United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/7-78-202
October 1978
Environmental Assessment;
Source Test and Evaluation
Report—Chapman Low-Btu
Gasification
Interagency
Energy/Environment
R&D Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide'range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-202
October 1978
Environmental Assessment:
Source Test and Evaluation Report
Chapman Low-Btu Gasification
by
Gordon C. Page (Program Manager)
Radian Corporation
P.O. Box 9948
Austin, Texas 78766
Contract No. 68-02-2147
Exhibit A
Program Element No. EHE623A
EPA Project Officer: William J. Rhodes
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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ABSTRACT
This report presents the results of a Source Test and
Evaluation program conducted at a commercial Chapman low-Btu
gasification facility- The specific objectives were to: char-
acterize the waste streams and potential fugitive emission and
effluent streams from the facility, evaluate the applicability
of Level 1 sampling and analytical methodology to such a char-
acterization, and evaluate the particulate removal efficiency
of the product gas cyclone. All objectives were met. It was
found that Level 1 methodologies required some degree of modi-
fication in order to meet the program objectives. Overall
results from the chemical and bioassay testing indicated that
all waste and process streams examined contain potentially harm-
ful organic and/or inorganic materials. In the coal feeder vent
gases, examples of potentially harmful species include polycyclic
aromatic hydrocarbons (PAH's), CO and Cr. The potentially harm-
ful species found in the separator vent gases included PAH's,
amines, CO, NH3, C2-hydrocarbons, heterocylic nitrogen compounds,
Cr, V and Ag. A variety of trace elements in the gasifier ash
and cyclone dust were found at potentially harmful levels. These
elements included Be, P, Fe, Ca, Al, Li, Ba, Se, Pb, Cu, Ti, Cd,
Sb, V, Co, U, and Cs. The product gas cyclone was found to be
approximately 60 percent effective in removing particulate matter
from the raw product gas stream.
ii
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TABLE OF CONTENTS
Abstract ii
Figures viii
Tables x
Acknowledgements xiv
1.0 INTRODUCTION 1
1.1 PROGRAM SUMMARY 1
1.1.1 Plant Description 3
1.1.2 Test Program Description 5
1.2 CONCLUSIONS 8
1.2.1 Waste and Process Stream
Characterization 8
1.2.2 Evaluation of Level 1 Methodology 12
1.3 RESULTS OF THE SOURCE TEST EVALUATION 15
1.3.1 Total Plant 17
1.3.2 Gaseous Waste Streams 17
1.3.3 Solid Waste Streams 24
1.3.4 Potential Fugitive Emissions and
Effluents 26
1.3.5 Summary of Cyclone Particulate Removal
Efficiency Test 31
1.4 RECOMMENDATIONS 31
1.4.1 Future Data Needs 33
1.4.2 Methodologies Used 33
iii
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CONTENTS (Continued)
2.0 PLANT DESCRIPTION 39
2.1 PROCESS DESCRIPTION 39
2.1.1 Coal Handling 39
2.1.2 Gasification 41
2.1.3 Gas Purification 41
2.1.4 Water Treatment 43
2.1.5 Waste Stream Summary 43
2.2 PLANT OPERATION 45
2.3 PROCESS FLOW RATE AND MASS BALANCE
DETERMINATIONS 45
3.0 SAMPLING METHODOLOGY 49
3.1 DESCRIPTION OF SAMPLING POINTS 49
3.1.1 Coal Feedstock (1) 49
3.1.2 Coal Feeder Vent (2) 51
3.1.3 Gasifier Ash (3) 51
3.1.4 Separator Vent Gas (4) 51
3.1.5 Cyclone Dust (5) 52
3.1.6 Raw Product Gas (10) 52
3.1.7 Clean Product Gas (8) 52
3.1.8 Separator Liquor (6) 52
3.1.9 Tars and Oils (7) 54
3.1.10 Cyclone Inlet and Outlet (9, 10) ... 54
IV
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CONTENTS (Continued)
3.2 SAMPLING METHODOLOGY 54
3.2.1 Waste Stream and Potential Fugitive
Emission and Effluent Characterizations 56
3.2.2 Cyclone Particulate Removal Efficiency
Study 66
3.2.3 Samples for Additional Characteristics 70
4.0 ANALYTICAL PROCEDURES 72
4.1 INORGANIC SPECIES ANALYSIS 80
4.1.1 Gas Phase Analytical Procedures 80
4.1.2 Aqueous Media Analytical Procedures .. 85
4.1.3 Analyses of Solids Samples 94
4.1.4 Analyses for Trace Elements 94
4.2 ORGANIC SPECIES ANALYSIS 96
4.2.1 Gaseous Hydrocarbon Species Analyses . 98
4.2.2 Organic Extraction Procedures 99
4.2.3 Preparation and Analysis Methods 100
4.3 BIOASSAY ANALYSIS 104
4.3.1 Ames Test 105
4.3.2 Cytotoxicity Tests 106
4.3.3 Rodent Acute Toxicity Test 1°7
4.3.4 Fresh Water Tests 108
4.3.5 Salt Water Tests 108
v
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CONTENTS (Continued)
4.3.6 Soil Microcosm Test 109
4.3.7 Plant Stress Ethylene Test 109
5.0 TEST RESULTS H°
5 .1 METHODOLOGIES HO
5.1.1 SAM/ 1A Methodology HO
5.1.2 Bioassay Test Analysis HI
5.2 RESULTS 112
5.2.1 Total Plant 112
5.2.2 Gaseous Waste Streams 115
5.2.3 Solid Waste Streams 124
5.2.4 Potential Fugitive Emissions and
Effluents 136
5.2.5 Summary of Cyclone Particulate
Removal Efficiency Test 147
5.2.6 Additional Results 147
6 . 0 CONCLUSIONS AND RECOMMENDATIONS 153
6.1 WASTE AND PROCESS STREAMS i53
6.1.1 Gaseous Waste Streams 153
6.1.2 Solid Waste Streams L58
6.1.3 Potential Fugitive Emissions 159
6.1.4 Potential Fugitive Effluents 160
VI
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CONTENTS (Continued)
6.2 LEVEL 1 METHODOLOGY 161
6.2.1 Sampling Methodology 161
6.2.2 Analytical Methodology 164
REFERENCES 168
APPENDIX - BIOASSAY, INFRARED SPECTROPHOTOMETRY,
LIQUID CHROMATOGRAPHY AND LOW RESOLU-
' TION MASS SPECTROMETRY DATA FOR A
CHAPMAN GASIFICATION FACILITY 169
vii
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FIGURES
Number page
1-1 SCHEMATIC FLOW DIAGRAM OF A CHAPMAN LOW-BTU
GASIFICATION FACILITY 4
1-2 COMPARISON OF PARTICIPATE TRAIN AND ORGANIC
MODULE SAMPLES - COAL FEEDER VENT GAS 21
2-1 SIMPLIFIED PROCESS FLOW DIAGRAM FOR THE CHAPMAN
FACILITY SHOWING EMISSIONS STREAMS 40
3-1 SIMPLIFIED PROCESS FLOW DIAGRAM FOR THE CHAPMAN
FACILITY SHOWING WASTE AND PROCESS STREAMS AND
SAMPLING POINTS 50
3-2 SCHEMATIC DIAGRAM OF SAMPLING ARRANGEMENT USED
ON THE OUTLET OF THE CYCLONE 53
3-3 SCHEMATIC DIAGRAM OF CYCLONE INLET SAMPLE POINT. 55
3-4 SOURCE ASSESSMENT SAMPLING SCHEMATIC 58
3-5 GRAB SAMPLE COLLECTION AND PREPARATION SYSTEM . . 62
3-6 SCHEMATIC OF THE EPA METHOD 5 SAMPLING TRAIN ... 64
3-7 SCHEMATIC DIAGRAM OF PARTICULATE SAMPLING TRAIN
USED AT THE CYCLONE 67
3-8 SCHEMATIC DIAGRAM OF SAMPLING ARRANGEMENT USED
ON THE INLET OF THE CYCLONE 68
3-9 VELOCITY PROFILE AT THE INLET AND OUTLET OF THE
CYCLONE 69
4-1 ANALYTICAL FLOW SCHEME FOR COAL FEEDER VENT
GASES 74
4-2 ANALYTICAL FLOW SCHEME FOR SEPARATOR VENT GASES. 75
4-3 ANALYTICAL FLOW SCHEME FOR CYCLONE DUST AND
GASIFIER ASH 76
Vlll
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FIGURES (Continued)
4-4 ANALYTICAL FLOW SCHEME FOR SEPARATOR TAR 77
4-5 ANALYTICAL FLOW SCHEME FOR SEPARATOR LIQUOR 78
4-6 ANALYTICAL FLOW SCHEME FOR PRODUCT GAS SAMPLES .. 79
5-1 COMPARISON OF PARTICULATE TRAIN AND ORGANIC
MODULE SAMPLES FOR COAL FEEDER VENT GASES 116
ix
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TABLES
Number Page
1-1 MULTIMEDIA WASTE STREAMS AT THE CHAPMAN FACILITY .. 7
1-2 PROCESS STREAMS IDENTIFIED AS POTENTIAL SOURCES
OF FUGITIVE EMISSIONS AND EFFLUENTS 7
1-3 CHARACTERISTICS OF WASTE STREAMS AND POTENTIAL
FUGITIVE EMISSIONS AND EFFLUENTS FROM THE CHAPMAN
FACILITY 9
1-4 CONCLUSIONS FROM EVALUATION OF LEVEL 1 SAMPLING
METHODOLOGY DURING THE TEST PROGRAM AT THE CHAPMAN
FACILITY 14
1-5 CONCLUSIONS FROM EVALUATION OF LEVEL 1 ANALYTICAL
METHODOLOGY DURING THE TEST PROGRAM AT THE CHAPMAN
FACILITY 16
1-6 MASS BALANCE AROUND THE CHAPMAN FACILITY 18
1-7 SUMMARY OF SAM/1A AND BIOASSAY TEST RESULTS FOR
TOTAL PLANT WASTE STREAMS AND POTENTIAL FUGITIVE
EMISSIONS AND EFFLUENTS 19
1-8 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR COAL FEEDER VENT GASES 22
1-9 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR SEPARATOR VENT GASES 23
1-10 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR GASIFIER ASH 25
1-11 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR CYCLONE DUST 27
1-12 SUMMARY OF DEGREE OF HAZARD VALUES FOR MEG CATE-
GORIES ESTIMATED TO BE IN THE RAW PRODUCT GAS
STREAM 29
1-13 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR SEPARATOR LIQUOR 30
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TABLES (Continued)
1-14 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR BY-PRODUCT TAR 32
1-15 RECOMMENDATIONS FOR FUTURE DATA NEEDS FOR
WASTE STREAMS 34
1-16 RECOMMENDATIONS FOR FUTURE DATA NEEDS FOR
POTENTIAL FUGITIVE EMISSIONS AND EFFLUENTS 35
2-1 WASTE STREAMS AT THE CHAPMAN FACILITY 44
2-2 SUMMARY OF PROCESS STREAMS IDENTIFIED AS POTENTIAL
SOURCES OF FUGITIVE EMISSIONS AND EFFLUENTS 44
2-3 MASS BALANCE AROUND THE CHAPMAN GASIFICATION
FACILITY 47
3-1 SAMPLING AND ON-SITE ANALYSIS SCHEDULE - CHAPMAN
GASIFIER SOURCE TEST EVALUATION PROGRAM 57
4-1 SUMMARY OF ANALYSES PERFORMED 73
4-2 AQUEOUS PHASE ANALYSES BY STREAM. 86
4-3 WATER QUALITY ANALYSES ON SEPARATOR VENT GAS
CONDENSATE 87
4-4 WATER QUALITY ANALYSES ON SEPARATOR LIQUOR 89
4-5 SAMPLES ANALYZED FOR TRACE ELEMENT COMPOSITION ... 95
4-6 STREAMS SAMPLED FOR ORGANIC SPECIES ANALYSES 97
5-1 MASS BALANCE AROUND THE CHAPMAN GASIFICATION
FACILITY i 113
5-2 SUMMARY OF SAM/1A AND BIOASSAY TEST RESULTS FOR
TOTAL PLANT WASTE STREAMS AND POTENTIAL FUGITIVE
EMISSIONS AND EFFLUENTS 114
5-3 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR COAL FEEDER VENT GASES 117
5-4 SUMMARY OF TEST RESULTS - COAL FEEDER VENT GASES . 119
XI
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TABLES (Continued)
5-5 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR SEPARATOR VENT GASES 123
5-6 SUMMARY OF TEST RESULTS - SEPARATOR VENT GASES 125
5-7 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR GASIFIER ASH 129
5-8 SUMMARY OF TEST RESULTS - GASIFIER ASH 131
5-9 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR CYCLONE DUST 133
5-10 SUMMARY OF TEST RESULTS - CYCLONE DUST 134
5-11 SUMMARY OF DEGREE OF HAZARD VALUES FOR MEG CATE-
GORIES ESTIMATED TO BE IN THE RAW PRODUCT GAS
STREAM 137
5-12 SUMMARY OF THE LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR THE SEPARATOR LIQUOR 138
5-13 SUMMARY OF TEST RESULTS - SEPARATOR LIQUOR 140
5-14 SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST
RESULTS FOR BY-PRODUCT TAR 143
5-15 SUMMARY OF TEST RESULTS - SEPARATOR TAR 144
5-16 PARTICIPATE LOADINGS IN THE PRODUCT LOW-BTU GAS
ENTERING AND EXITING THE HOT CYCLONE 147
5-17 SUMMARY OF ADDITIONAL WATER QUALITY PARAMETERS FOR
THE SEPARATOR LIQUOR AND SASS TRAIN CONDENSATE FROM
THE SEPARATOR VENT 149
5-18 PROXIMATE AND ULTIMATE ANALYSES RESULTS FOR THE
COAL FEED, GASIFIER ASH, CYCLONE DUST AND AND BY-
PRODUCT TAR 150
5-19 RESULTS FOR GASEOUS SPECIES IN THE RAW AND CLEAN
PRODUCT GAS 151
XII
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TABLES (Continued)
6-1 CHARACTERISTICS OF WASTE STREAMS AND POTENTIAL
FUGITIVE EMISSIONS AND EFFLUENTS FROM THE
CHAPMAN FACILITY 154
6-2 RECOMMENDATIONS FOR FUTURE DATA NEEDS FOR
WASTE STREAMS 156
6-3 RECOMMENDATIONS FOR FUTURE DATA NEEDS FOR
POTENTIAL FUGITIVE EMISSIONS AND EFFLUENTS 157
6-4 CONCLUSIONS FROM EVALUATION OF LEVEL 1 SAMPLING
METHODOLOGY DURING THE TEST PROGRAM AT A CHAPMAN
FACILITY 162
6-5 CONCLUSIONS FROM EVALUATION OF LEVEL 1 ANALYTICAL
METHODOLOGY DURING THE TEST PROGRAM AT THE CHAPMAN
FACILITY 166
Xlll
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ACKNOWLEDGEMENTS
The following personnel are acknowledged for their
contributions during the preparation of this report: J. M.
Harless, M. P. Kilpatrick, W. C. Thomas, R. V. Collins, W. E.
Corbett, K. J. Bombaugh, B. J. Bolding, L. A. Rohlack, C. E.
Hudak, K. A. Swenson, and G. C. Page.
Guidance and review by W. J. Rhodes and T. K. Janes of
EPA/IERL-RTP also aided significantly in the successful comple-
tion of this source test and evaluation program.
xiv
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SECTION 1.0
INTRODUCTION
Radian Corporation of Austin, Texas, under a 3-year
contract to the Environmental Protection Agency (EPA) is per-
forming a comprehensive environmental assessment (EA) of low-
Btu gasification technology. A major portion of this assessment
involves source test and evaluation (STE) programs at operating
low-Btu gasification facilities. The ultimate objective of each
STE program is the attainment of necessary data for evaluation
of: (1) environmental and health effects of multimedia waste
streams from low-Btu gasification facilities, and (2) equipment
required for control of problem waste streams.
1.1 PROGRAM SUMMARY
EPA has developed methodologies for assessment of
potential health and ecological effects of multimedia waste
streams emitted to the environment. Radian applied these metho-
dologies in an STE program for assessment of multimedia waste
streams from a facility having a Chapman low-Btu gasifier. The
results, conclusions, and recommendations are presented in this
report.
In the Chapman gasifier, coal is reacted with steam
and oxygen (air) in a single-stage, fixed-bed, atmospheric
pressure vessel. In the Chapman facility tested, the raw, low-
Btu gas is treated in cyclones and direct contact quench/coolers
to remove particulate matter, tars and oils.
The Chapman facility was selected for STE for the
following reasons.
It is an operating commercial gasifier to
which access could be gained.
It has a well-defined operating history.
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Its single-stage, fixed-bed, atmospheric pressure
gasifiers are representative of gasifiers currently
in commercial use in this country.
It uses bituminous coal, a widely available
feedstock.
It is equipped with a gas quenching and scrubbing
system that provides a means of evaluating tar and
oil by-products associated with a gas quenching
operation.
It provides an opportunity to obtain particle
removal efficiency data for a hot cyclone.
The specific objectives of the STE program conducted
at this Chapman facility were to:
characterize the multimedia waste streams leaving
the facility, using Level 1 sampling and analytical
methodologies (Ref. 1),
characterize the process streams in the facility
which represent potential sources of fugitive
emissions and effluents using Level 1 sampling
and analytical methodologies,
evaluate the particulate removal efficiency of
the product gas cyclone, and
evaluate the applicability of Level 1 sampling and
analytical methodologies to multimedia waste and
process streams in low-Btu gasification facilities.
All objectives were met. Overall results from chemical and bio-
logical testing indicate that all waste and process streams exa-
mined contain potentially hazardous organic and/or inorganic
materials. The results generally were confirmed by bioassay
screening tests.
The product gas cyclone was found to be approximately
60 percent efficient in removing particulate matter (coal dust,
ash and tar) from the raw product gas stream.
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During this program it was found that modifications to
Level 1 methodologies were required to achieve the program's ob-
jectives. With these modifications, Level 1 methodology can be
considered effective for screening potentially hazardous waste
streams associated with low-Btu gasification facilities.
1.1.1 Plant Description
The Chapman facility under examination produces a low-
Btu gas which is used as combustion fuel for process heaters.
The facility is equipped with 12 operational Chapman gasifiers.
However, current fuel demands are low and can be met by operating
only two gasifiers at any specific time.
A block flow diagram of the Chapman facility is given
in Figure 1-1. Major multimedia waste streams and feed streams
are indicated in the figure.
Three operations are conducted at the Chapman facility:
coal handling, gasification, and gas purification (particulate
removal and gas quenching and scrubbing). The operations con-
sist of one or more discrete steps, as follows.
Coal handling - consists of delivery and storage
of presized Virginia bituminous coal in hopper cars,
along with conveying and storing this coal in the
gasifier feed hoppers.
Coal gasification - consists of producing raw, low-
Btu gas from coal using fixed-bed, atmospheric
pressure, single-stage Chapman gasifiers. The coal
enters the gasifier through a rotating feeder (bar-
rel valve) and is spread across the bed by a distri-
bution arm. The coal is then reacted with a steam/
air mixture to produce a hot (840-950°K, 1050-1250°F)
low-Btu gas. Ash is collected in a water-sealed
ash pan and removed by an ash plow. Pokeholes lo-
cated on top of the gasifier are opened periodi-
cally to permit the insertion of rods to break up
any coal agglomerates that form in the gasifier.
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Figure 1-1.
SCHEMATIC FLOW DIAGRAM OF A CHAPMAN
LOW-BTU GASIFICATION FACILITY
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Gas purification -
Particulate removal - consists of cyclone removal
of particulate matter from the hot, low-Btu gas.
The particulate matter consists of devolatilized
coal particles, tar, and ash.
Gas quenching and scrubbing - consists of remov-
ing tars and oils from the hot gas and cooling
the gas to 320°K (120°F) using in-line sprays
followed by two tray scrubbers and a spray scrub-
ber. Tar-laden quench liquor is sent to a tar/
liquor separator where the tars settle to the
bottom. The tars are removed periodically and
used as an auxiliary fuel in a coal-fired boiler.
The quench liquor is cooled and recycled to the
gas quenching and scrubbing processes. Accumulated
quench liquor is sent to a forced evaporator for
treatment. Ideally, water problems are minimized
by operating the gasifier such that there is no net
accumulation of water in the process.
1.1.2 Test Program Description
In order to meet the objectives of this STE program,
as outlined in Section 1.0, a number of operating parameters
were examined. These included:
process flow rate/mass balance,
character of waste streams,
character of potential fugitive emissions, and
cyclone particulate removal efficiency.
In addition, the effectiveness of Level 1 methodologies was mon-
itored closely. These efforts are summarized briefly in the
following paragraphs.
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Process Flow Rate/Mass Balance Determinations^ -
During the program, process flow rates were determined
for:
coal feedstock,
gasifier ash,
product gas,
cyclone dust, and
tars and oils.
A mass balance around the facility during the test period was
calculated from these data.
Waste Stream Characterizations -
The waste streams from the Chapman facility are listed
in Table 1-1. The streams sampled and analyzed by Radian are
indicated with an asterisk. Criteria for selection of streams
for sampling included accessibility, plant operation and poten-
tial for pollution. For example, process heater flue gas was
not sampled because the heater was located in a restricted area.
Evaporator vapors were not sampled because no spent quench
liquor was sent to the evaporator during the test.
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Table 1-1. MULTIMEDIA WASTE STREAMS AT THE CHAPMAN
FACILITY
Gaseous Emissions
- Coal Feeder Vent Gases*
- Pokehole Gases
- Separator Vent Gases*
- Evaporator Vapors
- Process Heater Flue Gas
- Tar/coal Combustor Flue Gas
Liquid Effluents
- Spent Quench Liquor
Solid Wastes^
- Gasifier Ash*
- Cyclone Dust *
*Indicates the waste streams sampled during the test program.
Potential Fugitive Emissions and Effluents
Characterizations -
The process streams in the Chapman facility are listed
in Table 1-2. These streams, identified as potential sources of
fugitive emissions and effluents, were sampled and analyzed as
part of Radian's test. The data collected from the quench liquor
and by-product tar is also valuable as an aid to the prediction
of control technology and end-use requirements for similar streams
in future facilities.
Table 1-2. PROCESS STREAMS IDENTIFIED AS POTENTIAL
SOURCES OF FUGITIVE EMISSIONS AND
EFFLUENTS
Gaseous Stream
- Raw Product Gas
Liquid Stream
- Recirculating Quench Liquor
Solid Stream
- By-Product Tar
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Cyclone Particulate Removal Efficiency Study -
The particulate removal efficiency of the cyclone in
the raw product gas stream was also studied during this test.
Particulate concentrations were measured in the product gas
stream before and after the cyclone, and the removal efficiency
was determined.
Level 1 Methods Evaluation -
During both the sampling and analysis phases of this
test, the performance of the Level 1 procedures was closely
monitored. At the termination of the test, the applicability
of the various procedures to coal gasification facilities and
samples was evaluated.
1.2 CONCLUSIONS
The conclusions drawn from the results of the STE pro-
gram conducted at the Chapman facility fall into two categories:
those resulting from the characterization of waste and process
streams, and those resulting from the evaluation of Level 1
methodology.
1.2.1 Waste and Process Stream Characterization
An overall summary of the character of the waste and
process streams at the Chapman facility is presented in Table
1-3. As indicated in this table, all of the streams tested con-
tained potentially hazardous organic and/or inorganic materials.
In the case of cyclone dust and coal feeder and separator vent
gases, this conclusion is confirmed by the results of the bio-
assay screening tests. However, in the case of the gasifier ash,
the degree of hazard indicates a moderate potential hazard while
bioassay tests indicate a low potential. Specific conclusions
regarding the character of the various waste and process streams
are given in the following sections.
8
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Table 1-3. CHARACTERISTICS OF WASTE STREAMS AND POTENTIAL FUGITIVE EMISSIONS AND
EFFLUENTS FROM THE CHAPMAN FACILITY
Stream Description
Stream Degree of Hazard
Health Ecological Bioassay Tests
Stream Source Concern Concern Health** Ecologicalc
Remarks and Conclusions
Gaseous Waste Streams
• Coal Feeder "Vent Gas
Coal feeder
High
High
Separator Vent Gas
Tar/liquor
separator
1 x 10B
1 x 10s
High
Solid Waste Stre
• Gasifier Ash
5 x 103
8 x 10s
The SAH/1A analysis and the bioassay test results of
this waste stream Indicated that it may have poten-
tially hazardous health and ecological effects. How-
ever, it should be emphasized that this stream should
NOT be a waste stream from new gasification plants,
and should be controlled by recycling to the gaslfler
inlet air or product gas or by combusting it in a
boiler or flare. The organic content ID this stream
was high with the major classes of organlcs being
polycyclic aromatic hydrocarbons (PAH's), heterocy-
clic nitrogen compounds and phenols. Gaseous com-
pounds in the product gas (CO, HZ , CR*, HjS, COS,
HCN, etc.) were also found in the coal feeder vent
stream.
The results from the bioassay tests and SAM/1A anal-
ysis Indicated that this stream may have potentially
hazardous health and ecological effects. As for the
coal feeder vent stream, this stream should NOT be a
waste stream from new gasification plants. It may
be controlled by recycling to the gasifler inlet air
or product gas or by combusting it in a boiler or
flare. The organic concentration in this stream was
high, with the major organic classes being PAH's and
phenols. Gaseous compounds in the product gas (CO,
Hj, CH», H2S, COS, HCN, etc.) were also found in the
separator vent stream.
The results of a SAM/LA analysis of the gasifier ash
Indicated that It may have a moderate potential for
hazardous health and ecological effects. However,
the results of the bioassay tests showed that the ash
had a low potential for hazardous health and ecolog-
ical effects. The extractable organic concentration
in the ash was ^20 yg/g; trace element concentra-
tions were similar to the amounts of trace elements
found in the ash from coal-fired builers. The major
trace elements found in the ash were alkali metals.
Leaching tests are needed to' determine appropriate
design for landfills as final ash disposal sites.
Continued
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Table 1-3. (Continued)
Stream Description
Stream Source
Stream Degree of Hazard
Health Ecological
Concern Concern
Bloassay Tests
Healthb Ecological
Remarks and Conclusions
Cyclone Dust
Hot -Cyclone
8 x 10s
High
Potential Fugitive
Emissions
Raw Product Gas
Potential Fugitive
Effluents
* Separator Liquor
(liquid)
Gasifler and
hot cyclone
pokeholes
Tar/liquor
separator
High
By-product Tar
(solid)
Tar/liquor
separator
1 x 10B
High
High
From the results of a SAH/1A analysis, the cyclone
dust could be potentially hazardous. The ecolog-
ical bioassay test (soil microcosm) Indicated that
the dust had a high potential for hazardous effect,
while the health effects test showed the dust had
a low potential. The concentration of extractable
organics In the dust was low (t>40 Mg/g). The trace
elements having the highest concentrations were P,
K, Si and Fe. The carbon content of the dust was
high C^92Z) which indicates that the dust Is simi-
lar to devolatilized coal. If the dust is to be
disposed of in a landfill, leaching tests are
necessary; however, combustion of the dust is
probably required before disposal.
Fugitive emissions will contain tar participates,
volatile organics and Inorganics in potentially
hazardous concentrations. The characteristics of
these emissions will be similar to those of the
coal feeder vent gas.
The separator liquor contained high levels of
organics. These consisted primarily of thiols,
phenols and heterocyclic aromatlcs. High levels of
cyanide, ammonia, fluoride and sulfate were also
found. High concentrations of sulfide were not found
which may indicate that hydrogen sulfide sorbed in
the quench either escapes as HiS in the vent gases or
is oxidized to sulfate. Separator liquor vas found
to be very toxic to aquatic species and should not
be discharged without prior treatment.
The by-product tar was the most potentially hazardous
sample tested. A wide range of organics vas found
to be present. The main classes of organics were
PAH's and heterocyclic nitrogen, oxygen and sulfur
compounds. High levels of trace elements were
also found.
a Degree of Hazard for a stream is the sum of the estimated concentrations of components (or classes of components) in the stream divided by their
respective MATE values.
b
Health tests Include: Ames, Cytotoxicity (WI-38, RAM) and Rodent Acute Toxicity
C Ecological tests Include: soil microcosm, plant stress ethylene, fresh water bioassay (algal, daphnia and fathead minnow) and salt water bioassay
(algal, shrimp and sheepshead minnow).
Source Assessment Model/1A
e Degree of Hazard values were estimated from the coal feeder vent gases by assuming a 1:10 gas to air dilution in the vent stream.
NC: Test not conducted
-------
Gaseous Waste Streams -
Coal feeder vent gas - The coal feeder vent gas con-
tained organics, inorganic gases and trace elements at potentially
hazardous concentrations (greater than their Minimum Acute Tox-
icity Effluent (MATE) values). The bulk of the organics con-
sisted of tar particulates. Volatile organics were also present.
Their compositions were significantly different from those of
the tar particulates. The volatile organics had a higher propor-
tion of polycyclic aromatic hydrocarbons (PAH's) while the tar
contained a higher proportion of heterocyclic aromatics. The
tar particulates in the coal feeder vent had organic character-
istics which were different from those of the separator tar, with
the coal feeder vent tar having higher concentrations of PAH's,
heterocyclic nitrogen compounds and phenols. The gaseous inor-
ganic compounds found in the coal feeder vent stream appeared
in concentrations higher than their respective MATE values.
Separator vent gas - The separator vent gas contained
volatile organics and inorganics at potentially hazardous con-
centrations (greater than their MATE values). Volatile organics
consisted primarily of PAH's and phenols. The inorganics con-
sisted of gaseous inorganic compounds and a variety of trace
elements.
Solid Waste Streams -
Gasifier ash - Very low levels of organics were found
in the gasifier ash (^20 ug/g). The major trace elements found
were alkali and alkaline earth metals. Trace element concentra-
tions were similar to those found in ash from coal-fired boilers.
Cyclone dust - Very low levels of organics were found
in the cyclone dust (^40 yg/g). The dust was similar to devola-
tilized coal, as indicated by its carbon, oxygen and hydrogen
content. A wide variety of trace elements were found, but
generally at"much lower concentrations than those found in the
gasified ash. The major trace elements found were K, Si, P and
Fe.
11
-------
Potential Fugitive Emissions -
Raw product gas - The gasifier and hot cyclone poke-
holes are potential sources of fugitive emissions of raw product
gas. Raw product gas contains tar, particulates and volatile
organics and inorganics at potentially hazardous concentrations.
Potential Fugitive Effluents -
Separator liquor (liquid) - The tar/liquor separator
is a potential source of fugitive effluent of separator liquor.
The separator liquor contains high levels of organics, primarily
thiols, phenols and heterocyclic aromatics. High levels of
cyanide, ammonia, fluoride and sulfate were also found. Sulfide
was not found at high concentrations, which may indicate oxida-
tion of the sulfide to sulfate or escape as H2S in the vent gases
Higher concentrations of trace elements were found in the sepa-
rator liquor than in the by-product tar.
By-product tar (solid) - The tar/liquor separator is
also a potential source of fugitive effluents of by-product tar.
The by-product tar was the most potentially hazardous material
tested, and was found to contain a wide range of organics and
inorganics. The main organic constituents were PAH's and hetero-
cyclic nitrogen, oxygen, and sulfur compounds. Fewer trace ele-
ments were found in the by-product tar than were found in the
other streams tested. However, some trace element concentrations
exceeded their respective MATE values.
1.2.2 Evaluation of Level 1 Methodology
Level 1 sampling and analytical methodology was evalu-
ated as part of the overall program. In order to meet the
objectives of this program, certain modifications to the Level 1
sampling and analytical methodologies were made. These modifi-
cations do not reflect official changes in Level 1. In most
cases, the streams and samples that required modifications are
somewhat unique to coal gasification facilities and do not
represent a majority of the waste streams that can be effec-
tively sampled and analyzed by Level 1 techniques. Conclusions
drawn from the evaluation are presented in the following
sections.
12
-------
Sampling Methodology -
Level 1 methodology for grab sampling of gas streams
required certain modifications to suit the conditions encountered
during this STE program. The modifications included: (1) pre-
conditioning sample containers, and (2) pretreatment of samples
to eliminate interfering components such as particulates, tar,
oil, and water.
Level 1 methodology for grab sampling of liquid and
solid streams was adequate for accomplishment of the test objec-
tives. Procedures for selection of sample points for Level 1
testing were generally straightforward.
Specific details and conclusions drawn from the evalu-
ation of Level 1 sampling methodology are presented in Table 1-4.
Analytical Methodology -
Level 1 methods gave satisfactory results in the
following areas: liquid chromatographic separation, low resolu-
tion mass spectrometry and sparks source mass spectrometry.
Problems were encountered using chemiluminescence for NO and NO
determinations and using the test kits for hardness, nitrate and
nitrite analyses. On site experiments indicated that reducing
gas constituents in the gaseous samples to be analyzed for NO
and NOX caused problems in the chemiluminescense technique. EPA
Method 7 procedure for NOX determinations is recommended for
analyzing gaseous streams containing reducing gas constituents.
The problems encountered using the test kits were probably due
to the high levels of organics in the separator liquor sample.
Alternate methods used to analyze gaseous species were
used because of the need to obtain quantitative data for input
to control technology development (i.e. gaseous sulfur species),
the Level 1 detection limits were too high (i.e. NH3 and HCN) or
a comparible" technique was easier to use. Sulfur species were
analyzed using a column to obtain quantitative data on H2S, COS,
CS2 and S02 in the gaseous streams sampled. Impinger techniques
were used for NH3 and HCN determinations. For fixed gases, a
Fisher Gas Partitioner was used to separate N2 and 02 and permit
quantification of the other species on a single sample injection.
13
-------
Table 1-4.
CONCLUSIONS FROM EVALUATION OF LEVEL 1 SAMPLING METHODOLOGY
DURING THE TEST PROGRAM AT THE CHAPMAN FACILITY
Sampling Methodology
Remarks and Conclusions
Gas Sampling
• Grab sampling
SASS train sampling
Level 1 methodology for collecting grab samples of gas streams required certain modifications
to suit the conditions encountered during this STE program. The modifications included:
(1) preconditioning sample containers and (2) pretreatment of samples to eliminate interfering
species such as tars and condensables.
A pretreatment train was necessary for removal of participates, tar, oil, and water from
certain gas samples since these impurities would Interfere with the analysis for gaseous
species. Problems were encountered in the use of a filter to remove tar and particulates.
It was concluded that the tar/partlculate layer on the filter sorbed significant amounts of
sulfur species.
The source assessment sampling system (SASS) must be modified when sampling gaseous streams
containing high levels of tar, oil and/or water vapor. When sampling the coal feeder vent, the
filter in the particulate collection module frequently became plugged with tar. To alleviate
this, the temperature in the particulate module was reduced in 'order to collect a majority of
the tar as particulates in the cyclones, instead of as a highly viscous fluid on the cyclone
filter. When sampling streams that have a high moisture content, such as the separator vent,
additional cooling was required in the SASS train organic module. This modification has been
made in the new SASS train operating Instructions.
In most cases, sampling gaseous waste streams that contain high concentrations of tars, oils
and/or moisture will involve either modifying the SASS train or using an alternate method.
For example, in-line filters and/or electrostatic precipltators may be used to collect tars
and oils.
Liquid and Solid Sampling
The Level 1 procedures for sampling liquid waste streams and potential fugitive effluents were
adequate and generally straightforward.
-------
During the analysis of trace elements, the Parr bomb
solution contained high concentrations of Ca, K and P. These
needed to be factored into the evaluation of the SSMS data.
During analyses for organic species, the extraction
techniques specified by Level 1 methodology were found to be
inadequate. Mass recoveries were generally lower than desired
and certain highly polar organics were not extracted by Level 1
techniques. Extraction with methylene chloride at two pH's may
solve this potential problem. Problems were encountered with
Level 1 methods for total chromatographical organics, especially
with heavy organic loading. In those cases, the resulting
chromatograms were too complex for reliable application of the
specified integration technique. Gravimetric determinations
presented problems. Specifically, problems in weighing
samples that had a very low concentration of organics arose
when only a small quantity of sample was contained on the watch
glass. A scum formed over the surface of certain samples which
could have prevented the volatile material from being evaporated
Specific details and conclusions drawn from the evalu-
ation of Level 1 methodology are presented in Table 1-5.
1.3 RESULTS OF THE SOURCE TEST EVALUATION
The results of the STE program performed at a Chapman
gasification facility are divided into the following areas:
total plant,
gaseous waste streams,
solid waste streams,
: potential fugitive emissions and effluents, and
hot cyclone performance.
The Level 1 chemical and bioassay test results of each of the
above areas are discussed in the following text.
15
-------
Table 1-5.
CONCLUSIONS FROM EVALUATION OF LEVEL 1 ANALYTICAL METHODOLOGY DURING
THE TEST PROGRAM AT THE CHAPMAN FACILITY
Analysis Methodology
Remarks and Conclusions
Gaseous Species
* Nitrogen Oxides
• NHa and HCN
• Sulfur Species (H2S, COS, CS2, S02)
• Fixed Gases (CO, H2, C02, 02, N2 , CH,,)
Inorganics
• Test kits for aqueous phase analysis
• Trace Elements
Organics
• Extraction Techniques
• Total Chromatographable Organics (TCO)
• Gravimetric
• Liquid Chromatography (LC)
Infrared (IR) and Low Resolution Mass
Spectrometry (LRMS)
Analysis of NO by chemiluminescence in nil of the g,is stream samples was found to be adequate;
however, the technique did not work for analyzing NOX • This was probably caused by the presence of
reducing gases in the 'sample. EPA Method 7 is recommended for NOX analysis.
The gas chromatography technique specified by Level 1 was not sensitive enough for determination of
NHs or HCN in the gas samples. NHs and HCN samples were collected in impingers and analyzed by wet
chemical methods.
The gas chromatography technique used to analyze sulfur species
order to give better separation than the Level 1 procedure.
S, COS, CSa , and $62) was used in
The Level 1 procedure for fixed gases analysis was modified. A Fisher Gas Partltioner was used so
that nitrogen and oxygen could be separated and the other species quantified on a single sample
injection.
The test kits specified by Level 1 were found to give adequate results in most cases. However,
results could not be obtained when using these kits for the determination of nitrate, nitrite, or
hardness, probably because of the high organic content in the separator liquor.
The Parr bomb solution contained high concentrations of Ca, K, and P and needed to be factored into
the SSMS data evaluation.
The extraction techniques specified by Level 1 were found to be inadequate for extracting aqueous
samples and XAD-2 resins containing highly polar organic compounds. Total mass recoveries using
the Level 1 procedure ware Jess than 50% for aqueous samples and approximately 70% for XAD-2
resins.
Problems arose when using the procedure for determining TCO's for most of the organic extracts.
This was especially true when high amounts of organics were present because the resulting chromato-
grams were so complex that the integration techniques could not be used reliably.
Problems were encountered with inaccuracy when weighing small quantities of organics obtained from
liquid chromatography fraction. Also, it appeared possible that volatile organics might be trapped
within a sample during evaporation. A scum formed on the surface of certain samples which could
prevent or significantly hamper the evaporation of volatile organics. Such problems could result In
inconsistency in mass balances calculated from these data.
The liquid chromatography method specified by Level 1 was capable of handling a loading of op to 400
mg. Even though there was significant overlap of compounds In different LC fractions, the LC
procedure was adequate for obtaining results specified by Level 1.
The amount of information obtained from the IR spectra was of minimal value for compound class
Identification because of the complex nature of the samples. Most of the Identifications were made
from the results of the LRMS analyses of the LC fractions. Compound identification using LRMS was
also difficult because of the complex nature of the sample, and may not be valid.
-------
1.3.1 Total Plant
The mass balance of the major input and output streams
around the gasification facility is given in Table 1-6. During
the test, two gasifiers (No's. 2 and 3) were operating at a
combined capacity of approximately 60 percent, with the No. 3
gasifier at a higher capacity than the No. 2 gasifier. The
total mass of the streams exiting the plant was found to be
within 16% of the total mass entering the facility.
The results from the SAM/1A analysis and bioassay tests
of the multimedia waste streams, and the potential fugitive
emissions and effluent streams are presented in Table 1-7. In
most cases, the results of the SAM/1A analysis (degree of hazard
values) compared favorably to the bioassay test results. Excep-
tions were noted with the results for gasifier ash and separator
liquor. For the ash stream, the degree of hazard values indica-
ted a moderate potential for hazardous health and ecological
effects, while the bioassay tests indicated a low potential. The
health degree of hazard for the separator liquor indicated mod-
erate potential for hazardous effects, while the health bioassay
tests indicated low potential.
