniques extensively developed
in refinery industry.
Use Tedlar or Teflon bag.
Test method for H,s In natural gas.
(a) Reasonable specifications attainable
using numerous available commercial instru-
ments .
(b) First and only wrlteup of a continuous
system.
(c) Long term unattended operation period.
A-44
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Requires handling glassware near the
stack port. '
(b) Requires an overnight absorption period
prior to analysis. However, method pre-
scribes manner of obtaining results after 2
hours.(results 3% low).
(c) Interferences from inorganic nitrates,
nitrites, organic nitrogen.
(d) SO. may consume part of absorbing
solution leaving inadequate amount for NO .
(e) Role of some constituents of combustion
as interfering substances has not been
thoroughly Investigated.
Measures NO only.
Measures NO only.
(a) Caution required to thoroughly mix
cadmium hydroxide absorbing solution.
(b) Standard disadvantages associated with
midget bubbler wet chemical methods.
(c) Handling concentrated acids.
Questionable applicability above SO ppm
(101) or 23 mg/m .
(a) The specification does not address
sampling interface problems.
(b) Need for in-stack calibration hasn't
been fully researched.
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
See Cross-Stack In-Situ discussion
under SO..
See In-Sltu Non-Extractive discussion
under SO..
Analysis titration should be con-
ducted at sampling location. Titration
should never be made in direct sun-
light.
See Detection Tubes discussion under
so2.
See Method 3 discussion under SO.
Use neutral CdSO^ solution in place of
zinc acetate absorbing solution.
Methylene Blue Method.
See Simple Displacement Bomb dis-
cussion under SO..
See Method 3 discussion under SO..
This is not a method per se. It is
a set of instrument and sampling
system performance specifications.
A-45
-------
TABLE A-2 (continued).
INTEREST
AREA
C02 (cont.)
HC1
HCN
METHOD
OPTION
EPA
Performance
Specification No. 3
(cont.)
Detection Tube
Simple
Displacement Bomb
Cross-Stack
In-Sltu
Impinger Train
Detection Tube
Simple
Displacement Bomb
EPA Method 3
Cross-Stack
In-Sltu
Intersoclety
Committee
(Reference
Method 201)
ASTM
D2036-72
Detection Tube
Simple
Displacement Bomb
EPA
Method 3
REFERENCES
196, 198
13.6, 211,
323
105, 59,
288, 132,
160
216, 70,
196, 166,
152
196, 198
13.6. 211,
323
288
6
13.7, 311
196, 198
13.6, 211,
323
116
METHOD
ADVANTAGES
(d) Address sampling location and potential
stratification.
(a) Low to high concentration range.
(b) Reasonable accuracy (±10%)..
(c) Method using distilled H20 in implngers,
few interferences (166) . • '
The only method for continuous measurement
of HC1.
Reference method with proper wrlteup
specifying exact procedures, accuracy,
required apparatus, etc.
(a) Reference method by ASTM.
(b) Extensive experience in applying method
to various situations.
A-46
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Typical midget implnger train sampling
situation requiring handling glassware and
wet chemicals in the field.
(b) Interference from silver salts (216).
(c) May suffer from interference from
sulfate or chloride ions in participates
(70).
Needs additional refinement before
commercially available.
Sulfate interferences (can be corrected
for).
(a) Wet chemical method requires use of
highly toxic reagents.
(b) Requires adoption of a "water" method
for sampling.
1
1
2
1 and 2
1 and 2
1 and 2
2
1 and 2
1 and 2
See discussion of Detection Tubes
under SO..
See discussion of Simple Displacement
Bomb under SO..
Basic Orsat analysis.
See Cross-Stack In-Situ discussion
under SO..
Sample drawn through sodium hydroxide
(8).
Halide interferences in method (152).
Range from 2 ppm to 2% by volume (198) .
See Detection Tubes discussion under
S02.
See Simple Displacement Bomb
discussion under S02-
See Method 3 discussion under SC.
See Cross-Stack In-Situ discussion
under SC^.
Reference impinger method
Two impingers in series each with
15 ml 0.5N KOH (311).
ASTM method for cyanides in water.
Range from low ppm to 2% by volume
(198).
See Detection Tubes discussion
under SO^.
See Simple Displacement Bomb
discussion under SO..
See Method 3-discussion under SO..
A-47
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
HF & F
EPA Method 13A
119, 25,
92
EPA Method 13B
119, 25,
92
Detection Tube
Los Angeles
County
Wet Chemical
196, 198
200
261, 204
(a) Isokinetic sampling for particulate and
gaseous total fluoride emissions using estab-
lished Method 5 type train.
(b) Three percent relative standard deviation
from replicate Inter-laboratory determination
study with range of 39 to 350 mg/1.
(c) Reasonably stable sample.
(d) Stainless steel probe.
(e) Routine Method 5 type train operation.
(f) Automatically obtains necessary data to
calculate fluoride emissions.
(a) Isokinetic sampling for particulate and
gaseous total fluoride emissions using estab-
lished Method 5 type train.
(b) Accuracy reported to be 1-5 percent
(electrode measurements).
(c) Routine Method 5 type train operation.
(d) Routine sample removal and cleanup.
(a) Could be adapted for a wet chemical
method of sampling.
(b) Applicable above 1 ppm.
A-48
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Fluorocarbons such as freons not
quantitatively collected.
(b) Chloride Ion Interference.
(c) See particulate sampling table for
general Method 5 disadvantages.
(d) Sensitivity not determined.
(a) Fluorocarbons such as freons not
quantitatively collected.
(b) Sensitivity not determined.
(c) During lab analysis, Al In excess of
300 mg/1 and silicon dioxide in excess of
300 mg/1 will prevent complete recovery of
fluoride.
(d) Temperature change in sample will
significantly affect electrode response.
(e) Glass probe required.
(f) Gas reaction with glass probe may be
incomplete if probe becomes coated with
particulate.
(a) Requires field updating for current
stack sampling in the presence of many other
gases that could Interfere. (Aluminum
sulfate and phosphate (204).)
1 and 2
1 and 2
1 and 2
1 and 2
SPADNS Zirconium Lake Method.
Fluoride determined Instead of HF.
Covers range from 0-1.4 g/ml fluoride.
Filter inserted either prior to first
impInger or after third.
Whatman type filter required.
Method designed for testing Primary
Aluminum plants.
Specific Ion Electrode Method.
Fluorides determined instead of HF.
Covers range of 0.02-2000 mg/ml.
Same sample train as Method 13A.
Method designed for testing Primary
Aluminum plants.
HF and F. react with heated glass probe
to form gaseous silicon tetrafluoride
which hydrolyzes in the water impingers
to form fluoslliclc acid and insoluble
orthoslllcic acid.
See Detection Tubes discussion under
so2.
1.5 to IS ppm range.
Caustic solution impinger train.
Impinger train containing zirconium
oxychloride octahydrate-salochrone
cyrhlne R solution.
Spectrophoto analysis.
Specific for HF.
A-49
-------
TABLE A-2 (continued).
INTEREST
AREA
III.
Inorganic
Gas Sampling
CO
0,
L
METHOD
OPTION
EPA Method 10
Detection Tube
Simple Displace-
ment Bomb
Reduction Methods .
Oxidation Methods
Complexatlon
Methods
Cross-Stack
In-Sltu
Performance
Specification
No. 3
Detection Tubes
Simple Displace-
ment Bomb
EPA Method 3
REFERENCES
112, 94
196, 198
94
13.6, 211,
323
94
94
94
281, 132
114, 107
196, 198
13.6, 211,
323
116
METHOD
ADVANTAGES
(a) Can use silica gel to remove moisture
(need to correct sample gas volume) .
(b) Grab sampling, allowed.
(c) Either continuous or manual methods can
be used.
Simple, reasonably quick measurement
technique.
Polaragraphlc or paramagnetic as discussed
In (4 and 5) may be used If meet specifi-
cations.
A-50
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) HO Interference.
(b) Does not address gas stratification in
the continuous mode (weakness of a single
point sampling).
Major interfering gases include CC^, S02.
and NC>2.
Typical precision is reading (in%) ±0.3.
Low volume measurement.
(a) Orsat analysis technique limited to
0.3% precision.
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
Integrated grab sample technique or,
continuous sampling. Analysis using
NDIR.
Use condenser for moisture removal
in continuous sampling.
Use Ascarite to remove CO. prior to
NDIR.
See Detection Tubes discussion
under SO..
See Simple Displacement Bomb dis-
cussion under SO..
This Includes other wet chemical
techniques and reduction techniques.
CO has a very low solubility in
aqueous solutions. (Also too low In
organic solvents).
Method essentially requires grab
sampling as described in EPA Method
10.
Methods utilize catalytic conversion
of CO to CO .
Well known Orsat technique involving
selective scrubbing by a liquid
reagent.
See Cross-Stack In-Situ discussion
under SO..
See CO. discussion.
See Detection Tubes discussion under
so2.
See Simple Displacement Bomb dis-
cussion under SO..
See Method 3 discussion under SO..
A-51
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
(cont)
Paramagnetic
70, 196
Polarometrlc
196
NH,
KJeldahl Method
(Nesslerization)
61, 287,
216, 278,
196
Indophenol Blue
Technique
278, 196
ASTM
D1426-71
(a) An Instrumental technique that has been
used on combustion sources for many years.
(b) Reasonably selective technique.
(a) An Instrumental technique that has been
used on combustion sources for many years.
(b) Good for low concentration ranges.
(c) Less expensive than paramagnetic and more
rugged.
(d) Accuracy of 0.2-0.5 vol. % in 0-25%
range.
(a) Precision approximately -2%.
(b) This is the most common primary method
used to sample and analyze for ammonia.
(c) Gives both particulate (if penetrate
filter) and gaseous NHj.
(d) Can use commercially available midget
implnger sampling systems.
(a) Common and familiar sampling equipment.
(a) See above.
(b) Advantage over Nessler reagent when
determining low NH, concentrations in that H S
does not interfere (196).
(c) Detection limit and reproduclbillty
correspond to Nessler reaction.
A-52
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) NO and NO also magnetic but effect is
probably on oraer of 0.2 percent oxygen by
volume.
1 and 2
(a) Less accurate than paramagnetic (196).
1 and 2
(a) Interference from certain amines and
calcium in excess of 250 mg/1.
(b) Routine problems associated with
handling glassware and reagent chemicals
in the field (i.e., wet chemical method).
(c) May need to add potassium permanganate
to H.SO, to eliminate 1US and formaldehyde
from reacting with Nessler reagent (196).
(a) See above.
(b) Potential Interference from formalde-
hyde, nitrite, sulfite (196).
1 and 2
1 and 2
An instrumental technique that could
be used to satisfy Performance Specif-
ication No. 3
Relies on the magnetic susceptibility
of oxygen.
Requires appropriate sample point
selection and stratification inves-
tigation for emission measurements.
An instrumental technique that could
be used to satisfy Performance
Specification No. 3.
Requires appropriate sample point
selection and stratification inves-
tigation for emission measurements.
Standard impinger collection in O.lN
To insure distinct end-point, the
indicator solution should be added
to the boric acid solution Immediately
prior to use.
A continuous ambient type monitor
using this technique was developed
and used by EPA. •
Primarily for stack concentration
ranges.
Collected the same way as above, then
reacted with alkaline phenol and sodium
hypochlorlte and adsorbents measured
on a Colorimeter.
The "Non-Referee" method presented
here is an analysis technique similar
to the Nesslerization technique.
Thus, the sampling procedure here is
to collect in an impinger train.
This method is for NH3 in water and
only addresses analytical issues.
Use Kjeldahl for sampling.
A-53
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
(cont.)
H20
Detection Tube
Simple
Displacement Bomb
EPA
Method 4
196, 198
13.6, 211,
323
116, 70,
50
Adsorption
116, 70,
50
Wet and Dry
Bulb
Temperature
70
Detection Tube
NDIR
196, 198
25
Very simple; easy to use.
(a) Reasonably simple for accuracy obtained.
(b) Very simple analysis (volume measurement
and silica gel weighing).
(c) Applicable to very low to very high
moisture streams by varying sample time.
(d) Commercially available or easy and
Inexpensive to construct.
(e) Extensively evaluated for quality
assurance.
(a) Very simple technique--can sample large
or small volumes depending on moisture content.
(b) Commercially available and inexpensive.
Indicators available to Indicate saturation.
(c) Extensively used in industry for manual
and automatic collection.
(a) Reasonably simple manual technique.
(b) Some units are commercially available.
(c) Acceptable technique below 212°F.
One of the better techniques for continuously
monitoring moisture in stack gas.
A-54
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
Careful selection to avoid Interferences.
(a) Requires handling wet chemical-type
glassware (I.e., manual method).
(b) Problems if gas stream is saturated
and laden with moisture droplets that
could penetrate the filter.
(c) Note color of condensate. In some
gas streams, other gases may also condense
out giving erroneous results
(a) Care required to avoid loss of
condensate prior to absorbent if cooling
gas required.
(b)• May also collect some organics (a
dark color on the surface indicates organic
collection).
(c) Limited to 300°F (50).
(a) Difficult to Judge wet bulb
temperature with confidence that equi-
librium has been reached (above 212°F
the wick dries out).
(b) Particulates on wet bulb can cause
errors after a period of buildup.
(c) Practically limited to 212°F.
(a) The concentration range is limited
to 0-5%.
(b) Usually applied to ppm range
concentrations.
1 and 2
1 and 2
1 and 2
From ppm to 107, volume range.
See Detection Tubes discussed
under SO..
See Simple Displacement Bomb
discussed under SO..
Moisture is condensed and determined
volumetrically.
Since this train also includes silica
get prior to the pump, this method is
a combination of condensation and
adsorption.
Condensation generally applies to
51% moisture.
Procedure is to draw a volume of gas
through a tube of adsorbent like
silica gel and weigh for collected
moisture.
Essentially a dessication technique.
Remove particulates prior to
absorption.
Essentially consists of two temper-
ature measurements.
Requires using psychometric charts.
See Detection Tubes discussion
under SO..
Continuous measurement of moisture is
a complicated task due to the usual
wide range in stack gas concentrations
and the continuous maintenance
problems associated with uncontrolled
condensation prior to the sensor.
Typically, the stack temperature is
too high to maintain in a heat-traced
sample line up to an NDIR to get
continuous readings prior to any
moisture condensing out.
A-55
-------
TABLE A-2 (continued).
INTEREST
AREA
HO (cont.)
cs2
METHOD
OPTION
EPA Method 3
Cryogenic
Absorbing
Simple
Displacement Bomb
EPA Method 3
Simple
Dlspacement Bomb
Detection Tube
Wet Chemical
REFERENCES
116, 196,
94
196
116
13.6, 211,
323
196, 198
166, 94,
261, 146,
152
METHOD
ADVANTAGES
(a) Probable complete collection of COS at
cyrogenlc temperatures.
(a) Sampling contractors are familiar with
and routinely use wet chemical techniques.
Thus, this method could easily be Incorpo-
rated In a multi-gas sample train.
(b) Range of one method allows determination
down to a few ppm (146) . Imp Inge r train
(with analysis on spectrophotometer) also
pre-scrubs to remove H S.
(c) Range of another method Is about 5-50 ppm
(152) but requires passing gas through lead
acetate paper to remove H,S prior to collection
A-56
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Difficult determination In presence of
1 and 2
C0
2>
(a) Not a method per se, just a specified
technique familiar to most GC operators.
The sampler must complete the train design.
(b) Routine difficulty in obtaining and
operating a field cryogenic sampling opera-
tion at the stack. More difficult than
routine wet chemical sampling.
1 and 2
1 and 2
(a) Wet chemical impinger trains are more
difficult to handle and operate in the field
than automatic instruments (not available in
this case).
(b) Care to select a train to address
H.S interference.
(c) Method as described in may not
be sensitive for ambient concentration
levels 2-3 ppm.
1 and 2
COS is odorless and highly toxic
(196). See Method 3 under S02
discussion.
Gas chromatographic analysis (196).
Few methods are presented in the
literature that specifically apply
to COS. This is not a method per
se but another technique of
obtaining a sample for GC analysis
that involves passing the sample
over silica gel at -78°C for a
preliminary concentration (196).
See Simple Displacement Bomb
discussion under S02-
See Method 3 discussion under SO-.
See COS above.
A primary method of collecting a sam-
ple for gas chromatographic analysis.
See Simple Displacement Boob discussion
under S0«
Applied to concentrations up to 60 ppm
(198).
See Detection Tubes discussion under
so2.
Several wet chemical techniques are
presented in the literature (146,
152, 166).
CS2 Is not very soluble in aqueous
solutions but soluble in many
organic solvents (94).
The usual problem of single point
sampling should be addressed by con-
ducting a gas stratification investi-
gation.
A-57
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
CS2 (cont.)
Hg
IV.
Organic Gases
Wet Chemical
(cont.)
SASS
218, 173,
2
Hot
Integrated Grab
311, 34
Integrated
Grab Sampling
116
(d) Another method (166) allows determination
of H2S, C&2 and methyl mercaptan In one simple
train.
(a) Most important advantage is that the
sampling system isoklnetically collects
participates (for organic analysis) and
gaseous organics simultaneously.
(b) The train is designed to collect both
both volatile and non-volatile organics
simultaneously.
(c) A reported advantage of the system is
the high sample rate and thus shorter
sampling periods. A definite and more
significant advantage is the ability of the
train to simultaneously collect many
pollutants.
(d) Describes adsorption trap system for a
full range of typical stack temperatures.
(a) Confidence in collection of more volatile
organics.
(b) By operating a one bag system, It is
reasonably easy to obtain a sample.
(a) Eliminates concern for loss of low
molecular weight materials.
(b) On-site GC can be used for quick and
convenient field analysis.
A-58
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Low molecular weight materials
may penetrate the adsorption trap.
(b) A serious weakness is that the
system has not been field tested and some
of the components are not commercially
available.
(c) Isokinetlc sampling; however, at this
date the system cannot traverse for mass
emission rate due to constant flow.require-
ment for cyclones'(particle sizing portion).
(d) A.D. Little quartz filters (or
equivalent) are recommended but may
not be available.
(a) Cumbersome field instrument, primarily
designed for special'situation sampling.
(b) Possible organic material'loss
mechanisms Include collection on quartz
wool and condensation on bag walls.
Material collected on quartz wool may be
subsequently analyzed.
1 and 2
1 and 2
1 and 2
(a) Reactions may occur on walls or in
condenoer.
(b). Bag leakage.
1 and 2
See "Particulate Sampling Options"
table.
See SASS discussion in "Particulate
Sampling Options" table.
Teflon coating for filter holder
should not be used.
