&EHV
United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/2-79-201
November 1979
Research and Development
Sampling and Analysis of
Reduced and Oxidized
Species in Process
Streams -
Final 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 nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-201
November 1979
Sampling and Analysis of Reduced and
Oxidized Species in Process Streams -
Final Report
by
R.F. Maddalone, L.L. Scinto, and M.M. Yamada
TRW Defense and Space Systems Group
One Space Park
Redondo Beach, California 90278
Contract No. 68-02-2165
Task No. 221
Program Element No. INE624
EPA Project Officer: Frank E. Briden
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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Figures,
CONTENTS
Paje
.. iv
Tables v
Introduction
2
Executive Summary
Major Tasks 28
Task! Level 1 Manual Revision/Project Start-Up 28
Task 2 Limestone FGD Demo Support 29
Task 3 Support to Ocean Incineration 38
Task 5 SASS Train Level 1 Checkout 46
Task 7 ' Inorganic Compound Identification 48
Task 8 Sampling and Analysis of Reduced Inorganic
Compounds 80
Task 9 Coal Monitoring Instrumentation 97
Task 10 Coal Sul fur Measurements 1 °3
Task 12 Continuous Flow Impactor 119
Task 13 Understanding S03 Data 123
Task 14 KVB Test Support 131
Task 21 Test Data Model ing 134
Task 22 Evaluation of Dry Sorbents and Fabric Filtration
for FGD 147
Task 24 Process Measurement Symposium 151
Task 26 Total Particulate Mass Emission Sampling Errors.... 162
Task 32 . Support to Level 1 Environmental Assessment Study.. 165
Task 36 Inorganic MEG Compounds and Level 1 Assessment 170
Task 42 Support Services to Level 1 Environmental
Assessment Performance Evaluation 173
Task 47 Automatic Sulfur Trioxide Monitor 176
Task 48 Analysis Using Ion Chromatography 180
Task 49 NIPSCO Mass Emission Monitor 187
Task 51 EPA/TVA Limestone FGD Support 189
Task 53 Input to Level 1 Manual Revision 194
Task 57 At-Sea Incineration Environmental Impact Report... 196
ii
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CONTENTS (Continued)
Page
Task 62 pH and Chloride Electrode Evaluation 197
Minor Tasks i 203
Task 11 Mass Emission Monitor Demonstration 203
Task 16 NBS Meeting 203
Task 28 SASS-S02 Tests 208
Task 29 S03 Measurement Presentation 208
Task 33 Denver X-Ray Meeting 208
Task 44 Particulate Measurement Meeting 210
Task 45 SASS Train Thermal Control Alternate 210
Task 46 Stepwise Arsenic Process 210
Task 54 Fate of PCBs in Rollins Plant Fire 211
Task 58 Workshop Presentation 212
Reports Issued 213
References 217
m
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FIGURES
Paje_
1. Brink Impactor Set-Up 33
2. MRI Impactor Set-Up 34
o/r
3. Controlled Condensation System Set-Up
4. Perkin Elmer KBr Pellet IR Scan of PMB-0085 Flyash 62
5. Perkin Elmer 521 IR Scan of PMB-0085 Flyash (5X) 63
6. Sample PMB-0085 FBC Flyash 64
7. Mechanical Precipitator Flyash Spectrum 66
8. Electrostatic Precipitator Flyash Spectrum 67
9. Cyclone from HVSS (INLET) Flyash Spectrum 68
10. Filter Catch from HVSS (INLET) Flyash Spectrum 69
11. Calibration Curves for As^/As"1"5 71
12. TGA of FBC Material (Nitrogen Atmosphere, 5°C/min) 73
13. TGA's of Flyash and Model Compounds 75
14. SASS Distribution for PH3, AsH3 and SbH3 86
15. SASS Distribution of Reduced Sulfur Species 87
16. SASS Distribution of Reduced Nitrogen Species 88
17. SASS Distribution of Hg, Se, and Metal Carbonyls 89
18. Typical Chromatogram for Reduced Inorganic Gases Using 93
Porapak QS
19. Reduced Gas Evolution Apparatus 94
20. Reconstructed Gas Chromatogram of the Hydrides Produced by 95
Reduction Procedure
21. Table of Contents for Coal Monitoring Instrumentation Report 99
22. Experimental Apparatus 125
23. Quartz Filter Holder 127
24. Symposium Meeting Program 153
25. Inside View of Automatic SO., Monitor 177
iv
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TABLES
Page
1. TIE Task Expenditures by Area 3
2. Results of Waste Analysis 41
3. Experimental Conditions 54
4. XRD Detection Limits of Inorganic Compounds of Environmental 55
Interest
5. Residue "A" Tentative Identifications 57
6. Residue "B" Tentative Identifications 57
7. Useful IR Bands 58
8. Infrared Bands of Some Common Nitrates (CM ) 59
9. Infrared Bands of Some Common Sulfates (CM" ) 60
+3 +5
10. As /As Speciation Tests Recovery Error Results 70
11. PIXE vs. AAS as Procedure 77
12. Industries and Processes Producing Reduced Inorganic Species 82
13. Collection Solutions for Representative Reduced Species 90
14. Field Test Results for Arsine 92
15. Comparison of Organic Sulfur Determinations (% W/W by 105
Difference)
16. Comparison of Sulfur Forms Analysis Methods 107
17. Total Inorganic Sulfur Comparison 108
18. Organic Sulfur 109
19. Comparison of Inorganic Speciation Methods 111
20. Sulfur Forms Analysis of Liquified Coal 113
21. Evaluation of Solid Sorbents for SO Sorption under Plasma 115
Conditions
22. Results of Flyash Tests 128
23. Recommendations for Solution Preservation 181
-Continued-
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TABLES (Continued)
Pa^e
104
24. Retention Time of Various Ions Found in Wet Scrubbers
25. Direct Comparison Between TVA and TRW Sample Analysis for
the Lime/Limestone Wet Scrubber
1 no
26. Survey of FGD pH Measurements
27. Chloride Ion Measurements
28. Current Research in Measurements of Inorganic Species
29. Current Research in Applications of X-Ray to Environmental 209
and Occupational Health Analyses
VI
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INTRODUCTION
This program (EPA Contract No. 68-02-2165) was sponsored by the
Process Measurements Branch of the Industrial Environmental Research
laboratory at Research Triangle Park, North Carolina. The original
program officer was Dr. Robert Statnick, and the current program
officer is Mr. Frank Briden. Under this contract, TRW conducted a
program for the evaluation, development, testing and field adaptation of
measurement techniques for elemental analysis and inorganic compounds
identification in process and effluent streams. The primary objective of
this program was to provide the measurement methodologies required for
environmental assessment and control technology development projects
related to the stationary source, energy and industrial process programs
of the EPA. TRW was responsible for conducting both the basic development
effort and the programs necessary to apply and evaluate the application
of these and other sampling and analytical techniques on specific
engineering studies.
Many of the tasks initiated covered short-lived or routine activities
and were not reported. The tasks covered in this final report represent the
technical work performed under this program. This report contains an
executive summary which describes the entire program in each of the
individual areas defined in the program scope of work. Following this
summary are detailed reports on each of the key tasks in the program.
Descriptions and objectives of each task are discussed followed by the
technical approach, techniques used, and results applicable to each task.
Appropriate recommendations and comments are included at the end of each
task discussion. In addition to a discussion of major tasks, a brief
synopsis of <100 hour tasks follows the major tasks. A compilation
of reports issued by task on the program are found in Section 4.
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SECTION 1
EXECUTIVE SUMMARY
The work performed on this contract can be divided into six major
work areas:
1. Measurement Methods Evaluation and Development
2. Methods Adaptation and Application Studies
3. Measurement and .Test Program Reviews
4. Sampling and Analytical Support
5. Preparation of Guidelines and Procedures
6. Conduct Symposia and Training Sessions.
It was the original intent of the program to direct the bulk of the
work into R&D activities. Based on areas 1 and 2 TRW spent approximately
66% of the hours in pursuit of new methods or on the evaluation and
adaptation of available methodology.
Program work areas are shown in Table 1 along with the tasks
performed and percentage of the hours expended for each area. Of
particular note are tasks 7, 8, 10, 13, 47, 48 and 62 in the Measure-
ment Methods Evaluation and Development area. These tasks dealt
with state of the art environmental sampling and analysis methods
for oxidized (Task 7) and reduced (Task 8) inorganic species; coal
sulfur measurements (Task 10); SOg measurements (Tasks 13 and 47);
ion chromatography (Task 48); and process measurement of pH and Cl"
(Task 62). The following pages will summarize the tasks performed
in each of the six work areas.
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TABLE 1. TIE TASK EXPENDITURES BY AREA
Area
Tasks
% of Total
Expenditures
1. Measurement Methods Evaluation and
Development
2. Methods Adaptation and Application
Studies
3. Measurement and Test Program
Reviews
4. Sampling and Analytical Support
5. Preparation of Guidelines and
Procedures
6. Conduct of Symposia and Training
5,7,8,10,12,13,28*.46*.47,48,62
2,11*,21,36,45*,22,49
9,26,54
14,32,42,51
1,3,53,57
* * * * *
16 ,24,29 ,33 ,44 ,58
60
15
2
10
10
*M1nor task, <100 hours.
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1.1 AREA 1; iMEASUREMENT METHODS EVALUATION AND DEVELOPMENT
Area 1 tasks encompassed a broad range of topics of current concern
in environmental measurement technology. Tasks were undertaken to develop
new techniques and evaluate existing methods in the fields of inorganic
compound identification, sulfur/SO measurement, and particulate emissions
assessment. Seven major tasks were performed in the three indicated
fields:
1. Inorganic compound identification
• Task 7 - Inorganic Compound Identification (oxidized species)
• Task 8 - Sampling and Analysis of Reduced Inorganic Compounds
2. Sulfur/SO measurement
A
• Task 10 - Coal Sulfur Measurements
t Task 13 - Understanding SOgData
t Task 47 - Automatic Sulfur Trioxide Monitor
3. Particulate emissions assessment
• Task 5 - SASS Train Level 1 Checkout
• Task 12 - Continuous Flow Impactor
4. Process Measurement Development
• Task 48 - Analysis Using Ion Chromatography
§ Task 62 - pH and Chloride Electrode Evaluation
In addition, two minor (<100 hours) tasks were performed:
• Task 28 - SASS-S02 Tests
• Task 46 - Stepwise Arsenic Process
1.1.1 Major Task Summaries for Area 1
Task..7. - Inorganic Compound Identification--
Task 7 involved one of the most extensive efforts in the program. It
was devoted to the study of measurement procedures for inorganic compounds,
While this task was broad in its nature, its main goal was to advance the
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state of the art for identifying specific inorganic compounds 1n samples
of environmental interest. In this first year of work several subtask
areas were investigated:
• Literature review - references on compound Identification for
specific elements (e.g. As, Se, Sb, Hg, Cd, and Zn) were compiled.
• X-ray diffraction - determination of the sensitivity of specific
compounds in an environmental matrix were made.
• Infrared analysis - references on IR and FTIR were compiled and
a comparison of the two methods made.
• Selective reduction of As /As* - a chemical approach to the
+3 +5
selective reduction of As /As in aqueous environmental samples
was Investigated.
• Mass thermal analysis - studies were initiated to determine if
volatile inorganic compounds could be thermally desorbed from the
surface of collected particulate matter.
• Special studies - potentially useful new analytical methods and
procedures were cursorily studied.
In addition to these specific areas of research conducted under this
task, TRW has supported EPA/IERL programs in the area of advanced inorganic
analysis. In this role, TRW was charged with design, testing and application
of advanced analysis schemes for the determination of compounds from process
streams including FBC bed materials and combustion source emission streams.
As an end result TRW developed a comprehensive inorganic compound identific-
ation scheme, which has been detailed in a technical manual for inorganic
compound identification.
The major accomplishments and conclusions in each of the six subtask
areas are discussed in the sections below.
Literature Survey — The literature survey compiled and organized over 300
•journal articles on a wide range of topics. Computer searches for analysis
methods for the elements arsenic, barium, beryllium, boron, cadmium,
chlorine, copper, fluoride, lead, manganese, mercury, nickel, selenium,
tin, vanadium, and zinc were completed. This literature is currently
filed by method at TRW. This file was constantly updated during the
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course of the contract.
X-Ray Diffraction Studies — The main goal for X-ray diffraction studies
performed at TRW was to investigate the analytical capability of a typical
commercial X-ray diffractometer to detect small amounts (1-10%) of various
materials of environmental interest. Performance of an XRD unit.was
evaluated by tests on laboratory and field samples.
X-ray diffraction technique is a relatively simple analytical tool
widely used for qualitative and quantitative identification of various
crystalline compounds present in a amorphous matrix. However, the
sensitivity of the X-ray diffraction method is inferior to other methods,
and the sensitivity may vary depending on the compound under study and the
matrix. Sensitivity tests were therefore run on laboratory samples of
pure compounds in an amorphous matrix. Detection limits for numerous
inorganic oxides and sulfates were determined from the results of these
sensitivity tests. Since sample handling procedures may also affect
analytical results, alternate techniques for this procedure were tested.
XRD analyses of industrial samples of FBC fly ash and thermally/chemically
treated coal char identified many constituents of these materials successfully.
However, because of the overlap of several compounds, unambiguous identi-
fication of all spectral lines was not possible. In particular, it was
found that the Na2C03 spectra did not correspond to the literature values
and hence, identification of it within the samples was impossible. This
particular result was nonetheless expected from work by other investigators.
In general,, results showed that XRD analysis of environmental samples
is possible, but that problem areas still exist. Sample mounting methods
need to be developed to either analyze material impacted directly on glass
fiber filter without sample modification. One possible technique is to
use Freon as the solvent and ultrasonic cleaner to break-up the filter.
Filtration or density gradiant separation could be used to remove the glass
fibers.
Low sensitivity of XRD compared to other methods of analysis remains
a problem. Methods to improve the sensitivity of the XRD technique
include use of more sophisticated equipment or computer averaging
6
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techniques. The latter method should be further studied.
Infrared Spectroscopy Studies — In the total compound analysis scheme,
infrared analysis can potentially identify anions present in the sample
and determine the compound containing the anion.
Technical problems that must be addressed include effect and control
of moisture content in the sample. It is expected that the samples will
have to be dried to a constant water content to simplify the analysis
problem. In preparing samples that contain reactive materials such as
bisulfates for IR analysis, KBr should not be used due to possible anion
exchange reactions.
A series of IR spectra were obtained for five different flyash
samples. These samples were analyzed by conventional IR and FTIR in the
mid-IR region. While further work will be needed to identify the bands, the
high quality of the spectra and the obvious changes in the position and
strengths of various bands shown in the FTIR spectra clearly indicates the
utility of FTIR over conventional IR in recognizing changes occurring
in the sample. Also, the ability of the FTIR to subtract background
spectra can be used to remove unwanted materials. While 40 scans were
averaged in this test, 400 or 4000 scans could have been made to improve
sensitivity.
Work should be continued on IR to:
• Study the effects of sample conditioning*on the structure of the
compounds. Work is needed to "normalize" samples so that spectral
shifts due to hydration, crystalline form or sample matrix do not
occur or are identified.
• Study the direct analysis of material impacted on glass filter to
see if this information can be used to supplement direct XRD
analysis.
• Study the subtraction capability of FTIR to establish guidelines
on subtraction procedures for complex mixtures. The goal is to
subtract different samples from each other to emphasize differences
in the samples, such as particulate matter collected at the inlet
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or outlet of an FGD.
i O ^.C
As*3/As*5 Speciation - A procecure was tested to selectively reduce As /As
in aqueous environmental samples to permit separate analysis of each species.
A comprehensive test matrix was run to quantify sample recovery and analytical
errors in the procedure. Samples containing As+3 and As , both separately
and combined, were analyzed using several different reaction chemistries.
Results showed a favorable accuracy and recovery for As ; however,
recovery of As+5 was low. Further work is necessary to find the cause of
this low As recovery.
Mass Thermal Analysis — A proposed method to analyze for possible thermal
desorption of volatile inorganic compounds from the surface of collected
particulate matter using TGA/MS was tested.
It was concluded that this technique is useful in determining the
gross thermal characteristics of a sample. For example, a TGA run could
provide information as to the amount of moisture in a sample, likely
decomposition temperatures of the mixture components, and overall thermal
stability. This type of information could be of value in selecting a drying
cycle for a mixture prior to analysis. However, determination of small
quantities (<1%) of materials does not appear to be very promising unless
reproducible results can be obtained from a known mixture. This was not
the case for the FBC material.
Special Studies — Proton induced X-ray emission (PIXE), SEM-EDX, and
Electron Microprobe analyses were evaluated as new and potentially important
analytical tools in environmental measurement. Specific advantages and
limitations for each method were identified. PIXE was found to be useful
on some sample types, but would be of limited use as a general analytical
tool without extensive modification. SEM-EDX was found to be adequate for
high resolution morphology studies of environmental particles. Techniques
which warrant further study for their use in elemental depth profiling
include Scanning Auger Microanalysis (SAM), ESCA, and SIMS.
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Task 8 - Sampling and Analysis of Reduced Inorganic Compounds—
The objective of Task 8 was to develop a sampling and analytical
system to determine the emission rate of specific reduced inorganic compounds.
The list of reduced compounds included metal hydrides, elements, and non-
metal hydrides. The overall goal was a sampling and analysis accuracy of
+ 25 percent and a precision of ± 30 percent.
Results in several subtask areas are summarized below.
• Literature survey - The survey suggested a general lack of material
on compound identification for reduced Inorganic materials. In
a few cases, the literature gave specific examples or suggested
methods of analysis. These references and methods were given in
the final report.
• Laboratory testing - Methods for generation of volatile metal
hydrides were tested. These production methods have been
established as quantitative and are the first step in evaluating
a sampling and analysis procedure. The details of the procedure
together with current analysis data have been reported in detail
in monthly progress reports.
• Field testing - The SASS train was tested for its suitability for
sampling reactive inorganic species for subsequent compound
identification. Sampling for solid inorganic species from
particulate material may be possible using the SASS, however,
reduced inorganic gases will either be lost or chemically modified
due to .their inherent susceptibility to oxidation.
Task 10 - Coal Sulfur Measurements--
A need existed for a more accurate procedure for analysis of organic
sulfur in coal. As part of Task 10, TRW proposed two entirely new coal
organic sulfur analysis procedures, both based on the selective removal of
organic sulfur species present in coal via selective oxidation in an
oxygen plasma instrument. The first procedure entailed the determination
of organic sulfur by difference between two highly accurate and precise
BaS04 gravimetric procedures: one performed on the starting coal and one
9
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performed on the resultant ash from an oxygen plasma decomposition o
coal matrix. The second procedure is the direct determination of organic
sulfur by collection of S02/S03 on solid sorbents placed in the outlet line
from the plasma asher.
Organic sulfur analyses using the indirect gravimetric procedure were
compared with results obtained on aliquots of the same coals using standard
ASTM D2492 procedures with pyritic sulfur being determined using both the
alternate atomic absorption (AA) technique and the standard titrimetric
procedure. The results showed that both the plasma ashing and the ASTM-AA
procedures gave consistent results, while the ASTM titrimetric procedure
gave widely discrepant results that tended to be significantly low for
untreated Appalachian coals. Thus, in reference to evaluation of coal
cleaning processes, it appears that the ASTM procedure gave results that
were virtually independnet of the past history of the coal.
The direct organic sulfur analysis technique via sorbent trapping of
evolved SOV species during plasma ashing was shown to be a viable technique.
A
Not only could this technique be used for organic sulfur but the concept
could be expanded to include other organically bound species such as I, Cl,
and nitrogen. However, the physical limitations of currently available
plasma ashing systems are incompatible with the proposed technique. This
is an engineering problem and could be solved by redesigning currently
available ashing chambers.
Task 13 - Understanding SOj Data--
The objective of this task was to develop a stack sampling procedure
for the measurement of the mass emission rate of sulfuric acid within a
precision of +10% but not to exceed +20%. Subtasks were devoted to the
selection and testing (laboratory and field) of the HoSO. sampling train.
Sampling and analysis systems were evaluated on the criteria of
selectivity, sensitivity, accuracy, precision, ease of operation, and
reliability. The controlled condensation system (CCS) developed by
Goksoyr and Ross was selected for additional study over the selective
absorption system which is the basis of EPA Method 8.
Laboratory and field tests showed that:
• The accuracy of the CCS, both in the laboratory and in the field,
was acceptable.
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• No significant oxidation of S02 occurred on the filter to the CCS.
• Coal fly ash on the filter did not catalyze S02 oxidation in the
CCS, but did reduce the amount of HgSO, collected.
• The coefficient of variance of the HoS04 output at the coal-fired
utility tested was estimated to be +B5/L This high CV$ implies
that to obtain a good average ^SCty value from this type of source,
it will be necessary to take a large number of samples spread out
over a period of days.
/
Task 47 - Automatic Sulfuric Acid monitor --
The objectives of this task were to design, construct, and test an
automatic sulfur trioxide monitor based on the Goksoyr-Ross coil capable
of providing reasonably accurate measurements (+20%) of sulfuric acid
concentration in process streams.
The unit was designed to be sturdy and easy to operate in the field,
with the capability to operate unattended for continuous periods on the
order of 24 hours. Provisions to easily modify the unit were part of the
design.
A field test unit was constructed and laboratory tests completed.
The unit operated continuously for 11 hours and its results compared
favorably with manual CCS measurements that were made.
Task 5 - SASS Train Level 1 Checkout—
The performance of one of the first SASS trains was evaluated during
tests conducted on board the incinerator ship M/T Vulcanus. Results of
these tests were used to evaluate analytical procedures set forth in the
first IERL-RTP Level 1 manual.
Problem areas for further study under other tasks and contracts were
identified in Task 5. These solution-oriented studies, conducted after
completion of Task 5, eventually led to refinements of the Level 1
procedures such as the quartz-lined Parr bomb method. These refinements
have all been addressed and the resulting recommended Level 1 modifications
assembled as TRW's input to the Level 1 revisions under Task 5.
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Task 12 - Continuous Flow Impactor—
Task 12 was a pioneering effort to develop a continuous flow impactor
based on a concept first suggested by TRW. The purpose of the task was to
determine the feasibility of an impactor in which the collection "surface" is
the interface between two opposing jets.
A test unit was designed, constructed, and laboratory tested. Basic
proof-of-principie tests on the unit were successful, demonstrating a tech-
nically viable and field acceptable hardware concept. Performance of
the unit is expected to be comparable to presently available staged impactors.
Refinements to the prototype unit were investigated, with the following
results:
• Preliminary design studies indicate that a staged impactor can easily
be integrated into a sampling probe to perform in-situ particulate
size distribution measurements.
t Feasibility of a simple optical system compatible with the in-situ
sampling hardware was shown analytically.
• The continuous flow impactor has a potentially greater accuracy
capability than standard impactors since it inherently avoids the
traditional problems of particulate bounce and reentrainment.
Potential applications for the continuous flow impactor include control
device evaluation, continuous monitoring of particulate emissions for reg-
ulatory purposes, and collection of particles in an inert atmosphere to
quench chemical reactions. Based on the results of this task, further testing
of the laboratory unit and the proposed optical system is recommended.
Subsequently, development of a field-worthy instrument should be undertaken.
*
Task 48 - Analysis Using Ion Chromatography—
This task involved the development of an analytical scheme using ion
Chromatography to determine specific ions in lime/limestone wet scrubbers
and in dual-alkali process streams. Working with synthetic mixtures and
actual samples from the Tennessee Valley Authority Shawnee Test Facility
at Paducah, Kentucky, TRW staff developed procedures for 1) sample
collection; 2) sample preservation; and 3) the separation of solutions,
slurries, solids and solubles in cake. The accuracy and precision of
12
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this new analytical scheme was shown and a detailed analytical procedures
manual was written. Methods for the qualitative and quantitative
analysis of sodium, potassium, magnesium, calcium, chloride, total
oxidizable sulfur, sulfate, sulfur, nitrate, carbonate and hydroxide
were emphasized.
Task 62 - pH and Chloride Sensitive Electrodes —
This task was an outgrowth of a symposium attended by representatives
of the EPA, TRW, TVA and the University of Cincinnati. One of the concerns
expressed was the applicability of chloride and pH electrodes in automated
systems controlling aspects of flue gas desulfurization units operations.
An initial survey of 8 utilities showed chloride measurements were of
interest only where high concentrations were found. On the other hand, all
facilities relied on pH measurements to monitor the operation of the FGD.
The second part in this task was an evaluation of the performance of
self-cleaning electrode and a standard pH electrode. Comparing these two
with one another, as well as with a laboratory pH electrode and meter setup,
revealed the following:
• The accuracy and precision of the self-cleaning and standard type
electrode.
9 Scaling was a confirmed maintenance problem with the standard type
electrode.
• Clogging of the screen surrounding the electrode was a maintenance
problem with the self-cleaning electrode used in slurry streams.
• For continuous periods of operation greater than two weeks in
slurry streams, the self-cleaning electrode required slightly
less maintenance.
1.1.2 Minor Task Summaries
Two tasks in Area 1, Measurement Methods Evaluation and Development,
required less than 100 hours for completion. The first, Task 28 (SASS-S02
Tests) was an investigation to determine if the SASS train condensation
modules could be used to collect HgSO, while avoiding a large positive
error due to SOp oxidation in either gas or liquid phases. Oxidation of
sulfur species in the SASS train was quantified, the results indicating that
use of the SASS train to measure H^SO* was not appropriate.
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Task 46 (Stepwise Arsenic Process) evaluated the proposed Level 1
arsenic procedure based on atomic absorption spectrometry in terms of its
accuracy, precision, percentage recovery and efficiency of usage. The
results of the task identified the most reliable techniques of analysis and
quantified the level of accuracy and precision which could be expected
from the proposed procedure.
1.2 AREA 2: METHODS ADAPTATION AND APPLICATION STUDIES
Tasks in Area 2 were designed to investigate new applications for exist-
ing methods in process stream sampling and analysis. New applications for
both hardware and software were developed and tested. Applications included
process measurements at two FGD facilities, computer modeling of test
data, prediction of the utility of Level 1 methods in assessing MATE levels
of inorganic MEG compounds, and flow measurement evaluation studies.
Five major tasks were performed:
• Task 2 - Limestone FGD Demo Support
• Task 21 - Test Data Modeling
• Task 22 - Evaluation of Dry Sorbents and Fabric Filtration for FGD
• Task 36 - Inorganic MEG Compounds and Level 1 Assessment
• Task 49 - NIPSCO Mass Emission Monitor
1.2.1 Major Task Summaries
Task 2 - Limestone FGD Demo Support--
Methods of. sizing dry aerosols and measuring SOo were applied to
characterizing influent and effluent gas streams from a Flue Gas Desulfuri-
zation (FGD) unit. The sizing method for the dry particulate matter enter-
ing the FGD process was selected by the EPA to be a manual technique
utilizing a Brink Impactor. A manual system for the FGD process effluent
stream was chosen on the basis of a literature survey, contacts with
experts in the field, and an evaluation of available information. The
method chosen was the Meterology Research, Inc. Cascade Impactor used out
of stack. Finally, a method for S03 (H2S04 vapor) was developed based on
14
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the Controlled Condensation (Goksoyr/Ross) method and was successfully
tested under laboratory conditions. In addition to these method adapta-
tion and application areas, on-site training and support were provided by
TRW personnel and a procedures document for FGD process measurements was
prepared.
Quality assurance activities under Task 2 were extensive. In the
procedures document describing the aerosol sizing and S03 sampling pro-
cedures, information was provided on 1) equipment care and usage; 2) guide-
lines for laboratory techniques; 3) specific critical area checklists for
each procedure; 4) data interpretation aids to monitor the quality of the
results achieved; 5) specific maintenance and calibration schedules; and
6) troubleshooting and repair schemes.
In addition to this documented quality assurance activity, an on-site
training session was given to train the TVA personnel on the use of all
the equipment and procedures. Throughout the program, senior TRW personnel
were available for consultation over the phone or for troubleshooting in
the field.
Based on the Task 2 work, it was recommended that:
• Continued on-site and verbal assistance be provided to the Shawnee
Test Facility in the area of trace element sampling and analysis.
• Support be given to improve process measurement at the FGD units.
control strategies be developed based on improved process
urement of such species as S0.~, SO., , Ca+2, and Mg+2.
New
measurement
J4
Task 21 - Test Data Model ing—
The objective of this task was to develop test (computer) models which
permit a chemist to evaluate, a priori, and the variation in his test
results using assumptions based on his experience.
The computer program developed answered the following.questions:
• A chemist will take either 2 or 3 samples (replications) for a
particular test. What kind of results can be expected? To evaluate
the results the analyst can input either a + range or the actual
a along with the nominals.
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• A chemist has three populations of known mean and standard de-
viation (or +_ percent range) values. What are the mean and
standard deviation values of a new population defined as sums_
of three samples, one from each of the three original populations?
• A chemist again has three populations of known mean and standard
deviation (or + percent range) values. The populations are now
comprised of the original unknown (or summation) population and
any two of the three originally known populations which define
the summation population. What are the mean and standard de-
viation values of the remaining third original population
(presently unknown)?
Task 22 - Evaluation of Dry Sdrbents arid Fabric Filtration for FGD--
This study, which was an extension of preliminary work on the dry sor-
bent baghouse FGD concept done in 1976, encompassed six aspects of fabric
filtration with simultaneous SCL removal by dry sorbents:
1) Calculation of the cost of a baghouse and the associated sorbent
system.
2) Calculation of the cost of the disposal options.
3) Estimation of the sorbent cost, including mining cost for nahcolite,
cost of trona and a sensitivity study of cost versus quantity.
4) Sensitivity studies of operating costs and annualized costs
versus such parameters and assumptions as sulfur content and
boiler size.
5) Recommendations for parameters and ranges to use in a test program.
6) Feasibility of using Mag-Ox as a sorbent.
The cost estimates conformed to the methods and terminology used in the
TVA FGD Process Cost Study (completed in 1974 and revised in 1976).
Task 36 - Inorganic MEG Compounds and Level 1 Assessment--
This task was initiated to theoretically predict:
• If Level 1 Environmental Assessment is capable of detecting the
inorganic Multimedia Environmental Goal (MEG) compounds and
elements at their Estimated Permissible Concentrations (EPC).*
• Where in the Source Assessment Sampling System each inorganic
compound and element is likely to be found.
*The original task effort was redirected to substitute Maximum Acute Toxicify
Effluent (MATE) levels for EPCs.
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• What MEG compounds, elements and valence states can be predicted
in Level 1 aqueous samples.
t The nature of difficulty in detecting MEG compounds at EPC levels
by non-Level 1" techniques.
Organometallic MEG compounds were not included in this study.
After analyzing the capability of Level 1 to detect MEG compounds and
elements, actual Level 1 data were assessed to compare values obtained and
limits of detection with MATE Levels (EPCs).
Conclusions arising from the Task 36 effort were:
§ The Level 1 Environmental Assessment protocol is capable of de-
tecting most MEG elements at the concentration levels imposed by
the EPC X 100 criteria.
• Beryllium at the EPC X 100 level of interest is theoretically not
detectable by current Level 1 techniques.
• Arsenic, selenium, thallium, chromium, silver, lithium, antimony
and cadmium are theoretically not detectable at the EPC X 100
level of interest in some of the SASS components.
a Detectability problems have not yet been encountered for MEG
elements at coal-and oil-fired systems sampled.
• In water samples, beryllium and arsenic at EPC X 100 levels of
interest are not detectable by current Level 1 techniques.
Task 49 - Mass Emissions Monitor Demonstration—
In this task, hardware and methodology for continuous high and accuracy
flow and gas composition measurements in large stationary source stacks
and ducts were to be demonstrated. Prior work sponsored by the EPA had pro-
duced a multiple point gas sampling probe which showed potential for great-
ly enhanced accuracy over single point continuous sampling techniques
without a substantial cost or maintenance impact. Agreement was reached
with the NIPSCO power plant in Gary, Indiana to test a new wet scrubber
and to even use Dieterich Standard Annubars, a multiple point pilot
tube probe already installed in the stack for volumetric flow measure-
ments. The field effort was severely hampered by scrubber downtime
or by sampling system downtime. Limited data did reveal significant
compositional stratification at the test site,
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1.2.2 Minor Task Summaries
Two minor (<100 hour) tasks were performed under Area 2, Methods
Adaptation and Application Studies. In Task 11 (Mass Emission Monitor
Demo), an industrial site was selected to demonstrate the application
of continuous flow measurements, gas sampling hardware, and methodologies.
From a thermodynamic analysis of the SASS train thermal control system,
a design and cost estimate for an alternate system was developed, as part
of Task 45 (SASS Train Thermal Control Alternate).
1.3 AREA 3: MEASUREMENT AND TEST PROGRAM REVIEWS
Area 3 task objectives were to assess the validity and accuracy of
measurement methods in environmental sampling and analysis technology.
Critical reviews were made of existing methods for measuring coal mass
flow, composition and total mass emissions from stationary sources, and
the fate of PCBs at a plant fire. Two major tasks were performed:
• Task 9 - Coal Monitoring Instrumentation
t Task 26 - Total Particulate Mass Emission Sampling Errors
1.3.1 Major Task Summaries
Task 9 - Coal Monitoring Instrumentation--
The purpose of the task was to investigate the state of the art for
continuous coal mass flow and composition measurements, both to determine
current capabilities, and to investigate the need for EPA involvement in
research and development efforts. The types of flow investigated were dry
coal flow (typically on a belt) and wet coal slurry flow. Composition-
type measurements are performed on small samples (few grams) with laboratory
instruments and on dry slipstreams with various instruments currently under
development. Measurement in slurries is presently limited to only slurry
density.
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Based on the results of a literature search, vendor and user contacts,
and a field trip, information was obtained on coal measurement instrumenta-
tion, both available and under development. Information compiled along with
user data was then used to compare the various instruments. Additional
calculations and analyses were performed by TRW to determine system limita-
tions and errors. A final report, in the form of a technical manual, was
prepared.
Some of the major conclusions of Task 9 were:
• Weight belt devices, either electromechanical or nuclear, and
electromagnetic flow meters (typically coupled with nuclear density
gages) are the most used devices for dry coal flow measurement and
wet coal slurry flow measurement, respectively", and will be
acceptable for most situations.
• Development of neutron activation instruments is proceeding well,
with a sulfur meter expected as a production item within the next
few years. Hopefully, this will be followed by modified versions
capable of determining moisture and heating value. Neutron acti-
vation devices are of particular interest because they hold the
promise of sampling entire coal streams, thus eliminating the
major problem with present equipment - that of obtaining a re-
presentative sample of small quantity.
• The most reasonable area for IERL investigation in the near future
is how to make the best uses of available and soon-to-be-avail able
instrumentation to control the operation of stationary sources.
Such control could minimize pollutant emissions through direct
combustion control and/or optimizing operation of devices such as
wet scrubbers. The greatest ultimate value of coal monitoring
instruments is not as monitoring sensors, but as components in an
active control system, either on sources of direct coal combustion,
or in coal cleaning plants.
Task 26 - Total Particulate Mass Emission Sampling Errors--
The task objective was to determine the accuracy of particulate mass
emissions as determined by techniques in "IERL-RTP Procedures Manual:
Level 1 Environmental Assessment."
A standard error analysis was performed based on the assumption of a
fully entrained particle model with a factor to allow for gas-particle slip.
Error equations were derived, and individual error terms were evaluated
using instrument characteristics, typical source characteristics, and
methodology details.
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The major conclusion of the Task 26 study was that the SASS train and
Method 1 procedures are sufficiently accurate as Level 1 methods. Addi-
tional conclusions were:
• A SASS train operated in accordance with "IERL-RTP Procedures
Manual: Level 1 Environmental Assessment" sampling at a single
point will have a sampling accuracy of a factor of +2 or better
in most locations such as stacks or control device inlets. Under
worst case conditions, such as at an ESP outlet, it will have an
accuracy of about a factor of +3, due to stratification.
• In single point sampling, the mapping error (non-representativeness
of the selected point) will be the largest individual error in the
system. By using a 16-point traverse rather than sampling at
a single point, stratification errors are minimized. Using this
method, sampling accuracy of the SASS train could be improved
to about +25 percent.
• Additional stratification data should be obtained at sites such as
full-scale, coal-fired power plants for important locations: control
device inlets, control device outlets, and stacks. Such data should
be used for the development of single point sampling methodology.
t Results suggest that for hardware of a given accuracy, there will
exist specific procedures to optimize system performance (achieve
close to maximum accuracy while minimizing manpower requirements
and sampling times). Work should be continued to prepare an IERL-
RTP Procedures Manual in this area.
1.3.2 Minor Task Summaries
One minor (<100 hours) task was performed in Area 3, Measurement and
Test Program Reviews. In Task 54, Fate of PCBs in Rollins Plant Fire, the
objective was to investigate the fate of polychlorinated biphenyl compounds
(PCBs) that were stored in a tank farm on a chemical disposal site when a
disastrous fire occurred in December, 1977. The primary question was what
new environmentally hazardous products may have been formed under the
conditions existing at the time of the accident.
This study concluded that under certain conditions polychlorinated
biphenyl compounds may serve as precursors for the formation of other environ-
mentally undesirable compounds. The most probable class of compounds
formed are dibenzofurans. the reaction pathways to these compounds seemed
to be favorable under oxygen deficient combustion conditions and low
temperature. Conversely, it seems improbable that dibenzo-p-dioxins are
20
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formed under similar conditions. If dibenzo-p-dioxins were to be formed,
they would come from the dibenzofurans that are initially generated from
the PCBs. Formation of polycyclic aromatic hydrocarbons (PAH) is possible
via pyrolysis of PCBs in oxygen deficient conditions that could have exist-
ed in the Rollins fire.
1.4 AREA 4: SAMPLING AND ANALYTICAL SUPPORT
TRW provided various kinds of support to several Level 1 assessment
activities by other contractors under three major Area 4 tasks. TRW pro-
vided on-site sampling/analysis assistance, laboratory analysis of split
samples, consulting services, quality assurance and logistical support.
The following specific tasks were completed:
§ Task 14 - KVB Test Support
• Task 32 - Support to Level 1 Environmental Assessment Study (Radian)
• Task 42 - Support Services to Level 1 Environmental Assessment
Performance Evaluation
• Task 51 - EPA/TVA Limestone FGD Support
1.4.1 Major Task Summaries
Task 14 - KVB Test Support—
TRW supported KVB Engineering in a Level 1 sampling effort on an
experimental coal-fired boiler at KVB's Tustin, California facility. TRW
services were required for:
• Determining the adequacy of the sampling test as a Level 1
Environmental Assessment in accordance with the draft copy of the
Level 1 Procedures Manual.
• Answering any questions from KVB which might arise concerning the
requirements on the draft IERL procedures manual.
t Analyzing samples in accordance with the Level 1 procedures in
parallel with KVB's analytical subcontractor, Calspan.
The emphasis in the use of the data generated under this task was on
the mass balance. In this regard, the SASS was an effective unit perform-
21
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ing well within the Level 1 error limits of a factor of 2-3. The cumulative
percentage differences between the SSMS values and the special case analyses
values for total quantities trapped in the SASS train, and for the theo-
retical ideals for baghouse and coal feed, all showed excellent repro-
ducibility in terms of precision. The SSMS technique proved more re-
liable than AA or colorimetry for As, Hg and Sb because of the lower de-
tection limits for SSMS.
Task 32 - Support to Level 1 Environmental Assessment Study--
TRW was assigned by PMB to assist, advise, and instruct Radian
Corporation in conducting a Level 1 Environmental Assessment (EA) of a
low BTU coal gasification pilot plant at the Holston Army Ammunition
Arsenal. Under this task, TRW provided instruction to Radian personnel
on Level 1 procedures, on-site sampling and analysis support, and basic
quality assurance and consulting services. In addition to merely con-
sulting, TRW used its involvement in this task to contribute to the over-
all development of Level 1 methodology.
Task 32 was important in that it provided a necessary evaluation
mechanism for the Level 1 EA protocol as applied to a source of un-
usually high organic content. Invaluable experience was gained in this
teamed effort, which provided an excellent blend of sampling and analyti-
cal expertise. Future teaming activities are strongly recommended.
Task 42 - Support Services to Level 1 Environmental Assessment Per-
formance Evaluation--
Task 42 was part of TRW's participation with RTI, ADL, Radian, and
SoRI in collaborative testing to define the precision of the SASS and the
Level 1 analysis procedures.
The overall project was divided into two phases. Phase I field
sampling, assessed SASS performance and Level 1 field analysis procedures
at an aluminum smelter. Phase II efforts were directed at the Level 1
laboratory analysis procedures. TRW assisted in Phase I with logistical
and manpower support for the on-slte sampling effort (including pre-
test site survey), and in Phase II with analytical laboratory support
22
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Although remarkable progress has been made toward defining the details
of the Level 1 procedures in the relatively short period of time since they
were first published, considerable ambiguities remain which can lead to
differences in the interpretation of the procedures. That such differences
exist was evident in both phases of the effort. The seriousness of these
potential interpretive differences will hopefully be addressed in RTI's
summation of this collaborative testing.
Task 51 - EPA/TVA Limestone FGD Support--
This task involved providing support to process measurement activities
at the EPA Shawnee Wet Limestone Test Facility in Paducah, Kentucky. Five
major concerns have been investigated: recommending particle sizing
and trace elements analysis approaches; reviewing and recommending
sampling techniques and analysis methods for trace elements and compounds;
recommending sampling procedures to identify sulfur forms; evaluating
the feasibility of sampling liquid aerosols at a mist eliminator; and
developing automated methods to measure scrubber process stream para-
meters, thereby improving control of the scrubber operation. Each
problem was addressed either at a briefing or in a research report.
1.5 AREA 5: PREPARATION OF GUIDELINES AND PROCEDURES
TRW efforts in Area 5 have involved parallel efforts in the pre-
paration and revision of the EPA publication "IERL-RTP Procedures
Manual: Level 1 Environmental Assessment" and in the development and
evaluation of Level 1 analytical procedures. The following major
tasks were grouped under Area 5, although guidelines and procedures were
prepared to some extent under many other tasks.
