x>EPA
United States
Environmental Protection
Agency
Industrial Environmental Research EPA-600/7-79-202
Laboratory August 1979
Research Triangle Park NC 27711
Pollutants from Synthetic
Fuels Production:
Environmental Evaluation
of Coal Gasification
Screening Tests
Interagency
Energy/Environment
R&D Program Report
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4, Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide-range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/7-79-202
August 1979
Pollutants from Synthetic Fuels Production
Environmental Evaluation of Coal
Gasification Screening Tests
by
D. G. Nichols, J. G. Cleland, D. A. Green,
F. 0. Mixon, T. J. Hughes, and A. W. Kolber
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
Grant No. R804979
Program Element No. EHE623A
EPA Project Officer: N. Dean Smith
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
-------
POLLUTANTS FROM SYNTHETIC FUELS PRODUCTION:
ENVIRONMENTAL EVALUATION OF COAL GASIFICATION SCREENING TESTS
ABSTRACT
A series of screening test runs have been performed using a laboratory-
scale, fixed-bed coal gasifier in order to study the potential pollutants
generated during the gasification of various coals. Potential pollutants have
been identified and quantitative analyses performed for tars, aqueous conden-
sates, volatile organics, primary gases and reactor residues. Tar partition
fractions have also been generated and studied for each coal providing dis-
tributions of insolubles, organic acids, organic bases, polar neutrals,
nonpolar neutrals, and polynuclear aromatic hydrocarbons. Species showing the
greatest potential for adverse health effects are: phenolic species and
polynuclear hydrocarbons in the tars and aqueous condensates; carbon monoxide,
benzene, and hydrogen sulfide in the primary gas streams; and trace elements
in the reactor residues, including arsenic, lead, and mercury. Bioassay tests
on various coal gasification effluents also have been performed. The crude
tars showed significant potential for inducing mutagenic changes in living
cells. The organic tar bases, polynuclear aromatics, and polar neutrals were
found to be responsible for this behavior. Overall, this study indicates that
the potential environmental problems of coal conversion, while reasonably
complex, can be resolved through a systematic approach involving chemical
testing and process control.
m
-------
TABLE OF CONTENTS
Section Page
Abstract 11 i
List of Figures v
List of Tables vi
Acknowledgements viii
1.0 Introduction 1
2.0 Screening Test Experiments 5
2.1 Coals Gasified 5
2.2 Reactor and Signal Processor 6
2.3 Sampling and Analysis 12
2.4 Bioassay Samples 17
3.0 Environmental Assessment Approach 18
3.1 Laboratory Gasification 18
3.2 Sampling and Analysis 19
3.3 MEG Methodology 21
3.4 Bioassay Tests 21
4.0 MEG Methodology Results 27
4.1 Introduction 27
4.2 Health-Based Results 27
4.3 Ecology-Based Results 62
4.4 Other Findings 63
5.0 Bioassay Results 66
5.1 Coal Dust Bioassays 66
5.2 Effluent Bioassays (Ames) 70
5.3 Effluent Bioassays (CHO) 80
6.0 Discussion of Results 84
6.1 Chemical Analysis Results 84
6.2 MEG Methodology Results 88
6.3 Bioassay Results 95
6.4 Other Considerations 102
7.0 Conclusions 105
References 108
Appendix 112
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LIST OF FIGURES
Number Page
1 Gasifier and sampling train 7
2 Partition scheme for crude tars 14
3 PNA fraction of coal gasifier tar by capillary GC-FID 15
4 Chinese hamster ovary cells in culture, control sample (25 yg
(DMSO). (Magnification: HOx) 68
5 Chinese hamster ovary cells in culture, Upper Freeport coal dust
sample (lOmg/ml). (Magnification: HOx) 69
6 Ames bioassay plates (Salmonella strain TA-98) 77
7 Ames bioassay plates (PNA fraction from Illinois No.6 coal
gasifier tar) 78
8 Ames bioassay plates (base-fraction from Wyoming subbituminous
coal gasifier tar) 79
9 Ames bioassay results for gasifier tar samples and tar fractions
from three gasification runs using Wyoming subbituminous coal
(Runs No.33, 35, and 47) 96
10 Ames bioassay results for gasifier tar samples from four separate
coals 97
11 Ames bioassay results for organic base fractions of gasifier tar
samples from four separate coals 98
12 Ames bioassay result for gasifier tar and fractions from Wyoming
coal 99
13 The effect of cadmium on the growth of Chinese hamster ovary
cells in culture 103
-------
LIST OF TABLES
Number Page
1 Operating Conditions for Selected Screening Tests 9
2 Tar and Partition Results for Selected Screening Test
Results (g produced/g coal loaded) 15
3 Primary Elements of Gasifier Tars 20
4 Comparison of Health and Ecology Based DMEG Values for
Aqueous Phase Pollutants 22
5 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.6, Illinois No.6 28
6 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.16, Illinois No.6 30
7 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.20, Illinois No.6 32
8 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.21, Illinois No.6 34
9 Potential Environmental Poollutants Ranked Via Discharge
Severity, Run No.23, Illinois No.6 36
10 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.25, Montana Rosebud 38
11 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.26, Montana Rosebud 40
12 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.32, Wyoming Subbituminous 42
13 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.33, Wyoming Subbituminous 44
14 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.35, Wyoming Subbituminous 46
15 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.36, North Dakota Lignite 48
16 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.38A, Illinois No.6 50
17 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.38B, Illinois No.6 52
18 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.41, Western Kentucky No.9 54
19 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.43, North Dakota Lignite 56
20 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.44, Illinois No.6 53
VI
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LIST OF TABLES (continued).
Number Page
21 Potential Environmental Pollutants Ranked Via Discharge
Severity, Run No.45, Wyoming Subbituminous 60
22 Ames Bioassay Results for Raw Coal Dust Samples 67
23 Chinese Hamster Ovary Cell Bioassay Results on Raw Coal Dust
Samples 71
24 Ames Bioassay Results for Coal Gasifier Effluents (Coal Type:
Western Kentucky No.9) 72
25 Ames Bioassay Results for Coal Gasifier Effluents (Coal Type:
Wyoming (Smith-Roland) Subbituminous 75
26 Ames Bioassay Results for Gasifier Tars and Tar Fractions .... 81
27 Cytotoxicity of Coal Gasifier Tars and Fractions to Chinese
Hamster Ovary Cells in Culture 82
28 Selected Pollutant Production in A Laboratory Coal Gasification
System (yg compound produced/g carbon converted) 86
29 Maximum Production of Consent Decree Pollutants in Screening
Tests 87
30 Severity Ranking of Pollutants in Coal Gasification Screening
Effluent Runs 89
31 Substances Having Environmental Impact Potential Identified in
RTI Laboratory Gasifier Effluent Streams (various coals) .... 90
32 Substances Having Environmental Impact Potential Identified in
Kosovo Effluent Streams (Yugoslavian Lignite) 91
33 Substances Having Environmental Impact Potential Identified or
Expected in Lurgi Gasification Effluent Streams (various coals):
Lignite to Bituminous) 92
34 Substances Having Environmental Impact Potential Identified in
Wellman-Galusha Gasifier Effluent Streams (Feed Coal:
Pennsylvania Anthracite) 93
35 Substances Having Environmental Impact Potential Identified
in Chapman Gasifier Effluent Streams (Virginia Bituminous
Coal) 94
36 Ames Bioassay Test Results of Coal Gasification Samples (Highest
Mutagenic Response Observed in Non-Toxic Dose Range) 100
vii
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ACKNOWLEDGEMENTS
The research project "Pollutants from Synthetic Fuels Production," has
been sponsored by the U.S. Environmental Protection Agency (EPA) through the
Fuel Process Branch, Industrial Environmental Research Labroatory, at Research
Triangle Park, North Carolina. The guidance of Dr. N. Dean Smith, Project
Officer, Mr. William J. Rhodes, Program Manager, and Mr. T. Kelly Janesj
Branch Chief, are herewith gratefully acknowledged. Dr. Smith's contributions
in planning and review were also quite valuable.
Substantial contributions and collaboration have been provided by a number
of personnel at the Research Triangle Institute (RTI). These persons include
John Pierce, William McMichael, Robert Truesdale, and Tina Webb of the Process
Engineering Department. From the Environmental Measurements Department major
inputs were provided by Peter Grohse and Santosh Gangwal. Mary Beth Wilkie,
Douglas Minick, Jesse McDaniel, Thomas Wolff, and Charles Sparacino of the
Chemistry and Life Sciences Division made significant contributions via
chemical and bioassay testing.
vm
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1.0 INTRODUCTION
A research project directed to the study of the environmental aspects
of the production of synthetic fuels from fossil energy resources is being
conducted at the Research Triangle Institute in Research Triangle Park,
North Carolina. A report on the facility construction and preliminary tests
was prepared. That report describes the design and construction of the
gasification facility including the reactor and associated coal feed system,
the sampling and analysis system development, as well as the related data
collection and chemical analysis capability. This report has been prepared
as a companion to reports previously issued on (1) coal gasification screening
test results and (2) the sampling and analysis methodology which has been
2 3
developed for use in the project. '
Some 38 gasification tests have been conducted to provide screening
test results relevant to potential pollutants generated from the gasification
of the alternative types of coal available for use in the United States. The
initial work was directed toward establishing the range of operating conditions
over which the laboratory reactor could be successfully operated as well as
the development of analytical chemical methods for the sampling and analysis
of the streams which exit the gasifier. More importantly, this project has
been directed toward the gasification of a range of coal types and the
extensive chemical analysis of the product gas, aqueous condensate, gasifier
tar, and reactor residue. The fossil fuel sources which have been utilized
include Illinois No.6 coal, Western Kentucky No.9 coal, Pittsburgh No.8 coal,
Montana Rosebud coal, Wyoming subbituminous (Smith-Roland)coal, and North
Dakota Beulah-Zap lignite.
Generally, the gasifier operating conditions have been chosen to approxi-
mate those of large scale gasifier operations producing low heating value fuel
gas or synthesis gas. However, coal has been fed to the laboratory gasifier
via a pressurized lockhopper in such a manner that the complete charge of the
hopper has been passed to the reactor in a single cycle. Thus, the coal feed
has been a batch process while the addition of air and steam to the gasifier
-------
has involved continuous flow throughout a gasification test run. Hence,
operation of the gasification reactor during the screening tests is referred
to as being in the semi batch fixed-bed mode. (A continuous coal feeder has
been added to the laboratory gasifier for subsequent gasification test runs.)
The effluent concentrations from semi batch runs are averaged by inte-
gration over the time of the run so as to simulate the steady-state concen-
trations of a continuous process. In this manner, the semi batch reactor
produces effluent concentrations which appear to provide a reasonably good
simulation of gas product compositions from full scale process gasifiers. The
composition of the oils and tar resulting from the RTI laboratory gasifier has
been found to compare quite closely to similar material produced in larger
scale units in regard to both quantity and composition where comparable data
are available.
Future reports on the work of this project will be directed toward the
generation and control of potential pollutants in coal gasification under
various operating conditions. Studies using the laboratory gasifier have
involved variation in various quantities so as to determine the influence of
coal type, coal particle size, reactant flow rates, chemical additives, and
other factors. The information being generated in this project is intended to
provide a basis for the assessment of the potential health and the environ-
mental significance of the effluents from coal gasification processes. The
project results should also lead to suggested process modifications and/or
control technology developments which can achieve substantial reductions in
potential emissions.
The environmental assessment of processes for the generation of clean
fuels from coal was initiated earlier this decade as described by Magee, Hall,
4
and Varga. That work provided focus to tha currently existing data base on
the nature of the existing technology for the production of synthetic fuels
from fossil fuel resources and the chemical nature of the various process
streams to the extent that such was known at that time. The need for an
environmental assessment methodology was given impetus by the increased
importance of energy independence for the country. The basis for this
methodology has been the "multimedia environmental goals" (MEGs) which repre-
sent an attempt to quantitate the objectives to be achieved in controlling
emissions as well as ambient concentrations of chemical constituents from
-------
process operations. MEGs quantities have been provided in an extensive compi-
5 6
lation. ' More than 600 master list entries of chemical species have been
arranged into categories. A total of 85 categories (26 organic and 50 in-
organic species) have resulted. Each compound or species is assigned a
"discharge multimedia environmental goal" and an "ambient multimedia environ-
mental goal" for each of the primary environmental media, viz., air, water,
and land. The discharge multimedia environmental goals (DMEGs) which are used
in this study generally carry two subscripts, be they explicit or implicit.
The first defines whether the value refers to air (A), water (W), or land (L);
the second, whether the value refers to human health (H) or the ecological
environment (E). In this study, the health-based DMEG values were used
primarily. The ecology-based DMEG values were used only to generate a compara-
tive ranking of pollutants. No ambient multimedia environmental goal values
were used in this study.
Discharge severity is a measure or index of degree to which the concen-
tration of a particular substance is at a potentially hazardous level in a
discharge (effluent). Discharge severity values which are dimensionless are
computed as the quotient of the stream discharge concentration and the DMEG
value. Discharge severity values must be distinguished as to the physical
phase to which they refer as well as to whether the value is computed for
health or for ecological effects.
The environmental assessment methodology being developed by EPA also
includes a systematic approach for the biological testing of samples. Bio-
assay procedures are designed to complement the chemical and physical pro-
cedures which are also in use as a part of an integrated environmental assess-
ment program. In this study the Ames mutagenicity test and the Chinese hamster
ovary cell mutagenicity and cytotoxicity assays were used based on the various
considerations of cost, time requirements, reliability, and degree of public
acceptance. These and other available short-term tests for carcinogens,
8 9
mutagens, and other genotoxic agents have been described in recent reports. '
The preliminary results from the bioassays conducted as a part of this project
have been recently presented.
Generally, it must be emphasized that neither the use of a laboratory
reactor nor the chemical/biological testing program of this study guarantees
that results therefrom will necessarily be duplicated in full scale gasification
-------
systems involving equipment designed and personnel trained for commercial
operation. Yet, an attempt was made to generate results having some (high)
degree of scalability to commercial gasification plant size within the con-
straints of time and funds available.
The more general impacts of large-scale synthetic fuel plants are now
receiving attention in the country, particularly in the coal producing states.
Potential impacts from coal mining, transport, processing, conversion, and end-
product use include significant social and economic aspects in addition to the
environmental and occupational health aspects. Methodological techniques to
analyze socio-economic impacts are now available, and, the continuing progress
being made in the development of an integrated, multimedia environmental assess-
ment approach for synthetic fuels processes is reported in the "Environmental
Review of Synthetic Fuels," a quarterly publication of the EPA Industrial
Environmental Research Laboratory, Research Triangle Park, NC 27711.
-------
2.0 SCREENING TEST EXPERIMENTS
The semibatch gasification test runs which have been conducted in the
RTI laboratory gasifier have been numbered 1 through 58. Runs 1 through 6
are referred to as preliminary tests, Runs 8 through 45 are referred to as
screening tests, and Runs 46 through 58 are designated parametric test runs.
These designations have been applied to distinguish among the objectives at
play during the time period when these runs were performed. Generally however,
all the Runs 1 through 58 represent screening tests in the sense that alter-
native coal types were being studied (screened) under various operating
conditions. The parametric test sequence involved a more systematic approach
in that the feed rates of air, steam, and other additives were carefully
controlled so as to examine the specific influence of these operating condi-
tions (parameters). It is the intent of this report to present primarily
results for the Runs 7 through 45, particularly those runs for which a
judgment has been made that meaningful data resulted therefrom. The fossil
fuel feed material utilized in Runs 7 through 58 have been described in
2
previous reports of this project.
2.1 COALS GASIFIED
The coals which have been utilized primarily in this project have been
Illinois No.6, Western Kentucky No.9, and Pittsburgh No.8 bituminous coals;
Montana Rosebud and Wyoming Smith-Roland subbituminous coals; as well as
North Dakot Beulah-Zap lignite. (A few runs were also made with other
materials including Western Kentucky No.11 coal char, Pennsylvania Red-
Bottom anthracite, and North Carolina humus peat.) These coals ranged in
heating value from 12,300 to 7,900 Btu/lb for the Pittsburgh No.8 and North
Dakota lignite, respectively. (The North Carolina humus peat possessed a
heating value of 5,000 Btu/lb.)
Other important characteristics of the primary coals used in this study
were volatile matter content, fixed carbon, sulfur content, and free swelling
index. The volatile matter content of the Western Kentucky No.9 and the
-------
Wyoming subbituminous coals were essentially the same at 38 percent, the
Illinois No.6 and Montana Rosebud coals were at 32 percent, and the Pittsburgh
No.9 coal was 29 percent. This latter coal possessed the highest fixed carbon
content at 57 percent; the Illinois No.6 was 47 percent; the Montana Rosebud
and Wyoming subbituminous were approximately 38 percent each with the North
Dakota lignite being 35 percent. The Western Kentucky No.9 coal possessed a
total sulfur of 4.8 percent of which 2.9 percent was organic sulfur and 1.8
percent pyritic sulfur. The remaining sufur was as sulfate, which was essenti-
ally negligible for the coals studied in this project. The sulfur content of
the Illinois No.6 coal was 3 percent which was distributed as 1.2 percent
organic and 1.7 percent pyritic. The Pittsburgh No.8 coal possessed a sulfur
content of 2.5 percent of which 1.3 was organic sulfur and 1.2 pyritic sulfur.
Further, the total sulfur content of the Montana Rosebud, Wyoming subbituminous,
and North Dakota lignite were the same at 0.6 percent. However, these three
coals varied in their sulfur distribution, the organic sulfur being 0.2, 0.1,
and 0.5 percent, respectively for these coals.
The free swelling index was also measured for the coals used in this
project. The Pittsburgh No.8 coal possessed a free swelling index of 7, which
was so high that successful conversion of this coal to a high level of carbon
conversion was not feasible in the fixed-bed laboratory reactor. The Western
Kentucky coal possessed a free swelling index of 4 while the Illinois No.5
coal possessed a value of 3. The free swelling index for the other coals
utilized were negligibly low.
2.2 REACTOR AND SIGNAL PROCESSOR
The reactor was constructed from a nominal 3-inch diameter (7.5 cm),
schedule 160, type 310 stainless steel pipe and is approximately 1.2 m in
length. Above it is located the coal hopper and coal feed system. This
consists of a nominal 2-inch (5 cm) diameter, schedule 40 steel pipe, which is
approximately 0.5 m in length. The sight glass joints are connected to the
coal feed system with flanges at each end. The sight glass permits the
operator to view the descent of solid feed as it is added to the reactor. A
pneumatically actuated Jamesbury stainless steel ball valve is located between
the feed hopper and the reactor. Once the coal solids have been admitted into
the reactor space, a bed of solids exists within the reactor which is supported
by a flow distributor (see Figure 1).
-------
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L
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IT
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Figure 1. Gasifier and sampling train.
-------
Steam and other gases are introduced into the bottom of the gasification
reactor below the distributor plate. The reactor operating conditions and
other data are presented in the Table 1. The steam is generated in a series
of three furnaces. The steam supply tubing has been insulated to prevent heat
losses. Strip heaters are also utilized in order to ensure that superheated
steam is fed to the reactor under closely controlled conditions.
The gas stream then passes to the tar trap where a volume of approximately
8 liters is available for the accumulation of tar and aqueous condensate.
This trap may be tapped periodically for removal of the accumulated material.
This trap is water-cooled in order to remove the latent heat of condensation
from the accumulated material. The product gases then pass from the tar trap
and through the high-pressure enclosure, expand to near ambient pressure
through a backpressure regulator and enter a glass sampling system for collec-
tion and analysis of major effluents.
A number of pressure and temperature values are continuously monitored,
periodically recorded and available for digital display. Pressure transducers
are used to continuously monitor the pressure of the nitrogen or air, the
steam feed and the product gas stream. Thermocouples are located at the
outlet of each of the three steam furnaces, at the steam inlet to the reactor
and in the bottom and top of the coal hopper. In addition, the reactor furnace
contains thermocouple detectors in each of its three zones. The reactor
thermowell contains six distinct thermocouple locations over the length of the
reactor. Further, thermocouples are located at the product gas outlet and
within the tar-condensate trap.
The three steam generating furnaces are controlled by a single Lindberg
control system. Over long periods of time, temperatures may be controlled at
steady-state levels representing the desired saturation and/or superheat steam
condition.
The vertical furnace that surrounds most of the reactor during operation
is controlled in essentially the same manner as the three steam generating
furnaces. This furnace does, however, contain three independently operated
heated zones, each of which can demand a maximum of 2.6 kW. The furnace
controller allows the selection of temperatures in the range of 200ฐC to
1200ฐC for each zone. The three-zone electric furnace controller contains a
datatrack programmer which will permit the introduction of any preselected
temperature sequence for the three zones.
8
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TABLE 1. OPERATING CONDITIONS FOR SELECTED SCREENING TESTS
Steam (g)
Air (g)
Coal (g)
Air/Coal
Steam/Coa
Air/ Steam
T * ฐC
max
Carbon
Conversior
Sulfur
Conversior
Tar Yield
(g/g Coal)
Run 6
Illinois No. 6
Bituminous
5796
350
1034
5.6
.060
820
67.1
93.6
.0154
Run 44
Illinois No. 6
Bituminous
1084
4753
1250
.87
4.38
976
87.7
91.9
.0210
Run 16
Illinois No. 6
Bituminous
3704
1350
1569
.86
2.4
.35
941
89
93
.036
Run 20
Illinois No. 6
Bituminous
3672
1368
1578
2.3
.37
1006
84.5
86.0
.0342
Run 21
Illinois No. 6
Bituminous
4713
1720
1543
1.1
3.1
.35
984
97
98
.033
Run 23
Illinois No. 6
Bi tumi nous
1952
3288
1594
2.1
1.2
1.8
1020
96
95
.033
*Time-averaged maximum bed temperature
-------
Table 1 (continued).
Steam (g)
Air (g)
Coal (g)
Air/ Coal
Steam/Coal
Air Steam
max
Carbon
Conversion
(*)
Sulfur
Conversion
(*)
Tar Yield
(g/g Coal)
Run 25
Montana
Rosebud
748
2482
1491
1.7
.50
3.4
1006
99.7
85
.018
Run 26
Montana
Rosebud
McKay
Subbituminous
1332
346**
1488
1.3
.18**
1010
99.9
98.7
.0192
Run 31
Pittsburgh
No. 8
Residue
892
1249
443
2.0
2.8
975
66.4
64.8
NA
Run 32
Wyomi ng
Smith/Roland
Subbituminous
500
2073
1360
.37
4.1
976
99.5
92.5
.0110
Run 33
Wyomi ng
Subbituminous
500
2097
1396
1.5
.36
4.2
1010
98.9
91
0.012
Run 35
Wyomi ng
Subbituminous
527
2461
1420
1.7
.37
4.6
790
97
85
.029
*Time-averaged maximum bed temperature
**0xygen
-------
Table 1 (continued).
Steam (g)
Air (g)
Coal (g)
Air/ Coal
Run 36
North Dakota
Lignite
639
1939
1444
1.3
Steam/Coal .44
Air/Steam
Tm * ฐC
max
Carbon
Conversior
<*)
Sulfur
Conversior
(*)
Tar Yield
(g/g Coal]
3.1
916
99.7
91
.013
Run 38G
Illinois No. 6
Bituminous
404
1499
NA
.54
3.71
963
NA
NA
NA
Run 41
Western
Kentucky
Bituminous
1390
3060
1250
2.5
1.1
2.2
1034
99.8
98
.030
Run 43
North Dakota
Lignite
422
2022
1458
1.4
.29
4.8
914
99.4
80
.0072
Run 45
Wyoming
Smith/ Roland
Subbituminous
600
2290
1427
.42
3.8
932
96.5
92.6
NA
Run 47
Wyoming
Smith/Roland
Subbituminous
528
2275
1430
.37
4.3
946
98.1
94.3
.0208
Run 51
North Dakota
Lignite
447
1430
1491
.30
3.2
939
99.99
74
.0119
*Time-averaged maximum bed temperature.
-------
Pressure, temperature, and flow rate signals from the reactor control
system are provided to the signal processor for collection, reduction, analysis,
storage and reporting. The data acquisition system includes a signal processor
(DEC PDP-11/34) with 64K words of memory, dual disk drive, an alpha-numeric
CRT and a 30 cps DECwriter. (This signal processor and its accessories have
been programmed for data processing in support of the gas chromatographic units
which are used to analyze gaseous effluent samples.)
The CRT terminal and the hard copy printer (DECwriter) have a full keyboard,
which permits dialog between the system and its users. These terminals are used
for entry of operator's commands, display of process conditions and the generation
of messages and data lists.
2.3 SAMPLING AND ANALYSIS
Details of the sampling techniques and chemical analysis procedures which
have been developed and used in this project are discussed in detail in a
3
separate report. However, a brief description of these subjects is appropriate
here.
The effluent gas stream from the fixed-bed reactor passes through a particu-
late trap which is insulated to maintain hot gas conditions. This is immediately
followed by a refrigerated condenser unit which removes aqueous condensate and
low volatile organic material at the system pressure. The condenser unit is
followed by a backpressure regulator.
A glass sampling system has been installed on the low pressure side of the
backpressure regulator. This system includes ports for grab samples and a
valving system for direct adsorbent cartridges. A port also exists for removal
of a continuous gas stream for infra-red analysis. Further, the primary gas
stream passes through a continuous dry gas meter to measure the total volumetric
flow of the effluent stream.
Raw gas samples were collected periodically during the gasification test.
These samples were contained in special glass sample bulbs and maintained under
controlled conditions in a specially designed sample storage chest. These
samples are analyzed for primary (permanent) gases, sulfur-containing gases,
and volatile benzene-related species.