Requires water-cooled probe for high
temperature stacks.
System consists of a heated
partlculate filter (quartz wool)
followed by a short heat traced
teflon line leading to a four
compartment bag. Each compart-
ment has a capacity of one cubic
foot and is made of teflon. The
compartments are activated for
preset time periods of equal
duration to obtain equal emission
segments during a short period (up
to six minutes total). The system
is maintained at 300°F during
transport to the field lab and
manifold sample for extraction.
Only used for THC, CO, and CH^ in
the field.
EPA Method 3 sample train (also a
part of EPA Method 10).
Appropriate method for certain
classes of organlcs, depending on
volatility.
A-59
-------
TABLE A-2 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
Organic Gases
(cont.)
Solvent
Scrubbing
218
Condensation
218
Porous Polymer
Adsorbents
218
Chemical
Substrate
Adsorption
218
Can be combined with a Method 5 partlcu-
late train to simultaneously volatile and non-
volatile organlcs. Organic material is
extracted from the absorbing solution with a
suitable solvent.
(a) Simple technique unless attempting to
collect specific species using complex
temperature programming procedures.
(b) Used for both ambient and source emission
monitoring. , .,
(c) Commonly applied technique.
(d) A wide range of organlcs may be collected.
(a) Water vapor Is not strongly adsorbed. High
humidity streams may be sampled.
(b) A variety of adsorbent-materials are avail-
able-- (selective sampling is possible).
(c) Porous polymers, can be used up to
temperatures of 300°C.
(a) Activated charcoal adsorbs a broad range
of organlcs.
(b) Technique is used by NIOSH.
(c) Reasonably simple technique.
A-60
-------
TABLE A-2 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Solvent selection may be difficult;
the sample should: (1) be easily removed
without sample loss, (2) be safe,
(3) not react with the system, and
(4) not be found in the system.
(b). Subsequent evaporation of solvent
results in sample concentration.
(c) Difficult to collect low boiling point
materials.
(a) Collection efficiencies vary with
substance being collected.
(b) Condensed water may plug trap and
react with absorbed organics.
(c) Cryogenic trapping requires special
equipment.
(a) Needs additional field verification.
(b) Some adsorbents are expensive.
(c) Usually'low sample rate due to
pressure drop through adsorber.
(d) Higher molecular weight compounds are
more readily adsorbed than low molecular
weight compounds.
(e) Solvent extraction is required.
(a) Sample recovery may be incomplete.
(b) Charcoal may act as a catalyst.
(c) Desorption (by heating) may affect
chemical changes (e.g., thermally allowed
rearrangements). (Pyrolysis may occur.)
1 and 2
Not a highly refined method and thus
not generally recommended.
1 and 2
Not a recommended technique.
1 and 2
Potentially the best method for
collection (and concentration) of
organics.
A porous polymer adsorbent is specified
as part of the SASS train
1 and 2
Silica gel and activated carbon are
commonly used.
A-61
-------
TABLE A-2 (continued).
INTEREST
AREA
Organic Gases
(cont.)
METHOD
OPTION
Detection Tube
Battelle
Adsorbent
Kaiser Tube
REFERENCES
196, 198
218
218
METHOD
ADVANTAGES
Inexpensive and commonly used.
(a) Uses Method 5 train design, t (Isp-
klnetlc sampling Is used.)
(b) Primarily designed to sample Polycyclic
Organic Material (POM).
(c) The adsorbent trap is designed to be an
Integral part of a Soxhlet extraction
apparatus.
(d) Validation studies have been conducted.
(a) Efficient collection of low molecular
weight materials is possible.'
(b) Kaiser tube is reasonably simple.
A-62
-------
TABLE A-2 (concluded).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Interferences are common, i.e.,
detection tubes lack selectivity;
(b) Detection tubes are available only for
a-limited number of specific compounds.
(a) Requires controlled temperature water
bath for absorber.
(b) Some water vapor is also condensed in
cooler.
(c) Needs additional field testing.
(d) Aqueous SO. may react with and thus
alter the collected material (218).
(a) System operates at -160°C. Cryogenic
equipment is required.
(b) Needs extensive field testing.
(c) Difficult to collect- samples iso-
klnetically (combined system).
1 and 2
1 and 2
See Detection Tubes discussion'
under SO,,.
Essentially a Method 5 type train;
i.e., the absorber is placed after
the filter and before the impingers.
Appears to be an excellent system
based on limited studies.
Consists of a polymer packed tube
cooled to -160 C; designed to sample
low molecular weight materials.
A-63
-------
TABLE A-3. METHOD OPTIONS FOR LIQUID SAMPLING
INTEREST
AREA
I.
Stationary and
Partial Stream
Cut Sampling
-
METHOD
OPTION
Dipper
Tap
Thief
Continuous
Automatic
REFERENCES
13.1, 13.2,
13.3, 13.5
13.1, 13.2,
13.3, 13.5
13.1, 13.2,
13.3, 13.5
METHOD
ADVANTAGES
(a) Can be used for slurry sampling.
(b) No site preparation.
(c) Simple and Inexpensive method.
(a) Can be used for slurry sampling In
well-mixed flow regions.
(b) Representative sampling of liquid
streams having a small solids content
(I.e., less than 5% by weight).
(c) Simple and relatively Inexpensive.
(a) Determination of stratification of
constituents possible.
(b) By sampling at different depths of a
tank or open channel, a mean concentration
of pollutants can be determined.
(c) No site preparation.
(d) Simple and Inexpensive.
(a) Continuous operation.
(b) Free from human factor bias.
(c) Various types .commercially available.
(d) Rapid short-term fluctuations that may be
overlooked by automatic samplers are accounted
for.
(a) Automatic operation
(b) Free from human bias.
(c) Various types available.
(d) Can be set to take flow-proportional
samples.
(e) High-volume samplers have been shown to
produce the most representative samples of
all In-line automatic samplers for streams
with significant levels of large, suspended
materials.
A-64
-------
TABLE A-3 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Bias of sample possible from
stratification effects.
(b) Bias possible from human factor
(a) Tap must be installed.
(b) Bias possible from human factor.
1 and 2
Bias possible from human factor.
1 and 2
(a) Clogging of intake lines is usually
frequent for slurry streams.
(b) Installation and maintenance
necessary.
(a) Sample can be biased by not taking a
full stream cut—this bias would be
prevalent for the solids materials or non-
mlsclble liquid components.
(b) Installation and maintenance
necessary.
1 and 2
For sampling homogeneous liquids at
open tanks, ponds, open channel
streams and discharge points of lines.
Heterogeneous streams (i.e., those
containing appreciable solids or non-
misclble liquids) can be sampled only
at well-mixed regions in open channels
or at discharge points of lines.
For homogeneous liquids, a tap can be
Installed In tank or line In any
convenient location.
For heterogeneous liquids, tap must
be Installed In well-mixed region of
line.
Bias from human factor can be
minimized by tap sampling a small
amount of liquid continuously during
the entire test period rather than a
large volume over a short period of
time.
Applicable for open tank or open
channel sampling of heterogeneous
liquids.
Applicable to in-line sampling of
liquids.
A-65
-------
TABLE A-3 (continued).
INTEREST
AREA
II.
Full Stream
Cut Sampling
III.
Methods
Applicable
to Organic
Pollutants
METHOD
OPTION
Dipper
Automatic Vezln
Sampler
Automatic
Straight Line
Sampler
Carbon adsorption —
Chloroform
Extraction
Carbon Adsorption--
Carbon Alcohol
Extraction .
Other Adsorption
Methods
REFERENCES
13.1, 13.2,
13.3, 13.5
13.1, 13.2,
13.3, 13.5
13.1, 13.2,
13.3, 13.5
111
111
METHOD
ADVANTAGES
(a) Stratification effects are minimized or
eliminated from sample.
(b) Can be used for slurry sampling.
(c) No site preparation.
(d) Simple and Inexpensive.
(a) Automatic operation.
(b) Without human factor bias.
(a) Motion of sampler through stream gives
most representative sample of any automatic
full -stream cut type.
(b) Same as (a) and (b) for Vezln sample.
(a) Automatic or continuous sampling.
(b) Can quantify trace organic pollutants In
liquid stream without the necessity of large
sample quantities.
(a) Same as (a) and (b) for Chloroform
Extraction.
(b) Greater extraction efficiency than
chloroform.
Should have greater collection and extraction
efficiencies than carbon adsorption methods
A-66
-------
TABLE A-3 (concluded).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Access to discharge point of line is
key limiting factor.
(b) Possible bias from human factor.
(a) Not as accurate as a straight-line
sampler.
(b) Installation and maintenance .
necessary.
(a) Can be used only at discharge point
(b) Requires more maintenance than Vezin
Sampler.
(a) For short-term tests a high sampling
flow rate (greater than 0.25 gpm) is
required. High flow rates, however, would
tend to plug the adsorber column if the
stream has high suspended solids, resulting
in decreased adsorbing efficiency.
(b) All organic components are not
extracted.
(c) Chloroform is a carcinogen.
Same as (a), (b), and (c) for Chloroform
Extraction.
Have not yet been field tested.
1 and 2
Stratification effects are minimized
with full stream cut techniques.
Applicable for sampling at discharge
points of lines or sampling open
channels.
Applicable only to in-line sampling.
The sampler should be calibrated
against the full stream cut grab.
Same calibration as for Vezin sampler.
Can be used to sample for organics in
liquids from tanks, ponds, open
channels, or lines by using appro-
priate sampling device.
Can be used in conjunction with other
sampling options.
Due to the questionable efficiencies
of extractive techniques, this method
cannot be used to accurately quantify
mass emission rates.
Same as 'for Chloroform Extraction.
Same as for Chloroform Extraction.
Some materials being investigated
are polyurethane foam, XAD-2 resin,
and other porous polymers.
A-67
-------
TABLE A-4. METHOD OPTIONS FOR SOLID SAMPLING
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
I.
Stationary
Sampling
Simple Grab
297
Coning
and Quartering
297, 8.6,
8.7, 8.33
Plpeborer
297
Auger
297
(a)
(b)
(c)
(d)
(e)
(a)
(b)
Readily and quickly performed.
Special equipment unnecessary.
Small amount of material involved.
No site preparation is required.
Simple and Inexpensive.
Readily performed.
Less chance of size segregation than with
simple grab.
(a) Readily and quickly performed.
(b) Representative sample with regard to size
segregation.
(c) Thief-type pipeborer is available to
sample at different levels of container.
(d) Site preparation not required.
(a) Same as (a), (b), and (d), for plpeborers.
(b) Can be utilized for denser materials than
plpeborers can.
(c) Can be machine driven.
A-68
-------
TABLE A-4 (continued).
METHOD; ..
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Bias from size segration in pile.
(b) Bias from small sample size.
(c) Bias from human factor .possible.
(a) Time-consuming operation.
(b) Bias from size segration still
possible.
(c) Bias from human factor'possible.
(d) Large gross sample required.
(e) To minimize contamination of sample,
clean surface and area required.
(f) Moisture loss possible due to amount
of handling. .
(a) When used to sample sacks or drums,
the containers should' be well mixed
prior to.sampling to avoid cross-sectional
variation.
(b) Useful only for fine, dry material.
(c) Slot width should be large .com-
pared with material particle'size.
(d) To assure'representative sampling of
piles, more than one sample must be taken
and then riffled to size required for
analysis.
(a). Same as (a) and (d) for pipeborer.
1 and 2
1 and 2
Samples taken from stationary sources
are usually not as representative as
those taken from other.source cate-
gories (e.g., lines, conveyors, etc.)
File or container sampling only.
Method consists of taking several
shovelfuls of material from various
parts of the pile or container.
A minimum of four shovelfuls should
be taken.
Coning and Quartering, is a sample
reduction technique which is used in
conjunction with various grab
sampling techniques
Option applicable only to pile or
container sampling where the material
to be sampled is of a powdery nature.
Sampling option applicable only to
pile or container. Material can be
of a granular nature.
A-69
-------
TABLE A-4 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
II;
Partial Stream
Cut Sampling
Grab
297, 8.7
Riffler
297, 8.33,
235
Whistle Pipe
297, 235
(a) • Readily and quickly performed when
accessibility to belt on discharge point
of stream is unhampered. •
(b) No site preparation is required. .
(c) Simple and inexpensive. °"
(a) Material can be fed manually or con-
tlnously to rlffler.
(b) Can be used as final step in sampling
methodology for sample reduction.
(c) Various types available, including Jones,
flat, and bank types.'
(d) Human bias eliminated when operated in
continuous mode.
Same as (a), (b) and (d) for rlffler.
A-70
-------
TABLE A-4 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Bias can result from cross-sectional
variations in the stream.
(b) Bias from human factor possible.
(a) Bias possible due to cross-sectional
variations in the stream.
(b) Distortion of the dividing edges occurs
with use, resulting in sample bias.
(c) Excessively damp material or foreign
objects could clog sampler.
(d) Damp, fine material could stick to
edges of sampler, biasing the result.
(e) For continuous sampling, installation
of device necessary.
Same as for riffler.
Partial stream cut samples are not
as representative as full stream cut
or stopped belt samples.
Samples can be taken from discharge
point of solids stream or from mov-
ing belt or ladder conveyor.
In sampling at the discharge point, a
container is moved through a portion
of the falling stream. The sampling
container should have an opening of
at least three times the diameter of
the largest particle. Motion through
the part of the stream to be sampled
should be uniform and repeatable.
In sampling from a belt conveyer, a
portion of the solid stream is di-
verted into the container.
In most cases, if partial stream cut,
manual grab sampling is possible,
then so is the more representative
manual full stream cut sampling
options. For this reason, it is rec-
ommended that full steam cut sampling
be used whenever a choice is possible.
Samples can be taken continuously
from a moving stream by diverting a
portion of the stream into the
sampler.
Samples can also be taken by grab
techniques and then fed into the
riffler for sample reduction.
Same as for riffler.
A-71
-------
TABLE A-4 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
III .
Full Stream
Cut Sampling
Fractional
Shoveling
297, 8.7
Grab
297, 8.7,
8.33
Pneumatic
Samplers
125
Rotating Samplers
(arc, oscillating
and swinging types)
297, 8.7,
235, 125
(a) Readily and quickly performed.
-(b) Applicable to larger lots than coning
and quartering.
(c) Can be more reliable than coning and
quartering.
(d) No site preparation Is required.
(e) Simple and Inexpensive.
(a) Readily and quickly performed.
(b) No site preparation Is required.
(c) Simple and Inexpensive.
(a) Automatic operation available with
pheumatic or auger types of discharge.
(b) Can be used for pneumatic transport lines
or any enclosed solid stream.
(a) Automatic operation.
(b) Various types available including Vezin,
Chas. Snyder, Snyder, and Brunton.
(c) Provide representative samples.
(d) Easy accessibility for repair.
(e) Small headroom requirements for Brunton
type.
(f) Stainless steel construction available.
(g) Vezin type sampler can be used In
pneumatic conveying lines.
A-72
-------
TABLE A-4 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY.
LEVEL
REMARKS
(a) Should not be used when lumps of
material greater than two inches in dia-
meter are present.
(b) Due to size segregation, can be
inaccurate when only a portion of a pile
is taken.''-
(c) Bias from human factor possible.
(a) Bias from human factor possible.
(b) Can be used only where a container can
be moved through falling stream or belt
discharge.
(c) For repeatability, sample must-be
taken with a smooth, uniform motion for
all increments.
(d) Sampling container must be held at
right angles to the stream.
(a) One point, non-isokinetic sampling
would result, in bias.
(b) Installation necessary.
(c) Calibration procedure with stopped
belt sampling should be performed before
being employed.
(d) Sampling container must be held at
right angles to the stream.
(a) Damp or foreign material can clog
samplers.
(b) Maintenance required.
(c) Sampler takes more material from the
edges of the stream cross-section than from
the center.
(d) Not as representative a sample as with
straight line sampler.
(e) Some types such as the Vezin have
relatively large headroom requirements.
(f) Installation is required.
1 and 2
1 and 2
1 and 2
Should be used only when other full
stream cut sampling options not
available.
Method can be utilized whenever
shoveling is used to convey material.
One shovelful is taken as a sample
increment periodically.
Samples taken at discharge point of
solids stream.
This method should be employed only
when sample is gathered under the
supervision of an experienced tester
to minimize bias from human factor.
For sampling pneumatic transport line
or enclosed solid stream.
While recommended for use for trace
sampling of solids in reference 3, it
has not been field tested extensively
enough for use without a calibration
procedure based onparticle size and
mass flow rate.
Samples taken at point where solids
stream is freely falling vertically
in vertical section of transport line.
Sample scoops should be deep enough
to prevent small particle elutriation
or splatter.
Speed and frequency of the cutting
device are the principle variables
in sampler operations.
Should be calibrated against stopped
belt technique.
Cutter openings should be three times
the diameter of the largest piece of
material sampled.
Speed of cutter should be low enough
to prevent segregation or rejection
due to disturbing the stream.
A-73
-------
TABLE A-4 (continued).
INTEREST
AREA
III. (cont.)
IV.
Stopped Belt
Sampling
METHOD
OPTION
Straight
Line
Samplers
ASTM
Pulverized
Coal
Sampler
ASME
Pulverized Coal
Sampler
Grab
REFERENCES
297, 8.33,
235, 125
8.3
18
8.33
METHOD
ADVANTAGES
(a) Same as (a) , (c) , and (f ) for rotating
samplers.
(b) Sampling device spends equal time In each
portion of the stream, making- straight line
samplers the most representative of all
automatic samplers.
(a) Provides means of sampling in pneumatic
lines with minimum amount of equipment.
(a) Same as (a) for ASTM sampler.
(b) Rugged construction.
(a) Highest reliability of all sampling
methods.
(b) Readily and quickly performed.
A-74
-------
TABLE A-A (concluded).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) More maintenance is required Chan
for rotating samplers.
(b) Installation Is required.
(a) Limited to material in size range of
pulverized coal (60-90% through 200 mesh).
(b) Sampling is non-isokinetic and bias
can occur.
(c) Vacuum bag could break under high
pressure.
(d) Ports in line necessary.
(a) Could probably be modified to include
material of 1/4 inch size but may be Im-
practical depending on port size necessary.
(b) Same as (b) for ASTM sampler.
(c) Compressed air used for aspiration.
(a) Requires stopping of conveyor every
10 to IS minutes during test period.
(b) Bias from human factor possible, but
can be reduced by systematic sampling.
1 and 2
1 and 2
1 and 2
1 and 2
Same as for Rotating Samplers.
Samples taken at point where solids are
freely falling from discharge point of
bin, conveyor, etc.
For sampling in pneumatic lines only.