1.3.2 Gaseous Waste Streams
The gaseous waste streams tested in this program were
the coal feeder and separator vent streams. The results of the
SAM/1A, chemical and bioassay tests for each stream are presented
in the following sections.
Coal Feeder Vent Stream -
The coal feeder vent stream contained organics and
inorganic components similar to those found in the raw product
gas stream. The tarry material collected in the particulate
module of the SASS train was significantly different from the
material collected in the organic module. The predominant or-
ganic categories found in both the organic module and the parti-
culate module samples were PAH's, heterocyclic aromatics, and
phenols. However, PAH's represented almost 80% of the organics
from the organic module, while in the particulate module each
of the above three categories accounted for ^20-40% of the
organics found. Additionally, small quantities of a wider
17
-------
Table 1-6. MASS BALANCE AROUND THE CHAPMAN FACILITY
Stream Description
INPUT STREAMS
Air
Steam
Coal Feed
TOTAL
OUTPUT STREAMS
Gasifier Ash (dry)
Cyclone Dust
Cooled Product Gas **
By-Product Tar
TOTAL
INPUT MINUS OUTPUT
kg/s
% of INPUT
No. 2
Gasifier/
Cyclone
0.33*
0.068*
0.129
0.527
0.0085
0.00067
0.420*
0.0129*
0.442
0.085
16
Flow Rate
No. 3
Gasifier/
Cyclone
0.44*
0.092*
0.175
0.707
0.010
0.00094
0.569*
0.0175*
0.597
0.11
16
(kg/s)a
Total
Facility
0.77
0.16
0.304
1.234
0.0185
0.00161
0.989
0.0304*
1.040
0.19
16
aKg/s = 7938 Ib/hr
* Back calculated by ratioing coal feed rate data.
** Based on gas molecular weight of 25.4.
18
-------
Table 1-7. SUMMARY OF SAM/1A AND BIOASSAY TEST RESULTS FOR
TOTAL PLANT WASTE STREAMS AND POTENTIAL FUGITIVE
EMISSIONS AND EFFLUENTS
Degree of Hazard3 Toxic Unit Discharge0
Health Ecological Health Ecological Bioassay Tests
Concern Concern Concern Concern Health" Ecological6
Gaseous Waste
Streams
•Coal Feeder
Vent Gas 4 x 107 8 x 10s 2 x 106 5 x 10*
•Separator
Vent Gas 1 x 108 1 x 10s 6 x 107 6 x 10s
Solid Waste
Streams
•Cyclone
Dust 2 x 103 8 x 10s 3 x 103 1 x 107
•Gasifier
Ash 5 x 103 8 x 105 9 x 10" 2 x 107
Potential
Fugitive
Emissions
•Raw Product
Gas 4 x 10B 8 x 106 ND ND
•Separator
Liquor 3 x 10s 2 x 10s ND ND
•By-Product
Tar 1 x 10" 2 x 107 ND ND
High High
High NC
Low High
Low Low
NC NC
Low High
High High
aDegree of Hazard is defined as the ratio of a pollutant's concentration in a stream to its minimum
acute toxicity effluent (MATE) value.
Potential for hazardous health and ecological effects can be estimated by the following:
Potential Effect Degree of Hazard
High >107
Moderate 10s - 107
Low 102 - 105
Inconclusive <10
cToxic Unit Discharge is determined by multiplying the value of Degree of Hazard by the waste
stream flow rate (gases: NmVsec, liquids: S./SBC, solids: g/sec).
dHealth tests included: Ames, Cytotoxicity (WI-38 , RAM), Rodent Acute Toxicity
^Ecological* tests included: Soil microcosm, plant stress ethylene, fresh water bioassay, and
salt water bioassay
NC - Test not conducted
ND - Flows not determined for potential fugitive emissions or effluents
19
-------
variety of organic categories, including the volatile ones, were
found in the organic module. The concentrations of the various
organics found in the particulate module and organic module
samples are compared in Figure 1-2.
A summary of the degree of hazard values for the Multi-
media Environmental Goals (MEG) chemical categories or compounds
found in the sample is shown in Table 1-8. Also shown in this
table are the results from specific bioassay tests. Positive
results were obtained from the Ames test while the plant stress
ethylene test showed negative results.
The information presented in Table 1-8 can also be
used as a basis for planning subsequent Level 2 chemical char-
acterization tests. A high priority for Level 2 chemical anal-
ysis is placed on MEG categories having degree of hazard values
greater than 100. Medium and low priorities are given to cate-
gories having degree of hazard values between 10-100 and 1-10,
respectively. Based on these prioritization criteria, a higher
priority exists for a detailed characterization of fused aroma-
tic hydrocarbons and their derivatives, CO, and Cr than for the
other chemical categories listed in this table.
It should be emphasized that this waste stream probably
will not be present in new low-Btu gasification facilities. In
new facilities, this stream will probably be controlled by com-
bustion in a flare or incinerator or by recycling to the gasifier
inlet air.
Separator Vent Stream -
A summary of the results from the Level 1 chemical
analyses and bioassay tests for the separator vent stream is
presented in Table 1-9. The separator vent stream contained
significant concentrations of a variety of classes of organic
compounds, particularly methane and other aliphatic hydrocarbons,
amines, phenols, PAH's, and heterocyclic organics. Most of the
degree of hazard values for the organic classes were greater
than 1.
The concentrations of most of the inorganic species
were lower than their respective MATE values. However, high
concentrations of NH3, HCN, NO, N02, CO, and H2S were found.
20
-------
100 -i
90
80
"]
60 -\
Z of
Individual 50
SMiple
40 H
30
25
20
15
10
5
MEG Category
D
Legend
CHjClt washes of
particulate train
Combined organic
module extracts
£
4J
o 4
33
JZL
5
£
Sulfonic
Sulfoxid
Benzene
Benzene
O M
•H a)
U o
o -a u
ss-g
eterocy
ompound
MEG Number
Figure 1-2. COMPARISON OF PARTICULATE TRAIN AND ORGANIC MODULE SAMPLES -
COAL FEEDER VENT GAS
-------
ro
Table 1-8.
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR COAL
FEEDER VENT GASES
Priority for Level 2 Degree of Hazard
Chemical Analysis Range
'"lO7 - 10"
10s - 107
High \ 105 - 10s
10* - 105
103 - 10*
102 - 10s
Compound Categories Found From
Level 1 Chemical Analysis
Health Concern Ecological Concern
Fused aromatic
hydrocarbons and
their derivatives
-
- C2 hydrocarbons
-
Cr CO
Results of the Bioassay Tests
Test Results
Health3
• Ames P
• WI-38 (ECsi))b 4 x 10~*
• RAM (ECso)b >2 x 10~3
Ecological
• Plant Stress
Ethylene N
Medium
10 - lO'
Low
- 10
Heterocyclic nitrogen NH
compounds , carboxyllc
acids & their derivatives,
amines , sulf onic acids and
sulf oxides, phenols, Hg,
U, CO
Ci, thiols, benzene and
substituted benzene hydro-
carbons, heterocyclic sulfur
compounds, Al, NHa , P, As, Hz
Cu, Cd, NO, C02, HCN
s , V, Hg
P: Positive
N: Negative
Health bioassay tests were performed on the XAD-2 extract from the coal feeder vent gases
ECso's were calculated on the XAD-2 extract for the coal feeder vent gases by:
ECso
JECso reported
Jin \li of extract
[per ml culture
mg of organics
extracted per mfc
of extract
[ng of organics I
per Hm' of
rent gas I
^J
Dm1 vent gas/mil culture
-------
Table 1-9.
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR
SEPARATOR VENT GASES
Priority for Level 2 Degree of Hazard
Chemical Analysis Range
1
High ,
rio7 - 10"
106 - 10'
105 - 10s
10* - 10s
103 - 10*
102 - 103
Compound Categories
Found From
Level 1 Chemical Analysis Results of the Bioassay Tests
Health Concern
Fused aromatic
hydrocarbons and
their derivatives
-
-
-
Amines
Heterocyclic
Ecological Concern Test Results
Health
• Ames SP
• WI-38 (EC50)b 7 x 10"G
2 • RAM (ECso) 1 x 10~S
NH3
CO, V
Medium
Low
{.„.
10'
- 10
nitrogen compounds,
Cr, Ag, CO, phenols
Heterocyclic sulfur com-
pounds, Cu, NOz, NH3, P, HzS
Methane, halogenated
aliphatic hydrocarbons,
carboxylic acids &
their derivatives, Li,
HCN, P, As, COz , Fe, Si, U,
Ci, Ce hydrocarbons
HCN, Hg
SP: Slightly positive
aHealth tests were performed on the XAD-2 extract from the separator vent gases
ECso were calculated on the XAD-2 extract for the separator vent gases by:
jECso reported
ECso = in yS, of extract
Iper mJt culture
mg of organics
extracted per mi
of extract
= Nm^ vent gas/mi culture
-------
The trace element concentrations were generally low, with Na,
K, Ca, P, Fe, Cu, and Ag found in the highest concentrations.
The chemical categories having the highest priority
for Level 2 chemical analysis are also shown in Table 1-9.
These categories are fused aromatic hydrocarbons and their
derivatives, amines, CO, NH3, heterocyclic nitrogen compounds,
Cr, V, Ag, and C2 hydrocarbons.
Slightly positive results from the Ames bioassay test
were obtained from the separator vent XAD-2 extract. However,
this stream probably will not be a gaseous emission from new
gasification facilities. It will probably be recycled to the
gasifier or product gas stream or combusted in a flare.
1.3.3 Solid Waste Streams
The solid waste streams from the Chapman gasification
facility were the gasifier ash and the cyclone dust. The Level
1 chemical and bioassay test results for these streams are pre-
sented in the following sections.
Gasifier Ash -
Table 1-10 presents a summary of the Level 1 chemical
and bioassay test results for the gasifier ash. The major trace
elements (>103 ug/g) identified in the ash were alkali metals,
alkaline earths, Al, Si, Ti and Fe. From the degree of hazard
values in Table 1-10, the elements with the highest priority for
Level 2 chemical analysis are Be, P, Fe, Ca, Al, Li, K, Ba, Se,
Pb, Cu, Ti, Cd, Sb, V, Co, U, and Cs.
The gasifier ash had the lowest toxicity in the soil
microcosm test, showed negative results in the Ames Test and gave
signs of low toxicity in the rodent acute toxicity test. These
results are not consistent with the degree of hazard values.
This inconsistency may indicate that further chemical character-
ization and/or bioassay testing are needed.
Leaching tests are needed for determination of the
types and amounts of trace elements that are leachable from the
24
-------
Table 1-10.
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR
GASIFIER ASH
Priority for Level 2
Chemical Analysis
High
Medium
Degree of Hazard
Range
(io5 - iok
1 10* - IO5
lio" - 10*
(lO2 - 103
| 10 - IO2
Compound Categories Found From
Level 1 Chemical Analysis
Health Concern Ecological Concern
P
Fe, Cu
Fe Ca, Al, Ti, Cd
Be, Li, Ca, Ba, Se, Ba, Pb, Se, Sb,
Cs, Cu V, Co, U
Mg, Sr, Al, Pb, P, Li, Mg, Cr, Be
Results of the
Test
Health
• Ames
• RAM (ECso)a
• R.A.T. .
- T DC n
IjfS 0
Bioassay Tests
Results
N
>300
>L
Ecological
• Soil Microcosm 4
Low
- 10
Sb, Ti, Cr, Co, Cd,
Si, Hg
Zr, V, U, Rb, F~
NO
O1
R.A.T.: Rodent Acute Toxicity test
N: Negative
L: Low toxicity (i.e., no significant effects noted)
aECso values are reported in (ig of solid per ml of culture
LDso values are in g of sample per Kg of rat
cSoil microcosm test results were ranked according lo toxicity. The gaslfier ash ranking of 4 was less toxic than the coal feed, cyclone
dust and by-product tar and more toxic than the separator liquor.
-------
ash. Bioassay tests should also be performed on the resulting
leachate.
The concentration of extractable organics in the ash
was ^20 yg/g. Further organic analysis is needed since certain
organic compounds, such as benzo-a-pyrene, have MATE values
significantly lower than 20 yg/g.
Cyclone Dust -
The results of the chemical and bioassay tests per-
formed on the cyclone dust are given in Table 1-11. No data for
organics are given in this table because the concentration of
extractable organics was small (^40 yg/g). However, further
organic analysis is recommended since certain organic compounds
have MATE values much lower than 40 yg/g.
The major trace elements (>103 yg/g) found in the
cyclone dust were Ca, Si, and P. While the concentrations of
most of the trace elements found in the cyclone dust were lower
than the concentrations found in the gasifier ash, most of the
concentrations still exceeded their respective MATE values. The
elements with the highest priority for Level 2 chemical analysis
are P, Ni, Mn, Fe, Pb, Ba, Sb, Ti, and Cu.
The bioassay tests for the cyclone dust indicated a
low potential for hazardous health effects; however, it was the
most toxic of the samples tested in the soil microcosm test.
Leaching tests are needed, along with bioassay tests of the
resulting leachate, if disposal in a landfill is to be consid-
ered. However, because of its high carbon content, cyclone dust
may prove to be a salable by-product.
1-3.4 Potential Fugitive Emissions and Effluents
Fugitive emissions and effluents from pumps, valves,
flanges, etc., can present significant health and environmental
hazards. Three process streams, raw product gas, separator
liquor, and by-product tar, were considered in order to assess
the hazard potential of fugitive emissions and effluents from
this process.
26
-------
Table 1-11.
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR
CYCLONE DUST
Compound Categories Found From
Priority for Level 2 Degree of Hazard Level 1 Chemical Analysis Results of the Bioassay Tests
Chemical Analysis Range Health Concern Ecological Concern Test Results
High
\tf -
10= -
10" -
103 -
102 -
f
Medium j 10 -
Low / 1 -
L
107
10s
10s
10*
103
102
10
P Health
_ Ames N
• RAM (EC50)a >1000
Mh, Fe, Cu, Ni ' R-A:^ b "
' - LDso >10
Pb, P, Mh, Fe, Ba, Pb, Sb, Ti
Ni Ecological
• Soil Microcosm 1
Cr, Cu, Ba Ca, Al, V, Cr
Li, Mg, Ca, Sb, Zr, Li, Mg, As, Co
V, Co, Si, Ti
R.A.T.: Rodent Acute Toxicity test
N: Negative
M: Medium toxicity (i.e., rats showed hair loss, eye discoloration, etc.)
aECso values are reported in ug of sample per tnSL of culture
LDs o values are in g of sample per Kg of rat
Soil microcosm test results were ranked according to toxicity. The cyclone dust was more toxic than the coal feed, ash, tar and separator liquor.
-------
Raw Product Gas -
The potential health and ecological effects of fugi-
tive emissions of raw product gas were estimated using the
results of chemical analysis of the coal feeder vent stream.
It was assumed that raw product gas was diluted 1:10 by air in
the vent stream. This dilution factor was based on the results
of gaseous species analyzed in both the raw product gas and
coal feeder vent gas. Table 1-12 shows the degree of hazard
values for MEG categories estimated to be in the raw product
gas. If significant quantities of this gas stream appear as
fugitive emissions, the compound classes with the highest prior-
ity for Level 2 chemical analysis are given in this table.
Separator Liquor -
The separator liquor was found to contain high concen-
trations of organic compounds, especially the polar species
expected to be associated with an aqueous medium. The major
organic categories identified were thiols, phenols, and hetero-
cyclic organics. Smaller amounts of carboxylic acids, glycols,
and PAH's were found. Most of these organic categories had
degree of hazard values greater than 1. A summary of the results
of the Level 1 chemical and bioassay tests is given in Table
1-13.
The results of the bioassay tests indicated that the
sample was very toxic to aquatic species; however, it was
least toxic in the soil microcosm test, and had negative results
for health effects tests. Because of its toxic effects on
aquatic species, it would be necessary to treat this liquor
before discharge.
Water quality parameters for the separator liquor were
also determined using test kits specified by Level 1 procedures.
The results of these analyses showed high levels of ammonia,
cyanide, fluoride, chloride, carbonate and sulfate in the liquor
However, the concentration of sulfide was lower than expected
This, coupled with the high sulfate levels, indicates that con-
siderable oxidation of dissolved sulfur species may occur. The
quench liquor also contained high levels of BOD and COD. 'in
addition, it contained high concentrations of suspended'solids
and total dissolved solids, was highly colored, and had a hieh
odor threshold number.
28
-------
N)
Table 1-12. SUMMARY OF DEGREE OF HAZARD VALUES FOR MEG CATEGORIES ESTIMATED TO
BE IN THE RAW PRODUCT GAS STREAM
Priority for
Level 2
Chemical Degree of
Analysis Hazard Rangea
o Q
. 108 - 109
High <
107 - 10e
106 - 107
105 - 106
10" - 105
103 - 101*
v. io2 - io3
Compound Categories Estimated in the Raw Product Gas
Health Concern Ecological Concern
Fused aromatic hydrocarbons and their derivatives ~
-
Cz hydrocarbons
_
Cr CO
Heterocyclic nitrogen compounds; carboxylic acids and NHa ; V; Hg
Medium
Low
n
10 - 10
1-10
their derivatives; amines; sulfonic acids and sulf oxides;
phenols; Hg; U; CO
• —
Heterocylic sulfur compounds; thiols; benzene and substi-
tuted benzene hydrocarbons; Al; NHs; P; As; Cu; Cd;
C02; NO; HCN;
C2, Cij and C6 hydrocarbons; heterocyclic oxygen compounds; HCN
Li; Tl; Si; Pb; Sb; S02; CS2; Cl; Ti; Zr; V; Fe; Co; Ni; Zn;
Ag
Degree of hazard values for the raw product gas were estimated using the chemical analysis results
from the coal feeder vent assuming a 1:10 dilution of raw product gas to air in the vent stream.
-------
Table 1-13. SUMMARY OF THE LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS
FOR THE SEPARATOR LIQUOR
Priority for
Level 2
Compound Categories Found from Level 1
Chemical Analysis
Results of the Bioassay Tests
VJii^uijki— a.j. utgi cc: *-> ±-
Analysis Hazard Range
105 - 106
High 1 W ~ W
\ 103 - 10*
_ 2 9
v. 10 - 10
Medium / 10 - 10 z
L
Low < 1-10
L
Health Concern
Ecological Concern
Fused aromatic hydrocarbons NHs
and their derivatives
Phenols
NH3 , CN~
Heterocyclic nitrogen
compounds
Thiols, Se
Heterocyclic sulfur
compounds , P , As , F ,
CN~, P
Phenols, fused aromatic
hydrocarbons and their
derivatives
Carboxylic acids and
their derivatives
Glycols and epoxides ,
As, Se
Ca, Fe, Cd
Test
Health
• Ames
• RAM (EC5o)a
• R.A.T.
- LDso
Ecological
• Fresh water
- Algal (ECso , 15 days)
- Daphnia (LCso , 48 hr)
- Fathead minnow
(LCs o , 96 hr)
• Salt Water0
- Algal (ECso, 12 days)
- Shrimp (LCs o , 96 hr)
~ Sheepshead minnow
(LCso , 96 hr)
• Soil microcosm
Results
N
>600
L
0.1-1.0%
0.11%
0.02%
0.53/0.41%
0.25%
0.16%
5
R.A.T.: Rodent acute toxicity test
N : Negative
L : Low toxicity (i.e., no significant effects noted)
ECso values are reported in pg of sample per ml of culture.
LDso values are reported in g of sample per Kg of rat.
ECso and COso values for fresh and salt water bioassays are reported in weight percent of sample.
Soil microcosm test results were ranked according to toxicity. The separator liquor was less toxic than the coal feed,
ash, cyclone dust, and tar.
-------
By-Product Tar -
The chemical and bioassay test results for the by-
product tar are shown in Table 1-14. As expected, high concen-
trations of organics were found. Most organic compound classes
present had a degree of hazard value greater than 1. A wide
range of trace elements were also identified, with the major
elements being K and S.
The by-product tar was one of the most toxic samples
collected. Positive results were obtained in the Ames and rodent
acute toxicity tests. The soil microcosm test also showed a
high potential for hazardous ecological effects. Because of
the potential hazardous health effects exhibited by this stream,
leaks around pumps, valves, etc. must be minimized and contained.
1.3.5 Summary of Cyclone Particulate Removal Efficiency Test
Particulates removed by cyclones in the gasification
process consisted of coal dust, ash and tar entrained in the raw
product gas stream. Overall particulate removal efficiency was
determined by collecting particulates in in-stream alundum thim-
bles placed at the inlet and outlet of a cyclone. The average
total particulate removal efficiency for the cyclone was 62 per-
cent with values ranging from 29 to 78 percent.
1.4 RECOMMENDATIONS
This section is divided into two categories:
future data needs, and
methodologies used.
Future data needs emphasize further chemical and bioassay test-
ing requirements. Recommendations for methodologies used are
primarily concerned with sampling and analysis procedures and
techniques used for assessment of potential health and ecolog-
ical effects from plant waste streams.
31
-------
Table 1-14.
S3
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR
BY-PRODUCT TAR
Priority for
Level 2
Chemical
Analysis
Compound Categories Found from Level 1
Chemical Analysis
Degree of
Hazard Ranee Health Concern
,. 10-10 Fused aromatic hydrocarbons
High J
and their derivatives
106 - 107 Phenols
10s - 106
10 - 10 Amines, benzene and substi-
\ tuted benzene hydrocarbons,
heterocyclic nitrogen com-
pounds
103 - 10* Halogenated aliphatic hydro-
carbons, heterocyclic sul-
fur compounds
>s- 102 - 103 Carboxylic acids and their
derivatives, Cr
Medium | 10 - 102 Ba, Pb, Cu, Cd
Low J 1-10 Aliphatic hydrocarbons,
1^ heterocyclic oxygen com-
pounds, Sb, Hg, Mg
Ecological Concern
Carboxylic acids and
their derivatives
—
Halogenated aliphatic
hydrocarbons , amines
Benzene and substi-
tuted benzene hydro-
carbons , phenols
Cu, Cd
Aliphatic hydrocarbons ,
Pb, Sb, Cr
Ba
As, V
Results of the Bioassay
Tests
Test Result
Health
' Ames P
• RAM (EC50)a >1000
' R.A.T. . H
- LD_n >10
5 0
Ecological
" Soil microcosm 2
R.A.T.: Rodent acute toxicity test
P : Positive
H : High toxicity
TSCso values are reported in yg of sample per ml of culture
LDso values are reported in g of sample per Kg of rat
Soil microcosm test results were ranked according to toxicity. The by-product tar was less than the cyclone
dust and more toxic than the coal feed, ash and separator liquor.
-------
1.4.1 Future Data Needs
Recommendations for future data needs on the multi-
media waste streams and potential fugitive emissions and efflu-
ents are summarized in Tables 1-15 and 1-16. Priorities for
Level 2 chemical and biological analyses of chemical compound
classes in each waste stream are based on the results of SAM/1A
analyses.
1.4.2 'Methodologies Used
Recommendations for the methodologies used are divided
into sampling methods, analysis methods, and SAM/1A analysis.
The methodologies, or modifications of them, were used in the
assessment of potential health and ecological hazards associated
with the multimedia waste streams and potential fugitive emis-
sions and effluents from the Chapman facility.
Sampling Methods -
Gas stream grab sampling - Two modifications to Level
1 methodology were used for collecting grab samples from gaseous
streams. These are as follows:
(1) Glass sampling containers for collecting gas
samples for sulfur species (H2S, COS, CS2, S02)
analysis should be silylated to assure that these
species will not react with and/or be sorbed on
the walls of the container.
(2) A pretreatment train is recommended for removal
of particulates, tars, oils and water from the gas
sample. Otherwise, these constituents will inter-
fere with subsequent analyses.
SASS train sampling - The following modifications to
the SASS train were used when sampling streams containing high
levels of tar/oil particulates and water vapor.
(1) The SASS train originally was not adequate in
sampling the coal feeder vent stream, which had a
high concentration of tars and oils. The filter
33
-------
Table 1-15. RECOMMENDATIONS FOR FUTURE DATA NEEDS FOR WASTE STREAMS
Total Stream
Degree of Hazard
Waste Health Ecological
Stream Concern Concern
Separator 1 x 10* 1 x 10*
Vent
Stream Components
High Priority
Degree of Haeard
10 - 10
Fused aromatic hydrocarbons
and their derivatives,
amines, heterocycllc
nitrogen compounds, CO,
HHS, Cr, Ag, V Ci hydro-
carbons, phenols
Priority for Level 2
Medium Priority
Degree of Hazard
10 - 10
Heterocyclic sulfur
compounds. Cu, HOX,
P, H2S
Chemical Analysis
Low Priority
Degree of Hazard
10-1
Methane, halogenated
aliphatic hydrocarbons,
carboxylic acida and
their derivatives,
Li. HCN, As, C02, Fe.
Hi, U, C6 hydrocarbons
Remarks &
Recommendat Ions
This stream should be controlled
In new gasification facilities.
Further characterization should
be directed toward the control
technique for this stream, e.g.,
If the control device for this
stream is combustion, then de-
tailed chemical characterization
around the combustor will be
necceaary. along with bloaasay
tests of the resulting combus-
tion products.
Coal Feeder 4 x
Vent
Fused aromatic hydrocarbons
and their derivatives, CO,
Cr, €2 hydrocarbons
Carboxylic acids and
their derivatives, amines,
sulfonic acida and aulfox-
idea, phenols, HHi, Hg.
U, V, heterocycllc nitro-
gen compound*
Methane, thiols, benzene ^ for tne separator vent stream,
and substituted benzene
hydrocarbons, Al, P, As,
&S, Cu, Cd, HO. CQ2.
HCN, heterocycllc sulfur
coopounda
this stream should be controlled
in new gasification facilities.
Further characterization should
be directed toward the control
technique for this stream, e.g.,
if this stream is to be controlled
by combustion (flaring, inciner-
ation, etc.). then detailed chem-
ical characterization around the
combustion proceas would be nec-
essary, along with bloassay tests
of tbe combustion products.
u>
Gasifier 5 x itf S x Iff Be, F, Fe, Ca, Al, LI,
Ash Ba, Se, Fb, Cs. Cu, Tl,
Cd, Sb, V, Co, U
Mg, Sr, Cr, Co, Si,
Zr, F, Rb, AH
Even though the amount of extrac-
table organica was low 0-20 ug/g),
certain organic constltutents may
exist at levels exceeding their
respective MATE values. There-
fore, further analysis of this ex-
tract is recommended. The analy-
sis should be directed specifically
toward identifying specific organic
species (i.e., benzo-a-pyrene).
The gasifier ash contained high
concentrations of trace elements;
however, the results of the bio-
assay tests indicated that the ash
had a low potential for hazardous
health or ecological effects.
Leaching tests are recommended
along with bioassay tests on the
resulting leachate.
Cyclone
Dust
Ni. Pb, P, Mn, Fe, Cu. Ba,
Sb, Tl
Cr, Ca, Al.V
Li, Mg, Zr, Co, As,
Si
As for the ash, further organ-
ic analysis is recommended for
specific hazardous organic
species in the extractable
organlcs in the cyclone dust.
Because of the high carbon
content, the cyclone dust
should be combusted or recy-
cled to the gasifier. If the
dust is to be landfllled,
leaching tests and bioassay
tests on the resulting leachae
are recommended'
-------
Table 1-16.
RECOMMENDATIONS FOR FUTURE DATA NEEDS FOR POTENTIAL FUGITIVE
EMISSIONS AND EFFLUENTS
Total Stream Stream Components Priority for Level 2 Chemical Analysis
Fugitive Degree of Hazard High Priority Medium Priority Low Priority
Emissions & Health Ecological Degree of Hazard Degree of Hazard Degree of Hazard
Effluents Concern Concern 109 - 102 102 - 10 10-1
Raw Product 6 x 10 B
Cae
8 x 10 b Fused aromatic hydrocarbons
and their derivatives, het-
erocyclic nitrogen compounds,
Cr, CO, carboxylic acids and
their derivatives, amines,
sulfonic acids and sulf oxides,
phenols, Kg, U, HH3 , V,
Cz hydrocarbons
Thiols, benzenes and substi-
tuted benzene hydrocarbons,
Al, P, As, Cu, Cd, H2S, COZ,
NO, HCN, methane, hetero-
cyclic sulfur compounds
Ci, and Ce hydrocarbons,
heterocyclic oxygen
compounds, Li, Tl, Si,
Pb, Sb, S02, CS2, Cl,
Ti, Zr, Fe, Co, Hi, Ag,
Zn
By-Produi
Tar
10'
Cn
Separator
Liquor
3 x 10s
Fused aromatic hydrocarbons
and their derivatives, phenols,
amines, benzene and substitu-
ted benzene hydrocarbons,
heterocyclic nitrogen and sul-
fur compounds, halogenated ali-
phatic hydrocarbons, carboxylic
acids and their derivatives,
Cu, Pb, Sb, aliphatic hydro-
carbons, Cr, Cd
Phenols, fused aromatic hydro-
carbons and their derivatives,
NHj, Or, heterocycllc nitro-
gen compounds, P, carboxylic
acids and their derivatives
Thiols, Se, glycols, and
epoxides, As
Heterocyclic oxygen
compounds, Hg, V,
Mg, As
Heterocyclic sulfur
compounds, F, Cl, Ca,
Fe, Cd
Remarks &
Recommenda Lions
Sources of raw product gas fugitive
emissions are primarily pokeholes
and abnormal process operation.
Because of the potentially hazar-
dous nature of the raw product gas,
control of pokehole emissions is
required. This can be achieved by
injecting an inert gas (steam or
C02) into the pokehole during poking
operations. Abnormal process oper-
ation (start-up, shutdown, upsets)
may require directing the raw pro-
duct gas to a flare or incinerator.
Further chemical characterization
around the flare or incinerator
is needed along with bioassay tests
of the resulting combustion
products.
The by-product tar was the most po-
tentially toxic material found in
this test. Potential fugitive
effluents of tar may occur around
pumps, flanges, and valves. These
effluents must be contained. Good
maintenance and material handling
procedures are required.
The bioassay tests for the separator
liquor indicated a low potential
for hazardous health effects, and
a high potential for hazardous eco-
logical effects. Fugitive efflu-
ents of the separator liquor may
occur around pumps, valves, flanges,
and surge tanks. These fugitive eff-
luents should be contained. Any
accumulation should be sealed in con-
tainers for disposal. Proper main-
tenance and handling practices should
be implemented.
Further chemical characterization of
the separator liquor is recommended
because of the inconsistency between
the health HATE values and the health
bloassay tests.
-------
frequently became plugged with tar, which acted as
a possible area*for sorption of gaseous sulfur
species. An alternate sampling system for collect-
ing samples from tar/oil laden streams is recom-
mended. This alternate system could include means
for collection of tars and oils with an electro-
static precipitator.
(2) Additional cooling in the SASS train organic
module was needed when sampling streams with high
moisture content (such as the separator vent
stream). This has been included in the new SASS
train operating instructions.
(3) Relocation of the XAD-2 cartridge to a point down-
stream of the condenser in the SASS train module
is recommended. Using this modification, conden-
sable organics are collected in the condenser,
while organic vapors are sorbed on the XAD-2
resin. This modification will also minimize
overloading the XAD-2 resin with organics that
have already condensed.
Analysis Methods -
Nitrogen oxides (NO^) - An alternate method, such as
EPA Method T,is recommended for determining NOX. This alternate
method should be suitable for determination of a wide range of
NOX concentrations.
Ammonia and hydrogen cyanide - The gas chromatography
technique specified by Level 1 was not sufficiently sensitive
for determination of the low levels of NHs or HCN in the gas
samples. NHs and HCN samples should be collected in impingers
and analyzed by wet chemical methods when low concentration of
these species are present.
Sulfur species - A modified gas chromatography tech-
nique using a Poropak QS column was used for analysis of sulfur
species (H2S, COS, CS2, and S02) and was found to give the
separation required for input data to control technology- How-
ever, problems were found with the Poropak QS packing because of
its reactivity toward S02. Additional packed columns for
separation of H2S, COS, S02, and CS2 have been evaluated. The
36
-------
following have proved satisfactory for gas samples obtained from
coal gasification facilities.
(1) 3% TCEP, 0.5% HaPO^ on mesh Carbopak B.
(2) 1% Carbowax 20 M, 0.5% H3P04 on mesh Carbopak B.
Fixed gases - A Fisher Gas Partitioner is recommended
to permit separation of nitrogen and oxygen and quantification
of other species on a single sample injection.
Test kits - Test kits specified by Level 1 were
found to give adequate results in most cases. However, results
could not be obtained using these kits for the determination of
nitrate, nitrite or hardness. Alternate methods for these tests
should be established for liquid streams containing high levels
of organic material.
Extraction techniques - The extraction techniques
specified by Level 1 were found to be inadequate for extracting
samples containing highly polar organic compounds. Alternate
extraction procedures, using methylene chloride, ether and
acidified ether, may be used to recover highly polar compounds.
Total chromatographable prganics (TCP) - Problems
arose in determining TCO s for most of the organic extracts.
This was especially true when high amounts of organics were
present. The resulting chromatograms were so complex that the
integration techniques were unreliable.
Gravimetric analysis - Significant variations were
observed in mass determinations when dilute and concentrated
samples of an extract were analyzed gravimetrically. It is
recommended that additional work be performed in order to deter-
mine the optimum mass range for such analyses.
SAM/1A analysis - The following recommendations con-
cern the use of SAM/1A as a rapid screening technique in the
assessment of potential health and ecological effects of waste
streams.
37
-------
(1) SAM/1A analyses should be used in conjunction
with bioassay tests for rapid screening of the
pollution potential of multimedia waste streams.
(2) SAM/1A may be used to determine, and prioritize
if necessary, those compounds and waste streams
that must be controlled and/or characterized
further (Level 2 analyses).
(3) The results of a SAM/1A analysis of a waste
stream can be affected by the "degree of hazard"
of only a few components in the stream. There-
fore, inexpensive "spot tests" for specific
compounds with low MATE values (such as the
test developed by EPA for benzo-a-pyrene) should
be developed.
38
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SECTION 2.0
PLANT DESCRIPTION
This section provides a brief description of the
Chapman facility and a summary of the operating data which were
collected during the test program.
2.1 PROCESS DESCRIPTION
The Chapman facility produces low-Btu gas which is
used as a combustion fuel for process heaters. The facility is
equipped with twelve operational Chapman gasifiers. However,
current fuel demands are low and can be met by operating only
two gasifiers at any specific time.
Three basic operations are used in the gasification
plant: a) coal handling, b) gasification, and c) gas purifi-
cation (particulate removal and gas quenching and scrubbing).
Water (process condensate) treatment is also practiced. A block
diagram of the operations used at this plant is presented in
Figure 2-1. This diagram also shows the major air, water, and
solid waste streams associated with each operation. In the
following text, each of these operations and their respective
waste streams are discussed in more detail.
2.1.1 Coal Handling
The coal handling operation at the facility consists of:
a) delivery and storage of presized Virginia bituminous coal in
hopper cars, b) conveying, and c) storing this coal in the gas-
ifier feed hoppers. No coal grinding, crushing, sizing or dry-
ing operations are used at the plant site. Emission of coal
dust is the only major environmental concern in this operation.
39
-------
Coal Bust
Coal Feeder Pokehole Liquor Trap
Vent Gases Gases Vapors
Fugitive
Separator
Vapors
Legend
Sample Point
Gasifier Cyclone Dust
Ash
By-Product Tars
and Oils to
Utility Boilers
Low-Btu Gas to
Process Furnaces
Figure 2-1. SIMPLIFIED PROCESS FLOW DIAGRAM FOR THE CHAPMAN FACILITY
SHOWING EMISSION STREAMS
-------
2.1.2 Gasification
The gas producers are single-stage, atmospheric,
fixed-bed, air-blown Chapman gasifiers. The coal feedstock
enters the top of each gasifier through a rotating feeder
(barrel valve) and is spread across the bed by a distribution
arm. Steam and air are introduced into the bottom of the gasi-
fier and pass through a grate which distributes these gases
evenly and also supports the coal bed. Ash from the gasifier
is collected in a water-sealed ash pan and removed from the unit
using an ash plow. The hot raw gas exits the top of the gasi-
fier at 840-950°K (1050-125CTF) and enters a cyclone. Pokeholes
located on top of the gasifier are opened periodically to permit
the insertion of rods to break up any coal agglomerates which
form in the gasifier. The rods are also used to check the depth
of the bed in the gasifier.
Waste streams associated with the gas production oper-
ation are: a) gaseous emissions released to the atmosphere from
the coal feeder valve, pokeholes, and leaks around the gasifier
seals; and b) moist ash which exits the bottom of the gasifier.
The ash is conveyed to a storage hopper and is trucked away
periodically for disposal.
2.1.3 Gas Purification
The gas purification operation consists of two dis-
crete steps: particulate removal and gas quenching and scrub-
bing, as described below.
Particulate Removal -
Particulate matter is removed from the hot, raw, low-
Btu gas in refractory-lined cyclones that operate at a tempera-,
ture slightly lower than the gasifier overhead temperature.
Each gasifier at the Chapman facility is^equipped with a cyclone
The particulates removed by the cyclones,consist of devolatil-
ized coal dust, ash and tar entrained in the raw gas. The
particulates collect at the bottom of the cyclones. Pokeholes
are located on the top of each cyclone and in the inlet and out-
let hot gas ducts to permit insertion of steam lances which are
used to break up agglomerated particulates.
41
-------
Gaseous waste streams from the cyclones consist of
pokehole vent gases and leaks. The collected particulates,
which constitute a solid waste stream, are combined with the
gasifier ash for disposal.
Gas Quenching and Scrubbing -
The hot gas leaving the cyclones is quenched by
spraying water into the exit lines from each cyclone. Excess
quench water is collected in a liquor trap (one trap for each
gasifier/cyclone), while the cooled gas from all operating gasi-
fiers enters a collecting main. Water sprayed inside this main
cools the gas to approximately 340°K (150°F). Tar and quench
liquor from the liquor traps and the collecting main are sent to
the liquor separator. Pitch (a lighter-than-water, tarry mate-
rial) and agglomerated particulates which accumulate in the
liquor traps are collected for periodic off-site disposal.
After the initial quenching step, the gas is cooled
further by water in two tray scrubbers which are operated in
parallel. Here, most of the tars, oils, and particulates are
scrubbed from the gas as it is cooled to approximately 330°K
(135°F).
The gases exiting the tray scrubbers are recombined
and compressed before entering a spray scrubber. In the spray
scrubber, some residual tars, oils, and particulates are removed
as the gas is further cooled to about 320°K (120°F). The efflu-
ent scrubbing liquor from both the spray and tray scrubbers is
sent to the liquor separator.
The liquor separator at the Chapman facility is a
large concrete tank (5 x 12 x 2 meters, 16 x 40 x 6 feet). Pro-
cess condensate and condensed tars and oils from the quenching/
scrubbing steps enter at one end of the tank. A series of
baffles minimizes the turbulence caused by the incoming liquor.
The tars and oils settle to the bottom of the separator and are
removed periodically for use as an auxiliary fuel in a coal-
fired boiler. A portion of the water from the liquor separator
is cooled in a set of cooling towers before being reused in the
spray scrubber. The remainder of the water is recirculated to
the other quenching and scrubbing steps.
42
-------
The gaseous waste streams from the quenching and
scrubbing processes include vapors from the liquor traps and the
liquor separator. A second gaseous waste stream from the liquor
separator is produced by a steam ejector which is used to purge
the vapor space above the liquor in the separator. The liquid
waste stream associated with this process is accumulated quench
liquor which is sent to an evaporator for disposal.
2.1.4 Water Treatment
Water treatment problems are minimized at this gasifi-
cation facility by operating the gasification process such that
there is no net accumulation of water. Adjustment of the water
content of the product gas may be made by regulating the amount
of steam to the gasifier and also by adjusting the temperature
of the clean product gas. If excess water (quench liquor)
accumulates, it is directed to a set of evaporators. Emissions
from this evaporation process should contain volatile materials
found in the quench liquor.
2.1.5 Waste Stream Summary
Waste Stream Characterizations -
The waste streams from the Chapman facility are listed
in Table 2-1. The streams sampled and analyzed by Radian are
indicated with an asterisk. Criteria for selection of streams
for sampling included accessibility, plant operation and poten-
tial for pollution. For example, process heater flue gas was
not sampled because the heater was located in a restricted area.