A Carle AGC-111-H automated gas chromatograph is used for the analysis of
the major product gases (H2> CO, C02, CH^, and N2). In addition, it has the
capability of monitoring ethane, ethylene, hydrogen sulfide, oxygen and water.
12
-------
The system utilizes three columns for analysis which includes a molecular
sie.ve-13X, a porapak N and a reference OV-101 column. The complete analysis
of all gases mentioned above can be accomplished every 15 minutes using a
series-bypass-backflush arrangement.
A continuous gas analysis system (Horiba) is also used throughout gasi-
fier runs. This system is housed in a portable cabinet and is used for
measurement of H2ป C02ป CO, ChL and 02 continuously. A sample conditioner
removes traces of condensibles from the gases via refrigeration (1ฐC) prior to
their entering the continuous analyzers. CH4> CO, and C02 are measured using
nondispersive infrared detectors, H2 using a thermal conductivity analyzer and
Op using a paramagnetic analyzer.
The tar samples are complex. Solvent fractional!on is performed before
direct analysis is undertaken. This approach is described in a companion
report. Solvent partition schemes have been devised, most notably by
researchers from the tobacco industry, in which group separations are accom-
plished on the basis of similar chemical properties, e.g., acids, bases, etc.
The latter approach is more practical, particularly if fractions are to be
chromatographed further. A detailed schematic of the partitioning procedure
used is shown in Figure 2 and is a modification of a method developed for air
particulate extracts. Partitioning results are summarized in Table 2.
Five fractions are produced by application of the scheme: acids, bases
and three neutral fractions. These three fractions are designated nonpolar
(aliphatics and 1-2 ring aromatics), medium-polar (polynuclear aromatic
hydrocarbons-PNAs) and polar (oxygenated material). Each group is then either
analyzed directly by gas chromatography/mass spectrometry (GC/MS), or is chroma-
tographed using high performance liquid chromatographic (HPLC) techniques.
Glass capillary gas chromatography has also been applied for quantitation
of PNA materials in tar. A chemically bonded temperature stable (300ฐC)
methyl-silicone capillary column was used. The 'GROB' splitless method of
sample injection is used and approximately 5-15 ug are injected for detection
of the heavier PNAs, e.g., benzo(g,h,i) perylene. The splitless technique
consists of injecting 2 to 3 yl of the sample and then 30 seconds later,
opening the splitter to remove the excess solvent. This prevents a long
solvent tail as illustrated in the accompanying chromatogram (Figure 3) in
which 21 PNAs have been identified based on retention times of standards. At
13
-------
Crude tar
Waah3x with 1MN8OH
CH2CI2 layer
Wart 2 x witfiH20
NaOH layers
Wash with CHjClj
CH2C12 layer
WaanZx with
10% H2SOซ
andlx with
HjO layer
I IpH-IOI
CH2Q2 layer
NaOH layer
Weshwrth
cyctofWJiene
Adjust to pH 2
with 6N HCI
Extract 3 x wttnCH2Oj
Cydohexane layer
111 Evaporate to
dryness
12) Dissolve in
CH2CI2
I [Organic AeidsJ
H2O layer
Adjust to pH 2 with 1 N HO
Extract 3 x with CH2CI2
AQ
CH2a2 layer .
Weeh 2 x with
H,0
H2S04 layer
fOrganic Acios|
AQ
Wash 2 x with
CHjCI2
H2SO4 layer
H20 layer
(pH-5)
Adjust 10 pH 12 with 10M NaOH
Extract 3 x wrthCH2CI2
Evaporate to
dryneea
Retidue
lOroanic BMOT|
WaahSx withCH2Q2
AQ
H20 layer
(11 Added
cydohexane
12) \rVaah3x with
4:1 CH3OH/H20
Adjust to pH 12 with IM NaOH
Extract 3 x with CH2CI2
[ Organic Bases I
AQ
Cydohexane layer , CH3OH/H20 layer
[11 Concentrate!
;2IWash6x ir
with CH3M02 11
Wash 4 x with cydohexane
Cydohexane layer
CH3NO2 layer
Evaporate to
drynes*
Cydohaxane layer
Evaporate to
dryness
CH3OH/H20 layer
Freeze dry
IPdarNeutraisI
[Nonpolar Neutrals!
Figure 2. Partition scheme for crude tars.
14
-------
Table 2. TAR AND PARTITION RESULTS FOR SELECTED SCREENING TEST RUNS
(q produced/g coal loaded)
^~"""-\Run No.
Coal Type**^^
Tar Acid
Tar Base
Polar Neutral
Nonpolar Neutral
PNA
Insolubles
Total Tar
16
I
0.0048
0.0022
0.0029
0.0107
0.0120
0.0035
0.0361
21
I
0.0033
0.0025
0.0017
0.0046
0.0176
0.0035
0.0331
23
I
0.0042
0.0023
0.0013
0.0036
0.0174
0.0037
0.0325
41
WK
0.0016
0.0021
0.0016
0.0038
0.0186
0.0024
0.0301
25
M
0.0018
0.0008
0.0008
0.0012
0.0112
0.0005
0.0163
33
W
0.0032
0.0004
0.0009
0.0025
0.0048
0.0002
0.0120
35
W
0.0086
0.0010
0.0027
0.0053
0.0103
0.0012
0.0291
36
Z
0.0016
0.0004
0.0005
0.0012
0.0043
0.0002
0.0082
43
Z
0.0018
0.0004
0.0007
0.0015
0.0024
0.0004
0.0072
*Coal Type: I
W
Illinois No.6,
Wyoming (Smith-
dap) lignite.
WK - Western Kentucky No.9, M = Montana Rosebud,
Roland) subbiutminous, and Z = North Dakota
15
-------
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
Naphthalene i
2-Meth. Naph.
1-Meth. Naph.
Acenaphtylene
Acenaphthena
Fluorene
Plienanthrena
Anthracene
Fluoranthene
Pyrene
Benzo(a)fluorene
Benzo(b)fluorane
Benzo(a)anthracene
Chrysene &
Triphenylene
Benzo(b)fluoran
thene
Benzo(k)fluoran-
thene
Benzol a) pyrena
Beiizo(a)pyrene
Perylene
Dibenzo(a, h)an-
thracene
Benzo(g, h, ilpery-
lene
Tป
IN
4,5
ฑ 13.14
T
3 MIN ;J j
I i ; . I M : .
TT:
INSTRUMENT:
4 CARRIER GAS:
MAKE UP:
DETECTOR:
HYDROGEN:
{AIR:
11NJECTION
MODE:
COLUMN:
TEMPERATURE:
SOLVENT:
i SAMPLE SIZE:
16 X 10 AMP FULL SCALE
VARIAN 3700
HELIUM 1.25 ml/min
HELIUM 29 ml/min
FID (280ฐ C)
30 ml/min
300 ml/min
GROB' SPLITLESS (250ฐ C).
VENT IN 30 SECONDS
25 m X 0.25 mm I.D. WCOT,
HIGH TEMP. OV101 (280ฐ +\
40ฐ C FOR 1 min. TO 270ฐ C
AT 4ฐ C/min, HOLD 40 min
n-Cg & CH2CI2 (1:11
1.9 /il. 5.5/ig/Ml
94 MIN
Figure 3. PNA fraction of coal gasifier tar by capillary GC-FID.
-------
present, it is planned to use this temperature stable column in a GC/MS for
confirmation of these compounds. In the' future, the capillary-GC-FID tech-
nique will be routinely applied to PNA analyses of coal conversion tars and
condensates.
2.4 BIOASSAY SAMPLES
Selected coal samples were introduced into a rotating jar mill for 16
hours to pulverize the samples. The coal dust so generated was sieve-classified
and retained for bioassay. Further, crude tars and related samples from selected
gasification tests in the RTI laboratory gasifier were tested in whole (neat)
form and as partitioned (see Figure 2).
The samples which have been subjected to bioassay in this project include
raw coal dusts from North Dakota lignite, Wyoming subbituminous coal, Western
Kentucky No.9 coal, and Illinois No.6 coal. These samples were prepared to
-200 mesh (-74 microns) using sieve screens. The bioassays used on the dusts
were the Ames mutagenicity screening test and the Chinese hamster ovary (CHO)
cell assays which employ growth kinetics and dona! efficiency. These latter
tests primarily measure the toxicity of mammalian cells, i.e., CHO cells, to
the samples under study.
The Ames and CHO assays were also employed to study effluents from the
RTI laboratory gasifier. These effluents included crude tar and selected tar
partitions from North Dakota lignite, Wyoming subbituminous coal (3 runs),
Western Kentucky No.9 coal, and Illinois No.6 coal. In addition, the aqueous
condensate and XAD-2 adsorbents were assayed for the run which used Western
Kentucky No.9 coal.
17
-------
3.0 ENVIRONMENTAL ASSESSMENT APPROACH
So as to achieve comprehensive environmental assessments for synthetic
fuel production processes, the Industrial Environmental Research Laboratory at
Research Triangle Park (IERL/RTP) has underway a program to develop procedures
for environmental assessment. These involve sampling and quantitative chemical
analyses of the various streams which discharge from synthetic fuel processes.
The methodology prescribes a systematic approach for interpreting data obtained
in the sampling and analysis campaigns. The use of multimedia environmental
goals (MEGs) provides the capability to quantify measures for the potential
severity of the process streams under study. Thus, the characterization of
waste streams involves not only a determination of their flow rate and chemical
constituents but a determination of the potential degree of severity to be
associated with each species and/or the entire stream. Further, a source
assessment methodology (SAMs) is under development in order to weight the
severity measures based on the mass flow rates of the streams in question.
3.1 LABORATORY GASIFICATION
The Research Triangle Institute is conducting a project to establish the
range of operating conditions over which a laboratory reactor can be success-
fully operated for the generation of environmentally significant samples.
This reactor has been utilized to generate samples from a range of U.S. coals.
These samples have been characterized via chemical and bioassay tests, the
data being subjected to MEG methodology so as to evaluate the degree of severity
of the individual chemical species contained in the various effluents of the
laboratory gasifier. This project is being conducted in support of the overall
environmental assessment program. More generally this program includes the
development of an environmental assessment data base for alternative coal
12-14
conversion processes. Additional specific results have been reported by
Bombaugh. More detailed studies have also been conducted. These studies
have been performed in relation to fixed-bed coal gasifiers, which represent
the gasification reactor type which has been developed to commercial scale.
Additional studies are underway throughout the country to develop other gasifi-
cation reactor types. Environmental considerations must also be applied in an
18
-------
overall environmental assessment program to these alternative types. Slagging
fixed-bed gasification has been under study at the Grand Forks Energy Technology
Center of the U.S. Department of Energy. Fluidized-bed gasification has been
under study at various locations throughout the United States, including the
18
Synthane process of the Pittsburgh Energy Technology Center and the Hygas
I g
process of the Institute of Gas Technology. (Additional interest exists
among various organizations in the development of entrained bed gasifiers.)
While the results of this study cannot be directly applied to either commercial
fixed-bed or other gasifier types, it does provide information as to the com-
pounds and magnitudes which can occur in process effluents be they fugitive
emissions or discharges.
In the RTI laboratory gasifier screening tests, steam-to-carbon ratios
have been investigated over the range from 0.4 to 18 g/g and air-to-carbon
ratios from 0 to about 4 g/g. Although the air-to-coal ratio has varied
depending upon the intended method of supplying heat to the reactor, the
steam-to-coal ratio has been predominantly in the range of 0.5 to 3.0 g/g.
(Excessive steam simply passes through the reactor and results in additional
aqueous condensate formation in the reactor condenser system). Maximum bed
temperatures have been in the range of 900 to 1000ฐC. Carbon conversions have
ranged from 52 to near 100 percent, oxygen-to-coal ratios from 0.0 to 0.9 g/g,
and steam-to-oxygen ratios from 0.9 to infinite. Both internal and external
heat has been supplied to the reactor system. (See also Table 1.)
3.2 SAMPLING AND ANALYSIS
The environmental assessment methodology which has been utilized encom-
passes both the Level 1 and Level 2 techniques for sampling and analysis.
These techniques have been described in various papers presented at the
20
symposia dealing with environmental aspects of fuel conversion technology.
As has been the case for the sampling and analysis activities relating to the
laboratory gasification project, the Level 2 approach has been utilized for
organic species while the Level 1 approach has been taken in most cases for
inorganic species. This means that specific compounds have been quantitated
where such is possible for organic species using gas chromatography or mass
spectrometer/gas chromatography techniques. For most inorganic species only
an elemental analysis has been feasible. Trace element analyses were achieved
both by atomic absorption spectrometry (AAS) and neutron activation analysis
(NAA). The Table 3 presents the major elemental composition of the gasifier tars,
19
-------
TABLE 3. PRIMARY ELEMENTS OF GASIFIER TARS
Weight Percent of Element in Tar
Run
No.
6
15
16
21
23
25
33
35
36
41
43
METC
METC
METC
Coal
Type
Illinois #6
Illinois #6
Illinois #6
Illinois #6
Illinois #6
Montana (Rosebud)
Wyoming Sub-bit.
Wyoming Sub-bit.
North Dakota
Lignite
West. Kentucky #9
North Dakota
Lignite
Montana (Rosebud)
West. Kentucky #9
New Mexico Sub-bit.
% C
78.7
87.5
87.6
87.7
86.0
88.6
86.5
83.0
86.1
86.3
82.3
78.0
80.0
84.4
% H
6.3
6.1
6.2
6.1
5.8
6.0
6.0
7.7
7.0
6.1
7.5
6.6
8.7
7.2
% N
1.3
1.3
2.1
1.4
1.6
0.8
0.8
1.5
1.3
1.6
1.8
1.1
1.9
1.7
% S
2.9
1.9
1.6
1.8
2.5
0.7
2.4
0.5
0.7
2.7
0.9
2.4
2.7
1.4
% 0
10.9
3.2
2.4
3.1
3.8
4.0
4.3
7.4
4.9
2.8
7.0
11.0
(6.7)
(5.3)
20
-------
3.3 MEG METHODOLOGY
The multimedia environmental goals (MEGs) methodology provides a method
to classify potential pollutants in a comprehensive manner. The discharge
multimedia environmental goal (DMEG) value provides a measure of the toxicity
or hazard potential of individual compounds or chemical species based on
existing data. This approach does, of course, encompass a "conservative"
feature. Compounds which possess no known threshold value for exhibiting
toxic mutagenic, carcinogenic or other health effects can be assigned MEG
values which are derived from those other compounds in the same chemical
category. MEG values so determined are referred to as supplemental MEG values.
No such MEG values have been used in this report, however. In addition to the
5 6
MEG compilations referred to earlier, ' additional reports have been issued
21 22
which increase the data base considerably. '
A comparison of DMEG (health) and DMEG (ecology) values is presented in
Table 4. Here it is seen that except for phenolic species and mercury the
health-based values are equal to or exceed the magnitudes of the ecology-based
values. Although both health-based and ecology-based values are used in this
study, the results are typically quite similar as to the potential severity of
the various compound categories which have been identified and studied herein.
3.4 BIOASSAY TESTS
The Level 1 environmental assessment approach for screening environ-
mentally significant samples includes a series of short-term bioassays for the
detection of acute biological effects. This includes both health-related and
ecological test. The health tests are provided to screen for both acute toxic
and potential chronic (i.e., carcinogenic) health effects. The health tests
include the Ames Salmonella typhimurium reverse mutation assay. This test
employs the Salmonella bacteria to screen complex process samples for their
mutagenic potential. Since mutagenicity is a forerunner to carcinogenicity,
then this technique can provide an initial screening of samples to determine
whether the sample may contain carcinogenic agents. Further, the Chinese
hamster ovary (CHO) cells provide a convenient medium in which to assay liquid
and perhaps solid samples. The additional assays included in the Level 1
biological series were not employed in this study. These include the rabbit
alveolar macrophage (RAM), aquatic ecological tests, and other suggested
procedures.
21
-------
Table 4. COMPARISON OF HEALTH AND ECOLOGY BASED DMEG*
VALUES FOR AQUEOUS PHASE POLLUTANTS
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
Name
benzene
naphthalene
phenanthrene
benzo(a)pyrene
phenol
cresol
2,4 xylenol
ammonia
ami no toluene
benzidine
hydrogen sulfide (or S=)
benzenethiol
sulfate (S04*)
thiocyanate (SCN~)
cyanide (CN-)
chloride (CT)
arsenic (As)
cadmium (Cd)
chromium (Cr)
copper (Cu)
iron (Fe)
lead (Pb)
mercury (Hg)
manganese (Mn)
selenium (Se)
DMEG(health) DMEG(ecology)
UQ'/A yg/i
4.5E4
7.5E5
2.5E4
3.0E-1
5.0
5.0
5.0
2.5E3
1.65E3
1.5E4
NA
7.5E3
NA
NA
5.0E2
1.3E6
2.5E2
5.0E1
2.5E2
5.0E2
1.5E3
2.5E2
1.0E1
2.5E2
2.5E2
1.0E3
1.0E2
NA
NA
5.0E2
5.0E2
5.0E2
5.0E1
4.0
1.0E2
NA
NA
NA
NA
2.5E1
NA
5.0E1
l.OEO
2.5E2
5.0E1
2.5E2
5.0E1
2.5E2
1.0E2
5.0E1
DMEGf health)
DMEG (ecology)
4.5E1
7.5E3
NA
NA
l.OE-2
l.OE-2
l.OE-2
5.0E1
4.1E2
1.5E2
NA
NA
NA
NA
2.0E1
NA
5.0EO
5.0E1
l.OEO
1.0E2
6.0EO
5.0EO
4.0E-2
2.5EO
5.0EO
* Discharge Multimedia Environmental Goals (DMEG) values.
22
-------
The assay of choice for initial biotesting of the coal gasification
fractions is the Ames Salmonella assay based on reverse mutation of histidine-
requiring mutants of Salmonella typhimurium to wild type upon addition of a
mutagen. Spot or plate-incorporation tests are commonly used, with activation
requirements for promutagens supplied by addition of an Aroclor 1254-induced
mammalian rat liver S-9 microsomal preparation. The accuracy of this system,
cost, time requirements (2 days), and reliability for a wide variety of
compounds has led to its acceptance for mutagenesis screening.
Coal dust samples and crude tars from coal gasification were tested along
with selected samples of raw condensate watar and XAD-2 adsorbent. The tars
were fractionated using a partitioning scheme (Figure 2) into six fractions;
acids, bases, polar and nonpolar neutrals, polynuclear aromatic hydrocarbons
(PNA) and cyclohexane insolubles.
Salmonella typhimurium strains TA 98, (used to detect frameshift mutations)
and TA 100 (used to detect base substitution mutations) were obtained directly
from Dr. Bruce N. Ames (Biochemistry Department, University of California,
Berkeley). NADPH (tetrasodium salt, Type 1) and known positive mutagens
(highest purity available) were obtained from Sigma Chemical Company. Dimethyl-
sulfoxide (spectrophotometric grade) and sucrose were obtained from the Fisher
Chemical Company. Agar was obtained from Difco Laboratories.
The procedures for handling the strains and preparing media components
26
were those of Ames, et al., with the following exceptions: (a) Craig-Dawley
male rat livers were used as the source for metabolic activation (S-9); NADPH
was added directly to the plate (per plate, 0.10 ml containing 320 mg NADPH);
(c) use of a 2.5 ml agar overlay rather than a 2.0 ml overlay; (d) S-9 micro-
somal preparation was diluted in 0.25M sucrose at a concentration of 3 mg
protein/ml and added at protein concentrations of 3.0 mg/plate for initial
testing; and (e) bacterial strains are centrifuged and concentrated in normal
saline at 10 cell/ml. After nontoxic doses were identified, additional
testing was performed with S-9 concentrations of 0.8, 1.5, 3.0 and 6.0 mg/
plate. The S-9 microsomal preparation was obtained from rats injected with
Aroclor 1254.
The standard is divided into four parts as follows:
23
-------
Toxicity Testing. Plate Incorporation Method
Some 200-300 cells per dish were plated in a histidine-positive overlay.
Tests were done with and without induced S-9. When plates did not contain S-
9, deionized water replaced NADPH solution and 0.25 M sucrose solution replaced
the S-9 microsomal preparation. Test compound was added at 0.1 ml/plate in
all tests. The viability ratio was calculated as the ratio of surviving
colonies, with sample, to colonies without sample. A value less than one
indicates toxicity of the sample compound; a value of one or greater indicates
no toxicity.
Mutagenesis Testing, Plate Incorporation Method
With S-9--To a tube containing 2.5 ml of histidine-negative overlay agar
was added 0.1 ml of S-9 microsomal preparation, 0.1 ml of NADPH (prepared by
dissolving 3.2 mg of Sigma NADPH in 1.0 ml of cold sterile deionized water),
0.1 ml of a solution of test material or positive control compound in dimethyl-
sulfoxide, and 0.1 ml of bacterial suspension [washed once and concentrated
g
10-fold in isotonic saline solution (8.5 g salt per liter)] to give ^10
cells per plate.
Without S-9Prepared as above, 0.1 ml of 0.25 M sucrose solution replaces
the S-9 microsomal preparation and 0.1 ml of deionized water substituted for
the NADPH solution.
The mutagenic ratio was calculated as the ratio of revertants/plate, with
sample, to spontaneous revertants per plate. (A mutagenic ratio of 3 or more
when the viability is greater than 0.5 is considered a positive response.)
Positive Mutagen Control Testing, Plate Incorporation Method
^
Using histidine-negative overlay, ^10 cells were plated in each dish.
Known mutagens were tested to assure that the strains are active and the S-9
preparation was activating promutagens to the desired levels. If known positive
controls did not show proper mutagenic activity, the test components (cultures
and/or S-9) are rejected. Control compounds used included sodium azide,
quinacrine HC1, 2-nitrofluorene, and 2-anthramine.
Sterility Testing. Plate Incorporation Method
Sterility tests were conducted with histidine-positive overlay plates,
using the amounts of components employed in the tests. Components tested were
sample(s), positive controls, solvent(s), water, 0.25M sucrose solution, saline,
microsomal preparation (S-9), and NADPH solution.
24
-------
Mammalian Cell Cytotoxicity Assays
Mammalian cells grown in tissue culture serve as a substitute for the
whole animal as a screening tool for assessing the cellular toxicity of
xenobiotics to mammals-. In this assay, a stable tissue-culture cell line with
well known growth characteristics and biochemistry serves as the test system.
The putative toxins challenge the cells by addition to the growth medium when
the cells are growing as a monolayer, attached to a plastic substrate (plastic
culture dish).
The cell type chosen for this study is the Chinese hamster ovary (CHO)
cell line introduced in 1967 as a parent diploid cell for the production of
mutant cells. The cell line is available from the American Type Culture
Association, and although no longer diploid, possesses a constant chromosome
number (ploidy), is fairly resistant to infections, is relatively easy to
maintain in culture on defined medium, and divides rather rapidly (12-14 hr
doubling-time) for a mammalian cell. The CHO cells grow in a uniform popu-
lation and the levels of various key metabolites involved in their metabolism
can readily be measured. The CHO cell exhibits consistent growth kinetics
when cultured under standard conditions and when provided with a standard
nutrient culture medium.
Inhibition of cell growth was determined in this study by two assay
methods. In the growth kinetics assay, cells were explanted onto a growth
substrate by seeding 10 cells into a 35 mm diameter plastic culture dish,
allowing 24 hr for cell attachment, and incubating with the compound to be
studied for 24 hr. The medium was then replaced with fresh medium, and the
dishes incubated for one one week, with cell counts of control and treated
cultures performed at 24 hr intervals. A control growth curve, exhibiting the
lag, logarithmic, and stationary phases of growth was also generated.
The second method quantitated the ability of a single CHO cell to give
rise to a viable colony (or clone) of cells. This cloning efficiency assay
was performed by seeding a small number of cells (200-1000) in a 60 mm culture
dish, allowing 24 hr for attachment, adding test substance, incubating for 24
hr, replacing medium, and incubating about 10 days, or until studies provided
an overall screening assay to quantitate general cytotoxicty. The parameters
measured are the ability of cells to grow and divided as members of a large
population, and the ability of a single cell to survive the toxic insult, and
given rise to progeny.
25
-------
Tissue culture was obtained from KC Biologicals (Lanexa, Kansas) and
from Grand Island Biologicals (NY). Cells were obtained from the American
Type Culture Association. Disposable tissue culture dishes, flasks and
pipettes were obtained from Corning Corporation. All water used in preparing
medium was tripled distilled after passing through ion-reducing resins.
26
-------
4.0 MEG METHODOLOGY RESULTS
The multimedia environmental goal values which have previously been
discussed have been utilized to evaluate results of the various gasification
tests conducted in the RTI laboratory gasifier.
4.1 INTRODUCTION
Four distinct effluent streams emerge from the laboratory gasification
facility. These are the product gas streams which have passed through a
condensate trap, the aqueous condensate, the tar (tars and oils), and the
reactor residue (ash). The composition of these streams have been determined
as previously described in this report. The concentrations of each stream has
been averaged over the duration of the gasification test runs so as to express
the individual components on a mass/unit volume basis in the case of gaseous
and liquid samples and component of unit mass sampled stream in the case of
tar and ash effluents. The concentration in each stream is then divided by
the appropriate DMEG value to achieve results in the form of discharge
severities. Since for many compounds both DMEG health and DMEG ecology values
were available, it was possible to compute a discharge severity health and
a discharge severity ecology for each of these species. The experimentally
determined concentrations are tabulated in the Appendix to this report and
the discharge severity values expressed by stream type are presented in
Tables 5 through 21.