Should be used only when sampling in
pneumatic line is necessary and
Vezin or pneumatic sampler is uncali-
brated.
Method entails performing a traverse
over the conduit cross-section.
Same as for ASTM sampler.
Sample taken from stopped belt.
Preferred technique. Care should be
taken that fines are brushed away
from the conveyor into the sampling
container along with the larger
pieces of material.
A-75
-------
TABLE A-5. METHOD OPTIONS FOR AIR-BORNE FUGITIVE SAMPLING
INTEREST
AREA
Fugitive
Particulates:
Diffuse Area
Sources
METHOD
OPTION
Emission
Factor Method
'
Downwind
Upwind -
Downwind:
Midwest Research
Institute Method
Upwind -
Downwind :
The Research
Corporation of
New England
Methodology
REFERENCES
73, 176
147
73
176
METHOD
ADVANTAGES
(a) Rough but adequate estimate of emission
rate.
(b) Sampling not required.
Simple and Inexpensive method for sampling
specific sources such as piles, which have
a diffuse emission cloud.
(a) Wind activated hi-volume samplers are
utilized.
(b) Samplers are mounted on a vertical tower
in a grid arrangement to determine emissions
from specific loading or unloading operations.
(c) Particle size measurements can be per-
formed by attaching an Anderson Impact or to
the hi-volume samplers, or by microscopic
examination of the filter.
Standard diffusion analysis is used in con-
junction with high-volume sampling to produce
emission rates for the source.
A-76
-------
TABLE A-5 (continued).
METHOD.
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
Emission factors may not be available
for the source under consideration or may.'
not be relatable to certain meterological
conditions prevalent at the site.
-(a) Must be placed into emission cloud
.area for accurate results.
(b) Non-isokinetic.sampling.
(a) Sampling.rates are pre-set to
isokinetic conditions for specific wind
velocities."', Inaccurate when the wind
speed varies'during the course o'f the
test. • '. - •
(b) Results from specific samplers'are
integrated over the length and height of
the pile in question. . This may be an
inaccurate method. <
(c) Particles are subject to re-entrain-
ment 'from the impactor surface due to
their dry nature-and may bias the
particle' size measurement.
Non-lsokinetic sampling.
1 and 2
Diffuse area source sampling is
concerned primarily with aggregate
piles and other fugitive sources
whose emission rate is controlled
largely by meterological conditions
such as rainfall and windspeed.
Techniques can also be applied on a
plant wide basis.
Applicable to any source where
emission factors exist.
Most applicable to sources having
high density fugitive cloud emission.
Not applicable to emissions on a plant
wide basis.
For accurate quantitative results, a
more sophisticated method must be used.
Applicable for emissions from both •
diffuse area and specific point
sources.
The source should be sampled during
high and low wind velocity periods
such that an estimation may be made
of a high and low emission rate. If
enough data is available, the
development of an emission factor
equation should be attempted.
Applicable for emissions from both
diffuse area and specific point
sources.
A-77
-------
TABLE A-5 (continued).
INTEREST
AREA
METHOD
OPTION
REFERENCES
METHOD
ADVANTAGES
Fugitive
Particulates:
Diffuse Area
Sources
(cont.)
Background
Operating Plant
Method
Fugitive
Particulates:
Specific Point
Sources
Quasi-
Stack
176
Roof-
Monitor
176
(b) Various partlculate sampling devices can
be used, Including filter impactor, piezoe-
lectric techniques, etc.
(c) Particle size' measurements can be" per-
formed with an Anderson impactor or by micro-
scopic examination of the filter.
(a) Most accurate measure of difference'be-
tween ambient .background and source contribu-
tion.
(a) Most accurate sampling technique where
point source can be hooded.
(b) Particle size and mass emission measure-
ments can be made directly.
(a) Can be used to sample multiple point
sources located within a single structure
where the emissions exit from the structure
through roof, door, windows, etc; ;
(b) Same as for (b) for Quasi-Stack.
A-78
-------
TABLE A-5 (continued).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(b) Diffusion equation assumes a Gaussian
distribution in both vertical and horizon-
tal direction.
(c) Particle resuspension is not assumed.
(d) No provision..for individual sampling
of aggregate loading or unloading is made.
(e) Variations of wind speed-and direction
would interfere with the .accuracy of the
results.
/,
(a) Time involved is usually'twice that
of other techniques.
(b). For accuracy, similar meterological
conditions should prevail for both samp-
ling periods.
(a) Applicable only where hooding is
possible.
(b) Low grain-loading and possible low
velocities would present a problem if a
conventional Method 5 train were used.
(c) Where many point sources are to be
tested, hooding and testing each individual
one would be an expensive and time-consum-
ing,operation. ' - '
- (d) The hood must be carefully designed
such that all particulate is collected.
(a) Cannot be used to isolate single
point emissions.
(b) Same as (b) for Quasl-Stack.
(c) For cost-effectiveness, this method
should be applied only when all emissions
exit through one opening.
Since the various sampling devices
other than filter impactIon have not
been extensively field tested, they
should not be used without on-site
calibration with hi-volume samplers.
Ambient data gathered during an ev-
vironmental .impact study can be used
for the background data or an exist-
ing plant operation should be halted
and any aggregate piles wetted and
covered. Applicable for determina-
tion of diffuse or-multi-point fugi-
tive sources' on a plant-wide-basis.
Should be used when emissions are
from specific point source only.
To increase accuracy, as many tests
as possible should be performed. For
this reason, due to the fact that a
low grain-loading.is anticipated, an
Isokinetic hi-volume- sampler is
recommended, such as the one develop-
ed by Radar Pneumatic. If
however, particle*size measurements
are to be performed, then the SASS
train should be used.
Same as for Quasi-Stack.
A-79
-------
TABLE A-5 (continued).
INTEREST
AREA
Fugitive
Participates:
Specific Point
Sources
(cont.)
Fugitive
Gases
METHOD
OPTION
Plume Sampling1
REFERENCES
''
147
METHOD
ADVANTAGES
*
(a) Particle size and mass emission measure-
ments can be made directly.
A-f
-------
TABLE A-5 (concluded).
METHOD
DISADVANTAGES
APPLICABLE
STRATEGY
LEVEL
REMARKS
(a) Testing many point sources would be
an expensive and time consuming operation.
This method consists of sampling a
fugitive plume with an' SASS train by
placing the nozzle directly into
the plume and sampling isokinetic-
ally.
The methods employed for sampling
fugitive gases are essentially the
same as those identified for ducted
gases (see Gas Sampling Options table)
A-81
-------
TABLE A-6. METHOD OPTIONS FOR INORGANIC GAS ANALYSIS
ANALYSIS
AREA
Ammonia
Carbon
Dioxide
Carbon
Monoxide
Chlorine
Hydrogen
Chloride
METHOD
OPTION
Gas' Chroma-
tography (GC)
Colorlmetrlc
Colorlmetrlc
Tltrlmetrlc
Colorlmetrlc
Specific Ion
Electrode (SIE)
Non-dispersive
Infra-red
(NDIR)
Thermal
Conductivity
Gas Absorp-
tion
GC
NDIR
GC
Colorimetric
Colorlmetric
Colorimetric
Colorlmetrlc
GC
Tltrimetrlc
Potentlo-
metrlc
Colorimetric
Dispersive IR
SIE
DETECTION
LIMIT
25ppm
25 ppm
25 ppm
25 ppm
1 ppb
1 ppm
10 ppm
25 ppm
25 ppm
10 ppm
25 ppm
1 ppm
1 ppm
1 ppm
1 ppm
1 ppb
1 ppm
1 ppm
0.5 ppm
1 ppm
SPECIAL
ANALYTICAL
CONSIDERATIONS
Poropak Q-column packing; gas bomb.
Absorption In IN HgSO^
Absorption in IN H2SO^
Absorption in IN H2S04
Sample on filter paper treated with oxalic acid.
Absorption with IN H SO, .
Remove H.O partlculates.
Remove partlculates.
Absorption In 6 M NaOH.
Gas bomb; molecular sieve column.
Water removal.
Gas bomb; molecular sieve column.
Absorption train.
Train constructed of glass, SS, or teflon.
Upper concentration limit of 10 ppm.
Train constructed of glass, SS, or teflon.
Upper concentration limit of 50 ppm.
Train constructed of glass, SS, or teflon.
Upper concentration limit of 300 ppm.
Gas bomb.
Implnger train. Upper concentration limit of
100 ppm.
Implnger train. Upper concentration limit of
10 ppm.
Remove HO.
Implnger train.
A-82
-------
TABLE A-6 (continued).
INTERFERENCES
Specific
_ +2 „ +2 +2 +1
Fe+2, Cr , Mn , Cu ,
Cu .
„ +2 „ +2 __+2 _ +3
Ca2 , Mg , FE , Fe ,
S , amines, ketones,
aldehydes, alcohols.
+2
Amines , Ca
Formaldehyde.
H20
Gases with high TC.
Other acid gases.
Specific.
H20.
Specific.
Specific.
Hal Ides, CN~, N0~.
Chlorides.
Chlorides.
Specific.
Specific.
Halldes, cyanides,
nitrites.
C02, H20.
Halldes
REFERENCES
13.4
216
13.4
272
304
33,221
94
94
94
94
94, 67
94, 273
8.21
8.21
40
31
8.9
8.32
221
97
APPLICABLE
STRATEGY
LEVEL
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
REMARKS
100% sampling efficiency assumed.
Kjeldahl method.
Ring Oven technique.
Calibration by known addition method.
Suitable for continuous monitoring.
Detection limit is detector dependent.
Mercuric Thiocyanate method.
Colldlne method.
Electron capture detector.
Chloride is a common contamlnent; use
delonlzed water In analysis.
Suitable for continuous monitoring. For
low concentration detection, long path
length required.
Calibration can reduce Interferences.
A-83
-------
TABLE A-6 (continued).
ANALYSIS
AREA
Hydrogen
Cyanide
Hydrogen
Fluoride
Hydrogen
Sulfide
Mercury
METHOD
OPTION
Potentiometrlc
GC
GC
Color imetrlc
SIE
Colorlmetric
GC
Paper tape
Colorlmetric
Tltrimetric
Colorlmetric
Potentiometrlc
Fluorescent
AA/FAAS
GC
Atomic Fluores-
cence
FAAS
FAAS
FAAS /Go Id
Amalgam
Cold Vapor
Colorlmetric
Tltrimetric
DETECTION
LIMIT
1 ppm
1 ppm
25 ppm
1 ppm
1 ppm
1 ppm
Ippb
10 ppb
1 ppm
1 ppm
1 ppb
1 ppm
1 ppb
1 ppb
1 ppm
1 ppb
1 ppb
1 ppb
1 ppb
1 ppb
1 ppm
1 ppm
SPECIAL
ANALYTICAL
CONSIDERATIONS
Implnger train.
Impinger train.
Gas bomb, Poropak Q column.
Implnger train.
Impinger train.
Impinger train.
Gas bomb.
Paper must be kept moist; sensitive to light.
Upper concentration limit of 50 ppm.
Use restricted opening bubbler.
Impinger train.
Impinger train.
Impinger train.
Collection on tape.
Absorption using Impinger train with IC1. Pyrex
glass, teflon, or polycarbonate containers
required. Sample acidified to pH_ for storage.
Absorption using implnger train.
Sample passed thru carbon column at 1350 C.
Absorption on iodine impregnated charcoal.
Absorption using a wire or chips.
+2
Mercury Is converted to Hg
Mercury must be +2 state.
Mercury must be +2 state/oxidation. Upper
concentration limit of 100 ppm.
A-84
-------
TABLE A-6 (continued).
INTERFERENCES
H2S.
SCN".
Specific.
Sulflde oxidants.
OH".
Many cations, Cl
Specific.
RSH, NH_.
SO,RSH.
RSH.
S02, RSH.
RSH, HCW.
RSH.
so2.
Specific.
CO, N2.
Negligible.
H.O vapor.
REFERENCES
266, 314
832
303
216
38, 87, 142
38, 226
11
11
38
38
65,263,27,21,
199,154,276,51,
42,175,72
27
277, 65, 154
154
175, 307
65
65
65
APPLICABLE
STRATEGY
LEVEL
1 and 2
1 and 2
TRW
1 and 2
1 and 2
1 and 2
1 and 2
1
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
REMARKS
Applied to biological samples and
water analysis.
Temperature control required during
analysis.
Flame photometric detector.
AgNO , HgCl , Ag(CN)" Pb(OAc) tested.
AgNOj best.
Rarely used. Lacks sensitivity. SO
Interference may be removed with FeCI,.
Sample must be analyzed Immediately.
SO.lnterfers seriously; method considered
unsatisfactory.
Useful for determination of organomercury
compounds .
Direct determination In air unsatisfactory.
(CO and N,, quench signal.)
Measured at 184. 9- nm.
Charcoal used to concentrate mercury and
remove possible interferences.
Current EPA method.
Water vapor interference may be removed
by heating cell or drying agents.
A variety of methods are possible; see
reference for discussion.
A variety of methods are possible; see
reference for discussion.
A-85
-------
TABLE A-6 (continued).
ANALYSIS
AREA
Mercury
(cont.)
Miscellaneous
Sulfur
Compounds
• (RSH, RSR,
COS, CTC)
Nitrogen
Oxides
Oxygen
Sulfur
Dioxide
METHOD
OPTION
Polarographic
Piezoelectric
GC
Titrlmetric
NDIR
Colorlmetrlc-
Chemi lumines-
cent
Paramagnetic
SIE
Electro-
chemical
UV
Gas Chroma-
tography (GC)
Phenol
Disulfonlc
Acid (PDS)
Fluorescence
Paramagnetic
GC
Combustion
Polarographic
Titrlmetrlc
NDIR
Fluorescent
DETECTION
LIMIT
1 ppm
1 ppb
1 ppb
1 ppm
5 ppm
1 ppm
1 ppm
10 ppm
1 ppm
20 ppb
1 ppm
10 ppb
1 ppm
1 ppb
O.OU
25 ppm
O.OU
7.
1 ppm
5 ppm
1 ppb
SPECIAL
ANALYTICAL
CONSIDERATIONS
Mercury must be +2 state/oxidation.
Mercury must be in elemental form.
Bomb sample, Poropak QS column.
Absorption using impinger train.
Dry sample.
Dilution of sample is required for analysis of
high levels of NO,.
Particulate removal.
Particulate removal.
Method is rate of flow dependent.
Particulate removal.
Gas bomb. Quantitative recovery from column
is difficult at low concentration levels.
Dilution necessary.
Particulate removal.
Gas bomb .
SO., acid gas removal.
_2
Acid gas removal with Cr.O.
Special train and Implngers required.
Sample should be dry.
Sample should be dry. Sample dilution is neces-
sary for high (>100 ppm) concentrations.
A-86
-------
TABLE A-6 (continued).
INTERFERENCES
Chlorine, water,
particulates.
Specific for Individual
components.
HCN.
Aromatic HC, CO , HO.
PAN, NH,, HC.
3
Other paramagnetic
species, e.g. 02>
HC1, HF, CO, S02.
H2S.
Specific.
Specific.
Water, particulates.
HC.
Other paramagnetic
gases, e.g. NO.
Specific.
CO, HC.
Specific.
Partlculate matter.
Aromatics, HO, COj.
Aromatlcs.
REFERENCES
65
263
87
327
33, 221, 216
326, 44, 185,
302, 201
197, 278
84, 183
146
101, 99, 102
14
38
299
155, 282
29
158
89,159,228,39,
293.24,216,278,
93,225,184
33, 221
302, 230
APPLICABLE
STRATEGY
LEVEL
1 and 2
1 and 2
1 and 2
1 and 2
2
2
2
1 and 2
1 and 2
1 and 2
2
1 and 2
2
2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
REMARKS
a variety of methods are possible; see
reference for discussion.
Water, chlorine, and particulates may be
removed with filter and trap. Suitable
for continuous monitoring.
Different columns described; for most
sensitive detection, FPD used.
Method depends on relative decomposition
rates of COS and CS. for separation; RSH
and H2S trapped prior to COS and CS. but
may be analyzed.
Suitable for continuous analysis.
NO specific.
NCL specific.
NO and NO measured. Continuous.
X
NO and NO measured.
£.
Interferences may be removed by
precipitation .
NO specific.
Continuous. NO specific.
To achieve lower limits , an ionization
detector or flame chemiluminescent detector
may be used.
NO specific.
Suitable for continuous monitoring.
Barium-Thorin method.
Suitable for continuous monitoring.
Suitable for continuous monitoring.
A-87
-------
TABLE A-6 (continued).
ANALYSIS
AREA
Sulfur
Dioxide
(cont.)
Sulfur
Dioxide
Sulfur
Trloxlde
Water
Vapor
METHOD
OPTION
UV
Electro-
chemical trans-
ducers
CG
Potentlo-
metrlc
Colorlmetrlc
Colorlmetrlc
H202 Titri-
metrlc
Piezo-
electric
Conducto-
metric
Correlation
Spec.
Second
Derivative
Spectroscopy
Tltrlmetrlc
Spectro-
photometrlc
Coulometric
Flame-
photometric
Raman
Spectroscopy
Condensation
NDIR
DETECTION
LIMIT
1 ppm
1
1 ppb
10 ppb
10 ppb
10 ppb
2 ppm
1 ppm
10 ppm
100 ppb
1 ppm
1 ppb
<1 ppb
<1 ppb
0.1%
25 ppm
SPECIAL
ANALYTICAL
CONSIDERATIONS
Sample should be dry.
Method is flow rate dependent.
Gas bomb.
Gas bomb.
Sample aspirated thru Tetrachloromercurate.
Filtration required.
Partlculate removal.
Sample conditioning.
Sample conditioning.
Sample conditioning.
Special train and impingers required.
Glass fibre filters acid washed.
Glass fiber filters acid washed.
Glass fiber filters acid washed.
Gas bomb.
Sample at 0.075. Heat sample line to pre-
vent condensation.
Sample kept above dew point.
A-f
-------
TABLE A-6 (concluded).
INTERFERENCES
Specific.
NO, H2S.
Specific.
Specific.
N02.
NO , H2S, 03, CH3SH,
C2«4
Acids, bases, partl-
culates.
N0?, partlculates.
Strong acid gases.
Specific.
Specific.
Moisture.
(HH4), S04-
(NH4), S04.
(NH4), S04.
Fartlculates.
Specific.
REFERENCES
296, 102
148
156, 57, 289,
87,233, 228
216, 328
278, 93, 216
252
216
128
148
126, 167
167
271
321, 216
163, 253
279, 216, 163
281
221
APPLICABLE
STRATEGY
LEVEL
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
2
1
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1
1 and 2
REMARKS
Suitable for continuous monitoring.