• Task 1 - Level 1 Manual Revision/Project Start-Up
• Task 3 - Support to Ocean Incineration
• Task 53 - Input to Level 1 Manual Revision
• Task 57 - At-Sea Incineration Environmental Impact Statement
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1.5.1 Major Task Summaries
Task 1 - Level 1 Manual Revision/Project Start-Up—
The objective of this task was to incorporate review comments on
the draft manual: "IERL-RTP Procedures Manual Level 1 Environmental
Assessment," describing methods for conducting Level 1 environmental
assessment. The draft was prepared under EPA Contract 68-02-1412,
Task 18. The final revised manual was prepared under this task. Be-
cause this was the first task under this contract, project start-up
costs were also incorporated into it.
Task 3 - Support to Ocean Incineration--
The technical objectives of this task were to:
• Evaluate at-sea incineration processes for the destruction of
chemical waste products, especially chlorinated organic mater-
ials, on board the Matthias III and M/T Vulcanus incinerator
vessels.
• Develop guidelines for incinerator design, operational controls,
monitoring methodology and acceptance criteria to be utilized
by EPA and IMCO in establishing at-sea incineration permit
requirements.
Operational, performance and emissions data were obtained by TRW
sampling teams for a series of burns on the Matthias III and on the
M/T Vulcanus. Based on these incineration data, TRW assisted EPA in
generating technical considerations and guidelines to be utilized in
international agreements on control of incineration at sea. EPA sub-
sequently submitted these recommendations to the IMCO Intersessional
Working Group for Incineration at Sea at their London, England meeting.
These guidelines will also be used to establish U.S. regulations.
Task 53 - Input to Level 1 Manual Revision—
This task was initiated in November 1977, to provide updated and
revised chapters on gas, vapor and particulate sampling, and inorganic
analysis (Chapters II, III, and VII). These revised chapters were sub-
mitted to Research Triangle Institute (RTI) to be incorporated into the
republication of the IERL-RTP Procedure Manual for Level 1 Environmental
Assessments.
24
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The revised chapters submitted under this task represented the
best currently available Level 1 methodology. Specific tasks conducted
on this contract and the Environmental Assessment of Conventional Combustion
Sources (EACCS) project examined and improved the inorganic analysis
procedures, and the over 50 Level 1 source tests performed on the EACCS
project provided practical experience in dealing with the requirements
and realities of field testing. These experiences in both the analytical
and sampling aspects of Level 1 methodology had been integrated into the
EACCS procedures manual as they evolved. With this task, these improve-
ments also became part of TRW's input to the revision of the IERL-RTP
Level 1 manual.
Task 57 - At-Sea Environmental Impact Statement Studies —
The objective of this task was to prepare portions of an environ-
mental impact statement for at-sea incineration of industrial wastes
documenting the effects on the environment which could result from the
adoption of international standards regulating incineration at-sea
activities.
The results of this effort were presented to the International
Maritime Consultative Organization at their June 1978 conference in
London.
i
1.6 AREA 6: CONDUCT OF SYMPOSIA AND TRAINING SESSIONS
Six tasks in this program were devoted to TRW participation in
symposia or presentations related to the TLE program. Only one, Task
24 (Process Measurement Symposium) required more than 100 hours labor.
Two of the symposia covered the general topic of environmental/process
measurements; the other four dealt with specific measurement techniques.
1.6.1 Major Task Summary
Task 24 - Process Measurement Symposium —
This task was devoted to the preparation and implementation of the
Symposium on Process Measurements for Environmental Assessments. The
conference was designed as a forum to present, discuss and evaluate
25
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measurement requirements, approaches and results within the broader
context of the entire Environmental Assessment Program area. Consider-
ing the wide-ranging scope of the Environmental Assessment Program area,
a broad cross section of industry and government were invited to partici-
pate in the conference proceedings and discussions.
The Symposium Staff consisted of two members from EPA; Ms. Brenda
Foil and Ms. Susan Sharpe, and three members from TRW; Ms. Mary McKay,
Mrs. Linda Rosenfeld and Mr. Chuck Weekley. The overall coordinator
for the Symposium was Dr. Eugene Burns and the Symposium General Chair-
man was Mr. James Dorsey. Papers were presented by the following TRW
personnel: R. F. Maddalone and L. E. Ryan (Inorganic Emissions Measure-
ments), J. W. Hamersma (Process Measurements of Conventional Combustion
Systems), and J. E. Cotter (Environmental Measurements Program at the
Paraho Shale Oil Recovery Facility).
1.6.2 Minor Task Summaries
Under Task 16 (NBS Meeting), a TRW representative attended the
National Bureau of Standards symposium on "Methods and Standards for
Environmental Measurement." Papers were presented in the following
areas:
t Single and multielement technique development
• Physical and chemical characterizations of aerosols
• Organometallic sampling and analysis
• Laser sensing methods
• Environmental standards
Task 29 (S03 Measurement Presentation) was a training session
given by TRW to IERL contractors on the methodology to measure H2S04
in particle laden flue gas streams. The presentation covered the use
of the controlled condensation procedure in the field and presented
laboratory data from Task 13.
Under Task 33 (Denver X-ray Meeting), a TRW representative attend-
ed the Denver Symposium on "Applications of X-Ray to Environmental and
26
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The revised chapters submitted under this task represented the
best currently available Level 1 methodology. Specific tasks conducted
on this contract and the Environmental Assessment of Conventional Combustion
Sources (EACCS) project examined and improved the inorganic analysis
procedures, and the over 50 Level 1 source tests performed on the EACCS
project provided practical experience in dealing with the requirements
and realities of field testing. These experiences in both the analytical
and sampling aspects of Level 1 methodology had been integrated into the
EACCS procedures manual as they evolved. With this task, these improve-
ments also became part of TRW's input to the revision of the IERL-RTP
Level 1 manual.
Task 57 - At-Sea Environmental Impact Statement Studies—
The objective of this task was to prepare portions of an environ-
mental impact statement for at-sea incineration of industrial wastes
documenting the effects on the environment which could result from the
adoption of international standards regulating incineration at-sea
activities.
The results of this effort were presented to the International
Maritime Consultative Organization at their June 1978 conference in
London.
1.6 AREA 6: CONDUCT OF SYMPOSIA AND TRAINING SESSIONS
Six tasks in this program were devoted to TRW participation in
symposia or presentations related to the TLE program. Only one, Task
24 (Process Measurement Symposium) required more than 100 hours labor.
Two of the symposia covered the general topic of environmental/process
measurements; the other four dealt with specific measurement techniques.
1.6.1 Major Task Summary
Task 24 - Process Measurement Symposium--
This task was devoted to the preparation and implementation of the
Symposium on Process Measurements for Environmental Assessments. The
conference was designed as a forum to present, discuss and evaluate
25
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measurement requirements, approaches and results within the broader
context of the entire Environmental Assessment Program area. Consider-
ing the wide-ranging scope of the Environmental Assessment Program area,
a broad cross section of industry and government were invited to partici-
pate in the conference proceedings and discussions.
The Symposium Staff consisted of two members from EPA; Ms. Brenda
Foil and Ms. Susan Sharpe, and three members from TRW; Ms. Mary McKay,
Mrs. Linda Rosenfeld and Mr. Chuck Weekley. The overall coordinator
for the Symposium was Dr. Eugene Burns and the Symposium General Chair-
man was Mr. James Dorsey. Papers were presented by the following TRW
personnel: R. F. Maddalone and L. E. Ryan (Inorganic Emissions Measure-
ments), J. W. Hamersma (Process Measurements of Conventional Combustion
Systems), and J. E. Cotter (Environmental Measurements Program at the
Paraho Shale Oil Recovery Facility).
1.6.2 Minor Task Summaries
Under Task 16 (NBS Meeting), a TRW representative attended the
National Bureau of Standards symposium on "Methods and Standards for
Environmental Measurement." Papers were presented in the following
areas:
• Single and multielement technique development
» Physical and chemical characterizations of aerosols
• Organometallic sampling and analysis
• Laser sensing methods
• Environmental standards
Task 29 (S03 Measurement Presentation) was a training session
given by TRW to IERL contractors on the methodology to measure HUSO.
in particle laden flue gas streams. The presentation covered the use
of the controlled condensation procedure in the field and presented
laboratory data from Task 13.
Under Task 33 (Denver X-ray Meeting), a TRW representative attend-
ed the Denver Symposium on "Applications of X-Ray to Environmental and
26
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Occupational Health Analyses." The Symposium was sponsored by the
Denver Research Institute, University of Denver and Phillips Electronic
Instruments. Papers were presented on the following instrumental methods
of analysis:
t X-Ray Diffraction
• Electron Microprobe
• Electron Microscopy
Under Task 44 (Particulate Measurement Meeting), a TRW representa-
tive attended the "Symposium on High Temperature, High Pressure Parti-
culate Control," in Washington, D. C., sponsored by EPA/DOE. Of
special interest were the presentations given in Session IV: Particle
Sampling and Measurement. With regard to particulate control techno-
logy, it was made clear that while there are various proposed techniques,
none are yet fully proven and operational.
Task 58 involved TRW1s participation in the workshop on Measure-
ment Technology and Characterization of Primary Sulfur Oxides Emission
from Combustion Sources, sponsored by the Environmental Sciences Re-
search Laboratory, EPA/RTP, during April 1978. Dr. R. F. Maddalone
presented a paper, "Sulfur Emissions Sampling and Analysis," detailing
work to improve techniques for sampling and analysis of S02> H2S04 and
particulate sulfate emissions from flue gas desulfurization units.
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SECTION 2
MAJOR TASKS
2.1 TASK 1 LEVEL 1 MANUAL REVISION/PROJECT START-UP
2.1.1 Objective
The objective of this task was to incorporate review comments on the
draft manual: IERL-RTP Procedures Manual Level 1 Environmental Assessment,
describing methods for conducting Level 1 environmental assessment. The
draft was prepared under EPA Contract 68-02-1412, Task 18. The final
revised manual was prepared under this task. Because this was the first
task under this contract, project start-up costs were also incorporated
into it.
2.1.2 Approach
The basic draft document was prepared under EPA Contract 68-02-1412,
Task 18. The objective of this task was to devise a cost effective set of
sampling and analytical procedures for Level 1 of the phased approach
to environmental assessment programs. This document presented for the
first time an integrated set of sampling and analytical procedures for
environmental assessment programs. As such, it was subjected to a detailed
review in June 1976 with representation of the Process Measurement Branch,
IERL/RTP and five other TLE contractors including Arthur D. Little, Inc.,
Aerotherm/Acurex Corp., Research Triangle Institute, Southern Research
Institute and The Research Corporation of New England. Based upon these
discussions, a new revision of the manual was prepared and submitted to
EPA in July 1976. This draft and further revision was discussed with
Dr. R. M. Statnick during August 1976. The final draft was published
in September 1976.
This task also served as the project start-up task. Under this
portion of the work, the project was organized, people assigned, task
orders initiated and a task work plan prepared.
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2.2 TASK 2 LIMESTONE FGD DEMO SUPPORT
2.2.1 Objectives
The technical objective of this task was to prepare a series of pro-
cedure documents for sizing dry aerosols and measuring SO, entering and
leaving a Flue Gas Desulfurization (FGD) unit and written for GS-4 personnel
or equivalent. The sizing method for the dry particulate matter entering
the FGD process was selected by the EPA to be a manual technique utilizing
a Brink Impactor. A manual system for the FGD process effluent stream was
chosen on the basis of a literature survey, contacts with experts in the
field, and an evaluation of available information. The method chosen was
the Meteorology Research Inc. Cascade Impactor used out of stack. Finally
a method for S03 (H2S04 vapor) was developed based on the Controlled Con-
densation (Goksoyr/Ross) method and was successfully tested under laboratory
conditions. In addition to these method development areas, on-site train-
ing and support was provided by TRW personnel.
4
The task was divided into three areas of effort:
1) Aerodynamic Size Distribution
Measurement of Dry Aerosols
2) Procedure for Sampling and Analysis of S03
3) Quality Assurance
2.2.2 Approach
Aerodynamic Size Distribution Measurement of Dry Aerosols-
Documents were prepared describing the methods for determination of
the size distribution of dry particulate matter at the inlet and outlet of
a flue gas desulfurization (FGD) process. The FGD process inlet measure-
ment system was a Brink Impactor while the outlet measurement system, which
must be suitable for extremely low grain loading, was selected from several
candidate systems.
The selection of the outlet impactor system was based on the following
criteria:
• Ease of assembly and.operation - GS-4 level technicians
should be able to operate the instrument.
t Ease of sample recovery - Sample removal should be accomplished
under field conditions with minimum of effort.
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• Construction material compatibility with sample and sampling
environment - The equipment should not corrode or in any way
contaminate the sample.
• Sampling period required for sample collection - Flow rates
should be maximized to collect adequate amounts of sample
for measurement in a reasonable sampling period under low
grain loading conditions.
• Sample capacity - The system should be flexible enough to
accurately size and collect particulate under high and low
grain loadings.
• System design to minimize wall losses and re-entra1nment -
All samples should be deposited in collection trays or cups.
Applying these criteria, the MRI impactor was selected. Procedure
documents describing the operation of the Brink and MRI impactors were
written and compiled in an overall procedure manual. This document
included: equipment lists, equipment assembly and preparation, on-site
set-up and operation, sample removal and handling procedures, and sample
weighing procedures. Other than making reference to known procedures
(such as EPA Methods 1 through 4), this document was designed to stand
by itself and be directed toward 6S-4 or equivalent personnel.
Procedure for Sampling and Analysis of $03--
A procedure to sample and analyze for SO* 1n flue gas prior to and
after FGD process was written. From TRW's knowledge of the S03 sampling
problem, the Controlled Condensation (Goksoyr/Ross Coil), Brink Impactor
and selective liquid Impingement appeared to be the methods available.
A literature evaluation of the systems was based on the following criteria:
• Sensitivity
• Selectivity
• Precision
• Accuracy
• Efficiency
• Ease of Operation
• Reliability/Maintainability
• Sample Recovery for Analysis
As a result of this evaluation the Controlled Condensation system was
tested in the laboratory simulating the conditions in the FGD unit, and
found to be precise and accurate.
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Quality Assurance —
This effort was devoted to develop methods that will ensure the over-
all quality of the data taken in the above procedures. Included in the
specific QA activities are:
f Critical checkpoint lists for each procedure
• Data validation procedures
• Maintenance schedules
t Troubleshooting procedures
• On-site assistance
2.2.3 Technical Discussion
Originally it was planned that a procedure for liquid aerosol sampling
would be developed. The initial recommendations were to use a KLD liquid
droplet aerosol counter. Previous experience at Shawnee with the KLD device
was positive, but some development work was expected. The main problem
with the device was the initial cost (^IZK). Consequently an alternate
approach was suggested and tested in the field. This approach used a
Brink impactor and a BMS-11 oven system to maintain isothermal conditions
throughout the sampling system to prevent incorporation or condensation
of moisture from the gas phase. The liquid aerosols collected would be
measured using an automated Karl Fischer analyzer after the collection
cups were rinsed with methanol.
In practice, temperature control proved to be very difficult with the
BMS-11 oven. A technical decision was made to discontinue this approach.
Concurrently, interest in the liquid aerosol sampling tests decreased, so
this requirement was deleted. The following sections briefly describe the
particulate sampling and SOg sampling systems.
Brink Impactor System—
The Brink impactor was used for the determination of the aerodynamic
size distribution of dry solids prior to the flue gas desulfurization (F6D)
unit. The Brink impactor with a specially designed internal cyclone
provided aerodynamic size distribution information between 0.3y to
10y in 6 distinct cuts. The recommended flowrate was 0.01 to 0.08 cfm.
31
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This procedure used the Brink impactor out of stack to sample the
particulate from the gas stream entering the wet scrubber. After the
large particles have been removed from the gas stream by the internal
Brink cyclone, the remaining particles in the gas stream are then separated
by a Brink Cascade impactor. By weighing each stage of the Brink impactor,
the aerodynamic size distribution was determined. Figure 1 shows the
Brink impactor and the associated support equipment.
The choice to out-of-stack sample with both the Brink and MRI was made
in order to heat the impactors at temperatures (^175°C) to minimize HgSO^
collection. In-stack heating could not accomplish this, so the choice
was made to go out of stack.
Control of the Brink was maintained by monitoring the AP across the
impactor using a magnehelic gauge. This procedure was much more accurate
than the Hg manometers used in the BMS-11.
Particle bounce was minimized by coating the collection stages with
Aprezon H. This grease was tested in the laboratory and in the stack and
showed little or no weight gain or loss under the specified sampling con-
ditions.
MRI Impactor System --
This method is applicable for determining aerodynamic size distribu-
tion of dry solid particles emitted from the TVA Shawnee flue gas desul-
furization (F6D) processes at a mass loading of 0.07 g/m3 (0.03 gr/cfm).
The Meteorology Research Inc. (MRI) Inertial Cascade Impactor is
designed to measure the aerodynamic size distribution between 0.3 and 30
microns -suspended in industrial gas streams at temperatures up to 200°C
(392°F) at a flow rate of 0.1 to 0.8 cfm.
As explained in the Brink procedure, out-of-stack sampling was
selected to allow higher operating temperature to minimize H2S04 fallout.
Heating of the MRI impactor as with the Brink was accomplished using
specially fabricated Glass-Cole heating mantles. Aprezon H greased
impactor stages were used to prevent particle bounce.' Figure 2 shows
the equipment set-up for the MRI.
32
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STACK
V
USE WIRE OR ROPE TO SUPPORT
IMPACTER FROM HOOK
BRINK WET
AEROSOL PROBE REDUCER
SS-400-R-4
RUBBER STOPPER
FOR GAS SEAL
,RAIL
BRINK CYCLONE
STAGE
HEATING
MANTLE
FILTER
HOLDER
UNION
CROSS
Figure 1. Brink Impactor Set-Up
33
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OrO
k\\\\\\\\\\\\\\\w
SKIN TEMPERATURE
THERMOCOUPLE
THERMOCOUPLE
TAP FOR IMPACT OR
GAS TEMPERATURE x
c
*
A
\
S
r
L\\\\\\\\\\\\\\\\\\\\\\\\\\\\
AEROTHERM
OVEN AND
CONTROL Uh
Z\ i
GLASS-COL
HEATING MANTLE
AND IMPACTOR
\
EC
•^,
^
/
/rrnf
i II
jj_jj
X\
MRI IN STACK
11T /TRANSFORM
>ll I /
I/ QUICK
y DISCONNECT
/ FITTING
i r
J L
. SUPPORT FOR
IMPACTOR
TO
AEROTHERM
IMPINGER
SYSTEM
STACK
AEROTHERM
PROBE
GAS FLOW
Figure 2. MRI Impactor Set-Up
34
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H2S04 Sampling—
The development of this method grew out of a basic gap in measurement
methodology for H2S04 in particle-laden gas streams. Currently there are
two EPA compliance methods for SOX measurements. In both EPA Method 6 and
Method 8, the H2S04 is separated from S02 by passing the gas stream through
an impinger of 80% isopropanol (IPA) followed by two impingers of 3% H202.
The IPA collects the H2$04 and passes the S02 into the H202 impingers where
it is oxidized and collected as H2S04. While these methods are the EPA
compliance methods, problems have been found in trying to measure H2S04 in
particle-laden streams using these systems. In both procedures inefficient
particle removal prior to the first impinger leads to variable positive
interferences from sulfate containing fly ash, and catalytic oxidation of
S02 in the IPA impinger. The precision of Method 8 has been studied, and
it was shown to be in excess of +_ 50%. Because of these problems, an
alternate H2S04 method is needed.
The controlled condensation procedure for collecting H2S04 is a
likely candidate because of its simplicity and clean separation of particu-
late matter, S02, and H2S04. This procedure is based on the separation of
H2S04 from S02 by cooling the gas stream below the dew point of H2$04 but
above the H20 dew point. Cooling is accomplished in a water-jacketed coil
(Figure 3) where the H2$04 is collected. Any aerosol not collected in
the coil is collected on the glass frit. Particulate matter is removed
from the gas stream prior to reaching the cooling coil by means of a heated
quartz filter placed after the heated glass probe and before the condensa-
tion coil. While the basic idea of a controlled condensation to separate
S03 from S02 had merit, the system design and operating parameters had
several built-in difficulties. Consequently, a laboratory study (Task 13)
was initiated by TRW to optimize:
• Probe, filter, and coil heating temperature
t Particulate removal system
• Filter selection
The result was a method capable of measuring H2S04 with a laboratory
precision of ±7%, using an improved filtration system and an inert filter
material.
35
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ADAPTER FOR CONNECTING HOSE
TC WELL
STACK
to
cr>
RUBBER VACUUM
HOSE
ASBESTOS CLOTH
INSULATION
GLASS-COL
HEATING
MANTLE
RECIRCULATOR
THERMOMETER
DRY TEST
METER
THREE WAY
VALVE
SILICA GEL
STYROFOAM
ICE CHEST
Figure 3. Controlled Condensation System Set-Up
-------
Quality Assurance—
The quality assurance activities under this task were devoted to
document procedures and on-site assistance and training. In the procedures
document describing the aerosol sizing and S03 sampling procedures, infor-
mation was provided on:
• Equipment care and usage
t Guidelines for laboratory techniques
• Specific critical area checklists for each procedure
• Data interpretation aids to monitor the quality of the
results achieved
t Specific maintenance and calibration schedules
• Troubleshooting and repair schemes.
In addition to this documented quality assurance activity, an on-site
training session was given to train the TVA personnel on the use of all
the equipment and procedures. Throughout the program senior TRW personnel
were available for consultation over the phone or for troubleshooting in the
field.
2.2.4 Summary of Results and Recommendations
As a result of this program, procedures for aerodynamic sampling at
the inlet and outlet of an F6D were developed and used at the Shawnee FGD
Test Facility. Using these procedures, Bechtel and TVA personnel studied
the mass percent penetration for the TCA and Venturi scrubber systems at
Shawnee.
As a result of this task, several areas of continuing or new work are
possible. It is recommended that:
• Continued on-site and verbal assistance be provided to the
Shawnee Test Facility in the area of trace element sampling
and analysis.
• Support be given to improved process measurement at the FGD
units.
• New control strategies be developid based on improved process
measurement of such species as SO*, SO,, Ca+S and Mg c.
37
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2.3 TASK 3 SUPPORT TO OCEAN INCINERATION
2.3.1 Objective
Disposal of chemical waste products in the United States has long
been accomplished via landfill and ocean dumping and more recently by
thermal destruction in land-based incinerators. Under EPA contract
68-01-2966, TRW has been involved in a program to evaluate the destruction
efficiency of various land-based incinerator types matched with specific
waste products. Sampling and analysis strategies were patterned some-
what after EPA methodology and philosophy. However, the EPA manual "IERL-
RTP Procedures Manual: Level 1 Environmental Assessment" was still in
preparation and not issued at that time.
Land-based incinerators must be equipped with costly effluent control
or recovery systems for removal of HC1 from the combustion gas stream for
disposal of chlorinated organic waste products, one of the major organic
chemical waste categories. This by-product then becomes a secondary
disposal cost. In contrast, incineration at sea does not require the HC1
recovery system. A remote ocean area, judiciously chosen, avoids the
problems of acid damage to population, vegetation and structures. The
ocean is a very large, slightly alkaline "scrubber" for neutralization of
the HC1, and the decrease in pH or increase in chloride content is
imperceptible.
In 1974, the EPA granted the first research permit for ocean incinera-
tion of chlorinated organic waste to the Shell Chemical Co., and test
burns were performed in the Gulf of Mexico that same year. Preliminary
evaluation of these tests, as reported in EPA Report #EPA-430/9-75-014,
together with test programs conducted in Europe by the Dutch, French, and
Germans, indicated that ocean incineration can be a viable; cost-effective
alternative to other disposal methods if adequate process control regula-
tions can be promulgated for protection of the environment.
38
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The technical objectives of this task, therefore, were to:
t Evaluate at-sea incineration processes for the destruction
of chemical waste products, especially chlorinated organic
materials, on board the Matthias III and M/T Vulcanus incin-
erator vessels.
• Dev=lo<, guidelines for incinerator design, operational
controls, -Storing methodology and acceptance criteria
to be utilized by EPA and IMCO in establishing at-sea
incineration permit requirements.
2.3.2 Technical Approach
The objectives are summarized in this series of subtasks having
the following technical requirements:
• Observe second test burn of organochloride waste aboard the
Matthias III incineration ship.
• Evaluate and report on incinerator operation, controls and
waste desr.ruction efficiency.
• Analyze teed waste samples for C, H, N, S, and Cl to support
combustion efficiency evaluation.
• Determine effect of incineration on surrounding waters by anal-
ysis for total organic content (TOC) and chlorinated organic
content.
• Acquire and perform statistical analysis of existing thermal
data to correlate wall temperatures with flame temperatures.
• Issue detailed reports on observations, analyses, calculations,
conclusions, and recommendations.
• Prepare a guidelines document for EPA to use in support of the
IMCO intersessional work group which is developing regulatory
and technical requirements on incineration at sea.
2.3.3 Results
Matthias III Test Burn —
The first Matthias III test burn was witnessed in June 1976 by TRW
on EPA Contract 68-01-2966, and a report was issued indicating technical
problems existed which precluded granting of an EPA permit for burning
U.S. wastes. This report (1) contains necessary background information
on the desian and operation of the Matthias III incinerator ani the
testina oerformed by the French. Subsequently, we were directed under
this task to witness a second test burn aboard the Matthias III in the
39
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North Sea in Auqust 1976, EPA was notified that operating and/or
desiqn modifications to correct the problems identified in Reference
1 had been completed. The purpose of the second trip was to
observe the performance of the incinerator ship, determine compliance with
EPA operational requirements, observe a preliminary burn of solid waste
and acquire and analyze seawater samples upstream and downstream of the
ship during the burn. Two liquid waste samples were also taken during the
test burn and anlyzed by TRW. The results are delineated in Table 2. A
variety of drummed solid wastes were also incinerated using the solids
inlet port and rotating table system in the furnace.
During this burn, equipment was installed and operated by Dragerwerk
AG to monitor CO, COp, CL and chlorinated organic emissions. The last
instrument apparently malfunctioned and was not operating during the test.
The following equation was used to compute combustion efficiency:
o2 - Cco\
N = ( - 1 - 1 X 100
A thorough, detailed report was issued for the second test burn
including tabulated C02, CO, 02 and run data, entitled "Status of Ocean
Incineration of Organic Chlorides Aboard Matthias III as of 3 September
1976". The conclusions of that report are highlighted here,
The Matthias III has shown a striking improvement in the combustion
of organic chloride wastes as compared to the burn of 5/31-6/3/76. Com-
bustion efficiency values considerably better than 99 percent have been
demonstrated throughout the present burn. The plume was consistently
white in color and the flame zone was maintained within the incinerator
stack.
Temperature measurements indicated the flame temperature in the
incinerator to be consistently above 1200°C, and to lie between 1240°C
and 1420°C. Wall temperature measurement was shown to be a predictor of
flame temperature.
40
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TABLE 2. RESULTS OF WASTE ANALYSIS
Carbon
Sample Wt. Percent
F/M/W-
1 43.8
F/M/W-
2 41.9
Hydrogen
Wt. Percent
5.3
5.5
Nitrogen
Wt. Percent
1.6
1.6
Halogens as
Chlorine
Wt. Percent
40.9
38.2
Sulfur
Wt. Percent
0.2
0.3
Oxygen
and
Other3
8.2
12.5
Specific
Gravity at
25°C
1.179
1.171
Thermal
Content
Kcal/Kg
5240
4960
aBy difference
-------
Seawater analysis for pH, total organic carbon and total chlorinated
organic matter revealed no detectable difference between upwind and down-
wind samples.
The EPA requirements for incineration of organochlorides at sea have
been met, in general, with the exception that warning and automatic shut-
down of the process upon a temperature fall below 1200°C have not yet been
incorporated into the system. However, data and thermocouple locations
for warning and shutdown at furnace temperatures of 1300 C and 1200 C,
respectively, have been determined.
The improvement in combustion efficiency appears to have been achieved
by increasing the relative amount of combustion air. This effect was
brought about by reducing the waste throughput by approximately a factor
of two.
Analysis of M/T Vulcanus Incinerator Temperature Data—•
The EPA Operational Requirements (1, 2) for ocean incineration of organic
chlorides include a requirement for emergency waste shutoff if the
temperature should drop below 1200°C in the incinerator. A statistical
analysis of data obtained during operation of the Vulcanus was made.
The detailed results were sent to the Task Officer in a separate letter
report.
The report gave the following conclusions:
• Correlation is poor between wall (thermocouple) and flame
(pyrometer) readings.
• Based on the data available, the wall temperature is not as
good a predictor for flame temperature as might be desirable.
• Using the best thermocouple data (controller, rear furnace)
a reading of 1062°C at the wall could be used to sound a
warning for 1300°C in the furnace, with a 0.80 probability.
» Similarly, a reading of 985°C would predict a front furnace
temperature of 1200°C with a 0.975 probability.
If additional data could be made available, better statistical pre-
dictions could probably be made. Approximately 40 data points (both wall
and flame) at two- or four-hour intervals would be useful. The methods
42
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of statistical analysis are the same as those used on the similar
Matthias III data. These methods are described in Reference 2, The data
on which the statistical analysis is based are taken from Table V-4, "Dis-
posal of Organochlorine Wastes by Incineration at Sea," EPA-430/9-75-014,
dated July 1975, pages 35, 36 and 37.
Additional operational, performance and emissions data were obtained
by the TRW sampling team aboard the Vulcanus during burning of Shell
Chemical Co. chlorinated organic wastes in March 1977 under EPA Con-
tract 68-01-2966 (Reference 3).
Guidelines for Intersessional Work Group on Incineration at Sea—
The purpose of this subtask was to assist EPA in generating technical
considerations and guidelines to be utilized in international agreements
on control of incineration at sea. EPA would subsequently submit these
recommendations to the IMCO Intersessional Working Group for Incineration
at Sea at their London, England meeting. It was also planned to employ
these guidelines to establish U.S. regulations.
Reference 4 is the document resulting from this subtask effort and
is entitled "Rationale for Annex A to Suggested Special Provisions for
Control of Incineration at Sea". The report describes the "rationale",
i.e., the technical justification and methodology, for Annex A require-
ments on:
• Section II - Test Methods of Characterize Waste
• Section III -Guidelines for Incinerator Operations and
Monitoring
• Section V — Procedures to Determine Harmlessness of Stack
Emission Products
Special acknowledgement is given here to the many contributions, sug-
gestions and general help provided by Dr. Ron Venezia, the Task Officer
at IERL and Mr. Russ Wyer, Deputy Director of the Oil and Special Materials
Control Division.
Trips and Special. Coordination —
By the nature of the work content and deliverables under this task,
extensive travel to meetings and the test sites and coordination with the
43
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incinerator ship operators, government and private agencies, etc., were
required. Three meetings at RTP with the IERL Task Manager and three meet-
ings at Washington with the Deputy Director of the Oil and Special Mate-
rials Control Division and others were supported to plan the site visit,
observation requirements, report format and to develop the regulatory
guidelines. A partial list of the firms and agencies interacting on this
task are as follows:
• EPA
- Oil and Special Materials Control Division, Washington, D.C.
- IERL, RTP
— Region VI
t U.S. Coast Guard
t French Atomic Energy Commission Cerbom and Ministry of
Environment
• Meneba, SBB - Matthias III
• Hansa Lines, Ocean Combustion Services - M/T Vulcanus
t Shell Chemical Company
• French Ministry
Advisory groups participating in one of the Washington meetings on
IMCO guidelines included U.S. Depts. of Commerce, Interior and Labor, the
U.S. Coast Guard, the Naval Research Laboratory, Shell Chemical Co. and
several public environmental groups.
2.3.4 Summary of Results and Recommendations
The accomplishments of this task have a valuable contribution to the
continuing development of efficient and safe disposal of hazardous organic
wastes by means of at-sea incineration. The work reported in this task
was an important facet of the overall EPA effort to establish:
t Minimum flame temperature at 1200°C for complete destruction
• The correlation of wall temperature as measured by a thermo-
couple with flame temperature as measured by an optical
pyrometer
• Fuel and combustion air feed rates
• Automatic emergency shutoff requirements
44
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of statistical analysis are the same as those used on the similar
Matthias III data. These methods are described in Reference 2, The data
on which the statistical analysis is based are taken from Table V-4, "Dis-
posal of Organochlorine Wastes by Incineration at Sea," EPA-430/9-75-014,
dated July 1975, pages 35, 36 and 37.
Additional operational, performance and emissions data were obtained
by the TRW sampling team aboard the Vulcanus during burning of Shell
Chemical Co. chlorinated organic wastes in March 1977 under EPA Con-
tract 68-01-2966 (Reference 3),
Guidelines for Intersessional Work Group on Incineration at Sea —
The purpose of this subtask was to assist EPA in generating technical
considerations and guidelines to be utilized in international agreements
on control of incineration at sea. EPA would subsequently submit these
recommendations to the IMCO Intersessional Working Group for Incineration
at Sea at their London, England meeting. It was also planned to employ
these guidelines to establish U.S. regulations.
Reference 4 is the document resulting from this subtask effort and
is entitled "Rationale for Annex A to Suggested Special Provisions for
Control of Incineration at Sea". The report describes the "rationale",
i.e., the technical justification and methodology, for Annex A require-
ments on:
a Section II - Test Methods of Characterize Waste
• Section III -Guidelines for Incinerator Operations and
Monitoring
• Section V - Procedures to Determine Harmlessness of Stack
Emission Products
Special acknowledgement is given here to the many contributions, sug-
gestions and general help provided by Dr. Ron Venezia, the Task Officer
at IERL and Mr. Russ Wyer, Deputy Director of the Oil and Special Materials
Control Division.
Trips and Special, Coordination—•
By the nature of the work content and deliverables under this task,
extensive travel to meetings and the test sites and coordination with the
43
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incinerator ship operators, government and private agencies, etc., were
required. Three meetings at RTF with the IERL Task Manager and three meet-
ings at Washington with the Deputy Director of the Oil and Special Mate-
rials Control Division and others were supported to plan the site visit,
observation requirements, report format and to develop the regulatory
guidelines. A partial list of the firms and agencies interacting on this
task are as follows:
• EPA
-Oil and Special Materials Control Division, Washington, D.C.
- IERL, RTP
- Region VI
• U.S. Coast Guard
• French Atomic Energy Commission Cerbom and Ministry of
Environment
t Meneba, SBB - Matthias III
• Hansa Lines, Ocean Combustion Services — M/T Vulcanus
• Shell Chemical Company
t French Ministry
Advisory groups participating in one of the Washington meetings on
IMCO guidelines included U.S. Depts. of Commerce, Interior and Labor, the
U.S. Coast Guard, the Naval Research Laboratory, Shell Chemical Co. and
several public environmental groups.
2.3.4 Summary of Results and Recommendations
The accomplishments of this task have a valuable contribution to the
continuing development of efficient and safe disposal of hazardous organic
wastes by means of at-sea incineration. The work reported in this task
was an important facet of the overall EPA effort to establish:
• Minimum flame temperature at 1200°C for complete destruction
• The correlation of wall temperature as measured by a thermo-
couple with flame temperature as measured by an optical
pyrometer
• Fuel and combustion air feed rates
• Automatic emergency shutoff requirements
44
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t Use of on-board equipment to monitor destruction efficiency
based on CO and COg measurements
• A U.S. EPA policy in support of international regulations to
be issued by IMCO.
Most recently, the technology developed by TRW under EPA sponsorship
for process control, monitoring, sampling and analysis was successfully
employed in meeting EPA Permit Requirements for the safe destruction of
11,000 metric tons of Herbicide Orange containing the hazardous trace
compounds, TCDD on board the M/T Vulcanus. It is anticipated that this
activity will lead to many similar benefits in the future.
45
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2.4 TASK 5 SASS TRAIN LEVEL 1 CHECKOUT
2.4.1 Objective
This task, which was one of the earliest in the TLE project, had
two separate though related objectives. One was to use and evaluate one
of the first SASS trains produced, both in general terms and specifically,
in regards to its use during the testing conducted on board the incinerator
ship M/T Vulcanus in the Gulf of Mexico. The second objective was to use
the samples collected in the SASS train evaluation portion of the task to
test and evaluate the recently published Level 1 analytical procedures.
2.4.2 Approach
The SASS testing was conducted on a 10 million Btu, TRW Low-NO burner
A
fired with No. 6 residual oil. The SASS was operated in the configuration
to be used for the shipboard tests which was: 15' water-cooled probe,
50' of heat-traced sample line, no cyclones, filter, XAD-2 module, and
impingers. The probe was positioned in the combustion chamber of the
burner and the train was operated at temperature for several consecutive
days and two sets of 30 m3 samples were collected.
These samples were analyzed following the IERL-RTP Level 1 procedures
manual. The complete organic scheme was tested including C7-C12 GC, LC,
Grav/IR, and LRMS. SSMS and analyses for Hg, As, and Sb were also per-
formed. Work on this task was initiated in June 1976 and completed in
November 1976.
2.4.3 Technical Discussion
The key element to understanding the contribution of this task is
timing. When this task was begun, there were only three SASS trains in exist-
ence and the IERL-RTP Level 1 manual had been first published in the same
month. Several contractors were scheduled to begin implementing the SASS
and the Level 1 procedures and a preliminary assessment of potential
problem areas was desired.
46
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Many of the problems identified in Task 5 were addressed very
quickly, thereby preventing the repetition of errors by several contractors,
This was particularly true of the SASS train problems such as poorly
sealing impinger caps, difficulties with the inflexible stainless steel
connecting tubes for the impingers, and failure of the Teflon o-ring
seals. These were relayed to Aerotherm/Accurex and appropriate changes
were implemented by them for subsequent SASS trains.
Work was also performed on this task to address serious inorganic
analytical problems with the Hg, As, and Sb methods. In each analysis,
procedural and matrix problems were encountered that impaired the
quality of data that could be produced. By analyzing numerous blanks
and spiked controls for each Level 1 sample matrix, modifications to
the methods were developed that met the Level 1 accuracy (± 2 to 3 factor)
requirements.
2.4.4 Summary of Results and Recommendations
The scope of this task did not include providing solutions to all
of the identified problems. Wherever possible solutions were offered,
however, other problems (e.g., stainless steel component contamination
in the Parr bomb procedure) became the subjects of in-depth examination
under other tasks and contracts. These solution-oriented studies
conducted after the completion of Task 5, eventually lead to refinements
of the Level 1 procedures such as the quartz-lined Parr bomb method.
Thus the chief result of Task 5 was to identify areas needing further
study. These areas have now, at the present time, all been addressed
and the resulting recommended Level 1 modifications have been assembled
as TRW's input to the Level 1 revisions under Task 5.
47
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2.5 TASK 7 INORGANIC COMPOUND IDENTIFICATION
2.5.1 Objectives
This task was devoted to the study of measurement procedures for Inor-
ganic compounds. While this task was broad in its nature, its main goal was
to advance the state of the art for identifying specific inorganic compounds
in samples of environmental interest. In this task several specific areas
were investigated.
• Literature review - references on compound identification
for specific elements like As, Se, Sb, Hg, Cd and Zn were
compiled.
t X-ray diffraction - determination of the sensitivity of
specific compounds in an environmental matrix.
• Infrared analysis - compilation of literature sources and
comparison of conventional IR and FTIR.
+3 +5
• Selective reduction of As /As - a chemical approach to
the selective reduction of As+3/As*5 in aqueous environ-
mental samples was investigated.
• Mass thermal analysis - studies were initiated to determine
if volatile inorganic compounds could be thermally desorbed
from the surface of collected particulate matter.
In addition to these specific areas of research conducted under this
task, TRW has supported EPA/IERL programs in the area of advanced inorganic
analysis. In this role TRW was charged with design, testing and application
of advanced analysis schemes for the determination of compounds from pro-
cess streams including FBC bed materials and combustion source emission
streams. As an end result TRW developed a comprehensive inorganic com-
pound identification scheme, which was detailed in a procedures manual for
Level 2 inorganic sampling and analysis.
2.5.2 Approach
In these sections the approach taken in each of the technical areas
investigated will be discussed.
Literature Survey--
An extensive literature investigation was conducted to survey avail-
able sampling and analytical methodologies for inorganic compounds in solid,
48
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liquid, and gaseous streams with particular emphasis on Instrumental
methods (e.g., XRD, IR, RAMAN, XRD, SEM-EDX, SIMS ESCA,.etc.). Efforts
were made to develop Information for each method on minimum quantity of
detectable material, minimum sample size required for analysis, precision
and accuracy of the method, costs, and commercial availability.
A literature search was conducted for the years 1970-1976 for the
journals Analytical Chemistry and Environmental Science and Technology.
Pertinent articles from these journals were obtained and the majority were
filed by type of analytical method used. Emphasis was given to the
Analytical Chemistry Reviews (April 1974, 1975, 1976) which summarize
current research conducted on inorganic compounds using each analytical
technique. In addition, Air Pollution Abstracts were reviewed (1971-1976);
all abstracts were scanned, and the most pertinent articles were abstracted
and/or ordered. A similar search was conducted on the NTIS search biblio-
graphy NTIS, PS-75/527, entitled: "Chemical Analysis of Aerosols and Air-
borne Particulates."
Search of in-house material was completed and literature not available
in-house was ordered. The accumulated file has been further refined
to identify the most definitive literature. Key authors and areas of con-
comitant interest have been tabulated. Telephone contacts were conducted.
As part of the on-going efforts, information was utilized on computer
searches. These include Lockheed DIALOG Information Retrieval Service
for Chemical Abstracts, Scisearch and NTIS data bases; SDC Search Service
Data Bases for Pollution abstracts.
The literature (journal articles, reports and books) obtained were
filed by analytical method to provide continuing back-up and state of
the art information to this task.
X-Ray Diffraction—
In this subtask work was conducted in three areas:
t Sensitivity studies of pure compounds in a matrix similar
to combustion source samples.
• Sample handling procedures for mounting and analysis of
samples.
t Analysis of actual combustion source samples to study
the practical application of XRD analysis.
