United States      Industrial Environmental Research  EPA-600/7-80-039
Environmental Protection  Laboratory          March 1980
Agency        Research Triangle Park NC 27711
Chemical and Biological
Characterization of
Leachates from Coal
Solid Wastes

Interagency
Energy/Environment
R&D  Program  Report

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                  RESEARCH REPORTING SERIES


Research reports of the Office of Research and Development, U.S. Environmental
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                                            EPA-600/7-80-039

                                                    March 1980
Chemical and Biological  Characterization
   of  Leachates from  Coal  Solid Wastes
                              by
                   R.A. Griffin, P.M. Schuller, J.J. Suloway,
                      N.F. Shimp, and W.F. Childers

                     Illinois State Geological Survey
                       Natural Resources Building
                        Urbana, Illinois 61801
                       Contract No. 68-02-2130
                      Program Element No. EHE623A
                    EPA Project Officer: N. Dean Smith

                 Industrial Environmental Research Laboratory
               Office of Environmental Engineering and Technology
                    Research Triangle Park, NC 27711
                           Prepared for

                 U.S. ENVIRONMENTAL PROTECTION AGENCY
                    Office of Research and Development
                        Washington, DC 20460

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                                 ABSTRACT


     Eleven coal  solid wastes were characterized chemically and mineralogi-
cally.  The wastes comprised three Lurgi  gasification ashes, mineral  residues
from the SRC-I and H-Coal  liquefaction processes, two chars, two coal-
cleaning residues, and a fly ash and water-quenched bottom ash (slag) from a
coal-fired power plant.  Leachates that were generated from the solid wastes
at  four  pH levels and under two different gas atmospheres were analyzed for
more than 40 chemical constituents.  These leachates were also used in soil
attenuation studies and in acute 96-hour static bioassays using fathead min-
now fry.

     Sixty constituents were determined in the solid wastes; the major ones
among them were Al, Ca, Fe, K, Mg, Na, S, Si, and Ti.  Concentrations of
other constituents such as B, Ba, Ce, Cl, Cr, F, Mn, Sr, Zn, and Zr were gen-
erally between 100 and 1000 ppm, and significant quantities (<100 ppm) of
trace metals were also present.  Of the approximately 60 chemical constitu-
ents measured in the solid wastes, a range of 2 to 13 in the aqueous extracts
generated in the laboratory from the individual wastes exceeded minimum
standards of water quality recommended by the federal government.

     The most significant mineral transformations that occurred during coal
conversion processing were those of the iron-bearing minerals.  For example,
pyrite—the predominant iron-bearing mineral identified in the feed coals-
was converted to pyrrhotite by processes that employed a reducing
atmosphere, such as liquefaction and charring.  Pyrite was converted
to the oxides—hematite, magnetite, and goethite—by processes that used an
oxidizing atmosphere, such as Lurgi gasification and power-plant combustion.
Pyrite remained unaltered in the coal-cleaning refuse.

     Thermodynamic speciation of inorganic ions and complexes in solution was
modeled using the computer program HATEQF.  One-hundred-fifteen aqueous spe-
cies were considered in the model, and saturation data were computed for more
than 100 minerals.  The model demonstrated that similar mineral phases con-
trolled the aqueous solubility of the major ionic species for all the wastes.
Furthermore, adsorption and coprecipitation of trace metals with iron, man-
ganese, and aluminum oxides and hydroxides were thought to be likely controls
on trace metal concentrations in the leachates.

     Study of the soil attenuation of soluble constituents leached from the
coal solid wastes used the dispersed soil method with three Illinois soils of
widely varying character.   The results showed that chemical constituents were
attenuated by the soils to a high degree.  The soil properties controlled the
degree of attenuation to a greater extent than the chemical composition of
                                     •m

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the waste leachates.   Elution of Mg, and in some cases Mn, from the soils
could present the greatest potential for contamination from land disposal.

     The results of 96-hour static bioassays indicated that the water-soluble
constituents in equilibrium with the wastes generally were not acutely toxic
to fathead minnow fry at near neutral pH's (7.0-8.5); however, there was com-
plete mortality in both the high- and low-pH leachates.   Mortality was iden-
tified as being caused by the combined effects of pH and total ionic strength
of the leachate.  Complex chemical, mineralogical, biological, and soil
attenuation factors must be integrated when assessing the environmental
impact of land disposal of solid wastes from coal utilization processes.