Suitable for continuous monitoring;
slow response.
Flame photometric detector.
NO. may be prevented from Interfering by
sulfurlc acid addition.
Interferences may be removed by scrubbers.
Suitable for continuous monitoring with
dilution.
All acidic and basic gases Interfere.
High NO level causes extensive fatigue.
2 minute analysis time. Continuous.
Continuous.
Continuous.
Barium-Thorln method.
Method may be applicable to measurement at
low ppm levels. May be suitable for con-
tinuous analysis.
Federal Register Method 4.
Suitable for continuous monitoring.
A-89
-------
TABLE A-7. METHOD OPTIONS FOR ORGANIC ANALYSIS
ANALYSIS
AREA
I.
Volatile1
Organic
Compounds .
General
Nitrogen,
Sulfur, or
Phospho-
rous con-
taining
Low
Molecular
Weight
Gases
Specific
Gases
Halogens,
Nitrates
and Con-
jugated
Carbonyls
Volatile gt
about 400 C
or less.
METHOD
OPTION
Gas Chrom-
atography (GC)
GC with Thermal
Conductivity
Detector* (FID)
GC with Flame
lonlzation
Detector (FID)
GC with Flame
Photometric •
Detector
•
GC with Helium
lonlzation
GC with
Coulometrlc
Detector
GC with
Electron
Capture ,,
(H3 or Nl )
1
DETECTION
LIMIT
Detector
Dependent
0.1%
1 ppm
10 ppb
10 ppb
1 ppm
SPECIAL
. ANALYTICAL
CONSIDERATIONS
On site sampling with use of bag or bomb. Typi-
cal sample Injection volume for liquids is
1-lOui; for gases l-50ml. The following list is
a general' guide to GC columns useful in organic
analysis.
Species Column
Acids C.-C- Chromosorb 101
C,-C10 FFAP
1 18
Alcohols C.-C, Poropak Q, Chromosorb 101
-
C. -C10 Silar 5CP, Carbowax 20M,: FFAP
1 ." '
Polyalcohols FFAP
Aldehydes C.-C Poropak N, DC-550, Ethofat
C--C18 Carbowax :20M, Silar 5CP
Amines Poropak Q/PEI, Poropak R
'Chromosorb 103, Pennwalt 223
Amides Versamid 900, Igepal CO-630
Esters Poropak Q, Dlnonylphthalate
Chromosorb 101 or 102
Ethers Carbowax 20M, Silar 5CP
Freons Poropak Q, Chromosorb 102
Glycols. . Chromosorb 107
Halides OV-210,. FFAP
Hydrocarbons OV-101, SE-30
Vcio
Aromatic Silar 5CP, Carbowax 20M
Oleflns C, and DC-550, DC- 703
greater
POM . Dexsll 300, OV-101, SE-30
Ketones Poropak Q, Chromosorb 102,
FFAP
Pesticides OV-101, OV-225, OV-1, OV-17,
SE-30
Phenols OV-17, Silar 5CP,
Carbowax 20M
A-90
-------
TABLE A-7 (continued).
INTERFERENCES
REFERENCES
APPLICABLE
STRATEGY
LEVEL
REMARKS
Generally quite
specific with proper
column selection
Sensitivity Is
limited.
No response to a
number of low molecu-
lar weight gases, e.g.
air, H20.
Selective for nitrogen,
sulfur, and phosphorous
containing species.
Columns are generally
limited to active
solids.
Selective detector
depending on titrant.
Selective for
electrophiles.
173,216,111,278,148,
32,198,222,9,288, 1 and 2
140,4,330,16,8.30,71,
248;i87;i72,63,53,180,
10.2,10.1,8;3i,330,
180,212,169,277
I I
88,39,227,79,168,7, 1 and 2
265,110,90,162,262,
195,62,210,268,291,
181,224,236,286,139,
181,286,236,224,179
268, 291
63,88
1 and 2
1 and 2
1 and 2
1 and 2
Technique applied widely to all types of
organic analysis; portable instruments are
available for on site stack gas analysis;
most commonly used technique for quanti-
fication in organic chemical analysis.
Response Is linear over a moderate range
of concentration; responds to all
compounds; most widely used detector; non-
destructive; temperature limit is 450C.
Destructive. Widest linear range of
operation gas supply (HO and 0 )
required; temperature limit of 500 C.
Destructive. Detector may also be used in
FID mode as a nonselective detector.
Temperature limit of 300 C.
Non-destructive. Detection limit is
dependent on column bleed. Usually
used to measure low molecular weight
gases; temperature limit of 100°C.
No calibration required for direct quanti-
tative results; detector may be non-
selective if all effluents are combusted;
destructive.
Non-destructive. Sensitive to water;
temperature limit for H3 is 225 C;
f-AmnAVA 14m4f- FA*- U4^3 |a •! CA°
temperature limit for Hi
small linear range.
is 350 C.
A-91
-------
TABLE A-7 (continued).
ANALYSIS
AREA
II.
Volatile and
Non-
Volatile
Organic
Separa-
tion by
Molecular
Weight
Separa-
tion by
Chemical
Class
Separa-
tion of .
Polar
Organic
Compound
III.
Class Identi-
fication
by Func-
tional
Group-
Compound
Identifica-
tion
METHOD
OPTION
(HPLC)
High Perfor-
mance Liquid
Chromatography
Gel Permeation
Chromatography
Bonded
Phase Liquid
Chromatography
(Reverse)
Thin- layer
Chromatography
(TLC)
Liquid-solid
Chromatography
Ion-Exchange
Chromatography
Dispersive
DETECTION
LIMIT
Detector
Dependent
UV-lO-'g
Rl-lmg
uv-io-9s
ug Range
UV- 10-98
RI-1 g
UV-10-98
jig Range
* Refractive
Index
Detector
SPECIAL
ANALYTICAL
CONSIDERATIONS
Sample from extraction of adsorbent trap,
filters, probe and "rough" class separation by
liquid Chromatography column.
-20mg of sample/100 ml of column volume.
Preparative columns can handle up to Ig samples.
jig quantities of samples required for analysis.
TLC supports (SiC>2 and A^C^); generally need
activation by heating at 110°G for 1 hour.
mg quantities of samples are necessary for
analysis.
Preparative columns can handle up to Ig
samples.
Thin. film. on. crystal/for micro determination;
micro-pressed disk, or micro-film technique.
A-92
-------
TABLE A-7 (continued).
INTERFERENCES
System dependent.
Molecular weight dif-
ferences of 15% can
be distinguished.
Rough class separa-
tions may be achieved.
Two dimensional TLC
possible.
Rather tedious.
Difficulty In separa-
ting homologous
series.
Limited use for com-
plex mixtures.
H.O generally not
suitable as solvent.
REFERENCES
15,189, 91,
144,295,62
265
162, 262
277
APPLICABLE
STRATEGY
LEVEL
2
2
2
1 and 2
1
1 and 2
1 and 2
REMARKS
Separation of wide variety of compounds,
especially applicable to high molecular
weight compounds and thermally sensitive
compounds; small sample size requirement.
Most common column packing Is a styrene-
dlvlnyl benzene polymer; mobile phase
must be compatible with support and
detection system - low refractive Index
allows more sensitive detection with RI
detector.
Class separation Is achieved by perform-
ing gradient elution on a reversed phase
column. Solvents chosen for gradient
elution must be compatible with detec-
tion system; mlcropartlcle (5-lOji)
reverse phase packing preferred.
Gradient elution difficult with RI
detection system.
TLC data may give data which is directly
applicable to HPLC. Color reagents may
be used on plate directly for class
Identification.
A useful technique for screening studies;
elution order is non-polar to polar
solvents; a preparative method for rough
class separation.
Used for separation of very polar organic
compounds; supplementary to reverse phase
liquid chromatography; used after se-
quential analysis has Identified an
Ionic fraction.
Dispersive IR systems are widely -
available; average resolution of 4 cm
over the spectral range (3800 cm~^,.=
6001cm~1) ; wavelength accuracy of —
cm above 2000 cm"1 (less than that
below 2000 cm ) • Wavelength reada-
bility should be better than 10 cm' at
wave numbers above 2000 cm"1 and better
than 5 cm"1 below 2000 cm .
A-93
-------
TABLE A-7 (continued).
ANALYSIS
AREA
Functional
group
Identification
(cont. )
IV.
Class Identi-
fication
Compound
Identifi-
cation
V.
Class
Identifi-
cation
VI.
Compound
Identifi-
cation
METHOD
OPTION
Fourier
Transform
IR
GC-IR
Nuclear Mag-
netic Reso-
nance CNMR)
H
With CAT*
NMR
Fourier Trans-
form CFT)
H1
NMR
FT
C13
*Computer
Averaged
Transients
UV-Vlsable
Spectroa-
copy
(200-1000 nm)
Mass
Spectros-
copy (MS)
Electron
Impact (El)
DETECTION
LIMIT
10-100
ng
0.4 g/peak
~lmg
-lO^g
lOug
Img
Varies
Widely; ,
10"Z-10"5
Molar
100-1000 Kgi
compound
dependent
SPECIAL
ANALYTICAL
CONSIDERATIONS
Thin film on crystal/KBr Pellet.
Gas cell.
Dissolution In suitable solvent.
Dissolution in suitable solvent.
Dissolution in suitable solvent.
Dissolution in suitable solvent.
Sample is dissolved In a suitable solvent
(UV/VIS inactive).
Several Injection methods possible (probe
Insertions preferred) ; temperature programming
of probe may give additional separation.
\
A-94
-------
TABLE A-7 (continued).
INTERFERENCES
H.O generally not
suitable as solvent.
Limited by sample
volatility.
Proton containing
solvents; paragmag-
netic materials.
Solvent should contain
no carbon or only one
type of carbon.
Sensitivity may be
limiting factor.
Limited by sample
volatility.
REFERENCES
277
277
277, 20, 264
APPLICABLE
STRATEGY
LEVEL
1 and 2
2
2
2
2
1 and 2
2
REMARKS
Greater sensitivity obviates need for
micro techniques; accuracy and resolution
as above, dedicated computer necessary
but considered an advantage; a very
useful screening technique.
Micro techniques may extend range down
to 10-100 ng range; useful for functional
group classification after "rough"
separation has been made. Computer of
average transients extends sensitivity
100X.
Fourier transform NMR Is 100-1000 X more
sensitive than CW NMR; micro techniques
may extend range 10-100 X lower; dedicated
computer required.
Large chemical shift range (600pptn) as
compared to H NMR (20ppo) which enhances
effective resolution. Ability to Iden-
tify functional carbons; most useful where
IR and MS give relatively little infor-
mation.
Useful in identifying functional groups
and certain types of compounds; sensi-
tivities are generally higher in UV region
used in conjunction with IR, NMR and MS.
Not a useful screening technique; computer
access to a large data base is essential.
A-95
-------
TABLE A-7 (continued).
ANALYSIS
AREA
Compound
Identifi-
cation/
Molecular
Weight
Compound
"identifi-
cation'
Molecular
Determi-
nation
METHOD
OPTION
Mass
Spectroecopy
Chemical
lonizatlon (CI)
GC-MS
El and CI
DETECTION
LIMIT
10-100 ug;
compound
dependent
10-100 ng;
compound
dependent
SPECIAL
ANALYTICAL
CONSIDERATIONS
Several Injection methods possible (probe
Insertion preferred) ; temperature programming
of probe may give additional separation.
As In GC analysis-
A-96
-------
TABLE A-7 (concluded).
INTERFERENCES
Limited by sample
volatility.
.»• •_
Limited by sample ;
volatility. •
1'
REFERENCES
APPLICABLE
STRATEGY
LEVEL
2
1 and 2
REMARKS
CH, and NH. are commonly used as Ionizing
gases; suitable standards are unavailable
at this time for CMS; of limited use as
screening technique.
El analyses have extensive data files
but are of limited value for Cl analy-
sis. Dedicated minicomputer is
essential for best results; quantifi-
cation may be achieved by specific
ion current integration or by total
ion current.
A-97
-------
TABLE A-8.
METHOD OPTIONS FOR ELEMENTAL ANALYSIS -
SPARK SOURCE MASS SPECTROMETRY
ANALYSIS
AREA
Elemental
Analysis:'
All elements
are, In
theory, able
to be analyzed
by this tech-
nique.
Elements pre-
ceeding lith-
ium are not
commonly
analyzed by
SSMS.
, Ar Mn
Ag Mo
' Al N
'As Na
Au Ne
B Nb
Ba Nd
Be Ni
Bi 0
Br Os
C P
Ca Pb
Cd Pd
• Ce Pr
Cl Pt
Co Rb
Cr Re
Cs Rh
Cu Ru
Dy S
Er Sb
Eu Sc
F Se
Fe Si
Ga Sm
Gd Sn
Ge Sr
H Ta
Ho Tb
Hf Te
Hg Ti
He Tl
I Tm
Ir V
;K W
Kr Xe
La Y
Li Yb
Lu Zn
jMg Zr
METHOD
OPTION
Spark Source
Mass
Spectrometry
(SSMS)
DETECTION
LIMIT
Liffiit of
detection may
be calculated
as Wfg)=(8.3x
10"13)M/A
where M=gram..
atomic weight
of an isotope
and A=relative
abundance of an
isotope.
Experimental
detection
limits.
Absolute (ne)
0.03 0.05
0.2 0.3
0.02 0.01
0.06 0.02
0.2 0.02
0.01 0.08
0.2 0.4
0.008 0.07
0.2 0.01
0.1 0.4
0.01 0.03
0.03 0.3
0.3 0.3
0.1 0.1
0.04 0.5
0.05 0.1
0.05 0.2
0.1 0.09
0.08 0.03
0.5 0.03
0.5 0.2
0.2 0.04
0.02 0.1
0.05 0.03
0.09 0.5
0.5 0.3
0.02 0.09
0.0008 0.2
0.003 0.1
0.4 0.2
0.6 0.2
0.1 0.1
0.1 0.2
0.3 0.04
0.04 0.5
0.1 0.4
0.1 0.07
0.006 0.5
0.1 0.1
0.03 0.1
SPECIAL
ANALYTICAL
CONSIDERATIONS
Method is able to analyze rag quantities of
materials but for precise results the sample must
be homogenous at submicron particle sizes.
Sample may be ashed prior to analysis as a con-
centration technique. Volatile' e'lements/'irequife
i low temperature or wet ashing procedures. Samples
must be conducting; non conducting samples may ;be
powdered and blended with . graphite or metal powder
and briquetted into the shape of electrodes.
A-98
-------
TABLE A-8 (concluded).
INTERFERENCES
REFERENCES
APPLICABLE
STRATEGY
LEVEL
REMARKS
.Spectral overlap:
- Molecular ions composed
of more than;one ele-
ment may be -detected;•
Inorganic .species of
the+type, MO ,-MQH- ,
;Mp^ , are likely "to be
formed; polyatomic
species may be -also be
formed. Common inor-
ganic interferences are:
145, 249, 229,
149, 129, 213,
260, 329, 320,
324, 295, 238,
307
Level 1
(Photp-
plate
Detection)
Level 2
(*P
Detection)
VV(47),
12Cs+(60)J
"Ca16^
iOrganic components pre-
terit in a sample may
.greatly complicate spec$i
tra interpretation
fcraause of extensive
'.molecular ion formation.
SSMS.is most useful quantitatively in
the range of 1-1000 ppm although range
extends from ppb (ideal conditions-
mqnoisotoplc) to %.
Precision and complexity of spectral
analysis for trace elements of interest
is, by in large, a function of the
complexity of the matrix material being
analyzed. Complex matrices imply the
following classification of trace -..
elements that may be detected by SSMS:
a) Monoisotopic trace elements which, in
the absence of gross interferences
(i.e., presence of a doublet), can be
used to obtain upper limits of their
concentration.
b) Multi-isotopic elements for which '
interference can be detected for all
isotopes buy may be determined by
examining isotopic ratios. These
values may represent only upper limits
of concentration.
c) Multi-isotopic elements for which
isotopic ratios are maintained for
at least two isotopes, which allows
for the dependable determination of
concentration. Elements for which' no •
lines are detected permit calculation
of an upper limit.
A mass spectrometer with sufficient resol-
ving power ( 6000) may remove many inter-
ferences; resolution however decreases'
with atomic weight; two types of detectors
are in common use - photoplate (simul-
taneous quantitative, determination of
elements) and electrical detection
(photomultiplier type). SSMS as a
Level 2 technique depends heavily on the
availability of good quantitative stan-
dards in a .suitable matrix. Independent
analysis may be used to establish sensi- -
tiylty factors and perhaps secondary
standards.
A-99
-------
TABLE A-9. METHOD OPTIONS FOR ELEMENTAL ANALYSIS -
ISOTOPE DILUTION MASS SPECTROSCOPY
ANALYSIS
AREA
Elemental
Analysis:
Any element
which has
either two or
more naturally
occurlng
stable Iso-
topes or a
long-lived
Isotope on
the mass
spectrometer
time scale.
H V Bd Gd
He Cr Ag Dy
LI Fe Cd Er
Be Nl In Yb
B Cu Sn Lu
C Zn Sb Hf
N Ga Te W
0 Ge I Re
Ne Se Xe Os
Mg Br Cs Ir
SI Kr Ba Pt
S Rb La Hg
Cl Sr Ce Tl
Al Zr Nd Sb
Ca Mo Pm Th
Ti Te Sm U
K Ru Eu Ru
Mn Ta Ho
Elements which
are not deter-
mined by this
technique are
as follows:
(1) Na, Sc,
Co, As, Y, Tb,
Tm
(2) F, P, Pr,
Au
Group (1) has
Isotopes with
half-lives
longer than
70 days which
could be used
under certain
circumstances.
METHOD
OPTION
Isotope
Dilution Mass
Spectroscopy
(IDMS)
DETECTION
LIMIT
IDMS is
inherently on
the same order
of sensitivity
as SSMS.
Sample prep-
aration usually
includes pre-
concentratlon
procedures
which can
Improve detec-
tion limits
100%.
See preceedlng
SSMS table.
SPECIAL
ANALYTICAL
CONSIDERATIONS
All chemicals used must have Impurity levels
well below the levels being measured.
Preparation of the spike is usually accomplished
by dissolving accurately weighed mg quantities
of the spike isotope and diluting to volume.
The sample is weighed and then dissolved in a
suitable solution. The spike solution must be
added as early as conveniently possible; sub-
sequent step must Insure that the sample and
spike are mixed thoroughly and in the same
chemical form. Once equilibrium is established
among the isotopes, quantitative recovery of the
element is no longer necessary, although a high
recovery is usually desirable to maintain high
sensitivity. Spike size should be adjusted such
that the final isotopic ratio is close to unity.
