United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
Research and Development
EPA-600/S7-80-178 Apr. 1981
Project Summary
Addendum to "Environmental
Assessment: Source Test and
Evaluation Report—Chapman
Low-BTU Gasification"
D. Scott Lewis and G. C. Page
This report is as an addendum to
"Source Test and Evaluation Report-
Chapman Low-Btu Gasification" pub-
lished by the Environmental Protection
Agency in-1978 (NTIS No. PB289
940). It contains detailed organic
analysis data on six streams, trace
element and organic data on the solid
waste leachates, and trace element
data on the feed coal. These data were
not included in the original report.
A total of six samples were analyzed
by gas chromatography/mass spectro-
metry to provide a detailed organic
characterization of waste streams and
potential fugitive emissions from an
operating Chapman low-Btu gasifica-
tion facility using Virginia bituminous
coal. The streams analyzed were: coal
feeder vent discharge, separator vent
discharge, separator liquor, separator
tar, gasifier ash, and cyclone dust. The
extractable organics in four of the six
samples were fractionated using an
acid-base-neutral fractionation scheme
prior to analysis, to simplify compound
identification.
All streams analyzed except the ash
and dust contained concentrations of
organic compounds at levels of con-
cern to health when evaluated by
Source Assessment Model/l A (SAM/
IA) methodology. Phenols in the
separator vent discharge, and liquor
along with fused polycyclics in the
coal feeder vent discharge and the
separator tar were identified as the
compounds of greatest concern. When
compared to screening data, potential
effects are lower, but relative ranking
of streams is essentially unchanged.
Trace element analysis was per-
formed on the feed coal. In addition,
trace element and organic loading
analyses were performed on Resource
Conservation and Recovery Act (RCRA)
and deionized water leachates of the
gasifier ash and cyclone dust. The
SAM/IA results indicated the ash and
dust had a low potential for health and
ecological effects. The concentrations
of all elements with RCRA specified
limits were significantly below those
limits.
This Project Summary was developed
by EPA's Industrial Environmental
Research Laboratory in Research Tri-
angle Park, NC, to announce key find-
ings of the research project that is fully
documentated in a separate report of
the same title (see Project Report
ordering information at back).
Introduction
Radian Corporation of Austin, Texas,
is performing a comprehensive envi-
ronmental assessment of low- and
medium-Btu gasification technology
under a contract with the Environmental
-------
Protection Agency (EPA). A major portion
of this assessment involves Source Test
and Evaluation (STE) programs at oper-
ating low-Btu gasification facilities.
In 1978, Radian Corporation, in con-
junction with EPA, conducted an STE
program at a commercial Chapman low-
Btu gasification facility. The objectives
of this program were, in part, to perform
chemical and bioassay screening tests
on the gasifier waste streams and
potential fugitive emissions (process
streams). These data were reported in
the Source Test and Evaluation Report
(STER) resulting from the Chapman STE
program (1).
The STE program did not include
detailed organic characterization of any
process or waste streams. It also did not
include trace element analysis of the
feed coal or trace element and organic
loading analyses of the solid waste
leachates. These analyses have now
been performed on samples taken during
the STE sampling campaign.
The purpose of this addedum to the
Chapman STER is:
O To report the results of the detailed
.organic analysis of the gasifier waste
streams and potential fugitive emis-
sions (process streams),
O to report the results of additional test-
ing of the feed coal and the leachates
from the solid waste streams, and
O to provide conclusions and recom-
mendations based on these addi-
tional data.
Results and Conclusions
This section summarizes the results of
the detailed organic analysis of the waste
streams and potential fugitive emissions
(process streams) from the Chapman
facility and compares the detailed or-
ganic data to the Source Assessment
Model/IA (SAM/IA) analysis (2) of the
chemical screening data. Summaries of
the trace element analysis of the feed
coal and the trace element and organic
loading analyses of the solid waste
leachates are presented.
Summary of the Results of the
Detailed Organic Analyses and
Their Comparison to the SAM/
I A Analysis of the Chemical
Screening Data
The SAM/IA is used to identify and
prioritize waste streams and potential
fugitive emissions (process streams)
that have potential for health and/or
ecological effects. Specific compounds
are assigned discharge multimedia
environmental goal (DMEG) values (3-
5). A DMEG value is a concentration of a
substance in a discharge stream esti-
mated not to cause adverse health or
ecological effects. Discharge severities
(DS) for individual compounds are
calcuated by dividing the discharge
concentration by the DMEG.Thetotalof
the individual DS values for the stream
is expressed as the total discharge
severity (TDS).When the discharge rate
of the stream is .multiplied by the DS
value for a component, the result is
expressed as the Weighted Discharge
Severity (WDS). The sum of the WDS
values for a stream is expressed as the
total weighted discharge severity (TWOS).