     This report was submitted in partial fulfillment of Contract no. 68-02-
2130 to the University of Illinois, and was executed by the Illinois State
Geological and Natural History Surveys under partial sponsorship of the U.S.
Environmental Protection Agency (EPA).  Work was completed in June 1979.
                                     iv

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                                 CONTENTS
Abstract	iii
Figures	vi
Tables . .	vii
Acknowledgments  	 	  x

      1.  Introduction	  1
                Purpose and experimental design   	  3
      2.  Conclusions  	  4
      3.  Recommendations	  6
      4.  Solid wastes from coal conversion and utilization  	  8
                Lurgi gasification 	  8
                Liquefaction: H-Coal  and SRC-I 	 10
                Additional coal solid wastes  	 12
      5.  Mineralogical and chemical  characterization
          of the coal solid wastes	14
                Analytical procedures   	 14
                Mineralogical characterization 	 15
                Chemical characterization  	 23
      6.  Aqueous solubility of coal  solid wastes  	 24
                Results of solubility analysis 	 25
      7.  Equilibrium solubility modeling of the  leachates
          from coal solid wastes	50
                Equilibrium solubility model  	 50
      8.  Soil attenuation of chemical constituents in leachates
          from coal solid wastes	59
                Introduction	 59
                Dispersed soil  methodology 	 59
                Experimental design  	 60
                Attenuation results  	 61
                Calculation of migration distance  	 68
      9.  Bioassays of leachates from coal solid  wastes	70
                Introduction 	 70
                Materials and methods used for bioassays	70
                Results of bioassay study  	 71
                Discussion of bioassay  results 	 79
     10.  Potential pollution hazard from coal solid wastes  	 83
                MATE values for solid wastes	83
                MATE values for leachates	87

References	93
Appendix:  List of publications	99

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                                   FIGURES
Number                                                                   Page
  1.  Flow scheme for gas production from the Lurgi process	9
  2.  SRC process schematic	11
  3.  H-Coal process schematic 	  13
  4.  Stability relations of iron oxides and sulfides in waste 	  51
  5.  Stability relations of manganese oxides and carbonates in water   .  53
  6.  Calcium sulfate equilibria of leachates from coal  utilization
      solid wastes	55
  7.  Calcium carbonate equilibria of leachates in contact with air
      from coal utilization solid wastes 	  56
  8.  Silicon dioxide and aluminum hydroxide solubility equilibria
      of leachates from coal utilization solid wastes  	 ...  57
  9.  Schematic diagram of dispersed soil methodology  	  60
 10.  Zinc concentrations vs. soil/leachate ratio for fly ash3 .....  62
 11.  Total Fe concentration vs. soil/leachate ratio  for SRCij	63
 12.  Manganese concentration vs. soil/leachate ratio for SRC  	  64
 13.  Manganese concentration vs. soil/leachate ratio for H-Coal   ....  64
 14.  Magnesium concentration vs. soil/leachate ratio for SRC  	  65
 15.  Boron concentration vs. soil/leachate ratio for Lurgi-Rosebud  .   .  66
 16.  Sulfate concentration vs. soil/leachate ratio for fly ash   ....  67
 17.  Ratio of concentration of Ca or S0i» in leachate after reaction
      with soil to the initial concentration vs. soil/leachate ratio .   .  67
 18.  Ratio of concentration of Ca or SO^ in leachate after reaction
      with soil to the initial concentration vs. soil/leachate ratio .   .  68
 19.  Percentages of mortality of fathead minnow fry resulting, from
      exposures to 24 leachates generated from three Lurgi gasification
      ashes and 7 buffered solutions of reconstituted water  	   .  72
 20.  Percentages of mortality of fathead minnow fry resulting from
      exposures to 16 leachates generated from SRC and H-Coal lique-
      faction residue and 7 buffered solutions of reconstituted water   .  72
 21.  Percentages of mortality of fathead minnow fry resulting from
      exposures to 16 leachates generated from a water-quenched slag
      and a fly ash and 7 buffered solutions of reconstituted water  .   .  73
                                      vi

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                              FIGURES (Continued)