The simplest technique is evaporation of some of
the solution onto the electrodes, but relatively
poor detection limits are obtained.
Electro deposition has been used with success as
a preconcentratlon step.
A-IOO
-------
TABLE A-9 (concluded).
INTERFERENCES
This technique Is
subject to very few
Interferences :
and few sources of
bias since complete
sample recovery is
unnecessary*
Interference from Iso-
topes or multiply- ;
charged species can
usually be calculated
or avoided by suitable
isotope selection.
This technique is
essentially free of
any matrix effects.
REFERENCES
26, 318
APPLICABLE
STRATEGY
LEVEL
2
REMARKS
IDMS complements conventional. SSMS. The
Utter first identifies tte elewata
and their approximate concentration*
and then IDMS is used to deternlae
accurately thoae elaoents of particular ^
Interest. --
The use of the Isotope dilution technique
generally Increases the number of steps
and the amount of time needed for a mass
spectrometric analysis (5 samples for
6 elements in 10-15 man days). Only
one or at most several elements may be
determined simultaneously by Isotope
dilution techniques.
The time per element could be reduced
substantially if the technique were put
on a production basis and if several
elements were determined simultaneously
using a single mixed spike solution.
Isotope dilution SSMS provides precise
absolute analyses for specific elements
over a very wide range of concentrations
without the need for standards. A major
use for ID-SSMS is the preparation of
SRM's.
A-IOI
-------
TABLE A-10. METHOD OPTIONS FOR ELEMENTAL,ANALYSIS -
NEUTRON ACTIVATION ANALYSIS
ANALYSIS
AREA
Elemental
Analysis:
The following
list Is a-
b ridged due to
space limita-
tions. For a
complete list-
ing of the
elements,
their reac-
tions, poten-
tial Inter-
fering ele-
ments, and es-
timated de-
tection lim-
its, see ref-
erence
pg. 284-327,,
Al
S
Ca
Ti
V
Cu
Na
Mg
Cl
Mn
Br
Tn
I
K
Ta
Zn
Br
As
Ga
Sb
La
Sm
Eu
W
Au
Se
Cr
Fe
Co
Nl
Ba
Se
Ag
Sr
Ce
Hg
Th
METHOD
OPTION
Neutron Actlva-
^Analysis
DETECTION
LIMIT
Range is from
detection limit
to %. Detec-
tion Unit is ;
in gg and is <
for slow
(thermal)
neutrons
0.04
25.0
1.0
0.2
0.001
0.05
0.2
3.0
0.5
0.003
0.02
0.0002
0.1
0.075
--
0.2
0.025
0.04
0.01
0.03
0.002
0.00005
0.0001
0.005
0.001
0.003
0.02
1.5
0.002
1.5
0.1
0.01
0.1
--
0.02
0.01
0.003
SPECIAL
ANALYTICAL
CONSIDERATIONS
Samples must be removed and Introduced to the
reactor In a reproducible manner. Sample size is
on the order of 100-500 mg. Direct analysis may
be performed on filter media. Glass fiber filters
are not appropriate because of .high trace metal
concentrations. Polystyrene filters have been
used for sampling; Whatman 41 filter paper has
been suggested as being an appropriate media also.
Quartz and polyethylene vials and polycarbonate
bags have been used as Irradiation containers.
The general experimentation method In a typical
activation analysis can be broken down Into the
following steps:
(1) Irradiation of weighed sample and standard
for a suitable time.
(2) Dissolution of the sample and standard and
addition of a known weight of the element being
determined as a carrier of the small amount of
analyte. Irradiated.
(3) Treatment of the sample such that the
carrier and analyte element are in the same
chemical form.
(4) Isolation of the element from other
radionudldes by chemical separations.
(5) Determination of the chemical yield of step 4
(6) Comparison of the activities of the sample
and standard under Identical conditions, making
corrections where needed for decay, self absorp-
tion, etc.
(7) Determination of the radio chemical purity
of the isolated active compound.
Under favorable conditions, steps 2-5 can be
omitted and the mass of analyte calculated from
the ratio of the activities.
A-102
-------
TABLE A-10 (concluded).
INTERFERENCES
See references:
Interferences include
both nuclldes which
may Interfere in diode
measurement, and possi-
ble Interfering nuclear
reactions which pro-
duce nuclldes of
Interest.
REFERENCES
32, 318, 46
^
APPLICABLE
STRATEGY
LEVEL
REMARKS
Method is, for a number of elements, non-
destructive and quite rapid. If high neu-
tron fluxes or nuclear reactors are used,
NAA Is an extremely sensitive method; no
blanks due to chemical reagents are needed.
High resolution Ge (Li) detectors allow a
wide variety of isotopes to be counted sim-
ultaneously. The system is amenable to com-
puter interface and can be almost complete-
ly automated.
For a number of elements, e.g., Cl, Br, Na,
Zn, the sensitivity is limited by the puri-
ty of the filter media.
For about 15 elements the sensitivity Is
limited by the matrix composition. Abun-
dant elearata such M' Si, Al, and Br give
rise to a large amount of radioactivity
and other elements may be difficult to de-
tect in their presence.
Mercury is particulary sensitive to inter-
ference and radiochemical separation may
be necessary to achieve the lower limits
of detection.
Two types of detectors are commonly used:
Ge(Li) and Nal(Tl).
Radiochemical separations are necessary for
many elements if a Nal(Tl) is the only
detector available. In general, chemical
separations may improve the sensitivity of
a number of elements, e.g., Cu, Zn, Ga, As,
Se, Ce, Sm, Eu, W, Au, Hg.
Analysis time delays fall into three time
periods: 1-15 mln., 20-30 hrs., 20-30 days.
Analysis is generally limited to approxi-
mately 30 elements for a given sample due
to interference effects.
The most generally useful and readily a-
vailable source for high sensitivity in
the determination of trace elements is the
nugljar reactor (10-10 neutrons
Ms).
A major advantage of this source is that
only one nuclear reaction (R(n, )P) usu-
ally occurs and the cross-section for the
reaction is usually quite high.
A-103
-------
TABLE A-ll. METHOD OPTIONS FOR ELEMENTAL ANALYSIS -
INSTRUMENTAL PHOTON ACTIVATION ANALYSIS
ANALYSIS
AREA
Elemental
Analysis:
Na
Cl
Ca
'Ti
cr
Nl
Zn
As
Br
Zn
Sb
I
Ce
Pb
METHOD
OPTION
Instrumental
Photon Activa-
ttqe: Analysis
(IPAA)
DETECTION
LIMIT
Detection
limits In mg:
2
0.4
30
0.9
4.5
0.05
3
0.2
30
0.2
0.3
0.2
0.4
12
SPECIAL
ANALYTICAL
CONSIDERATIONS
Sampling considerations are similar to NAA.
Sample may be Irradiated In polyethylene bag or
filter media may be pelletlzed for Irradiation.
A-104
-------
TABLE A-ll (concluded).
INTERFERENCES
27A1 24 25Mg
.If
50 ,
51™50 45gc
5*Fe, Fe
79
Br
141,,
Pr
REFERENCES
•.
t
32, 319, 80,
333, 318
• •
APPLICABLE
STRATEGY
LEVEL
1,2
REMARKS
1PAA is a nondestructive method of analy-
sis which is directly complementary to
NAA; Ti, Nl, As, 1 are comparatively easy
to analyze (interference free) as compared
to NAA.
Sensitivity is considerably less .than NAA.
Blank corrections for filter media may be
necessary
A-105
-------
TABLE A-12. METHOD OPTIONS FOR ELEMENTAL ANALYSIS -
X-RAY FLUORESCENCE
ANALYSIS
AREA
Elemental •
Analysis: .
The followr
Ing IB a 1 lot
of elements
for which
detection
limits have
been
reported.
Aluminium
Arsenic
Barium
Bromine
Bismuth
Calcium
Cadmium
Cerium
Cobalt
Chromium
Cesium
Cooper
Europium
Gallium
Gold
Indium
Iron
Lanthanum
Lead
Manganese
Mercury
'Molybdenum
Neodynlum
METHOD
OPTION
r
X-ray •
Fluorescence
;(XRF)
"•'
DETECTION
LIMIT
Detection
limits in jig
except where
noted. '
.5
0.1
0.1
2
lOOng/cm
Of
.6
0.1
Ot
.4
0.2
0.05
0.00006
0.2
0.00002
0.7
0.01
0.001/cm2
.1
0.009
0.1
0.0003
0.0002
0.2
0.07
0.3
SPECIAL
ANALYTICAL
CONSIDERATIONS
X-r«y intensities depend on the .matrix composition;
in addition, fluorescence intensities are highly .
matrix-dependent. Different particle sizes can
•have a significant effect on fluorescence inten-
sities. It is most important that standards and
sample be controlled carefully 'as to minimize
differences in chemical form and physical nature.
Virtually any -type of solid or liquid sample may
be easily prepared for analysis; -however, the
above criteria must be met to Insure reasonably
accurate and precise analysis.
There are five common methods used for quantifi-
cation in -XRF: (1) Absolute calculation method;
(2) Direct comparison -with suitable standards;
(3) Standard addition methods; (4) standard
dilution .methods; and (5) internal .standardization
methods .
Other quantification methods, used somewhat less
frequently are: thin film .method; x-ray .scatter
standardization; experimental correction and
absorption-enhancement .effects; and mathematical
correction of absorptlonfenhancement effects.
Sensitivity falls off rather rapidly below mange-
ese (atomic number 25) with an air path;
potassium (Z-13) with a helium path; and alumi-
num (Z-13) with a vacuum path. The detection limit
for a sodium (Z-ll) is only 0.1% for a sample in a
vacuum path Instrument. Furthermore, rather long
counting times (2-30. minutes) may be required to
achieve any of these detection limits. The
following -must be kept constant if accurate
.quantitative results are to be obtained: (1) The
source Intensity; (2) Geometric factors, including
the angles between the exciting x-ray beam and
sample surface, the absorption .path length, the
atmosphere around the sample, and the angle
between the measured fluorescence x-rays and the
detector; and (3) the constancy of the detector
system.
Calibration curves for heavy elements in a matrix
of light elements may produce a curve which is
concave or even parallel to the concentration
axis (e.g., lead in glass) making any analysis
Impossible. (This effect con be corrected, . .
however) .
A-106
-------
TABLE A-12 (continued).
INTERFERENCES
REFERENCES
APPLICABLE
STRATEGY
LEVEL
REMARKS
Spectral interferences
are Intimately related
to the resolving power
of the instrument'.
Different crystals have
different resolving
capabllityes in wave-
length — /ispersive
systems and in energy
dispersive systems.
Resolving power. may be
defined as:
325, 98
1 and 2
Where W, is defined as
full width at half maxi-
mum (in keV) and vaV is
the average pulse height
(in keV) . For a wave-
length dispersive
spectrometer, the re-
solving power is ap-
proximately 230. For an
energy dispersive sys-
tem, the resolving
power is ~12 with pro-
portional detectors and
~40 with semiconductive
detectors (Geli or Sill
S1L1).
The most common
spectral Interferences
originate from three
sources: (1) First
order transitions of the
same series from ele-
ments adjacent to the
analyte species in
atomic number; (2)
First order trans i-
of different series,
i.e., the L series of
A interfering with the
K series of B; and
(3) First order tran-
sitions of the analyte
species with higher
order transitions of
matrix elements.
Two types of x-ray spectrometers are in
common use; wave length dispersing
spectrometers and energy dispersive
spectrometers. Energy dispersive systems
offer a number of advantages over wave-
length dispersive systems. The most ob-
vious advantage is the rapid, olmultaneoua
analysis of many elements. The radiation
path length is also reduced so that a
greater flux of x-rays can be directed onto
the sample; this allows the use of radl-
active isotones as sources which in turn
makes small portable XRF units a reality.
A major disadvantage of energy dispersive!1
systems is the loss of resolving power as
compared to wave length dispersive systems.
Components for the two systems are the
same except that for energy dispersive
systems pulse height analysis is required
and radioactive Isotopes rather than x-ray
tubes can be used.
Detection limit is directly related to
time of counting; since there is no sample
consumption, measurement time is not sample
limited and counting times of several
minutes are not uncommon.
A-107,
-------
TABLE A-12 (continued).
ANALYSIS
AREA
Elemental
Analysis:
-
Nickel
Phosphorus
Potassium
Rhodium
Rubidium
Samarium
Scandium.
Selenium
Silicon
Strontium
Sulfur
Tellurium
Terbium
Thorium
Tin
Titanium
Uranium
Vanadium
Ytterbium
Yttrium
Zinc
Zirconium
METHOD
OPTION
X-Ray
Fluorescence.
(cont.)
DETECTION
LIMIT
0.06
0.001
0:5
100
0.003
4
0.4
0.02/cm2
170ppm
0.00007
8ng/cm
0.1
200
7
4ppm
0.001
0.00002
2
17ng/cm
7
0.22
0.00004
0.00002
SPECIAL
ANALYTICAL
CONSIDERATIONS
,
A-108
-------
TABLE A-12 (concluded).
INTERFERENCES
REFERENCES
APPLICABLE
STRATEGY
LEVEL
REMARKS
A-109
-------
TABLE A-13. METHOD OPTIONS FOR ELEMENTAL ANALYSIS -
PROTON INDUCED X-RAY ANALYSIS
ANALYSIS
AREA
Elemental
Analysis:
56Fe
69Ga
75
As
76,,
Se
85
Rb
94
Mo
Q,
Mo
94
Mo
94
. Mo
103
UJRh
102
Pd
104Pd
107
Ag
110
Cd
110 .
Cd
U1Cd
112Cd
113
In
115
In
U8Sn
119
120n
Sn
121Sb
133
Cs
139
La
140
Ce
142
Ce
141
Pr
151
Eu
153
• Eu
155
Gd
156
0 Gd
160
1DUDy
161
Dy
METHOD
OPTION
Proton Induced
X-ray Analysis
(-PIXA).
20 Mev proton
activation.
DETECTION
LIMIT
Detection lim-
its inpg and are
'. theoretical
;i.l X IO"2
;4.0 x IO"1
. „ .-2
1.9 x 10
2.6 x IO"2
-2
4.4 x 10
-3
4.2 x 10
-4
1.0 x 10
-4
3.4 x 10
-1
2.8 x 10
-2
1.1 x 10
-1
1.0 x 10
-4
5.8 x 10
-2
8.6 x 10
-2
2.3 x 10
-4
3.2 x 10
-1
2.4 x 10
-3
4.5 x 10
5.8 x 10*1
-3
2.2 x 10
i
7.8 x 10~*
-4
1.5 x 10
-4
6.6 x 10
-3
8.6 x 10
-4
2.1 x 10
-4
2.1 x 10
-3
4.3 x 10
-3
4.3 x 10
SPECIAL
ANALYTICAL
CONSIDERATIONS
Powder speclments, as a rule, present the great-
est problems. Sample should be ground to a size
of <10 u and followed by briquetting. Samples
may be fluxed and converted to a glass to reduce
sample inhomogeniety. . For solution work, con-
centration onto filter paper discs is useful.
: Sample size is in the range of 1-50 mg. If
analysis will take place on filter media, the
use of thin membrane filter media is recommended.
A-no
-------
TABLE A-13 (continued).
INTERFERENCES
REFERENCES
APPLICABLE
STRATEGY
LEVEL
REMARKS
See .References
32, 315, 135,
208, 83, 171,
134, 150, 318,
30
Accuracy is dependent on suitable choice of
standards in a matrix which Is as similar
to the sample matrix as possible.
PIXA is a comparative technique and thus
it is necessary that calibration standards
and samples to be analyzed are presented
to the spectrometer in an identical and
reproducible way.
Sample must be homogenous as a penetration
depth of 1-100 n occurs; surface heteroge-
neity effects are most critical for long
wavelength radiation and thus particular
care must be taken in sample preparation
with lighter elements such as F, Na, Mg,
Al, and Si.
A method of particular use in the trace
analysis of powders is the "shaking"
method which can reduce matrix effects.
Analysis is rapid, on the order of
minutes.
A-l
-------
TABLE A-13 (continued).
ANALYSIS
AREA
Elemental
Analysis:
165HO
165Ho
166^,
Er
167
Er
168Er
• 1?5Lu
177Hf
.178Hf
179Hf
182w
183,
W
19°0s
191lr
191lr
194Pt
197Au
203^
204Pb
79Br
81Br
102Pd
121Sb
113,,
Ca
132,,
Ba
160n
Dy
163n
Dy
Tl
METHOD
OPTION
PIXA -
20 MeV
(cont.1
DETECTION
LIMIT
3.5 x 10"2
3.0 x 10"4
1.5 x 10"4
1.5 x 10"4
1.5 x 10"4
-4
3.3 x 10
2.1 x 10*
1.3 x 10"3
1.6 x 10
-4
5.6 x 10
1.6 x 10"
8.2 x 10"
1.4 x 10"3
7.7 x 10"
7.3 x 10"
2.6 x 10"2
1.0 x 10"4
2.2 x 10*4
4,5 x 10"3
2.6 x 10"2
3.2 x 10"3
5.7 x 10"4
1.1 x 10"2
6.4 x 10"2
-4
1.1 x 10
-4
3.1 x 10
SPECIAL
ANALYTICAL
CONSIDERATIONS
See previous comments.
A-II2
-------
TABLE A-13 (continued).
INTERFERENCES
REFERENCES
32, 318
APPLICABLE
STRATEGY
LEVEL
1.
REMARKS
A-II3
-------
TABLE A-13 (continued) .
ANALYSIS
AREA
Elemental
Analysis:
Li
B
S
Ca
Ti
V
Cr
Fe
Ni
Cu
Zn
Ga
Ge
As
Se
Br
Rb
Sr
Y
Zr
Nb
Mo
METHOD
OPTION
FIX A
10 Mev Prdton
Activation
DETECTION
LIMIT
Detection limit
in ppb
Dependent on
radioisotope
24
190
22
10-3000
9
43
1-1200
61
5-150
3-400
6
4
5
40
1-40
5-10
1
1-1000
2
2-2000
30-40
5-40
SPECIAL
ANALYTICAL
CONSIDERATIONS
A-II4
-------
'TABLE .A-13 (concluded).