The TDS values and TWOS values are
used to rank streams in terms of poten-
tial effect and indicate the relative need
for detailed analysis. In the original
Chapman STER (1), potential degree of
hazard (PDOH) and potential toxic unit
discharge rate (PTUDR) were used in
place of and are synonymous with DS
and WDS, respectively.
The waste streams and potential
fugitive emissions subjected to detailed
organic analysis and theirtotal discharge
severities (TDS) and total weighted
discharge severities (TWOS) for extract-
able organics are given in Table 1. All
streams analyzed, except the gasifier
ash and cyclone dust, contain concen-
trations of organic compounds yielding
TDS health values greater than 1. In
addition, the total weighted discharge
severity for the ash indicates potential
ecological effects. However, it should be
noted that these potential ecological
effects are due primarily to phthalates.
Phthalates are common artifacts in
trace level organic analysis. The TWOS
ecology value for the ash is reduced to
0.2 g/sec from 7 g/sec if the concentra-
tions of the phthalates are excluded
from the calculations. The cyclone dust
has TWOS values for organic compounds
of less that 1 g/sec for both health and
ecology.
Of the potential fugitive emissions,
the extractable organics in the separator
tar have the highest potential for health
effects based on DMEG values for a
liquid. Although the tar contains at least
15 compounds with a discharge severity
(DS) >1, the primary compound con-
tributing to the TDS is benzo(a)pyrene
[B(a)P]. The analytical technique em-
ployed did not distinguish B(a)P from a
group of up to six isomers of the same
molecular weight (252). However, if it is
Table 1.
Detailed Organic Analysis: Results of the SAM/IA Analysis for All Organic Compounds
with Assigned DMEG Values Detected by GC/MS
TDS (Organics) TWOS (Organics)
Health
Ecology
Health
Ecology
Principal Compounds
Gaseous Waste Streams
Coal Feeder Vent Discharge
Separator Vent Discharge
Solid Waste Streams
Cyclone Dust
Gasifier Ash
Potential Fugitive Emissions
Separator Liquor
Separator Tar
4E4'
2E2
6E-6
2E-4
1E2
3E6
—
—
1E-1
4EO
1E3
—
2E3 (m3/sec)
1E2 (m3/sec)
IE -5 1 g/sec)
4E-3 (g/sec)
—
—
— Benzo(a)pyrene
— Phenols
2E-1 (g/sec) Phthalates
7E1 (g/sec) Phthalates
— Phenols
— Benzo(a)pyrene,
Phenols
'aEb-a x 70b
TDS: Total Discharge Severity
TWOS: Total Weighted Discharge Severity
-------
assumed that only 15% of the mass
attributed to B(a)P is actually contributed
by B(a)P, the IDS for the stream still
remains over 5E5 (5 x 105).
The extractable organics in the sepa-
rator liquor have potential effects for
both health and ecology, with organic
IDS values of 4E5and4E3, respectively.
For both health and ecology, phenols
comprise the major group of compounds
of concern with phthalates making a
minor contribution to the potential
ecological effects.
Recently, a change in the DMEG
values for phenol in water published in
"Multimedia Environmental Goals for
Environmental Assessment: Volume
IV," (5) from 5.0to 1.7E4//g/Lfor health
and from 5.0E2 to 3.0E3//g/Lfor ecology
has been suggested by Research Tri-
angle Institute, based on 1979 proposed
water quality criteria for phenols. The
proposed values for phenol are applied
to all phenolic compounds which had
previously been assigned DMEG health
and ecology values of 5.0 yt/g/L and
5.0E2 A/g/L, respectively.
The extractable organics from the
XAD-2 resin, organic module rinses,
probe rinse and condensate from both
the gaseous waste streams, the coal
feeder vent, and the separator vent
discharge streams have organic TDS
health values of 4E4and 2E2 andTWDS
health values of 2E3 and 1E2 mVsec,
respectively. The major compounds of
concern are B(a)P for the coal feeder
vent discharge and phenols for the
separator vent discharge.
A comparison of the TDS and TWOS
values (organics and inorganics) from
the chemical screening data and the
detailed analytical data for all the
streams sampled is given in Figures 1
through 3. The values for the chemical
screening data are calculated from data
given in the Chapman STER (1). Detailed
analytical data values are based on
inorganic data from the STER and
detailed organic data from gas chroma-
tography-mass spectrometry (GC-MS)
analysis.