4.2 HEALTH-BASED RESULTS
Based on the results of the multimedia environmental goals assessment,
it was found that a variety of compounds and compound types occur at concen-
trations which exceed the goal as expressed in DMEG form. However, the number
of compounds occurring at quite high values of discharge severity was found
to be relatively small. In the gas phase, carbon monoxide was determined to
possess the highest discharge severity (health) value. This was true without
regard to coal type. Next were compounds possessing a DS (health) order of
27
-------
TABLE 5. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #6, Illinois #6
Run #6
Flow Rate =
Gas Stream
6.7E-02 g/sec
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
MEG
Category
42B
53B
99A
53C
42B
13A
25A
13A
01A
ISA
18A
15A
01B
53D
53B
25A
15B
25A
15B
18A
21A
01A
ISA
Compound
Carbon monoxide
Hydrogen sulfide
Hydrogen
Carbonyl sulfide
Carbon dioxide
Methanethiol
Thiophene
C2H6S
Methane
C2-Phenols
Cresols
Benzene
Propylene
Carbon di sulfide
Sulfur dioxide
Methyl thiophene
Indene
Dimethyl thiophene
Methyl indene
Phenol
Naphthalene
Ethane
Toluene
Discharge
Seven ty
(Health)
10,000
1,000
100
10
10
10
10
10
10
10
10
1
1
1
1
1
1
1
1
1
1
Discharge
Severity
(Ecology)
1,000
1,000
10
10
10
1
Run #6 Condensate Stream
Flow Rate = 2.4E-01 g/sec
Rank
MEG
Category
Compound
Discharge
Severity
(Health)
Discharge
Severity
(Ecology)
none
28
-------
TABLE 5 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Run #6 Tar Stream
Flow Rate = 9.5E-04 g/sec
Rank
1
2
3
MEG
Category
49A
53A
46A
Compound
Arsenic
Sulfur
Lead
Discharge
Severi ty
(Health)
1,000
100
1
Discharge
Severity
(Ecology)
10
Run #6 Ash Stream
Flow Rate = 2.2E-02 g/sec
Discharge Discharge
MEG Severity Severity
Category Compound (Health) (Ecology)
54A Selenium 10 1
29
-------
TABLE 6. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #16, Illinois #6
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
H
15
16
MEG
Category
42B
15A
15A
53B
25A
99A
42B
53C
01A
ISA
53D
15B
15B
15B
15B
01B
Run #16 Gas Stream
Flow Rate = 1.3E-01 g/s
Compound
Carbon monoxide
Benzene
Toluene
Hydrogen sulfide
Thiophene
Hydrogen
Carbon dioxide
Carbonyl sulfide
Methane
Methanethiol
Carbon di sulfide
Indene
Methyl indene
Dimethyl biphenyl
C3-Benzenes
Propylene
ec
Discharge
Severity
(Health)
1,000
100
10
1,000
100
100
10
10
10
10
10
1
1
1
1
Discharge
Severity
(Ecology)
1,000
1,000
1,000
100
1
Rank
1
2
3
4
5
6
MEG
Category
ISA
68A
ISA
49A
82A
46A
Run #16 Condensate Stream
Flow Rate = 9.4E-02 g/sec
Compound
Cresols
Chromium
Phenol
Arsenic
Cadmi urn
Lead
Discharge
Severity
(Health)
100,000
1,000
10
10
10
10
Discharge
Severity
(Ecology)
1,000
10
100
1
10
30
-------
TABLE 6. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Rank
1
2
MEG
Category
21 C
21B
21C
18A
IOC
IOC
21 B
21A
21D
21A
15A
21A
53A
22C
18A
25B
21A
21C
22B
22D
22C
22B
23C
21A
22B
MEG
Category
49A
54A
Run #16 Tar Stream
Flow Rate = 3.1E-03 g/sec
Compound
Benzo(a)pyrene
Triphenylene
Dibenzo(a,h)anthracene
Cresols
Naphthalene
Benzidine
Benz(a)anthracene
Acenaphthylene
Benzo ( g , h , i ) pery 1 ene
Phenanthrene
Biphenyl
Acenaphthene
Sulfur
Benzo (b)f 1 uoranthene
Phenol
Benzothiophene
Anthracene
Benzo (e)pyrene
Fl uoranthene
Indeno (1,2, 3-CD ) pyrene
Benzo ( k ) f 1 uoranthene
Benzo(a)fluorene
Carbazole
1 -methyl naphthal ene
Benzo (b)fluorene
Run #16 Ash Stream
Flow Rate = 1.8E-02 g/sec
Compound
Arsenic
Selenium
Discharge
Seven' ty
(Health)
1,000,000
1,000,000
100,000
100,000
10
100
1,000
100
100
100
100
100
100
100
10
10
10
10
1
1
1
1
1
1
1
Discharge
Severity
(Health)
10
1
Discharge.
Severi ty
(Ecology)
1,000
100,000
10,000
100
100
Discharge
Severi ty
(Ecology)
1
31
-------
TABLE 7 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #20, Illinois #6
Run #20 Gas Stream
Flow Rate = 1.3E-01 g/sec
Rank
1
2
3
4
5
6
7
MEG
Category
42B
01 B
53B
99A
42B
53C
01A
Compound
Carbon monoxide
Ethyl ene
Hydrogen sulfide
Hydrogen
Carbon dioxide
Carbonyl sulfide
Methane
Discharge
Seven' ty
(Health)
10,000
1,000
100
10
10
10
Discharge
Severity
(Ecology)
1,000
10,000
100
1
Run #20 Condensate Stream
Flow Rate = 7.1E-02 g/sec
Discharge Discharge
MEG Severity Severity
Rank Category Compound (Health) (Ecology)
none
32
-------
TABLE 7 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Run.#20 Tar Stream
Flow Rate = 3.2E-03 g/sec
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
MEG
Category
21C
21A
49A
21A
23B
21 B
21 A
IOC
23B
22A
22B
82A
46A
218
21A
Compound
Perylene
Naphthalene
Arsenic
Phenanthrene
Ac ri dine
Chrysene
9-Methy 1 anthracene
Aniline
Qu incline
Fl uorene
Fluoranthene
Cadmium
Lead
Pyrene
2-Methyl naphtha! ene
Discharge
Severity
(Health)
10,000,000
10
1,000
1,000
1
100
100
10
10
10
10
1
1
1
Discharge
Severn ty
(Ecology)
100,000
100
1,000
100
10
Run #20 Ash Stream
Flow Rate = 2.1E-02 g/sec
Rank
1
2
MEG
Category
49A
54A
Compound
Arsenic
Selenium
Discharge
Severi ty
(Health)
100
1
Discharge
Severi ty
(Ecology)
1
33
-------
TABLE 8 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #21, Illinois #6
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Rank
1
2
3
4
5
6
7
8
9
10
11
12
MEG
Category
01 B
42B
53B
99A
42B
25A
13A
01A
53C
ISA
21A
53D
ISA
25A
ISA
18A
01B
MEG
Category
47B
18A
18A
18A
68A
49A
47A
48A
53A
18A
53A
57A
Run #21 Gas Stream
Flow Rate = 1.1E-01 g/sec
Compound
Ethyl ene
Carbon monoxide
Hydrogen sulfide
Hydrogen
Carbon dioxide
Thiophene
Methanethiol
Methane
Carbonyl sulfide
Xylenols
Naphthalene
Carbon di sulfide
Cresol s
C2-Thiophenes
Biphenyl
Phenol
Propylene
Run #21 Condensate Stream
Flow Rate = 1 .5E-01 g/sec
Compound
Ammonia
Cresols
Xylenols
Trimethyl phenol
Chromium
Arsenic
Cyanide
Phosphorus
Thiocyanate
Phenol
Sulfur
Chlorides
Discharge
Seven' ty
(Health)
1,000
1,000
100
10
10
10
10
10
10
1
1
1
1
1
1
Discharge
Severi ty
(Health)
1,000
10,000
10,000
1,000
100
100
1
10
1
1
1
Discharge
Severity
(Ecology)
10,000
1,000
100
10
1
Discharge
Severity
(Ecology)
100,000
100
100
10
10
10
100
100
10
10
34
-------
TABLE 8. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
Rank
1
2
3
MEG
Category
21C
18A
21C
21B
18A
21A
49A
21B
IOC
21D
21A
21A
21A
18A
23B
21B
22C
15A
21A
53A
22D
IOC
21C
25B
23B
22A
22B
22C
82A
23C
22B
21A
21A
21B
22B
24B
46A
MEG
Category
68A
49A
32A
Run #21 Tar Stream
Flow Rate = 2.2E-03 g/sec
Compound
Benzo(a)pyrene 1
Cresols
Dibenzo(a,h)anthracene
Triphenylene
Xylenols
Naphthalene
Arsenic
Benz(a)anthracene
Benzidine
Benzo(g,h,i)perylene
Phenanthrene
9-Methy 1 anthracene
Acenaphthylene
Phenol
Acridine
Chrysene
Benzo(b)F1uoranthene
Biphenyl
Acenaphthene
Sulfur
IndenoO ,2,3-cd)pyrene
Aniline
Benzo(e)pyrene
Benzothiophene
Qu incline
Fluorene
Fluoranthene
Benzo(k)fluoranthene
Cadmi urn
Carbazole
Benzo(a)fluorene
C2-(Alkyl)naphthalene
2-Methyl naphtha! ene
Pyrene
Benzo(b)fluorene
Dibenzofuran
Lead
Run #21 Ash Stream
Flow Rate = 9.3E-03 g/sec
Compound
Chromium
Arsenic
Beryllium
Discharge
Severity
(Health)
0,000,000
1,000,000
1,000,000
1,000,000
1,000,000
100
10,000
10,000
10
1,000
1,000
1,000
1,000
100
1
100
100
100
100
100
100
10
10
10
10
10
10
10
1
1
1
1
1
1
1
1
Discharge
Severity
(Health)
1,000
10
1
Discharge
Severi ty
(Ecology)
10,000
10,000
1,000,000
1,000
10,000
1,000
1,000
100
100
10
Discharge
Severity
(Ecology)
10
1
35
-------
TABLE 9 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #23, Illinois #6
Rank
1
2
3
4
5
6
7
8
9
10
11
12
Rank
1
2
3
4
5
MEG
Category
42B
15A
53B
99A
42B
01A
53C
15A
13A
13A
25A
53D
MEG
Category
ISA
ISA
68A
49A
ISA
Run #23 Gas Stream
Flow Rate = 1.6E-01 g/sec
Compound
Carbon monoxide
Benzene
Hydrogen sulfide
Hydrogen
Carbon dioxide
Methane
Carbonyl sulfide
Toluene
Methanethiol
C2HgS
C2-Thiophenes
Carbon di sulfide
Run #23 Condensate Stream
Flow Rate = 1.3E-01 g/sec
Compound
Cresols
Xylenols
Chromium
Arsenic
Phenol
Discharge
Severity
(Health)
1,000
1,000
100
10
10
10
10
1
1
1
1
Discharge
Severity
(Health)
10,000
10,000
100
100
10
Discharge
Seven' ty
(Ecology)
1,000
1,000
100
10
10
Discharge
Severi ty
(Ecology)
100
100
10
1
10
36
-------
TABLE 9 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Rank
1
2
3
4
MEG
Category
21C
21C
21B
IOC
21 B
21D
21A
15A
22C
21A
22D
21C
25D
22C
23C
22B
21A
46A
22B
MEG
Category
68A
49A
32A
54A
Run #23 Tar Stream
Flow Rate = 2.9E-03 g/sec
Compound
Benzo(a)pyrene 1
Dibenzo(aปh)anthracene
Triphenylene
Benzidine
Benz(a)anthracene
Benzo (g ,h , i ) peryl ene
Acenaphthylene
Biphenyl
Benzo(b)fluoranthene
Acenaphthene
Indeno(l ,2,3-cd)pyrene
Benzo(e)pyrene
Benzothiophene
Benzo ( k ) f 1 uoranthene
Carbazole
Benzo(a)fluorene
C2- ( Al kyl )naphthal ene
Lead
Benzo (b)fluorene
Run #23 Ash Stream
Flow Rate = 1.4E-02 g/sec
Compound
Chromium
Arsenic
Beryllium
Selenium
Discharge
Severity
(Health)
0,000,000
1,000,000
1,000,000
10
1,000
1,000
100
100
100
100
10
10
10
1
1
1
1
1
1
Discharge
Severity
(Health)
1,000
10
1
1
Discharge
Severity
(Ecology)
10,000
100
Discharge
Severity
(Ecology)
10
1
37
-------
TABLE 10 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #25, Montana Rosebud
Run #25 Gas Stream
Flow Rate = 2.3E-01 g/sec
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Rank
1
2
3
4
5
6
7
8
9
MEG
Category
42B
53B
ISA
47B
25A
42B
ISA
99A
53C
53D
21A
13A
01A
18A
15A
15A
18A
15B
MEG
Category
47B
18A
18A
68A
47A
ISA
48A
53A
53A
Compound
Carbon monoxide
Hydrogen sulfide
Benzene
Ammonia
Thiophene
Carbon dioxide
Toluene
Hydrogen
Carbonyl sulfide
Carbon di sulfide
Naphthalene
Methanethiol
Methane
Cresols
Biphenyl
Diphenylme thane
Phenol
Indene
Run #25 Condensate
Flow Rate = 7.2E-02
Compound
Ammonia
Cresols
Xylenols
Chromium
Cyanide
Phenol
Phosphorus
Thiocyanate
Sulfur
Discharge
Severity
(Health)
1,000
1,000
1,000
10
100
100
1
10
10
10
10
10
10
1
1
1
1
1
Stream
g/sec
Discharge
Severity
(Health)
1,000
10,000
1,000
1,000
10
10
10
1
Discharge
Severity
(Ecology)
1,000
1,000
1,000
1,000
100
1
Discharge
Severity
(Ecology)
100,000
100
10
10
1,000
100
100
10
38
-------
TABLE 10. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
1.1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
Rank
1
2
MEG
Category
21C
21C
18A
21C
18A
21B
ISA
ISA
21A
68A
21 B
21D
21A
21A
ISA
21A
IOC
23B
21B
15A
22C
22D
IOC
21C
82A
23B
22B
21A
23C
22B
22C
25B
21 A
21 B
22B
21A
21A
24B
MEG
Category
68A
32A
Run #25 Tar Stream
Flow Rate = 2.4E-03 g/sec
Compound
Perylene
Benzo(a)pyrene
Cresols
Di benzo (a , h )anthracene
Xylenols
Triphenylene
Tri methyl phenol
0-Isopropyl phenol
Naphthalene
Chromium
Benz(a)anthracene
Benzo (g,h,i)perylene
Phenanthrene
Acenaphthylene
Phenol
Acenaphthene
Benzidine
Acridine
Chrysene
Biphenyl
Benzo(b)fluoranthene
Indeno(l ,2,3-cd)pyrene
Aniline
Benzo (e)pyrene
Cadmium
Quinoline
Fl uoranthene
Anthracene
Carbazole
Benzo(a)fluorene
Benzo( k ) f 1 uoranthene
Benzothiophene
C2-(Alkyl)naphthalene
Pyrene
Benzo(b)fluorene
1 -Methyl naphtha! ene
2-Methyl naphtha! ene
Dibenzofuran
Run #25 Ash Stream
Flow Rate = l.OE-02 g/sec
Compound
Chromium
Beryllium
Discharge
Severity
(Health)
10,000,000
10,000,000
1,000,000
1,000,000
1,000,000
1,000,000
1,000,000
1 ,000,000
10
10,000
10,000
1,000
1,000
1,000
100
100
10
1
100
100
100
100
10
10
10
10
10
10
10
10
1
1
1
1
1
1
1
Discharge
Severity
(Health)
1,000
1
Discharge
Severity
(Ecology)
10,000
10,000
10,000
1,000
100,000
1,000
1,000
1,000
1,000
1,000
100
10
Discharge
Severity
(Ecology)
10
-------
TABLE 11 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #26, Montana Rosebud
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
Rank
1
2
MEG
Category
42B
ISA
53B
99A
42B
53C
47B
01A
15A
25A
ISA
ISA
25A
MEG
Category
68A
82A
Run #26 Gas Stream
Flow Rate = 1.5E-01 g/sec
Compound
Carbon monoxide
Benzene
Hydrogen sulfide
Hydrogen
Carbon dioxide
Carbonyl sulfide
Hydrogen cyanide
Methane
Toluene
Thiophene
Xylenols
Phenol
C2-Thiophenes
Run #26 Condensate Stream
Flow Rate = 1.2E-01 g/sec
Compound
Chromium
Cadmi urn
Discharge
Severity
(Health)
10,000
100
100
10
10
10
10
10
1
1
1
1
Discharge
Severity
(Health)
1,000
1
Discharge
Severity
(Ecology)
1,000
1,000
10
1
10
Discharge
Severi ty
(Ecology)
100
1
40
-------
TABLE 11 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Rank
1
2
MEG
Category
21 C
18A
18A
18A
21A
21A
ISA
23B
21B
2TA
53A
23B
22A
22B
21A
IOC
21A
21B
24B
MEG
Category
68A
32A
Run #26 Tar Stream
Flow Rate = 3.4E-03 g/sec
Compound
Perylene 10
Cresols
Xylenols
Trimethyl phenol
Naphthalene
Phenanthrene
Phenol
Acridlne
Chrysene
9-Methyl anthracene
Sulfur
Quinoline
Fluorene
Fluoranthene
Anthracene
Aniline
2-Methyl naphthal ene
Pyrene
Dibenzofuran
Run #26 Ash Stream
Flow Rate = 1 .3E-02 g/sec
Compound
Chromium
Beryl 1 i urn
Discharge
Severity
(Health)
0,000,000
1,000,000
100,000
100,000
10
1,000
100
100
100
10
10
10
10
10
1
1
1
Discharge
Severity
(Health)
1,000
1
Discharge
Severity
(Ecology)
1,000
1,000
100,000
1,000
1,000
10
Discharge
Seven' ty
(Ecology)
100
41
-------
TABLE 12. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run # 32, Wyoming Sub-bituminous
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Rank
1
2
3
4
5
MEG
Category
42B
ISA
53B
47B
15A
53C
99A
42B
01A
25B
47B
18A
13A
18A
21A
ISA
18A
ISA
MEG
Category
18A
18A
18A
47B
68A
Run #32 Gas Stream
Flow Rate = 2.2E-01 g/sec
Compound
Carbon monoxide
Benzene
Hydrogen sulfide
Ammonia
Toluene
Carbonyl sulfide
Hydrogen
Carbon dioxide
Methane
Thiophene
Hydrogen cyanide
Xylenols
Methanethiol
Phenol
Naphthalene
Xylenes
Cresols
Biphenyl
Run #32 Condensate Stream
Flow Rate = 8.4E-02 g/sec
Compound
Cresols
Xylenols
Phenol
Hydrogen cyanide
Chromium
Discharge
Severi ty
(Health)
10,000
1,000
100
1
1
10
10
10
10
10
10
1
1
1
1
1
1
1
Discharge
Severi ty
(Health)
100,000
10,000
100
10
100
Discharge
Severity
(Ecology)
1,000
1,000
10
100
100
10
Discharge
Severity
(Ecology)
1,000
100
1,000
1,000
10
42
-------
TABLE 12 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Run #32 Tar Stream
Flow Rate = 2.2E-03 g/sec
Discharge
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
MEG
Category
21C
ISA
18A
ISA
ISA
21A
68A
ISA
23B
21A
21 B
46A
21A
IOC
22B
21A
22A
23B
21B
21A
Compound
Perylene
Cresols
Xylenols
Trimethyl phenol
0-Isopropyl phenol
Naphthalene
Chromium
Phenol
Acridine
Phenanthrene
Chrysene
Lead
Anthracene
Aniline
Fluoranthene
9-Methyl anthracene
Fluorene
Quinoline
Pyrene
2-Methyl naphthal ene
Severi ty
(Health)
10,000,000
1,000,000
1,000,000
100,000
100,000
10
10,000
100
100
100
10
10
10
10
10
1
1
1
Discharge
Severity
(Ecology)
10,000
10,000
1,000
100
100,000
100
1,000
1,000
10
Run #32 Ash Stream
Rank
MEG
Category
Flow Rate = 8.6E-03
Compound
None
g/sec
Discharge
Severity
(Health)
Discharge
Severity
(Ecology)
43
-------
TABLE 13 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #33, Wyoming Sub-bituminous
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Rank
1
2
3
4
5
MEG
Category
42B
15A
53B
ISA
15A
99A
ISA
53C
01A
42B
18A
13A
15B
15A
21A
ISA
MEG
Category
ISA
ISA
68A
18A
82A
Run #33 Gas Stream
Flow Rate = 2.1E-01 g/sec
Compound
Carbon monoxide
Benzene
Hydrogen sulfide
Xylenols
Toluene
Hydrogen
Phenol
Carbonyl sulfide
Methane
Carbon dioxide
Cresols
Methanethiol
Indene
Biphenyl
Naphthalene
Diphenylmethane
Run #33 Condensate Stream
Flow Rate = 8.0E-02 g/sec
Compound
Cresols
Xylenols
Chromium
Phenol
Cadmi urn
Discharge
Severity
(Health)
10,000
1,000
100
100
1
10
10
10
10
10
10
10
10
1
1
1
Discharge
Severity
(Health)
100,000
10,000
100
10
1
Discharge
Severity
(Ecology)
1,000
1,000
10
100
10
Discharge
Severity
(Ecology)
1,000
100
10
100
1
44
-------
TABLE 13 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
Rank
MEG
Category
18A
21C
21C
ISA
18A
ISA
21B
68A
21C
21A
ISA
21 B
IOC
21A
21A
15A
21D
21A
21 B
IOC
23B
22C
21A
22A
21 C
21A
23B
82A
46A
25B
22D
22B
21A
21A
23C
22B
21A
22C
22B
MEG
Category
Run #33 Tar Stream
Flow Rate = 2.5E-03 g/sec
Compound
Xylenols 1
Peryl ene 1
Benzo(a)pyrene 1
Cresols 1
Trimethyl phenol 1
0-Isopropyl phenol
Triphenylene
Chromium
Di benzo (a ,h )anthracene
Naphthalene
Phenol
Benz(a)anthracene
Benzidine
Acenaphthylene
Phenanthrene
Biphenyl
Benzo(g ,h ,i )peryl ene
Acenaphthene
Chrysene
Aniline
Acridine
Benzo (b)fluoranthene
Anthracene
Fluorene
Benzo (e)pyrene
9-Methyl anthracene
Quinoline
Cadmium
Lead
Benzothiophene
Indeno(1 ,2,3-cd)pyrene
Fluoranthene
C2-(A1ky1)naphthalene
2-Methyl naphthal ene
Carbazole
Benzo(a)fluorene
1 -Methyl naphthal ene
Benzo (k)fluoranthene
Benzo (b)fluorene
Run #33 Ash Stream
Flow Rate = 8.3E-03 g/sec
Compound
None
Discharge
Severi ty
(Health)
,000,000
,000,000
,000,000
,000,000
,000,000
100,000
100,000
100,000
100,000
. 10
1,000
1,000
10
100
100
100
100
100
100
10
10
10
10
10
1
1
1
1
1
1
1
1
1
1
1
1
1
Discharge
Severity
(Health)
Discharge
Severi ty
(Ecology)
10,000
10,000
10,000
100
1,000
100,000
1,000
1,000
100
100
100
1
Discharge
Severity
(Ecology)
-------
TABLE 14. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #35, Wyoming Sub-bituminous
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Rank
1
2
3
4
MEG
Category
42B
21B
ISA
15A
99A
42B
18A
53C
ISA
13A
53B
01A
ISA
25A
15B
15A
MEG
Category
ISA
ISA
ISA
82A
Run #35 Gas Stream
Flow Rate = 2.4E-01 g/sec
Compound
Carbon monoxide
C16H10: 4 rings
Benzene
Toulene
Hydrogen
Carbon dioxide
Xylenols
Carbonyl sulfide
Phenol
Methanethiol
Hydrogen sulfide
Methane
Cresols
Thiophene
Indene
Biphenyl
Run #35 Condensate Stream
Flow Rate = 7.7E-02 g/sec
Compound
Cresols
Xylenols
Phenol
Cadmium
Discharge
Severi ty
(Health)
1,000
1,000
1,000
1
10
10
10
10
10
10
10
10
10
1
1
1
Discharge
Severity
(Health)
100,000
10,000
100
1
Discharge
Severity
(Ecology)
1,000
1,000
100
10
1
Discharge
Severi ty
(Ecology)
1,000
100
1,000
1
46
-------
TABLE 14. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
Rank
1
2
3
MEG
Category
18A
18A
21 C
ISA
21C
18A
21B
21A
18A
21 B
15A
21A
21A
21A
21A
23B
21 B
IOC
22C
21A
22A
21A
21A
22B
23C
22B
25B
21A
MEG
Category
68A
54A
32A
Run #35 Tar Stream
Flow Rate = 5.9E-03 g/sec
Compound
Cresols 10
Xylenols 1
Perylene 1
Trimethyl phenol
Benzo(a)pyrene
0-isopropyl phenol
Triphenylene
Naphthalene
Phenol
Benz(a)anthracene
Blphenyl
9-methyl anthracene
Acenaphthylene
Phenanthrene
Acenaphthrene
Acridlne
Chrysene
Aniline
Benzo(b)fluoranthene
Anthracene
Fluorene
C2-(alkyl)naphthalene
1 -methyl naphthal ene
Benzo(a)fluorene
Carbazole
. Benzo(b)fluorene
Benzothiophene
2-methyl naphthal ene
Run #35 Ash Stream
Flow Rate = 1.4E-02 g/sec
Compound
Chromium
Selenium
Beryllium
Discharge
Seven' ty
(Health)
,000,000
,000,000
,000,000
100,000
100,000
100,000
100,000
1
1,000
100
100
100
100
100
100
10
1
1
1
1
1
1
1
1
1
1
Discharge
Severi ty
(Health)
1,000
1
1
Discharge
Severity
(Ecology)
100,000
10,000
1,000
100
10,000
1,000
100
100
10
Discharge
Severi ty
(Ecology)
10
1
47
-------
TABLE 15. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #36, North Dakota Lignite
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Rank
1
2
3
4
5
6
7
MEG
Category
42B
15A
53B
15A
25A
13A
99A
42B
53C
18A
13A
01A
ISA
ISA
21A
15A
MEG
Category
ISA
47B
ISA
47B
68A
18A
49A
Run #36 Gas Stream
Flow Rate = 2.0E-01 g/s<
Compound
Carbon monoxide
Benzene
Hydrogen sulfide
Toluene
Thiophene
Methanethiol
Hydrogen
Carbon dioxide
Carbonyl sulfide
Xylenols
C2H6S
Methane
Phenol
Cresols
Naphthalene
Biphenyl
Run #36 Condensate
Flow Rate = 9.3E-02
Compound
Cresols
Ammonia
Xylenols
Hydrogen cyanide
Chromium
Phenol
Arsenic
ec
Discharge
Severity
(Health)
10,000
1,000
100
1
10
10
10
10
10
10
10
10
1
1
1
1
Stream
g/sec
Discharge
Seven ty
(Health)
100,000
1,000
10,000
10
100
100
10
Discharge
Severity
(Ecology)
1,000
1,000
10
100
1
Discharge
Severity
(Ecology)
1,000
100,000
100
1,000
1
100
1
48
-------
TABLE 15. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Rank
1
2
3
MEG
Category
21C
21C
ISA
21B