INTERFERENCES
REFERENCES
APPLICABLE
STRATEGY
LEVEL
REMARKS
10 Mev proton induced x-ray analysis .is •
able to analyze the lighter elements and
is thus complementary to 20 Mev PIXA
A-II5
-------
TABLE A-14. METHOD OPTIONS FOR ELEMENTAL ANALYSIS -
OPTICAL EMISSION SPECTROSCOPY
ANALYSIS
AREA
Elemental
Analysis:
Li, Na, Cu, A{
Be, B, Mg,.Al,
K, Ca, Sc, Ti,
V, Cr, Mn, Fe,
Co, Ni, Zn.Ga,
Ge, Rb, Sr.-Y,
Zr, Mo, Ru.Rh,
Pd, Cd, In.Sn,
Ca, Ba, La.Au,
Tl, Pb, Pr.Nd,
Eu, Tb, Dy.Ho,
Er, Tm, Yb.Lu,
F, Si, P, As,
Sb, Bi, Nb.Hf
Ta, W, Re, Os,
Ir, Pt, Hg,Th;
U
Ag
Al
Au
Ba
Bi
Ca
Cd
Co
Cr
Eu
Fe
Ga
Hg
I
In
Li
Mg
Mn
Ni
P
Pb
S
Si
Sr
Te
Ti
Tm
V
W
Y
Yb
Zn
METHOD
OPTION
Optical
Emission
Spectroscopy:
DC Arc Source
(AC Spark
Source)
RF Plasma
Torches
DETECTION
LIMIT
1 ppm
l-10ppm
it
ii
ii
ii
n
ii
ti
n
M
n
10-100ppm
n
tt
M
n
Values in ug
0.0001
o.ooi
0.001
0.0001
0.0005
0.001
0.00001
0.004
0.001
0.0002
0.01
0.001
0.00001
0.05
0.001
0.00005
0.0001
0.001
0.003
0.01
0.001
0.01
0.05
0.0002
0.001'
0.005
0.004
0.002
0.7
0.0006
0.0002
0.00001
SPECIAL
ANALYTICAL
CONSIDERATIONS
i *
Because typical sample size is -10-50 mg, the sam-
ple must be homogeneous. Sample homogeniety may be
attained by wet (chemical) ashing or grinding the
sample to fine powder. Wet ashing may also improve
detection limits by concentrating the sample. The
DC arc . source commonly uses a cup electrode into
which the sample is. placed. Plasma sources gener-
ally will accept either liquid or solid samples.
A-II6
-------
TABLE A-U (concluded).
INTERFERENCES
Generally emission
lines may be found
which are free of
spectral interferences
REFERENCES
'
APPLICABLE
STRATEGY
LEVEL
1,2
•'
; '
REMARKS
OES is most effective in the ppm to ~1%
range. Detection limits are highly matrix
dependent.
Analytical accuracy is dependent on the
choice of suitable standards in a matrix
which is as close as possible to the matrix
being analyzed.
The precision which may be achieved is con-
centration dependent; at lowest limits of
detection, precision decreases greatly.
Precision also suffers at high end of con-
centration range. At the high temperatures
present at the electrodes, formation of
compounds such as oxides, carbides, and ni-
trides may cause large changes in vaporiza-
tion behavior. Reactions may also occur in
the discharge zone which decrease the free
atom concentration and lower the intensity
of atomic lines. DC arc sources are re-
producible within -207. and as such are best
suited to qualitative or semiqualitative
analyses.
A-II7
-------
TABLE A-15. METHOD OPTIONS FOR ELEMENTAL ANALYSIS -
ATOMIC ABSORBANCE, ATOMIC FLUORESCENCE, ATOMIC EMISSION
ANALYSIS
AREA
Elemental
Analysis:
Aluminum
'Antimony
Arsenic
Barium
Beryllium
Bismuth
Boron
Cadmium
Calcium
Cesium
AA = Atomic At
FAAS = Flamelc
AF = Atomic F>1
AE = Atomic 'En
METHOD
OPTION
AA, FAAS, AF,
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
sorbance
ss Atomic Absorb
uorescence
is s ion
DETECTION
LIMIT
All values in
ppm unless
otherwise noted
(1% absorption)
0.1
-12
1 x 10 g
0.1
0.005
0.03/0.004
-12
5 x 10 g
0.04
20
0.03/0.004
-12
8 x 10 g
0.1
50
0.02
6 x 10"128
0.001
0.002
3 x'lO" g
0.008 .
0.1
0.04
4 x 10" g
0.005
2
3-10
2 x 10 g
3
0,991
8 x 10 1Jg
0.000001
2
0.002
4 x 10"13
0.02
0.001
O.'OS
2 x 10 g
0.5
nee
SPECIAL
ANALYTICAL
•CONSIDERATIONS
.Wavelengths in Angstroms. Second entry refers-
'to 'Flameless Atomic Fluorescence:
•Fuel in all cases is acetylene, C^.
Oxidant -is either -nitrous oxide or air:
N = Nitrous oxide
A = Air as oxidant
3962 (N)
3962
3962
3962
2175 (A)
2175
2315/231/5
2598
1937 (A)
1937
1937
2350
5536 (N)
5536
5336
2349 (N)
2349
2349/234/9
2349
2231 (A)
2231
^2231/3068
2231
2497 (N)
2497
5180
2228 (A)
2228
2228
3261
4227 (N or A)
4227
4227/3247
4277
8521 (A)
8521
8521
A-II8
-------
TABLE A-15 (continued).
INTERFERENCES
Interferences apply
only to AA and AF.
(C) •= Chemical inter-
ference
(M) = Molecular inter-
ference
(I) = lonlzation inter-
ference
Zn, Ca, Cu, Fe (C) ;
Alkaline earth metals
(I)
' Cu (C)
Al, Si (C); Alkalai
and alkaline earth
metal (I)
Ca, Mg, Na, K (M)
Fe (M)
SO "2, PO -3, Al,
sr
-------
TABLE A-15 (continued).
ANALYSIS
AREA
Chromium
Cobalt
Copper
Dysprosium
Erbium
Eurppium
Gallium
Gadolinium
Germanium
Gold
Hafnium
Holmium
Indium
Iridium
Iron
METHOD
OPTION
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
DETECTION
LIMIT
0,002
2 x 10 g
0.0015
0.005
0.002
2 x 10" g
0.0015
0.05
0.004
6 x 10" g
0.001
0.01
°-io
7 x 10 g
0.07
0.1
0.001
0.2
0.02
0.0006
°-§5
4 x 10 g
0.01
0.01
4
2
*-12
3 x 10 "g
0.1
0.5
°i°J
1 x 10 g
0.005
4
15
0.3
0.02
O.OJ
4 x 10 g
0.1
0.005
1
30
0.(jKJ4
1 x 10 g
0.003
0.05
SPECIAL
ANALYTICAL
CONSIDERATIONS
3579 (A)
3579
3759
4254
2407 (A)
2407
2407/2407
3454
3247 (A)
3247
3247
3247
4217 (N)
4217
4046
4008 (N)
4591 (N)
4594
4594
2874 (A)
2874
4872/4172
4172
3684 (N)
4402
2652 (N)
2652
2652
2428 (N)
2428
2676/2676
2676
3073 (N)
4104 (N or A)
4054
3039 (N or A)
4511
4511
2640 (N)
3801
2483 (A)
2483
2483/2483
3720
A-120
-------
TABLE A-15 (continued).
INTERFERENCES
Fe (C)
Ca, Mg, K, Na (M)
Ca, Na, K (M)
AL (C)
Fe, Ca (M)
Ca (M); SI (C)
REFERENCES
32
32, 197
APPLICABLE
STRATEGY
LEVEL
2
2
2
2
2
2
2
2
2
2
2
REMARKS
Interference may be reduced with NH.C1
Graphite furnace/carbon rod
2384 A, 2389 A (NRL)
Graphite furnace
2x10 g/FAR
2961 A (NRL)
Graphite furnace
2x10 /FAR
Carbon rod
Carbon rod
1x10" g/FAR
Graphite furnace
4x10 g/FAR
2511 A (NRL)
Carbon rod/graphite furnace
2. 0x10' g/FAR
A-I2I
-------
TABLE A-15 (continued).
ANALYSIS
AREA
Lanthanum
Lead
Lithium
Lutetium
Magnesium
Manganese
Mercury
Molybdenum
Neodymium
Nickel
Niobium
Osmium
Palladium
METHOD
OPTION
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
DETECTION
LIMIT
2
0.1
0.01
3 x Kf 12g
0.01
0.2
0 . 001
3 x 10" g
0.00003
3
1
0.003
-14
4 x 10 g
0.002
0.005
0.003
-13
4 x 10 g
0.005
0.5.
2 x 10 g
0.0002
40
0.03
-1 2
3 x 10 g
0.5
0.1
2
0.2
0.955
9 x 10 g
0.002
0.6
5
1
1
0.01
4 x 10 g
0.04
0.2
SPECIAL
ANALYTICAL
CONSIDERATIONS
3928 (N)
4418 (LaO)
2833 (A)
• 2833
4058/4058
4058
6708 (A)
6708
6708
3312 (N)
4519
2852 (A)
2852
2852/2852
2852
2795 (A)
2795
2795/2795
4031
2537 (A)
2537
2537/2537
2537
3133 (N)
3133
3133
3903
4925 (N)
2925
2320 (N)
2320
2320/2320
3415
4059 (A)
4059
2909 (A)
2746 (A)
2746
3405
3635
A-122
-------
TABLE A-15 (continued).
INTERFERENCES ,
Al, Th, Zr (C); Ca,
Mg, K, Na (I)
Sr (C)
Al, SI, P, S04"2 (C)
Cr (M); Si (C)
Fe, Sr, Mn, Ca, Al,
N03" (C)
Pr (S)
Ca (M)
REFERENCES
242, 206
32
APPLICABLE
STRATEGY
LEVEL
2
2
2
2
2
2
2
2
2
2
2
2
REMARKS
2203 A (NRL)
Carbon rod
1.5x10 g/FAR
Concentrations 5 ppm
Carbon rod
Interference eliminated with a La, Se,
or Ni buffer
Carbon-rod
1x10 g/FAR
Chemical interference may be reduced with
Ca buffer
Carbon-rod
5x10 g/FAR
Carbon rod
1x10 /Pt loop
Fe and Mn interference may be eliminated
with NH Cl
Carbon rod
4634 A line is less sensitive but inter-
ference free
2328 A (NRL)
Graphite furnace/carbon rod
5x10" g/FAR
Carbon rod
A-123
-------
TABLE A-15 (continued).
ANALYSIS
AREA
Phosphorus
Platinum
Potassium
Praseodynium
Rhenium
.Rhodium
Rubidium
Ruthenium
Samarium
Scandium
Selenium
Silicon
Silver
Sodium
METHOD
OPTION
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
-AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
--AE
AA
-FAAS
AF
AE
"AA
FAAS
•AF
'•AE
•AA
;FAAS
AF
AE
DETECTION
LIMIT
20
200
0.05
-11 .
1 x 10 g
0.15
0.2
0.003
4 x 10 8
0.0005
10
10
1
0.02
0.02
8 x 10 g
0.02
0.595
1 'x 10 g
O.'OOl
0.3
0.02
5
0.2
0.2
0.03
0.1/0.002
-1-2
9 x 10 g
0.04
°'^4
5 x 10 g
0.6
5
O.OQ1
i -x 10" .g :
0.001
0.02
;'0 .0008
1 x 10 g
0.0005
SPECIAL
ANALYTICAL
CONSIDERATIONS
1783 (A)
5400
2659 (A) .
1
2659
2659
2659
'7665 (A)
7665
7665
4951 (N)
4951
3461 (N)
3461
3435 (A)
' 3435
3435
7800 (A)
7800
7800
3499 (A)
3728 . • .
-4297 (N) .-.,
4760
3918 (N)
4020
1961 (A)
1961
1961
2516 (N)
2516
.2040
.2516
3281 (N)
3281
3281/3281
3281
5890 (A)
5890
5890
A-124
-------
TABLE A-15 (continued).
. - INTERFERENCES
Pd, Rh, -Au, Ir, Ru,
Os, Na (C)
Na (I)
.'„
;Na, Pt, Pd, Au, Ir,
Ru, Os
Na, K (I)
Cu (C)
Th (C)
. REFERENCES
254, 124, 137
APPLICABLE
STRATEGY
LEVEL
2
2
2
2
-i'"'
2
. 2
2
2
2
2
2
2
2
-'
REMARKS
Chemical interferences may be eliminated
with Cu buffer
Carbon rod
Carbon rod
Carbon rod
For lower detection limit analyze as
hydride
Carbon rod
Graphite furnace
Carbon. rod
Ixio"1 g/FAR
Carbon rod
A-125
-------
TABLE A-15 (continued).
ANALYSIS
AREA
Strontium
Tantalum
Tellurium
Terbium
Thallum
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Ytterbium
Yttrium
Zinc
METHOD
OPTION
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
AA
FAAS
AF
AE
DETECTION
LIMIT
0.005
-12
1 x 10 g
0.03
0.0002
5
5
0.05
-9
3 x 10 g
0.0005
200
o.?i
1 x 10 g
0.4
°-92
1 x 10 g
0.008
0.002
1
0.02
°-2§
3 x 10 g
0.05
0.3
°*1
4 x 10 g
4
0.2
3
0.5
30
°i?l
3 x 10 g
0.07
0.01
0.04
0.0002
0.3
0.4
0.001
-14
3 x 10 g
0.00002
50
SPECIAL
ANALYTICAL '
CONSIDERATIONS ,
4607 (A)
4607
4607
4607
2715 (N)
4813
2143 (A)
2143 :
2383
4327 (A)
4327
4319
2768 (A)
2768
3776/3776
3776
4106 (A)
3718
2246 (A)
2246
3034
2840
3643 (N)
3643
3199
3998
4009 (N)
4009
3585 (N)
3184 (N)
3184
3184
4379
3988 (N)
3988
4078 (N)
3621
2138 (A)
2138
2138/2138
2138
A-:|26
-------
TABLE A-15 (continued).
. l 1
INTERFERENCES
Al, P (C); Na, K (I)
Cu (C)
Na, P04"3 (C)
Fe, Al, Na, K, Mg, Ca
(M)
•i
REFERENCES
32
124
•
APPLICABLE
STRATEGY
LEVEL
2
2
2
2
2
2
2
2 ,
2
2
2
REMARKS
Chemical interferences may be eliminated
with a La buffer. lonization interference
levels off .above 100 ppm Na or K
Carbon rod
For lower detection limit analyze as
hydride
Carbon, rod
5x10" g/FAR
Carbon rod
Carbon rod
Graphite furnace
4x10 g/FAR
A-127
-------
TABLE ,A-15 (continued).
ANALYSIS
AREA
'METHOD
OPTION
DETECTION
LIMIT
SPECIAL
^ANALYTICAL
CONSIDERATIONS
Zirconium
AA
FAAS
AF
AE
3601 (N)
3601
A-128
-------
TABLE A-15 (concluded).
INTERFERENCES
REFERENCES
APPLICABLE
STRATEGY'
LEVEL
REMARKS
A-129
-------
TABLE A-16-. METHOD OPTIONS FOR ANION ANALYSIS
'• ANALYSIS-
AREA'
-J
?: .-3
',. ASO^-';
;,AsO~3'
JBr"
•.Br"
See i"
'(Titrimetric)
;Cl"
v<
•i
>CN~
1
;
:
(
.tc°3~
• F"
i.
i
[i~
',.
;i
;:NH4+
i
METHOD
OPTION'
'Colorimetric
GC
SIE
Titrimetric
SIE
Polaro-
graphic
Titrimetric
Potentiometric
Colorimetric
SIE
Polarographic
Colorimetric
Titrimetric
Gravimetric
SIE
Colorimetric
Colorimetric
Pblarograph'ic
Colorimetric
SIE
Titrimetric
Titrimetric
DETECTION-
LIMIT
:. 1 ppm
1 ppb
1 ppm
>50 ppm
1 ppm
2 ppm
1 ppm
1 ppm
1 ppm
2 ppm
<1 ppm
>1 ppm
>100 ppm
1 ppm
0.1 ppm
0.05 ppm
2 ppm'
1 ppb
''1 ppm
>50 ppm'
>1 ppm
SPECIAL
ANALYTICAL
CONSIDERATIONS
Heating; reaction improves' accuracy.
HO' must be- removed.
Bromide and iodide- are determined' together.
Bromide is- calculated-, as' the' difference- between
combined bromide and iodide: determination: and'
iodide determination'.
Mercuric or silver nitrate tltrant.
Chloramine T procedure.
Ig sample required
A-130
-------
TABLE A-16 (continued).
INTERFERENCES
N/A
None cited.
s"2, i", CN".
Fe, Mn, Organic matter.
s"2, CN", i", Br", SCN"
Cr04 , Fe+ , S03~2.
_2
S , oxidizing
substances.
-2
S , oxidizing
substances
OH", Al+3, Fe+3
Al+3
Hg (>0.1 ppm),
oxldring agents.
Br", Cl".
Fe, Mn, organic matter
Distillation procedure
REFERENCES,
8.40
298
97
8.9
97
161
161
205
161
8.32
8.32
8.10
182, 303,97
818
161
216
APPLICABLE
- STRATEGY
LEVEL -
1 and 2
1 and 2
1 and 2
2
1 and 2
2
1 and 2
2
1 and 2
2
1 and 2
1 and 2
2
1 and 2
1 and 2
2
2
2
1 and 2
2
1 and 2
REMARKS
As evolved as AgH_.
As evolved as 0,As
Interferences are removed by realtion
with CaO. See also Iodide, Tltrimetric.
Determined_slmultaneously with CN", F~,
SO," , SO " .
3 4
Chloride can be determined in all con-
centrations.
Thiocyanate system measured colori-
metrically .
Interference can be removed with lead
carbonate.
Determined simultaneously with Cl , F ,
Distillation removes interferences. Organic
compounds may be removed by extraction.
Distillation removes interferences. Organic
compounds may be removed by extraction.
Spadns method; distillation removes most
interferences.
Alizarin complexone method.
Determined simultaneously with Cl", CN ,
SO, , SO. .
3 4
Reducing agents interfere but are.
removed by treatment with KMnO,.
Interferences are removed by reaction with
CaO.
A-I3I
-------
TABLE A-16 (continued).
ANALYSIS
AREA
<
No3-
No3-/No2-
NO,-
N03-
-3
P04
S'2
-2
V
V
METHOD
OPTION
Colorimetric
Colorimetric
Colorimetric
Colorimetric
Colorimetric
Colorimetric
SIE
Colorimetric
Colorimetric
Colorimetric
Tltrimetric
SIE
Polarographic
Polarographic
Gravimetric
Turbidometric
DETECTION
LIMIT
0.05 ppm
0.1 ppm
10 ppm
0.05 ppm
0.05 ppm
0.05 ppm
1 ppm
1 ppm
0.01 ppm
0.01 ppm
1 ppm
>10 ppm
2-50 ppm
2-50 ppm
100 ppm
10 ppm
SPECIAL
ANALYTICAL
CONSIDERATIONS
Distillation and nesslerlzation procedure.