49
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In the first phase pure compounds were mixed with a suitable dilutant
to simulate the environmental matrix. This work was to provide baseline
sensitivity data from an experimental standpoint. Since mounting proce-
dures can appreciably affect the results of an XRD, a standardized approach
was developed to optimize test conditions. The end result was a study of
actual samples of fly ash, FBC bed material and coal char.
Infrared Analysis --
Infrared analysis provides a useful screening method to indicate the
presence of specific anions or even compounds. The work conducted in this
subtask consisted of:
• Compiling reference IR tables for inorganic materials in
the mid and far IR.
• Selection and testing of candidate mounting mediums
(mulls vs pellets).
t Comparison of FTIR and IR scans.
Selective Reduction of As+3/As+5 —
The goal of this subtask was to analyze process streams, stack gas
samples and solid parti cul ate specifically for inorganic As and As .
+3 +R
Chemical speciation of inorganic As and As provided:
t Information on the true toxicity of the sample.
t Back-up information if As203 and As205 cannot be seen by XRD.
• A means for analyzing for As and As+5 that passes through
SASS train parti cul ate collection system.
A method based on the selective reduction of inorganic As and As (Ref-
erence 5) was evaluated. The solution containing As+3 and As"1"5 was buf-
fered at specific pH's (1.5 and 4.5) and reducing agencts (NaCNBH- and
) are added. The evolved AsHg was captured via a cold trap and
organic solvent and could be analyzed by either f Tameless ASS, GC/ECD,
or D.C. discharge. The method as developed by Bramen (5) used a one-of-
a-kind D.C. discharge system to quantitate the amount of AsH-. This
subtask verified Bramen's work and attempted to extend it to conventional
AAS analysis.
-------
Mass Thermal Analysis--
Attempts to determine the type and quantity of volatile inorganic
compounds present in samples was made by monitoring the weight loss and
identifying the gas products using a TGA/MS analysis. TGA/MS is partic-
ularly suited to the identification of volatile components and within the
limits of the temperature program should be able to identify materials by
their degradation products.
Initial tests were conducted with a DuPont 951 TGA using:
t Pure compounds
• Pure compounds mixed with coal fly ash.
If these tests were successful, design and fabrication of a TGA/MS inter-
face was to be initiated.
Special Studies--
As the task continued, interesting and potentially useful methods
and procedures were cursorily studied. To date this task has looked at:
• The use of Proton Induced X-Ray Emission (PIXE) as an
accurate multielement analysis.
• SEM-EDX analysis of environmental samples.
2.5.3 Technical Discussion
The following paragraphs will discuss the major accomplishments in
each of the areas of research.
Literature Survey—
The literature survey conducted under this task compiled over 300
journal articles organized into a wide range of topics. In addition to this
literature, computor searches for analysis methods using the elements:
arsenic, barium, beryllium, boron, cadmium, chlorine, copper, fluoride,
lead, manganese, mercury, nickel, selenium, tin, vanadium, and zinc were
completed.
X-ray Diffration Studies--
X-ray diffraction technique is-a relatively simple analytical tool
widely used for qualitative and quantiative identification of various
51
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crystalline compounds present in a amorphous matrix. However, the
sensitivity of the X-ray diffraction method is inferior to other methods,
and the sensitivity may vary depending on the compound under study and the
matrix.
The main goal for X-ray diffraction studies performed at TRW during
this task was to investigate the analytical capability of a typical com-
mercial X-ray diffractometer (in this case a GE XRD-5) to detect small
amounts (1-10%) of various materials of environmental interest.
Sample Handling Procedure — The handling of environmental samples imposes
two major difficulties; first, small amounts of pure compounds are usually
mixed with an amorphous matrix and, secondly, the material can be impacted
on glass fiber filter which produces a background scattering which can
mask the diffraction pattern due to crystalline species. Two approaches:
removal of the actual sample from the filter, and sample preparation to
ensure the highest possible intensity were studied.
To simulate an environmental matrix, two candidates, silicic acid
(SiOg. x HpO) and ground glass were tested for use on an amorphous filler
for the laboratory samples. Both produced an amorphous background, but
silicic acid was easier to disperse. The sample preparation procedure
was:
1) The pure chemical compound, as well as silicic acid were
ground to achieve <40pm size.
2) The test compound and silicic,acid were weighed and pre-
mixed in a test tube. Then a mixture of collodion with
reagent grade ethanol in a 1:4 ratio was used as a suspension
medium in which the samples were mixed ultrasonically for
10 minutes. The 1:4 ratio of collodion and ethanol, as well
as dispersion time were found experimentally simply by
trial error and were kept constant during this series of
experiments. After 10 minutes of dispersion, the medium
looked very uniform.
3) Using a pi pet, the dispersed sample was spread over the
glass slide, on which the illumination area was framed using
masking tape. After VI0 minutes of drying in air, the
sample was ready to run on XRD-5.
52
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All laboratory samples (compound and silicic acid) and actual samples
tested were mounted on the glass slides in this fashion. In some cases
the material was impacted on a glass fiber filter and could not be easily
removed. In this case alternate methods such as using Scotch tape to
remove the particulate matter or direct analysis of the filter with the
particulate matter on it were tried. As it turned out, both of these
alternate methods did not provide as good results as the mechanical agita-
tion of the filter and collodion mounting of the material removed. The
reason for that seems to be due to a low pick up of sample by the Scotch
tape (^20 mg), or, in case of the filter mounted on a glass slide, the
high background due to amorphous scattering of the filter.
It should be mentioned, however, that the proposed sample preparation
technique in each particular case must be applied with care. The wetting
and drying properties of a particular environmental sample could differ
significantly, as it did in the case~ of studying filter and cyclone catch
from an Aerotherm HVSS, as well as the samples from the mechanical and
electrical precipitator of the Shawnee Test facility. In each case the
amount of collodion to disperse the sample was found to be different,
and it is believed that the right ratio of collodion and ethanol must be
found by trial and error. Another difficulty was the formation of cracks
during sample drying; this was most pronounced in the case of filter
catch. In these cases, it is recommended that the collodion suspension
be spread over a piece of double-sided Scotch tape mounted on the glass
slide. This technique prevented cracking in most cases.
Sensitivity Studies of Pure Compounds in an Amorphous Matrix— As real-
life samples usually consist of mixtures of various sulfates and oxides
imbedded in amorphous matrix, the sensitivity studies were undertaken
with the laboratory samples containing pure compounds mixed with an
amorphous filler. The total weight of the laboratory sample was chosen
to be 100 mg, which is the approximate amount of material that would be
available for analysis. The 100 mg samples were mounted on a glass slide,
and run on XRD-5 diffractometer in the 2e-range around the major diffrac-
tion peak.
53
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An inspection of XRD data shows that the most intense diffraction peaks
of sul fates and oxides are located at relatively low (^20°-300) diffrac-
tion angles, where due to divergence of the X-ray beam, the sample's
illumination area is maximized.
The experimental conditions listed in Tables were kept constant
during this series of measurements. The compounds studied at TRW, their
weight fraction in amorphous matrix, as well as the estimated detection
limits are tabulated in Table 4. According to the X-ray scattering
ability of each compound, the qualitative classification has been
suggested.
It should be noted that detection limits of the compounds listed in
Table 3 would be significantly lower if more sophisticated equipment
was used rather than the XRD-5 diffractometer. Limits of detection for
state of the art equipment approaches 0.05% for many compounds.
TABLE 3. EXPERIMENTAL CONDITIONS
Variable Conditions Employed
Radiation Cu,,
Ka
Filter Ni
High voltage 40 kv
Current 20 ma
Sample's irradiated area 15 x 35 mm
Counting rate 500 c.p.s.
Time constant 1-2 second
Detector Proportional
Detector's slit 0.2°
2e scanning speed 2 degree/minute
54
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TABLE 4. XRD DETECTION LIMITS OF INORGANIC COMPOUNDS
OF ENVIRONMENTAL INTEREST
Compound
CaS04
AS2°3
Hgso4
PbO
Cr203
Mn02
Se02*
voso4*
Weight
Fraction
in Sample
10
4
10
2
10
10
1
10
2
10
10
Intensity
(c.p.s.)
700
250
200
70
225
900
75
180
70
Estimated
Detection
Limit
(% W/W)
^1
2
^2
<1
3-5%
2
<\/10
^0
X-ray
Scattering
Ability
Strong
Intermediate
Strong
Strong
j,
Weak
Intermediate
Very broad
Very broad
The quality of X-ray spectrum is very poor, mainly due to difficulties
with proper dispersion of the sample.
55
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Analysis of the Actual Industrial Samples—
1. FBC Fly Ash (PMB-0085) - The X-ray diffraction pattern of this
fly ash, as identified in our study, contained CaS04 in both the
hexagonal and orthorombic forms, but none of the original CaO
present in feed material was found. Other compounds, namely
CaAl2Si208 and KA102 (or K2A124057) were tentatively found.
Based on standard additional techniques, the 100 mg sample con-
tained ^20 weight percent CaSO^. The less than ^10% deviation
of the intensity of the Si02 line, which ideally should be the
same in all three samples, implied that the error in the CaSO^
concentration measurement was not more than 10%.
2. Thermally and Chemically Treated Coal Char - Typically, for all
coal char investigated in our laboratory, the X-ray diffraction
spectra were obtained in the 2e of 5° to 50° range. Identifi-
cation was made on the basis of agreement within +0.02° of the
spacing of the compounds. Because of the overlap of several
compounds, unambiguous identification of all the lines was not
possible. In particular, it was found that the Na2C03 spectra
did not correspond to the literature values and hence, identifi-
cation of it within the samples was impossible. Tables 5 and 6
summarizes the compounds looked for and whether they were found.
Because of the thermal history of the sample, compounds which
were normally crystalline could exist in amorphous states, in
which case either no spectra or broad band spectra would be
obtained. If unambiguous identification was not attainable, the
presence of the compound was listed as "possible." A brief
description of each sample analyzed is given below.
a) Original Coal Char -The original char produced only 4 sig-
nificant lines. These lines can be assigned to either FeC
or carbon with a structure similar to graphite. A char
assignment based on 2e values was not possible. The only
other potential compound was Ca3Fe2Si'30,2.
b) Residue A - Residue A consisted originally of char, NaCOv
CaO, CaF2 prior to heating and steam treatment. All
these components were seen in the sample after heating
except for Na^COo. After treatment, the CaO and CaF,,
concentrations appeared to be less. The char components
were seen as well as a new compound, CaS. Three compounds
56
-------
[Na2Ca(C03)2, 035(5104)2003, CaCOs] were possibly identified
(Table 5) with CaC03 being the most probable. Finally the
presence of Ca-|oSi3oOi5F2 was inferred, but further work would
be required to identify it unambiguously.
c) Residue B - This sample originally contained char, KgCOa, and
CaO. The char lines (FeC or C, and CaaFezSisOl?) were present.
The presence of CaO was confirmed and appeared to be at a con-
centration greater than that left in Residue A. The quantity of
CaS found was less than was that in Residue A. The presence of
CaS04 was possible (Table 6). A series of compounds
[K2Ca(C03)2, Fe304, CaSiOs, CaFeSi04, 035(8104)2003] were
tentatively identified from their 20 values, out all were present
in the 1-3 percent w/w range or less.
TABLE 5. RESIDUE "A" TENTATIVE IDENTIFICATIONS
2e
Tentative Identification
26.6
29.2
33.2
35.4
43.0
FeC or C
; CaC03
Ca3Fe2Si3012; Ca5(Si04)2C03
Na2C03; Na2C3(C03)2
FeC or C; Na2Ca(C03)2; CaC03
TABLE 6. RESIDUE "B" TENTATIVE IDENTIFICATIONS
26
Tentative Identification
25.2
26.6
29.8
33.3
34.0
35.3
43.0
46.5
CaS04(?); CaSi03
FeC or C; CaSi03
Ca3Fe2Si3017; CaFeSi04; CaSi03;
CaFeSi04; Ca5(Si04)2C03
CaFeSi04; Ca5(Si04)2C03
Ca02
FeC or C
CaO,
57
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Infrared Spectroscopy Studies--
Both normal and far infrared are valuable tools in piecing together
the composition of a sample. Infrared and Raman spectroscopy were used to
analyze and identify lunar rocks during the Apollo program (6). The
investigators were able to correlate the fundamental vibrations of SiO^
with the bulk composition of the sample. Lunsford (7) used infrared
spectrophotometry to determine the chemical form of adsorbed S02 on various
metal oxides. In the total compound analysis scheme, infrared analysis
can potentially identify anions present in the sample and determine the
compound containing the anion. The former is fairly easy to accomplish
since most anions have characteristic bands that can be used for identifi-
cation. As Table 7 shows, the region from 1000 to 1500 cm" should be of
great use.
Besides simply identifying the anion, specific correlations are avail-
able for individual compounds. Several investigators (8, 9) have done
extensive work with inorganic compounds. Tables 8 and 9, respectively,
list the characteristic bands for several nitrates and sulfates. Clearly,
there are analytical frequencies which can be used to identify compounds,
especially if elemental analysis can reduce the number of possibilities.
TABLE 7. USEFUL IR BANDS
Anion
S0=
NO"
C03
Si°3
Absorption Bands (cm )
610 - 690 (m)
180 - 1130 (s)
610 - 640 (m, sp)
1350 - 1370 (s)
650 - 680 (m)
1430 - 1450 (s)
^900 - 1100 (vs)
m = medium, s = strong, sp = sharp, v = very
58
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TABLE 8. INFRARED BANDS OF SOME COMMON NITRATES (CM'1)
Compound
NaN03
KN03
Ca(N03)2-XH20
Fe(N03)3-9H20
Ca(N03)2-3H20
Pb(N03)2
Band Category^3'
VW
2428
1044
2431
W
807
M
836 sp
824 sp
820 sp
835 sp
836 sp
• 726
836 sp
S
-v/1430
-------
TABLE 9. INFRARED BANDS OF SOME COMMON SULFATES (CM'1)
Compound
Na2S04
K2S04
CaS04*2H20
MnS04-2H20
FeS04-7H20
CuS04
PbS04
Band Category ^a'
VW
990
W
645
1010 (sh)
1670
510 (vb)
607
1150 (sh)
1020 (sp)
1600 (sh)
M
318
2200 (b)
660
1025
1625
680
805
860
592 (sp)
623 (sp)
S
620
603
667
1630 (sp)
3410 (b)
825
3225 (b)
611 (vb)
3330 (b)
1200
<3300 (b)
VS
mo
1110
620
1130 (vb)
1135 (vb)
1090 (vb)
1090 (vb)
C7I
O
(a) V = Very, W = Weak, M = Medium, S = Strong, SH = shoulder, B = Broad, SP = sharp
-------
Technical problems that must be addressed include effect and control
of moisture content in the sample. The moisture content of the sample
will affect the degree of hydration of the compounds present in the sample.
It is expected that the samples will have to be dried to a constant water
content to simplify the analysis problem. Information from a T6A-DSC
analysis will be used to pick a drying temperature that provides water
removal without sample decomposition.
In preparing the sample for IR analysis, typically KBr is used as
the mulling agent. However, samples that contain reactive materials such
as acid sulfates can cause reactions by releasing HBr in a replacement
reaction. Aluminum oxide, which is transparent from 2.5 to 15u, has been
tried as an alternate mulling agent, but results have not been good since
the fly ash did not stick to the AlgO^. Silicon dioxide was also tried
(absorption at 1000 to 1100 cm"1) with the same results. Fused Si02 works
but it is very porous and can pick up contaminants quite easily. The
first alternative is to use Nujol or Fluorolube mulls between AgCl plates.
This combination minimizes ionic exchange problems as well as crystal
deformation that might be caused by the pelleting procedure.
FTIR Results — During the task, a series of IR spectra were obtained for
5 different fly ash samples. These samples were anlyzed by conventional
IR and FTIR in the mid-IR.
The first sample run was Fluidized Bed Combustor material (PMB-0085)
supplied by PMB. Figure 4 shows spectra for a 1 mg (A) and 2 mg (B)
dried sample placed in a KBr pellet and using a Perkin Elmer 521. Except
for the peaks at 600 cm"1, 670 cm"1 and 780 cm"1, the spectra was without
much detail. Another spectrum (Figure 5) using a mineral oil mull and
shown at 5X scale expansion is completely different as now the major band
is at 720 cm"1 which is not in the mineral oil spectra. While showing
reasonable intensity, the spectrum lacks fine detail. This same FBC
material was run on a Digalab FTS-14, using scale expansion and computer
averaging of 40 scans (Figure 6). The result was a clearly resolved
spectra with a wealth of bands shown. Bands associated with CaS04 are
61
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1400
1200
1000
800
600
Figure 4. Perkin Elmer KBr Pellet IR Scan of PMB-0085 Flyash
-l mg, (B)-2 mg
62
-------
I I I I I J I I I.I I I 1,1 I I I I Mil . I
Figure 5. Perkin El.er 521 1R Scan of PNB-0086
Flyash (5X)
63
-------
1200 1100 1000" 900 800 700
Figure 6. ; Sample PMB-0085 FBC Flyash
600
64
-------
clearly seen at 610 and 670 cm'1. Figures 7 through 10 show a series of
samples of flyash taken from the outlet of a coal-fired boiler at the TVA
Shawnee Power Plant in Paducah, Kentucky. The particle size essentially
decreases in these samples in the order of presentation. Of particular
interest is the HVSS filter catch compared to the HVSS cyclone catch.
Note the change in peak ratios at 770 and 600 cm"1 and the appearance of a
strong band at 670 cm"1 (SOT).
While further work will be needed to identify the bands, the high
quality of the spectra and the obvious changes in the position and strengths
of various bands shown in the FTIR spectra clearly indicates the utility
of FTIR over conventional IR in recognizing changes occurring in the
sample. Also,the ability of the FTIR to subtract background spectra can be
used to remove unwanted materials. While 40 scans were averaged in this
test, 400 or 4000 scans could have been made to improve sensitivity.
As+3/As+5 Speciation —
+3
The sensitivity for As in the initial experiments was quite low.
The low recovery was traced to the effect on pH of the addition of NaBH.
to the sample. The procedure being tested (Reference 5) relies on
+3
precise slection of the pH. The hydride of As is formed at a pH of
4-5 with NaBH4 while the As+5 hydride is formed (after the As"1"3 is removed)
at a pH of 1-2 with NaCNBH3 followed by NaBH4. In both, cases, the AsH3 is
confined in a LN2 trap. It was found using Bramen's procedure that the
addition of NaBH4 raised the pH in the reaction vessel to
-------
700
600
500
Figure 7. Mechanical Precipitator Flyash Spectrum
66
-------
Figure 8. Electrostatic Precipitator Flyash Spectrum
67
-------
Figure 9. Cyclone From HVSS (INLET) Flyash Spectrum
68
-------
Figure 10. Filter Catch From HVSS (INLET) Flyash Spectrum
69
-------
results and attempts to oxidize any As+3 (As203) that might be an impurity
in the As"1"5 (A205) produced no noticable drop in signal. Since the recom-
mended operating range of AAS for AsH3 analysis is 1 yg absolute, appro-
priate dilutions can be made to minimize the effect of this slight reaction
+5
+3
of As to As hydride formation chemistry. Once these preliminary
+3 +5
tests were completed, a calibration curve was run for As and As using
the specific hydride formation chemistry. The results are shown on
Figure 11. It was expected that both curves would be identical, since
hydride generation occurs from the +3 oxidation state. The difference
between the two curves reflects the difference in recovery for the two
methods. Since both curves showed good precision (<±10 percent), the
reason for the lower As recovery was not sought.
Combined samples of As /As"1"5 were then analyzed in the same solution
to test the coordinated recovery of the procedure. The results are shown
in Table 10. While recovery for As was reasonable throughout the values
tested, the results for As were less encouraging. The As recovery was
depressed further when both reaction chemistry systems were tried on the
combined sample.
TABLE 10. AS"1"3/AS*5 SPEC I ATI ON TESTS RECOVERY ERROR
RESULTS
Input (yg)
As+3/As+5
5/2.5
5/2.5
5/2.5
1/1
1/1
1/1
0.5/0.5
Recovered (yg)
As+3/As+5
4.9/3.0
5.3/3.6
5.2/2.8
Avg. 5.1/3.1
0.68/0.45
0.80/0.90
0.80/0.63
Avg. 0.76/0.66
0.48/0.43
Error (%}
As+3/As+5
-2/+20
+6/+44
+4/+12
-S2/-55
-20/-10
-20/-37
-4/-14
70
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0.7
8.25MLKHP(10%)
1.0 ML Kl (10%)
5.O ML OXALIC ACID (20%)
5.0
+3 +5
Figure 11. Calibration Curves for As /As
-------
These results indicate that the As /As specification using a LN2
cold trap and AAS is possible. Further work will be necessary to improve
the recovery of As+5. The fact that the calibration curves were different
for each oxidation indicates that procedural problems were not uncovered
by this feasibility study. Further work is necessary to find the cause
for this low As recovery.
TGA/MS Evaluation Results —
The original objective of this investigation was to determine the
feasibility of compound characterization and identification of mating the
analytical capabilities of TGA and MS. It was intended to couple the MS
directly to the effluent stream of the TGA to permit MS identification of
the volatile compounds. However, it was decided to first determine the
utility of TGA to characterize a sample of FBC flyash material and then to
determine the lowest concentration levels at which a compound in the FBC
material could be detected by TGA. The results of these -experiments are
presented in the following paragraphs.
Two samples of FBC material were run on the TGA (DuPont) under a
nitrogen atmosphere employing a 5°C/min heat-up rate and full scale deflec-
tion representing ^13% (w/w) of the sample. The data were reduced and
plotted (Figure 12) as percent weight retention versus temperature to
permit a direct comparison of the two runs. Although the results of the
two runs appear similar, close examination shows that variations between
the two runs was as much as 0.5% (w/w) in the temperature range from
200°C to 500°C and greater than 1% (w/w) at 880°C.
TGA scans were next run on three model compounds; ZnCl2> SeCL and
As203, to determine their thermal characteristics. The same conditions
were employed for the three model compounds as were used for the flyash
sample. Each compound was found to display a fairly sharp break in the
TGA scan and it appeared that the characteristic break points could be
used for compound identification.
Testing of the TGA approach for compound identification was performed
by examining mixtures of the flyash and the model compounds. Specifically,
mixtures were prepared by adding 1% (w/w) of each of the model compounds
to the flyash and TGA scan, then were run. The results obtained for the
72
-------
co
100
100
200
300
700
400 500 600
TEMPERATURE, °C
Figure 12. TGA of FBC Material (Nitrogen Atmosphere, 5°C/min)
800
900
-------
three mixtures are presented in Figure 13 together with the TGA scan
for flyash by itself. Only the As203 mixture shows behavior consistent
with what would be expected based on the behavior of the pure compounds.
A sample of As203 shows weight loss occurring at 250°C to 300°C. It can
be seen in Figure 13 that the As203 containing sample shows about a U
difference in weight loss between the flyash and the 1% mixture in this
temperature range. However, it is somewhat disturbing that the total
weight loss at 800°C is about the same for both samples where it is expected
that the mixture should display a 1% greater weight loss. The samples
containing the Se02 and ZnCl2 failed to show weight losses in the expected
temperature ranges of 250°C and 500°C, respectively.
To test this approach further, a flyash sample containing 5% w/w
As203 was prepared and run on the TGA. The results are also presented in
Figure 13. It is evident that the 5% mixture displays the expected
weight loss in the temperature range of 200°C to 300°C; however, the weight
loss does not represent the 5% w/w sample of As90* that was added to
L.
-------
z
o
VI
o
200
300
400 500 600
TEMPERATURE, °C
700
800
900
Figure 13. TGA's of Flyash and Model Compounds
-------
non-homogeneous mixture that was used in the TGA runs. (That is, a small
portion of the prepared mixture was used in a TGA run.)
It was concluded that this technique is useful in determining the gross
thermal characteristics of a sample. For example, a TGA run could provide
information as to the amount of moisture in a sample, likely decomposition
temperatures of the mixture components, and overall thermal stability. This
type of information could be of value, for example, in selecting a drying
cycle for a mixture prior to analysis. However, determination of small
quantities (<1%) of materials does not appear to be very promising unless
one can obtain reproducible results from a known mixture. This obviously
was not the case for the FBC material.
Special Projects Results—
Proton Induced X-Ray Emission (PIXE) — Energetic protons from a nuclear
accelerator can be utilized to provide a technique for quantitative, multi-
elemental analysis. The sample is prepared as a thin film and bombarded
with a beam of protons which produce characteristic X-ray emission from all
elements in the sample. The X-rays are detected by an energy-sensitive
semiconductor device and the data is processed by an on-line computer.
Proton excitation provides much better sensitivity than electron excitation
because the yield of characteristic X-rays compared to background radiation
is much higher. Protons have an advantage over X-ray excitation because
good sensitivity can be obtained for a much larger group of elements.
Quantitative analysis of the broad range of elements excited by energetic
protons is made possible by the use of an energy sensitive X-ray detector
and on-line computer data processing. A Si-Li detector provides good
energy resolution and high sensitivity for X-rays emitted from all elements
heavier than Mg. Electrical pulses from the detector are processed in an
advanced electronics system and sent to an on-line computer. While the
computer is recording X-rays from one sample it is also processing data
from the preceding measurement. The analysis results are available from
the computer at approximately the same time that new data accumulation is
finished.
76
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When a sample has only trace quantities of elements in a lightweight
matrix, PIXE analysis is not complicated. A common example is the analysis
of solids from an air sample collected on a hydrocarbon filter. However,
with most solid samples, one must deal with the problem of intense X-rays
from elements which are present in high concentrations. In order to apply
PIXE as a general analysis tool, it is necessary to use X-ray filters,
advanced electronic systems, and computer programs.
PIXE Results— A comparison of the As values obtained by PIXE was made to
the Level 1 procedure. The fly ash samples were prepared by aqua regia
extraction and then analyzed by arsine generation and quantttated by AAS.
The PIXE analysis was performed by Dr. Paul Simms at the Purdue University.
The results are shown in Table 11. It should be noted that the only prep-
aration required for PIXE was mounting the solid sample on a Mylar film.
The excellent agreement shows that PIXE might be useful as a supplement to
Level 1 analysis for As, and possible Hg and Sb. Since PIXE can also be
used to monitor major components, it can be used to quantitate major concen-
tration elements which exceed SSMS limits.
TABLE 11. PIXE VS. AAS As PROCEDURE
Sample
Mechanical Precipitator
Electrostatic Precipitator
HVSS Cyclone Catch
HVSS Filter Catch
— — ^^^aeaaai
PIXE (ppm)
53
213
163
1681
Wet Chemical (ppm)
46
202
149
1395
—
B^^BH^MM^^9^BBBMgaRC3ttsax==a==%:==s&s==i^^^=
77
-------
SEM-EDX/Electron Probe Microanalysis-- The samples must be conductive when
analyzed by SEM-EDX or Electron Probe Microanalysis (EPMA). This can be
accomplished by placing them on a conductive sample stage or by coating with
a film of conductive material, e.g., C, Pt, or Au. The coating technique
can interfere with surface topography and any subsequent EPMA analysis;
therefore, the use of a conductive stage is preferred. In these experiments,
the samples were "floated" over the face of the Cu stage with acetone and
run directly.
A problem was encountered with small, thin particles. These were
analyzed with EDX and the composition of the copper stage was obtained
rather than that of the sample. New sample stages were prepared by plating
a thick film (3 Mil) of high purity gold on the copper substrate. Gold
will not interfere, as does copper, with these samples. Also the Au stages
can be directly placed in the EPMA without further preparation.
It was found that samples prepared by the SEM operator and scanned
using the instrument for general morophological characteristics takes a
significant amount of time. It is much more efficient to mount the samples
using an optical microscope and then direct the SEM work. .This can be done
using a scribed sample stage. This will increase the quantity of SEM images
that can be conducted for the instrument time requested. Charging of the
particles may still cause blurring of the pictures obtained. The EDX
appears to be acceptable for bulk analysis but is not sensitive to trace
elements and is not capable of detecting any elements lighter than sodium.
2,5.4 Recommendations
Based on this the work completed in this task, the following areas
should be investigated:
• Literature search -The initial literature search performed in
this task developed a large data base of information. This
activity has been continued to a limited extent during the
course of Task 7. It is recommended that a general task be
initiated to perform a continuing and comprehensive search for
inorganic compound analysis methods.
78
-------
t XRD - Our work has shown that XRD analysis of environmental
samples is possible, but that several problem a?eas Still
cXl o U •
1) Sample mounting - methods need to be developed to either
analyze material impacted directly on glass fiber filters
or to develop removal techniques to separate the sample
from the glass fiber filter without sample modification
One possible technique is to use Freon as the solvent and
and ultrasonic cleaner to break-up the filter. Filtration
or density gradient separation could be used to remove
the glass fibers.
2) Sensitivity - Improved sensitivity through computer averag-
ing techniques should be studied to improve the sensitivity
of XRD.
a Infrared Analysis - FTIR has been shown to have certain advant-
ages over conventional IR in the areas of sensitivity and spectra
manipulation. Work should be continued to:
1) Study the effects of sample conditioning on the structure of
the compounds. Work is needed to "normalize" samples so
that spectral shifts due to hydration, crystalline form or
sample matrix do not occur or are identified.
2) Study the direct analysis of material impacted on glass
filter to see if this information can be used to supplement
direct XRD analysis.
3) Study the subtraction capability of FTIR to establish guide-
lines on subtraction procedures for complex mixtures. The
goal is to subtract different samples from each other to
emphasize differences in the samples, such as particulate
matter collected at the inlet or outlet of an FGD.
t Surface Analysis - SEM-EDX is adequate for high resolution
morphology studies of environmental particles, however, EDX is
not surface limited. Three separate techniques should be studied
for their use for elemental depth profiling:
1) Scanning Auger Microanalysis (SAM) -This technique is sur-
face specific and provides images of the particle on sur-
face analyzer surface structures. Argon ion etching is
also possible.
2) ESCA - This technique provides elemental surface data infor-
mation and can determine the oxidation state of many ele-
ments. This technique is especially useful for sulfur.
3) Secondary In Mass Spectrometer (SIMS) -This technique
provides a wider elemental range and higher sensitivity
for elemental depth profiling.
79
-------
2.6 TASK 8 SAMPLING AND ANALYSIS OF REDUCED INORGANIC COMPOUNDS
2.6.1 Objective
The objective of this study was to develop sampling and analysis
techniques for the determination of emission rates of specific reduced
organic compounds from stationary sources. The sampling and analysis
techniques established provide an accuracy of +25%, a precision of +30%
and are applicable to various industrial sources. For this work, reduced
inorganic compounds were defined as any metal or non-metal which is bound
to hydrogen, is in its zero oxidation state, or is bound to carbon.
2.6.2 Approach
The task was divided into five subtasks to better define the approach
taken:
• Subtask 1 -A literature survey was conducted to define the
sampling stream parameters of those sources suspected of pro-
ducing reduced inorganic effluents. The parameters defined were
used to determine the procedures to be used for sampling and
analysis and predict possible problems and interferences.
t Subtask 2 -A second literature review was made to define the
state-of-the-art for reduced inorganic compound sampling and
analysis. This review resulted in a preliminary sampling
and analysis plan for a specific set of reduced inorganic
compounds.
• Subtask 3 - The procedures outlined as a part of Subtask 2 were
tested and verified in the laboratory. The laboratory effort
was devoted to determination of possible interferences, detection
limits, special sampling hardware, etc.
• Subtask 4 - When a sampling and analysis procedure was shown
to be effective in the laboratory, it was further tested in the
field. The field test was used to critically evaluate the labora-
tory procedure on "real" samples and to better determine inter-
ferences and effects of stream parameters on sampling techniques.
t Subtask 5 - Documentation of findings was the result of this
task. A technical manual and guidelines document on sampling
and analysis of reduced inorganic species was ultimately pro-
duced.
80
-------
2.6,3 Technical Discussion
of Processes Generating Streams Containing Reduced
Literature searches, supplemented by analysis of the chemical and
operating parameters of individual processes and contacts with know-
ledgeable persons, were used to identify 1) industries which could be
sources of reduced inorganic species; 2) the nature of the reduced com-
pounds in specific effluent streams; and 3) methods which can be used to
sample the identified streams.
As a result, the following process parameters were selected as conducive
to the formation of reduced species:
• Operations in which hydrogen is present in significant quantity.
• Operations which are oxygen deficient.
• Processes which contain metal oxides in a partially reduced state,
because such oxides may interact with various agents to form re-
duced species.
• Processes which generate substantial quantities of carbon mono-
xide or nitrogen oxide in the presence of those elements capable
of forming carbonyls or nitrosyls.
Sixteen processes employed in at least seven industries were identified
as potential sources of effluents containing reduced inorganic species.
The identified industries are listed in Table 12, which also highlights
characteristics of the effluents from the process operations of interest.
Sampling Techniques for Reduced Inorganic Species-
Sampling procedures were chosen with the goal of obtaining samples
which could be analyzed within an accuracy of ±25%. Three practices were
found in common which were necessary to accomplish this: 1) samples must
be time integrated to account for process operating variances; 2) sampling
techniques must be sensitive enough to measure volumes, weights, and flows
with greater accuracy than ±25% and 3) sample contamination or loss must be
avoided.
81
-------
TABLE 12.
INDUSTRIES AND PROCESSES PRODUCING REDUCED INORGANIC SPECIES
oo
Process Idenflcatlon
1) Steel Plant
® Blast Furnace
.
® Sinter Plant
(D Wlndbox:
© Discharge
end:
© Coke Ovens
© Oven off
gas
(5) Quench
Tower
(D Sour
Quench
Hater
2) Coal Fired Boilers
Effluent Characteristics from Predominant Process Operations
Participate Data
Size
Distribution
15-901 < 74M
15-451 < 40 u
9-30X < 20 u
4-19X < 10u
1-10* < 5u
BOX < 100
10X < 10
Highly
Variable
95-97X >47p
Not
Applicable
Z5X < 10
49X < 20
m< 44
X *f*f>
gr/SCF
4-30,
7-10 avg.
0.2-3.2
1-5
1-15
0.05-0.1
2.9 to
3.7 avg.
0 40-140
© 60-138
© 30-460
® 148-230
© 0.03-0.2
2.1 M ft3 per
charge
900 M ft3 per
quench
Mater usually
sluiced; flow
variable and
cyclic
© 297-397
© 362-434
Temperature F
390 at throat
3000 at Furnace
100-400
100-300
< 1832
140-150
245-258
Moisture: Vol X
9.6
2-10
Variable
depending on
point in coking
cycle
Effluent con-
sists primarily
of steam
6.4
__., , , | ,| .•!, 1
Reduced Species Present in Primary Effluents
Cited From Literature
©
H2
HZS
©
Ni(CO}4, HCN. NH3
H2S, H2. COS, CS-,
NH.CN f
H
© ©
Ni(CO)4, HCN. H2,
NH1( NH.CN, COS.CS.
•J *T t
©
Cyanide and ammonia
species are cited in
the literature.
Distinct compounds
are not Identified.
©
Cr(CO)6 has been
cited in the litera-
ture, although this
is not a reducing
atmosphere.
Probable Stream
Based on Chemistry
©
FeS, HgS, MnS
COS, CaS, Fe(CO)5, Mn (C0)1()
COS, Fe(CO),
7
V-'
COS, Fe(CO),
3
©
AsH3, SbH3
The formation of a variety of
hydrides, carbonyl , and metal
sulfides Is possible.
© ©
The formation of a variety of
hjd rides, carbonyl s, and metal
sulfides is possible.
©
Metal sulfides, cyanides.
sulfur cyanides, and reduced
ammonia species.
©
If, however, the formation of
Cr(CO)e is possible, the
existence of other carbonyls
is also possible. CO concen-
trations may be as high as
70 ppm.
Q) Flow rate Is expressed In: © M SCFH or © M SCF/ton of product processed.
©* gaseous phase; (D - liquid phase;®* solid phase
(Continued)
-------
TABLE 12. (Continued)
Process Identification
Refinery Operations
a) Claus Plant
Till Gas '
(E) Fixed Bed
Catalyst
Regeneration
c) Moving Bed
Catalyst
Regeneration
® Fluid Coker
off -gas
Coal Conversion^
(a) Gasification and
Liquefaction
Operations
CD Coal
Preparation
© Quenching
and
Cooling
(D Fixed bed
Catalyst: Sam
Regeneration
0 Sulfur
Plant: Sam
® Tar
Separation
Fertilizer Manufacturer
Effluent Characteristics From Predominant Process Operations
Paniculate Data
Size
Distribution
i parameters an<
e as Claus Plan
6.3% < Su.
12* < lOu.
29* < 30)i,
34* < 40u
gr/SCF
1 species a
I above.
0.7 to 4.0
Flow Rate
s defined undi
0 16.5
(one
unit)
Temperature °F
Fixed and mov-
ing bed regen-
erable cata-
lysts function
at about 850
to 10000F at
300 to
700 pslg
r "Refinery Opera
201
Moisture: Vol *
tion," above.
Reduced Species Present in Primary Effluents
Cited from Literature
H2S, COS, CS2, NH3,
HCN
H2S, COS, CS?,
Ni(CO)4 [Co(CO)4]Z
H2S, COS, CS2, NH3,
Ni(CO)4, HCH
H2S, COS, CS2> NH3>
RCN. Ni(CO)4
Sulfides In rinse
solution and par-
ticulate. The full
spectrum of reduced
species are formed
in gasification.
Many of these are
incorporated into
the quench water.
©
Ni(CO)4. NH4CN. HCN
rlH^ § Hr
Probable Stream
Based on Chemistry
© ©
Spent chemicals from acid gas
.amine solution regeneration =
carbonyls, cyanides, sul fides.
Mo(CO)6; the formation of vari-
ous metal sul fides, hydrides
and carbonyls probable.
Metal sulfides and carbonyls
probable.
Dryer off gases may contain
carbonyls.
©
The existence of Arslne, Stlblne.
carbonyls and sulfides Is
irobable.
©
Cyanides, Nitrosyls.
CO
co
Stream parameters are highly variable depending on process design, see text.
(Continued)
-------
TABLE 12. (Continued)
Process Identification
Forest Products
Industry
0 Kraft Pulp Mills
© recovery
furnace
© lime kiln
© smelt
dissolving
Primary Nonferrous
Metals Industries
0 Copper
© roasting
furnace
© electrolytic
refining
© Lead
© sinter
machine
© Blast
furnace
© Zinc
© roaster
© sinter
machine
© Aluminum
© reduction
cell
Effluent Characteristics From Predominant Process Operations
Particulate Data
Size
Distribution
50-85X < 2u
95X < 25u
90X < 5u
15X < lOu
100X < lOu
0.03 to 0.3
14X < 5,
31X < 10
70X < 20
100X < 10
Submicron
particulate
gr/SCF
3-8
avg. 3-8
3-20
0.17-1.3
6-24
0.4-4.5
1-11
5-65
0.4-4.5
0.03-2.0
Flow Rate
0 20-568
^^
©278-568
© 7-50
45 SCF/air
dried ton
© 60-131
0 140
© 130
6-14
25-30
140
2000 to 4000
CFM/cell
Temperature F
270-650 avg.
350
400-900
170-200
600-890
250-600
150-250
730-900
320-700
Moisture: Vol I
20-40
400-600 Ibs/air
dried ton
670 Ibs/air
dried ton
Dew Point:
122-140
Reduced Species Present in Primary Effluents
Cited from Literature
©
H.S, Na S
2 2
©
HS
&
©
H,S, Na,S
L C.
©
Cu-S FeS
£
AsHj
©
PbS
©
ZnS
©
H.S
C
Probable Stream
Based on Chemistry
©
COS FeS
©
COS, FeS. MgS. CaS
©
Liquid tailings from refining
operations are likely to con-
tain selenides, tellurides,
and sulfides.
©
PbS, ZnS
ZnS, CdS, COS
©
ZnS, PbS, CdS
©
COS, NajS, CaS, A1?S3
Electrode is roncerned in the
reduction process; consider-
able CO is formed. Metal
carbonyls may therefore result.
00
Process data for electrolytic refining is highly variable; literature does not site specific flow data.
-------
The sampling techniques chosen for use with specific process streams
containing reduced inorganics included:
1) Solid - integrated composite
2-) Liquid - integrated composite
3) Gas - fugitive emissions
4) Gas - time integrated (non-particulate)
5) Gas - SASS train (particulate)
Although each method has restrictions and limitations, the applicability of
the SASS train was deemed worth particular study because it generally is not
suited for sampling reactive inorganic species for subsequent compound identi-
fication. The levels anticipated for reduced species are generally low and
chemical modification by the act of sampling will in some cases not allow for
subsequent analysis. Sampling for solid reduced inorganic species from
particulate material may be possible using the SASS; however, reduced in-
organic gases will either be lost or chemically modified due to their inherent
susceptibility to oxidation or thermal instability. By studying the chemistry
of several of the reduced species, an estimation of the probable locations of
specific compounds in the SASS train was made. This information is shown
graphically in the following figures: Figure 14, PH3, and SbH3; Figure 15,
reduced sulfur compounds, H2S, COS, and RSH; Figure 16, reduced nitrogen
compounds, NHs, HCN, and (CN)2; and Figure 17, Hg, Se, and metal carbonyls.
Sampling and_Ana]^_sis of Gaseous Reduced Inorganic Compounds —
The sampling and analysis procedures presented in the final report on
this task were compiled from literature searches, developed or modified in the
laboratory, and, in three cases, tested during a field study on an actual
source of reduced inorganic emissions — the Paraho Shale Oil Demonstration
Plant. The procedures are detailed and limited in application to specific
reduced chemical compounds. Some, in fact, are unique for a single substance.