18A
68A
21C
ISA
ISA
21A
21B
21A
IOC
49A
ISA
21 A
21 D
ISA
21A
22C
21 B
23B
21 A
21C
46A
82A
25B
21A
22A
23B
22B
22C
22D
22B
22B
21A
21A
23C
21 B
21A
MEG
Category
68A
49A
32A
Run #36 Tar Stream
Flow Rate ป 1.2E-03 g/sec
Compound
Benzo(a)pyrene
Perylene
Cresols
Triphenylene
Trimethyl phenol
Chromium
Di benzo (a ,h )anthracene
Xylenols
0-Isopropyl phenol
Naphthalene
Benz(a)anthracene
Acenaphthylene
Benzidine
Arsenic
Phenol
Phenanthrene
Benzo(g,h,i )perylene
Biphenyl
Acenaphthene
Benzo ( b ) fl uoranthene
Chrysene
Acridine
Anthracene
Benzo(e)pyrene
Lead
Cadmi urn
Benzothiophene
9-Methyl anthracene
Fluorene
Quinoline
Fl uoranthene
Benzo (k)fl uoranthene
Indeno(l ,2,3-cd)pyrene
Benzo(a)fluorene
Benzo(b)fluorene
1 -Methyl naphthal ene
C2-(Alkyl )naphthalene
Carbazole
Pyrene
2-Methyl naphthal ene
Run #36 Ash Stream
Flow Rate = 8.9E-03 g/sec
Compound
Chromium
Arsenic
Beryl 1 i urn
Discharge
Severity
(Health)
1,000,000
1,000,000
1,000,000
1,000,000
100,000
100,000
100,000
100,000
100,000
1
1,000
1,000
10
100
100
100
100
100
100
100
100
10
10
10
10
10
10
10
10
10
1
1
1
1
1
1
1
1
1
Discharge
Severity
(Health)
10,000
100
1
Discharge
Severi ty
(Ecology)
10,000
1,000
1,000
1,000
100
10,000
1,000
10
100
100
100
10
Discharge
Severity
(Ecology)
100
10
-------
TABLE 16 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #38P, Illinois #6
Run #38P Gas Stream
Flow Rate = 1.9E-02 g/sec
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Rank
1
2
3
MEG
Category
21B
42B
53B
ISA
15A
13A
53C
53D
53B
42B
ISA
ISA
13A
15B
25A
MEG
Category
ISA
ISA
ISA
Compound
Ci6H10: 4 rings
Carbon monoxide
Hydrogen sulfide
Xylenols
Benzene
Toluene
Methanethiol
Carbonyl sulfide
Carbon di sulfide
Sulfur dioxide
Carbon dioxide
Cresols
Phenol
C2H6S
Indene
Thiophene
Run #38P Condensate
Flow Rate = 3.0E-01
Compound
Cresols
Xylenols
Phenol
Discharge
Severi ty
(Health)
1,000
100
100
100
100
10
10
10
10
10
10
1
1
1
1
Stream
g/sec
Discharge
Severi ty
(Health)
10,000
10,000
1
Discharge
Severi ty
(Ecology)
100
100
100
100
Discharge
Severity
(Ecology)
100
100
10
50
-------
TABLE 16 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
Rank
MEG
Category
18A
18A
ISA
ISA
23B
21A
21A
21A
18A
IOC
21A
MEG
Category
Run #38P Tar Stream
Flow Rate = 1.4E-05 g/sec
Compound
Cresols
Xylenols
Trimethyl phenol
0-Isopropyl phenol
Acridine
Naphthalene
9-Methy 1 anthracene
Phenanthrene
Phenol
Aniline
Anthracene
Run #38P Ash Stream
Flow Rate = 1.4E-05 g/sec
Compound
None
Discharge
Severity
(Health)
100,000
100,000
100,000
100,000
100
100
10
1
Discharge
Severity
(Health)
Discharge
Severi ty
(Ecology)
1,000
1,000
1,000
100
1,000
1,000
100
100
Discharge
Severi ty
(Ecology)
51
-------
TABLE 17 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #3SG, Illinois #6
Run #38G Gas Stream
Flow Rate = 7.7E-02 g/sec
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
Rank
1
2
3
4
MEG
Category
42B
53B
15A
15A
53C
42B
99A
13A
53D
13A
01A
53B
25A
MEG
Category
ISA
ISA
ISA
49A
Compound
Carbon monoxide
Hydrogen sulfide
Benzene
Toluene
Carbonyl sulfide
Carbon dioxide
Hydrogen
Methanethiol
Carbon di sulfide
C2H6S
Methane
Sulfur dioxide
Thiophene
Run #38G Condensate
Flow Rate = 6.5E-02
Compound
Cresol s
Xylenols
Phenol
Arsenic
Discharge
Severity
(Health)
1,000
100
100
10
10
10
10
10
10
1
1
1
Stream
g/sec
Discharge
Severi ty
(Health)
100,000
100,000
10
100
Discharge
Severity
(Ecology)
1,000
100
100
100
1
Discharge
Severi ty
(Ecology)
1,000
1,000
100
10
52
-------
TABLE 17. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Rank
1
MEG
Category
ISA
ISA
ISA
21A
ISA
21A
49A
21A
21 B
21A
23B
22A
22B
21A
MEG
Category
49A
Run #38G Tar Stream
Flow Rate = 3.0E-03 g/sec
Compound
Cresols
Xyl enol s
0-Isopropylphenol
Naphthalene
Phenol
9-Methyl anthracene
Arsenic
Phenanthrene
Chrysene
Anthracene
Quinoline
Fluorene
Fluoranthene
2-Methyl naphthal ene
Run #38P Ash Stream
Flow Rate = 2.2E-02 g/sec
Compound
Arsenic
Discharge
Seven ty
(Health)
1,000,000
1,000,000
1,000,000
1
100
100
100
100
100
1
1
1
1
1
Discharge
Severi ty
(Health)
10
Discharge
Severity
(Ecology)
10,000
10,000
1,000
10,000
1,000
Discharge
Severi ty
(Ecology)
1
53
-------
TABLE 18. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #41, West. Kentucky #9
Run #41 Gas Stream
Flow Rate = 1.1E-01 g/sec
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Rank
1
2
3
MEG
Category
42B
15A
53B
ISA
42B
53C
99A
13A
01 A
13A
21A
18A
25A
15A
15A
ISA
15B
25A
MEG
Category
18A
18A
ISA
Compound
Carbon monoxide
Benzene
Hydrogen sulfide
Toluene
Carbon dioxide
Carbonyl sulfide
Hydrogen
C2H6S
Methane
Methanethiol
Naphthalene
Phenol
Thiophene
Biphenyl
Ctf-Benzene
Cresols
Indene
Methyl thiophene
Run #41 Condensate
Flow Rate = 6.5E-02
Compound
Cresols
Xylenols
Phenol
Discharge
Severi ty
(Health)
1,000
1,000
100
1
10
10
10
10
10
10
10
10
10
1
1
1
1
1
Stream
g/sec
Discharge
Severity
(Health)
100,000
10,000
10
Discharge
Severi ty
(Ecology)
1,000
1,000
100
100
10
Discharge
Severity
(Ecology)
1,000
100
100
54
-------
TABLE 18. POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
Rank
1
2
MEG
Category
21 C
ISA
21 B
18A
18A
21 C
18A
21A
21 B
21 A
IOC
23B
21 D
21A
15A
21 A
21A
22C
18A
21C
21A
25B
22B
22D
22A
21B
IOC
23C
23B
22C
21 A
24B
22B
21 A
MEG
Category
49A
54A
Run #41 Tar Stream
Flow Rate = 1.8E-03 g/se
Compound
Benzo(a)pyrene
Cresols
Triphenylene
Xylenols
Trimethyl phenol
Dibenzo(a,h)anthracene
0- I sopropyl phenol
Naphthalene
Benz(a)anthracene
Phenanthrene
Benzidine
Acridine
Benzo ( g , h , i ) pery 1 ene
Acenaphthylene
Biphenyl
9-Methyl anthracene
Acenaphthene
Benzo (b)fluoranthene
Phenol
Benzo (e)pyrene
Anthracene
Benzothiophene
Fluoranthene
Indeno(l ,2,3-cd)pyrene
Fluorene
Pyrene
Aniline
Carbazole
Qu incline
Benzo ( k ) f 1 uoranthene
2-Methy 1 naphthal ene
Dibenzofuran
Benzo(a)fluorene
1 -Methyl naphthal ene
Run #41 Ash Stream
Flow Rate = 4.8E-03 g/s
Compound
Arsenic
Selenium
c
Discharge
Severity
(Health)
10,000,000
1,000,000
1,000,000
1,000,000
100,000
100,000
100,000
10
1,000
1,000
10
100
100
100
100
100
100
100
10
10
10
10
10
10
10
1
1
1
1
1
1
1
ec
Discharge
Severi ty
(Health)
10
10
Discharge
Severity
(Ecology)
10,000
10,000
1,000
100
100,000
1,000
1,000
100
100
10
Discharge
Severi ty
(Ecology)
1
1
-------
TABLE 19 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #43, North Dakota Lignite
Run #43 Gas Stream
Flow Rate ป 2.6E-01 g/sec
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Rank
1
2
3
4
5
6
MEG
Category
42B
15A
15A
21B
53B
53C
99A
42B
13A
01A
13A
ISA
15B
53D
MEG
Category
18A
ISA
ISA
21C
21C
21 B
Compound
Carbon monoxide
Benzene
Toluene
C16H10: 4 rings
Hydrogen sulfide
Carbonyl sulfide
Hydrogen
Carbon dioxide
C2H6S
Methane
Methanethiol
Cresol s
Indene
Carbon di sulfide
Run #43 Condensate
Flow Rate = 1.1E-01
Compound^
Cresol s
Xylenols
Phenol
Benzo(a)pyrene
Perylene
Triphenylene
Discharge
Severi ty
(Health)
10,000
100
1
100
10
10
10
10
10
10
10
1
1
1
Stream
g/sec
Discharge
Severi ty
(Health)
100,000
100,000
TOO
100
100
10
Discharge
Severi ty
(Ecology)
1,000
1,000
100
10
1
Discharge
Severity
(Ecology)
1,000
1,000
1,000
56
-------
TABLE 19 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Rank
MEG
Category
18A
18A
ISA
ISA
21 C
21C
21 B
21C
21A
ISA
IOC
21 B
21 B
15A
21A
21A
21A
23B
21D
21A
22A
21A
23C
21A
22C
25B
21A
21A
22B
23B
IOC
MEG
Category
Run #43 Tar Stream
Flow Rate = 1.8E-03 g/se
Compound
Xylenols
Trimethyl phenol
Cresols
0-Isopropyl phenol
Perylene
Benzo(a)pyrene
Triphenylene
Di benzo (a ,h janthracene
Naphthalene
Phenol
Benzidine
Chrysene
Benz (a) anthracene
Biphenyl
Acenaphthylene
Phenanthrene
Acenaphthene
Ac ri dine
Benzo(g,h,i)perylene
Anthracene
Fluorene
9-Methyl anthracene
Carbazole
C2-(Alkyl)Naphthalene
Benzo(b)fluoranthene
Benzothiophene
1 -Methyl naphthal ene
2-Methyl naphthal ene
Fluoranthene
Quinoline
Aniline
Run #43 Ash Stream
Flow Rate = 2.2E-02 g/s
Compound
None
JC
Discharge
Severity
(Health)
10,000,000
1,000,000
1,000,000
1,000,000
100,000
100,000
10,000
10,000
1
100
10
100
100
100
100
100
100
10
10
10
1
1
1
1
1
1
1
1
1
ec
Discharge
Seven' ty
(Health)
Discharge
Severity
(Ecology)
100,000
10,000
10,000
1,000
10,000
1,000
1,000
100
100
1
Discharge
Severi ty
(Ecology)
57
-------
TABLE 20 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #44, Illinois #6
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Rank
MEG
Category
42B
15A
53B
53C
21B
ISA
42B
99A
25A
13A
01A
25A
53D
15B
13A
MEG
Category
Run #44 Gas Stream
Flow Rate = 1.2E-01 g/se<
Compound
Carbon monoxide
Benzene
Hydrogen sulfide
Carbonyl sulfide
C16H10: 4 rings
Toluene
Carbon dioxide
Hydrogen
Thiophene
C2H6S
Methane
Methyl thiophene
Carbon di sulfide
Indene
Methanethiol
Run #44 Condensate Stream
Flow Rate ป 6.5E-02 g/sec
Compound
None
w
Discharge
Severi ty
(Health)
1,000
1,000
100
100
100
1
10
10
10
10
10
1
1
1
1
Discharge
Severity
(Health)
Discharge
Severity
(Ecology)
1,000
1,000
100
100
1
Discharge
Severi ty
(Ecology)
58
-------
TABLE 20 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
(continued)
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Rank
MEG
Category
21C
18A
ISA
21A
ISA
21 B
23B
21A
21 A
ISA
21 A
22B
22A
21B .
23B
24B
21A
MEG
Category
Run #44 Tar Stream
Flow Rate = 1.8E-03 g/sec
Compound
Perylene 1
Xyl enol s
Cresols
Naphthalene
Trimethyl phenol
Chrysene
Acridine
Phenanthrene
9-Methyl anthracene
Phenol
Anthracene
Fluoranthene
Fl uorene
Pyrene
Quinoline
Dibenzofuran
2-Methyl naphtha! ene
Run #44 Ash Stream
Flow Rate ซ 1.5E-02 g/sec
Compound
Discharge
Severity
(Health)
0,000,000
100,000
100,000
10
10,000
1,000
100
100
10
10
10
10
10
1
1
1
Discharge
Severity
(Health)
Discharge
Severity
(Ecology)
1,000
1,000
100,000
100
1,000
100
Discharge
Seven' ty
(Ecology)
49A
Arsenic
100
59
-------
TABLE 21 . POTENTIAL ENVIRONMENTAL POLLUTANTS RANKED VIA DISCHARGE SEVERITY
Run #45, Wyoming Sub-bituminous
Rank
1
2
3
4
5
6
7
8
9
10
11
Rank
Rank
Rank
1
2
3
MEG
Category
42B
ISA
53B
15A
53C
99A
42B
01A
13A
25A
13A
MEG
Category
MEG
Category
MEG
Category
68A
54A
32A
Run #45 Gas Stream
Flow Rate = 4.6E-01 g/sec
Compound
Carbon monoxide
Benzene
Hydrogen sulfide
Toluene
Carbonyl sulfide
Hydrogen
Carbon dioxide
Methane
Methanethiol
Thiophene
C2H6S
Run #45 Condensate Stream
Flow Rate = 1.7E-01 g/sec
Compound
None
Run #45 Tar Stream
Flow Rate = 7.9E-03 g/sec
Compound
None
Run #45 Ash Stream
Flow Rate = 2.5E-02 g/sec
Compound
Chromium
Selenium
Beryllium
Discharge
Seven* ty
(Health)
10,000
1,000
100
1
10
10
10
10
10
1
1
Discharge
Severi ty
(Health)
Discharge
Severi ty
(Health)
Discharge
Severi ty
(Health)
1,000
10
1
Discharge
Severi ty
(Ecology)
1,000
1,000
10
100
1
Discharge
Severi ty
(Ecology^
Discharge
Severi ty
(Ecology)
Discharge
Severity
(Ecology]
10
1
-------
magnitude of 1000. These species included benzene, and pyrene, H2$. Although
the Illinois No.6 coal was primarily responsible for these constituents, the
pyrene was also found to occur with the North Dakota lignite and Wyoming
subbituminous while the H2S occurred at this same relative concentration for
the Western Kentucky No.9 coal. A number of other sulfur-containing species
were also found at DS values between 1 and 100 including thiophene, methane-
thiol, and ethanethiol.
In the aqueous condensate stream from the screening test runs it was
found that cresols and xylenols were most predominant in their discharge
severity values. These species occurred at an order of magnitude of 100,000.
The values were high for all of the coals tested. The cresol values were at
the maximum order of magnitude level for Illinois No.6, Western Kentucky No.9,
Wyoming subbituminous coal as well as North Dakota lignite. The xylenols
were at this maximum value for both the Illinois No.6 coal and the North
Dakota lignite. The element, chromium, was also detected at a significant
discharge severity level in the aqueous condensate stream, i.e., 10,000.
This should be regarded as an artifact of the laboratory gasifier system
since the stainless steel reactor tube can be regarded as being responsible
for such high chromium levels. The other significant compounds found in the
aqueous condensate stream were ammonia and trimethylphenol at discharge
severity order of magnitude value of 1,010; benzo(a)pyrene, perylene, phenol,
and arsenic at discharge severity order of magnitudes of 100; triphenylene,
cyanide, thiocyanate, cadmium and lead at discharge severity order of
magnitude values of 10.
The order of magnitude values which predominated in the gasifier tar
stream were perylene, benzo(a)pyrene, and phenolic compounds. Perylene
occurred at sufficiently high concentrations to provide a discharge severity
fc
J
8 7
of 10 for Montana Rosebud coal. The DS value for this compound was 10 for
Illinois No.6 coal. Benzo(a)pyrene gave rise to an order of magnitude 10
for Illinois No.6, Western Kentucky No.9, and Montana Rosebud coal while a
value of 10 was obtained for North Dakota lignite. The order of magnitude
of the discharge severities for both cresols and xylenols was 10 for Wyoming
subbituminous coal and North Dakota lignite, respectively. The cresols were
found at a DS ranking of 10 for Illinois No.6 and Montana Rosebud coal while
61
-------
the xylenols were found at a ranking of 10 for both Western Kentucky No.9 and
Wyoming subbituminous coal.
Four compounds were found in gasifier tar streams at discharge severity
order of magnitude 10 . These include triphenylene, dibenzo(a,h)anthracene,
trimethylphenol, and o-isopropylphenol. Both chromium and arsenic were found
at high orders of magnitude. The arsenic was found at DS value of 10,000 while
the chromium should be discounted since the laboratory reactor stainless steel
contained substantial chromium which was undoubtedly contributed to the products
of reaction. A large number of other organic species were also found at
significant values in the gasifier tar stream. These include benz(a)anthracene,
acenaphthylene, phenanthrene, 9-methylanthracene, benzo(g,h,i)perylene, chrysene,
and phenol.
The solid residue resulting from the gasification process may be referred
to as an ash since the reactor bed is exposed to oxidation conditions at the
air inlet. The solid residue stream was determined to contain three elements
which exceeded their DMEG values. These include chromium, arsenic, and
selenium. However, the substantial chromium content must be regarded as an
artifact due to erosion of the gasification reactor itself. Arsenic was
determined at a discharge severity (health) level of 100 for Illinois No.6,
Western Kentucky No.9 and Pittsburgh No.8 coals as well as the North Dakota
lignite. Selenium was also found at a DS level of 10 in residue from Illinois
No.6 and Western Kentucky No.9 gasification test runs. (Only a few results
have been presented in this work for the Pittsburgh No.8 seam coal. This is
due to the fact that it was not possible to successfully gasify this highly
caking coal in the RTI fixed-bed gasifier without pretreatment.)
4.3 ECOLOGY-BASED RESULTS
Tables 5 through 21 also present discharge severity (ecology) results
which were computed by dividing the effluent stream concentrations as shown
in the Appendix by the corresponding DMEG (ecology) values. Since the data
base of DMEG (ecology) values is somewhat less extensive than the corresponding
DMEG (health) compilation, then the number of compounds for which results can
be reported is therefore less.
62
-------
In the gasifier effluent gas stream, it was found that ethylene gave rise
to the highest DS (ecology) value, which was 10,000. At an order of magnitude
1,000 was the compounds carbon monoxide, hLS, benzene, toluene, and ammonia.
For the aqueous condensate stream, ammonia give rise to the highest DS
(ecology) value, which was 100,000. At an order of magnitude of 1,000 were
cresols, xylenols, trimethylphenol, and cyanide.
A substantially larger number of compounds were found in the gasifier tar
stream which exceeded their DMEG (ecology) values. At an order of magnitude
of 1,000,000 was naphthalene while cresols and xylenols were found at an order
of magnitude of 100,000. This was followed by trimethylphenol and benzidine,
which possessed an order of magnitude of 10,000. The additional compounds
occurring at DS values of 10 to 1,000 in order of magnitude included phenol,
isopropylphenol, biphenyl, acenaphthene, benzo(k)fluoranthene, aniline,
acridine, as well as the trace metals, arsenic, cadmium, and chromium. Again,
the chromium must be regarded as an artifact being derived from the stainless
steel metal which constituted the gasifier reactor shell. The gasification
residue in addition to chromium was found to contain arsenic at a DS (ecology)
value of the order of magnitude 10.
The results of this evaluation of the environmental potential for eco-
logical effects were found to be generally true for all the coals tested. The
North Dakota lignite was found to give high values for ammonia, cyanide, and
phenolic compounds, e.g., xylenols. High values were also obtained from the
eastern high volatile coals including the Illinois No.6 and Western Kentucky
No.9 coals. The Wyoming subbituminous coal was often found to give rise to
somewhat lower concentrations of the important species in the gasification
reactor effluent streams.
4.4 OTHER FINDINGS
The highest species concentrations in the reactor gas stream were found
to be contributed by carbon monoxide, methane, and hydrogen. These concen-
87 73
trations were 3.0 x 10 , 3.6 x 10 , and 2.7 x 10 pg/m , respectively. The
concentrations for hydrogen sulfide, benzene, and thiophene which were
7 f\ f\ ^
1.7 x 10 , 3.3 x 10 , and 2.3 x 10 pg/m . Maximum liquid discharge con-
centrations were found for phenol, cresols, and xylenols at 2.8 x 10 ,
63
-------
1.5 x 10 , 1.5 x 10 , and 3.7 x 10 yg/1, respectively. Methyl naphthalenes
2
were detected in aqueous condensate at 7.0 x 10 while chrysene, phenanthrene,
acenaphthene, and fluorene were determined at maximum concentrations of 160,
96, 57, and 57 yg/1, respectively. Inorganic species in the aqueous conden-
sate were found at maximum values for ammonia, cyanide, and thiocyanate at
7.9 x 106, 1.0 x 106, and 2.7 x 105 yg/1, respectively.
Maximum concentrations determined in gasifier tar from the RTI laboratory
gasifier were determined for xylenols, cresols, and trimethyl phenol at con-
54 4
centration values of 1.2 x 10 , 6.7 x 10 and 2.4 x 10 yg/g, respectively.
Additional compounds at maximum concentrations in the gasifier tar were
naphthalene, benzofluorene, pyrene, phenanthrene, and anthracene at concentra-
tions of 5.7 x 104, 3.4 x 104, 2.4 x 104, 2.3 x 104, and 2.3 x 104 yg/g,
respectively.
The actual quantity of hydrogen sulfide and carbonyl sulfide generated
per unit gram of carbon converted during the gasification process were deter-
mined for each of the coals gasified. The Western Kentucky No.9 coal gave
4 2
rise to 4.0 x 10 and 8.5 x 10 yg of each of these species per gram of carbon
converted, respectively. The production factors for hydrogen sulfide from the
other coals were less by at least one order of magnitude depending upon the
3 2
sulfur content of the coal in question. For example, 3.8x10 and 4.9 x 10
were the production factors for hydrogen sulfide for Illinois No.6 coal and
North Dakota lignite, respectively. The carbonyl sulfide values for these two
2 2
coals were 4.0 x 10 and 3.7 x 10 , respectively. Thus, it was found that the
hydrogen sulfide production level was directly related to the sulfur content
of the feed coal while the carbonyl sulfide level was lower but of essentially
the same magnitude for each of the coals gasified.