Figure 1 compares the TDS health
values for the detailed organic analytical
data and the chemical screening data
for the waste streams and potential
fugitive emissions from the Chapman
facility. In general, values derived from
the detailed organic and inorganic
analytical data are from 2 to 4.5 orders
of magnitude lower than values derived
from the chemical screening data.
However, therelative ranking of severity
JEW
1E9
1E8
1E7
1E6
1E5
1E4
1E3
1E2
1E1
1EO
Cb
-------
o
Uj
1E82
1E7
1E6
1E5
1E4
1E2
1EJ
1EO
pa ...
o ^
o <
ii
I i
o' cJ
i i
3
Q.
a'
Coal
Feeder
Vent
Discharge
Separator
Vent
Discharge
Cyclone
Dust
Gasifier
Ash
Separator
Liquor
Screening data: organics and inorganics (Source = Ref. 1 j
Detailed analytical data and inorganic data from Ref. 1.
1 Ecology values were not calculated for the separator tar
*aEb = a x 10"
3Major constituents contributing to TDS
Figure 2. A comparison of the total discharge severity ecology values ana
principal contributing compounds from the chemical screening
data and the detailed organic analytical data.'
stream ranking while ecology valuesare
little changed.
Summary of the Results of the
Gasifier Ash and Cyclone Dust
Leach ate Analysis
Both the gasifier ash and the cyclone
dust were leached using the Resource
Conservatio'n and Recovery Act pro-
cedure (6) and using the RCRA procedure
without the addition of a pH buffer. All
leachates analyzed have relatively low
potentials for health and ecological
effects. Organic loading analyses indi-
cate an absence of organics in the
leachates and therefore no contribution
by organics to the resulting TDS values.
The spark source mass spectrometry
(SSMS) results from the RCRA and
unbuffered leachates indicate differ-
ences in trace element concentrations.
The TDS values from the SAM/IA
analysis of the results along with the
principal contributing elements are
illustrated comparatively in Figure 4.
In general, the recovery of trace
elements in the leachates from the
solids is very low. Only arsenic in the
cyclone dust and arsenic, fluorine and
sulfur in the gasifier ash have recoveries
greater than 10%.
When the leachates are compared to
RCRA specified extract limits, all trace
elements present with RCRA limits are
significantly below those limits. Limits
and leachate concentrations for specific
elements are given in Table 2.
Relatively low DS values, an absence
of organic loading and low concentra-
tions of trace elements all indicate that
both the ash end dust should be given
low priority as potentially harmful
wastes.
Summary of the Results of the
Feed Coal Analysis
The feed coal was analyzed for trace
elements by SSMS. A total of 54 trace
elements were detected in the coal. Of
these, Al, Ca, Fe, Mg, P, K, Se, Sr, S and
Ti have mass flows in excess of 100
g/hr. The input rate for the feed coal
was 1094 kg/hr.
In general, the bulk of the trace
element mass exiting the gasifier in the
solid waste streams is found in the
gasifier ash with relatively low concen-
trations in the cyclone dust. Fifteen
elements were preferentially concen-
trated in the ash. These elements are Al,
Ba, Be, B, Ca, Co, Cu, Cd, Pb, Mg, Ni, Ru,
Sc, Sn and Ti.
Recommendations
Specific recommendations for consid-
eration in future Chapman gasifier STE
programs fall into two categories:
O additional data needs, and
O methodology recommendations
Data Needs
In general, the short term data needs
for an initial assessment have been met
for the waste streams and potential fu-
gitive emissions from the Chapman fa-
cility using Virginia bituminous feed
coal. The organic and trace element
characterization of the streams pre-
sented in this report, along with the data
already available in the Chapman STER
(1) should be sufficient to provide pre-
liminary guidance in the selection of a
control scheme to treat process and
waste streams with potential health and
ecological effects. Long-term (30-day)
monitoring to establish process variabil-
ity and data for additional coal types is
required to provide support for the de-
velopment of regulations. The com-
pounds and elements listed as "princi-
pal" contributors to the TDS values for
the streams, and any other compounds
which exceed regulatory standards
should be subjected to long-term moni-
toring in the input and output streams of
any control employed.
Additional data which are needed to
-------
1E8'
1E7
1E6
1E5
1E3
1E2
1E1
1EO
Coal
Feeder
Vent
Discharge
(m3/sec)
Separator
Vent
Discharge
(m3/sec)
Cyclone
Dust
(g/sec)
Gasifier
Ash
(g/sec)
1E6
1E5
1E4
I 1E3
1EO -
Coal
Feeder
Vent
Discharge
(m3/sec)
Separator
Vent
Discharge
(m3/sec)
Cyclone
Dust
(g/sec)
Gasifier
Ash
(g/sec)
Screening data: organics &
inorganics {Source = Ref. 1)
'aEb = a x 10 "
Figure 3.
