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

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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

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     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-

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   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

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