Due to the generally unstable nature of reduced inorganic compounds, the pro-
cedures require specialized sampling equipment and techniques. For the pur-
pose of sampling and analysis, reduced inorganic compounds can best be divided
into groups based on their acidic, basic or neutral characteristics. Stability
of the species to oxidation is also an important parameter as illustrated by
such metal hydrides as phosphine, arsine and stibine. Acidic species of in-
terest include hydrogen sulfide, mercaptans and hydrogen cyanide. The basic
85
-------
00
200-CMAX
3/1
1
1/i
COOLING
PROBE
CYCLONE CYCLONE CYCLONE FILTER
Var1able-H
AsH3
SbH3
Organometalllc forms of P, As, and Sb
L * Small concentration
M « Moderate concentration
H = Large concentration
XAD-2
SORKNT
1
1 ('
D
H
CONDENSATE
H2u2
©M
IMPINGERS
APS
APS
Figure 14. SASS Distribution for PH_, AsH- and SbH0
Jo 3
-------
oo
200*CMAX
1
I
PROBE
lOd 3? Ifi , <-°°IN6
CYCIONE CYClONt CYCIONE Rim I
-
COMPENSATE
COS
RSH
VL » Very small concentration
L « Small concentration
M - Moderate concentration
H » Large concentration
XAD-2
SOME NT
IMPtNGERS
APS
APS
G>H ®M
ETSlM &M-H
M.2T
H-H (pH Dependent)
Figure 15. SASS Distribution of Reduced Sulfur Species
-------
00
00
200-CMAX
1
PROBE
100
CYCLONE
3/1
CYCLONE
\n
CYCLONE FILTER
COOLING
(20-Q
xAD-2
SORKNT
a VL
) L-M
(3)
HCN
IM FINGERS
APS
APS
L * Small concentration
M = Medium concentration
H * Large concentration
Figure 16. SASS Distribution of Reduced Nitrogen Species
-------
00
20PCMAX
1
I
100 3*1 l/i ,
CYCLONE CYCLONE CYCLONE FILTER |
1
1
CYCLONE
©
CYCLONE
1
1
H
(D L
COOLING
(20-O
Variable j
Hg
Se
MCO
L * Small concentration
M * Medium concentration
H * Large concentration
xAD-2
SOME NT
IMPINGERS
APS
Variable
Figure 17. SASS Distribution of Hg, Se, and MCO
-------
group consists of ammonia and low molecular weight amines, while the neutral
class includes metals, hydrides, cyanogen and carbonyl sulfide.
A thoroughly developed, carefully studied method for the collection and
species identification of mercury and mercury compounds has recently been
published by Braman and Johnson (11). In light of this, this study did no
further work with these compounds.
Impinger trapping techniques using several impinger solutions were in-
vestigated for all other reduced inorganics. Overall, entrainment of the
compounds of interest in a reactive solution is direct, efficient and often
amenable to analysis without further treatment. Table 13 below summarizes
the requirements for collecting the several reduced species:
Table 13. Collection Solutions for Representative Reduced Species
Compounds
H2S, RSH, HCN
HCN
NH3, low M.W. amines
PH3, AsH3, SbH3
Se
Impinger
Solution(s)
Basic CdS04
Cone. H2S04
Dilute HC1
H202
H202
Comments
Pre-scrub NH3 from gas stream with
dilute HC1 containing impinger.
Other oxidizing reagents possible.
Other oxidizing reagents possible;
COS
(CN),
CaCl2+NH404
Dilute NaOH
also can use filter paper wetted with
strong cyanide solution.
Pre-scrub H-S from gas stream with
aqueous Cd(uH)2 containing impinger.
Post-scrub CS2 with KOH/alcohol
solution.
A preliminary examination of the capabilities of solid sorbents was
made. Because early results did not compare favorably with the efficiencies
and capacities of impinger collection systems, work was halted.
90
-------
Species of
Interest
H2S
NH,
COS, (CN),
Solid Sorbent
Tenax GC
XAD-2
Porapak QS
Chromosorb 103
Porapak QS
Test Results
Inadequate
Inadequate
Marginally acceptable at 0°C - problem
with low breakthrough volume.
Low breakthrough volume even at 0°C;
convenient if effluent gas stream
has high NH3 concentration.
Low breakthrough volume prevents
use with trace levels in effluents.
When field analytical equipment is available and the reduced inorganic
sample concentration in the gas stream is relatively high, grab sampling is the
preferred method. Rapid analysis in the field eliminates the requirement
for efforts to stabilize the samples and could be less expensive as well.
The chemical state of the sampled species often dictates the analysis
technique to be used. Impinger solutions, if relatively free of interfer-
ing materials can often be analyzed directly using ion specific electrodes,
or such classical wet chemical techniques as titration or gravimetry. For
more complex mixtures, regeneration of the original sample is often required
to minimize interference problems. For samples adsorbed on solid substrates,
thermal desorbtion or solvent extraction may be necessary prior to analysis.
Grab samples may be analyzed directly or after concentration.
The procedure to be used for analysis is dependent on the sample
matrix, possible interferences and the sampling technique. The techniques
used in this study on impinger entrained samples are summarized below. Details
of all procedures investigated were presented in the task final report.
Compounds of
Interest
Sample Preparation
H2S, RSH, HCN Acidify and purge
NH., and amines Neutralize, steam dis
J till, and purge
Analytical
Technique
GC with Porapak QS column using
TC detector (Figures 18, 19)
GC with Chromosorb 103 column using
micro-TC detector
91
-------
Compounds of Analytical
Interest Sample Preparation Technique
PHV AsH3, Destroy excess ^02, GC/MS (Figure 20) Much less soph-
SbRa acidify, reduce using Isticated technique desirable for
NaBH4, (Figure 19) routine work - perhaps 6C-FPD
Hg, Thermal desorption AA
Se ,Add 1% nickel to con- AA
vert sample to selenide
COS, CS2 Add barium Gravimetric determination as
(CN)2 - Modified Werner procedure (colori-
metric)
Field verification studies of the ammonia/amine procedure, the hydrides
procedure and the carbonyl sulfide procedure were successfully performed on
samples obtained at the Paraho Shale Oil Demonstration Plant. A total of
four individual samples were obtained from the recycle gas stream. These
samples were analyzed in triplicate using the procedures previously described.
The results of the analyses are presented in Table 14.
Table 14. Field Test Results for Arsine
Sample Volume
No. Sampled
1 0.15 M3
2 0.14 M3
3 0.13 M3
4 0.13 M3
Amount
Arsine
Detected
.025 yg
.035 yg
.045 yg
.060 yg
yg/M3
Arsine
0.17
0.25
. 0.35
0.46
Arsine was the only hydride detected in the samples analyzed and no
organometallic species were detected. The results of triplicate analysis
of the same sample were within +_ 20% relative. The deviation of the amount
of arsine found between samples is probably due to the small sample volumes
obtained and the non-homogeneity of the recycle gas stream due to process
variations.
92
-------
CH3CH2SH
(CM),
CO
HCN
Column Type: Glass 3mx4mm ID
Column Packing: Porapak QS, 80-100 mesh
Injector: 4 Port Teflon valve system
Detector: Thermal conductivity
Column Temperature: 25*C-120*C @
8*C/min after a 10 minute hold
at 25°C
I
4
I
6
RETENTION TIME (MINUTES)
Figure 18 Typical Chromatogram for Reduced Inorganic Gases Using Porapak QS
-------
to
SAMPLE OR REAGENT
INTRODUCTION PORT
TRAP
GC COLUMN
1
-n
TC DETEaOR
OR MASS SPEC
Figure 19 Reduced Gas Evolution Apparatus
-------
GAS CHROMATOGRAM
SAMPLE: 0.1MLOFGAS
SAMPLE RUN: ASPAS
CALIB. RUN: C91
SCANS 1 TO 500
RELATIVE
INTENSITY
vo
tn
SCAN
TIME
Figure 20 Resconstructed Gas Chromatogram of The
Hydrides Produced by Reduction Procedure
-------
2.6.4 Recommendations
A description was provided in the final report of the methodology for
the sampling and analysis of representative reduced inorganic compounds from
a variety of sources. Further research is required before the proposed
methodology can be routinely used in the field. Specific problem areas
include:
• Evaluate complex samples for interferences.
• Determine the recovery of all reduced species in mixtures described
by a statistical matrix.
• Determine the storage life of samples collected, i.e., impinger
and adsorbent trapped samples.
• Complete characterization of Porapak QS and other specialized
materials for use in adsorbent traps for selective compound
sampling.
• Design and evaluation of cartridge-type adsorbent traps that can be
stored for extended periods before and after use without changes
in efficiency for sampling or degradation of trapped samples.
• Establish conditions to permit rapid sampling and analysis of higher
molecular weight amines and mercaptans.
• Choose from existing sources or design selective detectors for
the identification and determination of reduced inorganic species.
• Improve or design new on-site monitors for reduced inorganic species
in effluent streams.
The sampling and analysis of reduced inorganic species is a very im-
portant area of study. Very few current environmental assessment programs are
using compound specific techniques for sampling and analysis. Therefore,
little information is being gained on the true risk associated with a given
source.
96
-------
2.7 TASK 9 COAL MONITORING INSTRUMENTATION
2.7.1 Objective
The purpose of the task was to investigate the state of the art for
continuous coal mass flow and composition measurements, both to determine
current capabilities, and to investigate the need for EPA involvement in
research and development efforts. The types of flow investigated were dry
coal flow (typically on a belt) and coal-water slurry flow. Composition-
type measurements are performed on small samples (few grams) with lab-
oratory instruments and on dry slipstreams with various instruments cur-
rently under development. Measurement in slurries is presently limited to
only"slurry density.
2.7.2 Approach
The task was divided into the following items:
• Literature search
• Vendor and user search and contact
• Evaluation of information
• Calculations and analyses
• Field trip
• Preparation of final report
The literature and vendor searches were used to determine available
instrumentation and status of instrumentation currently under development.
Compiled information, along with user data, was then used to compare the
various instruments. We then performed calculations and analyses of our
own to determine system limitations and errors. A brief trip to the
Pittsburgh/Morgantown area was undertaken to visit key facilities. A final
report, in the form of a technical manual, was then prepared.
The only significant deviation from the original plan was a contrac-
tual one - shortly after its inception, this task was transferred to
Contract 68-02-2613, where it became Task 2, "Evaluation of Equipment
97
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to Determine the Mass Flow of Coal in Process Streams." The latter task
title is somewhat misleading, since composition as well as mass flow was
considered. The title of the final report, "Assessment of Instrumentation
for Monitoring Coal Flowrate and Composition," is indicative of the work
performed.
2.7.3 Technical Discussion
The task was a paper study evaluation of instrumentation. The draft
final report was issued at the end of February 1978, and was published In
March of 1980. The draft report is a 150-page document. The Table of
Contents is presented as Figure 21 on the following page.
The task logically divided itself into two areas: flow instrumenta-
tion and analysis instrumentation. The two areas differ widely not only
in terms of being different types of measurements, but also in terms of
state of development.
Coal flow rate instrumentation, especially for belt conveyors, is very
accurate and reliable. Belt weighing devices are available from a large
number of vendors, are relatively inexpensive ($5,000-$!0,000 for a
1000 ton/hour capacity), and have accuracies in the range of ±0.1 percent
to ±1 percent of reading. Vendor and literature data were obtained for
this type of instrument, establishing wide availability and ease of use.
Extensive talks were held with the Southern Weighing and Inspection Bureau,
the acknowledged authority in this area (by the National Bureau of Stan-
dards). The Bureau's procedures for calibration and use of weigh belt
devices is presented in annotated form as an Appendix to the final report.
Belts are the most common means for short distance conveyance of coal at
. !S"
power plants.
Slurry flow measurement is not quite as accurate as conveyor belt
measurements, but various techniques, most notably the electromagnetic
flowmeter and the ultrasonic flowmeter, are readily commercially available.
At present, there is very little demand for coal slurry flowmeters. This
will likely change if long distance coal conveying in slurry pipelines
becomes more widespread. It is clear that existing instruments will be
usable for slurry applications which may arise in the future.
98
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for
Report
Abstract i11
List of Figures y
List of Tables V1-.j
Acknowledgements ^
Sections
I Introduction 1
II Principles of Instrument Operation 3
2.1 Coal Analysis Instruments 5
2.2 Flow Measurement Instruments 35
III Hardware Status 66
3.1 Coal Analysis Instruments 66
3.2 Flow Measurement Instruments 75
IV Ten Year Projection of Instrument Development 103
and Availability
V Summary and Conclusions 106
VI References 108
VII Glossary 112
VIII Appendix - Procedure for Weigh Belt Calibration 116
and Use
-------
Coal analysis instruments are of two types at present: laboratory
instruments, which analyze a very microscopic sample of coal, and a variety
of instruments, currently in various stages of development, which analyze
part or all of an entire coal stream for a specific property such as mois-
ture or sulfur. Laboratory instruments are dependent on complex sampling
systems which extract a gram-sized sample from thousands of tons of coal.
Also, there is necessarily a large time lag between the start of the sampl-
ing process and the completion of the analysis, meaning that this approach
cannot be considered as continuous, real-time monitoring.
The goal of continuous monitoring appears to be best attainable by
means of neutron activation instruments which can potentially analyze an
entire coal stream. The approach operates on a "number of counts" basis,
resulting in typical sampling times of about five minutes, with the output
being an average reading for the sampling period. This time response is
short enough that this type of device can be potentially used for control
purposes. The development of neutron activation instruments for coal anal-
ysis has been led in the U.S. by the Morgantown Energy Research Center
(DoE), which we visited in September 1977. At that time, we were told
that a commercial neutron sulfur meter would probably be available within
two to three years. We just received word, after sending the draft final
report to MERC, that due to a "reordering of priorities," they are stopping
work on neutron activation devices. This essentially means that no one
in this country is presently doing work in this area.
2.7.4 Summary, and Recommendations
The two-page summary section of the draft final report is presented
below. The section will be modified in light of MERC's stoppage of their
neutron activation work, and we will suggest that EPA consider the pos-
sibility of continuing this development of neutron activation analyzers.
Summary and Conclusions from "Assessment of Instrumentation
for Monitoring Coal Flow Rate and Composition"—
Relevant techniques were presented in detail to give a general under-
standing and to give an idea of fundamental limitations. For example, a
difference in ultimate utility between neutron activation devices and
100
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fluorescence radiation devices is shown by the fact that the former can
operate with a penetration depth of order one meter, while the latter is
limited to penetration depth of order one millimeter. This has strong
implications on instrument configuration and utility.
In contrast to the rather sophisticated physics of coal analysis
equipment, operation principles of most flow measurement devices are fairly
simple. This simplicity has meant that flow measurement devices have been
more easily developed, and have been in wide use for many years.
The material presented makes it clear that there are many techniques
available for the measurements of interest. Availability of instrumenta-
tion, however, is another matter, especially in the case of coal analysis
devices.
Instruments available now for coal analysis, with the exception of the
neutron moisture meter, are capable of analyzing only small samples, which
means that a sophisticated sampling system is required. The moisture
meter itself is actually a hydrogen indicator, which means that the coal
hydrogen content must be known independently to determine the moisture
content. It has been the observation of MERC personnel that the hydrogen
content in coal is in fact constant for a given coal type. Development
of neutron activation instruments is not proceeding well, but a sulfur meter
is expected as a production item within the next few yeats. It is hoped, this
will be followed by modified versions capable of determining moisture and
heating value. Neutron activation devices -are of particular interest
because they hold the promise of sampling entire coal streams, thus elim-
inating the major problem of obtaining a representative sample.
Weigh belt devices, either electromechanical or nuclear, and electro-
magnetic flowmeters (typically coupled with nuclear density gages) are the
most used devices for dry coal flow measurement and coal/water slurry flow
measurement, respectively, and will be acceptable for most situations.
Weigh belt technology is especially highly developed, in part due to reg-
ulatory considerations. Intrusive devices may be applicable to slurry
flow measurements, but this has not been clearly demonstrated as yet.
101
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Weigh belt devices are sufficiently advanced, and their use in many
situations sufficiently monitored by various regulatory agencies, that they
should not need EPA attention. Similarly, electromagnetic flowmeters are
a very standard item and do not appear to need attention, in terms of field
evaluations for example, except in unusual circumstances. As far as other
slurry flow measurement devices are concerned, we feel that a reasonable
approach is to let vendors demonstrate that their devices are acceptable
for (dense) coal/water slurries.
At such time as devices like the neutron sulfur meter become com-
merically available, IERL will likely wish to be involved in collaborative
testing or other evaluation of the devices. This, however, will not be
taking place for at least a couple of years.
Perhaps the most reasonable area for IERL investigation in the near
future is instrumentation/control systems which make use of the kinds of
instruments discussed in this report. The thrust of the investigation
would be to determine how to make the best uses of available and soon-to-
be-avail able instrumentation to control the operation of sources such as
coal-fired utilities to minimize pollutant emissions through direct com-
bustion control and/or optimizing operation of devices such as wet scrub-
bers. The greatest ultimate value of the instruments discussed herein is
not just as monitoring sensors, but as components in an active control
system, either on sources of direct coal combustion, or in coal cleaning
plants.
102
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2.8 TASK 10 COAL SULFUR MEASUREMENTS
2.8.1 Objective
The existing literature and pertinent authorities in the field of
sulfur analysis were surveyed in order to determine existing sulfur forms
methodology and the nature of the need for improved methodology. As a
result of this survey a need for a more accurate organic sulfur analysis
procedure was found. To fulfill this, TRW proposed two entirely new coal
organic sulfur analysis procedures, both based on the selective removal of
organic sulfur species present in coal via selective oxidation in an oxygen
plasma instrument. The first procedure entailed the determination of
organic sulfur by difference between two highly accurate and precise BaSO.
gravimetric procedures. One on the starting coal and one performed on the
resultant ash from an oxygen plasma decompositive of the coal matrix. The
second procedure is the direct determination of organic sulfur by analysis
of solid sorbents placed in the outlet line from the plasma asher used
to sorb effluent SO species.
3\
2.8.2 Approach
The first step in the verification of the proposed techniques was to
search the literature for pertinent information dealing with the reaction
of coal and coal minerals under oxygen plasma conditions. Few applicable
documents were found. Because of the sparcity of applicable information a
detailed evaluation of parameters that could affect the resultant accuracy
and precision of techniques had to be performed. The laboratory evaluation
of the two proposed techniques included the following:
I) Organic sulfur by difference between two BaS04 gravimetric
procedures.
• Feasibility of technique by comparison with organic
sulfur values determined using ASTM D2492.
t Reactivity of commonly occurring sulfide minerals
under plasma ashing conditions.
• Retention of sulfur by reaction with alkaline components
of coal ash.
103
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2) Direct determination of organic sulfur.
• Test various sorbent systems placed in outlet line of
plasma asher for efficiency in removing SOX species.
2.8.3 Technical Discussion
Coal Sulfur Forms Analysis with Indirect Determination of Organic
Sulfur «
This analysis procedure is based on the selective removal of the
organic matrix including organosulfur species from coal with a low tempera-
ture oxygen plasma. The inorganic sulfur species are quantitatively
retained in the remaining ash. The Inorganic sulfur in the ash is then
extracted with dilute nitric acid and determined gravimetrically as BaS04
or speciated by ASTM D2492.
An evaluation of the data in the following sections shows that (1) the
plasma procedure yields more accurate and precise results for inorganic
and organic sulfur than the ASTM procedures; (2) naturally occurring sul-
fides are not affected under plasma conditions; and (3) organic sulfur
species are not retained in the coal ash by reaction with alkaline com-
pounds. The actual procedure has been optimized and is ready for testing
in other laboratories.
Preliminary evaluation of the plasma ashing procedure was performed
on 13 coals. The organic analysis results, Table 15 show that when the
results are evaluated by coal basins, the ASTM-TRW-AA (an AA method developed
by TRW) and plasma ashing procedures give essentially identical results while
the standard ASTM procedure is low by 5-6%. In the case of the interior
basin coals, the ASTM procedures are in good agreement while the plasma pro-
cedure is low by 10%. Three of these coals are from the same area and
separate X-ray microprobe experiments have shown that they contain pyritic
sulfur that is unextractable by the ASTM procedures. If this unextractable
inorganic sulfur were extracted from the plasma ashed sample, this would be
the cause of the lower organic number. Table 15 also shows analysis of;sample
treated by the Meyers Process. When before and after treatment values'are
compared, both the plasma ashing and the ASTM-TRW-AA procedures give consis-
tent results, while the ASTM procedure gives widely discrepant results that
tend to be significantly low for untreated Appalachian coaTs. Thus, in
f
104
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TABLE ,5.
DETERmNATIoNs
— — — — . ___
Mine/Seam
• _ , — . — _
E Seam (ROM)
E Seam (Cleaned)
Delmont
(Upper Freeport)
RirH
D 1 1 U
(Lower Kittannlng)
Egypt Valley
(Pittsburgh)
Fox
(Lower Kittanning)
Williams
(Pittsburgh)
Lucas
(Middle Kittanning)
Brookdale #77
(Lower Kittanning)
Old Ben #21 b
(Illinois #6)
Old Ben #24b
(Illinois #6)
Old Ben #26b
(Illinois #6)
Inland Steelb
(Illinois #6)
• _
Treated(T)a
Untreated(U)
U
U
U
T
U
T
U
T
T
T
U
T
U
U
U
U
U
U
•
ASTM Procedure
Std.
-
0.48
0.57
0.51
0.60
0.25
0.74
0.22
0.50
1.34
2.03
1.18
1.18
1.19
1.38
0.32
0.48
0.63
1.66
1.38
1.81
TRW-AA
^^^~™^™^™"^"-™««iii™
0.46
0.66
0.57
0.68
0.79
0.74
0.54
0.55
1.78
1.81
0.90
0.91
1.48
1.40
0.50
0.48
0.60
1.57
1.34
1.80
— — — _____ _
Plasma
Ashed
—
0.52
0.59
0.60
0.65
0.81
0.64
0.62
0.55
1.97
1.81
0.90
0.92
1.42
1.41
0.49
0.46
0.45
1.57
1.19
1.66
a) Treated by Meyers Process to remove pyritic sulfur and
adjusted for mineral matter (ash) changes.
b) Eastern interior basin coals.
105
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reference to evaluation of coal cleaning processes, it appears that the ASTM
procedure gives results dependent on coal processing while the other two
procedures give results that are virtually independent of the history of the
coal. A thorough comparative evaluation of the proposed procedure with ASTM
methods was performed in triplicate on coals chosen to represent a
variety of ten seams in the Appalachian and Eastern Interior coal basins.
From the tabulation of results in Table 16, it is seen that the ASTM
titriraetric pyritic sulfur values exhibit a distinct negative bias when
compared to values determined by AA. The exact reason for this bias is
difficult to explain because the pyritic iron was determined on aliquots
of the same extract for both procedures. In addition, the same iron
standard was used for calibration of both analytical procedures. One possible
explanation for this bias is loss of iron during the iron hydroxide
precipitation, filtration and redissolution step which is necessary for the
titrimetric procedure but not for the AA determination. This explanation is
consistent when the total inorganic values (sulfate sulfur and pyritic sulfur)
determined using the two ASTM procedures are compared to the TRW plasma-
total inorganic values (Table 17); the results using the AA technique are
in excellent agreement with the values obtained in the plasma ash procedure
for the Appalachian coals. This agreement for total inorganic sulfur is
directly reflected in the organic sulfur values contained in Table 18. The
ASTM analyses of Eastern Interior Coals exhibit a positive bias for organic
sulfur when compared with the plasma procedure. This bias probably is
the result of the presence of very fine pyrite present in these coals which
is not extracted with nitric acid in the ASTM procedure. This is subs-
tantiated by the electron probe microanalysis studies which show measurable
amount. The presence of very fine pyrite can also explain the large
differences in total inorganic sulfur experienced with the tailings sample.
Additional experimentation was performed on 10 coals to test the
application of the ASTM sulfur forms extraction procedure on the plasma ash
and to compare the corresponding analysis of the whole coal. ASTM D2492
was used for both sulfate extraction and analysis. The analysis of pyritic
iron in the HNO^ extract was performed by the TRW-AA atomic absorption
method in both cases rather than a proposed ASTM-AA method. However, this
was done because TRW has found the ASTM method to be considerably less
106
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TABLE 16. COMPARISON OF SULFUR FORMS ANALYSIS METHODS
Mine
Old Ben 121
Old Ben 126
Inland Pea body
Martlnka
E-Seara
C-Prlme
Mathies
Lucas
Musklngum
Tailings from
Central Ohio
Coal Co.
Coal Seam
Illinois #6
Illinois 16
Illinois IS
L. K manning
U. Freeport
U. K1ttann1ng
Plttsburg
H. Kittanning
Meiggs Creek 19
Meiggs Creek #9
Coal Basin
Eastern Interior
Eastern Interior
Eastern Interior
Appalachian
Appalachian
Appalachian
Appalachian
Appalachian
Appalachian
Appalachian
Pooled Std. Dev.
Total Sulfur
Eschka
1.11 ±0.032
2.26 ±0.031
3.24 ±0.012
1.59 ±0.058
1.04 ±0.015
1.52 ±0.032
1.60 ±0.020
1.70 ±0.025
5.71 ±0.051
3.28 ±0.035
tO. 034
Leco
1.28 ±0.030
2.21 ±0.031
3.11 ±0.071
1.59 ±0.059
1.06 ±0.025
1.42 ±0.040
1.52 ±0.075
1.69 ±0.044
5.62 ±0.061
3.31 ±0.096
tO. 058
Pyrltlc Sulfur1 -ASTM
Titratlon3
0.32 ±0.045
0.65 ±0.036
0.94 ±0.028
1.16 ±0.097
0.25 ±0.010
0.74 ±0.040
0.57 ±0.026
0.67 ±0.006
1.87 ±0.066
1.87 ±0.074
±0.051
AAZ
0.48 ±0.066
0.77 ±0.006
1.03 ±0.006
1.33 ±0.130
0.34 ±0.006
0.90 ±0.007
0.66 ±0.006
0.82 ±0.006
2.42 ±0.040
1.92 ±0.170
±0.072
Sul fate
Sul fur3
ASTM
0.08 ±0.000
0.16 ±0.006
0.38 ±0.012
0.12 ±0.006
0.08 ±0.006
0.08 ±0.000
0.47 ±0.021
0.44 ±0.006
1.22 ±0.092
0.02 ±0.000
±0.030
Total Inorganic
TRW Plasma Ash
0.71 ±0.011
1.25 ±0,015
1.59 ±0.015
1.49 ±0.015
0.40 ±0.036
0.96 ±0.006
1.20 ±0.010
1.19 ±0.011
3.33 ±0.040
2.52 ±0.035
40.023
Extraction performed by ASTM 02492; both analysis were performed on same solution.
ZThe proposed ASTM Atomic Absorption procedure MBS used.
3ASTM D2492.
-------
TABLE 17. TOTAL INORGANIC SULFUR COMPARISON1
Coal
Old Ben #21
Old Ben #26
Inland Peabody
Martinka
' E-Seam
C-Prime
Mathies
Lucas
Muskingum
| Tailings from
Central Ohio Coal Co.
Pooled Standard
Deviation
ASTM Titration2
0.40
0.81
1.32
1.28
0.33
0.82
1.04
1.11
3.09
1.89
±0.059
ASTM AA3
0.56
0.93
1.41
1.45
0.42
0.98
1.13
1.26
3.64
1.94
±0.078
TRW Plasma
0.71
1.25
1.59
1.49
0.40
0.96
1.20
1,19
3". 33
2.52
±0.023
1. Sum of sulfate and pyritic sulfur for the ASTM methods and
determined directly in the plasma ashing method.
2. ASTM sulfate sulfur plus pyritic sulfur determined by titration
of pyritic Iron.
3. ASTM sulfate sulfur plus pyritic sulfur determined by the
proposed ASTM procedure for determination of iron by atomic
absorption.
108
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TABLE 18. ORGANIC SULFUR
Coal
Old Ben #21
Old Ben #26
Inland Peabody
', Martinka
i
i
! E-Seam
(
i C- Prime
Mathies
Lucas
Muskingum
Tailings from
Central Ohio Coal Co.
Pooled Standard Deviation
ASTM
i
Titration
0.71
1.45
1.92
0.31
0.71
0.70
0.56
0.59
2.62
1.39
±0.058
AA
0.55
1.33
1.83
0.14
0.62
0.54
0.47
0.44
2.07
1.34
±0.085
TRW
Plasma
0.40
1.01
1.65
0.10
0.64
0.56
0.40
0.51
2.38
0.76
±0.041
109
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precise. The principal deviations in the TRW method are the use of the
less sensitive iron line at 244.0 nm and the omission of lanthanum as a
background suppressant. These analyses, performed 1n triplicate, are
presented in Table 19. The following observations can be made upon
examining this table.
• Sulfate sulfur values are comparable between methods for the
Appalachian coals. (The single exception is the tailings
sample.) The eastern interior coals all exhibit a higher
sulfate content using the plasma procedure. From these
results it appears that not only is frambodial pyrite diffi-
cult to extract using the ASTM procedure applied to whole
coal but also the frambodial sulfate equivalent.
• Plasma ash pyritic sulfur was determined using a TRW atomic
absorption iron procedure which is substantially different
than the ASTM procedure. The pooled standard deviation of
the TRW procedure was calculated at +0.021 as compared to
+0.068 for the ASTM procedure. This shows a substantial
improvement in precision over the ASTM procedure.
• Comparison of pyritic sulfur values is seen to follow the
postulated trend with the Eastern interior coals (with the
exception of Old Ben #21) exhibiting a higher plasma pyritic
content than the ASTM values. Four of the Appalachian coals
show excellent agreement in pyritic sulfur comparison. The
Martinka, Lucas and Muskingum coals show some deviation
from expected values. The reason for this poor comparison
is unknown.
• The last three columns of Table 19 compare the total inorganic
sulfur values from each of the three techniques used. Com-
parison of these values shows the expected trend, i.e., high
total inorganic values for Eastern Interior coals using the
plasma procedures and agreement in values for Appalachian
coals (except the tailings sample). A least squares linear
regression analysis was performed to compare the total
inorganic values obtained using the two plasma procedures.
This results in a correlation coefficient of 0.992, a slope
of 1.03 and an intercept of -0.028 showing the excellent
agreement between the two methods.
t The double analysis required for inorganic speciation results
in a change in precision from +0.023 to +0.042. Thus, the
most precise value for organic sulfur is obtained when a
single total inorganic sulfur analysis is used.
110
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TABLE 19. COMPARISON OF INORGANIC SPECIATION METHODS
Coal
Old Ben 21
Old Ben 26
Inland Peabody
Marti nka
E-Seam
C-Pr1me
Mathies
Lacas
MusMngum
Tailings
Pooled Std. Dev.
Sulfate Sulfur
ASTM
0.08 ±0.000
0,16 ±0.006
0.38 ±0.012
0.12 ±0.006
0.08 ±0.006
0.08 ±0.000
0.47 ±0.021
0.44 ±0.006
1.22 ±0.092
0.02 ±0.010
±0.030
Plasma
0.22 ±0.015
0.29 ±0.064
0,53 ±0.074
0.23 ±0.002
0,10 ±0.006
0.16 ±0.009
0.59 ±0.028
0.47 ±0.013
1 .25 ±0.040
0.44 ±0.020
±0.036
Pyritlc Sulfur (AA)
ASTM(AA)
0,48 ±0.066
0.77 ±0,000
1,03 ±0,006
1.33 ±0.130
0.38 ±0,006
0,90 ±0.007
0.66 ±0.006
0.82 ±0.006
2.42 ±0.040
1.92 ±0.170
±0.068
Plasma
0.41 ±0.013
0.91 ±0.010
1.17 ±0.024
1.12 ±0.002
0.27 ±0f004
0.87 ±0.017
0,57 ±0.011
0.96 ±0.040
2.20 ±0,041
2.04 ±0.000
±0.021
Total Inorganic Sulfur
ASTM1
0.56
0.93
1.41
1.45
0.42
0.98
1.13
1.26
3.64
1.94
±0.078
1 2
Plasma
0.71 ±0.011
1.25 ±0.015
1.59 ±0.015
1.49 ±0.015
0.40 ±0.036
0.96 ±0.006
1.20 ±0.010
1.19 ±0.011
3.33 ±0.040
2.52 ±0.035
±0.023
Plasma
0.63
1.20
1.70
1.35
0.37
1.03
1.16
1.43
3.45
2.48
±0.042
Sum of sulfate and pyrltlc sulfur
"HN03 extraction and gravimetric sulfate
-------
Sulfur Speciatlon in Liquified Coal Samples —
The present state of the art for coal analysis is seriously deficient
for the sulfur forms analysis of samples in which the coal matrix has been
altered significantly. This includes coke, gasified or partially gasified
coal, and liquified coal samples. The problem lies in the fact that the
ASTM procedure relies on the assumption that the inorganic sulfur species
can be extracted from the surface or by penetration of the acid into the
coal pores. Thus, anything that changes the coal structure significantly
alters the basis for this assumption. Liquified coal is the worst case
because coal is changed into a liquid and as a result the inorganic species
are coated with a hydrophobic liquid. The plasma ashing procedure avoids
this problem by removing the organic matrix before any analysis is
attempted. In the experiments listed below no inorganic speciation was
attempted because the inorganic sulfur was expected to be very low and the
conditions under which the product was produced were expected to convert
all inorganic sulfur into iron sulfide, FeS.
Four liquified coal samples obtained from Sandia Corp. of Albuquerque,
New Mexico, were analyzed for total, inorganic, and organic (by difference)
sulfur content using the oxygen plasma analytical procedure, with a slight
modification to minimize frothing of volatile components of these samples.
The results summarized in Table 20 show that in addition to removal of
inorganic sulfur by filtration, substantial additional sulfur was removed
in the 430°C filtered runs. The Illinois No. 6 results show that this
method is capable of a high degree of precision, while the poor precision
on the Kentucky No. 11 results probably indicates a degree of nonhomogeneity
in the sample as the result of settling. It should be noted that this analysis
indicates that both forms of sulfur varied under the experimental conditions
employed. The form of sulfur that changes the most can be very important from
an engineering point of view in order to avoid an expensive design modification
that may not be appropriate. This type of information is not presently
available from ASTM or other procedures.
Direct Organic Sulfur Determination by Plasma Ashing and SO Sorption —
/\
One of the objectives of this task was to investigate the feasibility of
determining organic sulfur directly. Development of such a system would
be advantageous in that (1) a direct sulfur mass balance would be possible,
112
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TABLE 20. SULFUR FORMS ANALYSIS OF LIQUIFIED COAL
Sample*
Description
Illinois No. 6
Filtered
Unfiltered
Kentucky No. 11
Filtered
Unfiltered
Sulfur Analysis, % w/w
Total1
-0.52 ±0.010
0.75 ±0.023
0.67 ±0.112
1.11 ±0.136
2
Total Inorganic
0.02 ±0.007
0.10 ±0.014
0.02 ±0.014
0.06 ±0.021
Organic (by difference)
0.50 ±0.012
0.65 ±0.027
0.65+0.187
1.05+0.138
Ash Content
2.9, 2.6
6.2, 9.0
3.6, 5.7
5.4, 7.6
1
Average triplicate determinations
"Average of duplicates
Runs done at 430°C
*Runs done at 410°C
-------
(2) the necessity of performing an Eschka total sulfur and inorganic
sulfur analysis would be eliminated, (3) direct determination would
eliminate all the cumulative extraction and analysis errors, increasing
the precision and accuracy of the analysis, and (4) if all four sulfur
analyses (total, sulfate, pyritic, and organic) were performed directly,
an error analysis of the individual analysis would be possible.
The experimentation was based on the fact that organo sulfur compounds
contained in the coal matrix are converted into SOX during the oxygen plasma
decomposition. The preferred way of measurement is the use of solid sorbent
because of the time for decomposition, vacuum conditions, and presence of ,
oxygen and ozone in the exit gases. Based on data in current literature,
NaxC03, NaHCOg, NH.CCU, KOH, CaO and KMnO. deposited on silica gel and
molecular sieve 13x were selected for evaluation.
The results of 20 experimental runs are shown in Table 21. In all the
experiments, 17 to 41 percent of the added SCL was found retained within
the reactor chamber of the plasma asher. Because of the physical configuration
of the instrument, not all of the internal surfaces could be cleaned;
therefore, the reported total values could be low by an unknown and possibly
varying amount. The sorption of SO species on the chamber walls was unexpected
J\
and the mechanism is unexplained at this time. It is felt that the problem can
be circumvented. Using a different reactor design in smaller removable
chambers (for ease of cleaning) and placing the sorbent canisters either
within or directly' behind the reactor chambers would eliminate sorption
sites which cannot be cleaned without completely dismantling the instrument.
As redesign and fabrication were outside the scope of the task, further
experimentation was discontinued.
2.8.4 Conclusions and Recommendations
Conclusions--
A new technique for sulfur forms analysis has been developed in
response to a long term need by the coal cleaning commmunity for a more
accurate and precise procedure. In this method, low temperature oxygen
plasma ashing is used to selectively remove the organic matrix so that
inorganic sulfur can be extracted and analyzed without interferences
associated with the organic matrix. The inorganic sulfur can be analyzed
114
-------
TABLE 21. EVALUATION OF SOLID SORBENTS FOR SO., SORPTION UNDER PLASMA CONDITIONS
Sorbent System (mM)
Test
Number
1
2
3
4
5
6
7
8
9
10
11
12
Temperature
25°C
25°C
25°C
25°C
25°C
100°C
100°C
100°C
100°C
25°C
25°c
25°C
KMn04
•*
12
6
6
-
4.
4
10
-
KOH
13
•
6
m
26
4
•t
-
9
13X mole sieve
16/30 mesh
13X mole sieve
30/50 mesh
13X mole sieve
30/50 mesh
rerun
% Recovery
Reactor
Chamber
30
13
41
23
23
13
24
28
17
21
17
21
Sorbent
15
32
14
67
40
21
23
20
23
42
71
87
Total
45
45
55
90
63
34
47
48
40
63
88
108
(71
(Continued)
-------
TABLE 21. (Continued")
Sorbent System mM
Test
Number
13
14
15
16
17
18
19
.20
&
Temperature
c
25
25
25
100
25
25
100
25
KMn04
6
3
-
-
-
-
-
NaOH
10
10
-
-
10
-
-
NH VO,,
4 3
-
-
-
-
-
5
5
CaO
-
~
148
167
-
-
-
Activated Silica Gel Double Trap
40/80 mesh • i
% Recovery
Reactor
Chamber
34
37
36
23
33
20
41
36*
Sorbent
10
14 -
18
39
15
6
18
15*
Total
44
51
54
62
48
26
59
51*
Total of both traps
-------
for sulfur forms by a modified ASTM technique or total inorganic sulfur
by a highly accurate BaS04 gravimetric procedure. Specific findings are
listed below.
• Plasma ashing is greater than 99% specific to the organic
?acn2kts ^ cy se.Parate oxidation studies on FeS?(pyrite),
FeS, PbS, and ZnS. The converted sulfide minerals are oxi-
dized to sulfate. Thus, sulfur does not leave the system.
• Alkaline components such as CaCO-, or CaO do not retain orqanic
sulfur even when present at the 6% w/w level.
• The presence of iron and large amounts of nitrate does not
interfere with the BaS04 procedure for total inorganic sulfur.
The standard procedure to remove these possible interferences
results in reduced recoveries and an increase in the variance.
• The pH in the BaSOd precipitation must be adjusted to 1 to
avoid excessive solubilization of 83504. A PH greater than 1
can result in the precipitation of iron in certain cases.
• Sulfur forms analysis can be made on liquified coal which can-
not be analyzed by the ASTM procedure.
A detailed examination of the precision and accuracy of the proposed
method with the ASTM D2492, the proposed ASTM atomic absorption (AA)
modification to D2492, the TRW AA method, the Leco combustion method for
total sulfur, and the new plasma ashing method has shown that:
• Total inorganic sulfur can be determined with a precision of
+0.02% as compared to +0.05-0.08% for the ASTM procedure.
• The precision for proposed ASTM AA modifications of the ASTM
D2492 for pyritic iron is 0.06-0.7% as compared to 0.01-0.02%
for the TRW-AA procedure. The TRW method uses a less sensi-
time iron line and includes background correction rather than
background suppressing additives.
• The Leco combustion method gives results equivalent to the
Eschka method but with a reduction in precision from +0.02-
0.03% to +0.06%.
• Discrepancies between the actual values obtained by the ASTM
method and the plasma ashing method have been resolved in
favor of the plasma ashing method.
t Agreement between the ASTM-AA method and especially the
TRW-AA method is generally better than with the ASTM D2
117
-------
The feasibility of a direct organic sulfur analysis by plasma oxida-
tion with subsequent trapping of the organic SOX species on solid sorbents
placed in the exit port of the plasma reaction chamber has also been
demonstrated.
Recommendations--
The following recommendations are made:
• The oxygen plasma coal sulfur forms analysis procedure should
be further tested under round robin conditions to determine
variability between laboratories.
t A larger cross section of coal regions and seams should be
analyzed in replicate with results compared to ASTM D2492.
t Additional liquified coal samples, and samples obtained from
other types of coal desulfurization systems should be analyzed
by both the plasma and ASTM procedure (where applicable) and
results compared.
• A separate program should be initiated to develop the direct
determination of organic sulfur using the plasma technique
and the concept of solid sorbents. The effort should be scoped
to include hardware as well as methods development/optimization
and also investigation of other organically bound species such
as nitrogen and halogens.
118
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2.9 TASK 12 CONTINUOUS FLOW IMPACTOR
2.9.1 Objective
The purpose of the task was to determine the feasibility of an Tmpactor
in which the collection "surface" is the interface between two opposing
jets. The concept was first suggested by TRW in the "Particulate Sampling
and Support" proposal to PMB in 1975.
2.9.2 Approach
When the task started, the concept was solely that -a concept. No
analytical or experimental work had been done to determine feasibility.
The task was initiated with a brief literature search and analytical effort
to determine a key property of the device - stability of the interface
between two impinging jets. When evidence of good stability properties was
found, we proceeded with design, construction, and testing of a laboratory
instrument. Results of the test work were positive, showing separation
efficiencies similar to commercially available impactors. A draft final
report was then issued.
2.9.3 Technical Discussion
All of the primary task objectives were accomplished. Test hardware
was fabricated after an initial literature search indicated feasibility of
the concept. Particle separation testing showed good correlation between
the calculated and measured 50 percent cutoff points, which showed that the
device is functionally similar to a standard impactor. Preliminary design
work showed that it will be reasonable to integrate multistage hardware
into a probe capable of being inserted through a standard four-inch pipe
nipple, with an optical monitoring subsystem on each of five output streams.