Evaporator vapors were not sampled because no spent quench
liquor was sent to the evaporator during the test.
43
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Table 2-1. MULTIMEDIA WASTE STREAMS AT THE CHAPMAN FACILITY
Gaseous Emissions
- Coal Feeder Vent Gases*
- Pokehole Gases
- Separator Vent Gases*
- Evaporator Vapors
- Process Heater Flue Gas
- Tar/coal Combustor Flue Gas
Liquid Effluents
- Spent Quench Liquor
Solid Wastes
- Gasifier Ash*
- Cyclone Dust*
^Indicates the waste streams sampled during the test program.
Potential Fugitive Emissions Characterizations -
The process streams in the Chapman facility are listed
in Table 2-2. These streams, identified as potential sources of
fugitive emissions and effluents, were sampled and analyzed as
part of Radian's test. The data collected from the quench liquor
and by-product tar is also valuable as an aid to the prediction
of control technology and end-use requirements for similar
streams in future facilities.
Table 2-2. SUMMARY OF PROCESS STREAMS IDENTIFIED AS POTENTIAL
SOURCES OF FUGITIVE EMISSIONS AND EFFLUENTS
Gaseous Stream
- Raw Product Gas
Liquid Stream
- Recirculating Quench Liquor
Solid Stream
- By-Product Tar
44
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2.2 PLANT OPERATION
The Chapman coal gasification facility operates 24
hours per day with a production rate determined by the fuel
demand of the process heaters in an adjacent building. A single
gasifier is capable of producing gas at a rate that will fire a
minimum of two and a maximum of four heaters. During Radian's
tests, five process heaters were fired by gas from two gasifiers.
This indicates that the gasifiers were operating at approximately
60 percent of capacity.
Instrumentation for the gasifiers monitored the product
gas exit temperature, the saturation temperature of the gasifier
inlet air, and pressure drops across various segments of the
gasifier. The gas cleaning system was instrumented with flow,
temperature, and pressure indicators.
With the exception of the automatic fine adjustment of
the combustion air flow rate, all operating parameters for the
gasifier were controlled manually by the plant operators. These
parameters included:
coal feed rate,
gasifier ash removal rate,
depth of ash bed (location of fire zone), and
temperature of the gas exiting the gasifier.
The techniques used by the various operators for control of the
gasifiers varied slightly, but each produced gas of acceptable
quality.
2.3 PROCESS FLOW RATE AND MASS BALANCE DETERMINATIONS
During the test program, process flow rate data were
calculated for:
coal feedstock,
gasifier ash.
45
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product low-Btu gas,
cyclone dust, and
tars and oils.
Most of these data were collected at 8-hour intervals over a
48-hour period. Table 2-3 gives a summary of the average flow
rates calculated for each stream. The following text describes
the methods used to determine those flow rates.
Coal is fed to each gasifier through a device known as
a barrel valve, which is described in Section 3.1.2. A revolu-
tion counter is attached to the shaft of each barrel valve.
Readings were taken periodically from these counters. The
weight of coal delivered per revolution was determined by fill-
ing each of the three cavities of an uninstalled barrel valve
and then transferring the coal to a container for weighing.
Based on several such weighings, an average value of 52 kg (115
Ib) per revolution was obtained. Using this factor, the average
coal feed rates to the No. 2 and No. 3 gasifiers were determined
to be 0.139 kg/s (1030 Ib/hr) and 0.175 kg/s (1390 Ib/hr),
respectively. It should be noted that the actual coal feed
rate could be less due to material buildup in the barrel valve
cavities.
Gasifier ash is removed from the gasifier and dumped
into a hopper at the beginning of each shift. The ash level in
the hopper was recorded and the volume of ash removed calculated.
An ash sample was collected for moisture content and density
determinations. Based on these factors, average mass flow rates
of 0.0085 kg/s (68 Ib/hr) and 0.010 kg/s (80 Ib/hr) of dry
gasifier ash were calculated for the No. 2 and No. 3 gasifiers,
respectively. While the accuracy in determining the amount of
ash removed per shift is considered good, the time averages
calculated may contain considerable error since the amount of
ash removed per shift is at the discretion of the gasifier
operators. In fact, during the data acquisition period, ash
was not removed at all on several shifts.
Product gas flow rates were obtained from the plant's
instrumentation which consisted of an orifice meter and inte-
grating flow recorder. For a 6-day period, the average gas flow
rate was 0.871 Nm3/s (1950 scfm) . Raw product gas flow irate
46
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Table 2-3. MASS BALANCE AROUND THE
CHAPMAN GASIFICATION FACILITY
Stream Description
INPUT STREAMS
Air
Steam
Coal Feed
TOTAL
OUTPUT STREAMS
Gasifier Ash (dry)
Cyclone Dust
Cooled Product Gas **
By-Product Tar
TOTAL
INPUT MINUS OUTPUT
kg/s
% of INPUT
Flow Rate (kg/s)a
No. 2
Gasifier/
Cyclone
0.33*
0.068*
0.129
0.527
0.0085
0.00067
0.420*
0.0129*
0.442
0.085
16
No. 3
Gasifier/
Cyclone
0.44*
0.092*
0.175
0.707
0.010
0.00094
0.569*
0.0175*
0.597
0.11
16
Total
Facility
0.77
0.16
0.304
1.234
0.0185
0.00161
0.989
0.0304*
1.040
0.19
16
aKg/s = 7938 Ib/hr
* Back calculated by ratioing coal feed rate data.
** Based on gas molecular weight of 25.4.
47
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measurements were also made at the No. 2 cyclone inlet and out-
let during the cyclone characterization studies. These measure-
ments indicated the average No. 2 cyclone inlet and outlet raw
gas flow rates were 0.39 Nm3/s (870 scfm).
The dust removed from each cyclone at the beginning
of each shift was caught in large metal cans. The cans were
weighed and the total weight of cyclone dust determined. The
average mass flow rate of cyclone dust over the 48-hour period
was 0.67 g/s (5.3 Ib/hr) and 0.94 g/s (7.4 Ib/hr) for No. 2 and
No. 3 cyclones, respectively. Based on the grain loadings and
flow rate data obtained during the cyclone characterization
studies, the average cyclone dust flow rate for No. 2 cyclone
was calculated to be 0.62 g/s (4.9 Ib/hr).
The tars and oils which accumulate in the liquor sepa-
rator are pumped to a storage tank when the tar reaches a depth
of 0.6 m (25 in). Plant operators record tar levels in the
separator before and after each pumping. The flow rate of tar
calculated from these data was 0.25 m3/hr (66 gal/hr). Assuming
a specific gravity of 1.07, the mass flow rate of tar was deter-
mined to be 0.075 kg/s (590 Ib/hr). This number is subject to a
large degree of error due to uncertainties in the method of de-
termining the tar level. Based on coal deliveries and tar firing
records kept by plant personnel for the period May 1977 until
August 1977, a tar flow rate equal to 10 percent of total coal
deliveries is probably more accurate. Therefore, for an average
coal feed rate of 0.304 kg/s (2410 Ib/hr), the tar flow rate was
assumed to be 0.0304 kg/s (241 Ib/hr).
Flow rate measurements for the air and steam fed to
the gasifiers were not readily obtainable during the sampling
period. However, an approproximate air and steam flow rate was
back-calculated. First, it was assumed that all of the N2 in
the product gas was brought into the system with the inlet air.
This indicated that the inlet air mass flow rate was about 0.77
kg/s (6100 Ib/hr). During Radian's tests, the inlet air/steam
temperature was about 340°K (150°F). Assuming that the air was
saturated at this temperature, the steam flow rate was calcu-
lated to be approximately 0.16 kg/s (1300 Ib/hr).
48
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SECTION 3.0
SAMPLING METHODOLOGY
A summary of the sample points and sampling methods
selected for the Radian test of a Chapman coal gasification
facility is presented in this section. The first part describes
the locations of sampling points on each stream sampled and the
general sampling access methods used. The second part describes
specific sampling methods used for gaseous, liquid and solid
streams.
Level 1 sampling procedures were selected for all
waste and potential fugitive emission and effluent streams.
Alternate methods were applied only where these methods failed.
Particulate sampling for the cyclone efficiency test was per-
formed using in-line alundum filters.
3.1 DESCRIPTION OF SAMPLING POINTS
The sample point locations for Radian's test program
are indicated numerically in Figure 3.1. The following text
gives a brief discussion of each sample point location.
3.1.1 Coal Feedstock (1)
Presized coal is transported to the gasification facil-
ity by rail car, dumped into an underground bin, and then con-
veyed to a hopper directly above the gasifiers. Typically, coal
is unloaded from the rail cars during the day shift. The convey-
er belt that transports the coal to the overhead hopper was
stopped periodically and a "stopped-belt" coal sample was col-
lected by a plant operator.
During the Radian test program, coal samples were
collected and crushed by a plant operator every fifteen minutes
during the unloading operation. In addition, uncrushed coal
samples were collected for size analysis.
49
-------
Lrt
O
Coal Dust
Coal Feeder
Vent Gases
Pokehole Liquor Trap
Gases Vapors
Fugitive
Separator
Vapors
Gasifier Cyclone Dust
Ash
By-Product Tars
and Oils to
Utility Boilers
Low-Btu Gas to
Process Furnaces
Figure 3-1. SIMPLIFIED PROCESS FLOW DIAGRAM FOR THE CHAPMAN FACILITY
SHOWING WASTE AND PROCESS STREAMS AND SAMPLING POINTS
-------
3.1.2 Coal Feeder Vent (2)
Coal is fed to the gasifier by a device known as a
barrel valve. This device consists of a slightly tapered cylin-
der which has three recessed pockets in its surface. The cylin-
der rotates in a close fitting sleeve with a common horizontal
axis. Coal enters the pockets in the cylinder from above and is
dropped into the gasifier below as the cylinder rotates in the
sleeve. Some product gas from the gasifier will usually leak
past the barrel valve and into the coal feed chute. To minimize
the amount of gas leakage into the coal storage bins, the chute
is vented to the atmosphere. Due to a natural draft in the vent
line, ambient air from an inspection hatch located above the
barrel valve and, to a lesser extent, air from the coal storage
bin, are also drawn into the vent. The barrel valve vent gas
sampling port was installed in the 23 x 23 cm (9 x 9 in) vent at
a point which was accessible from the roof of the producer build-
ing approximately 3.5 m (12 ft) above the barrel valve.
3.1.3 Gasifier Ash (3)
Ash is usually removed from the water-sealed ash pan
once per shift. The quantity of ash removed is determined by
the operator and is controlled by the number of rotations made
by the ash pan during removal. The ash plowed from the pan falls
into a hopper and then into a drag chain trough. The ash is
conveyed to a storage silo and is hauled from the site daily by
truck. All of the ash samples were collected as the ash entered
the hopper of the No. 2 gasifier.
3.1.4 Separator Vent Gas (4)
Vapors above the liquor in the separator tank are
purged to the atmosphere using a steam ejector. The height of
the exhaust duct is about 23 m (75 ft). The separator vent
gases were sampled from a 7.6 cm (3 in) port approximately 4.5 m
(15 ft) from the top of the duct. Access to the sample port was
from a catwalk servicing the top of the three product gas
scrubbers.
51
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3.1.5 Cyclone Dust (5)
Dust collected by the hot cyclone immediately down-
stream of the No. 2 gasifier is emptied once per shift into the
same hopper used for the gasifier ash. Therefore, to preserve
its integrity, the cyclone dust sample was collected in a large
metal can placed inside the hopper. After collection, the can
was removed from the hopper, covered, and the dust allowed to
cool. When cool, the sample was transferred to sample storage
containers. This procedure was necessary because the tempera-
ture of the cyclone dust was approximately the same as the hot
product gas passing through the cyclone.
3.1.6 Raw Product Gas (10)
Raw product gas samples were obtained as the raw pro-
duct gas passed vertically through the cyclone dust sleeve situ-
ated directly on top of the cyclone. (Figure 3-2). This sampling
location was selected because quenching of the product gas begins
close to the cyclone exit. Access to the gas at this location
was made through a specially constructed packing gland which
replaced the pokehole cover on top of the cyclone exit duct.
3.1.7 Clean Product Gas (8)
Clean product gas samples were collected through a
valve located approximately 4.5m (15 ft) downstream of the
spray scrubber. The gas at this location had a positive pres-
sure of approximately 7.5 KPa (30 inches H20) and a temperature
of approximately 320°K (120°F).
3.1.8 Separator Liquor (6)
The hot product gas is both cooled and scrubbed of
tars and oils by recirculated separator liquor. Separator liquor
was sampled at the point where it entered the liquor trap of the
No. 2 gasifier.
52
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Packing
Gland
Stainless Steel
Probe
Quench Spray
Nozzles
Product
Gas To ''
Scrubbers
Alundum Filter
Holder and Nozzle
Gasifier
Floor Level
Outside Wall
of Cyclone
Cyclone Dust
Sleeve
Figure 3-2.
(24 in)
SCHEMATIC DIAGRAM OF SAMPLING ARRANGEMENT USED ON THE OUTLET
OF THE CYCLONE
-------
3.1.9 Tars and Oils (7)
Tars and oils are separated from the recycle quench
liquor in a concrete separator tank. Samples of tar and oil,
which settle to the bottom of the tank, were collected by lower
ing a "bailer" through the aqueous and tar layers to the floor
of the liquor separator. The bailer was then retrieved, and
the aqueous portion decanted. Additional samples of the tars
and oils were obtained as they were pumped to a remote storage
tank.
3.1.10 Cyclone Inlet and Outlet (9, 10)
Gas exiting the No. 2 gasifier was sampled in the
transition ducting between the gasifier and the cyclone. A
sample port was installed as shown in Figure 3-3. Access to the
gas stream was made through a packing gland attached to the gate
valve.
Outlet cyclone gas samples were obtained from the same
sample port as the raw product gas samples.
3.2 SAMPLING METHODOLOGY
As stated in Section 1.0, the objectives of the Chap-
man gasifier test program were to:
characterize the multimedia waste streams leaving
the facility, using Level 1 sampling and analy-
tical methodologies (Ref. 1),
characterize the process streams in the facility
which represented potential fugitive emissions,
using Level 1 sampling and analytical methodologies,
evaluate the particulate removal efficiency of
the product gas cyclone, and
evaluate the applicability of Level 1 sampling
and analytical methodologies to determine their
applicability to the waste streams from low-Btu
gasification facilities.
54
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A
t
Raw Gas
From
Gasifier
1
X"" "V
Start-Up
Vent
/
f
(^
)
1
Gate Valve
-------
The methodologies used to obtain samples necessary to achieve
these objectives are described in this section. In several
cases, established sampling procedures were not applicable
because.of the characteristics of the streams. In such cases,
modifications of equipment and procedures were made in order to
obtain the desired type and quantity of sample. In other cases,
alternative procedures were used to evaluate the applicability
of EPA's Level 1 methodology to waste streams from coal gasifi-
cation plants.
3.2.1 Waste Stream and Potential Fugitive Emission and
Effluent Characterizations
EPA's Level 1 sampling procedures were used to collect
samples for chemical and biological analyses. The sampling
procedures described in the following sections are discussed
according to the following stream sample classifications: gases
with particulates, gaseous species, liquids, and solids. A
summary of the samples taken during the test and the sampling
schedule is presented in Table 3-1.
Gases With Particulates^ -
Gaseous emission streams which contained entrained
particulate matter were sampled by using the high volume source
assessment sampling system (SASS train) shown in Figure 3-4.
A detailed description of this device and its operating param-
eters are given in the EPA Level 1 procedures document (Ref. 1).
The two gaseous waste streams that were sampled using the SASS
train were the coal feeder and the liquor separator vent gases.
Coal feeder vent gases - In addition to air, the coal
feeder vent gases contained raw product gas that had leaked past
the barrel valve. Preliminary velocity measurements made to
determine the correct sampling rate and nozzle dimensions showed
the gas velocity to be under 1.5 m/sec. In order to obtain
approximately 28 m3 of sample within a 5 hour sampling period
(as recommended by Level 1 procedures), isokinetic sampling would
have required an SASS train nozzle with a cross sectional area
of about 60 cm3. Since this was impractical, isokinetic sampling
was not attempted and a sampling rate was selected which would
give the required sample volume/sampling period as specified by
Level 1 procedures.
56
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Table 3-1.
SAMPLING AND ON-SITE ANALYSIS SCHEDULE - CHAPMAN
GASIFIER SOURCE TEST EVALUATION PROGRAM
Spray Scrubber
Outlet
Fixed Gases
C,-C,
NOX
Sulfur Gases
No. 2 Gasifier
Barrel Valve Vent
Fixed Gases
Ci-C6
NOX
Sulfur Gaaes
SASS (Radian)
SASS (EPA)
HCN
HH3
No. 2 Gasifier Raw
Product Gas
Particulate
Fixed Gases
C, -C6
NOX
Sulfur Gases
HCN
Separator Vent
Fixed Gases
Ci-C6
N0x
Sulfur Gases
SASS (Radian)
SASS (EPA)
HCN
NH3
Coal
Tar
eparator iquor
Producer Ash
Cyclone Ash
Pitch
M
8/2
AM
.9
PM
T
a/:
AM
10
PM
W
8/:
AM
1
PM
T
9/
AM
.
1
PM
X
X
x
F
'/
AM
X
X
2
PM
x
s
9
AM
x
X
'3
PM
x
S
9
AM
x
x
'4
PM
XX
XX
x
X
X
M
9
AM
x
x
X
X
X
!
^5
PM
XX
XX
x
XX
XX
T
9
AM
x
XX
X
x
X
'6
PM
X
••
X
X
X
X
W
9
AM
n
PM
!
: Sampling interval for the SASS train
• • Grab Sample
x • Flowrate measurement
57
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Ui
C»
Stack T.C.
./..
Convection
Oven
Filter
L__£^ LL
Dry Gas Meter Orifice Meter
Centralized Temperature
and Pressure Readout
Control Module
XAD-2
Cartridge
Gas Cooler
Imp/Cooler
Trace Element
Collector
Impinger
T.C.
0.0047. m*/s (10 cfm)
Figure 3-4. SOURCE ASSESSMENT SAMPLING SCHEMATIC
-------
Several problems were encountered in using the Level 1
procedures to sample the coal feeder vent gases, as follows.
The curved portion of the nozzle became
plugged by condensed tars.
The condensed tar particulates became
fluid after entering the heated probe
and cyclone assembly.
The tars that passed through the cyclones
formed a viscous mat on the filter.
As a result of these problems, fluidized tar passed from the
cyclone section and lodged on the filter, which then had to be
changed every 20 minutes.
To minimize nozzle plugging and to increase the time
interval between filter changes, the following procedure modi-
fications were made.
The goose-neck nozzle was replaced with a
straight nozzle.
The oven heater was turned off and the
main oven door left open.
With these modifications, a larger portion of the tar was col-
lected in the cyclones and the tar collected on the filter re-
mained solid. This increased the time interval between filter
changes from 20 minutes to 60-120 minutes.
Separator vent gases - EPA Level 1 procedures were
used with only one modification in sampling the separator vent
gas. Because of the high moisture content of this stream (%4070),
the cooling capacity of the SASS train organic module was ex-
ceeded. The problem was resolved by adding an additional pump
to the system. The additional pump circulated ice water through
the inner cooling jacket of the organic module, while the orig-
inal pump maintained ice water circulation through the outer
jacket. The organic module exit temperature was controlled by
manual adjustment of the cooling water flow rate. The lowest
gas temperature obtained in the organic module was 293°K (68°F).
59
-------
The probe temperature thermocouple failed while samp-
ling the separator vent stack, thus making the automatic con-
troller for the probe heating system inoperable. To avoid ter-
minating the run, a thermocouple was placed inside the probe case
and the probe heating system was controlled manually.
Sample recovery - Upon completion of each SASS train
run, the system was disassembled into four sections: probe and
nozzle, cyclones and filter, organic module, and impingers. The
entrance and exit of each section were covered with aluminum
foil which had been cleaned with methylene chloride. The train
was not disassembled further until the samples were recovered in
the mobile lab.
No particulates were recovered from the probe or the
cyclones on the SASS run at the coal feeder vent because the
material collected upstream of the filter was a very viscous tar
which coated any particulates present. After the coal feeder
run was completed, the probe was found to be completely plugged
with tar. To recover this material, the probe was heated and a
rod was used to remove most of the softened tar. The remaining
tar was recovered using a CH2C12 solvent rinse and a brass bris-
tle brush. Solvent rinses were used to recover the tar collected
on the cyclones and connecting tubing. The rinses from the probe
and nozzle were kept separate from the cyclone rinses.
Gaseous Species -
Samples for gas analysis were collected at the coal
feeder vent, the separator vent, the cyclone outlet (raw product
gas), and the spray scrubber outlet (clean product gas). The
species sought were Ci through C6 hydrocarbons, NO, NO , H2S,
S02, CS2, COS, HCN, NH3, and major (fixed) gases (CO, H2, C02,
N2, 02, CHO. The analytical techniques used are described in
Section 4.0.
Level 1 methodology specifies collection of gas samples
directly into a glass bomb or Teflon bag, with no conditioning
or pretreatment. This method was found to yield analytical
values which were much lower than those obtained using what
appear to be more reasonable methods.
60
-------
An alternate sampling system which was used for collec-
tion of gas samples from gaseous streams consisted of the fol-
lowing components:
heated sampling probe,
heated Teflon membrane filter (0.5y),
heated permeation gas drier,
pump, and
• sample container.
The system is shown schematically in Figure 3-5. The Teflon
membrane filter provided an inert medium for removal of tars
and oils and protection of the permeation drier, which was used
to remove water vapor from the gas sample. (Residual water
vapor in the sample could condense on the walls of the sample
container and sorb or react with gaseous species in the sample.)
The drier was heated to prevent condensation of water vapor on
the membrane walls. With the exception of the proprietary inert
membrane in the drier, all components of the sampling sy.stem
which came in contact with the gas stream were constructed of
stainless steel, glass or Teflon.
The sampling system, described above, also has two
optional modules (in-line filter and water trap) that were re-
quired when sampling the raw product and separator vent gases.
An in-line alundum filter was used to remove entrained particu-
lates and tars while sampling the raw product gas. A cold water
trap was placed in the system upstream of the Teflon filter
while collecting samples from the separator vent stream because
of the high moisture content of that stream.
Frequent membrane filter changes were necessary due to
the high tar and oil content of some gas streams. It was noted
from the results of the on-site analyses that the concentration
of some sulfur species in the gas stream appeared higher when
the filter was torn than when the filter was intact. Therefore,
it is possible that some of the sulfur species were either
sorbed by or reacted with the tar on the filter media.
61
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Gas In
Alundum Filter Holder
Used at Cyclone (OPTIONAL)
Teflon Bag
(Ci-Cs hydrocarbons)
f
k
1 ^ Stainless Steel Probe
Teflon Filter
r J~\ Permeation Drier
"^ /^ vL/hi ir^
\ If 1 4
i // f
pJuU 1 I
f Dry Air
Humid Air
^^ Glass Water Trap
=J
Rotometer/Flow
i
Controller
/
1 ^— ieij.ua u
^- Glass Bomb
(Sulfur species)
J ' bcoccnpaK Bag
Teflon-lined
Vacuum Sample
Pump
Used at the Separator
Vent (OPTIONAL)
Figure 3-5. GRAB SAMPLE COLLECTION AND PREPARATION SYSTEM
-------
The sampling train was well purged prior to filling
the sample container. All containers were purged with a minimum
of five sample volumes prior to sample collection. Teflon bags
with stainless steel valves were used for hydrocarbon and NOX
samples, polyethylene bags with stainless steel valves for fixed
gases, and glass bombs for sulfur species.
Gas chromatography is the recommended Level 1 proce-
dure for measuring HCN and NH3 in gaseous streams. However, the
concentrations of these gaseous species were usually below the
detection limits of the instrument. Therefore, samples for HCN
and NHs analysis were collected using an EPA Method 5 train (as
shown in Figure 3-6) . Samples were collected from single points
in the coal feeder and separator vent lines. The impinger solu-
tions used were 0.1 N NaOH for HCN collection, and 0.1 N H2SO^
for NH3 collection. The first two impingers in each train con-
tained 250 cm3 of the collecting solution, the third impinger was
dry, and the fourth contained preweighed silica gel. Gas was
passed through the train at a rate of 14 £/min (0.5 cfm) for 20
minutes. Three sampling runs were made at the coal feeder vent
and separator vent sampling points for each gas. At the comple-
tion of sampling, the impinger solutions were transferred to
polyethylene bottles. The probe and glassware washings and
filters were also retained for possible analysis.
A gas sample from the coal feeder vent was also col- .
lected for a biological screening test (plant stress ethylene
test). This test required 1.36 m3 of unfiltered sample. The
gas samples for this test were collected in large Tedlar bags
housed in 55-gallon fiber drums.
The Tedlar bags were first evacuated. Then the gas
sample was introduced through a Teflon tube attached to the
bulkhead fitting in the drum lid. The bags were filled at a
rate of 8 to 14 £/min. After filling, the bags were sealed and
the containers prepared for shipment. A total of 10 drums were
filled in this manner.
Liquids -
The only liquid samples collected during the test were
from the recirculating quench liquor. In the gasification plant,
separator liquor is allowed to flow continuously through the
separator liquor transfer line to the pitch trap to prevent the
line from becoming plugged. The separator liquor was sampled at
63
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Stack Temperature T.C.
£ *
Probe Temperature T.C.
Oven
//
,Filter
Pitot AP
Magnehelic
Oven T.C.
inger
Impinger
T.C.
Fine Adjustment
Gas Meter T.C. , Valve Ice Bath
Coarse Adjustment
alve
Air Tight
Vacuum Pump
Dry Test Meter
Orifice AP
Magnehelic
Vacuum
Gauge
Figure 3-6.
SCHEMATIC OF THE EPA METHOD 5
SAMPLING TRAIN
64
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the outfall of this line. The samples for organic analyses were
collected and stored in Teflon and glass containers. In addition,
approximately 2.5 m3 (85 gallons) of sample were collected for
other analytical and bioassay tests. These large volume samples
were collected in polyethylene carboys and in a 55-gallon drum
with a polyethylene liner.
Solids -
As part of the source test evaluation of the Chapman
facility, samples of coal, cyclone dust, "gasifier ash, and tar
were collected. The locations of each of these sample points
were specified in Section 3.1.
Coal samples were collected routinely by plant person-
nel using the "stopped-belt" technique as coal was transferred
from rail cars to the coal storage bins. Except for the coal
collected for size analysis, all samples were splits from samples
which were crushed to minus one-quarter mesh and riffled to
proper volume.
The gasifier ash was collected at the ash plow. A
stainless steel scoop was used for transfer of the ash to the
Teflon and polyethylene bottles. Effort was made to obtain a
representative sample by collecting ash from several points
around the ash plow and hopper. However, the sample collected
for moisture content determination was recovered from ash
directly above the plow.
Cyclone dust was dumped into the gasifier ash hopper
once per shift. With the cooperation of plant personnel, the
following collection method was used. A large metal can was
placed in the hopper directly under the cyclone dust discharge
chute. The hot cyclone dust (^8000K) was then emptied into the
can. The metal can was covered and the hot sanrale was allowed
to cool. Appropriate quantities of cooled sample were then
transferred to bottles for storage.
The separator tar samples were collected by lowering
a "bailer" through the aqueous and tar layers in the separator
tank. The bailer was then retrieved, and the aqueous portion
was decanted. Additional samples of the tar were collected as
it was pumped to a remote storage tank.
65
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3.2.2 Cyclone Particulate Removal Efficiency Study
Each gasifier at the Chapman facility is equipped with
its own refractory-lined cyclone. Particulates removed by the
cyclones consist of devolatilized coal dust, ash, and tar en-
trained in the product gas stream. Particulate concentration
(grain loading) data for particulate removal efficiency calcu-
lations were obtained at the inlet and outlet of a cyclone.
Figure 3-7 illustrates the sampling train used to collect par-
ticulates. The sampling train consisted of a stainless steel
probe fitted with an alundum thimble holder, sample transfer-
lines, three impingers, and pumping and metering equipment.^
Particulate matter was collected on a preweighed alundum thimble
placed in the thimble holder. Impinger solutions were used to
protect the pump. These solutions consisted of various col-
lecting media: deionized water; tetrahydronaphthalene; or tol-
uene. The first two impingers contained 250 cm3 of impinger
solution while the third was dry. Silica gel was eliminated
from the sampling train because it was found that organic com-
pounds which collected on the silica gel plugged the train with-
in minutes.
The inlet of the cyclone was accessible through a
10 cm (4 in) gate valve (Figure 3-8), while the exit of the cy-
clone was accessible through a pokehole on top of the cyclone
(refer to Figure 3-2). Prior to sampling, the velocity of the
gas stream was determined. A seven point velocity traverse
using an S-type pitot was made on the inlet, while a five point
velocity traverse using a standard pitot was made on the outlet.
The resulting velocity profiles are given in Figure 3-9. The
data in Figure 3-9 for the cyclone inlet are averages of two
separate measurements. After t ,e cyclone velocity was deter-
mined, required nozzle size and isokinetic sampling rates were
calculated.
At the start of each sampling run, the sampling probes
and alundum thimble holders were positioned properly in the cy-
clone. The thimble holder was allowed to warm up to the cyclone
temperature prior to sample collection to minimize condensation
of tars and oils in the thimble. Particulate samples were col-
lected isokinetically for periods ranging from 30 to 60 minutes.
After sampling, the thimble holder was removed from the stack
and a piece of aluminum foil was placed over the nozzle to pre-
vent entry of air and eliminate the possibility of autocombustion
in the thimble.
66
-------
Alundum
Filter Holder
Goose Neck or
Straight Stem
Nozzle
Packing
Gland
Impinger
inger
7
Stainless
Steel Pipe
Fine Adjustment
By Pas^ Valve ice Bath
Coarse
Adjustment Valve
£
Air Tight
Vacuum Pump
Dry Test
Meter
Figure 3-7. SCHEMATIC DIAGRAM OF PARTICULATE
SAMPLING TRAIN USED AT THE CYCLONE
67
-------
OO
Alundum
Thimble Holder
and Nozzle
Start-Up
Vent
Gate Valve
Stainless
Steel
Probe
Packing Gland
Figure 3-8. SCHEMATIC DIAGRAM OF SAMPLING ARRANGEMENT USED ON THE INLET
OF THE CYCLONE
-------
WEST
CYCLONE OUTLET
NORTH
5.24 m/s 4.79 m/s 3.90 m/s
SOUTH
61 cm
EAST
o>
oo
E
u
en
CM
L
CYCLONE INLET
I/I I/I
^ ^
e E
r- O
r- 00
• •
oo r-.
S E
O
00
oo oo
i/i
^>
E
en
en
ro
O 0 O O O O G
K
•53 cm-
ft/sec = 3.28 m/s
in = 2.54 cm
Figure 3-9. VELOCITY PROFILE AT THE INLET AND OUTLET OF
THE CYCLONE
69
-------
When the sampling equipment had cooled, the thimbles
were carefully removed and placed in plastic bags for storage.
The stainless steel probe and transfer lines were cleaned of
condensed organic matter. The impinger solutions, along with
any organic material which condensed in the impingers were
stored in polyethylene bottles.
Three impinger solutions were evaluated to determine
which was more efficient in removing organic matterial from the
gas stream: deionized water, tetrahydronaphthalene, and toluene.
With deionized water, most of the organic material
condensed on the glassware above the liquid level. However,
the organic material in the stream was not all removed by the
H20 impingers, as evidenced by small amounts of organic material
that collected on the inside walls of the tubing leading from
the impingers to the pump. A considerable amount of methylene
chloride and/or acetone was required for removal of the organic
matter from the impingers.
When tetrahydronaphthalene and toluene were used, most
of the organic material that condensed out of the gas remained
in the collection fluid. As a result, it was easier to remove
the organic material condensed in the impingers. There was also
a reduction in the amount of organic material that collected on
the inside walls of the tubing leading from the impingers to the
pump.
3.2.3 Samples for Additional Characterizations
One of the objectives of the test program at the Chap-
man facility was the evaluation of the applicability of Level. 1
procedures to environmental testing at coal gasification plants.
Also, in some cases it was considered desirable to collect addi-
tional data that would not be provided by Level 1 testing. The
additional data were collected using modified Level 1 and/or
additional sampling and analytical methods. The results of these
extra tests are presented in a separate report. The major vari-
ations from Level 1 sampling procedures were the modified SASS
train runs on the coal feeder vent gases and on the separator
vent gases.
In these SASS train runs, the procedure used for pre- *
paring and handling the XAD-2 resin differed substantially from
that specified in Level 1. Principally, the modification involved
70
-------
washing the resin with water, methanol, pyridine, and ether and
storing the resin in methanol prior to the run. This was done
to give lower baseline or "blank" values for the resin and also
because it improved the physical handling characteristics of
the resin. Another modification to the Level 1 procedure involved
placing the XAD-2 canister at the exit of the organic module,
which minimized condensation problems in the canister.
71
-------
SECTION 4.0
ANALYTICAL PROCEDURES
The analytical strategies and methodologies used in
the Chapman gasifier test program followed closely those des-
cribed in the Level 1 procedures manual (Ref. 1). However,
modifications and additions were made to some of the procedures
to correct identified analytical inadequacies and in compensa-
tion for unusal sample conditions encountered. The analytical
effort was conducted in two parts.
On-site analyses in Radian's mobile laboratory
1) Gas phase samples
2) Aqueous samples for water quality
parameters
Off-site analyses at Radian's Austin
laboratories
1) Elemental composition
2) Selected inorganic species
3) Water quality parameters
4) Organic extractions, separations
and analyses
Table 4-1 summarizes the Level 1 analyses performed on
each of the streams sampled at the test site. The overall analy-
tical schemes used for each sample are shown in Figures 4-1
through 4-6. As indicated in these figures, analyses outside
the Level 1 procedures were performed on some of the samples.
The results of these analyses and an evaluation of their com-
parability with Level 1 results are contained in a separate
document.
72
-------
Table 4-1. SUMMARY OF ANALYSES PERFORMED
Analyst*
Barrel
V«lv«
Coal Vent Cases
Gaslflar
Ash
Separator
Vent Cases
Cyclone
Dust
Separator
Liquor
Producer
Tar Gas
Elemental
by SSJB and AA
Proximate/Ultimate
Water Quality Parameter
Color
Conductivity
pH +
COD +
BOD +
IDS +
TSS +.
DO
Odor
Alkalinity +
Acidity +
TO, +
coT
Cl" +
Of
P~
Hardness
N07
NO,
SO^
s"
SON
Gases
C02
Hj
Ha
CH,
CO
Oj
HO/NO
H2S/COS/CS2/S02
HH3
HCN
BSCN
HF
BC1
Ci-C6
Organlcs
Level 1
Bloassay
t
x
x
X
X
X
x
X
X
X
X
X
X
X
X
X /
x x// x
+
•f
+
+
+
+
+
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
'
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
/ X /
X X»
•f Analysis performed on condensate
/ Analysis performed on extract
-------
AQ. ACID
IMPINGER
AQ. BASE
IMPINOER
GAS GRAB
r ^ x y
-\y ^
/^T7\
_ / HZ>02,\
Figure 4-1. ANALYTICAL FLOW SCHEME FOR COAL FEEDER VENT GASES
-------
Figure 4-2. ANALYTICAL FLOW SCHEME FOR SEPARATOR VENT GASES
-------
«H STOP
HSTOP
Figure 4-3. ANALYTICAL FLOW SCHEME FOR CYCLONE DUST AND GASIFIER ASH
-------
GRAV)
>C^
LEVEL I
LC
8 FRACTIONS
KH)
Figure 4-4. ANALYTICAL FLOW SCHEME FOR SEPARATOR TAR
-------
00
AQ
-*^^
-0
Figure 4-5. ANALYTICAL FLOW SCHEME FOR SEPARATOR LIQUOR
-------
Figure 4-6. ANALYTICAL FLOW SCHEME FOR PRODUCT GAS SAMPLES
-------
A description of the Level 1 analytical scheme for in-
organic species is contained in Section 4.1, while Section 4.2
presents a description of the scheme for organic species. In
addition to physical and chemical analyses, selected samples
were subjected to biological screening tests. These tests are
described in Section 4.3.
4.1 INORGANIC SPECIES ANALYSIS
Analyses for inorganic species and elements were per-
formed both on-site and off-site. The on-site portion included
gaseous sample analyses performed on filtered and dried grab
samples taken from the spray scrubber outlet, the No. 2 coal
feeder vent, the No. 2 cyclone exit, and the separator vent.
On-site Level 1 water quality analyses were also performed on
samples of separator liquor and on the condensate from the SASS
train gas conditioning module used during one sampling run on
the separator vent.
Additional water quality analyses were performed off-
site on samples of the separator liquor and the condensate from
the separator vent SASS train runs. Aqueous impinger samples
collected from the separator vent, coal feeder vent, and the
cyclone exit were also analyzed off-site.
Proximate and ultimate analyses of the coal feedstock,
cyclone dust, gasifier ash, and tar were conducted by other
laboratories. Appropriate samples from all of the above streams
were returned to Austin and analyzed for trace element content.
The procedures used for the inorganic analyses are
discussed in the following text.
4.1.1 Gas Phase Analytical Procedures
Grab samples of the coal feeder vent, separator vent,
raw product gas, and clean product gas streams were obtained
and analyzed on-site for each of the following groups of species
• Fixed gases (H2, N2, C02, 02, CSU, CO)
• Oxides of nitrogen (NO, NO ), and
X
80
-------
Sulfur species (H2S, COS, S02> CS2)
In addition, grab samples were taken for HCN, NH3, and (CN)2
analysis. However, the Level 1 techniques recommended for these
species proved to be unsatisfactory due to a lack of sensitivity,
and a substitute impinger technique had to be used.
Fixed Gases -
The fixed gas analyses were carried out on a Fisher
Model 1200 Gas Partitioner equipped with dual columns and dual
thermal conductivity detectors connected in series. The follow-
ing instrument operating conditions were used:
Column 1: 3 m x 0.32 cm aluminum, Columpak PQ
Column 2: 5.2 m x 0.47 cm aluminum, 13x molecular
sieve, 60-80 mesh
Carrier Gas: 8.57o H2 in He
Carrier Flow: 33 cm3/min
Oven Temp: 323°K
Injector Temp: Ambient
Bridge Current: 275 mA
Elution Order: C02, H2) 02, N2, CHi,, CO
These conditions represent a slight modification 'of
published Level 1 procedures, but have been found to give excel-
lent results. The published Level 1 procedure using a molecular
sieve 5A column at 313°K proved unsatisfactory because C02:is
retained and cannot be measured. A carrier gas of 8.5% (by
volume) hydrogen in helium was selected because it provided good
sensitivity and linear response over a wide range of hydrogen
concentrations in the gas samples.
Gas samples from the flexible, aluminized gas sampling
bags were introduced into the gas partitioner through a 1 cm3
sample loop. The loop and sample transport tubing were always
flushed with >5 residence volumes of sample gas before the
sample was injected.
81
-------
Each fixed gas component in the sample was quantified
by measuring its recorded peak height and comparing it to calib-
ration curves. The calibration curves were prepared on-site,
prior to the beginning of testing, in the following manner.
Three certified standard mixtures containing the six species of
interest were analyzed in triplicate on the partitioner, and the
average peak heights were plotted against the known concentra-
tions. Additional points were generated by diluting each of the
standards with nitrogen and analyzing the known dilutions. In-
strument performance was checked periodically by analyzing one
of the calibration mixtures and comparing the results with the
standard curves. The partitioner proved to be very stable
throughout the test period.
Oxides of Nitrogen =
Analyses for NO and NOX in each of the gas streams
samples were performed using a Monitor Laboratories Model 8430
Analyzer equipped with a Model 8750 Stainless Steel Converter.
This instrument determines the amount of NO present by measuring
its chemiluminescence when reacted with ozone. NOX is measured
by first converting the N0x to NO and then measuring the total
NO. None of the gas samples analyzed approached the instru-
ment's upper detection limit of 500 ppmv NO.
Samples from teflon sample bags were introduced into
the instrument by an internal pump through teflon transfer tubes.
The detector output was read from a panel-mounted meter set at
the appropriate scale. The sample was first introduced in the
NO mode, and the level of NO was measured. The instrument was
then changed to the NOX mode, and the combined levels of NO and
NO2 were measured.
The analyzer was calibrated daily at zero ppmv NO
using zero air and ambient air. It was then calibrated using a
stream of nitrogen containing a known amount of N02 in the 60-
100 ppmv range. This steam was generated in a Tracer Model 412
Permeation Chamber using certified N02 permeation tubes. The
second calibration was based on the analyzer manufacturer's
stated N02 to NO converter efficiency of 99%.