Temperate control during analysis is essential.
Sample is not stable.
Sample is not stable.
Sample is not stable.
Temperature and final acid strength influence
color.
Refrigerate sample at 4 C.
Refrigerate sample at 4 C.
Minimize contact with air.
Ignition of precipitate at 800°C.
A-132
-------
TABLE A-16 (concluded).
INTERFERENCES
Volatile organic
compounds .
Dissolved organic
matter oxidizing and
reducing substances.
el'. N02"
Ammonia primary amines
.Hg, Cu
-3 -7
Cl , PO | , NH ,
•Mn, Ca, Fe .
OH , strong oxidizing
or reducing agents.
Cl", Br", l".
+2 +2 -2
Fe , Sn , I2, Cr20? i
N/A
Fe,
_2
SO. , other reduced
sulfur compounds.
„ +2
Bg .
N/A
N/A
S03"2, N03", S102,
Suspended matter.
Color or suspended
matter.
REFERENCES
APPLICABLE
STRATEGY
LEVEL
1 and 2
2
2
2
2 .
2
2
2
2
2
2
2
2
2
2
2
REMARKS
Organic compounds may cause off colors.
Brucine Sulfate method.
PDS method; Chloride may be removed with
Cadmium^Copper reduction technique; N0_
and NO- determined separately.
L
Hydrazine reduction method.
Diazotization procedure.
Dichromate may be volatilized as CrCl,
with HCU>4. J
Stannous Chloride method.
Ammonium Molybdate-Pottassium
Antimonyl Tartrate method.
Zinc Acetate-Iodine procedure.
Determined simultaneously with Cl", CN~,
F", S04".
Determined simultaneously with Cl", CN",
F", so3".
Time consuming but accurate.
A fairly rapid method.
A-133
-------
TABLE A-17. METHOD OPTIONS FOR STANDARD WATER ANALYSIS
ANALYSIS
AREA
Acidity
Alkalinity
Ammonia
Biological
Oxygen
Demand
Carbonate
COD
Conductivity
Cyanide
Dissolved
Oxygen
Hardness
Hydrazine
Nitrate
Nitrate/
Nitrrite
,Nitrite
METHOD
OPTION
Titrimetric
Titrimetric
Colorimetric
Titrimetric
Titrimetric
Titrimetric
Electrometric/
Colorimetric
Titrimetric
Electrometric
Colorimetric
Titrimetric
Electrometric
Gravimetric
Titrimetric
Spectrometric
Spectrometric
Spectrometric
Spectrometric
Titrimetric
DETECTION
LIMIT
SPECIAL
ANALYTICAL
CONSIDERATIONS
Distillation into boric acid solution concen-
tration range, 0.05-1 ppm.
Distillation into boric acid solution concen-
tration range 1 ppm.
Compounds which are oxidized by 0 .
Evolution apparatus required is described in
reference.
pH measurement.
Dichromate method.
Sample should be analyzed within 24 hours.
Distillation into NaOH; chloramine T method.
Distillation into NaOH; titration with AgNO-.
Sample should be analyzed within 6 hours.
Values are reported in equivalents per million.
Values are reported in equivalents per million.
Sample should be analyzed as quickly as possible.
Absprbance does not follow Beer-Lambert
relation.
NO., is reduced to NO- and analyzed as for
nitrate.
Sample should be analyzed as soon .as possible.
Sulfanilic acid - diazotization method.
Permanganate titration.
A-134
-------
TABLE A-17 (continued).
INTERFERENCES
Suspended solids.
Suspended solids.
Volatile alkaline
organic compounds.
Incubation for 5 days
. at 20°C.
. Sulfides.
Compounds which affect
pH value other than
carbonate.
Compounds which are
oxidized by dichromate
anion.
Sulfides, fatty acids.
Sulfides, fatty acids.
Numerous and varied.
Compounds which are
able to oxidize N H, .
Turbidity, colored
samples.
Turbidity, Fe, Cu,
organic oils and
greases.
Amines, reducing
species.
Reducing agents.
REFERENCES
8.15
8.20
8.17
8.17
APPLICABLE
STRATEGY
LEVEL
1 and 2 ,
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
2
1
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
REMARKS
Various and point methods may be used.
Various end point methods may be used.
Sulfides are removed by scrubbing with
iodine solution. Other interferences
are removed by scrubbing with chromic
acid.
An estimation procedure for H-CO,, HCO, ,
co3 . L J J
Fe+2, N02", S03"2, Cl", Br", l" as well as
organic compounds are measured.
Sulfide interference removed by CdCO,
precipitation. Fatty acids are removed
by extraction with hexane.
Gravimetric method is referred method.
See reference for list of interference.
Hydrazine undergoes auto-oxidation easily.
For a complete discussion of interferences
see reference.
A-135
-------
TABLE A-17 (continued).
ANALYSIS
AREA
Partlculate
& Dissolved
Matter
pH
Phosphate
Sulfate
Sulfite
METHOD
OPTION
Filtration
and drying
Colorimetric
Electrometric
Gravimetric
Spectrometric
Spectrometric
Spectrometric
Gravimetric
Turbidimetric
Titrimetric
Titrimetric
Titriraetric
Titrimetric
DETECTION
LIMIT
0.1-6 ppm
>6 ppm
>3 ppm
SPECIAL
ANALYTICAL
CONSIDERATIONS
Test paper.
Glass electrode measurement.
Sample must contain >10 mg phosphate.
Sample concentration, 5-10 ppm.
Sample concentration, 2-25 ppm.
Sample concentration, 1-2 ppm.
Barium chloride precipitation.
Thorin indicator.
A-136
-------
TABLE A-17 (concluded).
INTERFERENCES
Numerous and varied.
See reference, PO,
See reference, S
+3
See reference, Fe ,
color.
See_reference, CrO, ,
SO." , S~2, turbidity.
Turbidity, dark color-
ation of sample.
SO'2, K+, Fe+2,. Al+3,
Pof J, F', N03'.
_2
See reference. S ,
heavy metal ions, N0?.
-2
See reference. S ,
Fe , N02", Co, Cu. .
-2
See- reference. S ,
Fe , N02', Cu, Co.
\
REFERENCES
•"•T
8.16, 8.29
8.23
8.23' •
8.23
•t
APPLICABLE
STRATEGY
LEVEL
1 and 2
1
-1 and 2
2
1
1
.:«'
2
1 and 2
1 and 2
2
2
2 -
REMARKS
See reference for list of interferences. •
Solids may be submitted for trace analysis. ,
Amino reduction method; orthophosphate
and total phosphate determined.
Only orthophosphate determined. Molybdo
yanado-phosphate method .
Ortho & total phosphate determined;
stannous chloride reduction method.
Cation interference may be removed by ion
exchange column.
Dead' stop titration technique.
Referee method.
Dead 'stop titration technique.
Referee method.
Visual end point. Non-referee method..
-
A-137
-------
TABLE A-18. METHOD OPTIONS FOR FUEL ANALYSIS
I.
CO
a-
**
*
**
ANALYSIS
AREA
AL:
Moisture
Ash
Volatile
Matter
Fixed
Carbon
Sulfur
Sulfur
Sulfur
Sulfur
Forms of
Sulfur
Phosphorus
Carbon
Hydrogen
Nitrogen
Oxygen
Carbon
Dioxide
Si02
A12°3
Fe2°3
Ti02
P2°5
Proximate Ah<
These analyi
METHOD
OPTION
Drying Oven
Combustion
Combustion
Combustion
Bomb Washing
Method-
Eschka
Method
Sodium Peroxide
Method
Gravimetric
Gravimetric
Titrimetric
Titrimetric
Combustion
Combustion
Kjeldahl
Gunning-
Method
By difference
Acid Decompo-
sition
Spectrometric
Spectrometric
Spectrometric
Spectrometric
Spectrometric
lysis.'
es plus sulfur c
DETECTION
LIMIT
-
'
imprise an ultima
SPECIAL
ANALYTICAL
CONSIDERATIONS
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
:e analysis.
A-138
-------
: TABLE A-18 (continued).
INTERFERENCES. ' '
';'•
.
-'
Titanium
REFERENCES
8^4
• 8'.4
8.4
8.4
8.4
8.4
8.4
8.28
8.35
8.35
8.4
8.4
8.4
8.4
8.4
8.27
8.38
8.38
8.38
8.38
8.38
APPLICABLE ;
STRATEGY
LEVEL
1 and 2
' 1 and 2
. 1 and 2
1 and 2
1 and 2
1 and; 2
1 and 2
1 and 2
1 and; 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
1 and 2
2
2
2
2
2
REMARKS
Various method options are described
within test.
Not commonly used.
Standard method for Sulfur in1 Ash. •
Distinguishs between sulfate sulfur,
pyritic sulfur, and organic s.ul fur; organic
sulfur is determined by difference.
Alternate procedure described for P
analysis where Ti is known' to be low.
Alternate methods are described.
Test is for carbonates in coal.
••'
'A-139
-------
TABLE A-18 (continued).
ANALYSIS
AREA
COAL (cont.)
CaO
.MgO
Na20
K20
Heating
Value
II.
RESIDUAL
OIL:
H,0 and
Bituminous ,
Materials
Sulfur
Sulfur
Sulfur
Heating
Value
METHOD
OPTION
Titrimetric
Titrimetric
Flame. Photo-
metric
Flame Photo-
metric
Combustion
Distillation
Bomb Method
Quartz Tube
Method
High Temperature
Method
Combustion
DETECTION
LIMIT
SPECIAL
ANALYTICAL
CONSIDERATIONS
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh- sieve.
Coal to, pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
Coal to pass 60 mesh sieve.
-15-20 ml of sample required.
-1 g sample required.
-1 g sample required.
-1 g sample required.
Combustion in 0. bomb with 1 ml of H.O under
30 atm. of 0,,.
A-140
-------
TABLE A-18 (concluded).
INTERFERENCES
Organic nitrogen
compounds.
Organic nigrogen
compound .
.'
REFERENCES
8.38
8.38
8.38
8.1
8.2
8.25
8.26
•
APPLICABLE
STRATEGY
LEVEL
2
2
2
2
1 and 2
2
1 and 2
1 and 2
1 and 2
1 and 2
REMARKS
Dean-Stark distillation apparatus.
Gravimetric determination.
Phosphorus and organo-metallic compounds
may also interfere. Chlorine may also
be measured by this test procedure.
•Titrimetric method. Nitrogen compounds
when present in concentrations above
0. 1% may interfere. Chlorine in con-
centrations-above 1% will interfere.
A-141
-------
TABLE A-19. METHOD OPTIONS FOR PHYSICAL CHARACTERIZATION OF SOLIDS
ANALYSIS
AREA
Particle
'Sizing
. *.
METHOD ;
OPTION
Dry Sieving
Wet Sieving
Micromesh
Membrane
Sieving
Incremental ;
Sedimentation '
Bulk
Sedimentation .
Centrifugal
Sedimentation
Air
Elutriation
liquid :
Elutriation
DETECTION
LIMIT
to 74ji
to 37|j.
to 5u
to 37p
•to 2u
to O.lu
to O.ljj.
'tO l|a
to 2u
'ADVANTAGES/
DISADVANTAGES
Attrition may take place if sieving .operation is
prolonged.
Timing of operation has been standardized by
•'ASTM for coal.
Other interferences include moisture .content, rel-
ative :humidity, electrostatic properties.
Same as for dry sieving with the .'exception that
agglomerating particles "are^tested in a more rep-
resentative manner by ^wet sieving.
Agglomeration of fine particles sever due to
electrostatic causes.
Applicable only to liquid suspensions.
Multiple backwash ings required.
Adequate dispersion of the particles in suspen-
sion is essential.
'Convective disturbances and evaporative effects
must be minimized.
Same. as for incremental sedimentation 'method ex-
cept that, in .some cases, air is ;the settling
medium and evaporative effects do not apply.
Same as for incremental sedimentation.
Agglomeration effects due to electrostatic attrac-
tion is 'the prime -interference. Particle attri-
tion is also common.
;Cut fractions contain .a .large ;amount :of under-
sized particles.
Electrostatic -effects are minimized.
•A-142
-------
TABLE A-19 (continued).
SPECIAL
CONSIDERATIONS
REFERENCES
APPLICABLE
STRATEGY
LEVEL
REMARKS
During and after samp-
ling, care must be taken
to minimize agglomera-
tion and attrition. In
reducing a gross sample
for analysis, special
concern should be given
to the representative-
ness of the sample to be
analyzed.
Same as for Dry Sieving.
Agglomeration effects
can be minimized by pre-
conditioning dust and
pans to 50 - 75% rela-
tive humidity.
Same as for Dry Sieving
Same as for Dry Sieving
Same as for Dry Sieving
Same as for Dry Sieving
Same as for Dry Sieving
8.3, 8.7, 8.42
8.41, 287
287, 338
338
338
338
338, 50
287, 338, 50
287, 338, 50
Same as for Dry Sieving
287, 50
Can be used as a first step in sizing.
Same as for Dry Sieving.
Applicable Level 2 technique when pre-
ceded by Dry or Wet Sieving
Same as for Micromesh
Determines equivalent particle diameter.
Examples of specific types of incremental
sedimentation analysis techniques are
pipet, diver, hydrometer, and photo-extinc-
tion. Usually associated with a liquid
medium.
Lower limit given applies only to Beta or
piezoelectric techniques.
Since a sedimentation and dispersing liquid
are both utilized in this technique, care
must be taken that only a small density
difference exists. This would prevent
particle entrapment at the Interface be-
tween the liquids.
For more representative results, each
fraction can be resuspended and the
process repeated several times.
A-143
-------
TABLE A-19 (continued).
ANALYSIS
AREA
METHOD
OPTION
DETECTION
LIMIT
ADVANTAGES/
DISADVANTAGES
Particle
Sizing
(cent.)
Centrifugal
Elutriation
Centrifugal
Coulter
Counter
to,
to 0.025(1
to 0.03(i
Optical
Microscope
to 0.4(i
Morphology
Polarizing
Light
Microscope
Electron
Microscopy
to 0.001(j
Attrition Is the prime'limitation.
Attrition is prime limitation.
An orientation correction factor must be applied
when fibrous particles are present. Also the
length to diameter ratio for other particles-must
be near unity.
The device is automatic and relatively quick, es-
pecially when compared to sedimentation .techniques
which can take up to 60 hours for the.smaller size
particles. ..,
There are no interferences with this technique if
proper precautions are taken. Accurate size de- •
termination is most dependent on the skill of the
mlcroscopist.
Particle identification Is dependent upon the num-
ber of characteristics (i.e., color,.shape, cleav-
age) determined and the skill and experience of
the microscopist.
Sample exposure to heat and vacuum in the-micro-
scope must be taken into .account when interpreting
the results. Transfer of electrostatic charge to
the beam could cause a rupture of the substrate or
particle migration. .
A-144
-------
TABLE A-19 (continued)
SPECIAL
CONSIDERATIONS
REFERENCES
APPLICABLE
STRATEGY
LEVEL
REMARKS
Same as for Dry Sieving
Same as for Dry Sieving
Same as for Dry Sieving
287, 338, 50,
19
287, 338, 50
287, 50
Particles must be dis-
persed on the slide in
a random manner without
causing shattering of
the particles. Agglom-
erated particles should
be deflocculated.
Same as for Optical
Microscope
1 and 2
147
1 and 2
Methods commonly used
for the collection of
submicron particles in-
clude membrane filters,
thermal preclpitatdrs
and electrostatic pre-
cipitators. These
287, 338, 50
The most common commercially available
centrifugal eluctriator is. the Bahco micro-
particle classifier. This is the standard
method of partlculate sizing specified in
the ASME Power Test Code. The Bahco must
be calibrated against optical methods.
Various models are commercially available.
Calibration against optical methods must
be performed.
Calibration is against monodispersed parti-
cles of known diameter.
Particle diameter should be no more than
30% of the aperture diameter.
A photomicograph taken in the field would
minimize any handling or storage inter-
ference.
This instrument is the standard tool for
for identification of particles down to
0.5n in diameter.
Level 1 analysis is limited to gross ident-
ification by shape, cleavage, structure and
color characteristics.
Level 2 analysis involves the determination
of as many characteristics as are necessary.
to provide a comprehensive particles iden-
tification.
Applicable to Level 2 sizing and morpho-
logy when the polarizing light micro-
scope does not provide sufficient informa-
tion.
A-145
-------
TABLE A-19 (continued).
ANALYSIS
AREA
Morphology
(cont.)
METHOD
OPTION
Scanning
Electron
Microscopy
Electron
Microprobe
DETECTION
LIMIT
to o.001|j
ADVANTAGES/
DISADVANTAGES
Same as for Electron Microscopy
Can be used to identify the chemical nature of
individual particles.
A-146
-------
TABLE A-19 (concluded).
SPECIAL
CONSIDERATIONS
methods are employed
•since handling of the
collected sample is
minimized. Since in
many cases these tech-
niques are not available
for sampling, interfer-
ence's from breaking and
agglomeration will
occur.
Same as for Electron
Microscopy
The mounting of the
sample is a critical
step in this procedure.
REFERENCES
287, 338, 50
APPLICABLE
STRATEGY
LEVEL
2
2
REMARKS
Allows for greater details in particle
morphology analysis.
If the Polarizing Light and Electron Micro-
scopes fail to provide enough information,
this technique can be used.
A-147
-------
TABLE A-20. METHOD OPTIONS FOR FLOW MEASUREMENT
METHOD!
DESCRIPTION
APPLICABLE
MEDIA
Standard
Pitot
Tube
"S" Type
Pitot
Tube
Hastings
Raydlst
Flare Gas
Flow Probe
A pressure probe method. Point velocity determination.
Differential pressure (stagnation minus static) at a point
in duct or stack is sensed by pitot tube connected to a
pressure transducer (e.g., manometer) and then related to
the velocity at that point.
A transverse is performed with points selected ac-
cording to FPA method 1. Flow rate is determined
from resulting velocity profile.
Effect of compressibility is usually handled through
use of a correction factor.
This is a manual traverse method and is not ordinarily
used for continuous monitoring systems.
Gas or
Liquid
A pressure probe method (see Standard Pitot Tube
discussion). Point velocity determination.
Gas or
Liquid
A pressure probe method. Point velocity determination.
Probe is variation of pitot tube with two openings at
probe tip which are connected together by an internal
stainless steel tube. A portion of this tube is heated
and thermo-electric sensors measure temperature gradients
along the wall of the tube, external to the flow stream.