Important questions to be answered during further development deal with
instrument accuracy, cost, reliability, and handling characteristics.
Basic proof-of-principie, including demonstration of a field acceptable
hardware concept, has been accomplished.
119
-------
Luna's work was very helpful in providing a basic understanding of
the stability of impinging gas jets. Because of the projected use for the
continuous flow impactor, process stream sampling, our hardware configura-
tion differed significantly from Luna's. It was one of these differences -
lack of active control over the individual inlet flowrates, which was the
source of the major flow instability observed early in the test program.
This instability was the single largest surprise received during testing,
although the probability of its occurrence is obvious in retrospect.
Particle separation testing went smoothly once all the equipment was
put in working order and the test setup was finalized. There was a signifi-
cant schedule loss due to failure of the first particle counter use — all
data were taken using a second counter. The particle generator operation
was consistent and reasonably trouble free. The main difficulty associated
with its use was a need to change solution strengths relatively often to
cover a range of particle sizes.
The separation test data are considered good for a first effort on
a new type of device. Explanations of data trends suggest that the
actual performance of the device was better than the test data show,
due to less than optimum placement of the sampling tube. If subsequent
testing shows this to be the case, as we believe it will, then the con-
tinuous flow impactor will have performance capabilities, in terms of
sharpness of cutoff, at least comparable to presently available staged
impactors. This capability, in addition to the basic advantage of con-
tinuous operation, make the device well worthy of further development.
The final subtask was a brief study to ensure that the instrument
could be packaged for in situ monitoring, and to investigate the use of
optical techniques to monitor the output streams. Based primarily on
laboratory test data, the current opinion is that packaging impactor
modules and optics in a probe to fit a standard four-inch pipe nipple will
not present a problem, nor will it have a notably adverse affect on
120
-------
accuracy. Loss of accuracy during extraction process would likely be
greater than that which will occur due to compromises required to obtain
an in situ instrument.
The next step in instrument development should be a very brief test
program to confirm the current thoughts on instrument performance. This
would consist of such tasks as oxygen analyzer testing plus a small amount
of particle separation testing with proper placement of the sampling tube.
This testing should be followed by a demonstration of the optical subsystem,
which could be done mainly with available in-house components. The follow-
ing stage would be development of a field usable prototype. The simplicity
of the continuous flow impactor components and assembly, its coordination
of many of the attractive features of traditional impactors and optical
particle counters while avoiding their primary drawbacks, and its potential
usefulness as a diagnostic and monitoring tool, all strongly recommend that
the effort begun during this task should be continued.
2.9.4 Summary and Recpmmendatlons
Within the scope of the current program, the next logical step is to
perform a small amount of laboratory testing to confirm that the present
thoughts on instrument operation are correct, and to obtain proper
calibration data. This should be followed by construction of an in-situ
two-stage device with collection on filters to verify the design of a
field unit and to demonstrate acceptable operation of a staged unit. We
can then proceed with development of the more complex optical system for
the continuous monitoring configuration in a future contract.
It was concluded that:
§ The concept of using two impinging jets for the purpose of inertial
particle separation has been shown to be technically viable.
• In addition, preliminary design studies indicate that a staged
impactor can easily be integrated into a sampling probe to perform
In situ particulate size distribution measurements.
• Feasibility of a simple optical system compatible with the in situ
sampling hardware has been shown analytically.
. The continous flow impactor has a potentially greater accuracy
capability than standard impactors since it in^"5nment
traditional problems of particle bounce and reentrainment.
121
-------
• Potential applications for the continuous flow impactor include
control device evaluation, continuous monitoring of particulate
emission for regulatory purposes, and collection of particles in
an inert atmosphere to quench chemical reactions.
• A basic understanding of these continuous flow impactor operational
characteristics has been attained. This can serve as a background
for development of a commercially viable instrument.
Based on these findings TRW recommends that:
• All small test programs should be carried out using the existing.
laboratory test unit in order to fully confirm the present
understanding of the device's operational characteristics.
t A second small test program should be initiated to demonstrate
the selected optical monitoring technique.
t The demonstrated performance and potential usefulness of the
continuous flow impactor argue strongly for development and
testing of a field worthy prototype instrument. This development
should be pursued.
122
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2.10 TASK 13 UNDERSTANDING S03 DATA
2.10.1 Objective
The objective of this task was to develop a stack saving procedure
for the measurement of the mass emission rate of sulfur trioxide within
a precision of £10% but not to exceed +20%.
2.10.2 Approach
This task consisted of subtasks devoted to the selection, laboratory
and field testing of the S03 sampling train. The selection subtask con-
sisted of a literature survey to find and evaluate potential S03 sampling
systems. The procedures found were evaluated based on:
• Selectivity
• Sensitivity
• Accuracy
• Precision
• Ease of Operation
• Reliability
Once the candidate procedure was selected, laboratory testing was
initiated.
The laboratory testing consisted of generating known streams of
HpS04 in the presence of varying amounts of S02, 02, and H20. In addition,
the' recovery of H2S04 was studied when flyash was placed on the quartz
filter.
After the operation of the S03 sampling system was optimized in the
laboratory, field tests were made at the Shawnee Test Facility in Paducah,
Kentucky. These tests were conducted at the inlet and outlet of the FGD
units at Paducah to determine the field utility of the equipment and
procedures developed.
2.10.3 Technical Discussion
Literature Survey—
The systems used to quantify H2S04 are based on selective absorption or
controlled condensation. Selective absorption uses an impinger with 80%
123
-------
isopropyl alcohol to collect the S03 and to pass the S02. The S02 is
collected in a back-up impinger of 3% H202. This method is currently
the basis of the EPA Method 8, a compliance test for sulfuric acid mist.
The major problem with this procedure is the lack of a pre-filter to
effectively prevent particulate matter from reaching the IPA impinger.
The particulate matter in the impinger can act either as a direct inter-
ferent by contributing S07 from sulfate salts, or as an indirect interferent
by catalyzing the S(L to S04 oxidation in the liquid phase through action
of trace elements like Fe, Cu or V.
The controlled condensation approach was first proposed by Knol (12)
and has been further developed by Goksoyr and Ross (13). The Goksoyr-
Ross system is the basis of an ASTM procedure for SO (14). In the con-
X
trolled condensation approach, S03 is separated from the gas stream by
cooling the temperature of the flue gas below the dew point for SCk but
above the dew point of H20. The resulting aerosol is either collected
on the walls of the cooling coil or on a back-up frit. Investigators
(15, 16) studying controlled condensation in the laboratory have found the
precision and accuracy to be +6% in synthetic gas streams.
On the basis of this prior work, the controlled condensation coil was
selected for additional study.
Laboratory Interference Studies --
A sulfuric acid generator based on the design of Lisle and Sensen-
baugh (15) was modified and used to provide test gas streams of varying
H2S04, H20, S02> 02, and N2. The generator was 12 mm OD quartz tube with
a side arm injection port to introduce liquids onto a heated coarse quartz
frit (Figure 22). The evaporator was wrapped with heating tape to !
vaporize solutions of H2S04 that were metered into the evaporator using a
syringe pump. Gas out temperatures ranged from 300°C-350CC. Adjusting the
H2S04 solution strength and flow produced a range of H2SO. and water
concentrations. The addition of the extra coarse quartz frit, ensured
an even flow and evaporation of the H2S04 solution. The original design
tended to produce bursts of steam as the solution droplets hit the hot
zone of the evaporator.
124
-------
BACK PRESSURE GAUGE
ro
tn
S02 (25%)
-1 II K
o
-til
SYRINGE PUMP
TEFLON TUBE
COARSE QUARTZ FRIT
EVAPORATOR
. HEATING MANTLE
TO IMPINGERS
AND PUMP
CONTROLLED
CONDENSATION
COIL
"PRELIMINARY EXPERIMENTS RAN WITH ASTM D-3226-73T
QUARTZ WOOL PLUG FILTER.
Figure 22. Experimental Apparatus
-------
The initial set of experiments sought to optimize H2S04 recovery by
changing the condenser temperature. In the course of these tests, in-
formation was also obtained on H2$04 absorption characteristics at different
temperatures. The tests showed that:
• Temperatures at or below 130°C were not adequate to prevent
H2S04 fallout in the probe or quartz wool section.
• Sulfuric acid collection efficiency over wide ranges of per-
centage moisture (4%-8%), H2S04 concentration (10-20 ppm), and
controlled condensation condenser (CCC) temperature (35°C-60°C)
was 95% with a coefficient of variance +6.7%.
Concurrent with the above studies, field tests of the controlled
condensation system conducted under Task 2 indicated significant portions
(30%) of the H2SO. were being collected on the quartz wool plug placed in
the probe to filter the flue gas particulate matter. At the same time, it
was noted that fine particulate matter was passing through quartz wool and
slowly plugging the CCC frit.
To solve these problems, an all-quartz filter holder (see Figure 23)
was designed and built. The filter holder was fabricated by placing a
coarse quartz frit in the female half of a standard taper joint and adding
a short extension to the male joint to form a seal when a filter pad made
out of Pall flex Tissuequartz was placed on the frit. Heating was
accomplished using a Glass-Col heating mantle, and outlet gas temperatures
were monitored with a thermocouple placed directly behind the frit.
The initial system checkout showed that gas temperatures above 250°C were
easily maintained. Tests were continued with this filter and it was
found that:
• New filter design proved to be inert to HpSO. and showed high
recoveries (92% - C.V. ±3.3%) for H2S04 concentrations from 1 to
28 ppm H2S04-
• No H2S04 was seen on filter when gas-out temperatures were above
250°C.
t Within the detection limits of the analysis scheme, no H2SO.
was found when S02 and 02 were passed through the filter.
126
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18/9
BALL
SPRING
ATTACHMENT
HOOKS
TISSUE QUARTZ
FILTER
THERMOCOUPLE
/ WELL
ro
•xi
18/9
SOCKET
STANDARD
TAPER QUARTZ
40/50
SEAL
EXTENTION
TO STD.
TAPER JOINT
EXTRA COARSE
QUARTZ FRIT
Figure 23. Quartz Filter Holder
-------
In addition to these tests where gaseous components were varied, known
amounts of flyash from the Shawnee Power Plant were placed on the quartz
filter and H2$04 recovery tests initiated. Table 22 summarizes the
results.
i TABLE 22. RESULTS OF FLYASH TESTS
Equivalent
Fly Ash
(g/m3)
1.3
1.3
1.3
0.13
ppm
H2S04
9
12
11
11
°2
8
8
8
8
ppm
so2
0
650
5300
700
Percentage H2SO, Found
Filter
15
14
11
0
CCC
81
86
87
89
Total
96
100
98
89
As Table 22 shows, reduced amounts of H^SO. were recovered in the
coil, though the HgSO^ mass balance (obtained through titrating the fly-
ash and expressing any alkalinity change in milliequivalents) was quite
good.
Field Tests --
Extensive field trials with the CCS were conducted on a pilot FGD
located at a TVA coal-fired power plant in Paducah, Kentucky. This
pilot facility is a prototype Flue Gas Desulfurization (FGD) Unit utilizing
wet lime or limestone SOp scrubbing chemistry. The feed for the unit is a
slipstream taken from the number 10 boiler either prior to or after the
ESP. The inlet flue gas mass particulate loadings were approximately
•3 3 3
11.4 g/nr3, 0.17 g/m , and 0.06 g/m , depending on whether the gas was
obtained directly from the boiler, from the outlet of the ESP, or from the
outlet of the FGD unit, respectively. Sulfur dioxide concentrations varied
from 2,000 to 4,000 ppm at the inlet and approximately 400 to 800 ppm exit-
Jig the unit. Gas temperatures and moisture percent varied from 165°C to
121°C and 8% to 17%, respectively, across the FGD unit.
128
-------
The field test consisted of simultaneous inlet/outlet H,S(L measure-
ments across the FGD unit taken over a period of approximately 5o days The
average inlet H2S04 value was 8.3 ppm (ranged from 0.4-24.8 ppm) while the
average outlet value was 3.1 ppm (ranged from 0.0 to 13.9 ppm). The coeffi-
cient of variance was +66.3%.
Since the inlet^^ coefficient of variance (CVT) represents the
sum, [(CVT) = [(CVS) + (CVM) ] V2] of source fluctuation (CV$) and method
error (CVM), the source fluctuation can be estimated by assigning a co-
efficient of variance to the field CCS. This coefficient of variance
reflects errors in reading temperature and pressures, accuracy of leak
rates, as well as rinsing recovery or titration errors which might affect
the ultimate calculation of the H2S04 concentrations. It is estimated that
the field accuracy of the CCS is +11%, and thus the coefficient of vari-
ance of the source is +65%. This high CV$ implies that to obtain a good
average H2S04 value from this type of source, it will be necessary to take
a large number of samples spread out over a period of days.
2.10.4 Summary of Results and Recommendations
As a result of this test program, these facts were learned about the
CCS:
1) The average laboratory coefficient of variance was +7%.
2) Oxidation of SO- did not occur at the recommended filter holder
temperatures with 4000 ppm S02 and 8% 02. Also fly ash from a
coal-fired utility placed on the filter did not have a catalytic
effect under those conditions.
3) When 0.3 g of fly ash equivalent to 1.3 g/m3 was placed on the
surface of the filter, the amount of HoS04 recovered was reduced
by M2% when a gas stream containing 10 ppm of ^504 was passed
through the system.
4) There appears to be a slight difference between H2SOft recovery in
the presence of fly ash with and without S02 but with the data
available at this time it is impossible to predict its exact
effect.
5) The coefficient of variance of the H2S04 output at the coal-
fired utility tested was estimated to be +6W.
129
-------
It is recommended that additional studies be performed that will refine
the current design of a controlled condensation system. Work is also
necessary to develop an automated version of the controlled condensation
system so that studies on the variable nature of S03 emissions can be re-
lated to changes in process operating conditions.
130
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2.11 TASK 14 KVB TEST SUPPORT
2.11.1 Objective
In July 1976, KVB Engineering conducted a Level 1 sampling effort in
accordance with the draft copy of the EPA-IERL Level 1 Procedures Manual,
on an experimental coal-fired boiler at the KVB facility in Tustin, Califor-
nia. The specific objectives of this task were to support KVB by:
1) Determining the adequacy of the sampling test as a
Level 1 Environmental Assessment in accordance with the
draft copy of the Level 1 Procedures Manual.
2} Answering any questions from KVB which might arise concerning
the requirements of the draft IERL Procedures Manual.
3) Analyzing samples in accordance with the Level 1 procedures
in parallel with KVB's analytical subcontractor, Calspan.
2.11.2 Approach
Prior to the sampling activity, consultations were held with KVB to
answer questions and assist in formulating the test plan. TRW personnel
were also present during the boiler testing to continue the process of
advising and supporting KVB. Samples taken from the coal-fired boiler
control device system and all parts of the SASS train were then distributed
in equal portions to Calspan and TRW Laboratories for analysis.
The sampling effort was conducted in accordance with the IERL-RTP
Procedures Manual for Level 1 Environmental Assessments.
In accordance with the EPA Technical Directive, the analysis format
was structured after the Level 1 procedures only where this approach was
compatible with the Calspan analysis plan. Reasonable adherence to the
Calspan analysis format was necessary in order to:
1) Provide a collaborative data base among KVB/TRW/Calspan, and
2) To attempt to provide a data base accurate enough to establish
a ±25 percent balance closure as called for in the task
technical directive.
131
-------
For these reasons, strict adherence to the Level 1 analysis procedures was;
not observed in all cases. As required by the IERL-RTP Level 1 Procedures
Manual, memoranda delineating specific Level 1 analysis deviations were
submitted to EPA IERL-RTP prior to the initiation of any analysis activities.
2.11.3 Technical Discussion
During the testing, KVB's experimental boiler was fired on Pittsburgh
#8 seam coal at an approximate rate of 93 kg/hr. A 30 DSCM SASS sample
was collected at an average of 93 percent isokinetic. A total of 77 grams
of particulate were collected in the SASS cyclones and filter, yielding
ample amounts of material for the chemical analyses. Samples were also
taken of the process solids (i.e., furnace slag, fire tube ash, lower stack
ash, duct ash, and baghouse ash) and feed coal in order to be able to
perform a mass balance. Analysis of these samples was performed according
to the Level 1 procedures with the addition of specific AAS determinations
for Se, Cd, Pb, and V. These elements were added to provide quantitative
data points for the mass balance examination.
The final report prepared under this task examined problems encountered
with Level 1 sampling and analysis procedures and presented conclusions
and recommendations where appropriate. Elemental analysis results were
tabulated in detail, and spark source mass spectrometry, atomic absorption,
and colorimetric values were cross-referenced to provide data comparisons.
Final results were presented as mass balance closures from the standpoint
of both coal feed and baghouse as they relate to the SASS sample catch.
Level 1 organic analyses were also performed on all samples with extended
LC/LRMS tests to increase accuracy and also to aid in evaluating the
procedure. Photomicrographs of the filters were presented along with
general observations concerning the entrained particulate.
2.11.4 Summary of Results and Recommendations
The emphasis in the use of the data generated under this task was on
the mass balance. In this regard the SASS was an effective unit performing
well within the Level 1 error limits of a factor of 2-3. The cumulative
percentage differences between the SSMS values and the special case analyses
132
-------
values for total quantities trapped in the SASS train, and for the
theoretical ideals for baghouse and coal feed, all showed excellent
reproducibility in terms of precision.
As with all trace element analyses, many elements could not be
quantified due to detection limit levels. This inherent problem appeared,
however, to be increased by the Parr bomb preparation procedure required
for all Level 1 samples by the Level 1 methods. This was attributed to
any one or all of the following three conditions:
1) Incomplete combustion of the samples, particularly
those consisting of primarily inorganic matrices.
2) Small quantity of sample used for ashing.
3) Dilution of the Parr solution by bringing to a
standard volume (100 mL) in volumetric flasks.
These reductions in analytical sample quantities could be avoided or
minimized by not bombing inorganic samples (for which the combustion is
unnecessary) and combining sequential combustions to provide more
concentrated solutions.
Another notable conclusion of this task was that the SSMS technique
is more reliable than the atomic absorption or colorimetric methods for
As, Hg, Sb since in all cases concentrations were above the detection levels
for SSMS, while in most cases concentrations were below the detection levels
for the atomic absorption and colorimetric methods.
This study also showed that trace elements are condensed throughout
the XAD-2 module. This observation resulted in the recommendation that
a nitric acid rinse step should be included in the XAD-2 module sample
recovery procedures.
133
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2.12 TASK 21 TEST DATA MODELING
2.12.1 Objective
The objective of this task was to develop test (computer) models which
permits a chemist to evaluate, a priori, the variation in his test results
using assumptions based on his experience.
2,12,2 Approach
The computer program (see attachments) answers the following
questions:
1) A chemist will take either 2 or 3 samples (replications) for
a particular test. What kind of results can he expect? To
evaluate his results he can input either a ± range or the
actual a along with the nominals.
The first example, Attachment A, provides results of eleven
tests of two samples each when sampling from a population
with a nominal value of 45 and a a of 1-.74. For this stan-
dard deviation, the coefficient of variation is only CV =
1.74/45(100) =3.8%. Still the scatter in percent range is
quite variable.
The second example, Attachment B, provides the same type of
results except three samples per test will be analyzed.
Here the nominal value is 77 and the variation was provided as a
percent range of 21.8. The reported percent ranges are quite
variable.
2) The chemist has three populations of known mean and standard
deviation (or ± percent range) values. He wishes to know
the mean and standard deviation values of a new population
defined as sums of three samples, one from each of the three
original populations. Replicated samples from this new popu-
lation should be available to enable the chemist to examine
the effect on the percent ranges (±) as a consequence of the
original population specifications.
The computer program accepts known mean and standard deviation
(or ± percent range) values of the three original populations
and using a pseudo-random number generator produces samples
from a normal distribution based on the given parameters.
The sum of one sample from each of these populations consti-
tutes a sample of the new population. Either two or three
samples per test are allowed and as many tests as desired may
be requested. Both sample mean and sigma, as well as the popu-
lation mean and sigma, are provided to enable the researcher
to compare the samples generated with the theoretical popu-
lation parameters. (See Attachment C.)
134
-------
Utilizing this program the chemist is able to specify one of
many sampling test plans, to examine the resulting test sam-
pling test plans, to examine the resulting test samples, and
to compare the test sample characteristics with those of the
population.
3) The chemist again has three populations of known mean and
standard deviation (or ± percent range) values. The popula-
tions are now comprised of the original unknown (or summation)
population and any two of the three originally known popula-
tions which define the summation population. The mean and
standard deviation values of the remaining third original
population (presently unknown) are now required. Replicated
samples for this remaining population should again be avail-
able to enable the researcher to examine the effect of the
given population parameters on the percent ranges (±).
The program accepts the known mean and standard deviation
values for the given populations. Using a pseudo-random num-
ber generator, samples from a normal distribution are pro-
duced based on the parameters for each of the given popula-
tions. The samples for the unknown population are produced
by subtracting from a summation population sample, one sample
from each of the first two populations. Either two or three
samples per test are allowed and as many tests as desired
may be requested. Both sample mean and sigma, as well as the
population mean and sigraa, are provided to enable the chemist
to compare the samples generated with the theoretical popula-
tion parameters. (Attachment D).
135
-------
TASK 21 - LISTINGS FOR PROGRAM "ROUTINE" AND ATTACHMENTS
FUNCTIONAL OUTLINE OF
PROGRAM "RANDOM"
(Usage described in task 21 write-up)
(Sample outputs presented in Attachment A and B of above)
READ INPUT. a.) NUMBER OF TESTS
b.) NUMBER OF SAMPLES/TEST, i.e., 2 OR 3
c.) NOMINAL VALUE FOR MEAN
d.) NOMINAL VALUE FOR SIGMA OR A PERCENT RANGE
e.) LAST RANDOM NUMBER USED BY RANDOM NUMBER GENERATOR
FOR EACH TEST
PRINT OUTPUT
TABLE
a.) OBTAIN EITHER 2 OR 3 NORMALLY RANDOM SAMPLES FROM
THE POPULATION DEFINED BY NOMINAL MEAN AND SIGMA/
OR PERCENT RANGE.
b.) CALCULATE THE MEAN, RANGE AND PERCENT RANGE (PLUS/MINUS)
OF SAMPLES OBTAINED.
a.) INDICATING TEST NUMBER, SAMPLES OBTAINED.
b.) MEAN, RANGE, AND PERCENT RANGE (PLUS/MINUS) OF
SAMPLES OBTAINED.
136
-------
PROGRAM RAMDnwtlMDuT, OUTPUT, TAPfc5,TAPE6)
DATA
REhlND 5
REWIND 6
DISPLAY *TYPF THC NQ. yF TtSTS*
ACCEPT MCASes
DISPLAY *TY»r TMr NUHBtP OF S AMPl tS /TEST, NQ. - 2 3R 3
ACC EP T T^(^
IFUOB .N^. ? .AND. 103 .ME. 3) IOB-3
GO TO
WRIT=(f>,->0)
A|1Ptt NUMBcR* t T?7, *wt AN* \ 36» *R ANGc*.
NG.*»T10,*l*,T19,*2*,T4<»,*PlUS/1IMUS*/)
GC TO ^n
WRITf (f>
NG.*»TIO»*1*»T19,*2*»T23,*3*»
A T53»*°LHS/MT*M'?*/)
90 DISPLAY *TYP= MnMiNAL VALUc FOR fFAK*
ACCEPT TM=AM
DISPLAY *TY»P 1 HP 2 PtSPLCTIVELY FOR SIGMA OR < RANGt IN«>UT*
ACCEPT IO»T
30
GO
2 DISPLAY *TYE>- MHMTNAL VALUs FJR
ACCf°T «?n
GC TO A
3 DISPLAY *TY»e < <>ANGc(fCTAL RANC-f/?)*
ACCENT
CALL GCTOC (^"JTA<>!:f;, 7hRANt)NU1»
ACC£»T(^>
DO 200 *-
I»0
XM6AN-0.0
XTDT-0.0
XMAX--XTN
DO 100 J"l»Tnn
137
-------
CALL FN«*NCLASTNUM,DEVlATt>
1-1*1
XTdT-xm+XTOT
IFWJ) .LT. y*IM) XMIN-X(J)
IF(X(J) .GT. XMAy) XMAX-X(J)
100 CDNT1NU1-
XHEAN-XTnT/PLnATCTOB)
WRITE(6*10) «,(XfL),L«l*iaB),XMFAN,RANGE*PRANGS
10 FORHATCIA^FQ.S)
ZOO CONTINU*
REWIND 5
DISPLAY (M L»«TNUH
REWIND 5
CALL R«»LPFf5MTA°e5,7HRANDNUM,7HJF667
-------
PROGRflH RflNOOmINPUT.OUTPUT.TflPE5.TflPE6J
DIMENSION X(31.CONST(2J
OflTfl CONST/1.128.1.693/
REMIND 5
REWIND 6
DISPLflY «TYPE THE NO. OF TESTS*
flCCEPT NCRSES
DISPLflY »TYPE THE NUMBER OF SRHPLES/TEST. N0.= 2 OR 3 ONLY.
__
FORMflTUTEST*.T9.«SflMPLE NUMBER.. T7.«HEfiN«T36.«RflNCE«.T44
..
PERCENT RflN&E«/« NO.*.T10.»1«.T19.»2».T44.»PLUS/HINUS*/1
139
-------
_4JL
FORHflT(«TEST«.T13.«SRMPLE NUMBER*.T36.*HERN*.T45.»RflNG£«.T53.
•PERCENT RRNGE*/* NO.«.T10.«l«.T19.*2*.T28."3*.
T53.*PLUS/HINUS"/)
90
DISPLRY »TYPE NOHINflL VflLUE FOR HERN*
flCCEPT ZMERN
DISPLRY »TYPE 1 OR 2 RESPECTIVELY FOR SICHR OR A RRNGC INPUT*
flCCEPT IOPT
FORHRT(R7)
GO TO{2.3).IOPT|
I
I PISPLflY «TYPE NOHINRL VflLUE FOR SIGtlfli
flCCEPT SD
fOO TO 4
IOISPLRY «TYPE ^ RflN&EtTOTRL
flCCEPT PCR
R=PCR«ZHERN«.02
SD=R/CONST(KKK)
a
CflLL G€TPF(SHTflPE5.7HRflNDNUH.7HJF66748)
[flCCEPT(S) LRSTNUR"]
_ _
< DO 200 K=l.NCflSE"s~y - - - > 4
140
-------
1
XMERN=0.0
XTOT=0.0
XMIN=1.0E06
XHflX=-XHIN
I
< DO 100 J=I.IOB >
I CflLL FNRN(LflSTNUn.DEVIflTE)
1 = 1*1
X(I)=ZMEflN+SD«OEVIflTE
XTOT=X(I)*XTOT
IF(X(J) .LT. XMIN)
•*
T
XHEflN=XTOT/FLOflT< IOB )
RflNGE=XMflX-XHIN
PRflNOE=RflNGE/( 0 .02*XMEflN )
WRITE! 6. 10) K.(X(L).L=l.IOB).XMEflN.RflNOE.PRflNCE
10
|FORhflT(t4.6F9.3) [
141
-------
200
I
CONTINUE |
REWIND 5
OISPLflY IS) LflSTNUM
REMIND 5
CflLL RPLPF(5HTflPE5.7HRflNDNUH.7HJF667481
142
-------
Attachment A
TYPE THE HD. OF TESTS
? 11
_TYPE THE NUMBER DF SRMPLES/TEST ,. MD.= £ DP 3 DMLY
'TYPE NDMINFU. VFILUE FDR riEfiri
? 45
TYPE 1 DR £ RESPECTIVELY PDR SIGMfi DR 5s RFlHGE INPUT
? 1
TYPE NDMIHFlL VFlLUE FDR SIGMFl
? 1.74
C LIST,TFlPE6
TEST SFIMPLE NUMBER
MD. 1 £
MEflM
RFlHGE
1
£
•-•>
o
4
5
6
7
8
9
10
11
45
46
44
44
44
4£
45
44
43
45
45
.£37
.178
.8£8
.9££
.7£1
.£08
-64£
.395
.639
.146
.917
47
49
46
47
47
47
44
45
44
45
46
.013
. 0£8
.807
.108
.003
.475
.716
.915
.78£
.£96
.800
46
47
45
46
45
44
45
45
44
45
46
.1£5
.603
.817
.015
.86£
.841
.179
.155
.£1.0
.££1
•-MTO
. •-'•_»'_'
1.776
£.851
1.979
£.186
£.£8£
5. £67
.9£6
1 ,5£0
1.143
.150
.88£
PERCENT RFlMGE
PLUS/MINUS
1 .9£5
£.994
£.160
£.375
£-488
5.873
1.0£5
1 .683
1 .£93
.166
143
-------
Attachment B
C LGD
TYPE THE HQ. OF TESTS
? 16
TYPE THE NUMBER DF SFlMPLES-'TEST j ND.= £ DP 3 ONLY
? 3
TYPE NDMINFtL VFlLUE FDR MEFlM
? 77
TYPE 1 DP £ RESPECTIVELY FDR SIGMFi DR ': PFlNGE IMPUT
? £
TYPE "; RFlNGE
? £1.8
C LIST!.TRPE6
TEST
MD.
SfiMPLE NUMBER
MEFlN RHNGE PERCENT RFlNGE
FLUS.'MINUS
i
.— ,
C.
3
4
5
6
7
8
9
10
11
1£
13
14
If
16
30.989
81 .095
64.664
86 . 037
97,18£
94.835
60.157
88.700
80.615
74.788
104.579
96.400
83.083
78.896
81.8£1
49 . 07£
68.073
96.980
93.688
8£.£66
87.578
83.84£
8£.160
55.831.
6£.766
91 .744
76.514
77.160
58.5E3
37.946
111.168
69.91£
86.691
96 . 1 78
8£.805
77.430
60.589
70.545
49.591
10£.££8
6£.595
100. £0£
78. 4 £9
59.34S
56.G03
95.89£
77.536
73.5£9
61.918
91 .418
80.386
81.911
81 .783
83 . 074
63.969
,-%.-, .-.e^-.
O C. • C. J •_'
68.658
88.911
86.508
77.636
66 . 0 36
70.911
90.175
64.171
55.701
15.885
£9.0£4
8.607
oo • --'9-^
£4. £90
3£.569
46.398
18.0£0
£5.414
£8.065
37 . 05£
£6.580
57.945
•7%O £ •?' 1
«.'-.• • O--' 1
£4.457
44.980
8.688
18.053
5.254
££.37£
14.6£0
£5.457
£8. £04
13.1£3
14.£9£
16. ££1
£3.86£
£0.1 £6
40.858
18 .648
19.056
144
-------
Attachment C
RX»I=GRPRfiN»G
TYPE 1 FDR TOTfiL PDPULfiTICN SDLN.
TYPE 2 FDR I MB IV PDPULflTION SDLN.
? 1
ORDER REQUIRED PflPflMETERS P< 1 > »Pf£> ,P<3> jP
DMITTIMG THE UNKNOWN PfiRRMETER
TYPE THE ND. DF TESTS
? 14
TYPE THE NUMBER DF SFiMPLES/TEST, ND.= £ DR 3 DMLY
? 3
TYPE MDMIMflL VflLUES FDR MEflN
? l£j£3.1 j.17,4
TYPE 1 DR £ RESPECTIVELY FDR SIGMfl DR * RflUGE INPUT
? 1
TYPE NDMINflL VflLUES FDR SIGMfl
C LIST»TflPE6
TEST SflMPLE NUMBER
MD. 1 £
MEftN RflNGE PERCENT RflNGE
PLUSXMINUS
1
•£
3
A
5
6
7
8
9
10
11
1£
13
14
45.859
49-719
58.759
56.751
51 .552
51 -483
59.491
51 .569
56. £79
50.899
49.4£1
5£.85£
51.055
50.634
54.41£
52.700
51 .586
54. 939 ~
53.50£
53.869
56.794
50.679
51 .£9£
50.734
55.193
56.884
50.079
51.118
59 . 1 05
44.80£
49-905
48.775
5£.591
53.470
44.645
54.079
57.898
56.544
57. £64
50.849
61.706
46.£6£
53.1£5
49 . 074
53.417
53.489
5£.548
5£.941
53.644
5£ . 1 09
55.156
5£.7£6
53.959
53.5£8
54. £80
49.338
13. £46
7.897
8.854
7.976
1.950
-£.386
14.846
3.399
6.607
5.811
7.84£
6.035
1 1 .6£7
4.856
1£.467
8.046
8. £88
7.456
1.855
£.£54
13.837
3.£6£
5.989
5.510
7. £67
5.638
10.710
4.9£1
SflMPLE MEflN = 5£.810
SflMFLE S"IGMfl p 3.79
PDPULflTIDN MEflN = 5£.500
PDPULflTION SIGMfl = 3.74
145
-------
Attachment D
LGD
TYPE 1 FDR TOTAL POPULRTION iDLN.
TYPE £ FDR INDIV PfJPULRTIDN SDL.N.
? £
OPI'ER REQUIRED PRPPMETEPS P< 1 > >P<£> >PC3> »P
OMITTING THE UNKNOWN PARAMETER
TYPE THE HO. DF TESTS
? 14
TYPE THE NUMBER DF SAMPLES-TEST. NO-= £ DR 3 ONLY
? 3
TYPE NOMINAL VRLUES FDR MEfiN
? 12,23.1.52.5
TYPE 1 DR £ RESPECTIVELY FDR SIGMA OR '/. RRNGE INPUT
? 1
TYPE NOMIHRL VRLUES FDR SIGMA
?. 1 ,£.3.7
C LSST.
t LIST.TAPE6
TEST SAMPLE NUMBER
ND. 1 £
MEfiN RRNGE PERCENT RANGE
PLUS/MINUS
1
£
3
4
5
6
7
8
9
10
11
1£
13
14
17.587
11.753-
17.136
£4.363
14.679
19.85£
17.6££
£0.251
14.418
10.475
18.174
13.70£
15.557
£0.567
£0.360
££.133
18.899
£1.794
£0.497
£7.115
9.156
17.461
£1 .£07
18.585
15.971
12. £06
12.461
9. £55
£5.360
17.338
15.564
19.352
10.357
10.892
16.554
19.748
7.305
15.706
12.502
5.397
£0.601
18.723
£1 .102
17.075
17.200
£1 .836
1 5 . 1 78
19. £86
14.444
19.153
14.310
14.9££
15.549
10.435
16. £06
16.182
7.774
10.379
3.335
5. .011
10.139
16. ££3
8.467
£.790
13.902
8.110
5.67£
8.306
8.140
11.311 '
18.419
30.394
9.696
11 .474
33.402
4£ . 059
£9.309
7. £84
48.575
£7.174
18. £40
39.798
£5.113
34.950
SAMPLE MEBH = 16.634
SfiMPLE SIGMA = 4.7£
POPULFlTIGN MEfiN = 17.400
PDPULftTIDN SIGMA = 4.3£
146
-------
2.13 TASK 22 EVALUATION OF DRY SORBENTS AND FABRIC FILTRATION FOR FGD
2.13.1 Objective
In 1976 the use of dry sorbents in a baghouse for treating exhaust
from a flue gas desulfurization unit (FGD) was examined by TRW for EPA and
by Bechtel Corporation for the Electric Power Research Institute (EPRI).
Both studies concluded that, based on available information, the dry sorbent/
baghouse FGD concept held considerable promise of economic advantage under
certain geographic, process and regulatory constraints. The optimistic
view of the concept, however, must be tempered by the fact that experimental
data were sketchy, certain major institutional and financial barriers existed,
and, most significantly, the available cost estimates were prepared and
presented by firms having a potential financial benefit in the eventual
commercialization of the process.
In order to further evaluate the concept prior to embarking on expen-
sive field test work, EPA requested that TRW conduct a more thorough study to
include independent assessment of sorbent costs, system capital costs, system
operating costs and disposal costs. The basic objective of this study was
to determine whether or not the apparent economic advantage exhibited by
the concept remains intact after independent, third-party evaluation and
whether the economic (and other) advantages are sufficiently large to warrant
further development of the process.
2.13.2 Approach
The goal was to estimate costs and evaluate problems associated with a
typical commercial utility dry sorbent/baghouse FGD system. By estimating
costs using a situation which approximates a "best case" and comparing
these costs with a currently available FGD system, it was possible to
determine if the dry sorbent/baghouse FGD process represents a substantial
breakthrough in FGD technology and can be expected to attain substantial
market penetration in the future.
"Best case" conditions were selected after examination of: current
trends in boiler design, coal supplies in the vicinity of potential sorbent
supplies, SO, removal requirements, and available experimental data on dry
sorbent performance. The conditions that were selected for detailed economic
evaluation were: 147
-------
t A new 500 MW boiler
• 1% sulfur western coal
• 750 mile (1,200 km) distance from nahcolite
supplies
• Semi-arid region with the water table 50 feet
(15 m) below the surface
• 400°F Baghouse temperature
• 70% S02 removal required.
Although additional refinement of conditions may produce a slightly
lower .cost base-case for this study, any conditions which are site specific
or narrow in application would be unrealistic since the equivalent of ten
500 MW installations would be required to support one commercial-scale
nahcolite mine. This is approximately 4% of the power output of the
committed fossil-fueled generating plants for the period 1977-1986.
2.13.3 Technical Discussion
Published experimental data indicate that nahcolite (impure NaHC03) is
the most promising sorbent for use in the dry sorbent baghouse flue gas de-
sulfurization (F6D) concept. Available data are adequate for cost estimation
that is on the order of -20 percent to +50 percent accurate. These data are
not, however, sufficient to permit potential users (electric utility compa-
nies) to accept commercial bids with confidence. A recent and rather exten-
sive pilot test conducted by Wheelabrator-Frye, Inc., Superior Oil Co., and
a raidwestern utility consortium may well provide sufficient data upon which to
base a commercial design. The extent to which these data will be made public
is not known at this time.
The reserves of nahcolite are adequate to supply even very extensive
application of the dry sorbent/baghouse FGD concept to western and midwestern
low sulfur coal-fired boilers. The material is not currently mined. A rea-
sonable commercial price for nahcolite (70 percent assay) is $25 per ton at
the mine mouth and $32.50 per ton at a power plant located approximately 750
miles (1,200 kilometers) from the mine site (northwestern Colorado). IRI and
Superior Oil have confirmed that a firm commitment for supplying nahcolite to
several large baghouse FGD installations would be necessary before any of the
three nahcolite lease holders would be able to invest the significant sums of
money required to open a nahcolite production mine.
148
-------
The wastes generated by a 500 MW application of the dry sorbent/baghouse
FGD process can be disposed of in an environmentally acceptable manner. The
basic disposal concept involves a landfill designed specifically to preclude
groundwater, surface water and rainfall from entering the deposit of soluble
waste material. The prevention of groundwater intrusion is accomplished
through careful site selection and exclusion of surface water and rainfall by
combination of dikes and an impermeable (butyl rubber) membrane placed over
the landfill site. Landfill costs for the concept and design described in
this report are estimated at $6 per ton of waste.
The dry sorbent/baghouse FGD process, when costed in the base case
selected for analysis in this study, shows capital costs of $46 per KW and an
annualized operating cost of 2.60 mills per kWh. This is 35% lower than the
base case limestone FGD process using those inputs which give a flue gas
composition of 4.3 x 106 Ib/hr flow, 36,500 Ib/hr ash, 8.17 x 103 Ib/hr
S02 and 3.8 x 10 Ib/hr moisture, equivalent to the nahcolite/baghouse FGD
system. The TVA cost estimates were computed to be $119 per KW and 4.08
mills per kWh for the capital costs and annualized operating costs, respec-
tively. Even in view of the accuracy of the cost estimating methods
(-20% to +50%), the cost differences between the dry sorbent/baghouse FGD
system and the limestone scrubbing FGD process must be considered promising.
This, in conjunction with the fact that the limestone scrubber is considered
one of the more economical of flue gas desulfurization schemes, makes the
dry sorbent/baghouse system seem quite favorable.
However, since the proposed concept is extremely sensitive to the
amount of sulfur removed (more than 40 percent of the annualized operating
costs for the dry sorbent/baghouse system fs for sorbent and waste disposal
compared with 3% for the limestone scrubbing process), applications to high
sulfur coal-firing may not be economically competitive with the limestone
scrubber.
Experimental data indicate that nahcolite utilization may approach
100% if the dry sorbent baghouse is operated at about 525°F (274°C). Tins
potential improvement in utilization would decrease the costs associated with
sorbent and disposal by about 30 percent over the base case studied in this
report. Since these costs represent slightly less than 45 percent of the
total annual cost, a potential savings of nearly 15 percent is possible.
149
-------
This savings would be somewhat offset by increased capital costs associated
with the higher flue gas temperatures. The net effect should amount to an
approximate 10 percent reduction in the base cost of 2.60 mills per kWh.
The new cost of 2.34 mills per kWh is lower than the limestone scrubbing
cost of 4.08 mills per kWh by approximately 40 percent.
The use of MgO as a dry sorbent in a regeneration scheme was briefly
examined. Kinetic data developed show that such a system, in conjunction
with the baghouse F6D concept is not feasible.
2.13.4 Recommendations
The dry sorbent/baghouse flue gas desulfurization process appears to
demonstrate an economic advantage over other currently available technologies
for flue gas desulfurization, when applied to western power plants burning
low sulfur coal as fuel. Thus, further demonstrations of the dry sorbent
FGD process utilizing nahcolite as a sorbent should be pursued. Since
the results of this analysis demonstrate that the dry sorbent process
FGD system becomes economically advantageous when operated at temperatures
in excess of those used for current demonstrations, a pilot plant study
appears warranted to provide confirming technical and cost data for this
study.
Since operation at extreme elevated temperatures of approximately 525°F
(274°C) holds some additional promise for cost reduction due to increased
utilization of the sorbent, the development of better test data at these
temperatures should be pursued. The use of existing test facilities may be
a possible route to obtain technical data in this area.
The data from tests currently in operation with Wheelabrator Frye, Inc.,
and Superior Oil Co., should be examined when they become available. Results
from these tests should be used to confirm data obtained from other sources
in developing the assumptions used in preparing this report. Additionally,
these tests may provide some additional data on nahcolite utilization rates
that can be expected at elevated temperatures.