No problems were encountered during NO analysis of any
of the gas samples or during NO analysis of the separator vent
gas. However, no reading was obtained when NOX analyses were
attempted on samples from the coal feeder vent, spray scrubber
82
-------
outlet, and No. 2 cyclone exit samples. After failing to iden-
tify any instrument malfunction, the following experiment was
performed. A stream of N02 in N2 was introduced into the ana-
lyzer from the permeation chamber. After the reading stabilized
at the correct concentration, indicating proper instrument
function, a stream of No. 2 cyclone exit gas was slowly mixed
with the calibration stream. After approximately 15-20 seconds,
the analyzer reading suddenly fell to zero. This indicated that
some chemical species in the gas sample, probably CO and H2,
were interferring with the analysis of N0x. This experiment
also indicated that the NOX value for the separator vent gas
should be questioned because it also contained CO and H2.
Sulfur Species -
The sulfur species (H2S, COS, S02, CS2) were analyzed
on a Hewlett-Packard Model 5730 Gas Chromatograph equipped with
a flame photometric detector (FPD). One cm3 aliquots of the
dried, filtered samples were withdrawn from the gas sampling
bombs with gas-tight syringes and injected directly onto the
column. The instrument conditions used for these analyses were:
Column: 0.86 m x 0.32 cm Teflon, Poropak QS,
80/100 mesh
Carrier Gas: N2
Carrier Flow: 35cm3/min
Injector Temp: 423°K
Detector Temp: 473 K
Oven Program: 313°K for 4 min0
32°K/min to 433 K
433 K for 4 min
Detector Flows: Air: 50 cm3/min
02 : 10 cm3/min
H2 : 50 cm3/min
This separation technique is different from that specified in
the Level 1 Manual, but Radian has found that the separation of
H2S and COS is more complete using the Poropak QS column. Also,
the total analysis time is considerably reduced. The detector
83
-------
output was recorded and integrated on a Hewlett-Packard Model
3380A Integrator/Plotter.
Instrument calibration was accomplished using a nitro-
gen stream containing known amounts of the four species. This
calibration standard was generated from permeation tubes. The
same injection technique was used for calibration as for sample
analysis. Standards were run each day prior to any sample ana-
lysis, and multiple standard injections were made until stable,
reproducible analyses were obtained.
The major problem encountered during on-site analysis
for sulfur species involved sample introduction into the chroma-
tograph. During early runs, the syringe, which was fitted with
a stainless steel Luer-Lok tip and Teflon plunger seal, was
cleaned with water and acetone and dried at 363°K after each
injection. However, the peak for H2S was considerably smaller
than expected in the standard mixtures, and the S02 peak was non-
existent. It was found that if the syringe was not cleaned
between runs, the H2S and S02 peaks increased in size on each
succeeding injection. After about the third run, the peaks ap-
peared to reach a maximum which remained constant. This gave
evidence to the apparent sorption of H2S and S02 in the syringe.
Negligible changes occurred in the responses of COS and CS2.
This information resulted in development of a "curing"
procedure for the sample injection syringe. The syringe was
filled with the standard gas mixture and allowed to stand undis-
turbed for fifteen minutes. Standard mixture samples were then
injected into the gas chromatograph until consecutive runs show-
ed no increase in either the H2S or S02 peaks. The syringe was
then considered cured, and samples were run. Consecutive sample
runs showed no increase in either the H2S or S02 peaks, indicat-
ing that the "curing" procedure was effective. Blank injections
of nitrogen using the "cured" syringe showed negligible memory
effects, i.e., negligible amounts of sulfur species were desorbed
from the syringe. This type of curing procedure was also used
for preparation of the glass sampling bombs prior to sample
collection.
Other Nitrogenous Species -
Gas grab samples for analysis of HCN, NH and (CN)2
were originally scheduled to be taken from each gaseous stream
tested. Analysis was to be conducted on a Fisher Model 1200 gas
chromatograph using a thermal conductivity detector as specified
84
-------
under the Level 1 protocol. However, calibration runs using
diluted samples of both NH3 and HCN indicated that the lower
detection limit for each species was approximately 2,000 ppmv.
The instrument conditions for these analyses were as follows:
Column: 2.8 m x 0.32 cm stainless steel, Poropak 0
100/120 mesh
Carrier Gas: N2
Carrier Flow: 35 cm3/min
Injector Temp: 373°K
Detector Temp: 373°K
Oven Temp: 353°K
Since these lower detection limits were higher than the
expected concentrations of the species in the actual process gas
sample, this method of analysis was abandoned. Instead, HCN and
NHs were sampled by pulling gas samples through basic, and then
acidic, impingers. The impinger solutions were then analyzed
for NH3 and HCN by standard wet chemical methods in Radian's
Austin laboratories.
4.1.2 Aqueous Media Analytical Procedures
The aqueous samples collected during the Chapman facil-
ity test fell into three categories: Condensate from SASS train
runs on the separator vent; the raw separator liquor; and
impinger solutions from sampling the separator vent, coal feeder
vent, and raw product gas. Analyses performed on these samples
consisted of water quality parameters (including inorganic
species) and elemental composition. Table 4-2 lists the specif-
ic analyses performed on each of the aqueous samples obtained
during the test.
Water quality analyses of the organic module conden-
sate from one SASS train run at the separator vent were divided
into two groups - those performed on the condensate before
extraction of organic species and those performed after the
CH2Cl2 extraction. Samples of unextracted condensate from a
second SASS train run on the separator vent were returned to
Austin for additional analyses. Table 4-3 summarizes the
analyses performed, location of analyses, and sample origins.
85
-------
Table 4-2. AQUEOUS PHASE ANALYSES BY STREAM
00
Separator Vent Condensate
Separator Vent Impingers
Coal Feeder Vent
Impingers
Raw Product Gas Impingers
Separator Liquor
14
o
•-i
o
CJ
X
4J
•H
_4
Conduct:
X
a
X
X
§
X
X
a
o
ta
X
X
en
B
X
X
en
en
H
X
X
§
X
o
T)
O
X
4J
•H
rTlkalin
X
X
1
X
X
X
X
o
o
X
i
o
X
X
X
X
I
g
X
X
X
X
X
'ft.
X
X
X
X
en
Hardnes
X
'I
X
X
'I
X
X
II ^
o
X
X
"en
X
X
•z,
CJ
en
X
X
X
X
X
4J
•H
0
X
X
m
4J
i
iH
W
X
X
-------
Table 4-3. WATER QUALITY ANALYSES ON SEPARATOR VENT GAS CONDENSATE
Unextracted Condensate
Run #1
Extracted Condensate
Run #1
Unextracted Condensate
Run #2
ta
ex
X
p
o
u
R
P
O
pq
R
CO
P
H
X
CO
CO
H
X
•H
C
•H
rH
rH
^
X
CO
g
X
1 N
0
*
1 m
0
*
"o
X
II
CO
X
!>-.
4-1
•H
0
<
X
1
CJ
X
R
I
i-i
CJ
R
t
fc
R
o
CO
R
oo
X = On-site analyses
R = Radian in-house analyses
* = Analysis method failed
-------
Water quality analyses of separator liquor were also
performed on unextracted and extracted samples. A summary of
the analyses, by sample type, is presented in Table 4-4.
Gas samples from the coal feeder vent, separator vent,
and raw product gas streams were sampled using both aqueous acidic
and basic impinger trains. The resulting impinger solutions were
returned to Austin and analyzed for the species shown in Table
4-2. The ammonia analysis was performed on the acidic impinger
solutions, while the other analyses were performed on the basic
solutions.
The following analytical procedures were used to deter-
mine the water quality parameters of the various aqueous samples.
Reagent test kits specified by Level 1 methods were used, when
available, for the on-site analyses. If no suitable kit was
available, standard laboratory procedures were used.
Biochemical Oxygen Demand (B.O.D.) -
B.O.D. was determined according to procedures specified
in Standard Methods for the Examination of Water and Waste Water
(ReF!3.). B.O.D. is a measure of the change in the amount of
dissolved oxygen in the sample when incubated in the dark at
293°K for five days. This change in dissolved oxygen is related
to the amount of organic matter which is assimilated and oxidized
by microorganisms. An initial dissolved oxygen concentration
was determined as described in the section on Dissolved Oxygen
and after five days, a final concentration was determined.
Chemical Oxygen Demand (C.O.D.) -
C.O.D. was also determined according to procedures
specified in Standard Methods for the Examination of Water and
Waste Water. In this method,the sample is combined with a
known quantity of potassium dichromate and sulfuric acid and
refluxed for two hours. The extent of the oxidation reaction is
determined by titration of excess dichromate with a standard
ferrous ammonium sulfate solution using ferroin as an indicator.
88
-------
Table 4-4. WATER QUALITY ANALYSES ON SEPARATOR LIQUOR
Unextracted
Liquor
Extracted
Liquor
^|
o
o
o
X
•rl
•H
J-l
O
3
C
o
CJ
X
EC
O,
X
§
o
X
O
O
ca
X
CO
Q
EH
X
CO
CO
H
X
O
a
X
^.j
o
X
•H
a
•H
I-l
cd
rH
X
Ps
4J
•rl
T3
•H
X
CO
ca
-------
Color -
True color was determined by visual comparison of a
filtered sample (Whatman GF/C glass fiber filter) with known
concentrations of a platinum-cobalt solution. Since the color
of the separator liquor sample was brown, it was difficult to
compare the sample to the standards but an estimate was made on
the basis of color intensity.
Conductivity -
Conductivity was determined using a YSI Conductivity
Meter Model 33-S-C-T. Conductivity in ymho/cm was determined
from the electrical conductance of a sample measured between
opposite faces of a 1 cm cube.
Dissolved Oxygen (P.O.) -
A Bausch and Lomb reagent test kit was used for dis-
solved oxygen determination. The test kit utilizes an azide
modification of the Winkler titration, which is based on the
oxidizing properties of dissolved 02- In this procedure iodine
is liberated and titrated with a standard sodium thiosulfate
solution. Starch was added as an end-point detector. The addi-
tion of starch is necessary for the detection of end-points in
brownish colored samples such as the separator liquor.
p_H -
An Orion pH meter was used to measure the pH of the
samples.
Solids -
Solids content was determined using the procedure out-
lined in Standard Methods for the Examination of Water and Waste
Water. Total suspended^ solids were determined by filtering
measured samples through a previously dried and tared fiber
filter (Whatman GF/C). The filter bearing the suspended solids
was then placed in an oven at 376°K and dried to a constant
90
-------
weight. The filtrate from the suspended solids determination
was transferred by pipet to a tared glass beaker. The beaker
was placed in an oven at 376°K, and dried to a constant weight
to determine Total Dissolved Solids.
Acidity „
Acidity was determined with a Hach test kit. This
test utilizes an acid-base titration in which the sample is
titrated with a standard NaOH solution to its phenolphthalein
end-point (pH 8.3) and the results reported as ug/m£ CaC03.
Alkalinity -
Alkalinity was determined using reagent test kits.
This determination involved an acid-base titration in which the
sample was titrated with a standard sulfuric acid solution to
the phenolphthalein end-point (phenolphthalein alkalinity) and to
the brom cresol green/methyl red end-point (total alkalinity).
The results are reported as ug/m£ CaC03• Both the Hach and the
Bausch and Lomb tests kits were used for the alkalinity deter-
minations. The powdered reagents from the Hach kit gave the
sharper end-point.
Ammonia -
Ammonia determinations were made both on-site and at
the Radian lab facilities in Austin. A Bausch and Lomb test kit
was used on-site. This involved the spectrophotometric measure-
ment of a colored complex produced by the Nessler reaction. In
the Radian labs, the sample was distilled from an alkaline buf-
fered solution. Ammonia which was driven off was captured in a
boric acid scrubbing solution and determined by titration using
a standard sulfuric acid solution.
Carbonate
Carbonate was calculated from the results of the
alkalinity and pH determinations. When the phenolphthalein
alkalinity is not zero and is less than the total alkalinity,
carbonate is present. The carbonate value was calculated by the
following formula:
91
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Carbonate = 2 x (phenolphthalein alkalinity -
hydroxide ion concentration)
The hydroxide ion concentration was calculated from the pH deter-
mination and was expressed as yg/mJl CaC03.
Chloride -
Chloride was determined according to procedures out-
lined in Standard Methods for the Examination of Water and Waste
Water. The chloride concentration was measured by potentiometric
titration using a standard silver nitrate solution. The end-
point is detected by using a chloride-specific ion electrode
which measures changes in potential as silver nitrate is added.
The end-point is that point at which the greatest change in
instrument reading occurs for the smallest increment of titrant
added.
Cyanide _
Cyanide was determined on-site by using a Hach test
kit. The analysis is based on the pyridine-pyrazolone reaction
in which the cyanide is first coupled with free chlorine to form
cyanogen chloride and then with pyridine to form a glutaconic
aldehyde. The aldehyde then reacts with l-phenyl-3-methyl-5
pyrazolone to form a highly colored blue dye. Both cyanide and
cyanate are measured by this method. If only cyanide is to be
determined, an initial distillation step must be included.
Cyanide was determined at Radian's facilities using
the following method. An aliquot of preserved sample was
placed in a cyanide distillation apparatus with an air purge.
The sample was acidified and refluxed, causing hydrogen cyanide
gas to be liberated from the sample. The cyanide gas was col-
lected in an NaOH solution and its concentration determined by
the colorimetric procedure described previously.
Fluoride _
Fluoride was determined using standard additives and
with a fluoride specific-ion electrode. Fluoride complexed by
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uranium, thorium, aluminum and iron is released by addition of a
citrate buffer which also serves to eliminate variances in pH and
ionic strength. The observed changes in potential can be related
directly to fluoride concentration.
Hardness _
Hardness was determined by the use of a Hach test kit,
Calcium and magnesium ion concentrations were determined by
adding disodium EDTA to the sample. The end-point of the reac-
tion is detected with Eriochrome Black T which has a red color
in the presence of calcium and magnesium and a blue color when
the cations are complexed with the Na2EDTA.
Nitrite -
Nitrite was determined with a Bausch and Lomb test kit.
The determination is based on the formation and colorimetric
measurement of a reddish purple dye produced by the coupling of
diazotized sulfanilic acid with naphthylamine hydrochloride.
Nitrate -.
Nitrate was determined with a Bausch and Lomb test kit.
Nitrate is changed to nitrite by cadmium reduction. The result-
ing nitrite is determined as described above. Correction was
made for any nitrite which was initially present in the sample.
Sulfate -
Sulfate was determined with a Bausch and Lomb test kit.
The sulfate in the sample was precipitated as BaSCU and the
turbidity of the suspended precipitate was measured at 420 nm on
a spectrophotometer.
Sulfide -
Sulfide was determined on-site using a Hach test kit.
The analysis is based on the ability of hydrogen sulfide and
acid-soluable metallic sulfides to convert N, N-dimethyl-p-
93
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phenylenediamine oxalate directly to methylene blue. The inten-
sity of the methylene blue color developed is directly propor-
tional to the amount of sulfide present in the original sample.
At Radian, sulfide was precipitated as zinc sulfide
and dewatered on a glass fiber filter. The filter was then
placed in a flask where sulfide was redissolved in a known acid-
iodine solution. After the sulfide was oxidized by the iodine,
residual iodine was then back titrated with thiosulfate solu-
tion until the blue color of a starch indicator disappeared.
4.1.3 Analyses of Solids Samples
The solid samples collected during the Chapman gasifier
test included gasifier ash, cyclone dust, and coal feeder vent
particulates. In addition, samples of separator tar and coal
feedstock were also collected. Ultimate analyses of the coal
were performed by the Institute for Mining and Mineral Research,
Lexington, Kentucky. The Institute used standard procedures for
these analyses.
4.1.4 Analyses for Trace Elements
All of the streams examined in the test program were
analyzed for trace elements (see Table 4-5) . The preparation of
samples and the analytical methods used in determinations for
trace element compositions were identical to those described in
the Level 1 Environmental Assessment Manual. Solid samples were
ashed in a quartz-lined Parr combustion bomb, and then dissolved
in dilute aqueous nitric acid. The resultant liquid samples
were then analyzed without modification.
Analyses for mercury, antimony, and arsenic were per-
formed at Radian using atomic absorption spectrophotometry.
Analyses for the remaining elements were made using spark source
mass spectrometry at the Commercial Testing and Engineering Lab-
oratories, Golden, Colorado. Blank samples were also run on the
Parr bomb itself and on clean XAD-2 resin samples.
94
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Table 4-5. SAMPLES ANALYZED FOR TRACE ELEMENT COMPOSITION
Coal Feed
Gasifier Ash
Cyclone Dust
Separator Liquor
Separator Tar
Separator Vent
^
XAD-2 Resin Extract
Condensate
(NHOzSzOe Impinger Solution
>.
Coal Feeder Vent
Particulate
r
XAD-2 Resin Extract
Condensate
aSaOs Impinger Solution
Parr Bomb Blank
XAD-2 Resin Blank
Combined for reporting purposes
95
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4.2 ORGANIC SPECIES ANALYSIS
The organic analysis of the samples collected during
the test included:
analyses for gaseous hydrocarbons,
extraction of the organics from liquid and
solid samples, and
preparation and analysis of the extracts
and rinses.
Level 1 methodologies were generally followed, although modifica-
tions were made where experience or unusual sample conditions
indicated that Level 1 methodologies would not yield satisfac-
tory data.
The organic analyses performed on-site and off-site
are given below:
On-site portion
1) gaseous hydrocarbons analyses
2) organic extraction of aqueous samples
Off-site portion
1) organic extraction of solid samples
2) preparation of organic extracts and
washes
3) analyses of extracts and washes
Table 4-6 lists the streams sampled for organic analyses.
The following sections describe the procedures used
for analysis of the organics in samples collected during the
test. Section 4.2.1 addresses the on-site gaseous hydrocarbon
species analysis. Section 4.2.2 describes the on-site and off-
site organic extraction procedures, while Section 4.2.3 describes
96
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the off-site preparation and analytical procedures used for the
organic extracts and rinses.
Table 4-6. STREAMS SAMPLED FOR ORGANIC SPECIES ANALYSES
Gaseous Condensable and/or
Streams (Stream Type) Organics Extractable Organics
Separator Vent (Waste Stream) X X
Coal Feeder Vent (Waste Stream) X X
Gasifier Ash (Waste Stream) X
Cyclone Dust (Waste Stream) X
Separator Tar (Process Stream) X
Separator Liquor (Process Stream) X
Raw Product Gas (Process Stream) X
Clean Product Gas (Process Stream) X
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4.2.1 Gaseous Hydrocarbon Species Analyses
Grab samples from each of the following gas streams
were caught in flexible Teflon bags and analyzed on-site for
light hydrocarbons (Ci-Cg):
coal feeder vent,
separator vent,
raw product gas (#2 cyclone exit),
and
clean product gas (spray scrubber
outlet).
Modified Level 1 procedures were used for these anal-
yses. This involved using a Hewlett-Packard Model 5730 gas
chromatograph equipped with a flame ionization detector (FID).
One cm3 aliquots of the gas samples were transferred from the
sampling bags by a gas-tight syringe and injected directly onto
the column. The instrument conditions for this analysis were:
Column: 2.8 m x 0.32 cm stainless steel, Poropak Q
100/120 mesh
Carrier Gas: N2
Carrier Flow: 40 cm3/min
Injector Temp: 423°K
Detector Temp: 473°K
Oven Program: 323°K for 16 min
4°K/min to 473°K
473°K for 16 min
The detector output was plotted and integrated on a
Hewlett-Packard Model 3380A Integrator/Plotter. Component con-
centrations were determined from peak areas as calculated by
the integrator.
98
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This instrument was calibrated by analyzing a standard
mixture of nitrogen containing 1000 ppmv each of methane, ethane,
propane, n-butane, n-pentane, and n-hexane. This calibration was
performed daily before the first sample was run. The standard
was analyzed until reproducible results were obtained three con-
secutive times for all six compounds. The average of these three
runs was then programmed into the integrator.
4.2.2 Organic Extraction Procedures
In this section, the procedures used to prepare
samples for organic analysis from gas, liquid, and solid samples
are described. The samples collected for organic analyses were
obtained from:
gaseous waste streams (coal feeder and
separator vent gases),
solid waste streams (ash and cyclone dust)
and by-product tar, and
aqueous process stream (separator liquor).
Gaseous Waste Streams -
The SASS train was used to sample the coal feeder
and separator vent gases. Two samples for organic analysis
were obtained from each of these runs. The first sample included
rinses of the nozzle, probe, and cyclones. For the SASS train
run on the coal feeder vent, these rinses were also filtered
and the resulting solids extracted with CH2C12. This extract and
the rinses were combined for organic analysis.
The second organic sample recovered from the SASS
train consisted of a combination of the CH2C12 rinses of the gas
conditioning module, the CH2C12 extracts of the condensate, and
the pentane extracts of the XAD-2 resin. The condensate was ex-
tracted on-site three times with a 1:10 ratio of solvent to
aqueous phase. The XAD-2 resin was returned to Austin and ex-
tracted with 2 liters of pentane in a Soxhlet extraction appara-
tus for 24 hours.
Level 1 procedures stipulate that all the organic
samples from the SASS train should be combined and analyzed as
99
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one sample. However, when the SASS train was used to sample the
coal feeder vent gases, the material rinsed from the particulate
module looked different from the material rinsed from the organ-
ic module. Therefore, these rinses were not combined, but were
analyzed as two separate samples.
The organic rinses from the particulate and organic
modules of the SASS train sampling of the separator vent appear-
ed to be similar. However, they were also treated as two separ-
ate samples, in order to be consistent with the analysis proce-
dure used for the coal feeder vent stream.
Solid Waste Streams and Tar -
Samples for organic analysis of the tar, gasifier,
ash, and cyclone dust were obtained by extraction. As pres-
cribed in the Level 1 procedures, appropriate quantities of each
sample were extracted with CH2C12 in a Soxhlet extraction appar-
atus for 24 hours. As anticipated, a major portion of the tar
sample (^60%) was extracted in this manner. However, only small
amounts of organics were obtained from the ash and dust samples:
-v 4 mg from 200g ash and ^ 13 mg from 363g of dust. According
to Level 1 criteria these quantities were insufficient to justi-
fy further separation and analysis.
Aqueous Process Stream
The sample for organic analysis of the separator
liquor was also obtained by extraction. This extraction was done
on-site and consisted of three separate extractions using a 1:10
ratio of CH2C12 to liquor. The three extracts were combined for
analysis.
4.2.3 Preparation and Analysis Methods
The organic contents of the extract solutions des-
cribed in the previous section were first quantified by gravi-
metric analysis, as described in a following section. The solu-
tions were then concentrated using a Kuderna-Danish concentration
apparatus. The degree of concentration was determined either by
the point of precipitate appearance or by visual determination
of the darkness of the solution. This typically resulted in con^
centrate volumes of 4-100 m£, containing 50-200 mg/m£ of organ-
100
-------
ever ^tractf n?d ^"l"?*1? b? gravimetric analysis. How-
™^m? becSae ffCKi™% dU8t and.&asi^ ash were concentrated
to j. .mx, oecause of their low organic content.
Following concentration, the samples were analyzed
using Level 1 procedures. As shown in Figure 4-1 through 4-6,
this entailed:
gravimetric analysis, (gravs)
total chromatographable organics (TCO)
analysis,
liquid chromatography (LC),
infrared spectrophotometry (IR), and
low resolution mass spectrometry (LRMS).
These techniques are discussed in the following text.
Gravimetric Analyses -
Gravimetric analyses were done on both dilute (0.5-
3.0 mg/m£) and concentrated (10-200 mg/mjl) extracts and on liquid
chromotography fractions. These analyses were performed by
transferring 1 ml of solution to a tared 5 cm glass watch glass,
and then allowing the solvent to evaporate until the sample
reached a constant weight (4 hour weighing intervals) at room
temperature in a dessicator. The watch glass was protected from
dust and other contamination by placing it in a glass Petri dish.
All weighings were performed on a Mettler H35AR analytical
balance to a reproducible accuracy of +0.2 mg.
The gravimetric determinations (gravs) presented one
of the more significant organic analysis problems. Generally,
the problem experienced with the gravs involved inconsistencies
in the resulting data for mass balances and flows within a
sample system. This probably was due to two factors. First, a
significant potential for inaccuracy existed when weighing the
samll amounts of organics obtained from the dilute solutions and
liquid chromatography fractions. Second, although the concen-
trated solutions were evaporated to a constant weight, a
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scum formed on the surface of certain samples which may have
hampered the evaporation of volatile organics.
Total Chromatographable Organics Analyses (TCP)
Total chromatographable organics are defined by Level
1 as those compounds which have gas chromatographic retention
times between n-heptane and n-hexadecane. TCO analyses were
carried out on a Hewlett-Packard Model 5710A gas chromatograph
equipped with a flame ionization detector and a Hewlett-Packard
Model 3380A Integrator/Plotter. Samples of 1 y£ were injected
by syringe and analyzed. The analyses were performed under the
following instrument conditions.
Column: 2.8 m x 0.2 cm i.d. glass, 10% OV-101
on 100-120 mesh Supelcoport
Carrier Gas: Na
Carrier Flow: 30 cm3/min
Oven Program: 303°K for 4 min
16°K/min to 523°K
523°K until after elution time
of Ci7 standard, then an
additional 5 min
Injector Temp: 523°K
Detector Temp: 523°K
Calibrations were performed using a methylene chloride solution
containing 380 ug/m£ each of normal alkanes from C6 through Ci?.
Calibrations of the integrator were done daily before and after
each group of samples were analyzed.
Two major problems were encountered during these anal-
yses: (1) a lack of internal consistency in the data collected
on dilute and concentrated samples, and (2) an inability of the
integrator to compute accurately the peak areas in the typically
complex chromatograms obtained. The TCO analyses of the initial
dilute extracts and of some of the liquid chromatography frac-
tions understated the TCO concentrations, compared to analyses
of concentrates. This apparently was caused by a failure to «
102
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detect many compounds present in very low concentrations. When
the sample was concentrated such compounds became detectable,
but a new problem arose. The samples from the gasification
process contained so many different chromatographable compounds
that the chromatograms of the concentrates were very complex.
Liquid Chromatography (LC)
Concentrated extracts from the following sources were
subjected to a Level 1 liquid chromatographic separation on
silica gel:
coal feeder vent SASS particulate train,
coal feeder vent SASS organic module,
separator vent SASS particulate train,
separator vent SASS organic module,
separator liquor, and
separator tar.
Due to the tarry nature of most of the samples, a modified Level
1 procedure was used for preparation of the sample for applica-
tion to the LC column. A volume of sample solution was mixed
with 500 mg of silica in a 5 m£ round-bottom flask fitted with a
two ball micro-Synder distillation column. The solvent was
evaporated slowly with constant agitation to prevent bumping.
Just before the silica reached dryness, 1 m£ pentane was added
and the evaporation was repeated. This step was then repeated
a second time. Afterwards, the silica was air-dried sufficiently
to allow it to be poured onto the head of a pre-packed LC
column. The LC separation was then carried out according to
Level 1 procedures.
Column loadings ranged from 100-600 mg of combined
gravimetric and TCO weight organics. Although some columns were
overloaded according to Level 1 specifications, no appreciable
degradation of separation was noted. Some spreading of bands of
organics across several fractions was observed, but the occur-
rence of this phenomenon did not appear related to column
loading. For all samples, the appearance of the columns after
chromatography indicated that a quantity of dark colored
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(probably tar) material had not been eluted. Usually the entire
column was dark brown or black.
Infrared Analyses (IR)
Infrared analyses were performed on a Perkin-Elmer
Model 238 grating infrared spectrophotometer. Samples were run
as thin films between two KBr windows. The only problems
encountered during the collection of spectra was that many of
these samples had tarry and semi-solid components which made it
difficult to obtain a good thin film. Consequently, it was
impossible to get good peak resolution in some of the spectra.
Interpretations of the spectra generated from these
tests were generally quite difficult. The complexity of the
samples caused the IR spectra to contain a multitude of peaks.
In many cases, compound class identification was difficult, espe-
cially from peaks in the fingerprint region. However, classes
of compounds identified separately in the low resolution mass
spectra analyses could usually be verified from the IR spectra.
Low Resolution Mass Spectrometry Analyses (LRMS) -
The low resolution mass spectrometry analyses were
performed on a Hewlett-Packard 5980A Series Mass Spectrometer
equipped with a disc storage data system. Spectra were obtained
from probe inlet sampling at both high (70 ev) and low (10 ev)
ionization voltages as described in the Level 1 manual.
Two problems were encountered during these analyses.
First, volatiles were lost during the solvent evaporation step
prior to sample input. And second, problems arose in selecting
which (of the up to 300) individual spectra from each sample
should be used in interpretation phase of the analyses.
4.3 BIPASSAY ANALYSIS
As part of the Level 1 testing effort at the Chapman
facility, selected samples of process and waste streams were
subjected to various bioassay screening tests. These tests can
be divided into either health or ecological effects tests.
104
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These tests, and the company or institute that performed them,
are listed below.
• Health Effects Test
- Ames (SRI International)
- Cytotoxicity (WI-38, RAM) (Arthur D. Little,
Inc.) (Northrop Services, Inc.)
- Rodent acute toxicity (Litton Bionetics)
Ecological Effects Tests
- Fresh water (algal, daphnia, fathead minnow)
(Battelle)
Salt water (algal, shrimp, sheepshead minnow)
(EG&G Bionomics)
Terrestrial (soil microcosm, plant stress
ethylene) (Battelle)
The procedures for each of the above tests are described in the
Level 1 Environmental Assessment Manual. The following text
presents a brief description of the methodologies used to per-
form these tests on selected samples.
4.3.1 Ames Test
The Ames test is used to measure the potential muta-
genicity (carcinogenicity) of a material. This test was
performed on the following samples:
coal feed,
coal feeder vent gas (XAD-2 extract),
gasifier ash,
cyclone dust,
tar,
105
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separator vent gas (XAD-2 extract),
and
separator liquor.
The Ames test performed on the above samples used Salmonella
typhimurium strains TA1535, TA1537, TA1538, TA98 and TA100.
These strains were all histidine auxotrophs. Strains TA98 and
TA100 are not specified in the Level 1 procedure, however, in
some cases they are more sensitive to mutagenic agents. The
Ames test has been proven to be 80 to 907o accurate in detecting
carcinogens as mutagens, and it has about the same accuracy in
identifying materials that are not carcinogenic. Therefore,
neither a positive or negative response proves conclusively that
a material is hazardous or nonhazardous to man.
4.3.2 Cytotoxicity Tests
Cytotoxicity tests are used to estimate the acute
cellular toxicity of a sample from an in-vitro cell mortality
test using a human lung culture (WI-38) and rabbit aveolar
macrophages (RAM). These tests were performed on the following
samples:
• coal feed (WI-38, RAM),
coal feeder vent gas WAC-2 extract
(WI-38, RAM),
gasifier ash (RAM) ,
• tar (RAM),
separator vent gas XAD-2 extract
(WI-38, RAM), and
separator liquor (RAM) .
The protocol, defined in the Level 1 Environmental Assessment
Manual, was used with the following modifications:
106
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Assays were conducted in tubes rather than
in 4-place cluster dishes.
Each culture tube was supplemented with
dyCi 1'*C-amino acids.
At the end of the 10-hour incubation period,
cells were washed three times with cold
phosphate buffered saline. Tricholoroacetic
acid-precipitable material in each tube was
collected on Gelman Type E filters and
counted for radioactivity in a Searle Mark
III scintillation counter.
The results of the cytotoxicity test are presented as cell
count EC5 o's.
4.3.3 Rodent Acute Toxicity Test
The rodent acute toxicity test is used to measure
the acute toxicity of a material in a whole animal by administer'
ing known levels of the sample to a small population of rats.
Samples analyzed by this test were:
coal feed,
gasifier ash,
cyclone dust,
tar, and
separator liquor.
Young addult rats (weighting 199 to 340 g and 10 to 12 weeks old
at the time of treatment) of the Charles River CE strain (CRL:
COBS CD (SD) BR) were used. The sample was administered to the
test animals (5 male and 5 female) in a single dose of 10 g of
sample per kg of animal weight. The rats were observed fre-
quently, and were weighed on the seventh and fourteenth days
after sample administration. Necropsies were performed on the
animals that survived 14 days. The mortality rate estimated
from this test was then extrapolated to give an LD50 value for
each sample.
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4.3.4 Fresh Water Tests
Fresh water bioassay tests were performed using
algae, daphnia, and fathead minnows. These tests are used to
give acute toxicity values for various concentrations of a
sample in fresh water. The separator liquor was the only
sample analyzed by these tests.
Algae Test -
Selenastrum capricornutum was the test species used
for the algae test. The maximum specific growth rate for each
sample concentration was obtained over the 15-day test. The
algae ECso (defined as the sample concentration which produces
a maximum specific growth rate equal to one-half that of the
controls) was obtained from dose-response plots of sample
concentration versus maximum specific growth rate.
Daphnia Test -
Cultures of the cladoceran Daphnia pulex were used
for the daphnia test. LCso values (defined as the sample con-
centration that will affect 50 percent of the test organisms)
were obtained by plotting sample concentration versus the
percent of organisms killed.
Fathead Minnow Tests -
Fathead minnows (Pimephales promelus) weighing approx-
mately 1 g and having a length of about 5 cm were used in this
test. LCso values (defined as the sample concentration required
to kill 50 percent of the fish) were calculated by plotting
sample concentration versus the percent of fish killed.
4.3.5 Salt Water Tests
Salt water bioassay tests were performed using marine
algae (Skelotonema costatum), grass shrimp (Palaempnetes pugio)
and sheepshead minnows(Cyprinodon variegatus).The procedures
for salt water bioassay tests are similar to the procedures
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for the fresh water tests described previously. The sample
tested for salt water bioassays was the separator liquor. ECs0
for algae and LCso for shrimp and minnows were obtained for the
liquor sample.
4.3.6 Soil Microcosm Test
The soil microcosm test is used to measure or rank
the toxicity of a material to the microorganisms found in soil.
The samples that were tested were:
coal feed,
gasifier ash,
• cyclone dust,
tar, and
separator liquor.
Measurements on C02 efflux and calcium export were made. The
results of these analyses were used to rank the samples accord-
ing to their soil microcosm toxicity. Dissolved organic carbon
measurements were not made on these samples.
4.3.7 Plant Stress Ethylene Test
Five-week-old soybean plants (Glycine max) were used
as the test organisms for the plant stress ethylene bioassay.
This test was performed on a sample of the coal feeder vent
gas. The amount of ethylene produced by the plants after
exposure to the gas sample was measured. A positive (increase
in ethylene production) or negative (no change in ethylene
production) is the result of this bioassay.
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SECTION 5.0
TEST RESULTS
In this section the methodologies used and the results
obtained in this STE program performed at a Chapman gasification
facility are presented.
5.1 METHODOLOGIES
The following methodologies were used to interpret the
data from the chemical and bioassay tests:
SAM/1A analyses, and
analyses of bioassay tests.
5.1.1 SAM/1A Methodology
The Energy Assessment and Control Division of the EPA's
Industrial Environmental Research Laboratory at Research Triangle
Park (IERL-RTP/EACD) has developed a standardized methodology
for interpreting the results obtained from environmental assess-
ment programs. This methodology uses Source Analysis Models
(SAM's) (Ref. 4 ), coupled with the Multimedia Environmental
Goals (MEG's) (Ref. 2).
The simplest member of the SAM's is SAM/1A. This model
provides a rapid screening technique for assessing the pollution
potential of gaseous, liquid, and solid waste streams. Major
simplifying assumptions implicit in the use of the SAM/1A meth-
odology include the following.
The substances currently in the MEG's are the
only ones that must be addressed at this time.
Transport of the components in the waste streams
to the external environment occurrs without
chemical or physical transformation of those
components.
110
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• Actual dispersion of a pollutant from a source
to a receptor will be equal to, or greater than,
the safety factors normally applied to acute
toxicity data to convert these data to estimated
safe chronic exposure levels.
The minimum acute toxicity effluent (MATE) values
developed for each substance are adequate for
estimating acute toxicity.
No synergistic effects occur among the waste
stream components.
These assumptions, along with the accuracy of the test data and
assumptions used in developing MATE values (Ref. 2), must be
considered when interpreting test results using a SAM/1A analy-
sis scheme.
In performing a SAM/1A analysis, values are determined
for degree of hazard and toxic unit discharge rate associated
with the pollutants and waste streams. The degree of hazard
for each pollutant is defined as the ratio of the pollutant's
concentration in the stream to its respective MATE value (health
and ecological). The degree of hazard for a waste stream is
determined by adding the degree of hazard values for each pollu-
tant in the stream. The toxic unit discharge rate for a com-
pound is determined by multiplying its degree of hazard value by
the waste stream flow rate.
Degree of hazard values were calculated for each MEG
category identified in the sample. The compound with the lowest
MATE value in that category (that also fell within the molecu-
lar weight range found in the sample by LRMS) was selected for
calculation of degree of hazard values.
5.1.2 Bioassay Test Analysis
The results reported for the bioassay tests were de-
rived from the reports submitted by the subcontractors perform-
ing the tests and from recommendations made by the Bioassay
Subcommittee formed by IERL/RTP. Comparisons were made between
the bioassay test results and SAM/1A analyses of the chemical
analysis results.
Ill
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5.2 RESULTS
The results of the STE program performed at the Chap-
man facility are divided into the following areas:
total plant,
gaseous waste streams,
solid waste streams,
potential fugitive emissions and effluents,
hot cyclone performance, and
results not reported in the Level 1 analysis.
The Level 1 chemical and bioassay test results of each of the
above areas are discussed in the following text.
5.2.1 Total Plant
The mass balance of the major input and output streams
around the Chapman facility is given in Table 5-1. During the
test, two gasifiers (No's. 2 and 3) were operating at a combined
capacity of approximately 60 percent, with the No. 3 gasifier
operating at a higher capacity than the No. 2 gasifier. The
total mass of the streams exiting the plant was found to be
within 16% of the total mass entering the facility.
The results from the SAM/1A analysis and bioassay tests
of the multimedia waste streams, and the potential fugitive
emissions and effluent streams are presented in Table 5-2. In
most cases, the results of the SAM/1A analysis (degree of hazard
values) compared favorably to the bioassay test results. Excep-
tions were noted with the results for gasifier ash and separator
liquor. For the ash stream, the degree of hazard values indica-
ted a moderate potential for hazardous ecological effects, while
the bioassay tests indicated a low potential. The health degree
of hazard for the separator liquor indicated moderate potential
for hazardous effects, while the health bioassay tests indicated
a low potential. *
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Table 5-1. MASS BALANCE AROUND THE
CHAPMAN GASIFICATION FACILITY
Stream Description
INPUT STREAMS
Air
Steam
Coal Feed
TOTAL
OUTPUT STREAMS
Gasifier Ash (dry)
Cyclone Dust
Cooled Product Gas **
By-Product Tar
TOTAL
INPUT MINUS OUTPUT
kg/s
% of INPUT
Flow Rate (kg/s)a
No. 2
Gasifier/
Cyclone
0.33*
0.068*
0.129
0.527
0.0085
0.00067
0.420*
0.0129*
0.442
0.085
16
No. 3
Gasifier/
Cyclone
0.44*
0.092*
0.175
0.707
,
0.010
0.00094
0.569*
0.0175*
0.597
0.11
16
Total
Facility
0.77
0.16
0.304
1.234
0.0185
0.00161
0.989
0.0304*
1.040
0.19
16
aKg/s = 7938 Ib/hr
* Back calculated by ratioing coal feed rate data.
** Based on gas molecular weight of 25.4.
113
-------
Table 5-2. SUMMARY OF SAM/1A AND BIOASSAY TEST RESULTS FOR
TOTAL PLANT WASTE STREAMS AND POTENTIAL FUGITIVE
EMISSIONS AND EFFLUENTS
Degree of Hazard '
Health Ecological
Concern Concern
Gaseous Waste
Streams
•Coal Feeder
Vent Gas 4 x 107 8 v 10s
•Separator
Vent Gas 1 x 10e 1 x 106
Solid Waste
Streams
•Cyclone
Dust 2 x 103 8 x 105
•Gasifier
Ash 5 x 103 8 v 10s
Potential
Fugitive
Emissions
•Raw Product
Gas 4 x 108 8 x 106
• Separator
Liquor 3 x 105 2 x 10s
•By-Product
Tar 1 x 10s 2 x 107
Toxic Unit Discharge
Health Ecological Bioassay Tests
Concern Concern Health™ Ecological6
2 x 106 5 x 10* High High
6 x 107 6 x 10s High NC
3 x 103 1 x 107 Low High
9 x 10" 2 x 10' Low Low
ND ND NC NC
ND ND Low High
ND ND High High
Degree of Hazard is defined as the ratio of a pollutant's concentration in a stream to its minimum
acute toxicity effluent (MATE) value.