2 3
Production factors for phenol varied from 4.3 x 10 to 1.4 x 10 yg of
phenol/g of carbon converted for Illinois No.6 and North Dakota lignite feed
materials, respectively. The production level of benzene, toluene, and
xylenes, was effectively the same order of magnitude for both Illinois No.6
coal and North Dakota lignite, respectively, being of the order of 10,000 yg/g
of carbon converted. Further, it was found that the production factors for
naphthalene were of the order of 1,000 yg/g of carbon converted for both
Illinois No.6 and Western Kentucky No.9 coals while for western coals, this
value was of the order of 600 yg/g of carbon converted. In fact, the pro-
duction factors for naphthalene and higher polycyclic aromatic hydrocarbons
64
-------
were found to depend upon reactor operating temperatures to a somewhat greater
degree than for other species studied.
65
-------
5.0 BIOASSAY RESULTS
The bioassay studies which have been conducted as a part of this project
include both the Ames mutagenicity assay and the Chinese hamster ovary cell
culture in both the growth kinetics and clonal efficiency modes. The environ-
mentally significant samples which were tested include raw coal dusts, crude
gasifier tars, tar partitions, aqueous condensate from gasification, and
volatile organics collected on XAD-2 resin.
5.1 COAL DUST BIOASSAYS
Results of the Ames bioassay for raw coal dust samples are presented in
Table 22. North Dakota lignite, Wyoming subbituminous coal, Western Kentucky
No.9 coal, and Illinois No.6 coal were prepared in dust form at -74 microns.
These dust samples were ultrasonically dispersed in the Ames bioassay medium
using a procedure previously developed for flyash samples. Since no mutagenic
ratio exceeded 3 it is concluded that these dust samples tested negative using
both the TA 98 and TA 100 bacterial strains with and without S-9 activation.
Moreover, the viability ratio provides evidence that the cells were capable of
surviving exposure to the coal particles in order to give meaningful results.
Only in the dust of North Dakota lignite was a toxicity found of the Salmonella
to the raw coal. This phenomenon occurred for both the TA 98 and TA 100
bacterial strains; a phenomenon which was found to be much less significant
for those samples containing S-9 activation. Hence, the raw coals were found
to be nonmutagenic at doses to 10 mg/plate.
These coal dust samples were also subjected to CHO growth kinetics and
clonal efficiency assays. Figure 4 displays a control culture of CHO cells at
140X magnification. This can be compared to Figure 5 in which CHO cells were
subjected to Upper Freeport coal dust at 10 mg/ml. Here it is seen that the
CHO cells have ingested the coal particles. It is believed that the classical
phenomenon known as pinocytosis has taken place in which the CHO cells have
surrounded and engulfed the coal particles. In spite of this incorporation
process, the raw coal dusts were found to be noncytotoxic to doses as high as
10 mg/ml.
66
-------
TABLE 22. AMES BIOASSAY RESULTS FOR RAW COAL DUST SAMPLES
Coal Type
North Dakota
Lignite
Wyomi ng
Sub-bituminous
Western Kentucky #9
Bituminous
Illinois #6
Bituminous
Dose
Mg/plate
1000
500
250
100
10
1000
500
250
100
10
1000
500
250
100
10
1000
500
250
100
10
Viability Ratio
TA 98
+MA -MA
.002
.030
.126
.557
.796
.835
.895
.868
1.02
.994
.91
.93
.74
.88
.87
.934
.887
.793
.653
.953
.000
.000
.003
.000
.879
.156
.819
.865
.826
1.00
.08
.82
.84
.76
.80
1.18
.989
1.08
.517
.776
TA 100
+MA -MA
.045
.344
.319
.795
.114
.786
.680
.844
.827
.872
1.20
1.12
1.31
1.29
1.17
.602
.508
.475
.413
.266
.004
.009
.004
.000
.060
.328
.342
.310
.328
.162
1.69
1.48
1.27
1.39
1.44
.467
.245
.226
.143
.277
Mutagenic Ratio
TA 98
+MA -MA
.525
.650
.750
.800
.800
.850
.975
1.07
.975
.950
.810
.900
.880
.800
.840
1.03
.975
.975
.800
.975
.571
.500
.392
.678
.857
.821
1.03
1.17
1.00
1.03
1.03
.980
1.05
1.13
1.19
1.03
.857
1.00
1.25
.928
TA 100
+MA -MA
.492
.615
.738
.665
.896
1.16
1.19
1.30
1.18
1.15
.93
.92
1.00
1.03
1.03
1.12
.83
.72
.95
.90
.285
.281
.251
.372
.779
.852
.900
.917
.900
.948
.94
1.10
1.04
1.07
1.06
1.07
1.06
1.12
1.04
NOTE: +MA is with S-9 activation, -MA is without such activation.
-------
Figure 4. Chinese hamster ovary cells in culture, control sample (25 pg DMSO)
(Magnification: 140x).
68
-------
Figure 5,
Chinese hamster ovary cells in culture, Upper Freeport coal dust
sample (lOmg/ml). Magnification: 140x).
69
-------
The low and medium designations provided on Figure 23 represent extrapo-
lations of the available data so as to account for higher dose levels; high
doses were not achieved since the capacity of the DMSO for coal dust was
limited. High, medium, and low designations indicate that the maximum accept-
able dose (50 percent inhibition level) is achieved at levels of 0.1 mg or less,
0.11 to 9.99 mg, and 10 mg or more.
5.2 EFFLUENT BIOASSAYS (AMES)
Initially Ames bioassay tests were conducted with bacterial strains TA
98, 100, 1535, 1537, and 1538. The TA 98 and 100 strains represent the
equivalent of TA 1538 and 1535, respectively, with PK 101 plasmid for ampi-
cillin resistance. These strains were employed both with and without S-9
activation. Early test results indicated that no additional information was
gained through the use of all five strains. Therefore, strains TA 98 and 100
were used exclusively in the subsequent Ames assays.
Tables 24 and 25 present dose response information for the Western
Kentucky No.9 and Wyoming subbituminous coal related samples, respectively.
These tables contain both viability ratios and mutagenicity ratios for bacterial
strains TA 98 and 100. Samples were assayed both with and without S-9 activa-
tions. It can be seen in Table 24 that phenocopies resulted in three samples.
For these samples changes of a nonmutagenic nature occurred in the laboratory
which mask the desired phenomenon.
Figure 6 displays photographs of Ames bioassay plates used for control
and standard compound testing. Also shown is a plate to which the acid parti-
tion from a crude tar derived from Wyoming subbituminous coal was tested. For
this plate, it can be seen that a negative result is achieved as compared with
the lower plate on which 2-aminoanthracene was tested.
The Ames bioassay plate which resulted from testing the PNA fraction of
crude tar associated with the gasification of Illinois No.6 is shown in
Figure 7. Doses of 25 and 500 mg/plate of PNA samples are shown as well as
S-9 doses of 1.5, 3.0, and 6.0 mg/plate. A value of 3.0 mg of S-9 per plate
was found to be optimal in this study for the samples under examination. The
organic base fraction from the crude tar resulting from the gasification of
Wyoming subbituminous coal was tested on Ames bioassay plates as shown in the
Figure 8. Utilizing an S-9 concentration of 3.0 mg/plate a dose-response
relationship for the organic base fraction was achieved. As shown the three
70
-------
TABLE 23. CHINESE HAMSTER OVARY CELL BIOASSAY RESULTS ON
RAW COAL DUST SAMPLES
COAL TYPE
North Dakota
Lignite
Wyomi ng
Subbituminous
Western Kentucky #9
Bituminous
Illinois #6
Bituminous
Pittsburgh #8
(West Virginia)
Upper Freeport
(Pennsylvania)
Mary Lee
(Alabama)
pg/2m1
125
50
250
100
250
100
250
100
250
100
250
100
250
100
Growth Kinetics
% Inhibition
20 (medium)
2 (low)
10 (low)
50 (medium)
0 (none)
0 (none)
0 (none)
0 (none)
28 (medium)
10 (low)
0 (none)
0 (none)
0 (none)
0 (none)
Clonal Efficiency
% Inhibition
11 (medium)
67 (medium)
33 (medium)
2 (low)
13 (medium)
11 (medium)
22 (medium)
20 (medium)
7 (low)
0 (none)
0 (none)
0 (none)
0 (none)
8 (none)
71
-------
TABLE 24. AMES BIOASSAY RESULTS FOR COAL GASIFIER EFFLUENTS
Coal Type: Western Kentucky #9
Sample
Crude Tar
Water Condensate
PNA
PN
Acids
Dose
pg/plate
1000
500
250
100
10
1000
500
250
100
10
1000
500
250
100
10
1000
500
250
100
10
500
250
100
10
Viability Ratio
TA 98
+MA -MA
.01
.01
.25
.77
1.03
1.28
1.28
1.20
1.15
.97
.01
.14
.54
.88
1.02
.61
1.00
.97
1.00
1.02
.00
.58
.73
.86
.01
.01
.01
.23
.91
1.10
1.10
1.05
1.04
1.03
.00
.04
.19
.60
.92
.06
.19
.73
1.07
.91
.00
.00
.68
.48
TA 100
+MA -MA
.01
.01
3.94
.88
1.10
1.14
1.04
.96
1.02
.87
.00
.07
.50
.99
.99
.72
1.00
1.00
1.00
.00
.72
1.07
1.04
.02
.01
.01
.01
.07
.96
.96
.89
.90
.98
.00
.02
.05
.44
.74
.02
.10
.75
.88
.00
.01
.30
.53
Mutagenic Ratio
TA 98
+MA -MA
.1
2.7
3.9
8.8
4.4
1.0
1.0
.9
.9
.9
26.4
24.5
23.8
9.5
2.4
9.0
9.8
3.9
1.2
.8
.2
1.6
1.5
1.4
.7
Phenocopies
.4
.8
.9
.8
1.0
.8
.9
1.0
Phenocopies
Phenocopies
3.6
2.2
1.2
.8
.8
.9
.8
.7
1.0
.2
.8
.9
TA 100
+MA -MA
.0
.5
1.2
1.5
1.6
1.1
1.0
1.1
.8
1.0
2.3
2.3
2.4
2.0
1.2
2.2
2.0
1.7
1.0
.6
.9
1.5
1.6
.4
1.1
.5
.6
.9
1.0
1.0
1.0
1.0
.9
1.0
.9
.6
.7
.9
.5
.9
1.0
1.0
.0
1.2
1.0
1.0
vl
ro
NOTE: +MA is with S-9 activation, -MA is without such activation,
-------
Table 24. con't.
Sample
Bases
NPN
Cyclohexane
Insolubles
XAD Steady State
XAD Surge
Dose
yg/plate
500
250
100
10
1
1000
500
250
100
10
1000
500
250
100
10
5000
1000
500
250
125
5000
1000
500
250
125
Viability Ratio
TA 98
+MA -MA
.12
.64
.76
.74
.90
.05
.36
.51
.86
.96
.32
.32
.66
.90
.81
.00
1.03
1.20
1.21
1.20
.00
.00
.26
.90
1.21
.06
1.02
.66
1.03
1.19
.11
.08
.26
.38
1.00
.00
.00
.00
.33
1.22
.00
.00
.01
.82
.93
.00
.00
.00
.00
.03
TA 100
+MA -MA
.14
.55
1.03
1.26
1.03
.01
.09
.44
1.07
1.11
.22
1.17
.91
1.30
1.00
.00
2.43
2.60
2.55
2.64
.00
.71
1.85
2.80
2.75
.00
.14
.55
.81
.82
.00
.00
.04
.005
.50
.00
.89
.02
.56
1.00
.00
1.61
2.17
2.50
2.30
.00
.01
.65
1.30
1.69
Mutagenic Ratio
TA 98
+MA -MA
16.4
15.1
17.2
9.2
1.8
.8
.7
1.0
1.5
1.1
.8
2.4
3.1
2.4
1.1
.7
1.2
1.2
1.2
1.2
1.2
.6
1.4
1.3
1.3
.1
.3
1.0
1.0
1.0
.3
.2
.1
.5
.6
.9
.2
.2
.5
.9
.9
.9
.9
1.1
1.2
1.0
.6
.6
.7
.9
TA 100
+MA -MA
.9 1.4
5.5 .8
8.6 1.1
6.5 1.1
1.18 1.0
1.0 .9
1.2 1.1
1.5 .6
1.6 1.0
1.6 1.4
1.4 .8
2.7 1.5
2.1 1.0
1.6 1.4
.9 1.6
.4 .0
1.1 .9
1.1 .9
1.0 1.1
1.0 .9
.2 .0
.8 .3
.9 .6
1.0 .7
.8 .7
CO
NOTE: +MA is with S-9 activation, -MA is without such activation.
-------
Table 24. con't.
Sampl e
XAD Control
Dose
jig/plate
1000
500
250
100
10
Viability Ratio
TA 98
+MA -MA
.02
.43
.92
.74
1.07
.00
.00
.02
.02
.10
TA 100
+MA -MA
.41
2.81
2.33
2.71
2.56
.01
2.11
2.41
2.50
2.28
Mutagenic Ratio
TA 98
+MA -MA
.9
1.2
1.2
1.1
1.3
.9
.7
1.1
1.0
1.1
TA 100
+MA -MA
.6 .4
.8 .6
.7 .8
.8 .6
.7 .7
NOTE: +MA is with S-9 activation, -MA is without such activation.
-------
TABLE 25. AMES BIOASSAY RESULTS FOR COAL GASIFIER EFFLUENTS
Coal Type: Wyoming (Smith-Roland) Sub-bituminous
Sample
Crude Tar
Water Condensate
PNA
PN
Acids
Dose
ng/plate
1000
500
250
100
10
1000
500
250
100
10
1000
500
250
100
10
1000
500
250
100
10
1000
500
250
100
10
Viability Ratio
TA 98
+MA -MA
.31
1.01
1.06
.88
1.06
1.08
1.34
1.04
1.30
1.10
.08
.61
.88
.91
.98
.21
.91
.89
.92
.93
.02
.85
1.46
.79
.75
.01
.00
.00
.63
.02
.88
.75
.74
.86
.87
.01
.08
.18
.55
.70
.02
.17
.73
1.03
.87
.01
.01
.34
.79
.83
TA 100
+MA -MA
.07
1.10
1.36
1.27
1.31
1.23
1.16
1.04
.93
.79
.03
.40
.76
1.47
1.64
.03
1.56
1.54
1.64
1.54
.01
.46
1.08
1.12
.98
.01
.03
.17
.69
1.48
.92
.82
.85
1.08
.76
.01
.04
.11
.14
1.33
.01
--
.02
.36
1.18
.01
.01
.02
.41
.95
Mutagenic Ratio
TA 98
+MA -MA
6.23
3.15
2.51
2.00
1.67
1.11
1.42
.99
1.30
1.04
17.32
2.20
2.88
2.15
1.27
8.88
3.31
2.35
1.96
1.16
.72
.91
1.05
.99
.73
.73
.73
.80
.75
.95
1.02
1.03
1.01
.81
.82
.28
.69
.81
.35
.55
.27
.39
.37
.54
.99
0
.17
.30
.64
.52
TA 100
+MA -MA
1.19 .60
1.66 .60
1.71 .75
1.43 .79
1.30 .91
1.39 1.34
1.09 .88
1.22 .85
1.00 .90
1.07 .92
1.09 .61
1.51 .78
1.81 .83
1.76 .65
1.21 .72
1.21 1.06
1.58 .55
2.00 .59
1.51 .86
1.13 .89
.57 .00
1.13 .45
1.11 .82
1.09 .90
1.04 .89
en
NOTE: +MA is with S-9 activation, -MA is without such activation.
-------
Table 25. con't
Sample
Bases
Dose
yg/plate
1000
500
250
100
10
Viability Ratio
TA 98
+MA -MA
.79
.87
.84
.85
1.15
.92
.80
.73
.56
.75
TA 100
+MA -MA
1.04
1.28
1.17
1.26
1.02
.60
1.08
1.03
.97
.98
Mutagenic Ratio
TA 98
+MA
12.31
6.95
3.73
1.59
1.06
-MA
.70
.67
.54
.62
.61
TA 100
+MA -MA
3.29
3.00
2.11
1.61
1.31
1.19
1.21
1.11
1.02
.79
NOTE: +MA is with S-9 activation, -MA is without such activation.
cr>
-------
DMSO 100 pi/plate
S-9 3.0 mg protein/plate
Acid 100 jig/plate
S-9 3.0 mg protein/plate
Negative mutagenicity test
Wyoming, 80725, run 35
2 Aminoanthracene 100 ug/plate
S-9 3.0 mg protein/plate
Figure 6. Ames bioassay plates (Salmonella strain TA-98)
77
-------
PNA 250 fig/plate
S-9 1.5 mg protein/plate
PNA 500 -pg/plate
S-9 3.0 mg protein/plate
PNA 500 pg/plate
S-9 6.0 mg protein/plate
Figure 7. Ames bioassay plates (PNA fraction from Illinois No.6 coal
gasifier tar).
78
-------
A
Base 125 pg/plate
S-9 3.0 mg protein/plate
Base 62.5 jig/plate
S-9 3.0 mg protein/plate
Base 25 jig/plate
S-9 3.0 mg protein/plate
Figure 8. Ames bioassay plates (base-fraction from Wyoming subbituminous
coal gasifier tar).
79
-------
plates contained 25, 62.5, and 125 ug of organic tar base fraction per plate.
The number of revertant colonies per plate is clearly seen to increase with
dose of sample.
The overall results from the Ames bioassays on gasifier tars and tar
fractions are presented in the Table 26. This table contains results for raw
crude tars as well as the tar base, tar acid, PNA, polar neutral, and nonpolar
neutral partition fractions. These represent samples obtained from the RTI
laboratory gasifier using North Dakota lignite, Wyoming subbituminous coal,
Western Kentucky No.9 coal, and Illinois No.6 coal.
Substantial potential mutagenicity was detected in the crude tar samples.
As can be seen in the table, the number of revertants/yg was 11 for the
Illinois No.6 coal, 8.7 for the Western Kentucky No.9 coal, and of the order
of 2 or less for the other crude tar samples. The highest specific activity
of any sample was obtained for the polar neutral fraction of crude tar obtained
from Illinois No.6 coal. This sample gave rise to 37.5 revertants/yg. The
other samples showing high activity were the base fractions from Western
Kentucky No.9 coal which gave rise to 33.8 revertants/yg, the tar base frac-
tions from North Dakota lignite giving 18 revertants/yg and the tar base
fraction from Run 35 which utilized Wyoming subbituminous coal giving 15.6
revertants/yg. Thus, it can be seen that while the largest single response
was achieved for the polar neutral fraction of Illinois No.6 coal, the primary
activity was possessed by tar base fractions from Western Kentucky, Wyoming
subbituminous coals, and North Dakota lignite.
5.3 EFFLUENT BIOASSAYS (CHO)
The results of cytotoxicity studies on coal gasifier tars and tar frac-
tions as obtained using Chinese hamster ovary cells in culture are presented
in Table 27. Here it is shown that crude tar samples, partitions of the crude
tars obtained via solvent partitioning as described earlier in this report,
XAD-2 resin samples and aqueous condensates were tested in both the growth
kinetics and clonal efficiency assays. At low concentrations, the aqueous
condensate sample showed a negligible influence on CHO cells. At higher con-
centrations, inhibition in the clonal efficiency test was determined at a
sample concentration of 125 mg/ml. Further, the XAD-2 control sample was
found to exhibit some cytotoxicity in the clonal efficiency assay but none in
the growth kinetics test. The surge and steady-state XAD-2 resins exhibited
80
-------
TABLE 26. AMES BIOASSAY RESULTS FOR GASIFIER TARS AND TAR FRACTIONS
Fraction
Raw Crude Tar
Tar Base
Tar PNA
Tar Polar Neutral
*Tar Acid
*Tar Nonpolar Neutral
Raw Crude Tar
Tar Base
Tar PNA
Tar Polar Neutral
*Tar Add
*Tar Nonpolar Neutral
Raw Crude Tar
Tar Base
Tar PNA
*Tar Polar Neutral
Tar Add
*Tar Nonpolar Neutral
Raw Crude Tar
Tar Base
Tar PNA
Tar Polar Neutral
*Tar Add
*Tปr Nonpolar Neutral
Raw Crude Tar
Tar Base
Tar PNA
Tar Polar Neutral
*Tar Acid
*Tar Nonpolar Neutral
Raw Crude Tar
Tar Base
Tar PNA
Tar Polar Neutral
*Tar Add
*Tar Nonpolar Neutral
Percent of Dose Rendering a Mutagenic Specific Activity
Crude Tar Response (ug) (revertants/ug)
100.0
4.6
36.3
7.8
23.6
17.1
100.0
3.3
40.0
7.5
26.7
20.8
100.0
3.4
35.4
0.3
29.6
18.2
100.0
2.5
36.3
7.8
30.7
27.8
100.0
7.0
61.8
5.3
5.3
12.6
100.0
6.7
66.7
3.6
6.7
11.3
Run No. 51 (North Dakota Lignite)
250,100
100,10
500,250.100,10
500,250,100,10
-
"
Run No. 33 (Wyoming Subbituminous Coal)
250,100
250,125.62.5
1000,500,250,100
250,125,62.5
-
Run Ho. 35 (Wyoming Subbituminous Coal)
500,250,100
125,62.5,25
500,250,100
-
-
*
Run No. 47 (Wyoming Subbituminous Coal)
500.250.100
100.50.25
500,250,100
500,250,100
-
"
Run No. 41 (Western Kentucky No. 9 Coal)
500,350,100,10
100,10,1
250,100,10
250,100
-
"
Run No. 44 (Illinois No. 6 Coal)
250,100.10
250,100
500,250,100
50,25.10
-
1.915
17.91
0.852
1.91
-
'
1.189
3.50
1.56
1.42
-
"
0.399
15.62
0.652
-
-
0.265
5.8
0.36
0.30
-
~
8.69
33.79
7.72
1.77
-
"
11.29
6.23
1.96
37.46
-
Activity2
(revertants)
191.5
81.5
30.9
14.8
-
127.2*
118.9
23.6
62.3
10.6
.
101.2*
39.9
53.7
23.1
.
-
76 ._8*
26.5
14.7
12.7
2.3
.
29.8*
869
235.9
477.0
9.4
-
722.3*
1129
47.0
131.1
136.0
-
314jl
Specific Activity (revertants with sample - spontaneous revertants)/dose.
Activity ซ specific activity x fraction mass per 100 wg of composite material (corrected for toxicity)-
*Nonmutagen1c.
Sum of mutagenlc activity for fractions comprising the crude tar.
81
-------
TABLE 27. CYTOTOXICITY OF COAL GASIFIER TARS AND FRACTIONS TO
CHINESE HAMSTER OVARY CELLS IN CULTURE
Sample
Western Kentucky Crude Tar
PNA
Polar neutrals
Adds
Bases
Non-polar neutrals
Cyclohexane
[nsolubles
XAO-2
Steady State
JWD-2
Surge
XAD-2
Control
HjO Condensate
Wyoming Crude Tar
PNA
Polar neutrals
Acids
Bases
H.O Condensate
Illinois #6 Crude Tar
PNA
Acids
Bases
Polar neutrals
Non-polar neutrals
3ฃ Total
Crude Tar
100.00
61.79
5.32
5.32
6.98
12.62
7.97
-
ป
-
-
-
100.0
36.26
7.76
30.7
2.54
-
100.00
66.67
6.67
6.67
3.63
11.25
Concentration
mg/ml
10.0
10.0
10.0
5.0
15.0
10.0
10.0
5.0
5.0
5.0
10.0
5.0
10.0
1.0
1.0
0.1
Concentrate
10.0
10. 0
5.0
0.1
2.5
10.0
mg Sample
Per 2 ml
250
100
250
100
250
100
125
50
375
150
250
100
250
100
125
50
125
SO
125
50
250
100
125
50
250
100
25
10
25
10
2.5
1.0
28
250
100
250
100
125
50
2.5
1.0
62.5
25
250
100
Growth
Kinetics
5 Inhibition
33
69
69
43
0
5
69
52
90
74
96
90
22
22
79
63
22
22
0
0
0
0
36
36
94
63
78
64
33
71
6
28
45
0
72
72
77
60
0
0
0
0
0
0
72
44
Clonal
Efficiency
% Inhibition
56
45
23
12
0
12
12
0
53
50
23
5
20
17
35
38
30
9
26
6
45
0
26
5
30
40
33
56
54
49
12
10
19
0
100
98
95
70
15
18
12
22
42
50
88
98
82
-------
some inhibition in both CHO tests with the steady-state sample showing a
somewhat more significant response.
The highest responses in the CHO growth kinetics assay resulted from both
crude tars and their partition fractions, including the organic bases, PNAs,
polar neutrals, and in some cases, the organic acid fractions. Similar
results were obtained for the clonal efficiency assay.
The crude tar samples from Illinois No.6 and Western Kentucky No.9 coal
gasification runs were found to possess the same level of cytotoxicity per
unit mass as was exhibited by the combination of their partition fractions.
However, the crude tar sample from the Wyoming subbituminous gasification run
was substantially less cytotoxic per unit mass than its partition fraction
equivalent. For the Illinois No.6 coal, the nonpolar neutral and PNA fractions
exhibited high cytotoxicity; for the Western Kentucky No.9 coal, the organic
bases, organic acids, and PNAs were found to be most cytotoxic; while for the
Wyoming subbituminous coal, the PNAs organic acids and polar neutrals exhibited
greatest cytotoxicity.