150
-------
con-
2.14 TASK 24 PROCESS MEASUREMENT SYMPOSIUM
2.14.1 Objective
This task is devoted to the preparation and implementation of the
Symposium on Process Measurements for Environmental Assessments. The
ference was designed as a forum to present, discuss and evaluate measurement
requirements, approaches and results within the broader context of the
entire Environmental Assessment Program area. Considering the wide-ranging
scope of the Environmental Assessment Program, a broad cross section of
industry and government were invited to participate in the conference pro-
ceedings and discussions.
2.14.2 Discussion
The Process Measurement for Environmental Assessments Symposium was
held at the Peachtree Plaza Hotel, Atlanta, Georgia, on February 13-15, 1978.
The meeting proceeded with a minimum number of problem areas and, in general,
has received high acclaim by the attendees. In general, the meeting speak-
ers stayed within their allocated presentation period and minimal disrup-
tion was caused by coffee breaks and lunch time periods. A total of 163
attendees and participants took part in the proceedings.
National coverage of the Symposium was afforded by the presence of
Mr. Stanton S. Miller, Managing Editor of "Environmental Science and
Technology". Special discussions were arranged with him and Dr. Gage,
Dr. Statnick, Jim Dorsey, and John Burchard.
Mr. Miller, submitted a draft copy of the story highlighting the Envi-
ronmental Assessment Symposium, which will be published in the May 1978
issue. The draft was reviewed and modified extensively to make it repre-
sent an accurate account of the technology transmitted in the Symposium.
A similar draft was submitted to J. Dorsey, cognizant EPA Project Officer,
for his review and editing. Stan Miller will now combine the two inputs
and prepare a story for publication. Discussions with Mr. Miller will be
held in Washington at OEMI to ensure that appropriate national recognition
is obtained for future EPA-supported meetings of this type.
151
-------
The major activity in completing final arrangements for the meeting was
the preparation of the meeting program. Specifically, some of the speakers
were tardy in presenting abstracts of their speeches and through a great
deal of last-minute effort it was possible to put together the meeting pro-
gram shown in Figure 24. The day after the program went to reproduction,
the paper on Environmental Assessment of a Waste/Energy System from Midwest
Research Institute was withdrawn because the sponsor of the project pre-
ferred to keep the information proprietary at this time. As a consequence
of this cancellation, it was decided to reduce the meeting agenda by one
paper and move the paper scheduled for Wednesday, 4:20 p.m. in the place of
the originally scheduled 3:40 p.m. paper. An announcement to this effect
was made by the Symposium Chairman during the initial announcement section
of the meeting.
Other activities included the printing of special tickets for the two
luncheons, social reception, tickets for a free drink (one to each attendee),
and two types of badges (one for attendees and one for participants). In
addition, a listing of recommended suggested restaurants in the Atlanta
area, together with a map, was printed for use by the attendees at the
meeting.
The Symposium Staff consisted of two members from EPA; Ms. Brenda Foil
and Ms. Susan Sharpe, and three members from TRW; Ms. Mary McKay, Ms. Linda
Schober and Mr. Chuck Weekley. The overall coordinator for the Symposium
was Dr. Eugene Burns and the Symposium General Chairman was Mr. James Dorsey.
152
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Welcome to Atlanta and the Process Measurements for En-
vironmental Assessment Symposium. In the four years since
the inception of EPA's Envirormental Assessment program,
considerable progress has been made toward defining
specific approaches to sampling and analyzing multi-
media effluents from energy and industrial processes.
The objective of this symposium is to bring together people
who are responsible for planning and implementing sampling
and analysis programs for multi-media environmental
assessments. The program consists of sessions defining
the uses of environmental assessment data, the techniques
for acquiring data, and users' field experiences with
environmental assessment measurement programs.
The exchange of ideas that goes on during these three days
should help all of us understand the most recent develop-
ments and findings in process measurements used in environ-
mental assessment data collection — and the problems that
remain to be solved and areas of future applied research.
This booklet contains a complete agenda for the three days
of the symposium, including abstracts of all papers that
will be presented, you'll also find times and places of
all special events, and where to go for information on
sightseeing in Atlanta.
I hope you find the symposium a valuable experience.
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James A. Horsey
Symposium Chairman
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General Information
Registration
BALLROOM LOBBY, 8TH FLOOR
SUNDAY, FEBRUARY 12 5:00 PM - 8;00 PH
MONDAY, FEBRUARY 13 7:30 AM - 4:00 PM
TUESDAY, FEBURARY It 7:30 AN - 1:00 PM
NEDNESDAY, FEBRUARY 15 7:30 AH - NOON
Symposium Meeting Room
PEACHTREE DUNHOODY ROOM IN THE BALLROOM ON THE 8TH FLOOR
Information Center
INCOMING MESSAGES HILL BE POSTED ON A BULLETIN BOARD IN THE BALLROOM LOBBY. CALLERS
SHOULD DIAL (404) 659-1400 AND ASK FOR THE EPA ENVIRONMENTAL ASSESSMENT MEETING REGISTRA-
TION DESK, DUNWOODY ROOM.
Special Events
LUNCHEONS - LUNCHEONS ARE INCLUDED IN THE COST OF REGISTRATION AND ARE SCHEDULED FOR
MONDAY AND TUESDAY AT 12:15 PM IN THE PEACHTREE LANE ROOM, ADJACENT TO THE SYMPOSIUM MEETING ROOM.
GET ACQUAINTED SOCIAL HOUR - TO BE HELD MONDAY, 13 FEBRUARY, 5:30 - 7:00 IN THE PEACHTREE LANE-ROOM.
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Participating EPA Officials and Session Chairmen
James A. Dorsey
John K. Burchardi
Stephen J. Gage
Robert P. Hangebrauck
Illllllllllllllllllllllllt
Symposium Chairman
Welcoming Address
Keynote Address
in Session Chairman
Larry Johnson ,.,.,.,•.. ,..••... Session Chairman
Charles H. Lochmullern ....•• •.• Session Chairman
Eugene A. Burns •"•• • Session Chairman
Karl J. Bombaugh ,,,.,111..,..,,, .,,„ Session Chairman
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Stephen J. Gage
Is Acting Assistant Administrator for. Re-
search and Development for EPA. He is re-
sponsible for planning, directing and coordi-
nating all Agency research activities cover-
ing air, water, toxic substances, radiation
energy, pesticides and solid wastes. He
joined EPA in 1974 as Acting Director of the
Office of Energy Research; in 1975, he became
the Deputy Administrator for Energy, Minerals
and Industry. Prior to joining EPA, he was
with the Council on Environmental Quality.
During 1971-73, Dr. Gage was a White House
Fellow. He joined the faculty at the
University of Texas in 1965 and became
Director of the Nuclear Reactor Laboratory
Robert P. Hangebrauck
is the Director of the Energy Assessment and
Control Division at the EPA's Industrial
Environmental Research Laboratory. Mr.
Hangebrauck received his B.S. from Cal-Tech
in 1959. He has served with the EPA and its
predecessor agencies for 17 years in various
capacities, including Chief of the Clean
Fuels and Energy Branch, Chief of the De-
monstration Projects Branch, Control Systems
Laboratory, and Assistant to the Director
of the Bureau of Engineering and Physical
Sciences. He 1s currently In charge of con-
ducting the divisions' research and develop-
ment programs to identify and control multi-
media pollutants discharged in the environ-
ment from stationary sources.
Larry Johnson
is an Analytical Chemist in the Process
Measurements Branch for EPA's Industrial
Environmental Research Laboratory-RTP. He
received his B.S. in Chemistry from Iowa
State University and his Ph.D. in Chemistry
from the University of Texas. Dr. Johnson
manages contracts to develop screening pro-
cedures for environmental assessment programs
and compound specific procedures for detail-
ed analysis of complex samples from in-
dustrial processes. He is also responsible
for evaluating the applicability of biologi-
cal screening tests to complex effluent
samples. He has specialized in the areas of
organic sampling and analysis for trace
components in Industrial feed stocks and
energy process effluents. Prior to joining
Eugene A. Burns
is Manager of the Chemistry and Chemical
Engineering Program for Systems, Science
and Software (S3). He received his B.A.
in Chemistry from Pomona College and his
Ph.D. in Analytical Chemistry from Massachu-
setts Institute of Technology. Over the past
25 years, he has held a variety of research
and management positions. Prior to joining
S3, Dr. Burns was employed by TRW for 15
years. As Manager, Chemistry Department,
one of his responsibilities was energy-
related environmental processes Including the
development of sampling and analysis methodo-
logy for characterizing process streams.
Previous experience includes Chief of the
Chemistry Section, Jet Propulsion Laboratory;
and Head of the Analytical Chemistry Section,
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in 1966. He received a B.S. in Mechanical
Engineering from the University of Nebraska
and M.S. and Ph.D. degrees from Purdue
University.
EPA In 1972, Dr. Johnson was employed as an
analytical chemist by PPG Industries and as
a research chemist by Monsanto.
Stanford Research Institute's Propulsion
Services Division.
John K. Burchard
Is the Director of the Industrial Environ-
mental Research Laboratory-RTP. He Is re-
sponsible for the management of programs to
develop and demonstrate cost-effective
technologies to prevent, control, or abate
pollution from industrial operations in-
volving energy and mineral resources. He
was recently appointed as senior ORD Official
for EPA's Environmental Research Center in
Research Triangle Park, N.C. Since joining
EPA in 1970, he has served in several
capacities - as Chief of the Laboratory's
Technical Analysis Section, Chief of the
Development Engineering Branch, and Assistant
Director. Before joining EPA, Dr. Burchard
worked in Industry for 10 years. He holds
B.S., M.S., and Ph.D. degrees in Chemical
Engineering from Carnegie Tech.
James A. Dorsey
Is Chief of the Process Measurements Branch
1n the EPA's Industrial Environmental Re-
search Laboratory-RTP. He received his B.S.
1n Chemistry from Florida State University.
He is responsible for integrated in-house/
contract programs for the development and
application of measurement procedures for
energy and Industrial processes. Prior to
joining EPA 1n 1964, J1m was employed by
Shell Oil Company as a research chemist.
He has over 20 years of experience develop-
ing sampling and analysis techniques using
advanced methods of instrumental analysis.
Current studies include the sampling and
analysis of organic and Inorganic trace
materials in gas, liquid and solid feed,
product and waste streams. Jim is a member
of the American Chemical Society and the Air
Pollution Control Association.
Charles H. Lochmuller
is an Associate Professor of Chemistry with
Duke University. He 1s a consultant to the
EPA Industrial Environmental Research
Laboratory/RTP Process Measurement Branch
in the areas related to the development of
analytical methodology for environmental
assessment and a member of its advisory panel
on organic analysis. Prof. Lochmuller was
one of the originators of the staged sampling
and analysis protocol for environmental
assessment process measurements. He received
his B.S. in Chemistry from Manhattan College
and his M.S. and Ph.D. degrees in Analytical
Chemistry from Fordam University. His re-
search Interests are In the area of funda-
mental aspects of the molecular basis for
selectivity In chemical separation methods.
His recent work includes areas of charged
particle Induced x-ray emission analysis and
Fourier Transform Magnetic Resonance Spectro-
scopy.
Karl J. Bombaugh
Is a Principal Scfentlst at Radian Corpora-
tion where he 1s responsible for the develop-
ment of strategies and systems for environ-
mental tests. He obtained his B.S. in
Chemistry from Juniata College. Over the
past thirty years, he has held a variety of
positions in both research and management.
His experience covers a broad range of
analytical and process technology, including
infrared spectrometry, both gas and liquid
chromatography, and on-stream analysis. As
Vice-president for Research and Development
at Waters Associates, he directed a group
who pioneered in the development of modem
high pressure liquid chromatography. He
has authored more than fifty publications
including chapters in several books. He
has served on the editorial advisory board
of the Journal of Chromatoaraphlc Science.
and the Eheinica'l Rubber Handbook of Chroma-
tp.qrsphy.:,. He Is now £ha
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NOTE: Approximately 10 minutes hive bun reserved 1n the 40-mlnute presentations
to accamwdate questions and answers. Speakers names appear In Italics.
Monday, February 13
8:40 a.m. WELCOMING REMARKS
Jotn K. aurohzrf. Director, IERL-RTP, EPA
8:50 a.m.
KEYNOTE ADDRESS
PROCESS MEASUREMENTS FOR ENVIRONMENTAL
ASSESSMENT
SUpltm f. Cage, Acting Assistant Administrator
for Research and Development, EPA
9:20 a.m.
ANNOUNCEMENTS
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A. OoF«y, Symposium Chairman, Chief,
Process Measurements Branch, IERL-RTP, EPA
9.25 .. m.
En vi ron mental Assessment Overview, Session I
B. P.
Director. Energy Assessment and Control Division, IERL-RTP, EPA, Session Chairman
I
9:30 a.m.
OEM OVERVIEW OF ENVIRONMENTAL ASSESSMENT
fobtrt H. SfcrtKia* and Dave Berg, Office of
[»«,„ M<»»I. >nH tnrfi.«»m> CM
Energy, Wnerals and Industry, EPA
The environmental assessment program which
has been ongoing for about four years Is to
effluents, and solid waste disposal practic-
es' Tn1s program has several major corn-
ponents; they are evaluation of emission
rates, evaluation of the degree of control
which 1s achieved with conventional effluent/
emission control equipment, evaluation of
the biological activity of environmental
samples, and estimation of "safe" emission
rates. The program which will be discussed
during these proceedings will focus upon the
techniques which will be utilized to acquire
these environmental samples and to analyze
them. This paper will present an overview
of the data requirements specified In
recent legislation to which the environmental
assessment program data base can Input.
10:10 a.m.
Coffee Break
10:40 a.m.
THE DOE INTEGRATED ASSESSMENT PROGRAMS
Rov Coofff, Division of Regional Assessments,
ESS, DOE
The Integrated Environmental Assessment pro-
grams of DOE are designed to support the
Assistant Secretary for the Environment 1n
the conduct of his responsibilities.
In order to fulfill these responsibilities,
particularly those associated with policy
guidance for the Department! there are three
kinds of assessment activities which must be
carried out. Since the Department 1s respon-
sible for developing a national energy pol-
icy, national environmental assessments of
this policy are required. Technology assess-
ments must be done in order to explore envi-
ronmental Issues which affect technology
development decisions and the levels of
environmental control required. Finally,
regional environmental assessments must be
carried out because environmental and social
Impacts of energy policies and technological
developments are very dependent upon the
specific characteristics of the region
Involved.
Examples of all three types of assessment
were recently completed 1n connection with
the National Energy Plan as submitted to
Congress. A national assessment of the
environmental Impacts associated with the
plan was made using a comprehensive simula-
tion model based on the SEAS system cali-
brated to the NEP assumptions for the period
1975 to 2000. Regional assessments were made
of the Impact of the plan on New England and
on Region VI where conversion from oil and
gas to coal 1s expected. Finally, technology
assessments were made of the prospects for
solar energy and of the Impacts of the coal
part of NEP on water needs, water quality,
solid waste, and local sodoeconomic
well-being.
11:20 a.m.
RELATED EPRI PROGRAMS
Ralph fto-hao. Electric
Research Institute
Present emphasis In EPRI's Environmental
Assessment Department 1s on atmospheric
pollution arising from coal-burning power
plants. The main goal of the Department is
to assess the Impact of the nation's in-
creasing energy production on biota.
particularly on people. The identification
of pollutants, their physico-chemical nature,
and their fate is the charge of the Depart-
ment's Physical Factors Program. New
measuring procedures have been developed or
Improved; including matrix Isolation spectro-
scopy for PAH analysis, and Hdar for remote
measurement of atmospheric pollutants.
Future research direction in pollutant
identification and characterization will be
on techniques for defining chemical specta-
tlon and on identification of new classes
of pollutants, especially those related to
coal conversion processes. A number of
field studies have been undertaken aimed
at gathering data for elucidating reaction
mechanisms and fate of pollutants. The $7
million SURE program 1s a massive effort In
measuring air quality In the Northeast In an
effort to clarify the relation between
regional, ambient concentrations of secondary
pollutants and emissions of primary pre-
cursors, ft"'
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12:15 p.m.
Luncheon — Peachtree Lane Room
1:30p.m. Environmental Assessment Overview, Session II
Jams Dortiy, Chief, Process Measurement Branch, IERL-RTP, EPA, Session Chairman
1:30 p.m.
EPA AIR PROGRAMS'USE OF ENVIRONMENTAL
ASSESSMENTS
C. Hhoods, Director, Control Programs
Development Division, OAQPS, EPA
Under the Environmental Protection Agency's
legislative authority, a variety of strate-
gies are available for controlling air pollu-
tion. Principal among these are direct emis-.
sion standards for specific new sources which
represent the best demonstrated control tech-
nology, direct emission standards for both
new and existing sources to minimize specific
hazardous pollutants, ambient air quality
standards for selected pollutants which are
necessary to protect the public health and
welfare, mobile source emission controls and
fuel additive standards which assist in pro-
tecting the public health and welfare, and
programs to prevent significant deterioration
of air quality.
This presentation describes these various
alternative strategies, and discusses how
environmental assessments can assist in
(1) setting priorities for the pollutants and
sources to be controlled, (2) selecting'the
strategy or combination of strategies to be
employed, and (3) assessing the necessary or
desired level of control.
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2:10 p.m.
AN INTEGRATED APPROACH TO THE
ASSESSMENT AND CONTROL OF INDUSTRIAL
POLLUTION PROBLEMS
Sugtnt S. B*Fltou, Director, Industrial
Pollution Control Division,
IERL-C1, EPA
EPA now has comprehensive legislative and
court mandates for regulating all pollution
.resulting from the production and use of
industrial chemicals and products. Empha-
sis is being placed on toxic and hazardous
pollutants. To aid EPA in focusing its atten-
tion and future efforts on those pollution
problems which have the greatest health and
ecological impacts, EPA has developed in one
organizational unit an approach for assessing
simultaneously the environmental impacts of
industrial pollution discharged to the air,
water, land and municipal systems. This mul-
timedia approach necessarily Involves the
active participation of the appropriate EPA
regulatory components and industry. Field
sampling and RD4D programs are Initiated
based upon the outcome of the Integrated
industrial assessment approach.
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2:50 p.m.
SOURCE ASSESSMENT METHODOLOGY
> V. Suglife. Monsanto Research Corp.
The Industrial Environmental Research Labora-
tory (IERL) of EPA has the responsibility for
ensuring that pollution control technology is
available for stationary sources to meet the
goals of environmental legislation. If con-
trol technology is unavailable, inadequate,
uneconomical or socially unacceptable, then
financial support Is provided for the develop-
ment of the needed control techniques for
Industrial and extractive processes.
IERL performs source assessments for deter-
mining the need to reduce emissions and dis-
charges from pollution sources. Health
effects data, environmental dispersion models,
monitoring data and engineering information
are used in performing the source assessment.
IERL decisions based on source assessments
are subject to errors because of the Inherent
uncertainties in the data used to generate
decision-making Information. This paper
presents a discussion of the steps Involved
1n performing source assessments, Informa-
tion used as an aid in IERL decision making,
elements of uncertainty in IERL decision
making, and specific guidelines to be used
in performing source assessments to minimize
incorrect IERL decisions.
3:30 p.m.
Coffee Break
3:45 p.m.
RELATED HEALTH EFFECTS PROGRAMS
StuUMg Sondhu, HERL-RTP, EPA
The growing concern for human health safety
due to the ever Increasing presence of a
wide variety of chemicals 1n our environ-
ment has been amplified by studies showing
strong associations between chemical, car-
clnogenesis, and mutagenesls.
The diversity of genotoxlc Insults Inflicted
by environmental chemicals and the need to test
a large number of chemicals, necesslates the
use of multi-level approach employing a
battery of tests at each level.
The emphasis on Level 1 battery Is on the
detection of gene mutation and primary DNA
damage. Included in the battery are blo-
assays using bacterial species; lower
eukaryotic species and tests for cyto-
toxldty.
The purpose of the Level 2 battery Is to
confirm or refute the results obtained in
Level 1. Included In Level 2 are specific
assays using mammalian cells in culture
for point mutations, chromosomal aberrations
and neoplastlc transformation.
The results obtained utilizing Level 1 bio-
assays for the analysis of parent compounds,
metabolites, and complex mixtures will be
discussed.
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4:25 p.m.
BIOLOGICAL TESTING METHODOLOGY
Kmnmth M. Duk», Battelle Columbus
Laboratories
Biological procedures for testing feedstocks
and waste streams of Individual processes
have been developed as part of EPA's phased
approach to Environmental Source Assessment.
The objectives of the first phase or level of
biological testing are to (1) provide pre-
liminary data on the biological effects of
feedstocks and waste streams, (2) Identify
problems in implementing the tests on the
streams, and (3) prioritize the streams
according to their relative hazard. The
Bloassay Subcommittee of lERL-RTP's Environ-
mental Assessment Steering Committee has
developed a Level 1 biological test protocol
to meet these objectives. The protocol
Includes four health tests and eight eco-
logical tests to be Implemented on liquid,
solid, and gaseous streams. Pilot studies
are underway to test and refine this proto-
col. Results indicate the phased approach
1s effective In directing environmental
assessment activities.
5:05 p.m.
Adjourn
5:30 p.m. — 7:00 p.m.
Social Recaption — Peachtree Lane Room
Tuesday, February 14
8:30 a.m.
Measurement Technologies, Session I
Larry Jtbuen, IERL-RTP, EPA, Session Chairman
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8:30 a.m.
SOURCE ASSESSMENT SAMPLING SYSTEM
DESIGN AND DEVELOPMENT
Datrtd Blake and J. M. Kennedy, Acurex/Aerothera
The Source Assessment Sampling System (SASS)
Is the primary sampling tool for Level 1
gaseous and partlculate emissions. The
design philosophy of the SASS Is reviewed.
Including an analysis of alternate configura-
tions that were considered during the con-
ceptual design phase. Accuracy limitations
of the SASS for particulate collection stems
primarily from difficulties 1n accurately
calibrating the cyclones. Cyclone cali-
bration methods and recent results are dis-
cussed. Possible SASS modifications to In-
crease utility and accuracy are also pre-
sented.
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9:10 a.m.
FIELD EVALUATION OF THE SASS TRAIN
AND LEVEL 1 PROCEDURES
rrmkUn Siritft, Eva 0. Estes and
Denny E. Wagoner, Research Triangle Institute
The results of a two-phased evaluation of
Level 1 environmental assessment procedures
are presented. Phase one was a field eval-
uation of the SASS train. Three sample runs
were made with two SASS trains sampling simul-
taneously and from approximately the same
sampling point. A method-5 train was used
to estimate the "true" particulate loading.
Comparisons of the SASS trains are made for
total particulate, particle size distribu-
tion, organic classes, and trace elements.
Phase two consisted of providing three par-
ticipating organizations with control samples
to challenge the spectrum of Level 1 analyt-
ical procedures. Estimates of intra- and
inter-laboratory precision are made.
9:50 a.m.
INORGANIC EMISSIONS MEASUREMENTS
nay P. Haddalant and Lorraine E. Ryan
Applied Technology Division, TRW DSSG
The analysis of Inorganic compounds requires
the coordinated use of a variety-of analyt-
ical techniques. This paper describes an
Inorganic analysis scheme consisting of an
initial sample characterization (stability,
elemental composition, and morphology), bulk
composition characterization (anion composi-
tion, surface characterization, and x-ray
diffraction data) and individual particle
characterization (single particle elemental
composition, x-ray diffraction pattern, and
morphology). The use of Multimedia Environ-
mental Goal (MEG) compounds and their Mini-
mum Acute Toxicity Effluent (MATE) values to
focus analysis activities will be described.
Data from a recent field test using this
approach wil.l be used to Illustrate the infor-
mation derived from these methods.
10:30 a.m.
Coffee Break
10:45 a.m.
MEASUREMENT OF ORGANIC EMISSIONS FOR
ENVIRONMENTAL ASSESSMENT
Philip I. Lfo-int, Arthur D. Little, Inc.
Systematic measurement methods are being.
developed for the determination of organic
species in emission and process streams.
The methods are structured on the Phased
approach developed by the Process Measure-
ments Branch of IERL-RTP. Level 1 analysis
methods have been tested and a reporting
format developed which is consistent with
a variety of assessment objectives. Level 2
procedures are focused on general broad spec-
trum analysis protocols and specific analyte
procedures such as for PCB's, PAH, etc.
Macreticular resins are being studied quan-
titatively to develop improved air and water
sampling methods.
11:25 a.m.
A CRITIQUE OF ORGANIC LEVEL 1
ANALYSIS
p*t*r V. Am and Robert J. Jakobten
Battelle ColuMxis Laboratories
An objective review of organic Level 1
analysis is provided. Present strengths
and weaknesses are pointed out and recom-
mendations are made concerning how improve-
ments may be made. Areas which are addressed
include the adequacy of sample size, the opti-
mum LC separation scheme - possible use of
HPLC, problems associated with contamination -
both in the field and as a result of adsorbent
degradation, the utility of FTIR. and LRMS
analysis.
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12:15 p.m.
Luncheon— Peachtree Lane Room
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Measurement Technologies, Session II
Oarltm taalmM*r, Duke University, Session Chairman
1:30 p.m.
FUGITIVE EMISSIONS MEASUREMENT
TECHNIQUES FOR ENVIRONMENTAL
ASSESSMENTS
atnry J. Kolnab*rg, The Research
Corporation of New England
The sampling and measurement techniques cur-
rently being employed or developed to deter-
mine the impact of Industrial fugitive emis-
sions on the environment are described.
Three general sampling techniques for air-
borne fugitive emissions and one for water-
borne fugitive emissions as stormwater runoff
are presented and evaluated with respect to
their inherent accuracies and limitations.
Site-specific modifications of the general
techniques used in recent studies at a variety
of industrial locations are described and the
results of the measurement programs reviewed.
Efforts toward the development of a fugitive
ambient sampling train for the measurement of
airborne particulate and organic emissions
are summarized.
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2:10 p.m.
SAMPLING AND ANALYSIS PROCEDURES FOR
SCREENING OF INDUSTRIAL EFFLUENTS
FOR PRIORITY POLLUTANTS
vttUm A. Tflliatd, Chief. Energy and
Mining Branch, Effluents Guidelines
Division, ONPS, EPA
The Environmental Protection Agency agreed to
review and revise regulations based on the
Best Available Technology Economically Achiev-
able for effluents in 21 industries categories,
as a settlement of several cases in the Dis-
trict Court for the District of Columbia.
An integral part of this process Is a tech-
nical study to determine whether or not com-
pounds from a list of 65 materials (single
compounds and undefined classes of compounds)
exist in industrial waste waters. The Efflu-
ent Guidelines Division in EPA has established
an unambiguous list of 129 compounds, referred
to as priority pollutants, which it believes
fulfills the requirements of the court order
and can be determined analytically.
To maintain consistent sampling and analyt-
ical procedures for 21 industrial studies,
EPA has developed a protocol of the sampling
and analytical methods to be used for the
screening of priority pollutants in waste
water. This protocol represents the incor-
poration of the current state of the art pro-
cedures for the sampling and analysis of the
priority pollutants. These analytical pro-
cedures include: purge and trap — gas
chromatography -mass spectrometry (SC/MS)
for volatile organic compounds; semi-volatile
organics are done by a liquid-liquid extrac-
tion with GC/MS and metals are determined
using an inductively coupled argon plasma
emission spectrometer.
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2:50 p.m.
ALTERNATIVE LEVEL 1 ANALYSIS METHODS
Karl Bmbaugh, Radian Corporation
This presentation provides a description of
some modifications and additions to the
Level 1 analysis scheme that were used to
characterize the emissions from coal gasi-
fication plants. While some of these modi-
fications go beyond the Intent of the Level 1
analyses, the experience gained from their
use should be of value to others performing
environmental analyses.
3:30 p.m.
Coffee Break
3:45 p.m.
SYNTHETIC FUELS PRODUCTION: ANALYSIS
OF PROCESS BY-PRODUCTS FROM A
LABORATORY SCALE COAL GASIFIES
CharU* H. Sparaoin*, Research
Triangle Institute
Methodology has been developed for the analy-
sis of the volatile (gas stream components)
and non-volatile (tars and condensates) mate-
rials produced as by-products during the gasi-
fication of coal. Volatile materials are col-
lected by entrapment on polymeric sorbents,
and analyzed directly by GC/MS. Non-volatile
materials are solvent extracted and/or parti-
tioned, and the resulting fractions are ana-
lyzed by SC/MS. Qualitative analyses for
each sample type have been carried out; quan-
titative approaches are under development.
4:25 p.m.
VAPOR-TO-PARTICLE CONVERSION OF
ORGANIC SPECIES FOLLOWING FOSSIL
FUEL COMBUSTION
D. I. s. tatuuik, «. Schur*. and
8. A. Tonkins, Colorado Stat* University
A mechanism of vapor-to-particle conversion
of organic species by adsorption onto par-
ticulate material is presented. Theoretical
consideration of this process predicts that
polycyclic aromatic and long chain aliphatic
species can undergo essentially quantitative
adsorption at temperatures encountered
directly following emission to the atmosphere;
that the process can occur in the order of
seconds; and that the process is complete
within a short distance of the emission
source. The results of both laboratory and
field experiments strongly support these
predictions and indicate that adsorption 1s
of primary importance in vapor-to-particle
conversion. The significance of this find-
ing with respect to the design and conduct
of sampling procedures is discussed.
SzOB D-ffVt.
Adiourn
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Wednesday, February 15
8:30 a.m.
Industrial Process Applications
Bugmt A. Bvma, Systans, Science and Software, Session Chairman
8:30 a.m.
ASSESSMENT OF ATMOSPHERIC EMISSIONS
FROM PETROLEUM REFINING
D. D. fottbrook, R. G. Wether-old, and
6. E. Harris, Radian Corporation
A study, funded by the U.S. EPA, 1s currently
being conducted In order to assess the atmos-
pheric emissions from petroleum refining
operations. To accomplish this assessment,
measurements of fugitive hydrocarbon and stack
emissions are being made at a number of refin-
eries throughout the country. Sources being
sampled include yalves, flanges, pumps and
compressor seals, process drains, pressure
relief devices, process vents, heater and
process stacks, cooling towers, API separa-
tors, dissolved-air flotation units, open
ditches, barometric pumps and holding ponds.
This paper describes the methods being
employed for the selection and screening of
the above sources and the criteria used for
making the sample - no sample decision.
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9:10 a.m.
TOXICITY OF SECONDARY EFFLUENTS
FROM TEXTILE PLANTS
Gary D. ffaalingat Monsanto Research
Corp. and Max Samfield, IERL-RTP, EPA
This study provides chemical and lexicological
baseline data on wastewater samples collected
from 32 textile plants in the United States.
Raw waste and secondary effluent wastewater
samples were analyzed for 129 consent decree
priority pollutants, effluent guidelines cri-
teria pollutants, and nutrients; Level 1
chemical analyses were also performed. Sec-
ondary effluent samples from the 23 plants
selected for study in the EPA/ATM! BATEA
Study (American Textile Manufacturers
Institute/best available technology eco-
nomically achievable) (Grant No. 804329)
were submitted for the following bioassays:
mutagenicfty, cytotoxicity, clonal assay,
freshwater ecology series (fathead minnows,
Dophnia, and algae), marine ecology series
(sheepshead minnows, grass shrimp, and algae),
14-day rat acute toxicity, and soil microcosm.
Based on the bioassay results, 10 of the 23
textile plants were found to have secondary
effluents sufficiently toxic to proceed to
a second'phase of the study. In the second
phase, samples will be collected from these
10 plants to determine the level of toxicity
removal attained by selected tertiary treat-
ment technologies.
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9:50 a.m.
NONFERROUS METAL PROCESSING
C. MtWt, D. Meek. J. 0. Burkle,
and G. Thompson IERI-C1, EPA
This paper provides Information on an
application of environmental assessment test-
ing for a selected number of copper smelters
as an example of the nonferrous metal pro-
cessing Industry. Details are provided re-
garding the sampling methodology and sub-
sequent analysis techniques used to charac-
terize the effluents for hazardous toxic
emissions. A discussion Is provided regard-
Ing the results of the findings In terms of
the quantities of emissions expected and the
potential errors of measurement. Some
specific toxic emissions were found to be
present In substantial quantities. Also
presented fs information regarding the
difficulties attendant to sampling smelter
effluent streams.
10:30 a.m.
Coffee Break
10:45 a.m.
PROCESS MEASUREMENTS OF CONVENTIONAL
COMBUSTION SYSTEMS
/. MDMTI Boiwra, Applied Technology
Division. TRH OSSS
The EPA program for emissions assessment of
conventional combustion systems Is the first
large scale application of Level 1 environ-
mental assessment procedures and Involves
170 combustion sources. To date, 36
sources have been sampled Including 10
residential, 11 Internal combustion, 4
Industrial and 11 utility sites. The
experience to date Indicates that the
Level 1 procedures are working well and
the sites sampled are very clean. The few
problems that were found by the Level 1
procedures are now being Investigated by
Level 2 methods. These results and a dis-
cussion of the way the Level 1 procedures
were adapted to the program will be reviewed.
11:25 a.m.
EMISSIONS TESTING OF GLASS
MANUFACTURING FURNACES
C. nmiin, IERL-C1 , EPA. R. Barrett.
Battelle Columbus Laboratories and
W. Blakeslee. Scott Environmental
Technology
The introduction of pollution control tech-
nology into the glass Industry has been very
slow because of the lack of understanding of
the nature of the effluent gas streams. Past
assessment studies of this industry have Indi-
cated a serious lack of emissions data on this
Industry. Therefore, a test program was Ini-
tiated by IERL-C1 to characterize emissions
from the glass manufacturing process and
particularly from glass furnaces. Ten dif-
ferent Installations were selected consist-
ing of furnaces in the 200 TPO range. The
test results indicated that although low in
opacity the glass furnace emission stream is
of complex nature and should not be considered
free of potentially dangerous pollutants,
SO*, NOx, and toxic heavy metals such as lead,
arsenic, selenium, and cadmium were found to
be present in the gas streams. Significant
portions of the metals were found in the back
half of the Method 5 train indicating either
their vaporous or fine participate nature of
the pollutant as they pass thru the filter.
Finally, paniculate size analysis indicated
a significant portion of the partlculate
matter may be below the minimum size range
at which classical control technology Is
efficient. Preliminary conclusions of the
test program indicate that additional
testing is required to define further the
characteristics of the fine partlculate
and condensable matter.
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12:05 p.m.
Lunch Break
1:30 p.m.
Energy Process Applications
Xael Bambaugh, Radian Corporation, Session Chairman
1:30 p.m.
COMPREHENSIVE ANALYSIS OF EMISSIONS
FROM FLUID1ZED-BED COMBUSTION
PROCESSES
X. S. Ha-tty, J. E. Howes, and N. Mack,
Battelle Columbus Laboratories and
R. D. Hoke, Exxon Research and
Engineering Co.
.Results of tlie comprehensive analysis of
emissions from a pressurized fluidized-bed
combustion unit (the Exxon Miniplant) will
be described as an illustration of the
methodology. The results will be discussed
in the context of the overall environmental
assessment of the process being conducted by
the United States Environmental Protection
Agency. The comprehensive analysis of the
fluidized-bed combustion emissions and proc-
ess streams involved approximately 740 meas-
urements on about 90 samples using more than
40 different inorganic, organic, and physical
analytical methods. A discussion will be pre-
sented covering the methodology which was used
for sample preparation, inorganic analysis,
organic analysis, and physical measurements.
Also, results of the analyses will be pre-
sented with the emphasis on quality control
procedures and accuracy and precision esti-
mates derived from the data.
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2:10 p.m.
ENVIRONMENTAL ASSESSMENT PROGRAM
FOR THE HY6AS PROCESS
L. J. Amtcuia, W. G. Balr, and 0. P. Olson,
Illinois Institute of Gas Technology
The Institute of Gas Technology is develop*
ing an environmental assessment of the HVGAS
process under contract to the U.S. Department
•of Energy (DOE). HYGAS is a second-generation
coal gasification process which uses hydro*
gen in a fluidized bed at high pressure and
temperature to maximize production of methane
(SNG) from all types of coal. HVGAS process
development is carried out in a 3 ton/hr
pilot plant which produces a nominal l.SMM
SCFD of pipeline-quality gas at 1000 Btu/ft3.
The main objective of the HVGAS Environmental
Assessment Program is to obtain and interpret
experimental data from the pilot plant syste-
matically to estimate pollutant production
for demonstration and commercial-scale HVSAS
coal gasification plants. Priorities have
been established to operate systems for sam-
pling, analysis, and data evaluation to define
the fate of potential pollutants generated
during operation of the pilot plant. The
assessment methodology for environmental data
acquisition and interpretation features these
sequential objectives:
• Identification of potential pollutants
in plant effluent streams,
• Development of sampling, preservation,
and analytical techniques,
• Process unit, stream, and species selec-
tion, and
• Quantitative descriptions of significant
pollutants.
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2:50 p.m.
CHARACTERIZATION OF SYNTHOIL/
SYNTHANE PROCESSES
A. d. Sharkty, Jr., Pittsburgh Energy
Research Center
Much of the analytical data required for proc-
ess development is also useful In developing
control technology and can assist in environ-
mental assessments. As part of the coal gasi-
fication and liquefaction process development
programs at the Pittsburgh Energy Research
Center, extensive determinations have been
made of the organic and trace element compo-
nents in process streams. An overview will
be presented of the major features of the
process streams, using the SYNTHANE and
SYNTHOIL processes as examples. Recently
completed trace element balances and investi-
gations of the heterocycllc nitrogen and
sulfur compounds associated with coal lique-
faction products will be described. Examples
of the use of a high-resolution mass spec-
trometry procedure to screen for possible
hazardous compounds will be given. Possible
revisions in proposed models for the struc-
ture of coal will be reviewed In the light
of new spectral data. Limitations to the
applications of conventional petroleum ana-
lytical methods to coal-derived fuels will
be discussed and required separation pro-
cedures described. Several of the remaining
challenges for the analysis of synfuels will
be reviewed.
3:30 p.m.
Coffee Break
3:45 p.m.
ASSESSMENT OF A PROTOTYPE WASTE/
ENERGY SYSTEM
M. F. Maraut, H. H. Miller and
P. H. Cramer, Midwest Research Institute
The initial process assessment of a proto-
type energy system Indicated a possible water
effluent environmental problem. Therefore,
intensive sampling and analysis was per-
formed. The results from the organic char-
acterization included the following analysis:
EPA Level 1; EPA Priority Pollutants; poly-
nuclear aromatic hydrocarbons; and poly-
chlorinated biphenyls. The effectiveness of
an aerobic wastewater treatment system was
also evaluated by characterization of organic
compounds before and after treatment. The
EPA Level 1 results are from methods that
include: gas chromatography (GO; infrared;
liquid chromatography; and direct inlet low
resolution mass spectrometry. The EPA Pri-
ority Pollutant results are on sample frac-
tions which include: volatlles, acid extract-
ables; base-neutral extractables; and pesti-
cides. The principal analysis technique is
GC/MS on packed columns with capillary GC/MS
on selected samples. The GC/MS data were also
Interpreted for nbnpHority pollutants for a
further characterization of the organic com-
pounds. The sample preparation and analysis
fay GC/MS were optimized for polynuclear aro-
matlc hydrocarbons (PNA). Selected samples
were further analyzed by high resolution MS
to characterize further the PNA present 1n
the samples. Polychlorinated blphenyl (PCB)
analysis consisted of: sample cleanup to
isolate PCB-containing fraction, deHvati-
zation of this fraction to convert any PCB
to decachloroblphenyl and detection by GC'
with electron capture. Those sample frac-
tions for which PCB was detected are analyzed
by GC/MS of the underivatized sample fraction
to confirm identification.
4:25 p.m.
ENVIRONMENTAL MEASUREMENT PROGRAM AT
THE PARAHO SHALE OIL RECOVERY FACILITY
Jaak S. Cotter, Environmental Engineering
Division. TRM
A multi-media sampling and analysis program
was conducted in 1976 and 1977 at Paraho's
shale oil demonstration plant in Colorado.
The work was sponsored by IERL-Cincinnati.
A number of different sampling methodologies
and analytical procedures were used, with
the objective of comparing measurement tech-
niques for accuracy, practicality, and cost
of implementation. A brief discussion of the
Paraho process Is included, and the sampling
and analysis rationale is given. Qualita-
tive and quantitative findings are reported.
Particular attention Is given to the special
needs of environmental assessment of vapor,
liquid, and solid waste by-products from oil
shale operations.
B:OS p.m-
Adjourn
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Symposium At A Glance
MONDAY, FEBRUARY UTH
TUESDAY, FEBRUARY WTH
WEDNESDAY, FEBRUARY 15™
C
ID
8:40 Welcoming Remarks
8:50 Keynote Address
9:20 Announcements
ENVIRONMENTAL ASSESSMENT I, R.