Potential for hazardous health and ecological effects can be estimated by the following:
Potential Effect Degree of Hazard
High >107
Moderate 10s - 107
Low 102 - 10s
Inconclusive <102
Toxic Unit Discharge is determined by multiplying the value of Degree of Hazard by the waste
stream flow rate (gases: Nm3/sec, liquids: Jl/sec, solids: g/sec).
Health tests included: Ames, Cytotoxicity (WI-38 , RAM), Rodent Acute Toxicity
Ecological tests included: Soil microcosm, plant stress ethylene, fresh water bioassay, and
salt water bioassay
NC - Test not conducted
ND Flows not determined for potential fugitive emissions or effluents
114
-------
5.2.2 Gaseous Waste Streams
The gaseous waste streams tested in this program were
the coal feeder and separator vent streams. The results of the
SAM/1A, chemical and bioassay tests for each stream are present-
ed in the following sections.
Coal Feeder Vent Stream -
The coal feeder vent stream contained organics and
inorganic components similar to those found in the raw product
gas stream. The tarry material collected in the particulate
module of the SASS train was significantly different from the
material collected in the organic module. The predominant or-
ganic categories found in both the organic module and the parti-
culate module samples were PAH's, heterocyclic aromatics, and
phenols. However, PAH's represented almost 8070 of the organics
from the organic module, while in the particulate module each
of the above three categories accounted for ^20-4070 of the or-
ganics found. Additionally, small quantities of a wider variety
of organic categories, including the volatile ones, were found
in the organic module. The concentrations of the various organ-
ics found in the particulate module and organic module samples
are compared in Figure 5-1.
A summary of the degree of hazard values for the Multi-
media Environmental Goals (MEG) chemical categories or compounds
found in the sample is shown in Table 5-3. Also shown in this
table are the results from specific bioassay tests. Positive
results were obtained from the Ames test while the plant stress
ethylene test showed negative results.
The information presented in Table 5-3 can also be
used as a basis for planning subsequent Level 2 chemical char-
acterization tests. A high priority for Level 2 chemical anal-
ysis is placed on MEG categories having degree of hazard values
greater than 100. Medium and low priorities are given to cate-
gories having degree of hazard values between 10-100 and 1-10,
respectively. Based on these prioritization criteria, a higher
priority exists for a detailed characterization of fused aroma-
tic hydrocarbons and their derivatives, heterocyclic nitrogen
compounds, NH3 , V, Ag, C2-hydrocarbons, CO, and Cr than for the
other chemical categories listed in this table.
115
-------
100
90
80
70 -
60 -
Z of
Individual 50
Sanple
40 -
30
25
20
15
10
5
MEG Category
MEG Number
Legend
CHjClj washes of
particulate train
Combined organic
module extracts
3.3
•SB
>> V
ss
.a
SI
Figure 5-1.
COMPARISON OF PARTICULATE TRAIN AND ORGANIC MODULE SAMPLES
FOR COAL FEEDER VENT GASES
-------
Table 5-3.
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR
COAL FEEDER VENT GASES
p
N
Priority for Level 2
Chemical Analysis
High
Medium
Low
-
: Positive
: Negative
"Health bioassay tests were performed
ECso's were calculated on the XAD-2
JECso reported 1
ECso - Jin p£ of extract]
per at culture
Degree of Hazard
Range
"lO7 - 10'
106 - 107
( 10s - 10s
10* - 10s
10s - 10*
102 - 10s
X
( 10 - 102
L
{ 1 - 10
I
on the XAD-2 extract
extract for the coal
Compound Categories Found From
Level 1 Chemical Analysis Results of the Bioassay Tests
Health Concern Ecological Concern Test Results
Fused aromatic - Health3
hydrocarbons and • Ames P
their derivatives . n_x ^^b 4 x 1()-»
• RAM (EC5o)b >2 x 10"'
- Cz hydrocarbons
Ecological
• Plant Stress
Ethylene N
Cr CO
Heterocyclic nitrogen NHs, V, Hg
compounds, carboxyllc
acids & their derivatives,
amines, sulfonlc acids and
sulf oxides, phenols, Hg,
0, CO
Ci, thiols, benzene and
substituted benzene hydro-
carbons, heterocyclic sulfur
compounds, Al, NHi, P, As, HzS,
Cu, Cd, HO, C02, HCN
from the coal feeder vent gases
feeder vent gases by:
|mg of organica 1 1 mg of organlca 1
x (extracted per mil x I per Hm9 of 1 " Nm' vent gas/mi culture
lof extract 1 1 vent gaa 1
-------
The estimated concentrations and degree of hazard
values for the organic and inorganic compounds in the coal feeder
vent stream are shown in Table 5-4. In this table, the estimated
component concentrations are presented under four categories:
the first three represent samples from distinct sources; the
fourth represents the stream total. Analytical results listed
under "Gases" were obtained on-site by analyzing gas phase sam-
ples. The results for organics under "Particulate Train" are
from analyses of the particulate train CH2C12 washes, while the
trace element concentrations are from SSMS analysis of the re-
covered particulates. Organic analyses results listed under
"Organic Module" are from the combined SASS organic module CH2C12
rinses, pentane extracts of the XAD-2 resin, and the CH2C12 ex-
tracts of the condensate. Trace element analyses reported under
this heading are a combination of the results from the XAD-2
resin, condensate, and the trace element impinger solutions.
Values reported for ammonia, cyanide and thiocyanate were obtain-
ed by analyses of acid/base impinger-scrubber solutions. The
degree of hazard values given in Table 5-4 were calculated from
the estimated total stream concentrations.
It should be emphasized that this waste stream probably
will not be present in new low-Btu gasification facilities. In
new facilities, this stream will probably be controlled by com-
bustion in a flare or incinerator or by recycling to the gasifier
inlet air.
Separator Vent Stream -
A summary of the results from the Level 1 chemical
analyses and bioassay tests for the separator vent stream is
presented in Table 5-5. The separator vent stream contained
significant concentrations of a variety of classes of organic
compounds, particularly methane and other aliphatic hydrocarbons,
amines, phenols, PAH's, and heterocyclic organics. Most of the
degree of hazard values for the organic classes were greater
than 1.
The concentrations of most of the inorganic species
were lower than their respective MATE values. However high con-
centrations of NH3, HCN, NO, N02, CO, and H2S were found. The
trace element concentrations were generally low, with Na, K, Ca,
P, Fe, Cu, and Ag found in the highest concentrations.
118
-------
Table 5-4. SUMMARY OF TEST RESULTS - COAL FEEDER VENT GASES
MEG Category
1. Aliphatic Hydrocarbons
-------
Table 5-4. (Continued)
MEG Category
Estimated Concentration (Ua/Nm')
Particulate Organic Stream
Gaaes Train Module Total
Degree of Hazard
(Estimated Stream
Cone./MATE Cone.)
Health
Concern
Ecological
Concern
Phenol, Polyhydric
C. Hydroxy Compounds with Fused Rings
Fluorenol, alkyl series
Naphthol, alkyl series
19. Halophenols
20. Nitrophenols
21. Fused Aromatic Hydrocarbons and Their Derivatives
(Benzo(a)pyrene)
' Acenaphthene
Acenaphthylene, alkyl series
Anthracene, alkyl series
Benzopyrene, alkyl series
Crysene
Naphthalene, alkyl series
Phenanthrene, alkyl series
Pyrene, alkyl series
22. Fused Non-Alternant Folycyclic Hydrocarbons
Fluoranthene
Fluorene
23. Heterocyclic Nitrogen Compounds (Pyrrole)
B. Fused Six-Membered Ring Heterocycles
Ac ridine
Azabenzopyrene, alkyl series
Azabenzofluoranthene, alkyl series
Azapyrene, alkyl series
Benzoquincline, alkyl series
Quincline, alkyl series
C. Pyrrole and Fused Ring Derivatives of Pyrrole
Benzocarbazole, alkyl series
Dlbenzocarbazole, alkyl series
Carbazole, alkyl series
Indole, alkyl series
24. Heterocyclic Oxygen Compounds (Tetrahydrofuran)
Benzonaphthofuran
25. Heterocyclic Sulfur Compounds (Benzonaphthothiophene)
Dibenzothiophene, alkyl series
8 x 105
x 10s
9 x 10! 4 x 107
8 x 10s 3 x 10* 8 x 105
1 x 103
10s
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
Organometallcs
Lithium
Sodium
Potassium
Rubidium
Cesium
Beryllium
Magnesium
Calcium
Strontium
Barium
Boron
Aluminum
Gallium
Indium
Thallium
1
1
0,
900
9
4
10
1
90
9
x 10" 8
.5 10
90
400
4
10
20
x 10* 100
10
10
1 x 10*
10
90
1 x 10s
10
10
30
1 x 10"
90
10
0.5
NA
8 x 10~2
2 x 10~2
8 x 10"2
4 x 10"'
2 x 10"2
1 x 10~2
2
2 x 10"2
0.1
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
Continued
120
-------
Table 5-4. (Continued')
Estimated Concentration (uz/Nm3)
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
MEG Category
Carbon
Carbon Dioxide
Carbon Monoxide
Silicon
Germanium
Tin
Lead
Nitrogen
Nitrogen Oxide
Ammonia*
Cyanide*
Phosphorus
Arsenic
Antimony
Bismuth
Oxygen (as 05)
Sulfur
Thlocyanate *
Sulfur Dioxide
Carbonyl Sulfide
Hydrogen Sulfide
Carbon Bisulfide
Selenium
Tellurium
Fluorine (as F )
Fluoride t
Chlorine (as Cl")
Chloride t
Bromine (as Br~)
Iodine (as l")
Scandium
Yttrium
Titanium
Zirconium
Hafnium
Vanadium
Niobium
Tantalum
Chromium
Molybdenum
Tungsten
Manganese
Iron
Ruthenium
Cobalt
Rhodium
Nickel
Platinum
Copper
Fartlculate Organic Stream
Gases Train Module Total
IxlO7
2 x IO7
1 x 10s 7 x
4 3
90 10
1 x 10*
3 x
1 x
90 90
<0.3 4
200 <2
1
500 10
1 X
4 x 10s
1 x 10*
1 -x 10s
2 x 10*
10 0.1
<10 <100
9
3 x 10* 30
7 x
70 0.1
1 2x
<0.8 0.4
2
200 900
0.4 1 x
8 70
9 <400
50 700
300
4
4
500 40
10 0.7
5
400 30
1 x IO7
2 x IO7
itf 8 x 10s
7
100
1 x 10*
10* 3 x 10*
10* 1 x 10*
200
4
200
1
500
10» 1 x 10*
4 x 10s
1 x 10*
1 x 10s
2 X 10*
10
<100
9
3 x 10*
IO3 7 x IO3
70
10" 2 1
1
2
1 x IO3
10s 1 x 10*
80
400
800
300
4
4
500
10
5
400
Degree of Hazard
(Estimated Stream
Cone. /MATE Cone.)
Health Ecological
Concern Concern
1
5 x IO2
0.8
NA
0.7
1
2
1
2
2
0.4
2 x IO"3
NA
NA
0.3
2 x IO"2
8
0.3
6 x IO"2
4 x 10~2
5 x IO"3
NA
0.9
NA
NA
2 x 10"S
2 x io"3
0.2
0.2
0.2
2 x IO"2
8x IO2
6 x IO"2
4 x IO"3
8 x 10~*
0.5
0.2
0.3
2
NA
2 x IO2
NA
NA
NA
NA
90
0.3
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
80
NA
NA
NA
NA
NA
NA
NA
NA
NA
121
-------
Table 5-4. (Continued)
MEG Category
Degree of Haurd
(Estimated Stream
Cone./MATE Cone.)
fartlculate Organic Stream Health Ecological
Gases Train Module Total Concern Concern
Estimates Concentration (ug/Nm9)
79.
80.
81.
82.
83.
84.
85.
Silver
Gold
Zinc
Cadmium
Mercury
Lanthanidea
Lanthanum
Cerium
Praseodymium
Neodymium
Samarium
Dysprosium
Actinides
Uranium
Thorium
2 0.1
1 x 10S <30
<30
500 <0.4
5 100
5 50
30 700
10
2 0.2
1 x 10S 0.3
<30 3
500 10
100 9 x 10"*
60 2 x 10~!
700 80
10 2 x 10~z
NA
NA
NA
50
NA
NA
NA
NA
- Wet chemical analyses of Impinger-scrubber solutions.
NA - MATE value not available
TR - Trace
t - Vet chemical analyses
122
-------
Table 5-5.
LO
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR
SEPARATOR VENT GASES
Priority for Level 2 Degree of Hazard
Chemical Analysis Range
High <
''lO7 -
10s -
10s -
10" -
103 -
102 -
""
Medium \ 10 -
^
1 -
10"
10'
106
105
10*
103
10a
10
Compound Categories Found From
Level 1 Chemical Analysis Results of the Bioassay Tests
Health Concern Ecological Concern Test Results
Fused aromatic - Health
hydrocarbons and • Ames SP
their derivatives .... ,0 ,„,, ^b _ in-s
• WI-38 (ECsoJ 7 x 10
Ca hydrocarbons b - .,.-5
-
-
Amines "^3
Heterocyclic CO, V
nitrogen compounds ,
Cr, Ag, CO, phenols
Heterocyclic sulfur com-
pounds, Cu, N02, NHa, P, HzS
Methane, halogenated HCN, Hg
aliphatic hydrocarbons,
carboxylic acids &
their derivatives, Li,
HCN, P, As, C02 , Fe, Mi, U,
Ci, Ce hydrocarbons
SP: Slightly positive
aHealth tests were performed on the XAD-2 extract from the separator vent gases
ECso were calculated on the XAD-2 extract for the separator vent gases by:
ECs
JECso reported
in p£ of extract
per mi culture
rag of organ:
extracted per
of extract
.OL vein gcist=a uy.
Ics I mg of organics I
er ml x per Nra3 of I
I I vent gas I
" Nm3 vent gas/mi culture
-------
The chemical categories having the highest priority
for Level 2 chemical analysis are also shown in Table 5-5. These
categories are fused aromatic hydrocarbons and their derivatives,
amines, CO, NH3, heterocyclic nitrogen compounds, Cr, V, Ag, C2-
hydrocarbons, and phenols.
The results of the bioassay tests performed on the
XAD-2 extract sample indicated a low to moderate potential for
hazardous health effects. Slightly positive results were ob-
tained in the Ames test.
•The estimated concentrations of organic and inorganic
compounds found in the separator vent gases are given in Table
5-6. Again, the estimated concentrations are presented under
four categories: the first three represent samples from distinct
sources, while the fourth represents the stream total. Values
for NH3, HCN and F~ were determined from the organic module con-
densate. The degree of hazard values shown in Table 5-6 were
calculated from the total stream concentrations.
As for the coal feeder vent, the separator vent stream
should not be a waste stream from new gasification facilities.
It will probably be recycled to the gasifier inlet air or product
gas or it may be combusted in a flare.
5.2.3 Solid Waste Streams
The solid waste streams from the Chapman gasification
facility were the gasifier ash and the cyclone dust. The Level
1 chemical and bioassay test results for these streams are pre-
sented in the following sections.
Gasifier Ash -
Table 5-7 presents a summary of the Level 1 chemical
and bioassay test results for the gasifier ash. The major trace
elements (>103 yg/g) identified in the ash were alkali metals,
alkaline earths, Al, Si, Ti, and Fe. From the degree of hazard
values in Table 5-7, the elements with the highest priority for
Level 2 chemical analysis are P, Fe, Cu, Ca, Al, Ti, Cd, Ba, Pb,
Se, Sb, B, Co, U, Be, Li and Cs.
124
-------
Table 5-6. SUMMARY OF TEST RESULTS - SEPARATOR VENT GASES
MEG Category
1. Aliphatic Hydrocarbons C7 (Nonanes)
A. Alkanes and Cyclic Alkanes
Alkanes, C6- C2S
Cycloalkanes
B. Alkenes, Cyclic Alkenes, Dlenes
Alkenes
2. Halogenated Aliphatic Hydrocarbons (Lindone)
A. Saturated Alkyl Halldes
Methyl Chloride
3. Ethers
4. Halogenated Ethers
5. Alcohols
6. Glycols, Epoxides
7. Aldehydes, Ketones
8. Carboxylic Acids and Their Derivatives
(3-Hydroxypropanolc Acid Lactone)
B. Carboxylic Acids with Additional Functional
Groups
Dlchlorobenzoic Acid
D. Esters
Aliphatic Esters
Phthalate Esters
9. Nitriles
10. Amines (Amlnotoluenes)
C. Aromatic Amines and Diamines
Aniline, alkyl series
11. Azo Compounds and Hydrazine Derivatives
12. Nltrosamines
13. Thiols
1.4. Sulfonic Acids, Sulfoxides
15. Benzene, Substituted Benzene Hydrocarbons
Benzene, alkyl series
16. Halogenated Aromatic Hydrocarbons
17. Aromatic Nitro Compounds
18. Phenols (2,2'-Dihydroxydiphenyls)
A. Monohydrics
Phenol, alkyl series
Phenyl Phenol
C. Hydroxy Compounds with Fused Rings
Indanol, alkyl series
Naphthol
19. Halophenols
2 x 10s 1 x 10* 1 x 10« 1
1 x 10s
1 x 10 2
1 x 10s
1 x 10
100
2 x 10! 2 v io5 2 x 10 '
TR TR
TR
2 x IO3 2 x 10s 2 x 10s 3x IO2
Continued
125
-------
Table 5-6. (Continued)
Estimated Concentration (He/No' )
20.
21.
MEG Category Gases
Nltrophenola
Fused Aromatic Hydrocarbons and Their Derivatives
Fartlculate
Train
2 K 103
Organic
Module
2 x 10!
Stream
Total
2 x 10s
(Estimated Stream
Cone. /MATE Cone.)
Health
Concern
1 x 10*
Ecological
Concern
MA
22.
23.
(Benzo(a)pyrene)
Acenaphthene
Acenaphthylene
Anthracene
Benzochrysene, alfcyl series
Benzoperylene, alkyl series
Benzopyrene, alkyl series
Chrysene, alkyl series
Dibenzopyrene, alkyl series
Dlhydrochrysene, alkyl series
Naphthalene, alkyl series
Fhenanthrene
Pyrene
Tetrahydroanthracene
Fused Non-Alternant Polycycllc Hydrocarbons
Fluoranthene
Fluorene, alkyl series
Heterocyclic Nitrogen Compounds (Dibenzo(c,d)carbazole)
B. Fused Slx-Membered Ring Heterocycles
Azabenzoperylene
Qulnolinev alkyl series
C. Pyrrole and Fused Ring Derivatives of Pyrrole
Benzocarbazole
Carbazole, alkyl series
Indolet alkyl series
TR
10"
TR
1 x 105
TR
1 x 10
1 X 10!
NA
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
Heterocyclic Oxygen Compounds (Tetrahydrofuran) 1 x 103
Heterocyclic Sulfur Compounds (Benzonaphthothlophene) 1 x 10s
Thiophene, alkyl series
Organometalics
Lithium
Sodium
Potassium
Rubidium
Cesium
Beryllium
Magnesium
Calcium
Strontium
Barium
Boron
Aluminum
Gallium
Indium
Thallium
Carbon
Carbonate
Carbon Dioxide 3 x 107
Carbon Monoxide 4 x io7
1 x 109
3 x 10s 3 x 10s
40
4 x 103
2 x 10s
0.5
200
2 x 10s
20
40
3
40
3
2 2 '
3 x 10'
4 x 107
2 * 10"9
50
2
8 x 10"2
NA
4 x 10"6
3 x 10~2
0.1
6 x 10~3
8 x 10"'
1 * 10"s
8 x 10~s
6 x 10~"
NA
3
9 x 102
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA *
3 x 102
Continued
126
-------
Table 5-6. (Continued)
MEG Category
43. Silicon
44 . Germanium
45. Tin
46. Lead
47. Nitrogen
Nitrogen Oxide
Nitrogen Dioxide
Ammonia *
Cyanide *
48 . Phosphorus
49. Arsenic
50. Antimony
52. Oxygen (as 03)
53. Sulfur
Sulflde
Sulfate
Thlocyanate *
Sulfur Dioxide
Carbonyl Sulflde
Hydrogen Sulflde
Carbon Disulfide
54. Selenium
55. Tellurium
56. Fluorine (as F )
Fluoride t
57. Chlorine
58 . Bromine
59. Iodine
60. Scandium
61. Yttrium
62. Titanium
63. Zirconium
64 . Hafnium
65. Vanadium
66. Niobium
67 . Tantalum
68 . Chromium
69 . Molybdenum
70. Tungsten
71. Manganese
72. Iron
73. Ruthenium
74. Cobalt
75. Rhodium
76. Nickel
77. Platinum
78. Copper
79. Silver
80. Gold
81. Zinc
Estimated Concentration (ug/Nm1)
Participate Organic Stream
Gaaea Train Module Total
300
8
30
4 x 10* 4 x 10*
3 x 10s 3 x 10s
7 x 10*
5 x 10* 5 x 10*
3 x 10" 3 x 101
10
<50
1 « 10*
2 x 10* 2 x 10*
<5 x 10* <5 x 10"
1 x 10* 1 x 10!
9 x 10s 9 x 10*
4 x 10* 4 x 10'
2 x 10' 2 x 10'
2 x 10* 2 x 10*
10
<50
200 200
200
9
1
<2
,. •,
40
500
100
300
400
<8
50
2 x 103
2
70
2 x 10'
1 x 10'
100
Degree of Hazard
(Estimated Stream
Cone. /MATE Cone.)
Health Ecological
Concern Concern
3 x 10~* NA
NA NA
0.2 NA
NA NA
30 NA
40 3 x 101
5 2
30 NA
5 NA
0.1 NA
NA NA
NA NA
NA NA
NA NA
0.7 NA
9 X 10"2 NA
10 NA
0.3 NA
5 * 10~Z NA
2 X 10"2 NA
0.1 NA
NA NA
NA NA
NA NA
4 X 10~* NA
7 X 10"! NA
0.1 NA
0.2 100
300 NA
8 x 10"2 NA
7 X 10"5 NA
1 x 10"2 NA
2 NA
4 X 10"2 NA
5 NA
10 NA
1 » 10* NA
3 x 10"2 NA
Continued
127
-------
Table 5-6. (Continued)
82.
83.
84.
85.
MEG Category
Cadmium
Mercury
Lanthanldes
Lanthanum
Cerium
Praseodymium
Neodymium
Samarium
Dysprosium
Actinides
Uranium
Thorium
Degree of
(Estimated
Estimated Concentration (Ua/Nm*) Cone. /MATE
Particulate Organic Stream Health
Gases Train Module Total Concern
0.9 9 x 10"2
<0.3 6 x 10"'
3 3 x 10"5
4 1 x 10""
40 4
Hazard
Stream
Cone.)
Ecological
Concern
NA
3
NA
NA
NA
NA - HATE values were not available
TR - Trace
* - Vet chemical analyses of Irapinger-Bcrubber solutions
t - Wet chemical analyses
128
-------
Table 5-7.
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR
GASIFIER ASH
Priority for Level 2 Degree of Hazard
Chemical Analysis Range
ELOS - 106
, ,
LO* - 105
LO3 - 10*
LO2 - 103
Medium < 10 - 10a
Compound Categories Found From
Level 1 Chemical Analysis
Health Concern Ecological Concern
P
Fe, Cu
Fe Ca, Al, Ti, Cd
Be, Li, Ca, Ba, Se, Ba, Pb, Se, Sb,
Cs, Cu V, Co, D
Mg, Sr, Al, Pb, P, Li, Mg, Cr, Be
Results of the
Test
Health
• AIDES
• RAM (ECso)a
• R.A.T. .
- LDso
Bioassay Tests
Results
N
>300
L
Ecological
• Soil Microcosm 4
Low
- 10
Sb, Ti, Cr, Co, Cd,
Si, Kg
Zr, V, U, Rb, F~
As
NJ
R.A.T.: Rodent Acute Toxicity test
N: Negative
L: Low toxicity (i.e., no significant effects noted)
3ECso values are reported in Ug of solid per ml of culture
LDso values are in g of sample per Kg of rat
-CSo.il .microcosm test results were ranked according to toxicity. The gasifier ash ranking of 4 was less toxic than the coal feed, cyclone
dust and by-product tar and more toxic than the separator liquor.
-------
The gasifier ash had the lowest toxicity in the soil
microcosm test, showed negative results in the Ames test and gave
signs of low toxicity in the rodent acute toxicity test. These
results are not consistent with the degree of hazard values.
This inconsistency may indicate that further chemical charac-
terization and/or bioassay testing are needed.
Table 5-8 shows the estimated concentrations of organ-
ics and inorganics along with their respective degree of hazard
values. The concentrations of extractable organics in the ash
was -^20 yg/g. Further organic analysis is needed since certain
organic compounds, such as benzo-a-pyrene, have MATE values
significantly lower than 20 yg/g.
Leaching tests are needed for determination of the
types and amounts of trace elements that are leachable from the
ash. Bioassay tests should be performed on the resulting
leachate.
Cyclone Dust -
The results of the chemical and bioassay tests per-
formed on the cyclone dust are summarized in Table 5-9. The
major trace elements (>103 yg/g) found in the cyclone dust were
Ca, Si, and P. While the concentrations of most of the trace
elements found in the cyclone dust were lower than the concen-
trations found in the gasifier ash, most of the concentrations
still exceeded their respective MATE values. The elements with
the highest priority for Level 2 chemical analysis are P, Ni,
Mn, Fe, Pb, Ba, Sb, Ti, and Cu.
The bioassay tests for the cyclone dust indicated a
low potential for hazardous health effects; however, it was the
most toxic of the samples tested in the soil microcosm test.
Table 5-10 shows the estimated concentrations and
degree of hazard values for the inorganics found in the cyclone
dust sample. The concentration of extractable organics was
small (^40 yg/g); however, further organic analysis is recom-
mended since certain organic compounds have MATE values much
lower than 40 yg/g.
130
-------
Table 5-8. SUMMARY OF TEST RESULTS - GASIFIER ASH
Degree of Hazard
(Estimated Cone. /HATE Cone.)
1-26
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
MEG Category
Organic Species
Lithium
Sodium
Potassium
Rubidium
Cesium
Beryllium
Magnesium
Calcium
Strontium
Barium
Boron
Aluminum
Gallium
Indium
Thallium
Carbon
Silicon
Germanium
Tin
Lead
Nitrogen
Phosphorus
Arsenic
Antimony
Bismuth
Oxygen (as 03)
Sulfur
Selenium
Tellurium
Fluorine (as F )
Chlorine (as Cl")
Bromine (as Br )
Iodine (as 1~)
Scandium
Yttrium
Titanium
Zirconium
Hafnium
Vanadium
Niobium
Tantalum
Chromium
Molybdenum
Estimated
Concentration (pg/g)
•v/20
70
1 x 10*
2 ,10*
10
6 x 10s
5 x 10*
2 x 10s
2 x 10s
20
3 x 10!
50
7 x 10s
300
20
800
<0.4
200
1 x 10s
30
< 200
50
<20
3 x 10s
90
30
20
30
Health
Concern
1 «. 10s
NA
5.5
2 x 102
30
1 x 102
20
2 x 10*
0.2
20
0.3
20
NA
40
30
<0.8
10
NA
3 x 102
<3
3 * 10"2
<0.7
20
6
6
3 x 10"2
60
Ecological
Concern
90
NA
NA
90
30
2 x 10s
NA
4 x 102
0.4
2 x 10*
NA
NA
NA
2 x 102
B x 10s
<4
5 x 102
NA
6 x 102
NA
NA
NA
2 x 10*
NA
1 x 102
NA
60
Continued
131
-------
Table 5-8. (Continued)
Degree of Hazard
(Estimated Cone./MATE Cone.)
Estimated Health Ecological
MEG Category Concentration (yg/g) Concern Concern
70. Tungsten
71. Manganese
72. Iron 1 x 10* 4 - 103 2 x 10*
73. Ruthenium
74. Cobalt 50 30 1 X 10*
75. Rhodium
76. Nickel
77. Platinum
78. Copper 1 x 10! 1 x 102 1 x 10"
79. Silver
80. Gold
81. Zinc
82. Cadmium <9 <90 <5 x 10s
83. Mercury <0.3 20 <0.6
84. Lanthanldes
Lanthanum 100 3 x lo"2 NA
Cerium 90 8 x 10~2 NA
Praseodymium
Neodymium
Samarium
Dysprosium
85. Actinldes
Uranium 400 3 4 x 102
Thorium
NA: MATE values were not available.
132
-------
Table 5-9.
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR
CYCLONE DUST
Priority for Level 2 Degree of Hazard
Chemical Analysis Range
High .
rio6 - io7
10s - 10"
10* - 10s
IO3 - 10*
10Z - 10s
C
Medium j 10 - 10*
Low /I - 10
I
Pb
Hi
Cr
Li
V,
Compound Categories Found From
Level 1 Chemical Analysis
Health Concern Ecological Concern
-
_
_
, P, Mn, Fe,
, Cu, Ba
, Mg, Ca, Sb, Zr,
Co, Si, Ti
P
_
Mh, Fe, Cu, Hi
Ba, Pb, Sb, Ti
Ca, Al, V, Cr
Li, Mg, As, Co
Results of the Bioassay Tests
Test Results
Health
• Ames N
• RAM (ECso)3 >1000
• R.A.T. t M
- LDso >10
Ecological
• Soil Microcosm 1
R.A.T.: Rodent Acute Toxicity test
N: Negative
M: Medium toxicity (i.e., rats showed hair loss, eye discoloration, etc.)
aECso values are reported in yg of sample per mH of culture
LDso values are in g of sample per Kg of rat
CSrjiL mierocosm test results were ranked according to toxicity. -Theacyclone dust was more toxic than the coal feed, ash, tar and separator liquor.
-------
Table 5-10. SUMMARY OF TEST RESULTS - CYCLONE DUST
1-26
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
MEG Category
Organic Species
Lithium
Sodium
Potassium
Rubidium
Cesium
Beryllium
Magneaium
Calcium
Strontium
Barium
Boron
Aluminum
Gallium
Indium
Thallium
Carbon
Silicon
Germanium
Tin
Lead
Nitrogen
Phosphorus
Arsenic
Antimony
Bismuth
Oxygen (as Oj)
Sulfur
Selenium
Tellurium
Fluorine (as F~)
Chlorine (as Cl")
Bromine (as Br )
Iodine (as l")
Scandium
Yttrium
Titanium
Zirconium
Hafnium
Vanadium
Niobium
Tantalum
Estimated
Concentration (u g/g)
•\,40
2
4 x 10s
3
500
2 x 10s
80
500
7
100
<10
2 x 10s
60
8 x 103
<0.4
100
300
100
2
10
200
30
20
Degree of Hazard
(Estimated Cone. /HATE Cone.)
Health Ecological
Concern Concern
3 3
NA NA
8 x 10"" NA
3 3
* 60
0.8 NA
50 1 x 102
8 it 10"2 0.1
0.6 50
<6 x 10"2 NA
6 NA
1 x 102 6 x lo2
3 x 102 8 x 10'
<0.8 <4
9 3 x 102
NA NA
>1 NA
1 x 10"9 NA
0.3 NA
1 1 * 102
2 NA
* 70
Continued
134
-------
Table 5-10. (Continued)
MEG Category
Estimated
Concentration (l*g/g)
Degree of Hazard
(Estimated Cone./MATE Cone.)
Health Ecological
Concern Concern
68. Chromium
69. Molybdenum
70. Tungsten
71. Manganese
72. Iron
73. Ruthenium
71. Cobalt
75. Rhodium
76. Nickel
77. Platinum
7°. Copper
79. Silver
80. Gold
81. Zinc
82. Cadmium
83. Mercury
84. Lanthanidea
Lanthanum
Cerium
Praseodymium
Neodymium
Samarium
Dysprosium
85. Actinides
Uranium
Thorium
30
200
2 x 10s
100
900
60
4 x 102
8 x 102
20
20
6 x 10"'
2 x 10~a
60
1 x 10!
4 x 10'
2 6
2 x 102 5 x 10s
90 9 x 10'
NA
DA
MA: MATE value was not applicable
135
-------
Leaching tests are needed, along with bioassay tests of
the resulting leachate, if disposal in a landfill is to be con-
sidered. However, because of its high carbon content, cyclone
dust may prove to be a salable by-product.
5.2.4 Potential Fugitive Emissions and Effluents
Fugitive emissions and effluents from pumps, valves,
flanges, etc., can present significant health and environmental
hazards. Three process streams, (raw product gas, separator
liquor, and by-product tar) were considered in order to assess
the hazard potential of fugitive emissions and effluents from
this process.
Raw Product Gas -
The potential health and ecological effects of fugi-
tive emissions of raw product gas were estimated using the
results of chemical analysis of the coal feeder vent stream. It
was assumed that raw product gas was diluted 1:10 by air in the
vent stream. This dilution factor was based on the results of
gaseous species analyzed in both the raw product gas and coal
feeder vent gas. Table 5-11 shows the degree of hazard values
for MEG categories estimated to be in the raw product gas. If
significant quantities of this gas stream appear as fugitive
emissions, the compound classes with the highest priority for
Level 2 chemical analysis are given in this table.
Separator Liquor -
The separator liquor was found to contain high concen-
trations of organic compounds, especially the polar species
expected to be associated with an aqueous medium. The major
organic categories identified were thiols, phenols, and hetero-
cyclic organics. Smaller amounts of carboxylic acids, glycols,
and PAH's were found. Most of these organic categories had
degree of hazard values greater than 1. A summary of the results
of the Level 1 chemical and bioassay tests is given in Table
5-12. 5
136
-------
u>
--J
Table 5-11. SUMMARY OF DEGREE OF HAZARD VALUES FOR MEG CATEGORIES ESTIMATED TO
BE IN THE RAW PRODUCT GAS STREAM
Priority for
Level 2
Chemical Degrees of
Analysis Hazard Rangea
^ 108 - 109
High <
107 - 10s
106 - 107 .
10s - 10s
10" - 105'
103 - 10*
w in2 _ in3
Compound Categories Estimated in the Raw Product Gas
Health Concern Ecological Concern
Fused aromatic hydrocarbons and their derivatives
-
Cz hydrocarbons
-
Cr CO
HeterorvrHr irit-rno-pn r-nmnrmnilR • rarfimrwl -ip ar-irls anH TJTTa • V- Ho-
Medium
Low
10 - 10
1-10
their derivatives; amines; sulfonic acids and sulf oxides;
phenols; Hg; U; CO
Heterocylic sulfur compounds; thiols; benzene and substi-
tuted benzene hydrocarbons; Al; NHs; P; As; Cu; Cd; H2S;
C02; NO; HCN;
C2, Cit and Cs hydrocarbons; heterocyclic oxygen compounds; HCN
Li; Tl; Si; Pb; Sb; S02; CS2; Cl; Ti; Zr; V; Fe; Co; Ni; Zn;
Ag
Degree of hazard values for the raw product gas were estimated using the chemical analysis results
from the coal feeder vent assuming a 1:10 dilution of raw product gas to air in the vent stream.
-------
Table 5-12.
00
SUMMARY OF THE LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS
FOR THE SEPARATOR LIQUOR
Priority for
Level 2 Compound Categories Found from Level 1
Chemical Hegi-PP nf Chemical Analysis
Analysis Hazard Range Health Concern
Ecological Concern
10 - 10 Fused aromatic hydrocarbons NHs
and their derivatives
High 1 10" - 1C)5 Phenols
] 103 - 10" NH3 , CN"
2 i n 3
>- 10 - ID Heterocyclic nitrogen
compounds
Medium < 10 - 102 Thiols, Se
L
Low S 1-10 Heterocyclic sulfur
^ compounds , P , As , F ,
CN~, P
Phenols , fused aromatic
hydrocarbons and their
derivatives
Carboxylic acids and
their derivatives
Glycols and epoxides ,
As, Se
Ca, Fe, Cd
Results of the Bioassay Tests
Test
Health
• Ames
• RAM (ECso)3
• R.A.T. ,
- LD50b
Ecological
• Fresh water0
- Algal (ECso , 15 days)
- Daphnia (LCso , 48 hr)
~ Fathead minnow
(LCso , 96 hr)
Salt Water0
- Algal (ECso , 12 days)
- Shrimp (LCso , 96 hr)
~ Sheepshead minnow
(LCso , 96 hr)
• Soil microcosm
Results
N
>600
L
>10
0.1-1.0%
0.11%
0.02%
0.53/0.41%
0.25%
0.16%
5
R.A.T.: Rodent acute toxicity test
N : Negative
L : Low toxicity (i.e., no significant effects noted)
ECso values are reported in yg of sample per ml of culture.
values are reported in g of sample per Kg of rat.
ECso and COso values for fresh and salt water bioassays are reported in weight percent of sample.
Soil microcosm test results were ranked according to toxicity. The separator liquor was less toxic than the coal feed,
ash, cyclone dust, and tar.
-------
The results of the bioassay tests indicated that the
sample was very toxic to aquatic species; however, it was least
toxic in the soil microcosm test, and had negative results for
health effects tests. Because of its toxic effects on aquatic
species, it would be necessary to treat this liquor before
discharge.
The estimated concentrations and degree of hazard
values for the organics and inorganics in the separator liquor
are shown in Table 5-13. The results of the water quality tests
showed high levels of ammonia, cyanide, fluoride, chloride, car-
bonate and sulfate in the liquor. However, the concentration of
sulfide was lower than expected. This, coupled with the high
sulfate levels, indicates that considerable oxidation of dis-
solved sulfur species may occur. The quench liquor also con-
tained high levels of B.O.D. and C.O.D. In addition, it con-
tained high concentrations of suspended solids and total dis-
solved solids, was highly colored, and had a high oder threshold
number.
By-Product Tar -
The chemical and bioassay test results for the by-
product tar are summarized in Table 5-14. As expected, high con-
centrations of organics were found. Most organic compound classes
present had a degree of hazard value greater than 1. A wide
range of trace elements were also identified, with the major
elements being K and S. Estimated concentrations and degree of
hazard values for organics and inorganics in the tar are shown
in Table 5-15.
The by-product tar was one of the most toxic samples
collected. Positive results were obtained in the Ames and rodent
acute toxicity tests. The soil microcosm test also showed a
high potential for hazardous ecological effects. Because of the
potential hazardous health effects exhibited by this stream,
leaks around pumps, valves, etc., must be minimized and contained.
139
-------
Table 5-13. SUMMARY OF TEST RESULTS - SEPARATOR LIQUOR
MEG Category
Estimated
Concentration (ug/&)
Degree of Hazard
(Estimated Cone./MATE Cone.)