83
-------
6.0 DISCUSSION OF RESULTS
Generally, the results which have been generated in this project on the
environmental evaluation of coal gasification screening tests are of four
types. First, concentration values for a wide variety of chemical compounds
and species have been generated for not only the gasifier gaseous stream but
the aqueous condensate, gasifier tar, and reactor residue (ash). Next,
production factors have been computed which express the mass of potential
pollutant generated in the laboratory gasifier per unit mass of coal converted
in the reactor. Then, based upon the MEG methodology, discharge severity
values have been computed base upon both DMEG (health) and DMEG (ecology)
values. Finally, bioassay results have been obtained for a variety of samples
using the Ames, CHO growth kinetics, and CHO clonal efficiency assays.
6.1 CHEMICAL ANALYSIS RESULTS
A compilation of experimentally measured concentrations for the various
species determined in the RTI laboratory gasifier product gas stream, aqueous
condensate stream, gasifier tar stream, and reactor residue (ash) stream have
been provided in the Appendix. These concentration values have been expressed
in standard units of measurement to facilitate the environmental analyses of
these data. As can be seen in Tables 1-1 through 1-4 a wide variety of com-
pounds were quantitatively analyzed. The chemical species which occurred in
highest concentrations in the gas stream were carbon dioxide, carbon monoxide,
methane, and hydrogen. (Nitrogen was also present as diluent in the stream
as a result of the nitrogen component of the air which was fed to the gasifier.)
Additional chemical species which represent potential pollutants include
hydrogen sulfide, benzene, thiophene, toluene, and ethane in this stream. A
substantial number of other compounds were also determined as can be seen in
these tables.
The organic species present in the aqueous condensate were primarily
phenol, cresols, xylenols, and related compounds. In addition, naphthalene
and its derivatives plus chrysene, phenanthrene, acenaphthylene and flourene
84
-------
were the predominant organic species present. The inorganic species which
predominated in the aqueous condensate stream were ammonia, cyanide, and
thiocyanate.
The gasifier tar stream contained significant quantities of xylenols,
cresols, and related phenolic compounds. Additionally, the tar was composed
of naphthalene, benzofluorene, pyrene, phenanthrene, anthracene, and a large
number of higher molecular weight polycyclic aromatic hydrocarbons. Addi-
tionally, substantial quantities of heterocyclic oxygen, nitrogen, and sulfur
species were present. Chromium, arsenic, lead, and selenium were the pre-
dominant elemental species of the reactor residue of environmental concern.
The concentrations in ug/g of residue for these species are presented for
selected run ash samples in Table 1-4. The chromium content of the various
gasifier effluent streams must be regarded primarily as an artifact of the
particular laboratory configuration used in these studies. This is a consequence
of the fact that the stainless steel reactor utilized in these studies possessed
a high chromium level from which significant contributions to the effluents
took place.
The production factors for selected chemical species from the RTI semi-
batch laboratory reactor tests have been compiled in Table 28. Here it is
seen that on a unit mass of carbon converted basis that hydrogen sulfide,
thiophene, phenolic species, benzene, toluene, and naphthalene were pre-
dominant. These chemical constituents were found to be present in the various
gasification test runs without regard to the particular coal being gasified.
While some variation in these production factors was found from one coal to
the next, it was generally true that the primary potential pollutants generated
in the laboratory gasifier can be taken to be effectively the same under the
conditions of these studies without regard to coal type.
The maximum production values for consent decree pollutants in various
screening tests have been compiled in Table 29. Of the organic species, it
was found that benzene and toluene are predominant of the order of 10,000 g/
metric ton of coal loaded to the reactor. A number of other significant
organic species were phenol, naphthalene, fluoranthene, and higher molecular
weight aromatic species. Ammonia was the most predominant inorganic species
which gave rise to a production factor of 5,000 g/metric ton of coal used.
Again, the chromium value in this table must be discounted due to the contri-
bution of chromium from the stainless steel reactor used in these studies.
85
-------
TABLE 28, SELECTED POLLUTANT PRODUCTION IN A LABORATORY COAL GASIFICATION SYSTEM
compound produced/g carbon converted)
Compound
hydrogen sulfide
carbonyl sulfide
thiophene
methyl thiophene
hydrogen cyanide
ammoni a
phenol
cresols
xylenols
benzene
tol uene
xylenes
naphthalene
anthracene
phenanthrene
Illinois No. 6
Bituminous
3.8E3
4.0E2b
1.8E3
3.2E2
NAC
NA
4.3E2
7.2E2
NA
5.0E3
3.5E4
8.9E1
1.2E3
7.1E2
2.2E2
Montana
Rosebud
4.6E3
1.5E2
5.2E1
1.1E1
1.2E2
8.7E3
1.3EO
8.3E2
1.0E3
1.9E2
1.0E3
8.9E2
5.9E2
2.0E2
5.9E2
Wyoming
Subbituminous
3.4E3
2.0E2
1.6E1
1.8E2
NA
NA
NA
2.7E3
8.9E2
3.1E3
3.3E3
8.1E2
6.3E2
1.5E2
7.2E1
North Dakota
Lignite
4.9E2
3.7E2
1.1E3
2.9E1
1.4E2
6.0E3
1.4E3
1.0E3
1.1E3
1.1 E4
3.1E3
8.3E2
5.2E2
2.1E2
1.3E2
Western Kentucky
No. 9 Bituminous
4.0E4
8.5E2
4.0E2
4.9E2
NA
NA
1.2E3
1.3E3
2.9E2
1.9E4
3.0E3
4.1E2
3.5E3
1.0E3
9.8E2
Results are expressed as "aEb" which should be interpreted as a x 10 .
Includes sulfur dioxide.
c NA = Not Available.
-------
TABLE 29 . MAXIMUM PRODUCTION OF CONSENT DECREE POLLUTANTS
SCREENING TESTS
IN
Exit Gas
Concentration
(yg/m3)**
Acenaphthene
Acenaphthylene
Anthracene*
Benzene
Benzo(a) anthracene*
Benzo(g,h,i)perylene
Benzo(a)pyrene*
Chrysene*
Dibenzo(a,h)anthracene*
Ethyl benzene
Fluoranthene*
Fluorene
Naphthalene*
Phenol*
Pyrene
Toluene*
Ammonia*
Antimony
Arsenic*
Cadmi urn*
Chromium*
Lead*
4.6E4
1.5E5
1.8E5
3.4E6
5.8E4
2.3E4
4.6E4
7.9E4
3.6E4
1.1E5
2.6E5
6.0E4
8.4E5
7.4E5
1.9E5
7.5E6
2.1E6
4.5EO
2.2E2
3.0E1
1.1E3
5.5E2
(9)
(3)
(ID
(12)
(3)
(3)
(3)
(ID
(3)
(8)
(13)
(13)
(13)
(12)
(13)
(12)
(2)
(7)
(8)
(8)
(7)
(7)
Production
Factors
g/metric ton
1.2E2
3.8E2
6.7E2
1.3E4
1.5E2
5.9E1
1.2E2
2.8E2
9.2E1
4.2E2
1.0E3
2.3E2
3.0E3
1.6E3
7.4E2
2.0E4
5.0E3
1.5E-2
7.7E-1
l.OE-1
2.7EO
1.2E-1
Concentration exceeds DMEG value.
**Concentrations on moisture-free basis.
^ 'Number of gasifier runs examined.
87
-------
This table shows some 14 chemical compounds or species which exceed the
corresponding DMEG (health) values. The additional results obtained from
the MEG methodology analysis are presented in the next section.
6.2 MEG METHODOLOGY RESULTS
The results of the MEG environmental assessment of screening test
results were presented in Section 4 of this report. The results of this
analysis are summarized in Table 30 which presents severity rankings for the
potential pollutants of the RTI coal gasification effluent streams. Distinct
listings are presented for the gas, aqueous condensate, tar, and reactor
residue. These results were obtained utilizing the concentration values
presented in the Appendix to this report and the appropriate DMEG (health)
values for each of the compounds in question. The values in parentheses
in this table represent the order of magnitude of the discharge severity
determined using health-based data. As can be seen in this table, the
predominant species in terms of discharge severity were found in the tar
stream to be perylene, benzo(a)pyrene, phenolic species, and a number of
other compounds. Cresols, xylenols, and related phenolic compounds were
found at high levels in the aqueous condensate stream. Some representation
of polycyclic organic species in the aqueous condensate stream was also
found.
In the gas stream, the discharge severity ranking gave rise to carbon
monoxide as the predominant species while benzene, pyrene, hydrogen sulfide,
and other compounds were also present at reasonably high levels. Arsenic
and selenium were the two species of the reactor residue which appeared to
have potential health hazard significance.
A summary of the data on compounds which have been identified in various
coal gasification processes as a part of the EPA environmental assessment pro-
gram which possess potential for health hazard effects have been tabulated in
Tables 31 through 35. These tables represent data for the RTI laboratory
P 20
gasifier, the Kosovo Lurgi-type gasification plant of Yugoslavia, various
Lurgi results as available in the literature,23 the Wellman-Galusha gasifier
of the Glen Gery facility in utilizing Pennsylvania anthracite coal, and
the Chapman gasifier utilizing Virginia bituminous coal. 25 In Table 35, the
-------
TABLE 30. SEVERITY RANKING OF POLLUTANTS IN COAL GASIFICATION SCREENING TEST
EFFLUENTS RUNS
Tar Stream
Gas Stream
Aqueous Condensate Stream
CD
perylene (1Q8)
benzo(a)pyrene (107)
cresols (10 )
xylenols (107)
triphenylene (106)
dibenzo(a,h)anthracene (106)
trimethylphenol (106)
o-isopropylphenol (106)
(chromium (105))
arsenic (101*)
benz(a)anthracene (103)
acenaphtylene (103)
phenanthrene (103)
9-methylanthracene (103)
benzo(g,h,i)perylene (103)
chrysene (103)
phenol (103)
acenaphthene (102)
benzo(b)fluoranthene (102)
indeno(l ,2,3-cd)pyrene (102)
quinoline (10 2)
benzidine (10 2)
sulfur (102)
anthracene (10)
fluorene (10)
fluoranthene (1)
pyrene (10)
benzo(e)pyrene (10)
benzo(a)fluorene (10)
benzo(k)fluoranthene (10)
benzothiophene (10)
carbazole
cadmium (10)
lead (10)
carbon monoxide (10**)
benzene (103)
CieHlO: 4 rings (103)
hydrogen sulfide (103)
hydrogen (102)
carbon dioxide (102)
xylenols (102)
carbonyl sulfide (102)
thiophene (102)
methanethiol (10)
ethanethiol (10)
carbon disulfide (10)
sulfur dioxide (10)
phenol (10)
C2-phenol (10)
cresols (10)
ammonia (10)
hydrogen (sulfide (10)
naphthalene (10)
indene (10)
cresols (105)
xylenols (105)
(chromium (10U))
ammonia (103)
trimethyl phenol (103)
benzo(a)pyrene (102)
perylene (102)
phenol (102)
arsenic (102)
triphenylene (10)
cyanide (10)
thiocyanate (10)
cadmium (10)
lead (10)
Solid Residue (Ash)
(chromium (104))
arsenic (102)
selenium (10)
( ) - Order of magnitude of Dischatge Severity (health).
-------
TABLE 31. SUBSTANCES HAVING ENVIRONMENTAL IMPACT POTENTIAL IDENTIFIED IN
RTI LABORATORY GASIFIER EFFLUENT STREAMS (Various Coals)
Raw Product Gas
Aqueous Condensate
Tar
Ash
Methane
Methanethiol
Ethanethiol
Benzene
Toluene
Xylenes
Indene
Biphenyl
Phenol
Cresols
Xylenols
Naphthalene
Phenanthrene
Quinclines
Thiophene
Methylthiophene
Carbon Monoxide
Carbon Dioxide
Ammonia
Hydrogen Sulfide
Ethyl benzene*
Indan*
Anthracene*
Carbonyl Sulfide*
Carbon Disulfide*
Phenol
Cresols
Xylenols
Ammonia
Hydrogen Sulfide
Hydrogen Cyanide
Benzo(a)pyrene
Naphthalene*
Monoalkylnaphthalenes*
Acenaphthylene*
Phenanthrene*
Anthracene*
Fluoranthene*
Benzo(b)fluoranthene*
Benzo(h) f 1uoranthene*
Benzo(e)pyrene*
Biphenyl
Phenol
Cresols
Xylenols
Naphthylene
Anthracene
Phenanthrene
Quinolines
o-isopropylphenol
Trimethylphenol
1-Methylnaphthalene
2-Methylnaphthalene
C2-Naphthalenes
Pyrene
Benz(a)anthracene
Chrysene
Benzo(e)pyrene
Benzo(a)pyrene
Dibenz(a,h)anthracene
Fluoranthene
Benzo(b)fluoranthene
Benzo(k)f1uoranthene
Indeno(l,2,3-cd)pyrene
Acridine
Carbazole
Benzothiophene
Benzidine*
Indole*
Arsenic
Beryllium
Chromium
Iron
Manganese
Nickel
Selenium
Sodium
Aluminum*
Antimony*
Cadmium*
Cerium*
Chlorine*
Cobalt*
Copper*
Lanthanum*
Lead*
Magnesium*
Mercury*
Rubidium*
Samarium*
Scandium*
Thorium*
Titanium*
Uranium*
Vanadium*
Zinc*
*Substances which were also detected and are typically present in such samples, but were below the corres-
ponding DMEG (health) value.
Source: "Pollutants from Synthetic Fuels Production," Research Triangle Institute, U. S. Environmental Pro-
tection Agency Grant Project, August 1979.
-------
TABLE 32. SUBSTANCES HAVING ENVIRONMENTAL IMPACT POTENTIAL IDENTIFIED
KOSOVO EFFLUENT STREAMS (Yugoslavian Lignite)
IN
Lock Hopper
Vent Gas
Rectisol
Inlet Gas
Phenosolvan
Effluent Water
Generator
Wastewater
Methane
Carbon Monoxide
Carbon Dioxide
Benzene
Hydrogen Sulfide
Carbonyl Sulfide
Methanethiol
Ethanethiol
Ammonia
Hydrogen Cyanide
Methane
Carbon Monoxide
Carbon Dioxide
Benzene
Hydrogen Sulfide
Methanethiol
Ethanethiol
Hydrogen Cyanide
Carbonyl Sulfide*
Ammonia*
Phenolics
Cyanide*
Chloride*
Cyanide*
Chloride*
vo
*Substances which were also detected and are typically present in such samples, but were below the corres-
ponding DMEG (health) value.
NOTE: Analyses were unavailable for other streams for comparison with other gasification plants.
Source: Kosovo Gasification Test Program ResultsPart II: Data Analysis and Interpretation, K. J. Bombaugh,
et al,; Sym. Env. Aspects of Fuel Conv. Tech., U. S. Environmental Protection Agency, ORD/IERL,
Hollywood, FL, April 1979.
-------
TABLE 33. SUBSTANCES HAVING ENVIRONMENTAL IMPACT POTENTIAL IDENTIFIED
OR EXPECTED IN LURGI GASIFICATION EFFLUENT STREAMS
(Various Coals: Lignite to Bituminous)
Product Gas
Carbon Dioxide
Carbon Monoxide
Methane
Hydrogen Sulflde
Ammonia
Mercaptans
Thiophenes
Carbonyl Sulflde*
Carbon D1sulf1de*
Hydrogen Cyanide*
Tar
Lithium
Beryllium
Magnesium
Calcium
Strontium
Barium
Boron
A1 um1 num
Silicon
Lead
Phosphorus
Arsenic
Selenium
Titanium
Vanadium
Chromium
Manganese
Iron
Nickel
Mercury
Cerium*
Cobalt*
Copper*
Sal Hum*
Germanium*
Molybdenum*
Rubidium*
Antimony*
Scandium*
Uranium*
Yttrium*
Z1nc*
Zirconium*
Sodium*
011
Benzene
Toluene
Xylenes
Styrene
Indan
1 ,2-Benzofuran
Indene
Naphthalene
Thiophenes
Arsenic
Barium
Beryllium
Cobalt
Chromium
Mercury
Lithium
Manganese
Nickel
Lead
Selenium
Aluminum
Iron
Silicon
Boron*
Copper*
Molybdenum*
Phosphorus*
Rubidium*
Antimony*
Scandium*
Strontium*
Vanadium*
Yttrium*
Z1nc*
Calcium*
Sodium*
Titanium*
Magnesium*
Sas Liquor
Phenol
Cresols
Xylenols
Catechols
Resourcinols
Lithium
Beryllium
Selenium
Fluoride
Chromium
Nickel
Mercury
Aluminum*
Calcium*
Iron*
Sodium*
Silicon*
Titanium*
Magnesium*
Silver*
Arsenic*
Boron*
Barium*
Cerium*
Cobalt*
Copper*
Molybdenum*
Manganese*
Phosphorus*
Lead*
Rubidium*
Antimony*
Scandium*
Strontium*
Uranium*
Vanadium*
Yttrium*
Z1nc*
Zirconium*
Ash
Lithium
Beryllium
Magnesium
Calcium
Strontium
Bari urn
Aluminum
Carbon
Silicon
Lead
Phosphorus
Arsenic
Zirconium
Vanadium
Chromium
Manganese
Iron
Nickel
Sodium*
Titanium*
Chloride*
Silver*
Boron*
Cadmium*
Cerium*
Cobalt*
Cesium*
Copper*
Fluoride*
Gallium*
Germanium*
Mercury*
Molybdenum*
Rubidium*
Antimony*
Scandium*
Selenium*
Tellurium*
Uranium*
Tungsten*
Yttrium*
Zinc*
Substances which were also detected and are typically present-In such samples, but were below the corres-
ponding DMEG (health) value.
Source: M. Ghassemi, et al., Environmental Assessment Report: Lurgi Coal Gasification Systems for SfIG,
EPA-600/7-79-120, May 1979.
92
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TABLE 34. SUBSTANCES HAVING ENVIRONMENTAL IMPACT POTENTIAL IDENTIFIED
IN WELLMAN-GALUSHA GASIFIER EFFLUENT STREAMS
(Feed Coal: Pennsylvania Anthracite)
Coal Hopper Gas
Methane
Carbon Dioxide
Carbon Monoxide
Iron Carbonyl
Hydrogen Sulflde
Carbonyl Sulflde*
Carbon D1sulf1de*
Sulfur Dioxide*
Ash Sluice Hater
Barium
Chromium
Iron
Lanthanum
Lithium
Benzenethiol*
Phenols & Cresols*
Benzo(e)pyrene*
D1benz(a,h)pyrene*
Ammonium Ion*
Hydrogen Cyanide*
Thlocyanate*
Selenium*
Ash
Aluminum
Arsenic
Barium
Beryllium
Bismuth
Cadmium
Calcium
Chromium
Cobalt
Copper
Hafnium
Iron
Lead
Lithium
Magnesium
Manganese
Nickel
Selenium
Silicon
Silver
Strontium
Thorium
Titanium
Vanadium
Zirconium
Antimony*
Mercury*
Cyclone Dust
Aluminum
Antimony
Arsenic
3ar1um
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Fluoride
Gallium
Hafnium
Iron
Lead
Lithium
Magnesium
Manganese
Mercury
Nickel
Selenium
Silicon
Silver
Thallium
Thorium
Titanium
Vanadium
Zinc
Zirconium
Naphthalene*
Phenanthrene*
Fluorene*
Antimony*
Substances which were also detected and are typically present in such samples, but were below the corres-
ponding OMEG (health) value.
Source: W. C. Thomas, et al.. Environmental Assessment: Source Test and Evaluation ReportWeiIman-Galusha
(Glen Gery) Low Btu Gasification, August 1979.
93
-------
TABLE 35. SUBSTANCES HAVING ENVIRONMENTAL IMPACT POTENTIAL IDENTIFIED
IN CHAPMAN GASIFIER EFFLUENT STREAMS
(Virginia Bituminous Coal)
Codl Feeder
Vent Gas
Carbon Dioxide
Carbon Monoxide
Nitrogen Oxide
Ammonia
Cyanide
Hydrogen Sulflde
Carboxyllc Adds
Amines
Thiols
Sulfonlc Adds
Benzenes
Phenols
Heterocycllc Nitrogens
Heterocycllc Sulfurs
Aluminum
Tin
Lead
Phosphorus
Arsenic
Chromium
Mercury
Uranium
Nitrites*
Heterocycllc Oxygens*
Lithium*
Potassium*
Magnesium*
Calcium*
Strontium*
Barium*
Boron*
Gallium*
Thai 11 urn*
Silicon*
Lead*
Antimony*
81 smuth*
Sulfur Dioxide*
Carbonyl Sulflde*
Carbon Olsulflde*
Selenium*
Fluorine*
Fluoride*
Chloride*
Scandium*
Yttrium*
Titanium*
Zirconium*
Vanadium*
Niobium*
Molybdenum*
Tungsten*
Manganese*
Iron*
Cobalt*
Nickel*
Stiver*
Z1nc*
Lanthanum*
Cer1 urn*
Thorium*
Separator
Vent Gas
Carbon Dioxide
Carbon Monoxide
Nitrogen Dioxide
Ammonia
Cyanide
Hydrogen Sulflde
Carboxyllc Adds
Amines
Phenols
Fused Aromatic Hydro-
carbons
Heterocycllc Nitrogens
Heterocycllc Sulfurs
Lithium
Phosphorus
Arsenic
Chromium
Iron
Nickel
Copper
Silver
Uranium
Sulfur Dioxide*
Carbonyl Sulflde*
Carbon Olsulfide*
Heteroycllc Oxygens*
Sodium*
Magenslum*
Rubidium*
Calcium*
Strontium*
Barium*
Boron*
Aluminum*
Gallium*
Silicon*
Lead*
Antimony*
Selenium*
Fluorine*
Fluoride*
Scandium*
Titanium*
Zirconium*
Vanadium*
Molybdenum*
Tungsten*
Manganese*
Cobal t*
Z1nc*
Cadmium*
Mercury*
Lanthanum*
Cerium*
Ash
Lithium
Rubidium
Beryllium
Magnesium
Calcium
Strontium
Barium
Aluminum
Silicon
Lead
Phosphorus
Antimony
Selenium
Fluorine
Titanium
Zirconium
Vanadium
Chromium
Iron
Cobalt
Copper
Cadmium
Mercury
Uranium
Boron*
Gallium*
Arsenic*
Yttrium*
Niobium*
Lanthanum*
Cerium*
Separator
Liquor
Ammonia
Cyanide
Thlols
Phenols
Fused Aromatic Hydro-
carbons
Heterocyclic Nitrogens
Heterocycllc Sulfurs
Phosphorus
Arsenic
Selenium
Fluoride
Chloride
Carboxyllc Acids*
Lithium*
Rubidium*
Magnesium*
Calcium*
Barium*
Boron*
Silicon*
Antimony*
Fluorine*
Chlorine*
Scandium*
Byproduct
Tar
Carboxyllc Adds
Amines
Benzenes
Phenols
Fused Aromatic Hydro-
carbons
Heterocycllc Nitrogens
Heterocycllc Oxygens
Heterocycllc Sulfurs
Magnesium
Barium
Lead
Antimony
Chromium
Copper
Cadmium
Mercury
Rubidium*
Strontium*
Boron*
Gallium*
Arsenic*
Bismuth*
Selenium*
Yttrium*
Titanium* 1 Vanadium*
Yttrium*
Zirconium*
Niobium*
Tungsten*
Iron*
Copper*
Silver-
Cadmium*
Mercury*
Lanthanum*
Niobium*
Lanthanum*
Cerium*
Cerium* '
Cesium*
Substances which were also detected and are typically present 1n such samples, but were below the corresponding
(health) value.
Source: G. C. Page, Environmental Assessment: Source Test and Evaluation ReportChapman Low 8tu Gasification,
EPA-600/7-78-ZOE, October 1978.
94
-------
substances possessing environmental impact potential for the Chapman gasifier
utilizing Virginia bituminous coal are presented for five distinct process
streams. These are the coal feeder vent gas, separator vent gas, reactor
residue (ash), separator liquor, and byproduct tar stream.
6.3 BIOASSAY RESULTS
The Ames bioassay results for gasifier tar samples and tar fractions from
three gasification runs using Wyoming subbituminous coal (Runs 33, 35, and 47)
are shown in Figure 9. The consistency of the results among the three crude
tar samples is clearly seen. It is evident here from the dose-response
relationship for the organic base fraction of the tars that this fraction
possesses high potential mutagem'city.
The crude tar samples from four distinct coals are shown in Figure 10 to
vary markedly in their response in the Ames bioassay. The Illinois No.6 and
Western Kentucky No.9 coal-derived tars were highly toxic to the Salmonella
typhimurium, unlike the tars from the Wyoming subbituminous coal and North
Dakota lignite. A similar comparison of the results of the Ames bioassay with
the organic base fractions is shown in Figure 11. Here only the sample derived
from Western Kentucky No.9 coal was found to be highly toxic to the bacteria.
All of these samples gave high mutagenic ratios, as is seen in this figure.
In order to achieve meaningful results for mutagenic response with the
assay it is necessary to correct the data to a constant level of cell survival,
i.e., remove the toxicity effect. This has been done for the data of this
study; an example is shown in Figure 12. The number of revertants per plate
shown in this figure are corrected to a 100 percent cell survival basis.
The Ames and CHO assays on raw coal dust were found to indicate no muta-
genic potential based on the techniques utilized in this study. Generally, it
is recommended that particulate solids which are tested in bioassay studies
should be reduced to 5 micron size or less. The samples tested in this study
were at 74 micron or less. However, it is believed that based on the techni-
ques employed and the evidence at hand indicating that the particles used in
this study were incorporated into the CHO cells that meaningful results were
obtained.