9
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9:30
10:10
10:40
11:20
12:15
C|j
tfl
1:30
2:10
2:50
3:30
3:45
4:25
OEMI Overview
Coffee Break
DOE Integrated Assessment
EPRI Programs
J. Burchard, IERL-RTP, EPA
S. J. Gage, AA ORO, EPA
J. Dorsey, IERL-RTP, EPA
Hangebrauck, IERL-RTP, EPA
R. Statnlck, OEMI, EPA
R. Cooper, E4S, DOE
R. Perhac. EPRI
Luncheon, Peachtree Lane Room
ENVIRONMENTAL ASSESSMENT II, J. Dorsey, IERL-RTP, EPA
OAQPS Use of EA
Industrial Process EA
Source Assessment Methods
Coffee Break
Health Effects Programs
Level 1 Bloassay Methods
R. Rhoads, OAQPS, EPA
E. Berfcau. IERL-C1, EPA
T. Hughes. Monsanto
S. Sandhu, NERL, EPA
K. Duke, Battelle
5:30 - 7:00 Social Reception, Peachtree Lane Room
MEASUREMENT TECHNOLOGIES I , 1
8:30
9:10
9:50
10:30
10:45
11:25
12:15
SASS Train Development
Field Evaluation of SASS
and Level 1
Inorganic Emissions
Coffee Break
Organic Emissions
Level 1 Critique
Luncheon, Peachtree Lane
MEASUREMENT TECHNOLOGIES II,
1:30
2:10
2:50
3:30
3:45
4:25
5:05
Fugitive Emissions
Priority Pollutants
Analysis
Alternative Level 1
Coffee Break
Coal Tar Analysis
POM Characterization
Adjourn
.. Johnson, IERL-RTP, EPA
D. Blake, Aerotherm
F. Smith, RTI
R. Maddalone, ATO, TRW
P. Levins, ADL
P. Jones, Battelle
Room
C. Locnmuller. Duke U.
H. Kolnsberg, TRC
W. Telllard, EGD, EPA
K. Bombaugh, Radian
C. Sparaclno, RTI
D. Natusch, Col. St. U.
INDUSTRIAL PROCESSES, E. Burns, S
3
8:30
9:10
9:50
10:30
10:45
11:25
12:00
1:30
2:10
2:50
3:30
3:45
4:25
Petroleum Refining
Textile Industries
Non-Ferrous Metals
Coffee Break
Conventional Combustion
Systems
Glass
Lunch Break
ENERGY PROCESSES, K.
FBC Processes
Hygas
Syntholl/Syn thane
Coffee Break
Waste/Energy System
011 Shale Processes
D. Rosebrook, Radian
G. Rawlings, Monsanto
G. Nichols, IERL-C1,
M. Hamersma, ATD, TRW
EPA
C. Darvln. IERL-C1. EPA
Bombaugh, Radian
K. Murthy, Battelle
L. Anastasla, IIGT
J. Sharkey, PERCj DOE
M. Marcus, MRI
J. Cotter, EED, TRW
5:05 Adjourn
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2.15 TASK 26 TOTAL PARTICULATE MASS EMISSION SAMPLING ERRORS
2.15.1 Objective
The task objective was to obtain an estimate of sampling errors in the
measurement of total participate mass emissions from stationary sources.
More specifically, it was desired to determine the accuracy of particulate
mass emissions as determined by techniques in "IERL-RT,P Procedures Manual:
Level 1 Environmental Assessment."
2.15.2 Approach
The approach taken was to perform a standard error analysis, based on
the relevant equation of motion, hardware characteristics of sampling sys-
tems, and sampling methodology. The result of the effort was a fifty-page
report which concluded that the accuracy of the SASS train as used for
Level 1 assessment work has an accuracy of "factor of ± 2 to 3" or better,
as required by the Level 1 procedures.
The draft final report was submitted at the completion of 100 technical
hours. At the request of the Project Officer, there was an extensive
rewrite, including putting most of the technical derivations in appendices,
in order to obtain an optimum format for the designated audience.
2.15.3 Technical Discussion
. The error analysis was quite straightforward. The basic approach used
was a fully entrained particle model with a factor to allow for gas/
particle slip. Given this equation of motion, a standard error analysis
as was done in EPA-600/2-76-203, "Flow and Gas Sampling Manual." The error
equations were derived, and individual error terms were evaluated using
instrument characteristics, typical source characteristics, and methodology
details.
Basic results showed a SASS train accuracy of about a factor of ± 2
or better at places such as stacks and inlets to control devices, and a
factor of ± 3 at a control device outlet. These accuracies are for a
162
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can
a six-
single point sample. Results also showed that the SASS train accuracy
be dramatically improved, to about ± 25 percent or better, by using
teen point traverse in lieu of a single sample point. Along with the SASS
train evaluation, calculations were also performed for a "maximum accuracy-
train - a hypothetical sampling train using the best available commercial
hardware. Since for single point sampling the greatest error is due to
particle stratification in the stream, the single point accuracy of the
SASS and "maximum accuracy" train was found to be virtually identical. For
a 16-point traverse, however, the calculated accuracy of the "maximum
accuracy" train was in the range of 10% - 16%, significantly better than
the SASS train. The most important result as far as IERL is concerned was
that the accuracy of the SASS train and Method 1 procedures was found to be
as claimed.
2.15.4 Summary and Recommendations
From this task it was found:
1) Level 1 total particulate mass emission assessments:
• A SASS train operated in accordance with "IERL-RTP Pro-
cedures Manual, Level 1 Environmental Assessment" sampling
at a single point will have a sampling accuracy of a fac-
tor of ±2 or better in most locations such as stacks or
control device inlets. Under worst case conditions, such
as at an ESP outlet, it will have an accuracy of about a
factor of ±3.
t The degree of anisokinetic sampling induced by the SASS
train design and operation has a negligible effect on sys-
tem accuracy.
• In single point sampling, the mapping error (non-repre-
sentativeness of the selected point) will be the largest
individual error in the system.
t Sampling accuracy using the SASS train could be improved
to about ±25 percent by using a 16-point traverse rather
than sampling at a single point.
2) General
• For traverse sampling, the largest individual error will
normally be in collected particulate mass, due to amso-
kinetic sampling and flow/probe misalignment.
• System accuracies of ±10 percent to ±16 percent can be
achieved using commercially available equipment and a
16-point traverse. These accuracy levels, while no*
required for environmental assessment, indicate potential
accuracies for control device evaluation testing.
163
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It is recommended that:
• The SASS train in its present state is recommended for Level 1
assessment work, using single point sampling. A modified trav-
erse (along a single line) should be considered for places such
as ESP outlets to minimize errors due to stratification.
• Additional stratification data should be obtained at sites such
as full-scale, coal-fired power plants for the three general
types of most important locations: control device inlets, con-
trol device outlets, and stacks. Such data should be obtained
with a single (or identical) train(s) to isolate the stratifi-
cation data.
t Development of methodology to optimize single point sampling
accuracy through judicious selection of the sampling point
should be pursued through analysis of stratification data and
proof of principal source testing for proposed techniques.
• There is a need for lightweight, high volumetric flow sampling
hardware and associated procedures to perform quick (1-2 hour)
surveys to determine particulate stratification in sources so
that appropriate techniques can be used for longer term source
assessment testing.
t Additional error analysis work should be performed for size
fractionating sampling techniques. The present analysis applies
only to the total particulate mass determination.
• Although this report does not deal specifically with Method 5
hardware and procedures, results suggest that for hardware of
a given accuracy, there will exist specific procedures to opti-
mize system performance (achieve close to maximum accuracy while
minimizing manpower requirements and sampling times). Work
should be continued to prepare an IERL-RTP Procedures Manual
in this area.
164
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2.16 TASK 32 SUPPORT TO LEVEL 1 ENVIRONMENTAL ASSESSMENT STUDY
2.16.1 Objective
Radian Corporation, Austin, Texas, is conducting a Level 1
Environmental Assessment (EA) of a low BTU Coal Gasfication Plant at the
Holston Army Ammunition Arsenal. TRW has been assigned by PMB to assist,
advise, and instruct Radian in all phases of this Level 1 pilot study.
Four subtasks describe the full scope of Task 32. There are:
Subtask 1. Prior to Field Analysis —
TRW would establish a working relationship with Radian. This working
relationship includes an initial home office visit to establish in them a
comprehensive understanding of the philosophy, sampling protocols, and
equipment required to conduct a Level 1 EA, instruction of Radian's per-
sonnel in Level 1 sampling and analytical procedures and determining the
extent of a quality assurance program.
Subtask 2. During the Field Analysis—
TRW would provide "on site" sampling and analysis assistance when
Radian is in the sample acquisition phase and field analysis phase. This
assistance would include, but not be limited to: identification/correction
of deviations from the promulgated Level 1 procedures; identification/
correction of sampling and/or analytical deficiencies, preparation of a
letter report describing problems, solutions, and ease with which the pro-
cedures were used.
Subtask 3. Analysis of Samples at Radian's Site—
TRW would follow the analysis of the samples which were acquired.
If analysis problems occur, it would be the responsibility of TRW to advise
the PMB Project Officer and the EA contractor's Project Officer of the
difficulty and obtain concurrence to perform additional analyses on the
sample. It is TRW's responsibility throughout the pilot study to assure
the EA Project Officers that they will obtain the information which is
required.
165
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Subtask 4. Reporting'—
At the conclusion of this effort, the contractor will prepare a
report which identifies areas that require additional sampling and/or ana-
lytical research and development to improve Level 1 procedures. This docu-
ment will include the ideas of each monitoring contractor who was involved
in each pilot study.
2.16.2 Approach
This is basically a consulting task. However, TRW's approach has been
to not only aid Radian in their efforts but also to contribute to the over-
all development of the Level 1 methodology.
2.16.3 Technical Discussion
The major work areas of this Task have been completed. Therefore, the
following technical discussion is organized to report sequentially on each
subtask described in Section 1.0.
Prior to Field Analysis--
TRW visited Radian's Laboratories with the PMB Project Officer in late
March 1977. Key personnel contacts were established and the Level 1 phi-
losophy, sampling protocols, sampling equipment operation, and analytical
procedures were discussed in detail with Radian's performing team.
On 15 April 1977 TRW compiled and submitted to PMB a report on the
"Problems and Deficiencies, Level 1 Environmental Assessment Procedures".
This was to serve as the discussion basis of a meeting held on May 2 and
3 at RTP between the PMB contractors involved in the Level 1 pilot studies
(RTI, ADL, and TRW). At that time various modifications were agreed upon
and adopted to the Level 1 sampling and analysis protocol. These were:
• Various changes in field GC operations to accommodate particu-
lar instrumental differences.
• Gas Sampling Tedlar bags acceptable for gas sampling.
• Adoption of a new sample combination scheme.
• Approval and incorporation of a new organic analysis scheme.
166
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Action items which were assigned to the PMB contractors as a result of this
meeting were:
API
• Conduct a meeting with the Level 1 pilot study and the PMB ron
tractors to standardize the LRMS procedure and ?nterpreSion
IRW
• Develop a contamination-free Parr Bomb Procedure.
• Investigate and resolve the recovery problems of As, Sb and Ha
from the impinger solutions. y
t Provide step-wise procedures for As by the silver diethyl dithio-
carbamate procedure, Hg by the cold vapor technique and Sb by
the Atomic Absorption Spectrometry procedure.
ADL held their coordination meeting in late May and TRW participated.
TRW delivered to PMB the developed procedures on 3 June 1977 in letter
report form.
During this period letters and telecons with Radian were actively
answering the sampling and analytical inquiries and their test plan was
reviewed. Arrangements were also made to have a TRW representative pre-
sent during the field sampling activities.
During the Field Analysis
Radian field test was conducted in August. The TRW representative
was present during their Level 1 acquisition phase on August 30 and 31.
He participated in decisions concerning modification of the sampling pro-
cedures for the high tar content vent sampled. These included but were
not limited to:
• The downtime realized for changing of plugged filter. This
would result in a longer total sampling time to acquire the
Level 1 required 30M3. Therefore, it was decided to change
the filter as often as necessary and sample as long as possible
to acquire a reasonable quantity of sample. Documentation of
the exact sampled volume was made.
• High tar condensation was observed in the cyclones. Plugging
was also a problem experienced. Two additional Problems
resulted from this condition. One was the loss of PJ^icle
size separation and the other was the lack of adequate tar
removal by the methylene chlor de nnse^ "^JiS Se^lones
better separation could be achieved without heating the cyclones
167
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and allowing greater tar condensation. This also reduced the
plugging problem. Methylene chloride/methanol and mixtures
were used for additional tar removal.
Analysis of Samples at Radian's Site —
On November 10th and 11th a TRW representative visited Radian to
t-
observe the Level 1 sample analysis phase of the pilot study and assist
with problems. Briefly the findings of this visit can be summarized as
fol1ows:
• The high tar content prevented analysis to proceed along "particu-
late" breakdown Level 1 guidelines.
t The high organic, sulfide and cyanide levels in the separator
liquid sample produced interferences with several of the field
water quality tests and made the odor and alkalinity measure-
ments incapable of being conducted due to health hazards.
t Methylene chloride was found to extract only between 31-35%
of the organics present. Other solvent systems, therefore
were implemented.
• Fractions 4 through 8 of the liquid chromatographic separation
were smeared to the extent that the Infrared Spectroscopy and
Low Resolution Mass Spectrometry were difficult to interpret.
• The Gas Chromatographic, TCO, analysis if conducted exactly by
the Level 1 procedure was not quantifiable because of extremely
high loading on the column.
• Various alternative organic analysis procedures were discussed.
These would all be considered "Level 2" in nature. However,
the validity of proceeding to Level 2 organic sampling and
analysis is well justified from the Level 1 data and proved
Level 1 to be viable both in sampling and analysis.
Report!ng--
The final documentation on this task was sent at the end of
May 1978. Additional reporting requirements have been met with monthly
progress reports and letter reports.
2.16.4 Summary of Results and Recommendations
In summary, this task has provided a necessary evaluation mechanism
for the Level 1 Environmental Assessment protocol as applied to an unusu-
ally high organic content stream. The sampling and analytical insight
168
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gained from this test has been valuable to the evolution of the Level 1
methodology. When the test's final evaluation and Level 1 recommendations
have been made, documentation will exist to aid future teams in conducting
sampling and analysis on similar sites.
This type of team effort can be valuable to future activities. The
combination of an EA with a PMB contractor provides an excellent blend of
sampling and analytical expertise.
169
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2.17 TASK 36 INORGANIC MEG COMPOUNDS AND LEVEL 1 ASSESSMENT
2.17.1 Objective
This 100-hour task was initiated to theoretically predict:
• If Level 1 Environmental Assessment is capable of detecting
the inorganic Multimedia Environmental Goal (MEG) compounds
and elements at their Estimated Permissible Concentrations (EPC).
• Where in the Source Assessment Sampling System each inorganic
compound and element is likely to be found.
• What MEG compounds, elements and valance states can be pre-
dicted in Level 1 aqueous samples.
• The nature of difficulty in detecting by "non-Level 1" techni-
ques MEG compounds at EPC levels.
Organometallic MEG compounds were not included in this study.
This basic study was completed in June 1977. The task was
reopened to address the current list of MEG compounds (November 1977)
at their Minimum Acute Toxicity Effluent (MATE) levels. The draft docu-
ment issued in June 1977 was revised using MATE'S in place of
EPC's.
2.17.2 Approach
Two general approaches were taken. One was to theoretically discuss
the capability of Level 1 to detect the MEG compounds and elements at
their EPC concentrations. The other was to assess actual Level 1 data and
compare values obtained and limits of detection with the EPC's.
2.17.3 Technical Discussion
The theoretical discussion which predicted the capability of Level 1
to detect MEG compounds at their EPC concentrations simply back-calculated
from the EPC's the probable quantity present in a 30M3 sample (EPC con-
centration in yg/M3X 30M3). The effects of SASS distribution and sample
combinations, preparation, and the specific analytical techniques detec-
tability were then considered. Based on these predictions most of the
inorganic elements at EPC's were detectable by the Level 1 analytical tech-
niques. Problem elements, because of the Level 1 factor of 3 accuracy,
were identified.
170
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A discussion of SASS distribution based on actual run data was also
part of the approach. Through the knowledge of concentration levels of
MEG compounds probable in common sources, and comparison of these actual
values and actual limits of detection with the EPC's, problematic MEG com-
pounds were identified. In general, detectability problems (at the time
of this original study) at coal- and oil-fired plants had not been encountered.
The investigation of Level 1 water samples considered the MEG inor-
ganic compound's physical properties and predicted the probable MEG species
present based on solubility and stability. The MEG inorganic elements were
also tabulated comparatively with the detection limit for each element in
water by SSMS and the Level 1 wet chemical techniques. Level 1 was found
to be viable for most MEG's with problems possible when EPC levels of Be and
As are sought because of the Level 1 accuracy requirements.
The "non-Level 1" techniques recommended for the detection of problem-
atic MEG compounds and elements were:
t Sample concentration by a factor of 10(100 mL to 10 mL)
t Graphite Tube Atomic Absorption Spectroscopy (AAS)
2.17.4 Summary of Results and Recommendations
The results and recommendations from the "Draft on Inorganic MEG Com-
pounds and Level 1 Assessment Detection Capability" (Document #28055-6008-
TU-81) dated 30 June 1977 were as follows:
Conclusions--
t The Level 1 Environmental Assessment protocol is capable of
detecting most MEG elements at the concentration levels imposed
by the EPC X 100 criteria.
• Beryllium at the EPC X 100 level of interest is theoretically
not detectable by current Level 1 techniques.
. Arsenic, selenium, thallium, chromium, silver lithium, antimony
and cadmium are theoretically not detectable at the EPC X 100
level of interest in some of the SASS components.
t Detectability problems have not yet been encountered for MEG
elements at coal-and oil-fired systems sampled.
171
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Recommendations —
• Investigate the recovery, detection limits and costs of analyzing
Be, As, Se, Th, Cr, Ag and Cd standards at the predicted EPC
concentrations, by the graphite tube atomic absorption spectro-
scopic technique after a sample concentration procedure.
Recommendations were also made to revise this draft document using
MATE concentrations in place of the EPC, and tt was completed tn May 1978.
172
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2-18 TASKn
2.18.1 Objective
The objective of this recently completed task was to support TRW's
participation with RTI, ADL, Radian, and SoRI in collaborative testing of
the SASS and the Level 1 analysis procedures. The purpose of the overall
test program was to define the precision of the Level 1 procedures.
2,18.2 Approach
The effort consisted of two verification phases. Phase I involved a
field sampling effort in which SASS performance and field procedures were
evaluated. Field sampling teams from Radian, SoRI, and TRW participated
in the Phase I effort which was conducted at an aluminum smelter. The
collaborative sampling effort involved the use of three trains (two SASS
and one method 5) during three sampling runs. This matrix allowed the
rotation of the trains such that each participating team used each train
once.
Phase II involved a similar collaborative effort directed at the
Level 1 laboratory analysis procedures. Three types of samples were pre-
pared by ADL, one of which was directly derived from the samples acquired
in Phase I, and the other two were specially compounded with known mixtures.
Only RTI, who acted as the central study coordinator, was informed by ADL
of the composition of the specially prepared samples. All analyses were
conducted in strict accordance with procedures as specified in the EPA-
IERL Level 1 manual. The only instances involving modifications or devi-
ations from the Level 1 manual were when newly revised, EPA approved pro-
cedures superceded them. These new procedures were documented by RTI and
supplied to all contractors participating in this study.
2.18.3 Technical Discussion
The collaborative sampling matrix involved the use of three trains
(two SASS and one method 5), rotated in such a way that each contractor
173
-------
used each train once. This rotational matrix is illustrated by the
following example:
Test 1
Test 2
Test 3
SASS 1
SoRI
TRW
RADIAN
SASS 2
RADIAN
SoRI
TRW
Method 5
TRW
RADIAN
SoRI
In the performance of this phase of the task, TRW not only supplied
a sampling crew but also:
t Acted as key contact with Kaiser Aluminum to arrange schedules
and logistics for the sampling effort.
• Performed a pre-test site survey.
• Arranged for the installation of sampling ports.
• Supplied one of TRW's mobile source assessment vans equipped
to perform on-site weighings, GC analysis, and general
Level 1 support.
The results of the Phase I efforts were recorded and reported by RTI.
RTI also coordinated the Phase II analytical testing, collected all data
from the participating contractors, and is in the process of preparing a
report on the collaborative results.
TRW supported the Phase II effort by analyzing the selected samples
provided by RTI (prepared with the support of ADL). These samples were
submitted to the standard Level 1 scheme in routine use by TRW on the
"Environmental Assessment of Conventional Combustion Systems" program, and
all results along with copies of raw data were reported to RTI.
/
2.18.4 Summary of Results and Recommendations
Although remarkable progress has been made toward defining the details
of the Level 1 procedures in the relatively short period of time since they
were first published, there remain considerable ambiguities which can lead
to differences in the interpretation of the procedures. That such differ-
ences exist was evident in both phases of the effort. The seriousness of
these potential interpretive differences will hopefully be addressed in
RTI's summation of this collaborative testing.
174
-------
As a result of an ongoing project at TRW involving the environmental
assessment of stationary combustion sources, a detailed, highly specific
rendition of the Level 1 procedures has been written. This document is
called the "Emission Assessment of Conventional Combustion Sources Pro-
cedures Manual for Sampling and Analysis" (EPA Contract 68-02-2197) and
is written in a format which is amenable to standardization and which has
been successful in its implementation. It is thus recommended that a
similar, detailed format be used in the revised publication of the Level 1
procedures. Using this kind of format there can be very little doubt as
to specific procedural directives.
175
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2.19 TASK 47 AUTOMATIC SULFUR TRIOXIDE MONITOR
2.19.1 Objective
The objective of this task was to develop an automatic sulfur
trioxide monitor based on the Goksoyr-Ross coil capable of providing
reasonably accurate measurements (±20%) of sulfur trioxide concentration
in process gas streams. The unit was to be designed for continuous,
unattended operation for periods on the order of 24 hours.
2.19.2 Approach
The task was divided into the following items:
• Design of the prototype unit
• Construction and laboratory tests
• Field test evaluation
t Preparation of final report and operations manual
The unit was designed with the idea of facilitating field handling, and
for ease of operation. The final design was submitted to IERL/RTP and
work began on construction of the prototype unit. The hardware buildup
was aimed specifically at providing a unit capable of operation in a field
environment, thereby necessitating sturdy construction. The unit was
designed to be easily modified if necessary, and had an extremely flexible
control system installed.
The laboratory tests and field tests will be performed to determine
the monitor's performance capabilitites, particularly under actual field
conditions. Upon successful completion of these tests an operations manual
with the system's description will be written, as well as a final report
summarizing the test results.
2.19.3 Technical Discussion
The monitor was designed in two units; the probe unit which contains
the glass sampling train and conductivity cell (Figure 25) and the con-
trol unit, which contains the automatic sequencer, electrical distribution
panel, and pumps. The sampling train was designed of all pyrex or quartz,
and the solenoid valves utilized were of all Teflon construction so that
176
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CYCLINDRICAL
QUARTZ
FILTER
CONTROLLED!!
CONDENSATION
COIL
TEMPERATURE
CONTROLLER
CONST;
TEMPERATURE
BATH
CONDUCTIVITY;5;
Figure 25. Inside View of Automatic S03 Monitor
177
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the acid solution would not contact any metallic components. The function
of the monitor's components are controlled by a sequencer which has eleven
separate timing channels, each variable from 0 to 999 seconds. The
sequencer operates the components in specific cycles according to the
sampling time desired. The output of the unit is in terms of solution
conductivity; a conductivity cell measures the conductivity of a rinse
solution which has washed through the Goksoyr-Ross coil, thereby providing
data on the amount of acid in the solution. Through calibration, this can
be related to sulfur trioxide concentration in the sample gas.
A series of engineering sketches was prepared showing the design of
each major component in the two units, and a complete list of parts and
suppliers was submitted to IERL/RTP. The control system was of consider-
able importance and therefore a considerable amount of time was devoted to
its design and construction. Versatility and ease of timing alteration
were of prime importance. The sampling system components were manufactured
of quartz and/or pyrex in order to withstand the temperature and acid solu-
tion without degradation. The entire sampling system from probe inlet to
the controlled condensation coil is heated to 288°C to prevent acid conden-
sation prior to the coil. All components necessary for the measurement of
conductivity are water-jacketed at 60°C ± 1°C to provide temperature sta-
bility. This is essential for accurate conductivity measurements.
2.19.4 Summary and Conclusions
The field test unit has been successfully operated both in the laboratory
and in the field at the Tennessee Valley Authority Shawnee Power Plant.
The probe unit itself weighs 41 kg and is 91 x 76 x 30 cm in overall
dimensions. The glassware components are firmly mounted with shock-reducing
mounts to reduce stress on the glass in field operation. The control unit
components are temporarily mounted in an electronic enclosure for the
laboratory tests. Connections to the probe unit are a series of quick
disconnect fittings and thermocouple jacks. This facilitates set-up in
the field since both units are self-contained.
Laboratory testing showed the monitor capable of a linear response to
sulfuric acid concentrations as low as 0.5 ppm during a 7 minute sampling
cycle, with variations in conductivity output of + 4%. Smaller concentrations
may be detectable within this accuracy by increasing the length of the
178
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sampling cycle. Tests utilizing a sulfuric acid mist generator at the
probe inlet showed that the system recovers 92% of the acid injection.
Variations in system performance at the extreme range of conductivity
measurable indicated an accuracy of +92 under laboratory conditions.
The system was also shown to be unaffected by S02 in as high as 4000 ppm
concentration. All tests were performed with the system operating in
the fully automatic mode to duplicate field conditions as closely as
possible.
A one-week field test was performed at the Shawnee facility. No
problems were encountered in setup of the equipment; however, the sampling
probe and replacement were destroyed in shipment. Initial tests were
begun using a repaired probe while new probes were being prepared. A
continuous test of 3.75 hours in duration was performed at the inlet to
the venturi-scrubber, where high particulate loadings were encountered
o
(11 g/m ). During this test, it was necessary to add an impinger and absorber
to remove condensed water from the vacuum lines. This water vapor damaged
the differential pressure meter so that a dry gas test meter was added to
obtain an accurate gas flow reading. Manual samples were taken with a
manual Goksoyr-Ross system to provide reference data; the measurements
agreed within +7% at 20 ppm concentration.
Due to shutdown of the scrubber being sampled, the equipment was moved
to the inlet of a second scrubber. An endurance test was started with a new
probe and clean filter and condensation coil. During a 12-hour continuous
run, measurements with the automatic system agreed with spot measurements
taken with the manual system within +435 at 8 ppm.
A problem occurred which prevented longer continuous tests. It appeared
that a heavy oily substance was being condensed and trapped on the conden-
sation coil frit, thereby plugging it and stopping the monitor's operation.
Subsequent tests with a new condensation coil provided only 2 hours more of
continuous operation.
The results of the successful laboratory and field tests were documented
in a final report submitted in September 1978. A comprehensive Operations
and Maintenance Manual was also prepared.
179
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2.20 TASK 48 ANALYSIS USING ION CHROMATOGRAPHY
2.20.1 Objective
The task was devoted to the development of an analytical scheme
utilizing ion chromatography to determine specific ions in dual-alkali
process streams. The goals of the task were to: develop a sample collec-
tion plan; develop a sample preservation plan; develop a separation pro-
cedure for solution, slurry, solids, and solubles in cake; demonstrate
the accuracy and precision of the analytical scheme; and write an analytical
procedure manual.
2.20.2 Approach
Sampling programs were prepared for a venturi/spray tower (limestone)
scrubber and a pilot dual alkali scrubber. These two types of scrubbers were
selected because they are representative of current technology and future
technology. The specific facilities finally chosen were the Tennessee Valley
Authority (TVA) Shawnee Test Facility, Paducah, Kentucky, and the Arthur D.
Little pilot dual alkali scrubber.
Working both with samples from the Shawnee facility and with synthetic
mixtures, procedures were established to preserve samples, separate liquids
from solids in the field, and to accurately and precisely analyze the samples
for the species of interest: sulfate, sulfite, chloride, carbonate, nitrate,
calcium, magnesium, sodium, and potassium.
2.20.3 Technical Discussion
A sample preservation plan was developed for a typical dual-alkali wet
scrubber process. Samples from the process streams are separated into
two groups, solids and solutions. Solution samples and filtrate from slurry
samples are further divided into five groups and preserved on site
according to Table 23. Solid samples, solids from slurry samples and filter
cake samples are not preserved but just placed into containers. These actions
ensure that equilibria between species in these samples are preserved whenever
it is necessary. Preservatives and holding times are specified to prevent
deterioration of species susceptible to chemical changes.
180
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TABLE 23. RECOMMENDATIONS FOR SOLUTION PRESERVATION
Measurement
Total oxidizable sulfur
Sulfate
Hydroxide
Acidity
Carbonate
Chloride
Calcium
Sodium
Magnesium
pH
Total Sulfur
Nitrate
Container
Plastic
Plastic
Plastic
Plastic
Plastic
Preservative
Cool, 4°C
HN03 to pH 2
Cool, 4°C
Detection on site
Cool, 4°C
Zn Acetate
Cool, 4°C
H2S04 to pH 2
Holding Time
24 hrs
6 mos
7 hrs
. 24 hrs
24 hrs
00
-------
A separation procedure for solution, slurry, solid and solubles in
cake was developed. The separation procedure is divided into two parts:
liquids sample and solid samples. Slurry samples will be filtered and solids
which pass through the 0.5y Fluoropore filter will be considered in solution.
The recommended filter is 0.5ym Gelman Acupore. Acupore
filters are both chemically clean and inert to most organic and corrosive
solvents. Furthermore, Acupore does not have a tendency to absorb metals on
its surface. If a slurry sample is found ,to contain a large amount of solids,
pre-filtration is necessary using another Teflon filter, Millipore Mitex.
This filter is available in a lOy-pore size and is designed to act both as a
membrane and depth-type filter. The larger pore size of the Mitex filter
allows for a higher solid content without clogging. Pre-filtration with
Mitex followed by filtration through 0.5ym Acupore should produce a
solids-free solution.
Solid samples will be dissolved in concentrated nitric acid and
the resulting solution or slurry will then undergo the same treatment
as the liquid samples.
The analytical scheme for anion analysis had to overcome two major problems:
f\ f)
NOg and SO, ions had very similar retention times, and COl ions could not
be detected in the presence of the anions of interest because COZ ions were
part of the eluent solution. In order to determine all the anions of interest
in a sample, the anion sample would have to be run three separate times on the
ion chromatograph using two different sets of columns.
The analytical scheme for anion analysis finally developed involves these
basic procedures:
1. The first anion sample run determines the amounts of chloride,
total oxidizable sulfur (TOS), and sulfate. The columns employed
in the ion chromatograph are the Dionex anion separator and
suppressor with a Na2C03/NaHC03 solution as the eluent.
2. The second anion sample run determines the concentration of nitrate.
The ion chromatographic columns and conditions are the same
except that the anion sample is pretreated with H905. The
peroxide provides two services: it oxidizes the SuTfur in the
solution to S0| so that the total sulfur can be determined in
the sample; it oxidizes S0§ to S0| thus deconvoluting the SO^/NO?
peak overlap. J
182
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3. The third amon sample run determines the amount of carbonate.
rnUr*CSr°mf °9-a|l1S ?6t Up with a B1oRad AG ™ suppressor
coluran=and water is the eluent. The single suppressor separates
the C03 ions from all other anions.
4. Hydroxide can not be determined by ion chromatography -
Alternative approaches to the hydroxide problem are acid/base
titration or pH determination.
In the analytical scheme for cation analysis, calcium, magnesium, and
sodium were separated and detected by ion chromatography with a Dionex separ-
ator and suppressor column. Calcium and magnesium were separated with a
p-phenylenedramine dihydrochloride eluent while sodium was separated using a
nitic acid eluent.
The analytical scheme for cation analysis can be summarized as follows:
1. The first cation sample run determines the amounts of sodium. The
columns employed in the ion chromatograph are the Dionex cation
separator and suppressor with a HN03 solution as the eluent.
2. The second cation sample run determines the amount of calcium
and magnesium. The same type Dionex cation columns are used as
in Step 1, but a p-phenylenediamine dihydrochloride solution is the
new eluent. Two separate sets of Dionex cation columns must be
employed for cation detection because p-phenylenedramine dihyd-
rochloride tends to degenerate the column packing material and this
would cause an interference with the sodium separation. The nitric
acid eluent for sodium does not separate the calcium and magnesium.
Table 24 lists retention times and corresponding operating parameters of
the various ions present in wet scrubber samples.
The accuracy and precision of the analytical scheme was tested using
real samples from the lime/limestone wet scrubber at the TVA Shawnee Plant
in Paducah, Kentucky. Table 25 shows a direct comparison between TVA and
TRW sample analysis for the lime/limestone wet scrubber. Because the
values reported for magnesium and sodium varied greatly, the samples were
determined a second time by atomic absorption at TRW and these new results
were in line with the ion chromatography values. These results indicate
that there must be a shift in the solution equilibrium because of the time
difference between sampling at Paducah and analysis at TRW. A check of
the pH of the sample solutions showed that all the solutions decreased in
acidity to almost neutral or basic. A shift in pH would account for the
differences in the magnesium concentration reported because magnesium oxide
is only slightly soluble in solution. On the other hand, the chloride
183
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TABLE 24. RETENTION TIME OF VARIOUS IONS FOUND IN WET SCRUBBERS
m
•MHH^H^^^^^VMHAMfl
Species
Cl"
S0=
N03
so;
co3
ca+2
Mg+2
Na+
K+
••••^^^^^•^M^^
Cone.
10 ppm
10 ppm
10 ppm
10 ppm
10 ppm
10 ppm
10 ppm
10 ppm
10 ppm
M«^^»W^M*^*^BI*i«»^^^»«
Retention
Time
4.5 min
10
8
16
6
12
8
7
12
••^•^V^HMHW^M^I-WBW
Dionex
Separator
Column
Anion
3 x 500
Anion
3 x 500
Anion
3 x 500
Anion
3 x 500
BloRad
6 x 500
Cation
6 X 250
Cation
6 x 250
Cation
6 x 250
Cation
6 x 250
•n»ii»n« 1 1 i i • • • ma 1 1
Dionex
Suppressor
Column
Anion
6 x 250
Anion
6 x 250
Anion
6 x 250
Anion
6 x 250
None
Cation
9 x 250
Cation .
9 x 250
Cation
9 x 250
Cation
9 x 250
••••M^MM^i^lW^MIWi^M
Flow Rate
302
30%
30%
30%
30%
40X
40X
40X
40X
•MMBMHBMWHOMMHMMViWW
Eluent
0.003M NaHC03/
0.0025M Na2C03
0.003M NaHC03/
0.0025M Na2C03
0.003N NaHC03/
0.0025M Na2C03
0.003M NaHOy
0.0025M Na2C03
Mater
For both
Cations
0.001 M
p-phenylene-
dlamlne
dlhydrochloride
.005N HN03
.005N HN03
^^••••••••RI^HH^
Temp.
24°C
248C
24°C
24°C
24°C
24°C
24°C
24°C
24«C
-------
TABLE 25. DIRECT COMPARISON BETWEEN TVA AND TRW SAMPLE ANALYSIS FOR THE LIME/LIMESTONE WET SCRUBBER
00
en
- - • —
Species
Calcium
Magnesium
Sodi urn
Sulfate
Chloride
•••••••••••••••••(••••^^
Method of Analysis
Atomic Absorption (TVA)
Ion Chromatography (TRW)
Atomic Absorption (TVA)
Ion Chromatography (TRW)
Atomic Absorption (TRW)
Atomic Absorption (TVA)
Ion Chromatography (TRW)
Atomic Absorption (TRW)
Ion Exchange (TVA)
Ion Chromatography (TRW)
Potentiometric (TVA)
Ion Chromatography (TRW)
Concentration (in ppm)
TVA Sample Identification
#5253
604
551
8219
10506
11025
186
172
32994
34000
2676
2726
#5254
624
618
5269
5030
192
197
195
17584
16209
1418
1454
#5255
618
614
4629
5536
55
99
102
17700
16660
1418
1485
#5256
667
541
8179
10014
10490
47
92
31442
34404
2614
2675
-------
concentration would not be susceptible to changes in pH, and this was
confirmed by the good correlation between the TVA and TRW values. Sodium
ion concentration should not vary with changes in pH but only two of the
four TVA determinations showed good agreement with the TRW results. The two
values which disagree are approximately one-half less than the TRW values
and this could be accounted for by a dilution factor mistake or a calibra-
tion mistake on the AA. Sulfate ion concentration would constantly increase
with time because any sulfite present would oxidize to sulfate. The TRW
values for sulfate show both high and low values compared to the TVA results
but both sets of analysis still show good agreement. The variations between
the TVA and TRW sample analysis seems to be due to sampling and time between
analysis and not an instrumental problem.
2.20.4 Conclusions
The results of this work have been compiled in a procedures manual,
"Chemical Analysis of Wet Scrubbers Utilizing Ion Chromatorgraphy," which
describes how to collect and preserve samples as well as how to perform
qualitative and quantitative analysis for sodium, potassium, magnesium,
calcium, chloride, TOS, sulfate, sulfur, nitrate, carbonate and hydroxide.
186
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2.21 TASK 49 MASS EMISSIONS MONITOR DEMONSTRATION
2.21.1 Objective
The principal objective of this task was to demonstrate hardware and
methodology for continuous high accuracy flow and gas composition measure-
ment in large stationary source ducts and stacks. The technology being
demonstrated was developed under previous EPA sponsored programs, and
showed the potential for large accuracy increases over single point
continuous sampling techniques without a substantial system cost and main-
tenance impact. The technology also has the capability to be used for
active process control in addition to passive monitoring.
2.21.2 Approach
The gas sampling portion of the system differs from current continuous
extractive sampling practices only in that a special (patented) type of
multiple point gas sampling probe is used. The probe has a single outlet,
and so is quite similar in use to a standard single point gas sampling
probe. In the preferred approach, volumetric flow is measured by means
of a Dieterich Standard Annubar, which is a kind of multiple point pitot
probe with a single differential pressure as the output. Since the
specialized equipment being demonstrated was "front end" hardware, the
approach taken was to find a location where a full sampling system was in
operation and then perform the task by substituting our probes, so that
we could made use of the rest of the system (sample lines, gas conditioner,
analyzers, recorders, etc.). The only identified site at which we could
do this was the NIPSCO coal fired power plant in Gary, Indiana, where TRW's
Environmental Engineering Divison was running a demonstration test on a
novel type of wet scrubber. An agreement was negotiated whereby our stack
gas sampling probe would be substituted into their system, and we would
make use of Annubars already installed in the stack. In addition, we
would supply a separate system upstream of the scrubber to measure volu-
metric flow and bulk gas composition (N2> C02, 02). The test period was
planned to be two weeks in a "hands-off" mode.
187
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2.21.3 Results
The field effort was for the most part unsuccessful. The scrubber
was down for repairs during most of the test. At this particular site,
that meant that the flue gas was diverted to another stack, so that stack
measurements could not be obtained. A few days before the scrubber came
back on, the EED sampling system broke down and was down for the remainder
of the test. No stack measurements were obtained, even though the test
period was lengthened by a week in anticipation of the scrubber coming
back on line.
At the upstream location, volumetric flow data had to be recorded
manually due to a malfunction in our printer. Excessive flue gas tempera-
tures led to an early failure of the multiple point gas sampling probe.
The one significant observation made during the test came from comparisons
of continuous single point data from our upstream location and from an EED
monitoring location further downstream. Systematic shifts in gas composi-
tion measurements at the two locations revealed the presence of significant
compositional stratification, the problem the multiple point probe was
designed to handle.
2.21,4 Recommendations
The observed presence of significant compositional stratification at
the test site reinforced the need for further work in the area of high
accuracy continuous monitoring.
188
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2.22 TASK 51 EPA/TVA LIMESTONE FGD SUPPORT
2.22.1 Objective
The task was devoted to supporting process measurement activities at
the EPA/TVA Shawnee Wet Limestone Test Facility in Paducah, Kentucky. The
initial tasks were devoted to the investigation of trace element vs particle
size distribution and liquid aerosol sampling of flue gas streams. The
investigation involved study of: stack samplers and particle sizing;
basic theory, limits of detection, limitations and cost of multielemental
analytical instrumentation; instrumentation for compound identification
and surface analysis; liquid aerosol sampling.
2.22.2 Approach
The principal topics of concerns requiring technical support have
been
1) recommending particle sizing and trace elements analysis approaches
2) reviewing and recommending sampling techniques and analysis methods
for trace element and compounds
3) recommending sampling procedures to identify sulfur forms
4) evaluating the feasibility of sampling liquid aerosols at a
mist eliminator
5) developing automated methods to measure scrubber process stream
parameters and thereby improve control of the scrubber operation.
Each has been discussed either at a symposium or in a carefully researched
report.
2.22.3 Technical Discussion
Trace Element Sampling and Analysis--
A report consisting of four sections was written discussing stack
samplers, trace multi elemental analysis instrumentation, instrumentation
for compound identification, and recommended combinations of stack samplers
and analytical instrumentation. A variety of sampling equipment for flue gas
particle sizing were discussed, including an: Aerotherm high volume stack
sampler, an Aerotherm source assessment stack sampler, and a Meteorology
Research, Inc., Impactor (Model 1503). A brief discussion of the bas1C
189
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theory behind the trace elemental analytical techniques, including limits
of detection, lists of limitations and analysis costs for Atomic Absorption
Spectroscopy, Spark Source Mass Spectrometry, Inductively Coupled Plasma
Optical Emission, Neutron Activation Analysis, and Proton Induced X-Ray
Emission was given, as was a brief description of the instrumentation
necessary for compound identification and surface analysis: X-Ray Powder
Diffraction, Scanning Electron Microscope, Electron Probe Microanalysis,
Secondary Ion Mass Spectrometry, and ESCA/Auger.
Sulfur Form Sampling and Analysis--
A document was prepared which describes how the controlled condensation
system can be modified to collect sulfate particles, H2S04, S02, HC1 and HF.
Recommended analytical procedures were included.
Liquid Aerosol Sampling--
The task was to measure the mass flow and size distribution of water
droplets at the inlet and outlet of mist eliminators at the TVA Shawnee Wet
Limestone Test Facility.
The following stream characteristics were considered representative:
T: 50°C
Droplet Loading: of order 2-20 grains/SCF at inlet
0.02 grains/SCF at outlet
Gas Velocity: 2.5 - 3.5 m/s at inlet
18 m/s at outlet
Humidity: 100% + droplets
Inlet: 2.5 m diameter.
The water content of saturated air 9 50°C was approximately 45 grains/SCF,
and a 1°C change from 50°C altered the water content by about 2.5 grains/SCF.
This means that any measurement technique would have to be highly isothermal
in order to avoid altering the raio of liquid to gaseous water, which would
result in a meaningless measurement. Thus, any extractive technique would
not be feasible. Two approaches to the problem were considered. The first,
an in situ optical approach, was eliminated because a suitable optical
measuring device is not now commercially available. The second approach was
droplet counting and sizing by means of a hot wire or hot film sensor.