Health Ecological
Concern Concern
1. Aliphatic Hydrocarbons (Nonanes, Heptanes)
A. Alkanes and Cyclic Alkanes
Alkanes, Ci0-Ci»
Cycloalkanes
B. Alkenes, Cyclic Alkenes, Olenes
Alkenes
2. Halogenated Aliphatic Hydrocarbona
3. Ethers
4. Halogenated Ethers
5. Alcohols
6. Glycols, Epoxides (Ethylene Glycol)
A. Glycols
Alkyl Glycols
7. Aldehydes, Ketones
8. Carboxylie Acids and Their Derivatives (Malelc,
Acid, Acetic Acid)
A. Carboxylic Acids
Heptenoic Acid
9. Hitriles
10. Amines
11. Azo Compounds and Hydrazlne Derivatives
12. Nitrosamines
13. Thiols (Perchloromethanethiol)
Thiophenol, alkyl series
Thiophenol, Phenyl, alkyl series
14. Sulfonic Acids, Sulfoxides
15. Benzene, Substituted Benzene Hydrocarbons
Benzene, alkyl series
16. Halogenated Aromatic Hydrocarbons
17. Aromatic Nltro Compounds
18. Phenols (all listings)
A. Monohydrlcs
Phenol, alkyl series
B. Dihydrics, Polyhdrics
Benzene, Dihydroxy
Benzene, Polyhydroxy
C. Hydroxy Compounds with Fused Rings
Acenaphthenol
Indanol, alkyl series
Napthol, alkyl series
19. Halophenols
20. Nitrophenols
21. Fused Aromatic Hydrocarbons and Their Derivatives
(Benzo(a)pyrene, Naphthalene)
Acenaphthylene
Anthracene
Benzopyrene
Naphthalene
Phenanthrene
Pyrene
22. Fused Non-Alternant Polycyclic Hydrocarbons
3 x 10*
2 x 10
0.3
1 x 10s
1 x 10s
7 x 10"'
7 x 10"z
10
1 » 102
5 x 10
TR
3 x 10
NA
6 x 10*
6 x 10'
1 x 10s
3 x 10s
1 x 103
Continued
140
-------
Table 5-13. (Continued)
MEG Category
23. Ueterocyclle Nitrogen Compounds (Dibenzo(c
C. Pyrrole and Fused Ring Derivatives of
Benzo (a) carbazole
Carbazole
24. Heterocyclic Oxygen Compounds
Estimated
Concentration (pg/l)
,d)carbazole) 5 x 10s
Pyrrole
TR
25. Heterocyclic Sulfur Compounds (Benzonaphthothlophene) 5 x 10'
Dlbenzothlophene, alkyl series
26. Organometalics
27. Lithium
28 . Sodium
29. Potassium
30. Rubidium
31. Cesium
32. Beryllium
13. Magnesium
34. Calcium
35. Strontium
36. Barium
37. Boron
38 . Aluminum
39. Gallium
40. Indium
41. Thallium
42. Carbon
Carbon Monoxide
Carbon Dioxide
Carbonate
43. Silicon
44. Germanium
45. Tin
46. Lead
47 . Nitrogen
Ammonia
Cyanide (Alkali)
Nitrate
Nitrite
Nitric Oxide
Nitrogen Dioxide
48 . Phosphorus
49 . Arsenic ,
50. Antimony
51. Bismuth
52. Oxygen (as 03)
53. Sulfur
Hydrogen Sulfide
Carbonyl Sulfide
Sulfur Dioxide
Carbon Dlsulfide
Thiocyanate *
Sulfide
Sulfate
3
2 x 10*
10
1
2 x 10»
2 x 10'
80
300
9 x 10'
2 x 106
2 x 10*
30
5 x 10s
1 x 106
2 x 10*
800
70
<8 x 10?
70
<1 x 10*
1 x 10*
Degree of Hazard
(Estimated Cone. /MATE Cone.)
Health Ecological
Concern Concern
3 x 10* NA
3 MA
9 x 10"' 8 x 10"3
NA NA
6 x 10~' NA
8 x 10"' NA
2 x 10~2 2 x 10"»
8 x 10~2 1
2 x 10~' NA
6 x 10"J 0.1
0.2 0.4
NA NA
1 x 10"2 NA
NA NA
2 x 10s 1 * 10!
2 x 10s * x 10*
1 4 x 10*
3 20
9 x 10"' 0.4
NA NA
NA NA
NA NA
NA NA
Continued
141
-------
Table 5-13. (Continued)
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
MEG Category
Selenium
Tellurium
Fluorine (as F~)
Fluoride *
Chlorine (as Cl")
Chloride *
Bromine (as Br~)
Iodine (as l")
Scandium
Yttrium
Titanium
Zirconium
Hafnium
Vanadium
Niobium
Tantalum
Chromium
Molybdenum
Tungsten
Manganese
Iron
Ruthenium
Cobalt
Rhodium
Nickel
Platinum
Copper
Silver
Gold
Zinc
Cadmium
Mercury
Lanthanides
Lanthanum
Cerium
Neodymium
Samarium
Dysprosium
Actinides
Uranium
Thorium
Degree of Hazard
(Estimated Cone. /MATE Cone.)
Estimated Health Ecological
Concentration (tlg/H) Concern Concern
2 x 103 40 80
2 x 105 <5 x 10~2 NA
2 x 10! 4 NA
200 2 x 10"* NA
3 x 10' 2 NA
300 NA HA
300 NA NA
2 3 x 10"6 NA
5 3 x 10~* NA
100 1 x 10"' 0.1
10 1 « 10"" NA
8 2 x 10"S NA
10 7 x 10~* NA
1 x 10= 0.9 4
10 2 x 10~* 0.2
2 8 x 10"' 0.4
5 0.1 5
<3 * 10"* <3 x 10"5 <1 x 10"C
7 4 x 10"6 NA
3 5 x 10"B NA
* Determined by wet chemical methods.
NA: MATE value was not applicable
TR: Trace
142
-------
Table 5-14.
LO
SUMMARY OF LEVEL 1 CHEMICAL AND BIOASSAY TEST RESULTS FOR
BY-PRODUCT TAR
Priority for
Level 2
Chemical Degree, of
Analysis Hazard
s io7 -
High J
IO6 -
10s -
10* -
Range
IO8
IO7
IO6
10b
Compound Categories Found from Level 1
Chemical Analysis
Health Concern
Fused aromatic hydrocarbons
and their derivatives
Phenols
-
Amines, benzene and substi-
Ecological Concern
Carboxylic acids and
their derivatives
—
Halogenated aliphatic
hydrocarbons , amines
Benzene and substi-
Results of the Bioassay
Tests
Test
Health
* Ames
• RAM (EC50)a
' R.A.T. ,
D
D50
Ecological
" Soil microcosm
Result
P
>1000
H
2
103 - 10"
IO2 - IO3
tuted benzene hydrocarbons,
heterocyclic nitrogen com-
pounds
Halogenated aliphatic hydro-
carbons, heterocyclic sul-
fur compounds
Carboxylic acids and their
derivatives, Cr
tuted benzene hydro-
carbons , phenols
Cu, Cd
Aliphatic hydrocarbons,
Pb, Sb, Cr
Medium <
Low J
10 - IO2
1-10
Ba, Pb, Cu, Cd
Aliphatic hydrocarbons ,
heterocyclic oxygen coin-
pounds, Sb, Hg, Mg
Ba
As, V
R.A.T.: Rodent acute toxicity test
P : Positive
H : High toxicity
fcCso values are reported in Ug of sample per ml of culture
LDso values are reported in g of sample per Kg of rat
°Soil microcosm test results were ranked according to toxicity. The by-product tar was less than the cyclone
dust and more toxic than the coal feed, ash and separator liquor.
-------
Table 5-15. SUMMARY OF TEST RESULTS - BY-PRODUCT TAR
Degree of Hazard
(Estimated Cone./MATE Cone.)
Estimated Health Ecological
MEG Category Concentration (yg/g) Concern Concern
1. Aliphatic Hydrocarbons (Nonanes, Heptanes) 1 x 10s 3 5 x 102
A. Alkanes and Cyclic Alkanes
Alkanes, Cio-Cja
2. Halogenated Aliphatic Hydrocarbons (Lindone) 4 x 10* 3 x 10s 2 x 10s
A. Saturated Alfcyl Hydrocarbons
Methyl Chloride
3. Ethers
4. Halogenated Ethers
5. Alcohols
6. Glycols, Epoxides
7. Aldehydest Ketones
8. Carboxylic Acids and Their Derivatives (Phthalates) 4 * 10* 3 x 10* 2 x 107
D. Esters
Aliphatic Esters
Fhthalate Esters
9. Nitriles
10. Amines (Methyl Anilines, Aminonaphthalene) 6 x 10* 2 x 10* 3 * 10s
C. Aromatic Amines and Diamines
Aniline, alkyl series
11. Azo Compounds and Hydrazine Derivatives
12. Nltrosamines
13. Thiols
14. Sulfonlc Acids, Sulfoxides
it
15. Benzene, Substituted Benzene Hydrocarbons (Indene, 4 x 10 3 x 10* 2 x 10*
Alkyl Benzene)
Benzene, alkyl series
16. Halogenated Aromatic Hydrocarbons
17. Aromatic Nitro Compounds
18. Phenols (all listings)
A. Monohydrics 8 x 10* 8 x 106 8 x 10*
Phenol, alkyl series
19. Halophenols
20. Nitrophenols
21. Fused Aromatic Hydrocarbons and Their Derivatives 3 x 10s 1 » IQ' HA
(Dibenz(a,h)anthracene)
Acenaphthene, alkyl series
Acenaphthylene, alkyl series
Anthracene, alkyl series
Benzopyrene, alkyl series
Chrysene, alkyl series
Coronene, alkyl series
Naphthalene, alkyl series
Phenanthrene
Pyrene, alkyl series
22. Fused Non-Alternant Polycyclic Hydrocarbons TR
Fluoranthene
Continued
144
-------
Table 5-15. (Continued)
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
Estimated
MEG Category Concentration (ug/g)
Heterocyclic Nitrogen Compounds (Dibenzo(c,d)carbazole) 2 x 10s
A. Fused Six-Member ed Ring Heterocycles
Qulnoline, alkyl series
C. Pyrrole and Fused Ring Derivatives of Pyrrole
Carbazole, alkyl series
Heterocyclic Oxygen Compounds (Tetrahydrofuran) 1 * 10s
Benzonaphthofuran
Heterocyclic Sulfur Compounds (Benzonaphthothiophene) 1 x 10!
Organometallcs
Lithium
Sodium
Potassium 3 x 10*
Rubidium 0.5
Cesium
Beryllium
Magnesium 2 x 102
Calcium
Strontium 20
Barium 50
Boron 1
Aluminum
Gallium <9
Indium
Thallium
Carbon
Silicon
Germanium
Tin
Lead 50
Nitrogen
Phosphorus
Arsenic <0.2
Antimony 80
Bismuth « 5
Oxygen (as 03)
Sulfur 2 * I"'
Selenium 3 x 10"s
Tellurium
Fluorine (as F~) 20
Chlorine (as Cl")
Bromine (as Br )
Iodine (as l") 5
Scandium <1
Yttrium *
Titanium
Zirconium
Hafnium
Vanadium 1
Degree of Hazard
(Estimated Cone. /MATE Cone.)
Health Ecological
Concern Concern
7 x 10* NA
6 NA
3 x 101 NA
NA NA
1 x 10"* NA
1 0.3
0.2 NA
50 10
0.01 0.02
<0.06 NA
90 5 x 102
<0.4 <2
6 2 x 102
0.4 NA
NA NA
3 x 10"2 6 x 10~2
<0.3 NA
NA NA
6 x 10"" NA
3 x 10"2 NA
0.2 2
7\ — . . 3
145
-------
Table 5-15. (Continued)
MEG Category
Estimated
Concentration (lig/g)
Degree of Hazard
(Estimated Cone./MATE Cone.)
Health Ecological
Concern Concern
66.
67.
68.
69.
70.
71.
72.
73.
lit.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
Niobium
Tantalum
Chromium
Molybdenum
Tungsten
Manganese
Iron
Ruthenium
Cobalt
Rhodium
Nickel
Platinum
Copper
Silver
Gold
Zinc
Cadmium
Mercury
Lanthanides
Lanthanum
Cerium
Praseodymium
Neodymium
Samarium
Dysprosium
Actinldes
Uranium
Thorium
<5
50
<_ 8 x 10
100
NA
100
300
<6
6 x 10~'
30
<60
3
1 x 10"S
4 x 10"'
3 x 10!
<3 x 10s
0.1
NA
MA
NA: MATE value was not available
TR: Trace
146
-------
5.2.5 Summary of Cyclone Farticulate Removal Efficiency Test
Particulates removed from the raw product gas stream
consisted of coal dust, ash and tar. Overall particulate removal
efficiency was determined by collecting particulates in in-stream
alundum thimbles placed at the inlet and outlet of a cyclone.
The average total particulate removal efficiency for the cyclone
was 62 percent with values ranging from 29 to 78 percent. Table
5-16 shows the average particulate loadings found in the product
gas entering and exiting the hot cyclone.
TABLE 5-16 PARTICULATE LOADINGS IN THE PRODUCT LOW-BTU GAS
ENTERING AND EXITING THE HOT CYCLONE
Run
Number
1
2
3
4
Particulate
Inlet
1.1
1.5
1.7
2.4
Concentration (ug/Nm3 )
Outlet
0.79
0.36
0.57
0.54
Cyclone Removal Efficiency
(%)
29
76
66
78
5.2.6 Additional Results
Additional results not reported in the Level 1 summary
tables were:
'• additional water quality parameters,
• proximate and ultimate analyses, and
product gas analyses.
147
-------
Water Quality Parameters -
Additional water quality data were obtained on the
separator liquor and on the condensables collected during the
separator vent stream SASS train run. These data are shown in
Table 5-17. Both samples contained high levels of BOD and COD.
The separator liquor also contained high levels of dissolved and
suspended solids, which was to be expected for the recirculating
quench liquor.
Proximate and Ultimate Analyses -
Table 5-18 lists the results of the proximate and
ultimate analyses performed on the coal feedstock, gasifier ash,
cyclone dust and by-product tar. The heating value and free
swelling index for the coal feed are also reported in this table.
From the data in Table 5-18, it appears that the
cyclone dust is a char-like material (e.g., devolatilized coal).
Also, only minor quantities of sulfur are present in the ash
and tar.
Product Gas Analyses -
The data collected from analyses of the raw and clean
product gases are presented in Table 5-19. Also included in this
summary is the estimated composition of the coal feeder vent gas
without its dilution air. All of the data presented were obtain-
ed from on-site analyses of gaseous grab samples, except for HCN
which was sampled through aqueous base impinger-scrubbers and
analyzed by standard wet chemical methods.
The concentrations presented for the four sulfur species
in the raw product gas are suspiciously low, compared to previous-
ly reported data for coal gasification facilities. As previously
mentioned, gas samples collected through tar-laden filters tended
to lose sulfur species, presumably by sorption into and/or
reaction with the tar. Because the raw product gas was sampled
through multiple filters, to prevent tar from plugging the sampl-
ing train, it is possible that the results of the sulfur species
analyses are not representative of the actual concentrations
present in the raw product gas.
148
-------
TABLE 5-17. SUMMARY OF ADDITIONAL WATER QUALITY PARAMETERS FOR
THE SEPARATOR LIQUOR AND SASS TRAIN CONDENSATE FROM
THE SEPARATOR VENT
Color (Pt-Co units)
Odor (Threshold No.)
PH
TDS (Vig/nfc)
TSS (yg/nA)
COD (yg/m£)
BOD (yg/m£)
DO (yg/m£)
Conductivity (ymhos)
Hardness
Alkalinity (as CaC03 ) (Ug/m&)
Acidity (yg/m£)
Separator
Vent SASS
Condensate
NC
NC
9.56
218
14.5
8200
3900
NC
NC
*
2880
NA
Separator
Liquor
5000
4000
7.66
6300
144
22,200
6530
ND
32,000
*
i
2140
NA
* Level 1 test method failed.
SASS: Source Assessment Sampling System
NC: Test not conducted
ND: Not determined
NA: Not applicable
149
-------
TABLE 5-18. PROXIMATE AND ULTIMATE ANALYSES RESULTS FOR THE COAL
FEED, GASIFIER ASH, CYCLONE DUST AND BY-PRODUCT TAR
Wt% (DAF)
Carbon
Hydrogen
Nitrogen
Sulfur
Oxygen (by difference)
Wt% (as received)
Volatiles
Fixed carbon
Ash
Moisture
Heating Value
MJ/Kg
Btu/lb
Coal Gasifier
Feed Ash
83.75 *
5 . 25 ND
1.90 ND
0.62 0.21
8.48
36.32
56.67
5.61 ND
1.40 ND
31.82
13,690
Cyclone By-Product
Dust Tar**
92.42 77.30
0.93 6.06
1.69 1.42
0.70 0.52
4.26
ND
NR
12.53 0.97
-
Free Swelling Index 5.0
Source: All analyses were performed by the institute for Mining and Minerals
Research (IMMR), Lexington, KY.
* Interference in the analysis
** All analyses for the tar are on an "as received" basis
ND: Not determined
DAF: Dry, ash free basis
-: Analysis not performed
150
-------
Table 5-19. RESULTS FOR GASEOUS SPECIES IN THE RAW AND CLEAN PRODUCT GAS
Ul
Raw Product Gas
#2 Cyclone Over-head
Estimated Coal Feeder
Vent Gas Without
Dilution Air
Clean Product Gas
after the
Final Spray Scrubber
Nitrogen
Carbon Dixoide
Oxygen
Hydrogen
Carbon Monoxide
Nitric Oxide
Nitrogen Dioxide
Hydrogen Sulfide
Carbonyl Sulfide
Carbon Disulfide
Sulfur Dioxide
Cyanide (as HCN)
Hydrocarbons
Methane
Cz (as ethane)
Cs (as propane)
C"t (as butane)
Cs (as pentane)
CB (as hexane)
7
1.7
1.7
1.3
2.5
1.1
2.8
7.5
2.4
1.8
1.0
1.4
8.4
3.3
2.2
1.2
2.7
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
10"
10a
107
107
10"
10s
NA
10s
10*
10"
10*
105
10"
10s
106
10s
10s
106
(56%)
(8.5%)
(1.2%)
(14.5%)
(19.7%)
(96 vppm)
(251 vppm)
(28 vppm)
(7 vppm)
(6 vppm)
(86 vppm)
(1.5%)
(6.3 x 103 vppm)
(1.7 x 103 vppm)
(884 vppm)
(358 vppm)
(706 vppm)
2
2.1
1.2.
1.4
1.1
2.4
4.5
1.2
1.3
8.4
2.1
2.3
9.4
2.3
x 107
x 108
x 10s
NA
x 10s
x 105
x 10s
x 10*
x 10s
x 10s
x 106
x 106
x 106
x 105
x 106
(23%)
(16%)
(100 vppm)
(900 vppm)
(39 vppm)
(70 vppm)
(15 vppm)
(97 vppm)
(1.8%)
(6.3 x 103 vppm)
(1.1 x 103 vppm)
(870 vppm)
(280 vppm)
(660 vppm)
6
1
1
1
2
1
4
8
6
2
1
8
3
2
1
2
.8 x
.7 x
.4 x
.3 x
.7 x
.3 x
.4 x
.3 x
.1 x
.9 x
.4 x
.5 x
.6 x
.6 x
.1 x
.6 x
10 "
108
107
107
108
105
NA
10s
10*
10*
10*
NA
108
106
10G
10s
10s
106
(54%)
(8.8%)
(1.0%)
(14.9%)
(21.3%)
(109 vppm)
(291 vppm)
(31 vppm)
(18 vppm)
(10 vppm)
(1.9%)
(6.4 x 103 vppm)
(1.8 x 103 vppm)
(998 vppm)
(327 vppm)
(686 vppm)
Units: Pg/m3 (vol % or vppm)
NA: Not analyzed
-------
Since the gas emitted from the coal feeder vent was
determined to be raw product gas diluted with air, an estimate
of the raw gas composition was made by subtracting out the dilu-
ent air from this stream. The gas to air ratio was estimated to
be approximately 1:10, based on the average analyses of H2, Oz,
CO, NO, and hydrocarbons in the raw product gas, clean product
gas and coal feeder vent gas. The estimated concentrations of
most species correspond closely to those found in the actual
product gas analyses. However, the sulfur species concentrations
estimated from the coal feeder vent analyses are considerably
higher than those found in the raw gas. This might be expected
since the coal feeder vent grab sample was not pulled through
a tar-laden filter. However, the estimated concentrations for
sulfur species should not necessarily be considered more repre-
sentative than those found by analysis of actual samples from the
raw product gas stream.
The sampling and analyses of the clean product gas
were accomplished without interferences from tar or water. The
analytical results for this stream are also shown in Table 5-19.
152
-------
SECTION 6.0
CONCLUSIONS AND RECOMMENDATIONS
Conclusions and recommendations developed as a result
of the STE program conducted at the Chapman facility fall into
two categories: those resulting from the characterization of
waste and process streams and those resulting from the evaluation
of Level 1 methodology.
6,1 WASTE AND PROCESS STREAMS
An overall summary of the character of the waste and
process streams at the Chapman facility is presented in Table
6.1. As indicated in this table, all of the streams tested con-
tained potentially hazardous organic and/o.r inorganic materials .
In the case of cyclone dust and coal feeder and separator vent
gases, this conclusion is confirmed by the results of the bio-
assay screening tests. However, in the case of the gasifier ash,
the degree of hazard indicates a moderate potential hazard while
bioassay tests indicate a low potential.
Recommendations for future data needs are presented in
Tables 6-2 and 6-3. Priorities shown for Level 2 chemical and
biological analyses of chemical compound classes in each waste
stream are based on the results of SAM/1A analyses. Specific
conclusions and recommendations based on the characterization of
waste and process streams at the Chapman facility are given in
the following text.
6.1.1 Gaseous Waste Streams
Coal Feeder Vent Gas -
The coal feeder vent gas contained organics', inorganic
gases and trace elements at potentially hazardous concentrations
(greater than their MATE values). The bulk of the organics con-
sisted of tar particulates. Volatile organics were also present,
Their compositions were significantly different from those of
153
-------
Table 6-1.
CHARACTERISTICS OF WASTE STREAMS AND POTENTIAL FUGITIVE EMISSIONS
AND EFFLUENTS FROM THE CHAPMAN FACILITY
i Description
Stream Degree of Hazard
Health Ecological Bioassay Teats
Stream Source Concern Concern Health** Ecologicalc
iarha and Conclusions
GascoujL Waste Streams
• Coal Feeder Vent Ga
Coal feeder 4 x 107 8 x 10s
High
High
Separator Vent Gas
Tar/liquor 1 x 10° 1 x 10s
separator
High
Ul
Solid Waste Sere
- Gasifier Ash
5 x 103
8 x 10s
The SAM/JA analysis and the bioaasay test results of
this waste stream indicated that it may have poten-
tially hazardous health and ecological effects. How-
ever, it should be emphasized that this stream should
NOT, be a waste stream from nev gasification plants,
and should be controlled by recycling to the gaslfier
inlet air or product gas or by combusting it in a
boiler or flare. The organic content in this stream
was high with the major classes of organicB being
polycyclic aromatic hydrocarbons (PAH's), heterocy-
clic nitrogen compounds and phenols. Gaseous com-
pounds in the product gas (CO. Hz , CR*. H2S, COS,
HCH, etc.) were also found in the coal feeder vent
stream.
The results from the bioassay tests and SAK/1A anal-
ysis indicated that this stream may have potentially
hazardous health and ecological effects. As for the
coal feeder vent stream, this stream should NOT_ be a
waste stream from new gasification plants. It may
be controlled by recycling to the gaslfier inlet air
or product gas or by combusting it in a boiler or
flare. The organic concentration in this stream was
high, with the major organic classes being PAH's and
phenols. Gaseous compounds in the product gas (CO,
B2, CH», HZS, COS, HCH, etc.) were also found in the
separator vent stream.
The results of a SAM/1A analysis of the gasifier ash
indicated that It may have a moderate potential for
hazardous health and ecological effects. However,
the results of the bioassay tests showed that the ash
had a low potential for hazardous health and ecolog-
ical effects. The extractable organic concentration
in the ash was ^20 (Jg/g; trace element concentra-
tions were similar to the amounts of trace elements
found in the ash from coal-fired boilers. The major
trace elements found in the ash were alkali metals.
Leaching tests are needed to determine appropriate
design for landfills as final ash disposal sites.
Continued
-------
Table 6-1. (Continued)
Stream Description
Stream Degree of Hazard
Health Ecological
Concern Concern
Bioassay Teats
Healthb Ecological0
Remarks and Conclusions
Cyclone Dust
Hot -Cyclone 2 x 10a
High
Ul
Ln
Potential Fugitive
Emissions
Raw Product Gas
Potential Fugitive
Effluents
* Separator Liquor
(liquid)
Gasifier and
hot cyclone
pokeholes
Tar/liquor
separator
4 x 10s
10s
2 x 10s
High
By-product Tar
(solid)
Tar/liquor
separator
1 x 10*
2 x 107
High
High
From the results of a SAH/1A analysis, the cyclone
dust could be potentially hazardous. The ecolog-
ical bloassay teat (soil microcosm) Indicated that
the dust had a high potential for hazardous effect,
while the health effects test showed the dust had
a low potential. The concentration of extractable
organlca in the dust was low C**40 Ug/g). The trace
elements having the highest concentrations were P,
K, SI and Fe. The carbon content of the dust was
high (^921) which Indicates that the dust is simi-
lar to devolatilized coal. If the dust Is to be
disposed of in a landfill, leaching teats are
necessary; however, combustion of the dust is
probably required before disposal.
Fugitive emissions will contain tar particulates,
volatile organics and Inorganics in potentially
hazardous concentrations. The characteristics of
these emissions will be similar to those of the
coal feeder vent gas.
The separator liquor contained high levels of
organics. These consisted primarily of thiols,
phenols and heterocycllc aromatics. High levels of
cyanide, anaemia, fluoride and sulfate were also
found. High concentrations of sulfide were not found
which may indicate that hydrogen sulfide sorbed in
the quench either escapes as HzS in the vent gases or
Is oxidized to sulfate. Separator liquor was found
to be very toxic to aquatic species and should not
be discharged without prior treatment.
The by-product tar was the most potentially hazardous
sample tested. A wide range of organics was found
to be present. The main classes of organics were
PAH's and heterocycllc nitrogen, oxygen and sulfur
compounds. High levels of trace elements were
also found.
Degree of Hazard for a stream is the sum of the estimated concentrations of components (or classes of components) in the stream divided by their
respective MATE values.
Health tests include: Ames, Cytotoxlcity (UI-38, RAM) and Rodent Acute Toxicity
C Ecological tests Include: soil microcosm, plant stress ethylene, fresh water bioassay (algal, daphnia and fathead minnow) and salt water bioassay
(algal, shrimp and sheepshead minnow).
Source Assessment Model/LA
e Degree of Hazard values were estimated from the coal feeder vent gases by assuming a 1:10 gas to air dilution in the vent stream.
MC: Test not conducted
-------
Table 6-2. RECOMMENDATIONS FOR FUTURE DATA NEEDS FOR WASTE STREAMS
Haste
Stream
Total Scream Stream Components Priority for Level 2 Chemical Analysis
Degree of Hazard High Priority Medium Priority Low Priority
Health Ecological Degree of Hazard Degree of Hazard Degree of Hazard
Concern Concern 10 - 10* 10-10
10-1
Remarks &
Recommendations
Separator 1 x ID* i x 10* Fused aromatic hydrocarbons
Vent and their derivatives,
amines, heterocycllc
nitrogen compounds, CO,
NHs, Cr, Ag, V C 2 hydro-
carbons, phenols
Heterocyclic sulfur
compounds, Cu, H02,
P, H2S
Methane, halogenated
aliphatic hydrocarbons,
carboxylic acids and
their derivatives,
Li, HCN, As, C02, Fe,
Nl, U, CE hydrocarbons
This stream should be controlled
in new gasification facilities.
Further characterization should
be directed toward the control
technique for this stream, e.g.,
if the control device for this
stream is combustion, then de-
tailed chemical characterization
around the combustor will be
neccesary, along with bioassay
tests of the resulting combus-
tion products.
Coal Feeder
Vent
Fused aromatic hydrocarbons
and their derivatives, CO,
Cr, C2 hydrocarbons
Carboxylic acids and
their derivatives, amines,
sulfonic acids and sulfox-
ides, phenols, NHs , Hg,
U, V, heterocycllc nitro-
gen compounds
Methane, thlols, benzene
and substituted benzene
hydrocarbons, Al, P, As,
HaS, Cu, Cd, NO. CO...
RCN, heterocyclic sulfur
compounds
As for the separator vent stream,
this stream should be controlled
in new gasification facilities.
Further characterization should
be directed toward the control
technique for this etream, e*g.t
if this stream is to be controlled
by combustion (flaring, inciner-
ation, etc.), then detailed chem-
ical characterization around the
combustion process would be nec-
essary, along with bioassay tests
of the coabustlon products.
Gasifier 5 x itf 8 x itf Be, P, Fe, Ca, Al, Li,
Ash Ba, Se, Pb, Cs, Cu, Ti.
Cd, Sb, V, Co, U
Mg, Sr, Cr, Co, Si, Hg,
Zr, F, Rb, As
Even though the amount of extrac-
table organics was low (^20 pg/g),
certain organic constitutents may
exist at levels exceeding their
respective HATE values. There-
fore, further analysis of this ex-
tract Is recommended. The analy-
sis should be directed specifically
toward identifying specific organic
species (i.e., benzo-a-pyrene).
The gasifler ash contained high
concentrations of trace elements;
however, the results of the bio-
assay tests indicated that the ash
had a low potential for hazardous
health or ecological effects.
Leaching tests are recommended
along with bioassay tests on the
resulting leachate.
Cyclone
Dust
Nl, Pb, P, Mn, Fe, Cu, Ba,
Sb, Ti
Cr, Ca, A1,V
Li, Mg, Zr, Co, As,
Si
As for the ash, further organ-
ic analysis is recommended for
specific hazardous organic
species in the extractable
organics In the cyclone dust.
Because of the high carbon
content, the cyclone dust
should be combusted or recy-
cled to the gasifler. If the
dust is to be landfilled,
leaching tests and bioassay
tests on the resulting leachae
are recommended.
-------
Table 6-3.
RECOMMENDATIONS FOR FUTURE DATA NEEDS FOR POTENTIAL FUGITIVE,
EMISSIONS AND EFFLUENTS
Total Stream
Fugitive Degree of Hazard
Emissions & Health Ecological
Effluents Concern Concern
Stream Components Priority for Level 2 Chemical Analysis
High Priority Medium Priority Low Priority
Degree of Hazard Degree of Hazard Degree of Hazard
109 - 102 102 - 10 10-1
Raw Product
Gas
8 x 106
By-Product
Tar
2 x 107
Ln
Separator
Liquor
105
Fused aromatic hydrocarbons
and their derivatives, het-
erocyclic nitrogen compounds,
Cr, CO, carboxylic acids and
their derivatives, amines,
sulfonic acids and sulfoxides,
phenols, Hg, U, NH3, V,
Cz hydrocarbons
Fused aromatic hydrocarbons
and their derivatives, phenols,
amines, benzene and substitu-
ted benzene hydrocarbons,
heterocyclic nitrogen and sul-
fur compounds, halogenated ali-
phatic hydrocarbons, carboxylic
acids and their derivatives,
Cu, Pb, Sb, aliphatic hydro-
carbons, Cr, Cd
Phenols, fused aromatic hydro-
carbons and their derivatives,
NHa, CH~, heterocyclic nitro-
gen compounds, P, carboxylic
acids and their derivatives
Thiols, benzenes and substi-
tuted benzene hydrocarbons,
Al. P, As, Cu, Cd, HjS, COj,
NO, HCN, metharp; hetero-
cyclic sulfur compounds
C« and CG hydrocarbons,
heterocyclic oxygen
compounds, Li, Tl, Si,
Pb, Sb, SOZ, CS2l Cl,
Ti, Zr, Fe, Co. Hi, Ag,
Zn
Thiols, Se, glycols, and
epoxides, As
Heterocyclic oxygen
compounds, Hg, V,
Hg, As
Heterocyclic sulfur
compounds, F, Cl, Ca,
Pe. Cd
Remarks &
Recommendations
Sources of raw product gas fugitive
emissions are primarily poVeholes
and abnormal process operation.
Because of the potentially hazar-
dous nature of the raw product gas,
control of pokehole emissions is
required. This can be achieved by
injecting an ineri gas (steam or
C02) into the pokehole during poking
operations. Abnormal process oper-
ation (start-up, shutdown, upsets)
may require directing the raw pro-
duct gas to a flare or incinerator.
Further chemical characterization
around the flare or incinerator
is needed along with bioassay tests
of the resulting combustion
products.
The by-product tar was the most po-
tentially toxic material found in
this test. Potential fugitive
effluents of tar may occur around
pumps, flanges, and valves. These
effluents must be contained. Good
maintenance and material handling
procedures are required.
The bioassay tests for the separator
liquor indicated a low potential
for hazardous health effects, and
a high potential for hazardous eco-
logical effects. Fugitive efflu-
ents of the separator liquor may
occur around pumps, valves, flanges,
and surge tanks. These fugitive eff-
luents should be contained. Any
accumulation should be sealed in con-
tainers for disposal. Proper main-
tenance and handling practices should
be implemented.
Further chemical characterization of
the separator liquor is recommended
because of the inconsistency between
the health MATE values and the health
bioassay tests.
-------
the tar particulates. The volatile organics had a higher propor-
tion of polycyclic aromatic hydrocarbons (PAH's) while the tar
contained a higher proportion of heterocyclic aromatics. The
tar particulates in the coal feeder vent had organic character-
istics which were different from those of the separator tar^with
the coal feeder vent tar having higher concentrations of PAH s
heterocyclic nitrogen compounds and phenols .
This stream should be controlled in new gasification
facilities. Further characterization should be directed toward
the control technique for this stream, e.g., if this stream is to
be controlled by combustion (flaring, incineration, etc.), then
detailed chemical characterization around the combustion process
would be necessary, along with bioassay tests of the combustion
products.
Separator Vent Gas -
The separator vent gas contained volatile organics and
inorganics at potentially hazardous concentrations (greater than
their MATE values). Volatile organics consisted primarily of
PAH's and phenols. The inorganics consisted of gaseous inorganic
compounds and a variety of trace elements.
This stream should be controlled in new gasification
facilities. Further characterization should be directed toward
the control technique for this stream, e.g. , if the control device
for this stream is combustion, then detailed chemical character-
ization around the combustor will be necessary, along with bio-
assay tests of the resulting combustion products.
6.1.2 Solid Waste Streams
Gasifier Ash -
Very low levels of organics were found in the gasifier
ash (^20 ug/g). The major trace elements found were alkali and
alkaline earth metals. Trace element concentrations were similar
to those found in ash from coal-fired boilers.
158
-------
Even though the amount of extractable organics was low
(^20 yg/g), certain organic constituents may exist at levels
exceeding their respective MATE values. Therefore, further ana-
lysis of this extract is recommended. The analysis should be
directed specifically toward identifying specific organic species
(e.g., benzo-a-pyrene).
Even though the gasifier ash contained high concentra-
tions of trace elements, the results of the bioassay tests indi-
cated that the ash had a low potential for hazardous health or
ecological effects. Leaching tests are recommended along with
bioassay tests on the resulting leachate.
Cyclone Dust -
Very low levels of organics were found in the cyclone
dust (^40 yg/g). The dust was similar to devolatilized coal,
as indicated by its carbon, oxygen and hydrogen content. A wide
variety of trace elements were found, but generally at much lower
concentrations than those found in the gasifier ash. The major
trace elements found were K, Si, P and Fe.:T
As for the ash, further organic analysis is recommended
for specific hazardous organic species in the extractable organics
in the cyclone dust.
Because of the high carbon content, the cyclone dust
should be combusted or recycled to the gasifier. If the dust is
to be landfilled, leaching tests and bioassay tests on the result-
ing leachate are recommended,
6.1.3 Potential Fugitive Emissions
Raw Product Gas -
The gasifier and hot cyclone pokeholes are potential
sources of fugitive emissions of raw product gas. Raw product
gas contains tar, particulates and volatile organics and inorgan-
ics at potentially hazardous concentrations.
159
-------
Because of the potentially hazardous nature of the raw
product gas, control of pokehole emissions is needed. This can
be achieved by injecting an inert gas (steam or C02) into the
pokehole during poking operations. Abnormal process operation
(startup, shutdown, upsets) may require directing the raw product
gas to a flare or incinerator. Further chemical characterization
around the flare or incinerator is needed along with bioassay
tests of the resulting combustion products.
6.1.4 Potential Fugitive Effluents
Separator Liquor (Liquid) -
The tar/liquor separator is a potential source of fugi-
tive effluent of separator liquor. The separator liquor contains
high levels of organics, primarily thiols, phenols and hetero-
cyclic aromatics. High levels of cyanide, ammonia, fluoride
and sulfate were also found. Sulfide was not found at high con-
centrations , which may indicate oxidation of the sulfide to sul-
fate or escape as H2S in the vent gases. Higher concentrations
of trace elements were found in the separator liquor than were
found in the by-product tar.
Degree of hazard values for the separator liquor indi-
cated a moderate potential for hazardous health and ecological
effects. The bioassay tests indicated a low potential for
hazardous health effects, and a high potential for hazardous
ecological effects. Fugitive effluents of the separator liquor
may occur around pumps, valves, flanges, and surge tanks. These
fugitive effluents should be contained. Any accumulation should
be sealed in containers for disposal. Proper maintenance and
handling practices should be implemented.
Further chemical characterization of the separator liq-
uor is recommended because the health MATE values indicated a
high potential effects while the bioassay tests indicated a low
potential.
By-Product Tar (Solid) -
The tar/liquor separator is also a potential source of
fugitive effluents of by-product tar.' The by-product tar was the
most potentially hazardous material tested, and was found to con-
tain a wide range of organics and inorganics. The main organic
160
-------
constituents were PAH's and heterocyclic nitrogen, oxygen and
sulfur compounds. Fewer trace elements were found in the
by-product tar than were found in the other liquid and solid
streams tested. However, some trace element concentrations ex-
ceeded their respective MATE values.
Potential fugitive effluents of tar may occur around
pumps, flanges, and valves. These effluents should be contained.
Good maintenance and material handling procedures are necessary.
6.2 LEVEL 1 METHODOLOGY
An evaluation of Level 1 methodology for sampling and
analysis of waste and process streams at the Chapman facility
revealed a number of deficiencies. With modification, Level 1
methodology was found to be adequate for a screening character-
ization of low-Btu gasification facilities. Conclusions and
recommendations regarding Level 1 methodology for sampling and
analysis are presented in the following sections.
6.2.1 Sampling Methodology
An overall summary of conclusions and recommendations
resulting from the evaluation of Level 1 sampling methodology
is presented in Table 6-4. The bases for this summary are
given in the following paragraphs.
Gas Sampling
Grab Sampling - In general, Level 1 methodology for
grab sampling of gas streams required certain modifications to
suit the conditions encountered during this STE program. The
modifications included: (1) preconditioning of sample contain-
ers, and (2) pretreatment of samples to remove interfering
components such as particulates, tar, oil and water.
Two modifications to Level 1 methodology were used for
collecting grab samples from gaseous streams. These are as
follows:
161
-------
Table 6-4.
CONCLUSIONS FROM EVALUATION OF LEVEL 1 SAMPLING METHODOLOGY
DURING THE TEST PROGRAM AT A CHAPMAN FACILITY
Sampling Methodology
Remarks and Conclusions
Gas Sampling
• Grab sampling
SASS train sampling
Level 1 methodology for collecting grab samples of gas streams required certain modifications
to suit the conditions encountered during this STE program. The modifications Included:
(1) preconditioning sample containers and (2) pretreatment of samples to eliminate interfering
species such as tars and condensables.
A pretreatment train was necessary for removal of particulates, tar, oil, and water from
certain gas samples since these impurities would Interfere with the analysis for gaseous
species. Problems were encountered in the use of a filter to remove tar and particulates.
It was concluded that the tar/partlculate layer on the filter sorbed significant amounts of
sulfur species.
The source assessment sampling system (SASS) must be modified when sampling gaseous streams
containing high levels of tar, oil and/or water vapor. When sampling the coal feeder vent, the
filter In the particulate collection module frequently became plugged with tar. To alleviate
this, the temperature in the particulate module was reduced in order to collect a majority of
the tar as particulates in the cyclones, Instead of as a highly viscous fluid on the cyclone
filter. When sampling streams that have a high moisture content, such as the separator vent,
additional cooling was required in the SASS train organic module. This modification has been
made in the new SASS train operating Instructions.
In most cases, sampling gaseous waste streams that contain high concentrations of tars, oils
and/or moisture will Involve either modifying the SASS train or using an alternate method.
For example, in-line filters and/or electrostatic preclpltators may be used to collect tars
and oils.
Liquid and Solid Sampling
The Level 1 procedures for sampling liquid waste streams and potential fugitive effluents were
adequate and generally straightforward.
-------
(1) Glass sampling containers for collecting gas
samples for sulfur species (H2S, COS, CS2, S02)
analysis should be sylilated to assure that
these species will not react with and/or be sorbed
on the walls of the container.
(2) A pretreatment train is recommended for removal
of particulates, tars, oils and water from the
gas sample. Otherwise, these constituents will
interfere with subsequent analyses.
SASS Train Sampling - Problems were encountered with
the SASS train when sampling streams containing high levels of
particulates, tar, oil, and water vapor. When sampling the coal
feeder vent, the filter in the particulate collection module
frequently became plugged with tar. To alleviate this, the
temperature in the particulate module was reduced in order to
collect a majority of the tar as particulates in the cyclones,
instead of as a highly viscous fluid on the cyclone filter.
When sampling streams that have a high moisture content, such
as the separator vent, additional cooling was required in the
SASS train organic module. This has been corrected in the new
SASS train operating instructions.