Purge gas Is injected Into the tubing in an arrangement
which forms a pneumatic bridge. At zero velocities the
bridge is balanced. As flow across the tip occurs, the
differential pressure developed unbalances the bridge
Gas
A-148
-------
TABLE A-20 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
a) 0.57o accuracy from 1.1 to
60.9 m/sec.
b) Less sensitive to probe
orientation than "S" type
pitot tube.
c) Not readily clogged in .
high particulate, high
moisture gas streams for short
time periods.
d) Stainless steel construc-
tion.
e) Can be water-cooled to
withstand temperatures up to
2000°F.
f) Relatively inexpensive.
g) May be used for liquids.
a) 0.5% accuracy from 2.7 to
30.9 m/sec.
b) 'Higher differential pressure
than standard pltot tube.
c) Greater resistance to
clogging in high particulate -
high moisture streams than
standard pitot tube.
d) Same as d), e), f), and g)
for Standard Fltot Tube.
e) Recommended in EPA
Method 2.
f) No insertion problem as with
standard pitot.
g) Bi-directional - will
show effect of reversal in
flow.
a) Corrosion and abrasion
effects negligible .
b) Since air is continuously
exhausting through the two holes
in the probe tip,, clogging is
almost impossible. .
c) Can operate in gas streams
up to 315 C.
a) Lower differential pressure
than "S" type.
b) When used in conjunction
with a long sampling probe it
is difficult to insert the
assembly into the duct.
c) Must obtain alignment of
probe axis with flow direction
(i.e., yaw sensitivity).
High yaw sensitivity.
a) Accuracy not better than
4.87. of reading for range of
2.74 to 30.48 m/sec.
b) High sensitivity at low
velocities accentuates zero
drift.
c) Must be isolated from
vibrations.
A port must be cut into duct
or stack. Size of port is
primarily determined by probe
assembly diameter.
This is the most accurate method
for point velocity determinations
Since ellipsoidal nose tube is
more accurate than hemispherical
type, its use is preferred.
Port must be cut into duct, as
with standard pitot tube.
Due to the availability of
electronic pressure tranducers,
the advantage of the "S" pitot
in having a higher differential
pressure is reduced.
Port must be cut into duct to
accommodate device.
Accuracy inadequacies make this
device unacceptable for use unless
other options are unavailable.
Sensitivity to vibrations would
indicate that single point probe
or rake must be used rather than a
reciprocating traversal mechanism.
A-149
-------
TABLE A-20 (continued).
METHOD
DESCRIPTION
APPLICABLE
MEDIA
Hastings
(cont)
Ellison
Annubar
Fluid Drag
Meter
Hot-Wlre
Anenometer
Hot-Film
Probe
and the sensors measured the shift In temperature
gradients along the heated portion of the tube. The
sensor output voltage is related to the gas velocity
by a calibration curve.
A pressure probe method. Pressure velocity averaging.
The stagnation pressure is sensed by four upstream
holes opening into the probe body while the static
pressure is sensed by a single hole facing downstream
and located In the center of the probe.
Gas
Uses a bonded strain gauge bridge to translate
deflection due to fluid forces on target disc
into an electrical signal proportional to the
square of the flow rate. Point velocity
determination.
Gas or
Liquid
Point velocity determination. A short length of
fine platinum wire is mounted at the end of a probe and
heated by electric current. The electrical resistance of
the wire is a function of its temperature. Flow of a gas
around the hot wire cools it, changing its resistance.
By holding either the voltage or current across or through
the wire constant, the change in amperes or voltage,
respectively, becomes a function of gas velocity. Probe
is connected to a Wheatstone bridge.
Traverse across duct to obtain velocity profile from
which volume flow rate can be determined.
Point velocity determination.
Variation of Hot-Wlre Anenometer.
A thin electrically conducting film is coated on
insulator located at probe tip. Film acts as
resistance.
Gas
Gas or
Liquid
A-150
-------
TABLE A-20 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
a) 7.27, accuracy for flow
(i.e., entire cross-section),.
This Is comparable to using a.
1% accurate point sensor and
row averaging concept.
b) Corrosion and abrasion'
effects are negligible due
to stainless steel construction.
c) Relatively inexpensive
compared to point sensor array.
a) 1% accuracy from 2.7 to
30.48 m/sec.
b) Resistant to chemical
attack If internal purge
is used.
c) Bi-directional.
d) ,Can be used for continuous
monitoring applications.
e) Can operate in gas streams
up to 260 C.
a) Very quick response to
velocity changes (low thermal
inertia).
b) Device is very small.
c) Can be used to obtain
velocities near walls.
a) Can be used for liquids.
b) More durable than Hot-Wire
device (suitable for high
velocity liquid flows).
a) Must be constructed for
specific location since
length of device and positioning
of high pressure ports are
duct specific.
b) Rear orifice is subject
to clogging.
a) Sensitive to orientation
in duct.
b) Two probes are necessary to
cover velocity range of 1.5 to
38 m/sec.
a) Calibration is complicated
(done by placement in stream
of same gas of known velocity).
b) Very delicate device.
c) Cannot be used successfully
with liquids.
Same as a) for Hot-Wire Aneno-
meter.
Installed in line.
Can be used in 'both circular
and rectangular ducts although
greater calibration factor
variation can be expected
for rectangular case.
Holes in annubar are located
according to specific duct
dimensions.
A port must be cut into duct to
accommodate device.
This is the most accurate method
for point velocity determinations,
readily applicable to continuous
monitoring situations.
The probe is attached to an
automatic reciprocating traversal
mechanism to obtain measurements
at various points. Tills is
less expensive than employing
a multiple sensor rake.
Port must be cut into duct
to accommodate device.
Best practical method for
measuring turbulent fluctuations
at a point.
Complete commercial setups
available.
See Hot-Wire Anenometer.
A-I5I
-------
TABLE A-20 (continued).
METHOD i
DESCRIPTION
APPLICABLE
MEDIA
Venturi
Meter
Flow
Nozzle
Orifice
Meter
An obstruction device.
Acts as an obstacle placed in path of flowing fluid
causing localized changes in velocity and, concurrently
pressure changes. Pressure differential between inlet
and minimum area (throat) section of device is measured
by taps located in wall and connected to a pressure
transducer (e.g., manometer). Differential pressure
is then related to ideal velocity and volume flow rate.
A portion of the pressure drop becomes irrecoverable
because of friction and turbulent losses. Actual volume
flow rate is obtained by multiplying ideal flow rate by
an empirical coefficient which depends on flow Reynolds
number and duct geometry as well as on characteristics
of device.
The effect of compressibility is handled through use of
a theoretical expansion factor.
An obstruction device (see Venturi Meter discussion).
Gas or
Liquid
Gas or
Liquid
An obstruction device (see Venturi Meter discussion).
The effect of compressibility is handled through use of
an experimentally determined expansion factor.
Several possible pressure tap locations can be used
(e.g., in flanges, at vena contracta, etc.).
Gas or
Liquid
A-152
-------
TABLE A-20 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
a) Most accurate of all
obstruction devices (1% of
total flow).
b) No solids accumulation
occurs.
c) Pressure recovery greater
than for other flow obstruction
devices (i.e., less head loss).
d) Suitable for continuous
flow measurements.
e) Can be installed in any pipe
orientation as long as it is
completely filled with fluid.
f) Can be used for gases.
g) Good resistance to
abrasion.
a) 3-47. accuracy.
b) Same as d), e)', f) , and
g) under Venturi Meter.
c) Requires less space than
Venturi Meter.
d) Less expensive than
Venturi Meter.
e) Can be installed at dis-
charge point.
a) 2-37. accuracy.
b) Same as d), e), and f)
under Venturi Meter.
c) Least expensive of all
obstruction devices.
d) Least space requirement of
all obstruction devices (may
often be installed between
existing pipe flanges).
e) Simpler installation than
other obstruction devices.
a) More expensive than other
obstruction devices.
b) Requires more space than
other obstruction devices.
c) More difficult to install
than other obstruction devices.
a) Lower pressure recovery
than Venturi Meter.
b) Relatively difficult to
install properly.
a) Poorest pressure recovery
of all obstruction devices
b) Especially susceptible to
inaccuracies resulting from
wear and abrasion.
c) Lower accuracy than other
obstruction devices.
d) Lower physical strength
than other obstruction devices
(may be damaged by pressure
transients, solids).
A major disadvantage of
obstruction devices is that
pressure drop varies as the
square of .the flow rate; thus,
for use over a wide range of flow
rates, pressure-measuring.
equipment of very wide range is
required, usually resulting in
poorer accuracy at the low flow
rates.
Installed in line.
See Venturi Meter discussion.
See Venturi Meter discussion.
Installed in line.
Should only be used in streams
of low solids content. Same
location requirements as
Venturi Meter and Flow Nozzle.
Various types of orifices (e.g.,
sharp edge, square edge, etc.)
are available.
A-153
-------
TABLE A-20 (continued).
METHOD
DESCRIPTION
APPLICABLE
MEDIA
Rotameter
Turbine
Meter
Magnetic
Flow
Meters
Ultrasonic
Flow Meter
A liquid flow meter operating on the physical principal
of fluid drag. Flow enters the bottom of a tapered
vertical tube causing a bob or "float" to nose upward.
For a given rate of flow, the float assumes a position .
in tube where the drag forces are just balanced by the
weight and buoyancy forces. Through careful design,
effects of changing viscosity or density may be minimized.
The position of the bob in the tube is taken as an
indicator of volume flow rate. Meter is installed
vertically.
Liquid
This meter use's the principle that the change in
momentum in a flow through a set of curved vanes
causes a torque to be exerted on the vanes. As
fluid moves through the meter, it causes rotation
of a small turbine wheel. A permanent magnet housed
in the wheel* hub rotates with the wheel, yielding
a varying magnetic field which Is detected by a
reluctance pickup in the meter casing. The frequency
of magnetic pulses indicates the flow rate.
'A noncontacting rate meter based on Faraday's law of
induced voltage. A short section of fluid conduit is
subjected to transverse magnetic flux. Fluid motion
induces voltage proportional to fluid velocity, which
is picked up by electrodes placed in conduit walls.
For fluids which are only slightly electrically conductive
(e.g., water), conduit is made of glass or other non-con-
ducting material. Alternating magnetic field is used for
amplification since output voltage is low.
Gas or
Liquid
Liquid
A noncontacting rate meter employing ultrasonic waves.
Similar piezoelectric or magnetostrictive transducers
are placed externally on the conduit a few Inches
apart. One serves as a 100-KHz energy source and the
other as a pickup. As the wave travels from source
to pickup, its normal velocity in stationary fluid
Liquid
A-154
-------
TABLE A-20 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
a) 1-2% accuracy.
b) Meter indication is
essentially linear with flow .',
rate.
c) Pressure loss fixed at all
flow rates.
d) Condition of flow readily
visible.
e) Many corrosive fluids can be
handled without complication.
f) Capacity can be changed
easily by changing bob and/or
tube. '
a) Accuracies + 1/2% within
specific flow range.
b) Good transient response.
a) Relatively expensive
b) Must be installed in
vertical position.
c) Bob not visible when opague
fluids are used.
d) Cannot be used for liquids
carrying large percentages
of suspended solids.
Installed in line.
a) 1% accuracy for flow
velocities of 1-10 m/sec with
increasing accuracy at higher
velocities.
b) Output signal can be con-
verted to volume or mass flow
rates.
c) Can be used for high solids
contents streams.
d) No resulting head loss;
totally unobstructed.flow.
e) Output is independent of
temperature, viscosity, density,
or turbulence.
f) Can be used for continuous
monitoring.
a) 2% accuracy.
b) No site preparation.
c) Can be used to measure
actual mass flow rate by deter-
a) Bearing maintenance
required.
b) Reduced accuracy at low
rates.
c) .• Liquid must be "clean"
(i.e., very low solids contents.
a) Expensive.
b) Liquid must be at least
slightly electrically
conductive.
c) Cleaning electrode
assemblies may be required.
Installed in line.
Available sizes from 1/8" to 8"
(line diameter).
Installed in line.
No location requirements.
For liquids with conductivity
values of 0.1 to 5 micro-Mhos
a special signal converter is
needed.
Extensively used for slurry
streams.
a) Expensive.
b) Temperature sensitive.
No site preparation required.
A-155
-------
TABLE A-20 (continued).
METHODI
DESCRIPTION
APPLICABLE
MEDIA
Ultrasonic
Flow Meter
(cont)
Positive
Displacement
Meter
Estimation
Using Pump
Characteristics
and Operating
Data
Estimation
by Equipment
Specifications
and Operating
Data
Estimation
by Tank
Level
Change
Calculation
by Trajectory
Method
will be either increased or decreased by fluid velocity,
depending on the relative motions. To minimize errors,
the functioning of the two transducers is reversed 10
times per second so that that phase shifts due to both
addition and subtraction of velocities are employed.
Relative phase shift is used to measure flow rate.
A displacement method.
For the nutating disk type, the fluid enters the meter
and strikes a disk which is eccentrically mounted. The
disk wobbles about its vertical axis and the fluid
moves through the meter. The volumetric flow is
proportional to the number of times the disk wobbles in
a given period of time.
For the rotary-vane type, a fixed amount of fluid is
trapped in a section of a rotating eccentric drum,
the rotations of which are proportional to flow.
Estimation method.
Horsepower, head, or rpm readouts, for pump can be
related to flow rate (i.e., capacity using
equipment performance curves supplied by
manufacturer.
Estimation method.
Some measurable quantity such as rpm of a screw
feeder, feeder table speed of a pulverizer, etc.,
can be related to mass flow rate using calibration
curves supplied by manufacturer.
Estimation method.
A stop watch is used to record the time for a given tank
level change. An average volume flow rate can then be
calculated.
Calculation method.
By measuring the position of a point on the trajectory
of the free jet downstream from the pipe exit,
the exit velocity may be determined
(if air resistance is neglected by the following
relation: Q = 1800 A X Gal (Water only.)
(Y)% Min
Gas or
Liquid
Liquid
Solid
Liquid
Liquid
A-156
-------
TABLE A-r 20 (continued).
ADVANTAGES
DISADVANTAGES
REMARKS
mining liquid density through
acoustical impedence technique.
d). Can be used for continuous
monitoring. •
e). ;No resulting head loss;
totally unobstructed.
a) .1% accuracy.
b) Direct flow measurement.
Simple; involves no flow
measurement.equipment.
a) Simple; involves no flow
measurement equipment.
b) Commonly used method.
c) Accuracy lot 1-2% claimed
by manufacturers.
Simple; involves no flow
measurement equipment.
a) Simple; involves no flow
measurement equipment.
b) Can be used ,,for full or
partially filled pipes.
c) Accurate:for rough flow
measurements (i.e., about 10-
20% accuracy) [of water, dis-
charge's .
a) 'Usually limited to clean
liquid streams.
b) If used for slurry '
applications, the solids would
damage the seals around the
blades.
Installed in line.
accurate. •
Not accurate.
A number of readings should be
taken over the time period of
interest to maximize accuracy.
A number .of readings should be
taken over the time period of
interest to maximize accuracy.
a) Will provide only average
value of volume flow rate over
time- period (not useful for
transient flow rate determi--
nations).
Pipe discharge must be
horizontal.
Applicable only when a tank
discharges or receives total
flow from or into a line during
selected time period.
Requires provision for observing
tank level changes. ,
A-157
-------
TABLE A-20 (continued).
METHOD
DESCRIPTION
APPLICABLE
MEDIA
Estimation
by Trajectory
Method
(Cont)
Direct
Weighing
Solids
Weighing
Devices
Where
A = Cross-sectional area of liquid in pipe (in
square feet).
X = Distance between end of pipe and vertical gage
measured parallel to the pipe (in feet).
Y = Vertical distance from water surface at discharge
end of pipe and intersection of water surface
with vertical gage (in feet).
Method consists of collecting all of discharge over
a measured period of time. The discharge can then
be weighed or the volume measured and the volumetric
or mass flow rate determined.
The weight of a belt, hopper, etc., is monitored
by measuring the total weight of equipment and
material and zeroing the gage at the reading of
the equipment alone.
Basic techniques include: the unevenly balanced
scale, the spring-balanced scale, pneumatic load
cell, hydraulic load cell, and the strain gage
load cell.
Liquid or
Solid
Solid
A-J58
-------
TABLE 20 (concluded).
ADVANTAGES
DISADVANTAGES
REMARKS
Simple and inexpensive.
a) 1-37. accuracy.
b) Commonly used.
c) Zero point calibration can
be performed during plant-
shutdown. '
i
d) Can be used for continuous
monitoring.
a) Accuracy limited by number
of observations.
b) Must be able to collect all
of discharge for unit period
of time.
a) Expensive.
b) Frequent recalibratlon
usually necessary.
No site preparation.
Permanent installation.
Bins,'hoppers, and belt feeders
are usually equipped with such
devices when accurate process
control is required.
A-159
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT NO.
EPA-600/7-77-009
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Procedures Manual for Environmental Assessment of
Fluidized-Bed Combustion Processes
8. REPORT DATE
January 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
I. PERFORMING ORGANIZATION REPORT NO.
H.I. Abelson and W.A. Ldwenbach
9. PERFORMING ORGANIZATION NAME AND ADDRESS
The Mitre Corporation
Metrek Division
McLean, Virginia 22101
10. PROGRAM ELEMENT NO.
EHB536
11. CONTRACT/GRANT NO.
68-02-1859, Task 7
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD
Task Final; 9/75-11/76
COVERED
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES IERL-RTP Project Officer for this document is W. B. Kuykendal,
919/549-8411 Ext 2557, Mail Drop 62.
16. ABSTRACT
The document describes recommended procedures for sampling and
analysis, for eventual use by source testing contractors, in support of the environ-
mental assessment of fluidized-bed combustion (FBC) technology. The phased
strategy involves two distinct levels of sampling and analysis. The document addres-
ses proposed generic units and corresponding case study units for the following
process configurations: (I) Atmospheric FBC of coal; (H) Pressurized, combined-
cycle FBC of coal; (m) Pressurized, combined-cycle FBC of coal (adiabatic combus-
tor); and (IV) Chemically active fluid bed (CAFB) gasification of residual oil. It
includes a compendium of method options, describing the sampling and analytical
state-of-the-art.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution
Fluidized Bed Processing
ombustion
Sampling
Analyzing
oal
Residual Oils
Air Pollution Control
Stationary Sources
Environmental Assess-
ment
Source Testing
13B
13 H, 07 A
21B
14B
211)
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report!
Unclassified
21. NO. OF PAGES
455
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
------- |