190
-------
Hot wire sensors have long been used in gas flows and in liquid flows
for velocity and turbulence measurements. It has more recently been verified
that hot-wire sensors can be used in two-phase flows (liquid droplets
dispersed in a gas) to measure droplet size. Fortunately, the droplet size
range in which the approach is practical is also the droplet size range of
interest for this specific problem. As a droplet contacts the heated wire,
it is captured through surface tension forces and remains attached to the wire.
It then evaporates, leaving the wire bare and "ready" for the next droplet
impact. The evaporation phase, for normal operating conditions, lasts from
one to ten milliseconds, according to the size of the initial droplet. The
wire is heated by means of an electric current to a specified temperature
above ambient. When a droplet at ambient temperature strikes the wire,
the increased heat transfer rate causes an increase in the amount of
current required to maintain the specified temperature (referred to as
overheat temperature). The current increase is actually measured as a
voltage increase. The droplet impact produces a voltage spike (typical
rise time to maximum voltage 0.1 msec), with the voltage dropping back
to its undisturbed value as the droplet evaporates. This peak height has
been observed to be a linear function of the droplet diameter.
The KLD Model DC-1 Droplet Counter is a commercial device specifically
designed to use a hot-wire sensor in the manner described above to measure
"the size and concentration of water droplets present in the stream of
scrubbers." It does have to be used conscientiously to get valid results,
especially with the higher gas velocity of the outlet. Several comments,
not in the operating manual, which could improve data follow:
t The instrument output is number of counts per unit time for a
specified size range. This immediately gives size distribution
at the sampling point, but total mass loading also requires
knowledge of the effective wire capture area, which is greater
than the wire cross-sectional area, and is a function of particle
size This type of information should be supplied by the manu-
facturer. Mass balance data comparisons are probably the best
way to check the instrument data accuracy, and droplet mass
flow, rather than size distribution, is needed to do mass balances.
• It is essential that sampling locations be chosen so that the
local droplet velocities are in the same direction as the local
gas velocity, the local gas velocity direction is known or can
be determined, and the probe can be accurately aligned with the
191
-------
wire axis normal to the flow direction. Alignment of the wire
axis normal to droplet direction of motion is required for
accurate, meaningful dataT
• When droplets evaporate, any solids will be left as a residue
on the wire. In a scrubber, of course, significant solids
content must be expected. Any residue will act as a thermal
insulator and degrade the accuracy of the data. This means that:
1) run times should be kept short to minimize deposition;
2) the sensor should be properly cleaned between runs; 3) it
must be realistically expected that there will be run-to-run
calibration shifts. These must be accounted for both in opera-
tion and data reduction.
t The factory should be consulted on how to get meaningful data
at gas velocities as high as 18 m/s, since the instrument specs
list a maximum gas velocity of 3 m/s.
• High droplet stratification levels must be expected. Data should
be acquired through sixteen-point traverses.
Automating Control of Wet Scrubber Systems— .
As a result of a meeting of representatives of EPA, TVA, TRW, Bechtel
Corporation and the University of Cincinnati, all of whom are concerned
with measuring key process stream parameters and developing control
strategies for wet limestone scrubbers, TRW investigated the following
questions:
• Evaluate state of the art on-line coal sulfur monitors.
• Investigate pH electrode systems which will withstand on-line
conditions in scrubber liquors. (This subtask resulted in the
issue of a task to study pH and chloride electrode operation in
wet scrubbers. A report of this work is contained in Task 62).
t Investigate non-conventional approaches to monitoring a variable
which accurately reflects pH.
• Conduct a literature survey for state of the art FGD monitor systems
to see what species are monitored by what methods. Specifically,
approaches to real time monitoring of S in coal, gas flow, SO?,
pH, COg, 505, SO^, C1-, Mg+2 and Ca+2 sh0uld be considered.
2.22.4 Recommendations
Recommendations were made in written reports on equipment and procedures
which would be best suited to a particular sampling and analysis problem.
For trace element sampling and analyses, taking samples with the source
assessment stack sampling (SASS) train and analyzing them by inductively coupled
192
-------
plasma optical emission spectrometry (ICPOES) will provide the best overall
performance and be the most effective. The MRI impactor provides the most
size information, but it is limited in sample size and does not collect
volatiles.
At this time, liquid aerosol sampling at a mist eliminator is practical
only with the careful use of the KLD Model DC-1 droplet Counter.
193
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2.23 TASK 53 INPUT TO LEVEL 1 MANUAL REVISION
2.23.1 Objective
This task was initiated in November 1977, to provide updated and
revised chapters on gas, vapor and particulate sampling, and inorganic
analysis (Chapters II, III, and VII). These revised chapters were submitted
to Research Triangle Institute (RTI) to be incorporated into the upcoming
republication of the IERL-TRP Procedure Manual for Level 1 Environmental
Assessments.
2.23.2 Approach
The revised chapters provided by TRW were the product of three primary
sources of methodology:
1. The current IERL-RTP Level 1 manual (EPA-600/2-76-160a)
2. Procedure modifications that have been compiled by RTI and
approved by PMB
3. The detailed and complete Level 1 sampling and analysis pro-
cedures manual produced by TRW for use on the Environmental
Assessment of Conventional Combustion Sources (EACCS) project.
The approach was to start with the current IERL-RTP manual, incorporate
the approved modifications from RTI, and then flesh-out ambiguous and overly-
terse areas with diagrams and descriptions from the EACCS manual.
2.23.3 Technical Discussion
The revised chapters submited under this task represented the best
currently available Level 1 methodology. Specific tasks conducted on both
the TLE and EACCS projects examined and improved the inorganic analysis
procedures, and the over 50 Level 1 source tests performed on the EACCS
project provided practical experience in dealing with the requirements and
realities of field testing. These experiences in both the analytical and
sampling aspects of Level 1 methodolgoy had been integrated into the EACCS
procedures manual as they evolved. With this task, these improvements have
also become part of TRW's input to the revision of the IERL-RTP Level 1
manual. For example, analytical studies have led to the development of
194
-------
the quartz-lined Parr bomb procedure and significant refinements to the
Hg, As, and Sb procedures to improve sensitivities and counteract problems
encountered with the matrix of certain types of Level 1 samples (e.g. per-
oxide and persulfate impinger solutions).
2.23.4 Summary of Results and Recommendations
The revisions of Chapters II, III and VII vere submitted in March 1978
and accepted by RTI for publication. (The second edition of the manual
was issued in October 1978 as document number EPA-600/7-78-201, PB 293 795).
195
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2.24 TASK 57 AT-SEA ENVIRONMENTAL IMPACT STATEMENT STUDIES
The objective of this task was to prepare portions of an environmental
impact statement for at-sea incineration of industrial wastes documenting
the effects on the environment which could result from the adoption of
international standards regulating incineration at sea activities.
The results of this effort were presented to the International
Maritime Consultative Organization at their June 1978 conference in London.
The final report was published in August. Background information on
incineration at sea included a brief history of European and U. S. activities,
a projection of the type and quantities of U.S. wastes which might be
incinerated at sea, a summary of proposed actions for construction of a U.S.
incineration ship, and a listing of U.S. legislation and regulations for
controlling incineration at sea.
In discussing the environmental impact of at-sea incineration of
organochlorine wastes, special attention is given to the problems of handling
hazardous wastes, i.e., potentially carcinogenic, mutagenic or teratogenic
substances, wastes containing metals and solid wastes. Incinerator
efficiencies and incinerator flame temperatures observed in successful
burns on the M/T Vulcanus are also given. Effects on the air quality and
water quality from emissions of HC1 , unburned wastes and metals are also
based on data obtained during actual burns on the M/T Vulcanus.
Disposal of organochlorine wastes by at-sea incineration is expected to
have only minimal socio-economic effects. Included in the discussion were
specific impacts on beach and shoreline recreation, recreational uses of areas
containing the burn zone, demographic impact, economic impact, land use,
and required public services.
Three alternatives to incineration at sea are reviewed: secure landfills,
land-based incineration and waste recovery by chlorolysis. A section on
adverse environmental impacts which are unavoidable particularly points out
the risks of accidental spillage. Finally the report included a statement
about the commitment of physical and biological resources which is irreversible
and irretrievable.
196
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2.25 TASK 62 pH AND CHLORIDE SENSITIVE ELECTRODES
2.25.1 Objective
The goal of this study was to determine the applicability of chloride
and PH electrodes in automated control systems. Included in this study was
a survey of chloride and pH electrode use in different flue gas desulfuri-
zation (FGD) systems and an evaluation test of an industrial pH electrode
system.
2.25.2 Approach
The study incorporated a survey of 8 companies utilizing pH and chloride
measurements. The methodology and more important, the utility of the measur-
ements were evaluated. When the utility of either electrode's measurements
was judged necessary for the majority of the surveyed companies, an
evaluation test of the appropriate electrode was to be planned. The purpose
of the evaluation test was to determine the applicability of the electrode(s)
in automated control system. The criteria for evaluation were in the areas
of maintenance, maintenance schedule, accuracy, precision, reliability, and
durability. Of these criteria maintenance was the most critical factor.
2.25.3 Technical Discussion
Uses of Chloride and pH Measurements-
Results of the 8 companies surveyed are presented in Tables 26 and 27.
The following paragraphs highlight the most significant comments received.
High chloride concentrations (as HC1) may cause internal FGD unit
corrosion. Of the companies surveyed only two had reported high chloride
levels and made routine chloride measurements in the laboratory on grab
samples.as a part of the normal FGD unit maintenance schedule. The integ-
ration of a chloride electrode into an automated system is only necessary
where high chloride concentration is a problem. The applicability of the
electrode for automation may take two directions. In one method, chloride
measurements are used as a warning device such that operators are notified
of high concentration levels and manual operations are used to correct
the situation. The alternate approach is to completely integrate chloride
measurements into an automated system such that high concentrations will be
automatically corrected by the control devices.
197
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TABLE 26. SURVEY OF FGD UNITS FOR pH MEASUREMENTS
UTILITY
1. Shawnee, EPA/TVA
Paducah, KY
2. Green River
Kentucky Utilities
3. Cane Run No. 3 & 4
Louisville Gas and
Electric
4. Bruce Mansfield
Pennsylvania Power
Company
5 Scholz Station
Gulf Power
(Southern Company
Services)
6. Sherburne County
Northern States Power
7. Col strip
Montana Power
8. Lawrence #4.
Kansas Power and
Light Company
KEY CONTACT
Gina Dallabetta
(415) 768-3567
S. V. Anderson
(502) 754-4541
Mary Pederson
(502) 566-4547
Tim Flora
(412) 643-5000
Randall E. Rush
(205) 870-6320
Wayne Salo
(612) 261-4100
Carl ton D. Grimm
(406) 723-5421
Kelly Green
(913) 296-6300
1 CHEMISTRY
OF
SCRUBBER
Limestone
Lime
Carbide-Lime
Lime
Dual Alkali
Sodium/ Calcium
Limestone
Ash
Limestone
COMMERICAL
pH MEASUREMENT
SYSTEM
Uniloc
No ultrasonic
cleaning
Uniloc
No ultrasonic
cleaning
Uniloc,
Leeds and Northrop
Ultrasonic
cleaning
Uniloc
No ultrasonic
cleaning
Uniloc
Leeds and Northrop
(Ultrasonic cleaning
on L&N in Reactor
only)
Uniloc
Ultrasonic cleaning
Electrofact (currently
being tested
Great Lakes
No ultrasonic
cleaning
Uniloc
ultrasonic cleaning
LOCATION 6f
pH ELECTBQDES &
pH VALUES
Inlet 5.5
Inlet 8-8.5
Middle 7.5-8
Outlet 5*5-7
Inlet 8-8.5
Middle , 7
Outlet >6~'
Discharge of
scrubber and
adsorber 7
Scrubber
Effluent 5.0-6.5
Reactor
Effluent 8.0-13.0
Outlet 4-6
Recycle 4.5-5.5
pump
discharge
Outlet 5-7
vo
CD
(Continued)
-------
TABLE 26. (Continued)
UTILITY
1. Shawnee, EPA/TVA
Paducah, KY
2. Green River
Kentucky Utilities
3. Cane Run
Louisville Gas and
Electric
4. Bruce Mansfield
Pennsylvania Power
Company
c Scholz Electric
3< Gulf Power
(Southern Company
Services)
6. Sherbourne County
Northern States
Power
7. Col strip
Montana Power
8. Lawrence #4.
Kansas Power and
Light Company
MAINTENANCE
3 times weekly
acid wash
Once a week
acid wash
Once a week
acid wash
3 times a week
acid wash
Once a week acid
wash or when
necessary, usually
less frequently
Once a week or
when necessary
acid wash
Once a week
acid wash
Less than once
a week
TYPE OF PROBLEMS
Scaling
No problems
Some type of scaling
With L&N less scaling
problem
No problems
Erosion of
electrodes
Coating on
electrodes (not
gypsum)
Erosion of
electrodes
Physical damage,
scaling
HOK pH DATA IS
EMPLOYED
Performance and
control scaling
Control scaling
General Operation
Control Scaling
Control or prevent
scaling - optimize
S0» scrubbing
Performance (not
critical to
operation)
Monitor chemical
corrosion & erosion
control relative
additive feed
Prevent scaling
Not used
AUTOMATED USE OF
pH ELECTRODES
NO
Yes - Control of
lime feed
Yes - Control Lime
feed
Yes - control lime
feed
No
No
No
Has automatic control
capabilities but not
used
10
vo
-------
TABLE 27. CHLORIDE ION MEASUREMENTS
Utilities
1. Shawnee Test Facility
EPA/TVA
Paducah, Kentucky
2. Green River Power
Station
Kentucky Utilities
3. Cane Run
Louisville Gas and
Electric
4. Bruce Mansfield
Pennsylvania Power
Co.
5. Scholz Station
Gulf Power
(Southern Co. ,
Services)
6. Sherburne County
Northern States
Power
Becker, Minnesota
7. Col strip
Montana Power Co.
8. Lawrence No. 4
Kansas Power and
Light Co.
Chemistry
Limestone
Lime
Carbine-
Lime
Lime
Dual-
Alkali
Sodium/
Calcium
Limestone
Ash
Limestone
Do You Take Cl"
Ion Measurements*
Yes
i
No
No
Yes-Grab samples
Yes
No
No
No
Reasons for
Sampling
Effect on pH i
measurement and
Cl" for corrosion
Cl" for corrosion
Cl" for corrosion
*The utilities which answered "No", in general, meant that their
system was not affected by Cl~ to the extent that specific measurements
had to be routinely performed.
200
-------
Although the potential exists for chloride electrode application in auto-
mated control systems, the limited interest of surveyed companies in chloride
measurements did not merit a pursuit of a chloride electrode evaluation test.
All companies surveyed measured pH with a standard non-self-cleaning
pH electrode. The location of measurement points and the desired pH values
varied considerably. Frequent acid washing of the electrode is necessary to
remove the hard scale which forms around the electrodes. Even though
ultrasonic cleaning shortens the electrode's life, three facilities have
resorted to this technique for cleaning them.
The three lime scrubber sites, were the only sites that utilized the pH
electrodes for an automated control system. This highlights the fact that
lime has a much more consistent chemical composition than limestone. A
system utilizing materials with consistent and predictable chemical
compositions is much easier to automate than a system with chemically incon-
sistent materials. Thus, it is expected that automated lime scrubbing
systems would be more prevalent than automated limestone systems.
It was found that accurate pH measurement of slurry streams is very
important for proper operation and prevention of scaling, corrosion and
erosion in an FGD unit. Paramount to successful pH electrode operation is the
prevention of residue buildup and erosion of the electrode, clearly the most
common problems among the utilities. The field evaluation test of a self
cleaning and standard-type electrode was designed to solve these problems and
to evaluate the applicability of the electrode in an automated system.
Evaluation of pH Electrode—
In this evaluation both the self-cleaning Electrofact 135G/Z electrode
and a standard Uniloc pH electrode were tested. Both electrodes were
placed in an external slurry pot fed from the venturi slurry stream at
the Shawnee Test Facility. A separate line was fed into the control
room so a grab sample could be taken and analyzed with a laboratory pH
meter. Both meter chart recorder readings were obtained for the on-line
electrodes.
Regular calibrations and measurements were obtained over a period of
576 hours; however, the two longest periods of continuous operation were
only 214 and 140 hours.
201
-------
Evaluation of the pH electrode test data revealed the following facts:
• The accuracy and precision of the self-cleaning and standard type
electrode were nearly identical during the duration of the test.
t Scaling was a confirmed maintenance problem with the standard-
type electrode.
t Clogging of the screen surrounding the electrode was a maint-
enance problem with the self-cleaning electrode used in slurry
streams.
• The overall maintenance of both the self-cleaning and standard
type pH electrode during continuous periods of operation less than
two weeks were equal in slurry streams.
• For continuous periods of operation greater than two weeks in
slurry streams, the self-cleaning electrode required slightly
less maintenance.
2.25.4 Recommendations
The following recommendations are made for the application of chloride
and pH electrodes to automated control systems in F6D units (slurry streams):
• Chloride measurements are not necessary unless FDD corrosion
(high chloride values) is a problem or accurate pH calculations
are required*
t For continuous periods of operation less than two weeks the use
of either the standard type or self cleaning pH electrode is
recommended.
• For continuous periods of operation greater than two weeks, the
self-cleaning electrode is recommended and should require less
maintenance.
• If the self-cleaning pH electrode is selected, the required main-
tenance should be significantly reduced when the wire screen sur-
rounding the electrode is removed or the screen mesh size is
increased.
• Additional comparisons at different FGD sites.
t Longer, uninterrupted periods of comparison.
202
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SECTION 3
MINOR TASKS
3.1 TASK 11 MASS EMISSION MONITOR DEMO
This task was concerned with the selection of a site to demonstrate
continuous flow measurement, gas sampling hardware and methodology. The
future objective was to verify adequacy of hardware and procedures over a
long time period. The NIPSCO facility In Gary, Indiana, was selected as
the site for the demonstration of the above activities. The effort
Initiated In this task was completed under Task 49.
3.2 TASK 16 MBS MEETING
Under this task a representative of TRW attended the symposia on
"Methods and Standards for Environmental Measurement." Papers were pre-
sented in the following areas:
• Single and multielement technique development
• Physical and chemical characterizations of aerosols
t Organometallic sampling and analysis
• Laser sensing methods
• Environmental standards.
Table 28 lists the individuals who presented papers and the subject
area.
203
-------
TABLE 28. CURRENT RESEARCH IN MEASUREMENTS OF INORGANIC SPECIES
Name
Address
Current Research
Potential Areas of
TIE Interest
Peter Pel la
PO
o
Edward Murray
Mohammad Fatemi
R.T. Ku
Peter Lott
NBS
Analytical Chemistry
Division
Washington, DC 20234
Stanford Research
Institute
333 Ravenwood Ave.
Menlo Park, Ca. 94035
NRL
4555 Overlook Avenue
Washington, DC 20375
MIT Lincoln Labs
244 Wood Street
Lexington, Ma. 02173
U. of Missouri
Chemistry Dept.
Kansas City, Mo.
The use of this film and
borate fusion powders are
being studied for use as
XRF standards.
Using differential absorp-
tion with NOg, S02, 03,
H20, HC&, H20, and CHy
were monitored.
Identification and quanti-
fication of asbestos fibers
using electrostatic align-
ment prior to XRD analysis.
Solid State lasers (PbSnTi)
used to measure CO over
1 kw
Particulate matter from Pb
smelters was identified
using XRD
The generation of known
particles and collection on
glassfiber filters as a
means of preparing XRF
standards for high volume
stack or ambient samplers.
The use of lasers to moni-
tor concentractions of HQ
and S03 (H2S04).
Sensitivity of XRD for
environmental compounds as
well as means of sample
preparation and standard
generation.
The use of lasers to moni-
tor in stack circumstances
of HCa, and $03 (H2S04).
Extending and quantifying
XRD analysis of environ-
mental samples to Hg, As,
and Cd compounds.
(Continued)
-------
TABLE 28. (Continued)
Name
Address
Current Research
Potential Areas of
TIE Interest
Robert Bramer
ro
o
(71
Eris Crecelius
Ronald Hurley
Eugene White
Donald Reamer
John GiIfrich
Mortega
Oanghorbani
U. of S. Florida
Dept. of Chemistry
Tampa, Florida
Bettelle
Richland, Wa 99352
Materials Research Lab
Penn State U.
University Park, PA
16802
U. of Maryland
Dept. of Chemistry
College Park, Md.
NRL
Code 6481
Washington, DC
Environmental Trace
Substances Research
Center
Columbia, Mo. .
Using selective solid sup-
ports to sample organomer-
cury, arsenic and selenium
compounds.
Studied as compounds
found in human urine
samples.
Sulfur forms in coal using
XRF
Samp!i ng organometal1i c
compounds with solid
absorbants followed by GC/
microwave detection.
Sulfur valince state using
a wavelength dispersive
XRF.
Extraction of trace ele-
ments in aqueous medis.
Using the solid supports
for sampling flue gas
streams.
Discuss the use of this
modification to Bramer's
techniques applied to pro-
cess water streams.
Application of XRF analysis
of sulfur forms to environ-
mental samples
Interferences to his col-
lection system, especially
S02 and H2S
Application of wavelength
dispersive XRF to differen-
tiate between other ele-
ments and their anions.
Discuss the possible GC
quantification and identi-
fication of metal ion
chelates, as well as cur-
rent research at ETSRC.
(Continued)
-------
TABLE 28,(Continued)
Name
Address
Current Research
Potential Areas of
TIE Interest
Lee Hanson
John Small
R. Stafford
ro
o
o>
E.S. Etz
Douglas Segar
David Burrell
Thermochemical
Institute
Brigham Young U.
Provo, Utah 84602
NBS
Analytical Chemistry
Division
Washington, DC
Dept. of Engineering
& Applied Science
Yale U.
Becton Center
New Haven, Conn. 06520
NBS Analytical
Chemistry Division
Washington, DC 20234
NOAA
Code C61
Rockville, MD 20852
Institute of Marine
Science
U. of Alaska
Fairbanks, Alaska
99701
Thermometric titration of
sulfur compounds in envi-
ronmental samples
SEM-EDX of individual
particles
Laser Raman of suspended
ambient sulfate particles,
Laser Raman of individual
particles collected on
membrane filter.
Liquid chromatography
separation of organometal-
lic compounds followed by
flame!ess AAS
Reverse voltametric anal-
ysis of complex ions in
saline waters
Application of this
approach to complex samples
such as those attained from
process gas streams.
Sensitivity for compound
analysis and potential of
SEM selective area diffrac-
tion for compound analyses.
Application of this
approach to real time iden-
tification of stack efflu-
ent particles.
Application of this
approach to material col-
lected in the cyclones on
filters of a SASS train.
Extension of this technique
to complex wast streams.
Application to process
streams where organic might
be present.
(Continued)
-------
Name
TABLE 28. (Continued)
Address
Current Research
Potential Areas of
TIE Interest
Richard Dinst
Gary Gravatt
NBS
Analytical Chemistry
Divison
Washington, D.C.
NBS
Analytical Chemistry
Division
Washington, D.C.
Anodic stripping yoltametry
to determine cadmium speci-
ation in natural waters.
Differential light scatter-
ing of polarized light
Extension of ASV to process
stream waters.
Development of a 'liquid
aerosol counter capable of
discrimination between dry
and liquid aerosols in the
same stream.
-------
3.3 TASK 28 SASS - S02 TESTS
The objective of this task was to determine if the SASS train
condensation module can be used to collect H2S04 while avoiding a large
positive error due to SCL oxidation in either gas or liquid phases. The
results of this task were:
t S02 (SO) oxidation to S03 (SO ranges from 0.05-0.9 percent.
t The above range makes a prediction of the expected background
level of SO^ difficult.
The following recommendations were made as a result of this task:
• Further tests should be run to measure the S02 oxidation rate to
develop a statistical base for predicting the potential $03
interference.
t Evaluations should be made of the effect of storage and analysis
procedures on the SO^/SO^ ratio.
3.4 TASK 29 S03 MEASUREMENT PRESENTATION
The objective of this task was to present to IERL contractors the
methodology developed by TRW to measure H2S04 in particle laden flue gas
streams. On February 22, 1977 the proposed quality assurance program for
the H2SO^ measurements at the Shawnee FCD Test Facility was reviewed by
Bob Statnick (IERL) and Frank Smith (RTI). On February 23, 1977, TRW gave
two presentations on the ^$04 measurement methodology concerning:
1. The use of the controlled condensation procedure in the field.
2. The presentation of the laboratory data from Task 13.
3.5 TASK 33 DENVER X-RAY MEETING
Under this task TRW representative attended the Denver Symposium on
"Applications of X-Ray to Environmental and Occupational Health Analyses".
The Symposium was sponsored by the Denver Research Institute, University of
Denver and Phillips Electronic Instruments. Papers were presented on the
following instrumental methods of analysis:
• X-Ray Diffraction
• Electron Microprobe
• Electron Microscopy
Table 29 lists the individuals who presented papers and the subject area.
208
-------
TABLE 29. CURRENT RESEARCH IN APPLICATIONS OF X-RAY TO ENVIRONMENTAL
AND OCCUPATIONAL HEALTH ANALYSES
Name
Address
Current Research
ro
o
10
J. Crouse
Phillip Cook
George Wadler
Kurt Heinrich
John Armstrong
Ed Peters
Ian Steward
Phil Russel
Bernard Harris
Colorado School of Mine
Environmental Research
Laboratory
Amoco Steel
NBS
University of Arizona
ADL
McCrane Associates
Denver Research
Institute
Battelle Columbus
Laboratory
XRD analysis of asbestos impurities
found in talc
XRD to monitor asbestos in air
XRD analysis of various silicon
phases
Electron microprobe analysis as a
qualitative technique
Electron microprobe techniques for
determination of fly ash composi-
tion
Transmission electron microscopy
analysis on asbestos
Asbestos in various tissues
TEM and SEM analysis of smog
X-ray fluorescence techniques for
total sulfur in natural and trented
coal.
-------
3.6 TASK 44 PARTICULATE MEASUREMENT MEETING
Under this task a TRW representative attended the "Symposium on High
Temperature, High Pressure Particulate Control". The Symposium was spon-
sored by EPA/DOE and was held in Washington D.C. on September 20 and 21,
1977. TRW's past experience most closely relates to the presentations
given in Session IV: Particle Sampling and Measurement. TRW has built an
extractive particle/slag sampling system for use in a high pressure coal
combustor, and informal exchanges of information took place with Aerotherm
engineers who have been working in the same area. With regard to
particulate control technology, it was made clear that while there are
various proposed techniques, none are yet fully proven and operational.
3.7 TASK 45 SASS TRAIN THERMAL CONTROL ALTERNATE
The objective of this task was to determine an alternate thermal
control system for the Source Assessment Sampling System (SASS) presently
being manufactured by Aerotherm Corporation, Mountain View, California.
This sampling system is utilized in EPA Level 1 Environmental Assessment.
The results of this task were:
t A thermodynamic analysis of the thermal control system was
performed to determine the requirement of the system under
normal and/or extreme operating conditions.
• The optimum system for the alternative design was composed
of two immersion coolers which would be used with the existing
cooling bath.
• Total cost for the modification to the system would be $1040.
3.8 TASK 46 STEPWISE ARSENIC PROCESS
The objective of this task was to evaluate a proposed Level 1 arsenic
procedure based on atomic absorption spectrometry in terms of its accuracy,
precision, percentage recovery, efficiency of usage. The results of the
evaluation were:
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1. For quantification, measuring the area under the absorbance
peak is more reliable than measuring peak height.
2. Sodium borohydrate reduces arsenic to arsine more effectively
than stannous chloride - zinc slurry (25% better response).
3. Stepwise arsenic procedure had a precision of less than 5%
(Level 1).
4. A relative error of 11 percent was obtained when analyzing a
NBS coal fly ash standard.
5. Greater than 85% of the arsenic added to each Level 1 sample
matrix was recovered.
3.9 TASK 54 FATE OF PCB's IN ROLLINS ENVIRONMENTAL SERVICES PLANT FIRE
The objective of this study was to investigate the fate of polych-
lorinated biphenyl compounds (PCB's) that were stored in a tank farm at a
chemical disposal site when a catastrophic fire struck the facility in
December 1977. The PCB's were selected for study because they are not only
toxic and environmentally long lived, but they may also serve as precursors
for the formation of new compounds which are even more toxic. This study
attempts to define what new products may have been formed under the conditions
that existed at the time of the accident.
Two compounds of particular concern that may have been formed are the
polychlorinated dibenzofurans and the polychlorinated dibenzo-p-dioxins. Both
of these compounds are highly toxic when partially chlorinated. Oioxins have
been shown to have pronounced fetotoxic and some teratogenic effects even in
the absence of any noticeable acute toxicity.
19 1 10 9
^
3 L' /I JJ sV all A I! J7
Dibenzofuran Dibenzo-p-dioxin
The formation of polycyclic aromatic hydrocarbons (PAH's) from PCB's
also is a concern because they are known carcinogens. PAH formation is
favorable under pyrolysis (no oxidizing species present) and oxygen deficient
conditions which were expected to have existed as a result of the fire.
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The study was divided into three major elements of activity. The first
activity was dedicated to the definition of the probable conditions to which
the PCB's were exposed. The second activity addressed the question of what
new products could be formed given the conditions that were defined in the
first activity. The approach employed to define the new products was to
allow the PCB's to react with the simple radical species likely to exist in
combustion processes. Particular emphasis was placed on the formation of
dibenzofurans and dibenzo-p-dioxins. Part of this activity was also directed
to a definition of how the PCB's and reaction products may have been dispersed
in the environment during the accident. The last activity summarized results
of commercial scale incineration of PCB materials for comparison to the
results of this study.
This study concluded that under certain conditions polychlorinated
biphenyl compounds may serve as precursors for the formation of other environ-
mentally undesirable compounds. The most probable class of compounds formed
are dibenzofurans. The reaction pathways to these compounds seemed to be
favorable under oxygen deficient combustions and low temperature. Conversely,
it seems improbable that dibenzo-p-dioxins are formed under similar
conditions. If dibenzo-p-dioxins were to be formed, they would come from
the dibenzofurans that are initially generated from the PCB's. Formation
Of polycyclic aromatic hydrocarbons (PAH) is possible via pyrolysis of PCB's.
in oxygen deficient conditions that could have existed in the Rollins fire.
3.10 TASK 58 WORKSHOP PRESENTATION
The Environmental Sciences Research Laboratory, EPA/RTP, sponsored a
workshop on Measurement Technology and Characterization of Primary Sulfur
Oxides Emission from Combustion Sources in North Carolina during
April 1978. The objectives were 1) to review and discuss current
measurement methods and problem areas for sulfur oxide emissions with
attention focused on sulfuric acid, sulfates and sulfur-bearing particulate
matter; 2) to review and discuss emission data based on application of
these methods to various combustion sources under different operating
conditions; and 3) to delineate and recommend areas in need of further
research and development. Dr. R. F. Maddalone presented a paper,
"Sulfur Emissions Sampling and Analysis," detailing work techniques
for sampling and analyzing S02, H2S04 and particulate sulfate emissions
from flue gas desulfurization units.
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SECTION 4
REPORTS ISSUED
Task 1.
Hamersma, J. VI., S. L. Reynolds, and R. F. Maddalone. IERL-RTP
Procedures Manual: Level 1 Environmental Assessment. EPA-600/2-76-160a,
June, 1976.
Task 2.
Maddalone R. F., A. Grant, D. Luciani, and C. Zee. Procedures for
Aerosol Sizing and S03 Vapor Measurements at TVA Shawnee Test Facility.
EPA-600/7-79-152, July, 1979.
Task 5.
Zee, C. A., D. 6. Ackerman, J. F. Clausen, M. L. Kraft, and S. L.
Reynolds. Draft Report. Evaluation of the SASS Train and Level 1
Sampling and Analysis Procedures Manual. Prepared for U. S. Environmental
Protection Agency under Contract No. 68-02-2165, Research Triangle Park,
No. Carolina, 1976.
Task 7.
Maddalone, R. F., L. E. Ryan, R. Delumyea, and M. M. Yamada. Technical
Manual for Level 2 Inorganic Compound Analysis. EPA 600/2-79-200,
November, 1979.
Task 8.
Beimer, R. G., H. E. Green, and J. R. Benson. EPA/IERL-RTP Procedures
Manual: Level 2, Sampling and Analysis of Selected Reduced Inorganic
Compounds. EPA-600/2-79-199, November, 1979.
Task 9.
Brooks, E. F., and C. H. Clendening. Assessment of Instrumentation
for Monitoring Coal Flow rate and Composition. EPA-600/7-79-196,
August, 1979.
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Task 10.
Hamersma, J. W., and M. L. Kraft. Coal Sulfur Measurements.
EPA-600/7-79-150, July, 1979.
Task 12.
Brooks, E. F., N. Gat, M. E. Taylor, T. E. Chamberlain, R. J. Golik,
and R. Watson. Development Study of a Novel Continuous-Flow Impactor,
EPA-600/7-80-014, January, 1980.
Task 13.
Maddalone, R. F. and N. Garner. Process Measurement Procedures:
H2S04 Emissions. EPA-600/7-79-156, July, 1979.
Task 14.
Reynolds, S. L., D. G. Ackerman, J. F. Clausen, M. L. Kraft, and
C. A. Zee. Draft Report, SASS Train and Level 1 Procedures Evaluation.
Prepared for the U. S. Environmental Protection Agency under Contract No.
68-02-2165, Research Triangle Park, No. Carolina, 1976.
Task 22.
Lutz, S. J., R. C. Christman, B. C. McCoy, S. W. Mulligan, and
K. M. Slimak. Evaluation of Dry Sorbents and Fabric Filtration for FGD.
EPA-600/7-79-005, January, 1979.
Task 26. '''
Brooks, E. F.. Total Particulate Mass Emission Sampling Errors.
EPA-600/7-79-155, July, 1979.
Task 32.
Kraft, M. L., and L. E. Ryan, Letter Reports:
1. "Problems and Deficiencies/Level 1 Environmental Assessment
Procedures," April 15, 1977
2. "Parr Bomb Combustion Procedures," May 6, 1977.
3. "Step-Wise Antimony, Mercury and Arsenic Procedures," June 3,
1977.
4. "Effecting the Recovery of As and Hg from Level 1 Impinger
Solutions," July, 1977.
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Task 36.
Reynolds, S. L., and L. E. Ryan, Draft Report. Inorganic MEG
Compounds and Level 1 Assessment Detection Capability. Prepared for U. S.
Environmental Protection Agency under Contract No. 68-02-2165, Research
Triangle Park, No. Carolina, 1977.
Task 45.
Knight, B. A. Alternative SASS Train Thermal Control System.
Prepared for U. S. Environmental Protection Agency under Contract No.
68-02-2165, Research Triangle Park, No. Carolina, 1977.
Task 46.
Yu, C. L., Draft Report. Atomic Absorption Analysis of Arsenic for
Level 1. Prepared for U. S. Environmental Protection Agency under Contract
No- 68-02-2165, Research Triangle Park, No. Carolina, 1978.
Task 47.
Knight, B. A., E. F. Brooks, and R. F. Maddalone. Development of an
Automatic Sulfur Trioxide Monitor. EPA-600/7-79-153, July, 1979.
Task 48.
Acciani, T. R., and R. F. Maddalone. Chemical Analysis of Wet Scrubbers
Utilizing Ion Chromatography. Prepared for U. S. Environmental Protection
Agency under Contract No. 68-02-2165, Research Triangle Park,
No. Carolina, 1978.
Task 49.
Brooks, E. F. Field Demonstration of High Accuracy Continuous Flow
and Gas Composition Methodology (Draft) prepared for EPA under Contract
68-02-2165, RTP, July, 1979.
Task 51.
Acciani, T. R. and R. F. Maddalone. Particle Sizing and Trace
Elements Analysis Approaches. Prepared for U. S. Environmental Portection
Agency under Contract No. 68-02-2165, Research Triangle Park, No. Carolina,
1978.
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Task 53.
Zee, C. A.; Hamersma, J. W.; Maddalone, R. F.; Ung, C. Y.; TRW
Input to Level 1 Manual Revisions - Chapters II, III, and VII. Prepared
for U.S. Environmental Protection Agency under Contract No. 68-02-2165,
Research Triangle Park, No. Carolina, 1978.
Task 54.
O'Rell, M. K. Fate of PCB's in Rollins Environmental Services Plant
Fire. Prepared for U. S. Environmental Protection Agency under
Contract No. 68-02-2165, Research Triangle Park, No. Carolina, 1978.
Task 57.
Fisher, H. J. At-Sea Incineration of Organochlorine Wastes:
Environmental Aspects and Impacts of Adopting International Regulatory
Standards, Prepared for U.S. Environmental Protection Agency under
Contract No. 68-02-2165, Research Triangle Park, No. Carolina, 1978.
Task 62,
Ung, C. Y., T. R. Acciani and R. F. MaddaTone, pH and Chloride
Sensitive Electrodes. EPA 600/2-79-202, November, 1979.
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SECTION 5
REFERENCES
1. "Status of Ocean Incineration of Organic Chlorides Aboard
Matthias III as of 29 June 1976," TRW Report. EPA Con-
tract 68-01-2966.
2. "Status of Ocean Incineration of Organic Chloride Aboard
Matthias III as of 3 September 1976," dated November 12,
1976, EPA Contract 68-02-2165.
3. "At-Sea Incineration of Organochlorine Wastes Onboard the
M/T Vulcanus," dated September 1977, EPA-600/2-77-196.
4. "Rationale for Annex A to Suggested Special Provisions for
Control of Incineration at Sea," dated 18 February 1977,
TRW Report on EPA Contract 68-02-2165.
5. Bramen, R. S., Justin, L. L. and Forebeck, C. C. , "Direct
Volatilization-Spectral Emission Type Detector System for
Nanogram Amounts of As and Sb". Anal. Chem. . 44, 2195 (1972).
6. Estep, P. A., Kovach, J. J., Waldstien, P. and Karr, C., "Infrared
and Raman Spectroscopic Studies of Structural Variations in
Minerals from Apollo 11, 12, 14, and 15 Samples," Geochimica Et
Cosmochimica Acta, 3. 3047 (1972).
7. Lunsford, J. H. , "Structure and Reactivity of Absorbed Oxides of
Sulfur," Dept. of Chemistry Texas A&M, PB-245-046, August 1974.
8. Miller, F. A. and Wilkins, C.H., "Infrared Spectra and Character-
istic Frequencies of Inorganic Ions." Anal. Chem.. 24_(8), 1253
(1252).
g Miller, F. A. and Wilkins, C. H., Bentley, F. F. and Jones, W. H.,
"Infrared Spectra of Inorganic Ions in the Cesium Bromide Region
(700-300cm-i)," Spectrochimica Acta. 16, 135-235 (1960).
in Kolthoff, I. M., Laitinen, H. A. and Lingane, J. J., jL Anu Chem.
Soc^., 59, 429 (1937).
n Bramen, R. S., and Johnson, D. L., "Selective Absorption Tubes and
' Emission Technique for Determination of Ambient Forms of Mercury
in Air," Environ. Scj. Technol . . 8, 996 (1974).
THox1de
217
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14. American Society of Testing Materials, Part 26, ASTM Method
D3226-73T, 1974.
15. E. S. Lisle and J. D. Sensenbaugh, "The Determination of Sulfur
Trioxide and Acid Dew Point in Flue Gases", Combustion, 3j>, 12
(1965).
16. J. N. Driscol and A. W. Berger, "Improved Chemical Methods for
Sampling and Analysis of Gaseous Pollutants from Combustion of
Fossil Fuels. Volume I, Sulfur Oxides", Wai den Research
Corporation, PB 209-267, June, 1971.
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J^PA-600/2- 79-201
4. TITLE ANBTUBTITLE
Sampling and Analysis of Reduced and Oxidized
Species in Process Streams—Final Report
7. AUTHOR(S)
R. F. Maddalone, L. L. Scinto, and M. M. Yamada
9. PERFORMING ORGANIZATION NAME AND ADDRESS
TRW Defense and Space Systems Group
One Space Park
Redondo Beach, California 90278
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
November 1979
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT MO
10. PROGRAM ELEMENT NO.
INE624
. CONTRACT/GRANT NO.'
68-02-2165, Task 221
GENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
OF
PERIOD COVERED
4. SPONSORING AGENCY CODE
EPA/600/13
,5. SUPPLEMENTARY NOTES j.ERL-RTP project officer is Frank E. Briden, Mail Drop 62, 919/
541-2557.
16. ABSTRACT
The report gives results of a program of over 60 tasks involving the eval-
uation, development, testing, and field adaptation of measurement techniques for
elemental analysis and inorganic compound identification in process and effluent
streams. Procedures for particulate sampling at the inlet and outlet of FGD systems
were developed. Methods for H2SO4 sampling in flue gas streams were developed
based on the controlled condensation of H2SO4 vapor (a manual procedure was used
as the basis for an automated H2SO4 monitoring instrument that was built and tes-
ted). Two procedure manuals were written for reduced and oxidized inorganic spe-
cies. The reduced species manual detailed GC and GC/MS procedures for identifying
organometallic compounds as well as homologous series such as RSH and RNH. The
oxidized species were identified using an integrated series of analytical methods such
as AAS ICAP XRD FTIR, ESCA, and SEM-EDX. The procedures developed,
applied'to samples from several EPA programs, showed that the analysis scheme is
applicable to most solid samples from combustion sources. Ion chromatographic
procedures were also developed for analyzing FGD system slurry streams The use
of PH and chloride electrodes for controlling FGD systems was investigated. The
methodology for coal flow monitors was reviewed. ,
KEY WORDS AND DOCUMENT ANALYSIS
Pollution
Sampling
Analyzing
Measurement
Inorganic Compounds
Reduction (Chemistry)
3 /DISTRIBUTION STA I bMbN l"
Release to Public
'•
EPA Form 2220-1
DESCRIPTORS
Oxidation
Industrial Processes
Aerosols
b.lDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Particulate
19. SECURITY CLASS (ThisReport)
Unclassified
20 SECURITY CLASS (Thispage)
Unclassified
c. COSATl Field/Group
I3F
14B 13H
11G
07D
07B
21. NO. OF PAGES
219
22. PRICE
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