An alternative system is recommended for collecting
samples from tar/oil laden streams. This alternative system
should include means for collection of tars and oils with an
electrostatic precipitator.
Relocation of the XAD-2 cartridge to a point down-
stream of the condenser in the SASS train module was used.
Using this modification, condensable organics are collected in
the condenser, while organic vapors are sorbed on the XAD-2
resin. This modification will also minimize overloading the
XAD-2 resin with organics that have already condensed and the
potential for gas channeling through the resin.
Liquid and Solid Sampling -
Level 1 methodology for sampling liquid and solid
waste and process streams was adequate, and generally straight-
forward.
163
-------
6.2.2 Analytical Methodology
Level 1 methods gave satisfactory results in the
following areas: liquid chromatographic separation, low reso-
lution mass spectrometry and sparks source mass spectrometry.
Problems were encountered using chemiluminescence for NO and
NOX determinations and using the test kits for hardness, nitrate
and nitrite analyses. On site experiments indicated that reduc-
ing gas constituents in the gaseous samples to be analyzed for
NO and NOX caused problems in the chemiluminescense technique.
EPA Method 7 procedure for NOX determinations is recommended
for analyzing gaseous streams containing reducing gas consti-
tuents. The problems encountered using the test kits were
probably due to the high levels of organics in the separator
liquor sample.
Alternate methods used to analyze gaseous species
were used because of the need to obtain quantitative data for
input to control technology development (i.e. gaseous sulfur
species), the Level 1 detection limits were too high (i.e. NHa
and HCN) or a comparible technique was easier to use. Sulfur
species were analyzed using a column to obtain quantitative
data on HaS, COS, CSa and S02 in the gaseous streams sampled.
Impinger techniques were used for NHs and HCN determinations.
For fixed gases, a Fisher Gas Partitioner was used to separate
Na and 02 and permit quantification of the other species on a
single sample injection.
During the analysis of trace elements, the Parr bomb
solution contained high concentrations of Ca, K and P. These
needed to be factored into the evaluation of the SSMS data.
During analyses for organic species, the extraction
techniques specified by Level 1 methodology were found to be
inadequate. Mass recoveries were generally lower than desired
and certain highly polar organics were not extracted by Level 1
techniques. Extraction with methylene chloride at two pH's may
solve this potential problem. Problems were encountered with
Level 1 methods for total chromatographable organics, especially
with heavy organic loading. In those cases, the resulting
chromatograms were too complex for reliable application of the
specified integration technique. Gravimetric determinations
presented some of the more significant problems. Specifically,
problems in weighing small samples that had a very low concen-
tration of organics arose when only a small quantity of sample .
164
-------
was contained on the watch glass. A scum formed on the surface
of certain samples which could have prevented or hampered
evaporation of volatile organics.
Specific conclusions drawn from the evaluation of
Level 1 analytical methodology are presented in Table 6-5.
Recommendations for modifications to the methodology are given
in the following paragraphs.
Specific Methods
Nitrogen oxides (NOx) - An alternate method such as
EPA Method 7,is recommended for determining NOX.
Ammonia and hydrogen cyanide - The gas chromatography
technique specified by Level 1 was not sufficiently sensitive
for determination of the low levels of NH3 or HCN in the gas
samples. NH3 and HCN samples should be collected in impingers
and analyzed by wet chemical methods.
Sulfur species - A modified gas,, chromatography tech-
nique using a Poropak QS column was used for analysis of sulfur
species (H2S, COS, CS2, and S02) and was found to give the
required separation for inputs to control technology develop-
ment. However, problems were found with the Poropak QS packing
because of its reactivity toward SOz. Additional packed columns
for separation of H2S, COS, S02, and CS2 have been evaluated.
The following have proved satisfactory for gas samples obtained
from coal gasification facilities:
(1) 3% TCEP, 0.5% H3P04 on mesh Carbopak B.
(2) 1% Carbowax 20 M, 0.5% HsPO,, on mesh Carbopak B.
Fixed gases - A Fisher Gas Partitioner is recommended
to permit Reparation of nitrogen and oxygen and quantification
of other species on a single sample injection.
Test kits - The test kits specified by Level 1 were
found to give adequate results in most cases. However, results
could not be obtained using these kits for the determination of
165
-------
Table 6-5.
CONCLUSIONS FROM EVALUATION OF LEVEL 1 ANALYTICAL METHODOLOGY DURING
THE TEST PROGRAM AT THE CHAPMAN FACILITY
Analysis Methodology
Gaseous Spec!eg
" Nitrogen Oxides
• Nil; and HCN
• Sulfur Species (H2S, COS, CS2, S02)
• Fixed Gases (CO, H2, C02, 02, N2, CH,)
Inorganics
• Test kits for aqueous phase analysis
• Trace Elements
Organics
• Extraction Techniques
• Total Cliromatographable Organics (TCO)
• Gravimetric
• Liquid Chromatography (LC)
Infrared (IR) anil Low Resolution Mass
Spectrc'metry (LRMS)
Remarks nnd Conclusions
Analysis of NO by chemilumlnescencc in all of the gas stream samples was found to be adequate;
however, the technique did not work for analyzing NOX. This was probably caused by the presence of
reducing gases in the sample. EPA Method 7 is recommended for NOX analysis.
The gas chromatography technique specified by Level 1 was not sensitive enough for determination of
NHu or HCN In the gas samples. Nlh and HCN samples were collected in impingers and analyzed by wet
chemical methods.
The gns chromatography technique used to analyze sulfur species (I12S, COS, CS2 , and S02) was used in
order to give better separation than the Level 1 procedure.
The Level 1 procedure for fixed gases analysis was modified. A Fisher Gas Partitioner was used so
that nitrogen and oxygen could be separated and the other species quantified on a single sample
injection.
The test kits specified by Level 1 were found to give adequate results in most cases. However,
results could not be obtained when using these kits for the determination of nitrate, nitrite, or
hardness, probably because oC the high organic content in the separator liquor.
The Parr bomb solution contained high concentrations of Ca, K, and P and needed to be factored into
the SSMS data evaluation.
The extraction techniques specified by Level 1 were found to be inadequate for extracting aqueous
samples and XAD-2 resins containing highly polar organic compounds. Total mass recoveries using
the Level 1 procedure were less than 50Z for aqueous samples and approximately 70% for XAD-2
resins.
Problems arose when using the procedure for determining TCO's for most of the organic extracts.
This was especially true when high amounts of organics were present because the resulting chromat<
grams were so complex that the integration techniques could not be used reliably.
ftcvmiL. ui AJKIIJ. i icimiiy iiijmpiT Liie evaporation 01 voiatl
inconsistency in mass balances calculated from these data
The liquid chromatography method specified by Level 1 was capable of handling i loading of up to 400
mg. Even though there was significant overlap of compounds in different LC fractions, the LC
procedure was adequate for obtaining results specified by Level 1.
The amount of information obtained from the IR spectra was of minimal value for compound class
Identification because of the complex nature of the samples. Most of the identifications were made
from the results of the LRMS analyses of Lhe LC fractions. Compound identification using LRMS was
also difficult because of the complex nature of the sample, and may not be valid.
-------
nitrate, nitrite or hardness. This was probably due to the high
concentration of organics in the separator liquor.
Extraction techniques - The extraction techniques
specified by Level 1 were found to be inadequate for extracting
aqueous samples and XAD-2 resins containing highly polar organic
compounds. Alternate extraction procedures using methylene
chloride, ether and acidified ether, can be used in order to
assure recovery of highly polar organics.
Total chromatographable organics (TCP) - Problems
arose in using the procedure for determining TCO's for most of
the organic extracts. This was especially true when high amounts
of organics were present. The resulting chromatograms were so
complex that the integration techniques were unreliable.
Gravimetric analysis - Significant variations were
observed in mass determinations when dilute and concentrated
samples of an extract were analyzed gravimetrically. It is
recommended that additional work be performed in order to
determine the optimum mass range for such analyses.
167
-------
REFERENCES
1. Hamersma, J. W., S. L. Reynolds and R. F. Maddalone, IERL-RTP
Procedures Manual: Level 1 Environmental Assessment. EPA-600/
2-76-160a, EPA Contract No. 68-02-1412.TRW Systems Group,
Redondo Beach, CA, June, 1976.
2. Cleland, J. G., and G. L. Kingsbury, Multimedia Environmental
Goals for Environmental Assessment, Volumes I and II, Final
Report.Report No. EPA-600-7-77-136a, b, EPA Contract No.
68-02-2612. RTI, Research Triangle Park, N.C., November,
1977.
3. American Public Health Assn., American Water Works Assn., and
Water Pollution Control Federation, Standard Methods for the
Examination of Water and Wastewater, 14th ed., Washington,
D.C., 1975.
4. Schalit, L. M., and K. J. Wolfe, SAM/1A: A Rapid Screening
Method for Environmental Assessment of Fossil Energy Process
Effluents, Draft. EPA Contract No. 68-02-2160. Acurex
Corporation/Energy and Environmental Division, Mountain
View, CA, January, 1978.
168
-------
APPENDIX
BIOASSAY,
INFRARED SPECTROPHOTOMETRY,
LIQUID CHROMATOGRAPHY AND
LOW RESOLUTION MASS SPECTROMETRY DATA
FOR A CHAPMAN GASIFICATION FACILITY
Page
Introduction 171
Coal Feeder Vent, Combined Particulate Train
CH2C12 Wash 177
Coal Feeder Vent, Combined Organic Module Extracts 189
Separator Vent, Combined Particulate Train
CH2C12 Wash 201
Separator Vent, Combined Organic Module Extracts 213
Separator Liquor, CH2C12 Extract 225
By-Product Tar, CH2C12 Extract 237
169
-------
APPENDIX
INTRODUCTION
The Level I bioassay and organic analyses methodology
given in the IERL-RTP "Procedures Manual: Level 1 Environmental
Assessment" was followed for the samples taken at the coal gasi-
fication test site. The samples analyzed are from the following
four locations.
• Coal Feeder Vent - The coal is fed to the gasifier
by a barrel valve. Since product gas from the gas-
ifier can leak past this barrel valve into the coal
feed chute, the chute is vented to the atmosphere.
The particulate catch and rinses were analyzed
separately from the XAD resin catch and organic
condensate from this location.
Separator Vent - Vapors above the liquor in the
separator are exhausted to the atmosphere using a
steam ejector. The sample taken from this loca-
tion was divided into a particulate catch and
rinses and an XAD resin catch and organic conden-
sate and analyzed separately.
Separator Liquor - The hot product gas is cooled
and scrubbed with recirculated separator liquor.
A sample of this liquor was extracted and analyzed.
By-Product Tar - A sample of the tar layer from
the liquor separator was extracted and analyzed.
A diagram of the coal gasification test site with these sample
points indicated is given in Figure A-l.
The results of the bioassay tests are summarized in
Table A-l. From these results, the coal feeder vent, separator
vent, and by-product tar may have a high potential for hazard-
ous health effects, while the gasifier ash, cyclone dust and
separator liquor may have a low potential. All the streams
except the gasifier ash may have a high potential for hazardous
ecological effects. »
170
-------
Coal Feeder Fokehole Liquor Trap
Coal Dust .Vent Gases Gases Vapors
Fugitive
Separator
Vapors
Gasifler Cyclone Dust
Ash
By-Product Tars
and Oils to
Utility Boilers
Evaporator
Gases
Low-Btu Gas to
Process Furnaces
Figure A-l. SIMPLIFIED PROCESS FLOW DIAGRAM FOR THE CHAPMAN FACILITY
SHOWING WASTE AND PROCESS STREAMS AND SAMPLING POINTS
-------
Table A-l. BIOASSAY TEST RESULTS FOR THE CHAPMAN COAL GASIFICATION FACILITY
K>
HEALTH TESTS
1. Ames
2. Cytotoxicity3
WI-38, ECso (cell count, Mg
solid, m3 gas /mi culture)
RAM, ECso (cell count, Mg
solid & liquid, m1 gas /mi
culture)
3. Rodent Acute Toxicity
LDso (g sample/kg rat)
Coal
Feed (s)
SP
>60
>1000
M
>10
Coal Coal Feeder
Feeder . Vent Gas
Vent XAD-2
Gas* (g) Extract*(g)
P
4 x 10"*
>2 x 10~*
-
-
Gasifier
Ash*(s)
N
-
>300
L
>10
Cyclone
Dust*(s)
N
-
>1000
M
>10
By-Product
Tar(s)
P
-
>1000
H
>10
Separator
Vent Gas
XAD-2 Separator
Extract* (g) Liquor (1)
SP N
7 x 10"5
>1 x 10"5 >600
L
>10
ECOLOGICAL TESTS
Fresh Water
Algal, ECso (15 days)
Daphnia, LCso (48 hours)
Fathead minnow, LCso (96 hours) -
Salt tfaterb
Algal, ECso (12 days)
filter/unfiltered
Shrimp, LCso (96 hours)
Sheepshead minnows, LCso
(96 hours)
Terrestrial
Soil microcosm 3
Plant stress ethylene
1.0 to 0.1%
0.11%
0.02%
0.53/0.41%
0.25%
0.16%
(g) : gas, (s): solid, (1): liquid
Indicates a plant waste stream
SP: Slightly positive
P: Positive
N: Negative
H: High toxicity
M: Medium toxicity (i.e., rats showed hair loss, eye discoloration, etc.)
L: Low toxicity (.i.e., no significant effects noted)
aECso's were calculated on the XAD-2 extract for the coal feeder and separator vent gases by:
ECso »
ECso reported
in y£ of extract
per m£ culture
mg of organics
extracted per mi
of extract
[ng of
?er N,
rent i
organicsI
Nms of
gas
Nms vent gas/mi culture
ECso fs and LCso's for f»-esh nnd salt water tests are presented in wt% of the sample in water.
C5oil microcosm tests are ranked from No. 1, the most toxic, to No. 5, the least toxic.
-------
The Level 1 organic analysis scheme that was used is
shown in Figure A-2. The results of infrared, liquid chromato-
graphy fractionation and low resolution mass spectrometry are
presented in the following tables.
173
-------
Extract as Necessary
Concentrate to 100 ml
i\ 121 131 4 151 161 171 8
TCO +• Grav
Level 1
Concentration Criteria
No
1 Stop
Stop
Figure A-2. LEVEL 1 ANALYTICAL SCHEME
174
-------
COAL FEEDER VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
175
-------
COAL FEEDER VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
INFRARED ANALYSIS
TCO = 1200 mg
Grav = 36000 mg
Total = 1600 mg/m3
IR:
Major Peaks, cm"
Intensity
Assignment
3650-2300
3050
2900-2840
1710-1690
1600
1440-1450
1375
1360
1330-1100
1030
950
880, 840, 810, 740
700
610
Comments : Strongly aromatic ,
probably present.
M
S
S
M
S
S
S
S
S
S
M
S
M
M
-NH, -OH
Aromatic CH
Aliphatic CH
Carbonyls
Aromatic ring, amines
Aliphatics
Aliphatics
Aliphatics, heterocyclic
0
Heterocyclic 0
Esters
Alkenes
Aromatic substitution
Aromatic substitution
Alkenes
heterocyclic N and heterocyclic 0
LC FRACTIONATION RESULTS
Quantity taken for LC: 6.97 mg TCO, 201 mg Grav, 0.56% Total
sample
Fraction
LC 1
LC 2
LC 3
LC 4
LC 5
LC 6
LC 7
LC 8
TCO mg
14
5.4
620
47
92
1600
130
45
Grav mg
2700
900
13000
7600
3200
16000
3800
2000
Total mg
2700
900
14000
7600
3300
18000
3900
2000
Total mg/m3
110
37
580
310
140
740
160
83
176
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COAL FEEDER VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 1
INFRARED ANALYSIS
TCO
Grav =
Total =
14 mg
2700 mg
110 mg/m3
IR:
Major Peaks, cm"
Intensity
Assignment
3600-3150
3040
2960-2820
1680-1600
1440
1400
1350
1090-1050
1010
720
Comments: Mostly aliphatics and
1100-1000 cm"1 may be
LRMS
Categories, present
Intensity
M -OH, water
W Aromatic CH
S Aliphatic CH
S Alkenes , water
W Alkanes
M Alkenes
W Alkanes
S Aliphatic ethers,
alcohols
S Alcohols
S Halogens
olefinics. Region from
stopcock grease.
REPORT
100 Aliphatic Hydrocarbons
Subcategories, specific compound
Intensity
100 Aliphatic Hydrocarbons
a. Alkanes, cycloalkanes
b. Alkenes
177
-------
COAL FEEDER VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 2
INFRARED ANALYSIS
TCO = 5.4 mg
Gray - 900 mg
Total = 37 mg/m9
IR:
Major Peaks, cm
3550-3100
2990-2820
1650
1450-1410
1370
1150
1100-1000
-i
Intensity Assignment
M -OH, water
S Aliphatic CH
M Water
M Silicone grease
M Aliphatics
M Aliphatics
S Silicone grease, R-0
Comments: No aromatic CH, no benzene substitution patterns.
LR/MS indicates phthalates and esters which cannot
be confirmed. Silicone grease is present.
LRMS REPORT
Categories, present
Intensity
100 Aliphatic Hydrocarbons
10 Carboxylic Acids and Their Derivatives
Subcategories, specific compounds
Intensity
100 Aliphatic Hydrocarbons
a. Alkanes
b. Alkenes, cycloalkanes
10 Carboxylic Acids and Their Derivatives
a. Phthalates
178
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COAL FEEDER VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 3
INFRARED ANALYSIS
TCO
Grav =
Total =
620 mg
13000 mg
580 mg/m3
IR:
Major Peaks, cm~'
3045
2990-2840
1900
1725-1650
1440
1395, 1375
1310, 1300
1260, 1240
1185
1160-1100
175, 1030
945
875, 840, 750, 710
615
Intensity Assignment
S Aromatic CH
S Aliphatic CH
M Aromatic overtones
M Carbonyls
S Aliphatics
S Aliphatics
S Esters
S Esters, aromatic ethers
S Aliphatic ethers
M Aliphatic ethers
M Aromatic ethers, alkanes
M Alighatics
S Aromatic substitution
W Halogens
Comments: Contains much aromatic material, possibly aldehydes,
some ethers, and a lot of PAH's. LR/MS does not
confirm the carbonyls or ethers.
LRMS REPORT
Categories, present
Intensity
100 Polycyclic Aromatic Hydrocarbons
Subcategories, specific compounds
Intensity
100
Polycyclic Aromatic Hydrocarbons
a. Napthalene, alkyl series
MW 128-156
b. Acenaphthylene
MW 152
c. Phenanthrene/anthracene
MW 178
d. Pyrene/fluoranthene
MW 202
e. Chrysene
MW.228
f. Benzopyrene, alkyl series
MW 252, 276, 302, 326, 352
179
-------
COAL FEEDER VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 4
INFRARED ANALYSIS
TCO - 47 mg
Grav - 7600 mg
Total - 310 mg/ma
IR:
Major Peaks, cm ' Intensity
3410 S
3350-3150 M
3045 S
2950-2800 S
2300 W
2210 W
1910 M
1720-1680 S
1460-1440 S
1380 S
1325 S
1265 S
1240 S
1190, 1150 S
1115, 1070, 1025 S
950 S
875, 840, 810, 745, 700 S
Assignment
-NH
-NH, -OH
Aromatic CH
Aliphatic CH
Isocyanates
Nitriles
Aromatic overtones
Carbonyls
Aliphatics
Aliphatics
Aliphatics, amides
Heterocyclic N
Esters, aliphatics,
aromatic ethers
Phenols, esters,
aliphatic ethers
Amines, phenols, ethers,
alcohols
Alkenes
Aromatic substitution
Comments: Much larger C-0, C-K regions from LC 3. PAH's still
? resent. Heterocyclic N and -0 probable, esters
ikely. LR/MS does not confirm carbonyl containing
compounds.
LRMS REPORT
Categories, present
Intensity
100
100
100
Polycyclic Aromatic Hydrocarbons
Heterocyclic Nitrogen Compounds
Polycyclic Aromatic Hydrocarbons
a. Pyrene, alkyl series
MW 202, 228, 252, 276, 302, 326,
100 Heterocyclic Nitrogen Compounds
a. Carbazole, alkyl series
MW 167
b. Benzocarbazole, alkyl series
MW 217
u. Dibenzocarbazole, alkyl series
MW 276
d. Azapyrene, alkyl series
MW 217
352
180
-------
COAL FEEDER VENT
COMBINED PARTICIPATE TRAIN CH2C12 WASHES
LC 5
INFRARED ANALYSIS
TCO
Grav =
Total =
92 mg
3200 mg
140 mg/m3
IR:
Major Peaks, cm ' Intensity
3650-3100 S
3050 S
2990-2840 S
2220 S
1710-1680 M
1600 S
1450-1440 S
1390, 1375 S
1350-1100 S
1265 S
1030 S
950 M
880, 820, 800, 740, 700 S
Assignment
-NH, -OH
Aromatic CH
Aliphatic CH
Nitriles
Carbonyls
Aromatic ring
Aliphatics
Aliphatics
Esters, heterocyclic 0,
heterocyclic N
Aromatic-NH
Aliphatic ethers,
alcohols
Alkenes
Aromatic substitution
Comments: Aromatic substitution patterns stronger than LC 4,
-NH and C-0 less well defined. Nitriles definitely
present, amines, and/or heterocyclic N. LR/MS still
does not confirm carbonyl compounds.
LRMS REPORT
Categories. present
Intensity
100 Heterocyclic Nitrogen Compounds
Subcategories, specific compounds
Intensity
ICO Heterocyclic Nitrogen Compounds
a. Naphthonitrile, alkyl series
MW 153, 167. 181, 195, 209
b. Azapyrene, alkyl series
MW 203, 217, 231
c. Azabenzofluoranthene
MW 227, 241, 255, 269
Other; Heterocyclic nitrogen compounds could contain some
oxygen, for example, m/e 195, 209, 223.
181
-------
COAL FEEDER VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 6
INFRARED ANALYSIS
TCO - 1600 mg
Grav - 16000 mg
Total - 740 mg/ms
IR:
Major Peaks, cm '
3650-2300
3050
2990-2840
1900
1710-1685
1665-1590
1450
1375
1265
1320-1100
1035
950
875, 810, 740, 700
Intensity Assignment
S -OH, -NH, water
S Aromatic CH
S Aliphatic CH
W Aromatic overtones
M Carbonyls
S Aromatic ring,
polyhydroxy aromatics
S Aliphatics
S Aliphatics
S Heterocyclic N, CH,C1
S Heterocyclic 0, N
M Phenols
M Alkenes
S Aromatic substitution
Comments: More acidic material than in LC 5. Phenols are pre-
sent, heterocyclic 0 and heterocyclic N probable.
LRMS REPORT
Categories, present
Intensity
100 Phenols
100 Heterocyclic Nitrogen Compounds
Subcategories, specific compounds
Intensity
100 Phenols
a. Phenol, alkyl series
MW 94, 108, 122
b. Naphthol, alkyl series
MW 144, 158
u. Fluorenol, alkyl series
MW 182, 196
100 Heterocyclic Nitrogen Compounds
a. Quinoline, alkyl series
MW 129, 143
b. Acridine, alkyl series
MW 179, 193
c. Azabenzopyrene, alkyl series
MW 253, 267
Other: There are lots of compounds between m/e 300-400 that
cannot be interpreted.
182
-------
COAL FEEDER VENT
COMBINED PARTICIPATE TRAIN CH2C12 WASHES
LC 7
INFRARED ANALYSIS
TOO
Grav =
Total =
130 mg
3800 mg
160 mg/m3
IR:
Major Peaks, cm'1
3500-2300
3050
2900-2130
1710-1685
1650-1630
1510-1500
1440
1375
1260
1300-1100
950
890-850. 780, 760, 730
Intensity
S
s
S
M
S
S
S
s
s
s
M
M
Assignment
-OH, -NH
Aromatic CH
Aliphatic CH
Carbonyls
Aromatic ring, g-
naphthols
Aromatic ring
Aliphatics
Aliphatics
Heterocyclic N
Heterocyclic 0, phenol's
Alkenes
Aromatic substitution
Comments: Heterocyclic 0 compounds probable, phenols and
heterocyclic N possible. IR does not confirm sulfur
compounds found by LR/MS.
LRMS REPORT
Categories, present
Intensity
100 Heterocyclic Oxygen Compounds
100 Carboxylic Acids and Their Derivatives
10 Sulfonic Acids, Sulfoxides
Subcategories, specific compounds
Intensity
100 Heterocyclic Oxygen Compounds
a. Benzonaphthofuran
MW 232, 246, 260
10 Carboxylic Acids and Their Derivatives
a. Malonic acid
MW 282
10 Sulfonic Acids, Sulfoxides
a. Aromatic Sulfoxides
MW 308
Other: IR shows no sulfur containing compounds. '•
183
-------
COAL FEEDER VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 8
INFRARED ANALYSIS
TCO - 45 mg
Grav = 2000 mg
Total = 83 mg/m3
IR:
Major Peaks, cm"1 Intensity Assignment
No IR bands for aliphatic or aromatic CH. Water is
present.
LRMS REPORT
Categories, present
Intensity
100 Carboxylic Acid and Their Derivatives
100 Carboxylic Acids and Their Derivatives
a. Esters, methyl esters of long chain
carboxylic acids
184
-------
ORGANIC EXTRACT SUMMARY, COAL FEEDER VENT SAMPLE, COMBINED PARTICULATE TRAIN
CH2C12 WASH
oc
LCI
LC2
LC3
LC4
LC5
LC6
LC7
Category
Int/mg/m3
LC8
Total organics,
mg/m3
TCO, rag
GRAV, mg
110
14
2700
37
5.4
900
580
620
13000
310
47
7600
140
92
3200
740
1600
16000
160
130
3800
83
45
2000
Aliphatic Hydrocarbons
Carboxylic Acids & Deriv-
atives
100/110
•
Polycyclic Aromatic
Hydrocarbons
Heterocyclic N Compounds
Phenols
Heterocyclic 0 Compounds
Sulfonic Acids and Sul-
foxides
;
100/34
10/3.4
100/580
100/155
100/155
100/140
100/370
100/370
10/13
100/130
10/13
100/83
Int: • Intensity
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACTS
186
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACTS
INFRARED ANALYSIS
TCO = 7900
Grav = 11000 mg
Total = 780 mg/m3
IR:
Major Peaks , cm * Intensity
3540 M
3506-3100 M
3050, 3010 S
2980-2820 S
1595 S
1510-1490 S
1450 S
1420 S
1385 S
1290-1300 M
1265 S
1185 S
1120-1100 M
1030-1000 M
940 M
905, 870, 850, 825, 805 M
Comments: Strongly aromatic sample,
and phenols .
LC FRACTIONATION
Assignment
-OH (free)
-NH, -OH (bonded)
Aromatic CH
Aliphatic CH
Aromatic ring
Aromatic ring
Aliphatics
Aliphatics
Aliphatics
Phenolic C-0
Heterocyclic N or 0
Ethers
Phenols , aromatics
Aliphatic ethers ,
alcohols
Alkenes
Aromatic substitution
probably rich in N-heterocycles
RESULTS
Quantity taken for LC: 310 mg TCO, 420 mg Grav; 3.94% Total
sample
Fraction TCO mg Grav mg
LC 1 370 130
LC 2 3600 2700
LC 3 130 2100
LC 4 99 380
LC 5 0.25 51
LC 6 870 1000
LC 7 0.76 150
LC 8 28 430
Total mg Total mg/m3
500 21
6300 260
2200 91
480 20
51 2.1
1900 79
150 6.2
460 19
187
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 1
INFRARED ANALYSIS
TCO = 370 mg
Grav • 130 mg
Total - 21 mg/m'
IR:
Major Peaks. cm"' Intensity Assignment
2980-2820 S Aliphatic CH
1460 M Aliphatics
1375 M Aliphatics
Comments: Mostly straight chain aliphatics, not much evidence
of extensive branching. IR does not show any
aromatics found by LR/MS.
LRMS REPORT
Categories, present
Intensity
100 Aliphatic Hydrocarbons
100 Aromatic Hydrocarbons
100 Polycyclic Aromatic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Aliphatic Hydrocarbons
a. Alkanes
b. Alkenes
c. Cycloalkanes
100 Aromatic Hydrocarbons
a. Benzene, alkyl series
MW 78-148
100 Polycyclic Aromatic Hydrocarbons
a. Naphthalenes, alkyl series
MW 128-156
188
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 2
INFRARED ANALYSIS
IR:
TCO - 3600 mg
Grav - 2700 mg
Total • 260 mg/ma
Major Peaks, em"
3050 S
3020 S
2970-2840 S
1920 W
1620 M
1590, 1505 S
1490, 1475, 1445, 1425 S
1395 M
1380 S
1320-1300 M
1265 M
1200-1185 S
1160, 1145, 1125 M
1080 M
985, 950 M
900, 840 S
830, 810, 780, 770, 735, 725 S
695 M
Assignment
Aromatic CH
Aromatic CH
Aliphatic CH
Aromatic overtones
Aromatic ring
Alkyl toluenes
Aliphatlcs
Allphatlcs
Allphatlcs
Amines, esters
Alkyl benzenes
Ethers, alcohols, esters
Aromatic overtones,
ethers
Alkyl benzenes
Alkenes
Aromatic substitution
Aromatic substitution
Aromatic substitution
Comments: Aromatic and aliphatic hydrocarbons, may contain
R-O-R although not confirmed by LR/MS, Possible com-
pounds: alkylated benzenes and similar aromatlcs,
benzo-pyrene, pyrene, perylene, phenanthrene,
anthracene.
LRMS REPORT
Categories , present
Intensity
100 Polycyclic Aromatic Hydrocarbons
Subcategories , specific compounds
Intensity
100 Polycyclic Aromatic Hydrocarbons
a. Naphthalene, aikyl series
MW 128-156
b. Acenaphthylene
MW 112-166
c. Acenaphthene
MW 154-168
d. Phenanthrene/anthracene
MW 178-192
r : Fluorene , indene
189
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 3
INFRARED ANALYSIS
TCO - 130 mg
Grav - 2100 mg
Total - 91 mg/m3
IR:
Major Peaks, cm"'
3045
2060-2840
1615
1590
1500-1470
1445
1395, 1375
1310, 1290
1188
950
875, 810, 735
830. 690
Intensity
S
H
M
M
M
S
H
M
S
M
S
H
Assignment
Aromatic CH
Aliphatic CH
Aromatic or olefinic
C-C
Aromatic ring
Aromatic ring
Aliphatics
Aliphatics
Aliphatics
Ethers
Alkenes
Aromatic substitution
Aromatic substitution
Weak Peaks: 1525
Comments: Very similar to LC 2, not as well resolved, aroraatics
stronger with respect to aliphatic CH.
LRMS REPORT
Categories, present
Intensity
100 Polycyclic Aromatic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Polycyclic Aromatic Hydrocarbons
a. Acenaphthylene, alkyl series
MW 152-166
b. Phenanthrene/anthracene, alkyl series
MW 178-192
t. Pyrene/fluoranthene
MW 202-216
d. Benzopyrene
MW 252-266
e. Chrysene
MW 228-242
190
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 4
INFRARED ANALYSIS
IR:
TCO = 99 mg
Grav - 380 mg
Total » 20 mg/m3
Maj or Peaks, em '
3510 W
3400 S
3400-3120 M
3040 M
2980-2825 M
2200 W
1620-1580 M
1490-1480 M
1445 S
1450-1400 M
1370 S
1325 S
1235. 1200 S
1020 M
840, 800 M
750, 720 S
Assignment
-OH
-NH
-NH, -OH
Aromatic CH
Aliphatic CH
Nitriles
Aromatic ring amines
Aromatic ring, amines
AromaCics
Aliphatics
Aliphatics
Aromatic amines
Ethers, alcohols
Aliphatic C-0
Aromatic substitution
Aromatic substitution
Comments: Definite -NH, probably includes aromatic amines and
N-heterocycles. Broad 1600 cm"1 region implies
aliphatic amines.
LRMS REPORT
Categories, present
Intensity
100 Heterocyclic Nitrogen Compounds
10 Thiols
Subeategories, specific compounds
Intensity
100
Heterocyclic Nitrogen Compounds
a. Carbazole, alkyl series
MW 167-181
b. Benzocarbazole, alkyl series
MW 217-231
Indole, alkyl series
MW 117, 131, 145, 159
10
Thiols
Aminothiophenol
MW 153
191
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 5
INFRARED ANALYSIS
TCO = 0.25 mg
Grav - 51 mg
Total - 2.1 mg/ra1
IR:
Maj or Peaks. cm"'
3600-3100
3100-3000
2980-2800
2120
1650
1600-1570
1470-1410
1375
1310-1130
1265
1200
1010
880. 830-800, 770, 745
690
Assignment
S -OH, -NH
H Aromatic CH
S Aliphatic CH
H Nltriles
S Water
S Aromatic ring
S Aliphatics
S Aliphatlcs
S Heterocyclic 0 or -N
S Sulfates
S Heterocyclic 0 or -N
S Aromatic ethers
M Aromatic substitution
W Aromatic substitution
Comments: Phenols probably present, aromatic oxygen and nitrogen
compounds possible. Also sulfur containing compounds.
LR/MS does not confirm oxygenated compounds.
LRMS REPORT
Categories, present
Intensity
100 Heterocyclic Sulfur Compounds
100 Heterocyclic Nitrogen Compounds
10 Nltriles
Subcategories, specific compounds
Intensity
100 Heterocyclic Sulfur Compounds
a. Dlbenzothiophene, alkyl series
MW 184, 198, 212
100 Heterocyclic Nitrogen Compounds
a. Acridine
MW 179
b. Benzo(d,e,f)carbazole
MW 191
10 Nitriles
a. Naphthonitrile, alkyl series
MW 153, 167, 181
192
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACT
LC 6
INFRARED ANALYSIS
IR:
TCO = 870 mg
Grav - 1000 mg
Total - 79 mg/m$
Major Peaks, cm '
Assignment
860,
Comments
3600-3250
3050
2950-2820
1700-1680
1610-1590
1550
1510-1500
1460-1450
1380
1265
1230-1210
1150, 1110
835, 810, 700
735
S
S
S
M
S
M
S
S
S
S
S
M
M
S
: Mainly phenols, cresols ,
some heterocyclic N.
LRMS
-OH
Aromatic CH
Aliphatic CH
Carbonyls
Aromatic ring, amines
Aromatic ring
Phenols
Aliphatics
Aliphatlcs
Carboxylic acids
Phenols
Phenols, esters
Aromatic substitution
Aromatic substitution
carboxylic acids, possibly
REPORT
Categories , present
Intensity
100 Phenols
10 Heterocyclic Nitrogen Compounds
Subcategories, specific compounds
Intensity
100 Phenols
a. Phenol, alkyl series
MW 94, 148
b. Benzene, dihydric, polyhydric
MW 110-126
c. Naphthols, alkyl series
MW 144, 158, 172
10 Heterocyclic Nitrogen Compounds
a. Acridine
MW 179
b. Benzoquinoline, alkyl series
MW 179, 192-207
193
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 7
INFRARED ANALYSIS
TCO - 0.76 mg
Grav = 150 mg
Total = 6.2 mg/m3
IR:
Major Peaks, cm
3600-2400
3050
2980-2820
1710-1670
1650-1560
1500
1455-1410
1400-1375
1340-900
840, 750
Intensity Assignment
S -OH, -NH
M Aromatic CH
S Aliphatic CH
S Carbonyls
S Aromatic and olefinic
C-C
M Aromatic ring
S Aliphatics
S Aliphatics
S C-0 and C-N
M Aromatic substitution
Comments: More aliphatic CH than aromatic, amines and
heterocyclic N and -0 possible.
LRMS REPORT
Categories, present
Intensity
100
10
Amines
a
Aniline, alkyl series
MW 79-135, 149
Naphthalene amine, alkyl series
MW 143-157, 171
Benzidine
MW 184
Heterocyclic Nitrogen Compounds
a. Quinoline, alkyl series
MW 129-157
b. Carbazole, alkyl series
MW 179-193, 207
194
-------
COAL FEEDER VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 8
INFRARED ANALYSIS
TCO = 28 mg
Grav « 430 mg
Total = 19 mg/m3
IR:
Major Peaks, cm ' Intensity Assignment
No IR bands.
LRMS REPORT
Categories, present
Intensity
Trace Carboxylic Acids and Their Derivatives
Subcategories, specific compounds
Intensity
Trace Carboxylic Acids and Their Derivatives
a. Chloroacetic acid
MW 94
b. Methyl esters of long chain carboxylic
acids
Other: m/e 73, 89, 112
195
-------
ORGANIC EXTRACT SUMMARY, COAL FEEDER VENT SAMPLE, COMBINED ORGANIC MODULE EXTRACTS
LCI LC2 LC3 LC4 LC5 LC6 LC7 LC8
Total organics,
mg/m3
TCO, mg
GRAV, mg
21
370
130
260
3600
2700
91
130
2100
20
99
380
2.1
0.25
51
79
870
1000
6.2
0.76
150
19
28
430
Category
Int/mg/m:
1
Aliphatic Hydrocarbons
Aromatic Hydrocarbons
Polycyclic Aromatic
Hydrocarbons
Heterocyclic N Compounds
Heterocyclic S Compounds
Thiols
Nitriles
Phenols
Amines
100/7
100/7
100/7
100/260
100/91
100/18
10/1.8
100/1
100/1
10/0.1
10/7.2
100/72
10/0.56
100/5.6
Int: Intensity
-------
SEPARATOR VENT
COMBINED PARTICIPATE TRAIN CH2C12 WASHES
197
-------
SEPARATOR VENT
COMBINED PARTICIPATE TRAIN CH2C12 WASHES
INFRARED ANALYSIS
TCO = 6.2 mg
Grav = 160 mg
Total - 11 mg/m3
IR:
Major Peaks, cm~
3600-3100
3040
2980-2840
1730-1680
1650
1590
1460-1400
1370
1300-1080
1070, 1020
870. 810
740
Intensity Assignment
M -OH. -NH
M Aromatic CH
S Aliphatic CH
W Carbonyls
S Aromatic ring, amines
S Aromatic ring
S Aliphatics
S Aliphatics
S Heterocyclic 0,
heterocyclic N
S Aliphatic C-0
M Aromatic substitution
S Aromatic substitution
Weak Peaks: 485, 460
Comments: Aromatic and aliphatic hydrocarbons, carboxylic acids,
heterocyclic N, heterocyclic 0 and phenols are probable.
LC FRACTIONATION RESULTS
Quantity taken for LC: 2.3 mg TCO, 57.6 mg Grav. 36.4% Total
sample
Fraction
LC 1
LC 2
LC 3
LC 4
LC 5
LC 6
LC 7
LC 8
TCO mg
0.14
0.03
0.08
0.06
0.03
-
-
0.03
Grav mg
28
11
19
19
22
47
14
22
Total mg
28
11
19
19
22
47
14
22
Total mg/m3
1.9
0.74
1.3
1.3
1.5
3.2
0.94
1.5
198
-------
SEPARATOR VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 1
INFRARED ANALYSIS
IR:
TCO - 0.14 mg
Grav = 28 mg
Total - 1.9 mg/m3
Major Peaks, cm"'
Intensity
Assignment
No IR bands with which to confirm LR/MS identification of
aliphatic hydrocarbons.
LRMS REPORT
Categories, present
Intensity
100 Aliphatic Hydrocarbons
1 Carboxylic Acids and Their Derivatives
1 Aromatic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Aliphatic Hydrocarbons
a. Alkanes, alkyl series
MW 86-268
composition: C6Hi j,-C2 gHi, 0
b. Alkenes, alkyl series
MW 84
1 Carboxylic Acids and Their Derivatives
a. Esters, phthalates
1 Aromatic Hydrocarbons
a. Benzenes, alkyl series
Other: 10 Sulfur, Se, MW 256
199
-------
SEPARATOR VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 2
INFRARED ANALYSIS
IR:
TCO = 0.03 mg
Grav = 11 mg
Total = 0.74 mg/m3
Major Peaks, cm"1 Intensity Assignment
IR sample heavily contaminated with silicone grease.