Detailed analytical data &
inorganic data from
Ref. J
A comparison of the total weighted discharge severity values from
the chemical screening data and the detailed analytical data.
assess the potential health ecological
effects are:
O a characterization of the combus-
tion products of the product gas, in
order to assess the possible effects
of burning the product gas,-
O a characterization of the gaseous
discharge from the quench liquor
forced evaporator,
a characterization of phthalates in
the gasifier ash to determine if
detected phthalates are artifactual,
and
a detailed characterization of the
polycyclic hydrocarbons, including
specifically, the speciation of the
252 molecular weight isomeric
group containing B(a)P for those
streams in which B(a)Pcontributes
the bulk of the potential health
effects.
Methodology
Recommendations
The analytical methodologies employ-
ed for the detailed analyses were satis-
factory except in the resolution of
polycyclic hydrocarbons. It is recom-
mended that samples high in polycyclics
should be analyzed by a technique such
as gas chromatography/mass spectro-
metry, using a liquid crystal column to
provide detailed data on specific environ-
mentally significant polycyclic hydro-
carbons such as B(a)P.
The comparison of RCRA and unbuff-
ered (deionized water) leaching pro-
cedures indicates that differences in
trace element concentrations occur in
the leachates derived from the two
procedures. It is recommended that
solid wastes should be leached using
both procedures to provide a better
characterization of possible leachates
entering the environment.
References
1. Page, G. C. Environmental Assess-
ment: Source Test and Evaluation
Report—Chapman Low-Btu Gasifi-
cation. NTIS Report PB-289 940,
EPA-600/7-78-202. Radian Corp.,
Austin, Texas, October 1978.
2. Schalit, L. M., and K. J. Wolfe.
SAM/IA: A Rapid Screening Method
for Environmental Assessment of
Fossil Energy Process Effluents.
NTIS Report PB-277 088, EPA-600/
7-78-015. Acurex Corporation/Aero-
therm Division, Mountain View,
California, February 1978.
3. Cleland, J. G., and G. L. Kingsbury.
Multimedia Environmental Goals for
Environmental Assessment: Volume
I and Volume II. MEG Charts and
Background Information. NTIS Re-
ports PB-276 919, PB-276 920,
EPA-600/7-77-136a,b. Research
Triangle Institute, Research Triangle
Park, NC, November 1977.
4. Kingsbury, G. L, R. C. Sims, and J. B.
White. Multimedia Environmental
Goals for Environmental Assess-
-------
ment: Volume III. MEG Charts and
Background Information Summaries
(Categories 1-12). NTIS Report
PB 80-115 108, EPA-600/7-79-176a.
Research Triangle Institute, Research
Triangle Park, NC, August 1979.
5. Kingsbury, G. L, R. C. Sims, and J. B.
White. Multimedia Environmental
Goals for Environmental Assess-
ment: Volume IV. MEG Charts and
Background Information Summaries
(Categories 13-26). NTIS Report
PB 80-115116, EPA-600/7-79-176b.
Research Triangle Institute, Research
Triangle Park, NC, August 1979.
6. Environmental Protection Agency.
Hazardous Waste Management Sys-
tem, Identification and Listing of
Hazardous Waste. Federal Register,
45(98):33084-33133, 1980.
•c
"<5
s
1E3'
1E2
1E1
1EO
&
— (0
Gasifier
Ash
Leachate
c
// 1
Cyclone
Dust
Leachate
TDS Ecology
1E3
1E2
1E1
1EO
a
- *
^
/
^
>
Gasifier Cyclone
Ash Dust
Leachate Leachate
RCRA Procedure
Deionized HzO Only
'aEb = a x 10 "
2Major constituents contributing to TDS.
Figure 4.
TDS values and principal contributing elements for the gasifier
ash cyclone dust leachates.
Table 2. Comparison Of Solid Waste Leachates And RCRA Extract Limits
RCRA Limits Gasifier Ash Leachate Cyclone Dust Leachate
Element
As
Ba
Cd
Cr
Pb
Se
Ag
(5/18/80)
(mg/L)
5.0
100
1.0
5.0
5.0
1.0
5.0
RCRA Dl HZQ
(mg/L)
o.or
2.0
<0.002
<0.003
0.0/0
0.002
<0.002
0.003
------- |