The Ames bioassay test results on coal gasification samples are summarized
in Table 36. These results are presented based on the methods of Ames, et al.,
for conducting Ames bioassay tests.26 the results are expressed in the so-called
95
-------
WYOMING SUB-BITUMINOUS
TA98
2000
1600
1600
Z 1400
g 1200
1000
600
600
400
200
CRUOC TAM
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n
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t
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40 i
30
10
100
2SO
500 10 100 250
SOO
Figure 10. Ames bioassay results for gasifier tar samples from four separate
coals ( percent cell survival, i revertants per plate, - control)
97
-------
ORGANIC BASE COMPARISON
TAM
2000
1900
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r 1400
ฃ 1200
>
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900
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1900
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10 100 290
oose
Figure 11. Ames bioassay results for organic base fractions of gasifier
tar samples from four separate coals (ง percent cell survival,
A revertants per plate,- controls).
98
-------
WYOMING GASIFICATION
RUNซJS
1000
MO
MO
700
MO
MO
4M
300
2M
100
CRUOt TAB
*.
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Figure 12. Ames bioassay results for gasifier tar and fractions from Wyoming
coal (t percent cell survival, A revertants/plate,
-------
o
o
TABLE 36. AMES BIOASSAY TEST RESULTS OF COAL GASIFICATION SAMPLES*
(Highest Mutagenic Response Observed in Non-Toxic Dose Range)
SAMPLE/FRACTION
Crude Tar
Polynuclear Aromatic
Hydrocarbon
Polar Neutral
Nonpolar Neutral
Organic Acid
Organic Base
Aqueous Condensate
Hexane Insoluble
XAD (surge)
XAD (steady-state)
North Dakota
Lignite
Run #51
M ( 8.4)
M (10.0)
M ( 7.4)
Neg.
Neg.
H (32.8)
NT
NT
Neg.
Neg.
Wyoming
Subbit.
Run #33
M ( 3.6)
M (12.3)
M ( 3.8)
Neg.
Neg.
H (31.2)
NT
NT
NT
NT
Wyoming
Subbit.
Run #35
M ( 4.6)
M ( 5.2)
Neg.
Neg.
Neg.
H (26.3)
NT
NT
NT
NT
Wyomi ng
Subbit.
Run #47
M ( 3.1)
M ( 5.7)
M ( 4.7)
NT
Neg.
H (29.1)
Neg.
NT
NT
NT
W. Kentucky#9
Subbit.
Run #41
H (19
H (24
M (13
Neg.
Neg.
H (42
Neg.
Neg.
Neg.
Neg.
.2)
.1)
.4)
.6)
Illinois#6
Run #44
H (14
M (31
H (28
Neg.
Neg.
M (30
NT
NT
NT
NT
.6)
.8)
.4)
.0)
*Brusick Scheme Result (max. revertants/spontaneous revertants):
H - High mutagenicity - mutagenic response occurs at a dose of less than 50 yg.
M - Medium mutagenicity - mutagenic response occurs at a dose of 499 to 50 yg/plate.
L - Low mutagenicity - mutagenic response occurs at a dose of 5000 to 500 yg/plate.
NT - Not tested.
Neg. - Negative Response at the highest concentration tested.
-------
27
Brusick notation. Here a high mutagenicity is indicated when a sample
results in a mutagenicity ratio of 3 or greater at a dose of less than 50 ug.
Medium mutagenicity is indicative of a mutagenic ratio of 3 or greater at a
dose between 50 to 499 yg/plate. While low mutagenicity is indicative of a
mutagenic of 3 or greater obtained at a dose of 500 to 5,000 yg/plate. A
negative response would be indicated if higher concentrations were required to
elicit a mutagenic ratio of 3 or greater. The viability ratio indicates
whether the bacterial cells were capable of surviving the environment created
by the test sample. A viability of 50 percent or greater is required before
results are given credance. The mutagenicity results which were obtained in
this study required metabolic activation (S-9) and were confined to frame-
shift mutagenesis, i.e., active with strain TA 98 only.
The organic base fraction of the crude tar samples were found to be
extremely mutagenic in these studies. This is indicated in Table 36, not only
because high mutagenicity ratings resulted via the Brusick scheme for results,
but also because the highest mutagenic response observed in the nontoxic dose
range was of the order of 30 for these samples. This mutagenicity ratio can
be compared with the values of 3 to 19 which resulted for the crude tar samples.
The crude tars did show medium to high mutagenicity as can be seen in the
table with the Western Kentucky and Illinois coals giving rise to high values;
the Wyoming subbituminous and North Dakota lignite samples showed medium
mutagenicity. It may also be noted that both the PNA and the polar neutral
fraction of the crude tars also gave rise to medium mutagenicity in the case
of the Wyoming subbituminous coal and North Dakota lignite samples while
somewhat higher mutagenic ratios were obtained for these same samples for the
Illinois No.6 and Western Kentucky No.9 derived samples.
It may also be noted that negative results were obtained not only for the
aqueous condensate, the XAD-resin cartridges from the surge and steady-state
periods of various gasification tests, as well as the nonpolar neutral, organic
acid and hexane insoluble partitions of the crude tar samples. It is important
to note that the mutagenic ratios obtained for the organic base fractions of
the crude samples substantially exceeded the mutagenic ratios of the crude
tars themselves. This phenomenon can be referred to as an "unmasking" effect
in which the constituents of the organic base fraction and for that matter,
the PNA, and in some cases polar neutral fractions, possess substantially
higher revertants/pg than the crude tar itself.
101
-------
Cytotoxicity was studied in this project using Chinese hamster ovary
(CHO) cell in culture. The raw coal dusts were noncytotoxic to doses as high
as 10/mg dish, although the cells seemed to ingest the dust particles, the
cell cytoplasm appearing filled with particles after 24 hours. The CHO cyto-
toxic activity of the crude tars was similar to their mutagenic activity.
Those crude tar extracts which were strongly mutagenic were also typically
cytotoxic and some of the tar extracts which were weakly mutagenic were also
weekly cytotoxic. Basic organic fractions derived from the tar extracts
showed strongly cytotoxic behavior and in this regard, the cytotoxicity
results were also similar to the mutagenic results.
Figure 13 provides evidence of the efficacy of the CHO assay for the
determination of cytotoxic effects from cadmium. Note that cell survival is
a strong function of the cadmium concentration. Generally, it is believed
that the Ames test may not be sensitive to inorganic species, particularly as
a measure of their potential mutagenicity. Separate assay studies using
perhaps CHO cells or other techniques should be useful in this regard.
6.4 OTHER CONSIDERATIONS
Earlier work on the nonisothermal conversion of coals under various
operating conditions included the study of a range of coals. Kinetic para-
meters were measured for a range of gaseous species, including H9S and
32
acetylene. However, the study was limited due to the sampling and analysis
methods employed and the focus on gaseous species to the exclusion of aqueous
condensate, tars, and reactor residue, which were examined in this study.
Comprehensive reviews of experimental data on coal conversion processes
33-35
has been prepared in other related work. These provide a useful data
base for synthetic fuel production processes. However, the present work is
equally comprehensive in terms of its attention to the broad array of chemical
constituents present while being more quantitative in nature.
Greenwood, et al. have compiled a handbook (summary) of existing federal
regulations and criteria relevant to fossil fuel resource conversion. Yet, as
this present study indicates, a number of additional considerations remain to
37
receive attention. Miller discusses the potential problem due to teratogens,
carcinogens, and mutagens. Southworth, et al. detail a specific example,
which considers the ecological potential of azarenes in freshwater systems.
102
-------
500
400
300
ZOO
100
90
80
70
60
SO
40
30
20
5 10
I ฐ
J 6
24
48
72 90
TIME (HOURS)
120
144
168
Figure 13. The effect of cadmium on the growth of Chinese
hamster ovary cells in culture.
Triplicate cultures of CHO cells are axplanted at 10s cells, 35 mm
dish, incubated 24 hours at 37ฐC in a 5Z C02 atmosphere, and CdCl2 at
10"8 M ( 4 ), 10"7 M ( ฃ ), and ICf 5 M ( ), was added in 25 ul
DMSO, and Che cultures incubated 24 hours (arrows), at which time the
medium was replaced with fresh medium and incubation continued, counting
cells at 24 hour intervals using an automated cell counter. Control
cultures were Incubated with 25 ul DMSO ( Q > 0 >
103
-------
Actually, the environmental health problems of synthetic fuel plants must
be first regarded from an occupational health and safety perspective. In-plant
workers can potentially receive greater exposures than persons in the general
geographical area of a synthetic fuel plant. The National Institute of Occu-
pational Health and Safety (NIOSH) has developed some useful information on a
39 40 41
few specific compounds including H~S, coal tar products, cresol, and
42
chyrsene. These and other data on existing Lurgi coal gasification facili-
ties provide the basis of preliminary planning of commercial facilities.
As pilot, demonstration, and commercial coal gasification facilities are
constructed and operated, more data will become available. Environmental
monitoring guidelines have been prepared through both the U.S. Department of
Energy and the Environmental Protection Agency for these facilities.
104
-------
7.0 CONCLUSIONS
The objectives of this project have included the construction and opera-
tion of a laboratory facility to conduct experimentation on a range of U.S.
coals under various operating conditions to determine the potential environ-
mental pollutants which may result therefrom. Thus, it has been sought to
determine a fundamental understanding of the nature of the potentail pollutants
as well as the importance of those factors which may influence the the pro-
duction of the various chemical species involved. This information is
intended to be used for guidance in the development of control technology and
the establishment of guidelines for environmentally safe synthetic fuel
plants.
A series of screening test runs has been conducted in the RTI laboratory
gasification facility. A variety of coals have been used including Illinois
No.6, Western Kentucky No.9, Montana Rosebud, Wyoming subbituminous coals and
North Dakota lignite. Chemical analyses of the coal, reactor residue (ash),
aqueous condensate, tars and primary gaseous products have been performed.
Emphasis has been placed upon determination of these organic constituents in
the effluent streams while importance has also been attached to inorganic
species in the various streams of the process. The process has involved not
only the laboratory gasifier and associated control and data collection system
(signal processor) but the development of appropriate sampling, chemical
analysis and biological evaluation techniques. Other reports have been pre-
pared on many of these subjects.
Roughly, it has been found that the chemical constituents of the gasifier
effluent streams, generated under appropriate conditions of temperature and
pressure to result in satisfactory reactor operation at air and steam rates
comparable to those of commercial significance, are very much the same without
regard to coal type within the range of coals studied in this project. The
actual concentration of individual species does in fact depend upon the coal
but more significantly, upon the operating conditions of the gasifier and the
process configuration relative to filters, traps, condensers, and other process
operations.
105
-------
A variety of chemical constituents have been identified as compounds
possessing potential for generating undesirable health effects not only to
in-plant workers but to the environment surrounding a synthetic fuels plant.
The gas stream has been identified to contain a variety of polynuclear
aromatic hydrocarbons, phenolic compounds, and sulfur-containing species in
addition to the primary gases of carbon monoxide and hydrogen. The aqueous
condensate stream was determined to possess substantial quantities of phenolic
compounds, i.e., phenols, cresols, and xylenols, at significant levels from a
health and/or ecological perspective. Moreover, the tar stream was also
found to contain a variety of phenolic and PNA species at significant concen-
tration levels based on health or ecology-related reference data.
Bioassays on the tar samples indicate that the organic base constituents
possess a high potential to create mutagenic changes while the PNA and polar
neutral fractions also possess moderate to high rankings. The other fractions
of the crude tar as well as the other effluent and related constituents of
the gasification process were found to be nonmutagenic. The reactor residue
is known to carry trace elements originating in raw coal which have some
potential to create severe health effects. These were found to be primarily
arsenic and selenium. (Chromium which was found in various of the gasifica-
tion reactor effluents is known to result primarily from the stainless steel
metal from which the gasification reactor was constructed.) It must be noted
that to date organometallic compounds have not been identified or quantitated
in this study. It is believed, however, that some of the trace element
constituents of raw coal may well exist in the gasification process system as
a part of organic molecules. These could have potential health effects if
released to the environment.
Fugitive emissions are known to be a problem area in the operation of
chemical process plants. No systematic approach to the consideration of
fugitive emissions has been taken in this study except through analysis and
examination of each of the effluent streams from the gasifier. The particular
nature and quantity of the various discharges to the environment which would
be a part of a commercial coal conversion facility is dependent upon many
factors including the environmental control standards prevailing or applicable
to that particular facility, the nature of the specific process being employed
along with the large number of processing operations to be included in the
plant.
106
-------
Various choices are involved in selecting a gasifier type for a synthe-
tic fuel plant as well as in the development of the process configuration.
Not only is it possible to recycle undesirable constituents, i.e., oils, tar,
and/or aqueous condensate, to the gasification reactor, but additional pro-
cess units may be installed to remove and/or contain any of the various
species present. However, this study is useful in that it provides a sub-
stantial data base for a number of U.S. coals under various operating con-
ditions. While the data were generated in a fixed-bed coal gasification
reactor, the data are also of interest in helping to understand other gasifica-
tion reactor types.
A versatile gasification system for laboratory use has been constructed
and operated. This facility has permitted an examination of various coals
and operating conditions. The various effluents were analyzed and charac-
terized. Operation of the facility under carefully controlled conditions in
which specifically determined variables are set at preselected values can be
performed and analyzed. This system gives rise to basic data for an under-
standing of pollutant formation and their control during coal gasification.
107
-------
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Ill
-------
APPENDIX
Page
Table 1-1: Concentration of Species in Gas Stream 1-1
Table 1-2: Concentration of Species in Aqueous Condensate 1-17
Table 1-3: Concentration of Species in Gasifier Tar 1-24
Table 1-4: Concentration of Species in Solid Residue 1-34
112
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TABLE 1-1. CONCENTRATION OF SPECIES IN GAS STREAM
(micrograms per cubic meter)
Compound
Mol. Wt.
OMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Methane
16
3.3E+6
5.9E+7
6.4E+7
2.8E+7
3.6E+7
3.4E+7
2.8E+7
1.7E+7
5.7E+7
3.7E+7
3.5E+7
2.5E+7
2.1E+7
2.2E+6
1.6E+7
3.5E+7
1 . 7E+7
2.1E+7
3.0E+7
Ethane
30
6.2E+6
6.5E+6
1 . 3E+6
9.0E+5
1 . 3E+6
--
--
Propane
44
9.0E+6
3.6E+6
2.9E+5
1.4E+5
1.6E+5
~
n-Butane
58
1 .4E+6
2.0E+5
5.2E+4
2.5E+4
6.5E+4
--
--
--
--
Isobutane
58
1.4E+6
4.0E+5
5.2E+4
2.5E+4
6.5E+4
Pentanes
72
1 .8E+6
--
3.2E+4
8.0E+3
--
--
--
--
--
--
--
--
Cyclopentane
70
3.5E+6
1.5E+4
1-1
-------
Table 1-1 (continued). GAS STREAM
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
3-Methylpentane
86
3.5E+5
6.0E+4
Methyl cycl open tane
84
3.5E+5
2.3E+4
Ethyl ene
28
5.7E+6
1.8E+6
2.4E+5
9.4E+5
Propylene
42
8.6E+6
2.1E+6
3.7E+5
l.OE+5
1.9E+5
1-Butene
56
9.1E+6
5.6E+4
--
2-Pentene
70
3.5E+5
--
2.1E+4
1-2
-------
Table 1-1 (continued). GAS STREAM (ug/m3)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38 P
38G
41
43
44
45
2-Methyl-l-Butene
70
3.5Et5
..
l.OE+4
~
Acetyl ene
26
2.7E+6
1.2E+4
3.0E+4
1.2E+4
Propyne
40
1.7E+6
1.4E+4
Benzaldehydo
106
5.9E+4
2.0E+0
1.2E+4
Acetophenone
120
4.1E+4
2.7E+4
--
--
Acetic Acid
60
2.5E+4
--
--
3.9E+4
1-3
-------
Table 1-1 (continued). GAS STREAM (yg/m3)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Methanethiol
48
l.OE+3
4.1E+3
8.6E+3
1.7E+4
4.0E+3
9.0E+3
8.7E+2
1.3E+4
4.9E+3
6.5E+3
l.OE+4
3.4E+4
4.5E+3
1.2E+4
l.OE+4
5.0E+3
1.6E+3
6.5E+3
C2H6S
62
l.OE-i-3
2.5E+4
--
--
4.0E+3
3.6E+2
--
3.0E+3
9.7E+3
4.6E+3
5.3E+3
3.0E+4
6.0E+3
1.4E+4
4.4E+3
Benzene
78
3.0E-H3
7.7E+3
1.1E+6
--
3.0E+6
2.5E+6
1.4E+6
4.4E+6
3.2E+6
2.1E+6
1 . 5E+6
2.3E+6
1 .8E+5
2.8E+5
3.3E+6
7.1E+5
1.7E+6
1.5E+6
Toluene
92
3.8E+5
5.7E+3
7.8E+6
l.OE+5
9.0E+5
2.1E+5
6.4E+5
1.1 E+6
8.4E+5
8.8E+5
6.2E+5
2.7E+5
2.5E+5
4.4E+5
4.1E+5
4.1E+5
8.4E+5
Ethyl benzene
106
4.4E+5
2.2E+4
8.2E+3
--
8.6E+4
8.0E+2
8.6E+4
5.8E+4
4.9E+4
--
8.0E+4
7.6E+4
7.4E+4
2.9E+4
2.1E+4
2.7E+4
1.5E+4
5.7E+4
Xylenes
106
4.4E+5
2.2E+4
2.0E+4
/
8.8E+4
4.0E+3
1.1 E+5
1.9E+5
--
7.3E+5
2.1 E+5
3.2E+5
1.7E+5
2.2E+5
1.6E+5
7.3E+4
1.3E+5
8.0E+4
2.9E+5
Biphenyl
154
l.OE+3
4.4E+2
4.0E+2
1.9E+3
3.0E+1
2.7E+3
6.2E+2
2.0E+4
1.2E+3
2.9E+3
1.2E+3
1.4E+3
7.8E+2
1.5E+3
9.6E+2
5.8E+2
--
1-4
-------
Table 1-1 (continued). GAS STREAM (ug/m3)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Diphenylmethane
168
l.OE+3
3.1E+2
--
2.7E+3
3.1E+2
3.9E+3
4.9E+2
1.3E+3
6.0E+2
4.7E+2
--
--
C2H7-Benzene
133
2.5E+5
1 . 1 E+4
3.8E+3
--
--
--
--
C4-Benzene
137
2.5E+5
4.6E+4
2.0E+3
~
~
--
2.5E+5
Cg-Benzene
149
2.5E+5
1.5E+4
--
--
--
--
--
--
--
--
Indan
118
2.3E+5
5.4E+3
1.3E+4
--
4.9E+3
2.0E+2
5.9E+2
1.5E+3
4.1E+4
2.0E+3
3.5E+4
7.8E+3
2.8E+3
2.5E+4
1.3E+4
7.8E-I-3
2.6E+3
--
Indene
116
4.5E+4
8.1 E+4
9.1E+4
1.9E+3
l.OE+2
6.3E+4
3.3E+4
4.0E+5
2.4E+4
2.5E+5
5.6E+4
3.4E+4
8.6E+4
--
1.3E+5
l.OE+5
l.OE+5
1-5
-------
Table 1-1 (continued). GAS STREAM (yg/nT)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Xylenes
106
4.4E+5
2.2E+4
2.0E+4
8.8E+4
--
.
1.8E+5
--
1.2E+4
3.0E+4
6.0E+4
Di ethyl benzene
134
2.3E+5
2.4E+3
--
Trimethyl benzene
120
1.2E+5
--
9.6E+2
--
--
--
--
--
--
--
Methyl indene
130
4.5E+4
7.1E+4
9.0E+4
/
--
--
--
2.6E+3
6.2E+3
C^-Benzenes
120
2.2E+5
6.2E+4
2.8E+5
1.1E+5
4.8E+4
1.5E+5
3.6E+4
4.9E+4
1.1E+4
1-6
-------
Table 1-1 (continued). GAS STREAM (yg/m3)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38 P
38G
41
43
44
45
Dimethyl biphenyl
182
l.OE+3
2.0E+3
--
Phenol
94
1.9E+4
2.9E+4
5.2E+3
--
2.8E+4
--
3.9E+4
3.1E+4
4.3E+5
6.4E+4
5.6E+5
2.4E+5
6.9E+4
9.1E+4
--
9.6E+4
8.3E+3
7.8E+3
--
Cresols
108
2.2E+4
1.2E+5
4.4E+3
--
6.9E+4
--
9.0E+4
1.1E+4
2.1E+5
3.5E+4
1.5E+5
1.1 E+5
5.9E+4
2.0E+5
6.2E+4
5.1E+4
1 . OE+4
Cp-Phenols
122
2.5E+4
3.8E+5
5.0E+3
--
--
--
--
--
--
--
--
Xylenols
122
1.3E+4
--
--
6.9E+4
--
2.2E+4
7.8E+5
6.4E+4
6.5E+5
2.8E+5
2.1 E+5
8.8E+5
3.6E+2
Naphthalene
128
5.0E+4
6.2E+4
2.8EH
1.7E+5
3.1E+3
5.9E+5
4.0E+4
2.6E+5
1.4E+5
1.2E+5
3.4E+4
l.OE+5
4.0E+4
--
5.6E+5
2.3E+4
4.5E+4
--
1-7
-------
Table 1-1 (continued). GAS STREAM (yg/nr)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
a-Methyl naphthal ene
142
2.3E+5
l.OE+3
2.8E+4
4.0E+4
--
--
2.4E+3
1.2E+3
0.9E+0
--
B-Methyl naphthal ene
142
2.2E+5
4.4E+2
5.0E+3
5.9E+4
2.1E+3
0.9E+0
Acenaphthene
154
1.6E+3
4.4E+2
5.2E+2
--
--
--
--
8.0E+3
--
2.0E+2
3.0E+2
1 . 3E+2
--
1.3E+3
4.0E+0
1.0E+0
--
Anthracene
178
2.4E+4
7.4E+1
5.7E+2
1.6E+3
7.0E+0
1.2E+3
6.2E+2
7.6E+3
4.0E+2
1.1 E+3
4.7E+2
4.0E+2
1 . 3E+2
1.8E+3
1.8E+3
7.1E+2
1-8
-------
Table 1-1 (continued). GAS STREAM Ug/m3)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Phenanthrene
178
1.6E+3
~
6.9E+2
7.8E+2
2.0E+1
--
6.9E-1
2.2E+2
Propenyl phenanthrene
218
2.4E+4
7.7E+0
--
--
--
CicHi2: 3 Rings
192
1.6E+3
--
--
8.0E+1
6.6E+1
--
2.3E+1
--
--
C16H1Q: 4 RingS
202
2.6E-1
--
j
--
1 . 7E+2
2.0E+2
--
3.8E+1
--
--
Pyrene
202
2.3E+5
l.OE+2
--
--
--
--
--
--
1 .8E+1
--
1-9
-------
Table 1-1 (continued). GAS STREAM (yg/mj)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Fluorene
202
9.0E+2
7.0E+0
3.1E+3
--
--
--
--
Fluoranthene
166
9.0E+5
7.0E+1
--
ซ
--
Pyridine
79
1.5E+4
--
--
ซ>
Benzofuran
118
5.3E+6
--
1 . 3E+5
--
2.1E+4
5.5E+4
l.OE+4
1.3E+5
7.9E+3
4.2E+4
6.2E+3
1 . 5E+4
3.1E+4
2.8E+4
2.2E+4
--
Methyl benzofuran
132
5.3E+6
l.OE+4
4.8E+0
--
--
__
1-10
-------
Table 1-1 (continued). GAS STREAM (yg/m3)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38 P
38 G
41
43
44
45
Dimethyl benzofuran
146
5.3E+6
1.2E+3
__
--
--
--
Di benzofuran
168
5.3E+6
2.0E+3
--
9.8E+3
1.2E+4
9.2E+2
1.8E+4
1.3E+3
8.4E+3
2.9E+3
3.2E+3
--
9.3E+2
3.5E+2
6.0E+2
Thiophene
84
4.5E+3
1.3E+5
4.0E+5
--
1.2E+5
6.6E+5
1.1E+4
4.1E+4
2.9E+4
4.2E+3
1.2E+4
2.2E+5
5.0E+3
l.OE+4
7.0E+4
4.0E+3
8.0E+4
2.1E+4
Methyl thiophene
98
2.3E+4
4.4E+4
1.7E+3
--
5.0E+3
9.3E+3
--
5.8E+3
3.2E+3
8.7E+4
1.6E+4
l.OE+5
imethyl thiophene
113
2.6E-I-4
4.4E+4
1.7E+3
1.6E+4
--
1.5E+4
--
--
1-11
-------
Table 1-1 (continued). GAS STREAM
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38 P
38 G
41
43
44
45
Cp-Thiophenes
112
2.6E+4
2.3E+3
--
7.8E+4
9.4E+4
1 . OE+3
3.0E+4
4.0E+4
1.6E+3
1.3E+4
9.3E+3
5.6E+2
6.5E+3
--
--
Benzothiophene
134
2.3E+4
3.7E+3
2.7E+3
--
1.6E+4
--
--
--
--
Sodium
23
5.3E+4
7.2E+1
--
--
Potassium
39
2. OE+3
--
--
--
7.8E+0
--
--
--
--
--
Aluminum
27
5.2E+3
--
--
--
--
--
--
--
--
--
--
--
TOC
12
4.0E+4
--
--
4.2E+3
--
--
--
--
--
--
--
1-12
-------
Table 1-1 (continued). GAS STREAM (yg/nr)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Carbon Monoxide
28
4.0E+4
2.1E+8
1.7E+8
2.6E+8
1.9E+8
1.4E+8
1.7E+8
3.0E+8
5.8E+8
3.3E+8
3.4E+8
1.9E+8
2.6E+8
9.6E+6
l.OE+8
1.9E+8
2.7E+8
8.0E+7
2.8E+8
Carbon Dioxide
44
9.0E+6
4.1E+8
3.0E+8
2.8E+8
3.4E+8
3.0E+8
4.7E+8
1.8E+8
3.2E+8
1.7E+8
8.4E+8
2.4E+8
2.0E+8
8.7E+7
2.7E+8
2.8E+8
1.7E+8
3.1E+8
1.8E+8
Lead i
207
1.5E+2
--
--
--
Ammonia
17
1.8E+4
2.3E+5
8.4E+4
--
ซ
--
Hydrogen Cyanide
17
5.0E+3
--
--
2.6E+4
--
3.0E+4
--
--
Arsenic
75
2.0E+0
--
l.OE+0
--
--
--
--
1-13
-------
Table 1-1 (continued). GAS STREAM (yg/nr)
Compound
Mol. Wt.
OMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
383
41
43
44
45
Antimony
122
5.0E+2
--
--
--
--
--
--
--
Sulfur Dioxide
64
1 . 3E+4
2.7E+4
--
--
--
--
Hydrogen Sulfide
34
1.5E+4
1.6E+7
8.5E+6
7.5E+6
7.6E+6
5.3E+6
1.7E+7
9.6E+5
2.5E+6
9.8E+5
8.8E+5
1.3E+5
--
1.8E+5
4.0E+4
--
--
Carbonyl Sulfide
60
3.8E+3
1.8E+5
8.8E+4
7.3E+4 ,
4.0E+4
2.2E+4
9.8E+4
3.1E+4
5.0E+4
1.8E+5
5.1E+4
6.8E+4
1 . OE+6
1.4E+6
4.2E+6
7.1E+6
6.4E+5
6. OE+6
1.2E+6
Carbon Disulfide
76
3.0E+3
1 . 1 E+4
1.7E+4
1.5E+3
l.OE+4
4.0E+3
4.4E+4
--
3.4E+3
7.5E+4
1.5E+5
1.4E+5
7.5E+4
1.5E+5
1.4E+5
1.5E+5
1.2E+5
2.9E+5
1.4E+5
1-14
-------
Table 1-1 (continued). GAS STREAM (yg/m3)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38 P
38G
41
43
44
45
Selenium
76
2.0E+2
l.OE+5
2.3E+4
2.0E+2
3.0E+3
1.3E+4
1.4E+3
Bromine
160
7.0E+3
Scandium
45
5.3E+4
1 .8E+5
Titantium
48
6.0E+3
Chromium
52
l.OE+3
Manganese
55
5.0E+3
/
Cobalt
59
5.0E+1
1-15
-------
Table 1-1 (continued). GAS STREAM (ug/m )
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
Copper
64
2.0E+2
38G 1
41
43
44
45
Cadmium
112
l.OE+1
Mercury
201
5.1E+1
Hydrogen
"2
4.1E+5
5.0E+7
3.0E+7
2.8E+7
2.7E+7
2.0E+7
1.5E+7
1.2E+7
3.3E+7
1.7E+7
1 . 6E+7
1 . 1 E+7
1.2E+7
6.6E+6
1.4E+7
1.1E+7
1.1E+7
1.4E+7
1-16
-------
TABLE 1-2. CONCENTRATION OF SPECIES IN AQUEOUS CONDENSATE
(micrograms per liter)
Compound
Mol. Wt.
OMEG
Run No.
6
16
20
21
23 !
25
26
31
32
33
35
36
38 P
38 G
41
43
44
45
Phenol
094
1.7E+4
2.0E+5
--
4.7E+4
1.3E+5
4.9E+5
5.9E+5
4.1E+6
3.3E+5
1.8E+6
l.OE+6
2.9E+4
7.7E+5
3.9E+5
2.7E+6
!l
Cresols
108
5.0E+0
3.4E+5
1.1E+5
1.6E+5
2.2E+5
3.6E+5
7.2E+5
3.6E+5
1.1E+6
5.3E+5
3.5E+4
8.6E+5
3.5E+5
1.5E+6
Xylenols
122
5.0E+0
6.8E+4
6.3E+4
1.8E+4
3.7E+4
1.6E+5
1.3E+5
2.3E+5
1.3E+5
2.6E+4
3.4E+5
4.9E+4
3.1E+5
4.8E+2
Trimethyl phenol
134
5.0E+0
--
1.8E+4
--
--
1 -Methyl naphthal ene
3.4E+6
--
1-17
-------
Table 1-2 (continued). AQUEOUS CONDENSATE (yg/L)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
2-Methyl naphtha! ene
3.4E+6
25 j
26
31
32
33
35
36
38P
38G
41
43
44
45
2.2E+2
Anthracene
8.4E+5
4.1E+1
Phenanthrene
2.4E+4
9.6E+1
Acenaphthylene
2.4E+4
5.7E+1
Chrysene
3.3E+4
1.6E+2
1-18
-------
Table 1-2 (continued). AQUEOUS CONDENSATE (Mg/L)
Compound Triphenylene
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
3.9E+0
0.5E+2
Fluorene
6.8E+5
5.7E+1
Fluoranthene
1.4E+6
2.8E+1
Benzo(a)pyrene
3.0E-1
3.6E+1
Benzo(e)pyrene
4.6E+4
2.1E+1
1-19
-------
Table 1-2 (continued). AQUEOUS CONDENSATE (yg/L)
Perylene
Mol. Wt.
DMEG
Run No.
5
16
20
21
23
25
26
31
32
33
35
36 |
38P
38 G
41
43
44
45
3.0E-1
I
--
--
"
2.1E+1
Benzo(k)fl uoranthene
2.4E+5
1.7E+1
Benzo(b)fl uoranthene
1 . 3E+4
3.3E+1
Lead
207
2.5E+2
1.3E+3
3.0E+1
1.2E+1
6.9E+1
1.4E+1
1 . 3E+1
2.1E+1
4.4E+1
Nitrates
078
1.4E+5
l.OE+1
l.OE+1
--
1-20
-------
Table 1-2 (continued). AQUEOUS CONDENSATE (pg/L)
Compound IjCyanide
Mol. Wt.
OMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
026
l.OE+3
--
3.5E+3
3.5E+3
--
1.3E+4
--
' --
36 i
38P
38G
41
43
44
45
i
--
Hydrogen Cyanide
027
l.OE+3
--
--
5.1E+3
8.6E+3
Ammonia
017
2.5E+3
4.0E+6
4.0E+6
7.9E+6
3.1E+6
5.3E+6
--
Phosphorus
031
1.5E+4
l.OE+2
l.OE+2
l.OE+2
--
Arsenic
075
2.0E+0
6.7E+1
2.3E+2
2.3E+2
l.OE+2
2.9E+1
9.7E+2
Sulfur
032
2.0E+5
5.7E+5
5.7E+5
8.4E+5
--
--
Thiocyanate
058
8.7E+3
2.7E+5
2.7E+5
2.1E+5
--
1-21
-------
Table 1-2 (continued). AQUEOUS CONDENSATE (yg/L)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Antimony
122
2.3E+2
1.5E+1
3.5E+0
9.6E+0
4.0E+0
--
--
Selenium
079
2.2E+1
--
--
Chlorides
035
1.3E+6
2.2E+6
--
1 . 1 E+6
--
Bromine
080
1.3E+6
--
--
--
--
--
Scandium
045
8.0E+5
--
Titanium
043
9.0E+4
--
Vanadium
051
2.5E+3
--
Chromium
052
8.0E-1
5.0E+2
2.9E+2
3.6E+2
4.6E+2
3.2E+3
3.4E+2
2.6E+2
1-22
-------
Table 1-2 (continued). AQUEOUS CONDENSATE (ug/L)
Compound
Mol. Wt.
OMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Manganese
055
2.5E+2
--
1.8E+2
Iron
056
1.5E+3
--
--
Cobalt
059
7.5E+2
--
--
--
Nickel
059
2.5E+2
--
--
Copper
064
5.0E+3
--
--
--
Zinc
065
8.4E+4
--
--
Cadmium
112
5.0E+0
9.6E+1
*
3.8E+0
1.3E-1
4.4E+0
8.5E+0
3.4E-1
7.3E+0
1.5E+1
1.3E-1
Mercury
201
l.OE+0
--
--
1-23
-------
TABLE 1-3. CONCENTRATION OF SPECIES IN GASIFIER TAR
(micrograms per gram of tar)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
!
43
44
45
Aniline
093
6.0E+4
1.5E+2
2.7E+2
-
3.8E+1
7.6E+1
1.3E+1
7.2E+1
4.8E+1
8.0E+1
9.3E+1
2.1E+1
3.8E+0
3.3E+0
Benzidine
184
3.0E+3
3.1E+3
5.0E+2
6.0E+2
2.0E+2
--
3.0E+2
2.0E-3
3.0E+2
4.0E+2
2.0E+2
Biphenyl
3.0E+3
1.9E+3
2.6E+3
2.2E+3
2.9E+3
--
--
2.1E+3
1.5E+3
3.8E+3
2.9E+3
2.1E+3
Phenol
094
3.4E+3
2.2E+2
2.9E+3
4.6E+3
4.3E+3
1.7E+3
3.5E+3
1.3E+4
1 . 1 E+4
5.6E+3
7.5E+2
2.9E+3
1.2E+3
5.1E+3
5.3E+2
Cresols
108
l.OE+0
5.3E+2
--
1.1E+4
1.4E+4
7.6E+3
1.1E+4
1 . 1 E+4
2.9E+3
2.7E+4
1.1E+4
2.3E+3
1.9E+4
8.6E+3
1.6E+4
1.4E+3
Xylenols
122
l.OE+0
--
2.7E+3
1.1 E+4
2.3E+3
5.2E+3
8.9E+3
2.2E+4
1.7E+4
8.4E+2
1.4E+3
1 . 1 E+4
4.8E+3
1.2E+5
2.0E+3
Trimethyl phenol
134
l.OE+0
--
--
2.5E+3
6.9E+2
7.9E+2
1.2E+3
2.7E+3
1.4E+3
1.7E+3
1 . 3E+3
--
1 . 7E+3
2.4E+4
1.7E+2
1-24
-------
Table 1-3 (continued). GASIFIER TAR (pg/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
o-Isopropyl phenol
134
l.OE+0
20
21
23 |
25
26
31
32
33
35
36
38P
38G
41
43
44
45
2.5E+3
--
1.9E+3
5.3E+2
9.5E+2
6.2E+5
5.0E+2
1.3E+3
5.4E+3
7.2E+2
2.9E+3
Naphthalene
128
1 . 5E+4
1.7E+3
2.3E+4
5.7E-H
2.6E+4
1.2E+4
6.5E+3
1 . 1 E+4
7.4E+3
1.6E+3
2.2E+6
8.4E+1
1.5E+3
8.5E+3
3.6E+3
1.8E+4
C2-(alkyl)naphthalene
6.8E+5
2.8E+3
1.1 E+4
7.4E+3
1.6E+4
6.4E+3
8.2E+3
6.9E+6
--
2.0E+3
7.9E+3
-Methyl naphthalene-
6.8E+5
5.1E+3
3.3E+3
2.5E+3
7.9E+3
--
5.2E+3
4.9E+3
7.1E+6
3.4E+3
4.9E+3
1-25
-------
Table 1-3 (continued). GASIFIER TAR (ug/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38 P
38 G
41
43
44
45
2-Methyl naphthalene
142
6.8E+5
4.8E+5
l.OE+4
4.3E+3
l.OE+4
2.2E+3
6.1E+3
6.3E+3
3.8E+3
4.3E+3
9.5E+2
3.8E+3
6.4E+3
4.5E+3
5.2E+3
Acenaphthylene
4.8E+3
7.8E+5
1.2E+4
1 . 1 E+4
1.8E+4
--
_.
4.8E+4
1.7E+3
1.5E+4
6.0E+3
3.1E+3
Acenaphthene
4.8E+3
2.7E+5
--
3.8E+3
2.7E+3
4.1E+3
--
--
2.2E+3
1.5E+3
3.9E+3
--
--
4.2E+3
1.8E+3
Anthracene
178
16.8E+4
1.1E+6
--
7.4E+3
6.2E+3
3.6E+3
1.5E+4
6.8E+3
2.6E+3
1.2E+4
1.1 E+3
3.2E+3
2.3E+4
6.7E+3
2.1 E+4
1-26
-------
Table 1-3 (continued). GASIFIER TAR (ug/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
Phenanthrene
178
4.8E+3
3.5E+3
2.3E+4
23 1
25
26
31
32
33
35
36
38P
38G
41
43
44
45
2.3E+4
1.8EH
1 . 5E+4
6.5E+3
3.4E+3
1.6E+3
7.4E+3
1 . 5E+3
4.1E+3
2.2E+4
2.3E+6
8.6E+6
9-Methyl anthracene
190
4.8E+3
--
1.8E+4
1.6E+4
3.1E+3
1.9E+3
2.0E+2
1 . 2E+2
1.9E+3
1.7E+2
4.8E+3
9.8E+3
4.3E+3
7.6E+4
1.7E+6
Benz (a) anthracene
13.4E-H
1.4E+3
1.3E+3
4.7E+3
2.8E+3
7.0E+3
4.0E+2
2.0E+2
2.1E+3
1.2E+3
l.OE+5
Triphenylene '
7.8E+0
2.0E+3
4.6E+3
3.2E+3
6.2E+3
6.0E+2
3.0E+2
2.5E+3
4.1E+3
l.OE+5
1-27
-------
Table 1-3 (continued). GASIFIER TAR (yg/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38 P
38 G
41
43
44
45
Perylene
252
6.0E+0
2.9E+3
3.7E+3
2.7E+4
1.2E+3
6.7E+3
1.1E+3
2.4E+2
8.3E+5
--
8.6E-H
1.5E+3
Fluorene
166
13.6E+4
7.4E+1
5.2E+3
8.0E+3
--
4.6E+2
7.3E+3
3.2E+3
4.2E+3
4.7E+3
1 . 7E+3
4.8E+3
5.9E+2
1 . 5E-I-3
7.5E+3
4.0E+3
5.1E+3
Fluoranthene
202
2.8E+5
6.2E+3
9.8E+3
1 . 3E+4
1 . 3E+4
1.1E+4
8.4E+3
1 . 3E+4
2.7E+3
4.1E+5
7.6E+3
5.0E+2
2.0E+3
3.4E+4
1 . 5E+3
1.6E+4
Benzo(g,h,i)perylene
13.0E+1
l.OE+2
1.8E+3
1 . 1 E+3
2.7E+3
--
6.0E+1
2.0E+2
--
2.0E+2
2.0E+1
--
Benzo(a)fluorene
15.4E+4
1.8E+3
2.6E+3
1.8E+3
4.1E+3
--
1.2E+3
1.1E+3
2.6E+3
--
9.0E+2
4.0E+2
1-28
-------
Table 1-3 (continued). GASIFIER TAR (vg/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
Chrysene
228
6.6E+3
5.9E+3
21 | 8.0E+3
23
25
26
31
32
33
35
36
38P
386
41
43
44
45
8.6E+3
7.3E+3
5.2E+3
8.7E+3
1.7E+3
6.9E+2
2.6E+3
2.5E+3
5.8E+3
1.8E+4
Pyrene
202
6.8E+3
1.8E+3
7.4E+3
9.0E+3
1.1E+4
l.OE+4
8.4E+3
1.2E+4
2.1E+3
1.2E+3
4.8E+3
3.4E+2
1.8E+3
2.4E+4
1.3E+3
1.7E+4
Dibenzo (a ,h) anthracene
2.8E+0
2.0E+2
2.8E+3
1.6E+3
3.4E+3
--
l.OE+2
3.0E+2
4.0E+2
2.0E+1
enzo(a)pyrene
6.0E+0
6.0E+2
3.5E+3
2.0E+3
2.7E+3
3.0E+5
5.0E+1
1.1E+3
1.7E+3
2.0E+1
enzo(e)pyrene
9.2E+3
4.0E+2
--
2.1E+3
1.2E+3
1.9E+3
--
--
3.0E+2
3.0E+1
6.0E+2
--
1.4E+3
l.OE+1
1-29
-------
Table 1-3 (continued). GASIFIER TAR (yg/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
Benzo(b)fluorene
15.4E+4
9.0E+2
1.7E+3
23 || 9-OE+2
25
26
31
32
33
35
36
38P
38G
41
43
44
45
2.4E+3
8.0E+2
9.0E+2
1.7E+3
6.0E+2
3.0E+2
Benzo(k)fluoranthene
9.6E+4
7.0E+2
1.6E+3
9.0E+2
1.2E+3
3.0E+2
4.0E+1
1.1 E+3
l.OE+3
2.0E+1
Benzo(b)fluoranthene
2.6E+3
l.OE+3
3.1E+3
1.8E+3
2.5E+3
4.0E+2
6.0E+1
1.4E+3
1.2E+3
3.0E+1
1-30
-------
Table 1-3 (continued). GASIFIER TAR (ug/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38 P
38G
41
43
44
45
IndenoO ,2,3-cd)pyrene
4.8E+3
l.OE+2
1.4E+3
8.0E+2
1.7E+3
--
5.0E+1
l.OE+2
3.0E+2
2.0E+1
Quinoline
4.8E+3
2.2E+3
3.1E+3
2.5E+3
2.9E+3
2.2E+3
9.7E+2
8.3E+2
1.2E+2
1.4E+3
8.0E+1
5.3E+2
1.1E+3
2.5E+2
7.6E+2
Acridine
2.8E+5
--
1.7E+3
1.7E+3
--
1.5E+3
7.7E+2
1 .4E+3
3.4E+2
2.0E+2
3.4E+1
l.OE+3
8.0E+2
1.2E+2
4.7E+2
2.5E+1
7.0E+2
Indole
3.2E+4
--
3.7E+1
5.8E+1
--
3.8E+4
3.8E+1
6.7E+0
1.2E+1
2.4E+1
2.3E+1
8.0E+0
2.4EH
6.7E+0
3arbazole
7.0E+4
8.0E+2
--
1.2E+3
1.2E+3
2.6E+3
6.0E+2
5.0E+2
5.0E+2
--
1.7E+3
9.0E+2
--
1-31
-------
Table 1-3 (continued). GASIFIER TAR (yg/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
1
Dibenzofuran
168
10.4E+5
8.9E+3
4.6E+3
7.4E+3
5.2E+3
5.4E+3
2.0E+3
3.4E+3
3.4E+3
1 . 4E+3
3.7E+3
8.1E+3
9.0E+2
9.2E+3
Benzothiophene
7.0E+4
6.6E+3
5.3E+3
3.6E+3
1 . 7E+3
8.0E+2
4.0E+2
3.3E+3
7.5E+2
2.3E+3
8.7E+3
4.7E+3
Lead
207
5.0E+1
8.5E-1
--
1.1E+0
3.1E-1
4.9E-1
3.3E+1
1.1E+1
7.3E-1
2.5E+0
7.0E+2
Arsenic
075
4.0E+0
1 . 3E+0
--
4.2E+0
1.9E+1
--
8.0E-1
--
Antimony
122
14.6E+1
--
--
--
--
7.0E-2
2.3E-1
1.2E-1
9.8E-2
5.0E-1
5.7E-1
--
Sulfur
032
4.0E+4
1.9E+4
1.6E+4
--
1.8E+4
7.1E+3
--
--
1-32
-------
Table 1-3 (continued). GASIFIER TAR (yg/g)
Compound
Mol. Wt.
OMEG
Run No.
6
16
20
21
Selenium
079
4.4E+0
23 |
25
i
26
31
32
33
35
36
38P
38G
41
43
44
45
__
--
--
Bromine
080
2.6E+5
Scandium
045
16.0E+4
--
--
Titanium
048
18.0E+3
--
Vanadium
051
5.0E+2
--
Chromium
052
16.0E+0
1.1E+1
4.1E+1
5.2E+0
9.4E+in
2.0E+2
Manganese"
055
5.0E+1
1-33
-------
Table 1-3 (continued). GASIFIER TAR (ug/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
Iron
056
3.0E+2
~
ซ ! --
26
31
32
33
35
36
38P
38G
41
43
44
45
Cobalt
059
15.0+1
--
Nickel
059
5.0E+1
--
Copper
064
6.0E+2
Zinc
065
16.8E+3
--
--
Cadmium
112
10.0E+0
3.5E-2
2.7E-2
1.3E-1
6.7E-2
1.7E-2
5.0E-2
Mercury
201
2.0E+0
--
--
--
--
1-34
-------
TABLE 1-4. CONCENTRATION OF SPECIES IN SOLID RESIDUE
(micrograms per gram of residue)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
Antimony
122
1 . 5E+3
--
..
--
25 1
26
31
32
33
35
36
38P
38G
41
43
44
45
~
--
--
--
Selenium
079
1.7E+0
l.OE+1
3.0E+0
2.6E+0
1.4E+0
1.7E-KJ
9.1E-2
~
5.8E+0
9.9E+0
8.6E+0
8.8E+0
Bromine
080
2.6E+5
--
--
--
--
--
Chloride
057
2.6E+5
--
--
3.0E-1
7.9E-1
l.OE-1
1.2E+0
Scandium
045
1.6E+6
--
--
--
Titanium
051
1.8E+5
--
--
--
--
--
--
1-35
-------
Table 1-4 (continued). SOLID RESIDUE (yg/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Vanadium
051
5.0E+2
--
6.5E+0
4.5E+0
4.9E+0
4.6E+0
3.4E+0
3.6E+0
Sodium
023
1.6E+7
--
--
Rubidium
085
3.6E+5
Beryllium
009
6.0E+0
--
--
Magnesium
024
1.8E+5
--
--
Aluminum
027
1.6E+4
--
--
--
--
Lead
207
5.0E+1
--
--
9.4E+0
4.9E+0
5.8E+0
--
2.3E+0
1.4E+0
3.0E-1
--
6.3E-1
Arsenic"
075
5.0E+1
--
1.3E+1
2.4E+1
1.2E+1
9.1E+0
--
--
4.1E+1
1.2E+1
7.2E+0
3.1E+1
2.2E+1
1-36
-------
Table 1-4 (continued). SOLID RESIDUE Ug/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38P
38G
41
43
44
45
Mercury
201
2.0E+0
3.1E-3
4.7E-3
3.8E-3
8.9E-3
9.1E-3
1 .OE-2
1.1E-2
Cerium
140
1.1E+5
--
Lanthanum
139
3.4E+5
--
--
~
Samarium
150
1.6E+5
--
--
--
Thorium
169
1.3E+2
--
--
--
1-37
-------
Table 1-4 (continued). SOLID RESIDUE (yg/g)
Compound
Mol. Wt.
DMEG
Run No.
6
16
20
21
23
25
26
31
32
33
35
36
38 P
38 G
41
43
44
45
Chromium
052
5.0E+1
2.5E+2
2.0E+2
1.2E+2
6.7E+2
1.9E+2
2.5E+3
1.8E+0
5.8E-1
2.0E+2
Manganese
055
5.0E+1
--
--
--
--
Iron
056
3.0E+2
Cobalt
059
1 . 5E+2
--
--
--
Nickel
059
4.5E+1
--
Copper
064
l.OE+3
--
--
Zinc
065
5.0E+3
Cadmi urn
112
l.OE+1
8.8E-1
7.1E-1
2.7E-2
7.3E+0
2.2E-1
5.0E-1
5.SE-1
1.1E-2
1-38
-------
TECHNICAL REPORT DATA
(Please read Inunctions on the reverse before completing)
. REPORT NO.
EPA-600/7-79-202
2.
3. RECIPIENT'S ACCESSION'NO.
AND SUBTITLE Pollutants from Synthetic Fuels Pro-
duction: Environmental Evaluation of Coal Gasification
Screening Tests
. REPORT DATE
August 1979
6. PERFORMING ORGANIZATION CODE
D.G.Nichols, J.G.Cleland, D.A.Green,
F.O.Mixon, T.J.Hughes, and A.W.Kolber
8. PERFORMING ORGANIZATION REPORT NO.
. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
EHE623A
11. CONTRACT/GRANT NO.
Grant No. R804979
2. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 8/78 - 7/79
14. SPONSORING AGENCY CODE
EPA/600/13
a.SUPPLEMENTARY NOTES ffiRL-RTP project officer is N. Dean Smith, Mail Drop 61, 919/
541-2708. Grant-related reports include EPA-600/7-78-171, EPA-600/7-79-200, and
EPA-600/7-79-201.
e. ABSTRACT Tlie j^p^t gives results of an environmental evaluation of 38 screening test
runs using a laboratory-scale, fixed-bed coal gasifier to study pollutants generated
during the gasification of various coals. Pollutants were identified and quantitative
analyses performed for tars, aqueous condensates, volatile organics, primary
gases, and reactor residues. Tar partition fractions were also generated and studied
for each coal providing distributions of insolubles, organic acids and bases, polar
and nonpolar neutrals, and polynuclear aromatic hydrocarbons. Showing the greatest
potential for adverse health effects are: oxygen-containing species and PNAs in the
tars and aqueous condensates; carbon monoxide, benzene, and hydrogen sulfide in
the primary gas streams; and certain trace elements in the reactor residues. Bio-
assays of various coal gasification effluents showed the crude tars and selected tar
fractions to have a potentially mutagenic character.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
. COS AT i Field/Group
Pollution
Coal Gasification
Tars
Condensates
Organic Compounds
Gases
Residues
Pollution Control
Stationary Sources
Synthetic Fuels
13B
13H
07C
07D
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
2O. SECURITY CLASS (This page)
Unclassified
21. NO. OF PAGES
150
22. PRICE
EPA form 2220-1 (t-73)
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