LRMS REPORT
Categories, present
Intensity
1
1
1
1
Aliphatic Hydrocarbons
Aromatic Hydrocarbons
Polycyclic Aromatic Hydrocarbons
Carboxylic Acids and Their Derivatives
Subcategories, specific compounds
Intensity
1 Aliphatic Hydrocarbons
a. Alkanes, alkyl series
1 Aromatic Hydrocarbons
a. Benzene, alkyl series
1 Polycyclic Aromatic Hydrocarbons
a. Napthalene, alkyl series
MW 128-156
1 Carboxylic Acids and Their Derivatives
a. Esters, phthalates
Other: 100 Silicones, cyclic polysiloxane, m/e 73, 135,
147. 197, 281
200
-------
SEPARATOR VENT
COMBINED PARTICIPATE TRAIN CH2C12 WASHES
LC 3
INFRARED ANALYSIS
IR:
TCO - 0.08 mg
Grav - 19 mg
Total - 1.3 mg/m3
Hal or Peaks, cm
3040-3000
2950-2800
1750-1650
1600
1440
1400-1360
1250
1150-900
800, 740
Assignment
W Aromatic CH
W Aliphatic CH
S Carbonyls
S Aromatic ring, alkenes
S Aliphatlcs
S Aliphatlcs
S Esters, phenols, ethers
S C-0
M Aromatic substitution
Comments: Substituted aromatics and possibly esters. Weak
spectrum.
LRMS REPORT
Categories, present
Intensity
100 Polycyclic Aromatic Hydrocarbons
1 Carboxylic Acids and Their Derivatives
.1 Fused Non-Alternant Polycyclic Hydrocarbons
Subcatefiories. specific compounds
Intensity
100 Polycyclic Aromatic Hydrocarbons
a. Naphthalene, alkyl series
MW 128-184
b. Acenaphthene
MW 154
c. Phenanthrene/anthracene
MW 178
d. Pyrene/fluoranthene
MW 202
c. Chrysene, alkyl series
MW 228
f. Benzopyrene, alkyl series
MW 252
g. Dibenzoperylene, alkyl series
MW 326
h. Benzoperylene, alkyl series
MW 352
i. Benzochrysene, alkyl series
MW 278
1 Fused Non-Alternant Polycyclic Hydrocarbons
a.. Pluorene
MW 166
201
-------
SEPARATOR VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 4
INFRARED ANALYSIS
TCO - 0.06 mg
Grav - 19 mg
>tal - 1.3 mg/ms
To
Major Peaks, cm '
3500-3300
3040-3010
2980-2800
1740-1680
1620-1550
1445
1400-1350
1300-1200
1070
920. 850, 670
Assignment
M -OH, -NH
H Aromatic CH
M Aliphatic CH
S Carbonyle
S Aromatic ring, alkenes
S Aliphatics
M Aliphatics
M Phenols, ethers, amines
S Aliphatic C-0, aromatic
overtones
W Aromatic substitution
Comments: Similar to LC 3, more carbonyl band, possibly
heterocyclic N.
LRMS REPORT
Categories, present
Intensity
100 Polycyclic Aromatic Hydrocarbons
100 Heterocyclic Nitrogen Compounds
100 Heterocyclic Sulfur Compounds
1 Carboxylic Acids and Their Derivatives
Subcategories, specific compounds
Intensity
100 Polycyclic Aromatic Hydrocarbons
a. Benzocoronene, alkyl series
MW 350-364
100 Heterocyclic Nitrogen Compounds
a. Azabenzoperylene
Other: Major comppunds in the fraction are in the m/e 250
m/e 420 range.
202
-------
SEPARATOR VENT
COMBINED PARTICIPATE TRAIN CL2C12 WASHES
LC 5
INFRARED ANALYSIS
IR:
TCO - 0.03 mg
Grav - 22 mg
Total - 1.5 mg/m3
Major Peaks, cm '
1720
3600-3100
3030 .
2980-2820
, 1710, 1695
1590
1510-1500
1440, 1370
1260
1190
1090, 1070. 1020
950, 880
800, 738
Assignment
M -OH, -NH
M Aromatic CH
S Aliphatic CH
S Carbonyls
S Aromatic ring, amines
S Aromatic ring
S Aliphatics
S Phenols, aromatic esters
S Aromatic ethers, amines
aliphatic ethers
S Aliphatic alcohols
S Alkenes
M Aromatic substitution
Weak Peaks: 1920-1860
Comments: Contains heterocyclic N and amines, probably alkyl
esters and phthalates, heterocyclic 0 and alcohols
are possible, not a heavily aromatic fraction.
LRMS REPORT
Heterocyclic Nitrogen Compounds
Heterocyclic Sulfur Compounds
Heterocyclic Oxygen Compounds
Carboxylic Acids and Their Derivatives
Heterocyclic Nitrogen Compounds
MW >217
100 Heterocyclic Sulfur Compounds
MW >270
100 Heterocyclic Oxygen Compounds
MW >276
1 Carboxylic Acids and Their Derivatives
a. Phthalates
Other: This fraction is similar to LC 4.
203
-------
SEPARATOR VENT
COMBINED PARTICIPATE TRAIN CH2C12 WASHES
LC 6
INFRARED ANALYSIS
TCO = neg.
Grav = 47 mg
Total = 3.2 mg/ms
IR:
Major Peaks, cm
3700-2200
3040
1680-1580
1460-1430, 1370
1275, 1255
1120-900
850-820
800, 740
680
Intensity Assignment
S -OH
S Aromatic CH
S Aromatic ring, alkenes,
amines
S Aliphatics
S Phenols
M Alkenes, alcohols, amines
M Aromatics, alkenes
M Aromatic substitution
W Alkenes, aromatic
substitution or
halogens
Comments: Phenols, possibly heterocyclic N or heterocyclic 0,
no carbonyls.
LRMS REPORT
Categories, present
Intensity
10 Phenols
10 Heterocyclic Nitrogen Compounds
Subcategories, specific compounds
Intensity
10 Phenols
a. Phenol, alkyl series
MW 94-150
10 Heterocyclic Nitrogen Compounds
a. Quinoline, alkyl series
MW 129-171
204
-------
SEPARATOR VENT
COMBINED PARTICIPATE TRAIN CH2C12 WASHES
LC 7
INFRARED ANALYSIS
TOO = neg.
Grav = 14 mg
Total = 0.94 mg/m3
IR:
Major Peaks, cm"
Intensity
Assignment
3600-2500
3020
2900-2840
1440
1375
1250, 750
Comments: Mostly water,
for carboxylic
S
W
M
S
W
W
probably phenols
acids.
-Ok, water
Aromatic CH
Aliphatic CH
Aliphatics , water
Aliphatics
CH2C12
, no good carbonyl band
LRMS REPORT
Categories , present
Intensity
100 Carboxylic Acids and Their Derivatives
10 Amines
Subcategories, specific compounds
Intensity
100 Carboxylic Acids and Their Derivatives
a. Dichlorobenzoic acid
MW 190
10 Amines
a. Aniline, alkyl series
MW 121-149
Other: Region between m/e 240 and 400 is very complex.
205
-------
SEPARATOR VENT
COMBINED PARTICULATE TRAIN CH2C12 WASHES
LC 8
INFRARED ANALYSIS
TCO = 0.03 mg
Grav = 22 mg
Total = 1.5 mg/m3
IR:
Major Peaks, cm"1 Intensity Assignment
No IR bands.
LRMS REPORT
Categories, present
Intensity
100 Alkyl Halides
10 Carboxylic Acids and Their Derivatives
Subcategories, specific compounds
Intensity
100 Alkyl Halides
a. Methyl chloride
MW 50-52
10 Carboxylic Acids and Their Derivatives
a. Esters, methyl esters of long chain acids
MW 278, 274, 287
b. Phthalates
MW 149
Other: 70 eV LRMS is too noisy to be interpreted.
206
-------
ORGANIC EXTRACT SUMMARY, SEPARATOR VENT SAMPLE, COMBINED PARTICULATE TRAIN CH2C12
WASHES
LC 1
LC 2
LC 3
LC 4
LC 5
LC 6
LC 7
LC 8
Total organic s
mg/m
• TCO, mg
, GRAV, mg
i
1.9
0.14
28
0.74
0.03
11
1.3
0.08
19
1.3
0.06
19
1.5
0.03
22
3.2
neg
47
0.94
neg
14
1.5
0.03
22
Category
Int/mg/m'
Aliphatic Hydrocarbons
Polycyclic Aromatic
Hydrocarbons
Heterocyclic N Compounds
Heterocyclic 0 Compounds .
Phenols
Amines
Carboxylic Acids and
Their Derivatives
Alkyl Halides
100/1.9
100/1.3
100/.43
100/.43
100/.48
100/.48
10/.048
10/1.6
10/1.6
10/.085
100/.85
100/.85
10/.14
10/.14
100/1.4
Int: Intensity
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
208
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
INFRARED ANALYSIS
TCO = 28000 mg
Grav = 34000 mg
Total = 4200 mg/m3
IR:
Major Peaks, cm"1
3510
3500-2100
3060-3020
2980-2840
1600, 1515
1475-1450
1380
1370-1300
1270-1170
1155
1110
1050-980
930
875, 845, 690
810, 785, 770, 750
Intensity Assignment
S Free -OH
S -OH, -NH
S Aromatic CH
S Aliphatic CH
S Aromatic ring
S Aliphatics
S Aliphatics
M Heterocyclic C-N
S Phenols
S Phenols, cresols
S Alcohols
M Alcohols
M Phenols
M Aromatic substitution
S Aromatic substitution
Weak Peaks: 2730
Comments: Predominately phenols with indications of hetero-
cyclic N.
LC FRACTIONATION RESULTS
Quantity taken for LC: 166 mg TCO, 202 mg Grav, in 0.59%
total sample
Fraction
LC 1
LC 2
LC 3
LC 4
LC 5
LC 6
LC 7
LC 8
TCO mg
14000
14000
9600
1200
4100
25000
800
200
Grav mg
7100
1900
1700
460
640
6300
700
1600
Total mg
21000
16000
11000
1700
4700
31000
1500
1800
Total mg/i
1400
1100
750
110
310
•- 2100
100
120
209
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 1
INFRARED ANALYSIS
TCO = 14000 mg
Grav = 7100 mg
Total = 1400 mg/m3
IR:
Major Peaks, cm Intensity
3080 W
2960. 2930, 2860 S
1465 M
1380 W
905 W
720 W
Assignment
Aromatic CH
Aliphatic CH
Aliphatics
Aliphatics
Alkenes
Aliphatics
Weaks Peaks: 1640
Comments: Predominately aliphatic hydrocarbons with some
branching, possibly contains a trace of aromatics.
LRMS REPORT
Categories, present
Intensity
100 Aliphatic Hydrocarbons
1 Aromatic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Aliphatic Hydrocarbons
a. Alkanes, alkyl series
b. Alkenes,
c. Cycloalkanes
1 Aromatic Hydrocarbons
a. Benzene, alkyl series
210
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 2
INFRARED ANALYSIS
TCO = uooo mS
Grav = 1900 mg
Total = 1100 ng/
IR:
Major Peaks, cm"'
3050, 3005
2960, 2910
2860
1595. 1505
1450
1385
1015, 1010
955, 940, 910, 845
810
780
765, 735, 690
715
470
Intensity Assignment
M Aromatic CH
S Aliphatic CH
M Aliphatic CH
M Aromatic ring
M Aliphatics
M Aliphatics
M Aromatic ethers
W Alkanes
M Aromatic substitution
S Aromatic substitution
M Aromatic substitution
W Aromatic substitution
M Aromatics
Weak Peaks: 1265, 1125, 610
Comments: Predominately aromatics with a good deal of aliphatic
substitution, probably PAH's.
LRMS REPORT
Categories, present
Intensity
100 Polycyclic Aromatic Hydrocarbons
1 Fused Non-Alternant Polycyclic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Polycyclic Aromatic Hydrocarbons
a. Naphthalene, alkyl series
MW 128-156, 170
b. Acenaphthene, alkyl series
MW 152-66
c. Phenanthrene/anthracene, alkyl series
d. Tetrahydroanthracene/phenanthrene
MW 184, 198
1 Fused Non-Alternant Polycyclic Hydrocarbons
a. Fluorene, alkyl series
MW 166, 182
211
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 3
INFRARED ANALYSIS
TCO = 9600 mg
Grav 1700 mg
Total 750 mg/m3
IR:
Major Peaks, cm
3050
3005
2860, 2860
2910
1595, 1505
1450, 1425
1385
1015, 1010
955, 940, 910
825
810, 765, 690
780, 735
Intensity Assignment
S Aromatic CH
M Aromatic CH
M Aliphatic CH
S Aliphatic CH
M Aromatic ring
M Aliphatics
W Aliphatics
M Aromatic overtones
W Aliphatics
W Aromatic substitution
M Aromatic substitution
S Aromatic substitution
Weak Peaks: 1195, 1185, 1125, 870, 610
Comments: Predominately aromatics, PAH1» and aliphatic
substituted aromatics.
LRMS REPORT
Categories, present
Intensity
100 Polycyclic Aromatic Hydrocarbon
1 Fused Non-Alternant Polycyclic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Polycyclic Aromatic Hydrocarbons
a.. Naphthalene, alkyl series
MW 128-156
b. Acenaphthylene, alkyl series
MW 152-180
c. Phenanthrene/anthracene, alkyl series
MW 178-192
d. Pyrene, alkyl series
MW 202-216, 230
e. Chrysene
MW 228, 242, 256
f. Dihydrochrysene
MW 230, 244
1 Fused Non-Alternant Polyoyclic Hydrocarbons
a. Fluorene, alkyl series
MW 166-182, 197
212
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 4
INFRARED ANALYSIS
TCO • 1200 mg
Crav • 460 mg
Total i 110 mg/ms
IR:
Major Peaks, cm"
3410
3070-3000
2960, 2929
2860
1630-1570
1480
1450
1375
1350-1300
1260
1190
1080
795
760, 715
740
Intensity Assignment
S -NH
W Aromatic CH
S Aliphatic CH
M Aliphatic CH
M Amines, aromatic ring
S Aromatic ring
S Aliphatics
W Aliphatics
W Amines
S Aromatic amines, ethers
S Alkanes
S C-N
S Aromatic substitution
W Aromatic substitution
M Aromatic substitution
Weak Peaks: 1150
Comments: Aromatic amines and heterocyclic N present.
LRMS REPORT
Categories, present
Intensity
100 Heterocyclic Nitrogen Compounds
10 Phenols
1 Carboxylic Acids and Their Derivatives
Subcategories, specific compounds
Intensity
100 Heterocyclic Nitrogen Compounds
a., Indole, alkyl series
MW 117-145
b. Carbazole, alkyl series
MW 167-181
c. Benzocarbazole
MW 217-231, 245
10 Phenols
a. Phenol, alkyl series
MW 94, 108, 122, 136, 150
Other: Thiophene MW 84-98
213
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 5
INFRARED ANALYSIS
TCO
Grav
Total
4100 mg
640 mg
310 mg/m3
IR:
Major Peaks, cm'1
3420
3020
2960, 2920
2860
2230
1730-1650
1590
1500, 1485, 1475
1460
1375, 1325
1260
1230, 1150
1195
1105
850, 840, 800
750
Intensity Assignment
S -OH
W Aromatic CH
S Aliphatic CH
M Aliphatic CH
W Nitriles
W Carbonyls
M Aromatic ring
S Aromatic ring
S Alkanes
W Alkanes, alcohols
M Phenols, esters, ethers
W Phenols
S Phenols, esters, ethers
M C-0
M Aromatic substitution
S Aromatic substitution
Weak Peaks: 1610, 1085, 925, 905
Comments: Predominately phenolic with nitriles and esters
probable.
LRMS REPORT
Categories, present
Intensity
100 Phenols
10 Heterocyclic Sulfur Compounds
1 Carboxylic Acids and Their Derivatives
Subcategories, specific compounds
Intensity
100 Phenols
a. Phenol, alkyl series
MW 94-170
b. Naphthol
MW 144, 158, 172
c. Phenyl phenol
10 Heterocyclic Sulfur Compounds
a. Thiophene, alkyl series
MW 84, 98
214
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 6
INFRARED ANALYSIS
TCO
Grav =
Total =
25000 mg
6300 mg
2100 mg/m3
IR:
Major Peaks, cm"1
Intensity
Assignment
3370
3030
2960, 2920, 2860
1595, 1510, 1495
1465
1380, 1310
1235
1150
1105
1065, 1040
995, 925
875, 840, 770, 705
805, 685
750
S
W
W
S
S
M
S
M
H
W
W
W
M
S
-OH, -NH
Aromatic CH
Aliphatic CH
Aromatic ring, amines
Aliphatics
Aliphatics
Phenols
Phenols
C-0
C-0
Aliphatics
Aromatic substitution
Aromatic substitution
Aromatic substitution
LRMS REPORT
Categories, present
Intensity
100 Phenols
10 Amines
Subcategories, specific compounds
Intensity
100 Phenols
a. Phenol, alkyl series
MW 94-136
b. Indanol, alkyl series
MW 134-148
c.
Naphthol
MW 144-158
215
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 7
INFRARED ANALYSIS
TCO = 800 mg
Grav = 700 mg
Total = 100 mg/m3
IR:
Major Peaks, cm ' Intensity Assignment
No IR bands
LRMS REPORT
Categories, present
Intensity
100 Phenols
10 Amines
Subcategories. specific compounds
Intensity
100 Phenols
a. Phenol, alkyl series
MW 94-136
10 Amines
a. Aniline, alkyl series
MW 107-149
216
-------
SEPARATOR VENT
COMBINED ORGANIC MODULE EXTRACTS
LC 8
INFRARED ANALYSIS
TOO = 200 mg
Grav = 1600 mg
Total = 120 mg/m3
IR:
Major Peaks, cm"1 Intensity Assignment
No IR bands except water.
LRMS REPORT
Categories, present
Intensity
Trace Carboxylic Acids and Their Derivatives
i
Trace Amines
Subcategories, specific compounds
Intensity
Trace Carboxylic Acids and Their Derivatives
a. Methyl esters of long chain carboxylic
acids
b. Esters, phthalates
Trace Amines
a. Aniline, alkyl series
MW 93, 107, 121
Other: Chloroacetic acid present, m/e 50, 52 major peaks.
217
-------
ORGANIC EXTRACT SUMMARY, SEPARATOR VENT SAMPLE. COMBINED ORGANIC MODULE. EXTRACTS
K3
1 — 1
00
LCI LC2 LC3 LC4 LC5 LC6 LC7 LC8
Total organics,
mg/m3
TCO, mg
GRAV, mg
1400
14000
7100
1100
14000
1900
750
9FOJ
1700
110
1200
460
310
4100
640
2100
25000
6300
100
800
700
120
200
1600
Category Int/rag/m3
Aliphatic Hydrocarbons
Polycyclic Aromatic
Hydrocarbons
100/1400
100/1100
100/750
Int: Intensity
-------
SEPARATOR LIQUOR
CH2C12 EXTRACT
219
-------
SEPARATOR LIQUOR, CH2C12 EXTRACT
INFRARED ANALYSIS
TCO - 490 rag
Grav - 680 mg
Total - 4.8 g/1
IR:
Maj or Peaks , cm
3700-3500
3040
2980-2900
2860
1590
1510, 1495
1465
1380-1340
1260-1200
1150
1110
1070
840, 810, 770
750, 690
ASBlgnment
S -OH
S Aromatic CH
S Aliphatic CH
M Aliphatic CH
S Aromatic ring
S Cresols, catechols,
aromatic ring
S Alkanes
S Alkanes
S Aromatic ethers
alcohols
S Aliphatic ethers
phenols
M Cresols
W Aliphatic C-0, C-N
M Aromatic substitution
Weak Peaks: 1040-1000, 925, 505
Comments: Aromatics, aliphatics, phenols, cresols appear to be
present. Heterocyclic N and possibly heterocyclic 0
is present. Carboxylic acids also are indicated.
LC FRACTIONATION RESULTS
Quantity taken for LC: 490 mg TCO; 680 mg Grav in 2.47. total
sample
Fraction
LC 1
LC 2
LC 3
LC 4
LC 5
LC 6
LC 7
LC 8
TCO mg
2.1
12
160
4100
6400
6500
3700
25
Grav mg
210
83
540
1800
7500
9200
5800
2400
Total mg
210
95
700
5900
14000
16000
9500
2400
Total mg/1
21
9.5
70
590
1400
1600
950
240
220
-------
SEPARATOR LIQUOR, CH2C12 EXTRACT
LC 1
IR:
INFRARED ANALYSIS
TCO = 2.1 mg
Grav = 210 mg
Total = 21 mg/1
Maj or Peaks, cm"1
3600-2000
2960-2850
1660-1580
1470-1370
1200-970
Intensity
S
S
S
S
S
Assignment
-OH
Aliphatic CH
H20
Aliphatics
Aliphatic C-0
Comments: Low molecular weight, linear aliphatics, very little
indication of aliphatic branching. Sample appears
to be wet.
LRMS REPORT
Categories, present
Intensity
100 Aliphatic Hydrocarbons
1 Aromatic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Aliphatic Hydrocarbons
a. Alkanes
b. Cycloalkanes
c. Alkenes
Other: MW up to 253, 295; aliphatics. Sulfur, S8, Intensity
10.
221
-------
SEPARATOR LIQUOR, CH2C12 EXTRACT
LC 2
INFRARED ANALYSIS
IR:
TCO = 12 mg
Grav = 83 mg
Total = 9.5 mg/1
Major Peaks, cm"1
3500-3000
2950-2920
1650
1400
Intensity
Assignment
HZ0
Aliphatic CH
H20
Aliphatics
Comments: Very similar to previous LC fraction. Primarily
aliphatic with evidence of moisture in the IR.
LRMS REPORT
Categories, present
Intensity
100 Aliphatic Hydrocarbons
1 Aromatic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Aliphatic Hydrocarbons
a. Alkane, alkyl series
b. Alkene, alkyl series
MW 168-196
Aromatic Hydrocarbons
a. Benzene, alkyl series
MW 92-106
Other: Sulfur, Se, Intensity 1.
222
-------
SEPARATOR LIQUOR, CH2C12 EXTRACT
LC 3
INFRARED ANALYSIS
TCO = 160 rag
Grav » 540 mg
Total - 70 mg/1
IR:
Major Peaks, cm'
3600-3100
3040
1730-1680
1600
1500-1419
1375
1260-1220
880
840, 810, 750
710
Assignment
W H20
H Aromatic CH
W Carbonyls
S Aromatic ring
S Aromatlcs, aliphatlcs
S Alkanes
S C-0 or C-N
S Conjugated aromatlcs
S Aromatic substitution
M Aromatic substitution
Comments: Fairly linear aliphatlcs, aromatlcs with little or no
functional substitution, most likely PAH's.
LRMS REPORT
Categories, present
Intensity
100 Polyeyclic Aromatic Hydrocarbons
Subcategorles, specific compounds
Intensity
100 Polyeyclic Aromatic Hydrocarbons
o. Naphthalene, alkyl series
b. Aeenaphthylene, alkyl series
MW 152-166
c. Phenanthrene/anthracene
MW 178, 192, 206
d. Pyren,e
MW 202, 216, 230
e. Benzopyrene
MW 252-268, 280
223
-------
SEPARATOR LIQUOR, CH2C12 EXTRACT
LC 4
INFRARED ANALYSIS
TCO - 4100 mg
Grav - 1800 mg
Total - 590 mg/1
IR:
Major Peaks, ca
Assignment
3600-3250
3050, 3015
2960-2850
1590
1505
1480, 1440, 1380
1330
1260
1230-1100
1050-1000
810-780, 765, 740, 690
Comments : Phenols present ,
also.
S
M
S
S
S
S
S
S
S
M
M
probably
-NH, -OH
Aromatic CH
Aliphatic CH
Aromatic ring, amines
Aromatic ring
Aliphatics
C-N
Heterocyclic N or 0
Heterocyclic 0
Cresols, alcohols
.Aromatic substitution
amines or heterocyclic N
LRMS REPORT
Categories, present
Intensity
100 Heterocyclic Nitrogen Compounds
10 Phenols
10 Heterocyclic Sulfur Compounds
Subcategories, specific compounds
Intensity
100 Heterocyclic Nitrogen Compounds
a. Benzocarbazole, alkyl series
MW 217-259
b. Carbazole, alkyl series
MW 167-195
10 Phenols
a. Phenol, alkyl series
MW 94-136
b. Naphthol, alkyl series
MW 144-172
10 Heterocyclic Sulfur Compounds
a. Dibenzothiophene, alkyl series
MW 184,198, 212, 226
224
-------
SEPARATOR LIQUOR, CH2C12 EXTRACT
LC 5
INFRARED ANALYSIS
TOO - 6400 mg
Grav » 7500 mg
Total - 1400 og/1
IR:
Major Peaks, cm"1
3600-2800
3060-3040
2960, 2920. 2860
1615-1590
1515
1490
1470-1450
1380
1360
1300-1175
1260
1150
1120
1050-900
840, 810, 770, 750, 690
Intensity
S
S
S
S
S
S
S
M
M
S
S
S
M
w
M
Assignment
-OH, -OH
Aromatic CH
Aliphatic CH
Aromatic ring
Aromatic ring
Aromatic ring
Aliphatics
Aliphatics
Aliphatics
Heterocyclic 0
Heterocyclic 0
Ethers, alcohols
Aliphatic ethers
Phenols
Aromatic substitution
Weak Peaks: 1555
Comments: Phenols, probably heterocyclic 0, possibly
heterocyclic N.
LRMS REPORT
Categories, present
Intensity
100 Phenols
10 Heterocyclic Oxygen Compounds
1 Heterocyclic Nitrogen Compounds
Subcategories, specific compounds
Intensity
100 Phenols
a. Phenol, alkyl series
MW 94-136, 150
b. Naphthol, alkyl series
MW 144-172
c. Acenaphthenol, alkyl series
MW 170, 184, 198
10 Heterocyclic Oxygen Compounds
a. Benzofuran, alkyl series
MW 118-132
225
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SEPARATOR LIQUOR, CH2C12 EXTRACT
LC 6
INFRARED ANALYSIS
TCO = 6500 mg
Grav - 9200 mg
Total - 1600 mg/1
IR:
Major Peaks. cm~' Intensity Assignment
3600-2800 S 'OH, -NH
3060-3040 S Aromatic CH
2960, 2929, 2860 S Aliphatic CH
1615-1590 S Aromatic ring
1515 S Aromatic ring
1490 S Aromatic ring
1470-1450 S Aliphatics
1380 H Aliphatics
1360 H Aliphatics
1300-1175 S Heterocyclic 0
1260 S Heterocyclic 0
1150 S Ethers, alcohols
1120 M Aliphatic ethers
1050-900 W Phenols
840, 810, 770, 750, 690 M Aromatic substitution
Comments: The -OH is more acidic than LC 5, phenols, and
probably heterocyclic 0 present.
LRMS REPORT
Categories, present
Intensity
100 Phenols
Subcategories, specific compounds
Intensity
100 Phenols
a. Phenol, alkyl series
MW 94-136
b. Indanol, alkyl series
MW 134-162
c. Naphthol, alkyl series
MW 144-172, 186, 200, 214
226
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SEPARATOR LIQUOR, CH2C12 EXTRACT
LC 7
INFRARED ANALYSIS
TCO - 3700 mg
Grav - 5800 mg
Total - 950 mg/1
IR:
Major Peaks, em'1
3600-2300
3050
2900-2850
1645
1620-1590
1510
1460-1440
1305-1415
1300-1150
1150-1050
830, 810, 765, 690
Assignment
S -OH
H Aromatic CH
M Aliphatic CH
S Alkenes
S Aromatic ring
S Aromatic ring
S Aliphatics
S Aliphatics
S Phenolic C-0
W Aliphatic C-0
W Aromatic substitution
Comments: Phenols definitely indicated, IR does not support
LR/MS thiophenols.
LRMS REPORT
Categories, present
Intensity
100 Phenols
100 Thiols
Subeategories, specific compounds
Intensity
100
100
Phenols
a. Benzene, dihydric, polyhydric
MW 110, 124, 138, 152
b. Naphthol
MW 138, 144
c. Phenol, alkyl series
MW 94
Thiols
a. Thiophenol, alkyl series
MW 110, 124, 138, 152
b. Thiophenol, phonyl, alkyl series
MW 186, 200, 214
227
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SEPARATOR LIQUOR
CH2C12 EXTRACT
LC 8
INFRARED ANALYSIS
TCO = 26 mg
Grav = 2400 mg
Total = 240 mg/1
IR:
Major Peaks, cm
3600-2600
2960-2850
1635
1600
1500
1450
1400-1350
1300-1150
1100-1050
1020
750
-i
Intensity Assignment
S -OH, H20
S Aliphatic CH
S Olefinic C
S Aromatic ring
S Aromatic ring
S Aliphatics
S Aliphatics
S Phenolic C-0
S Aliphatic C-0
S Aliphatics C-0 ,
M Aromatic substitution
Comments: Aliphatic carboxylic acids, quite probably, phenols
probable. Aliphatic alcohols are late for the LC
s cheme.
LRMS REPORT
Categories, present
Intensity
100 Glycols, Epoxides
100 Carboxylic Acids and Their Derivatives
Subcategories, specific compounds
Intensity
100 Glycols, Epoxides
a. Alkyl glycols
MW 118, 132, 146
100 Carboxylic Acids and Their Derivatives
a. Unsaturated carboxylic acid
MW 128, C7Hi202
228
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ORGANIC EXTRACT SUMMARY TABLE, SEPARATOR LIQUOR SAMPLE, CH2C12 EXTRACT
LC 1 LC 2 LC 3 LC 4 LC 5 LC 6 LC 7 LC 8
Total organics,
mg/1
TCO, mg
Grav , mg
21
2.1
210
9.5
12
83
70
160
540
590
4100
1800
1400
6400
7500
1600
6500
9200
950
3700
5800
240
25
2450
Category Int/mg/m3
ro
VO
Aliphatic Hydrocarbons
Polycyclic Aromatic
Hydrocarbons
100/19
100/9.5
100.70
Int: Intensity
-------
BY-PRODUCT TAR
CH2C12 EXTRACT
230
-------
BY-PRODUCT TAR, CH2C12 EXTRACT
INFRARED ANALYSIS
TCO = 66 mg
Grav = 1400 mg
Total = 770 g/kg
IR:
Major Peaks, cm
3600-2100
3050-3020
2960-2350
1600
1450
1375
1350-1100
1030
875
810
750
-i
Intensity Assignment
M -OH
M Aromatic CH
S Aliphatic CH
S Aromatic Ring, amines
S Aliphatics
S Aliphatics
S Phenols
W Alcoholic C-0
M Arpmatic substitution
S Aromatic substitution
S Aromatic substitution
Comments: Highly oxygenated material, phenols, substituted
nitrogen compounds or N-heterocycles possible.
LC FRACTIONATION RESULTS
Quantity Taken for LC:
6.5 mg TCO, 143 mg Grav in 9.9% total
samples
Fraction
LC 1
LC 2
LC 3
LC 4
LC 5
LC 6
LC 7
LC 8
TCO mg
6.1
3.6
68
10
35
30
0.6
7.4
Grav mg
200
71
470
190
120
560
180
160
Total mg
210
75
540
200
160
590
180
170
Total g/kg
110
39
280
100
83
310
95
89
231
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BY-PRODUCT TAR, CH2C12 EXTRACT
LC 1
INFRARED ANALYSIS
TCO = 6.1 mg
Grav = 200 mg
Total =• 100 g/kg
IR:
Major Peaks, cm"1 Intensity Assignment
3600-3100 M -OH
2910 S Aliphatic CH
2850 S Aliphatic CH
1640 W Water
1450 M Aliphatics
1370 W Aliphatics
Comments: Aliphatic hydrocarbons, no good indications of
halogens.
LRMS REPORT
Categories, present
Intensity
100 Aliphatic Hydrocarbons
Trace Aromatic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Aliphatic Hydrocarbons
a. Alkanes, Ci0-Ci8
b. Alkenes
232
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BY-PRODUCT TAR, CH2C12 EXTRACT
LC 2
INFRARED ANALYSIS
TCO = 3.6 mg
Grav = 71 mg
Total = 39 g/kg
IR:
Major Peaks, cm"1 Intensity Assignment
2590-2910 S Aliphatic CH
2850 M Aliphatic CH
1450 M Aliphatics
1375 W Aliphatics
Comments: Aliphatics, no strong halogen indications, no
strong aromatic bands.
LRMS REPORT
Categories, present
Intensity
100 Aromatic Hydrocarbons
10 Aliphatic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Aromatic Hydrocarbons
a. Benzene, alkyl series
MW 92-148
b. Naphthalene, alkyl series
MW 210, 224, 238
10 Aliphatic Hydrocarbons
a. Alkane, alkyl series
233
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BY-PRODUCT TAR, CH2C12 EXTRACT
LC 3
INFRARED ANALYSIS
TCO - 68 mg
Grav - 470 mg
Total - 280 g/kg
Major Peaks, em'1
3540
3040
2990-2850
1750-1670
1600
1440
1400
1375
1300
1260
1175
945
875
810
750
Assignment
W -NH
S Aromatic CH
S Aliphatic CH
M Carbonyls
S Aromatic ring
S Aliphatics
M Aliphatics
S Aliphatics
M Phenols, aromatic amines
N-heterocycles
M Aromatic amines,
aromatic esters
S Alyl phenols , amines,
S-0
M Aromatic esters,
aromatic amines
M Aromatic substitution
M Aromatic substitution
M Aromatic substitution
Weak Peaks: 2720, 465, 420
Comments: Aromatics, broad carbonyl peak is early in LC scheme
for aldehydes or ketones. Nitrogen compounds not
substantiated by LR/MS. Phenols are not likely nor
are they substantiated by LR/MS.
LRMS REPORT
Categories, present
Intensity
100 Polycyclic Aromatic Hydrocarbons
Subcategories, specific compounds
Intensity
100 Polycyclic Aromatic Hydrocarbons
a. Napthalene, alkyl series
MW 128-170, 184, 198
b. Acenaphthylene, alkyl series
MW 152, 166, 180
u. Acenaphthene, alkyl series
MW 154, 168, 182
d. Phenanthrene/anthracene, alkyl series
MW 178, 192, 206
e. Fluoranthene/pyrene, alkyl series
MW 202, 216, 230
f. Chrysene, alkyl series
MW 228
g. Benzopyrene, alkyl series
MW 252
Other: Fused polycyclic aromatics between m/e 300 m/e 400
234
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BY-PRODUCT TAR, CH2C12 EXTRACT
LC 4
INFRARED ANALYSIS
TCO - 10 rag
Gray - 190 mg
Total - 100 g/kg
IR:
Major Peaks, cm Intensity Assignment
3410 S -NH
3550-3150 M -OH, -NH
3040 S Aromatic CH
2950-2820 S Aliphatic CH
1600 S Aromatic ring, amines
1440 S Alkanes
1375 S Aliphaties, amines
1320 S Aliphaties
1260 S Aromatic amines
1230 M Aromatic amines or
esters
1190 M Aromatic amines
1025 M Aromatic ethers
875 M C-0, C-N
800 S Aromatic substitution
745 S Aromatic substitution
700 M Aromatic substitution
Comments: Stronger nitrogen indications than LC 3. Nitrogen
heterocycles probable, along with heavily substituted
aromatics, PAH's. Early in LC scheme for alcohols.
Possibly heterocyclic 0.
LRMS REPORT
Categories, present
Intensity
100 Polycyclic Aromatic Hydrocarbons
100 Heterocyclic Nitrogen Compounds
100 Heterocyclic Oxygen Compounds
Subcategories. specific compounds
Intensity
100 Polycyclic Aromatic Hydrocarbons
a. Coronene, alkyl series
MW 300, 326, 340, etc.
100 Heterocyclic Nitrogen Compounds
a. Carbazole, alkyl series
MW 167-209
100 Heterocyclic Oxygen Compounds
MW 280, 294, 308
235
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BY-PRODUCT TAR, CH2C12 EXTRACT
LC 5
INFRARED ANALYSIS
TCO - 35 mg
Grav - 120 mg
Total - 83 g/kg
IR:
Major Peaks, cm
3400
3050
3000-3800
2220
1600
1450
1380
1260
1190
1030
880
810
745
700
Assignment
S -OH, -NH
M Aromatic CH
S Aliphatic CH
W Nitriles
S Aromatic ring, amines
S Aliphatic C-C
S Aliphatic C-C
S Heterocyclic N, or -0
S Heterocyclic N, -0
M C-N, C-0
M Amines
S Aromatic substitution
S Aromatic substitution
M Aromatic substitution
Weak Peaks: 1680
Comments: Aromatic CH absorbance less than in the previous
fraction. Strong indications of amines and hetero-
cyclic N. The C-0 bands indicate either alcohols,
ethers, or heterocyclic 0. Nitriles are quite
probably present.
LRMS REPORT
Categories, present
Intensity
100 Heterocyclic Sulfur Compounds
10 Heterocyclic Nitrogen Compounds
10 Heterocyclic Oxygen Compounds
Subcategories. specific compounds
Intensity
100 Heterocyclic Sulfur Compounds
a. Dibenzothiophene, alkyl series
MW 184-212
10 Heterocyclic Nitrogen Compounds
a. Carbazole, alkyl series
MW 167, 181, 195
10 Heterocyclic Oxygen Compounds
a. Benzonaphthofuran, alkyl series
MW 246, 260, 274
236
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BY-PRODUCT TAR, CH2C12 EXTRACT
LC 6
INFRARED ANALYSIS
TCO - 30 mg
Grav 560 mg
Total - 310 g/kg
IR:
Major Peaks. cm~'
3600-2200
3080-3000
2980-2820
1600
1520-1050
900-800
740
700
Assignment
S -OH, -NH, -COOH
S Aromatic CH
S Aliphatic CH
S Aromatic ring, amines
S C-0, aliphatics,
aromatic ring
S Aromatic substitution
S Aromatic substitution
M Aromatic substitution
Comments: Huge acidic -OH region, spectrum broad and not well
defined.
LRMS REPORT
Phenols
Heterocyclic Nitrogen Compounds
Heterocyclic Sulfur Compounds
Heterocyclic Oxygen Compounds
Amines
Subcategories, specific compounds
Intensity
100 Phenols
a. Phenol, alkyl series
MW 94-136
b. Napthol, alkyl series
MW 144, 158, 172
Other: Due to the complexity of the LRMS, the heterocyclics can
not be interpreted into certain specific compounds.
237
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BY-PRODUCT TAR, CH2C12 EXTRACT
LC 7
INFRARED ANALYSIS
IR:
TCO - 0.6 mg
Grav - 180 mg
Total - 95 g/kg
Major Peaks, cm"'
3710-3150
3550-2250
3050
2950-2850
1600
1440
1375
1260
1260-1180
1080
860-780
750
Assignment
M -NH
S -OH, H20
S Aromatic CH
S Aliphatic CH
S Aromatic ring, amines
S Alkanes
S Alkanes
S Heterocyclic 0
M Heterocyclic 0
M Alcohols, alkyl phenols
W Aromatic substitution
S Aromatic substitution
Weaks Peaks.- 1640, 1630
Comments: Indicates phenols, possibly napthols. Weak peaks
possible for aliphatic and aromatic amines. LR/MS
does not confirm phenols or acidic -OH.
LRMS REPORT
Categories, present
Intensity
100 Amines
100 Heterocyclic Nitrogen Compounds
Subcategories. specific compounds
Intensity
100 Amines
a. Aniline, alkyl series
MW 93-121
100 Heterocyclic Nitrogen Compounds
a. Quinoline, alkyl series
MW 129-157
b. Hydroxyazanaphthalene
MW 145, 159, 173
Other: Lots of nitrogen containing compounds are indicated by
the data.
238
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BY-PRODUCT TAR, CH2C12 EXTRACT
LC 8
INFRARED ANALYSIS
IR:
TCO - 7.4 mg
Grav = 160 mg
Total • 89 g/kg
Major Peaks, cm
3600-3100
3050
2950
2850
1750-1690
1600
1530-1510
1445
1370
1320-1000
1260
1100
890
735
Assignment
M -OH, -NH, H 0
W Aromatic CH
S Aliphatic CH
M Aliphatic CH
M Carbonyls
S Aromatic ring
M Aromatic ring
S Alkanee
S Aliphatics
S C-0
S C-0
S Aliphatic alcohols,
ethers
M Aromatic substitution
M Aromatic substitution
Weak Peaks: 1400
Comments: Highly oxygenated, predominately aliphatic carboxylic
acids.
LRMS REPORT
Categories, present
Intensity
10 Alkyl Halides
10 Carboxylic Acids and Their Derivatives
Subcategories, specific compounds
Intensity
10 Alkyl Halides
a. Methyl chloride
MW 50-52
10 Carboxylic Acids ard Their Derivatives
a. Esters, methyl esters of long chain acids
MW 278, 274, 287
1 b. Phthalates
Other: m/e 146, m/e 147
239
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