Number                                                                   Page

 22.  Percentages of mortality of fathead minnow fry resulting from
      exposures to 16 leachates generated from high- and low-tempera-
      ture chars and 7 buffered solutions of recontituted water 	 73

 23.  Percentages of mortality of fathead minnow fry resulting from
      exposures to 16 leachates generated from a high-sulfur gob
      sample and a low-sulfur gob sample and 7 buffered solutions
      of reconstituted water	75
 24.  Percentages of mortality of fathead minnow fry resulting from
      exposures to 7 buffered solutions of reconstituted water	75
                                    TABLES


  1.  Material balance for gas production for the Lurgi process 	  9

  2.  Mineral composition of coals and coal solid wastes  	 16

  3.  Mbssbauer parameters for iron species in coals and coal
      solid wastes	18

  4.  Major elemental  composition and ash content of the solid wastes .  . 22

  5.  Minor elemental  constituents of the solid wastes  	 22

  6.  Chemical composition of two fly ash samples from the same
      power plant collected in different months	23
  7.  Chemical composition of Lurgi ash and slurry supernatant
      solutions of the ash from an Illinois No. 5 Coal at several  pH's  . 26
  8.  Chemical composition of Lurgi ash and slurry supernatant
      solutions of the ash from an Illinois No. 6 Coal at several  pH's  .28

  9.  Chemical composition of Lurgi ash and slurry supernatant
      solutions of the ash from a Rosebud Coal at several pH's  	 30

 10.  Chemical composition of H-Coal liquefaction waste and slurry
      supernatant solutions of the waste at several pH's  	 32

 11.  Chemical composition of SRC liquefaction waste and slurry super-
      natant solutions of the waste from a Kentucky Coal at several pH's. 34

 12.  Chemical composition of fly ash and slurry supernatant solutions
      of fly ash from an Illinois No. 6 Coal at several pH's	36

                                     vii

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                              TABLES (Continued)

Number                                                                   Page

 13.  Chemical  composition of water-quenched slag and slurry super-
      natant solutions of the slag from an Illinois No.  6 Coal
      at several  pH's	38
 14.  Chemical  composition of char (1800°F)  and slurry supernatant
      solutions of the char from an Illinois No.  6 Coal  at several pH's .  40

 15.  Chemical  composition of char (1200°F)  and slurry supernatant
      solutions of the char from an Illinois No.  6 Coal  at several pH's .  42

 16.  Chemical  composition of high-sulfur cleaning waste (gob)  and
      slurry supernatant solutions of the gob from an Illinois  No. 6
      Coal at several pH's	44
 17.  Chemical  composition of low-sulfur cleaning waste (gob) and slurry
      supernatant solutions of the gob from an Illinois No. 6 Coal
      at several  pH's	46

 18.  Elements  with concentrations exceeding recommended water  quality
      levels under laboratory test conditions 	  48

 19.  Mineral phases contributing to the control  of the ionic composi-
      tion of leachates from coal utilization solid wastes  	  54

 20.  Soil characteristics	  61
 21.  Summary of soil-attenuation behavior of chemical constituents
      in leachates from several coal solid wastes 	  62

 22.  Percentages of mortality of 1- to 6-day-old fathead minnow fry
      resulting from 96-hour exposures to the natural pH leachates
      of 11 coal  solid wastes	74
 23.  LC-50 values, their 95 percent confidence intervals, and  the
      amount of dilution necessary to eliminate mortality for three
      Lurgi gasification ash leachates  	  76
 24.  LC-50 values, their 95 percent confidence intervals, and  the
      amount of dilution necessary to eliminate mortality for H-Coal
      and SRC liquefaction leachates  	  77
 25.  LC-50 values, their 95 percent confidence intervals, and  the
      amount of dilution necessary to eliminate mortality for leachates
      generated from power plant slag and fly ash	78

 26.  LC-50 values, their 95 percent confidence intervals, and  the
      amount of dilution necessary to eliminate mortality for high-
      sulfur and low-sulfur gob leachates	79

                                     viii

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                              TABLES (Continued)

Number                                                                    Page

 27.  LC-50 values, their 95 percent confidence intervals, and the
      amount of dilution necessary to eliminate mortality for high-
      temperature and low-temperature char leachates ........... 80

 28.  Constituents in coal utilization solid wastes exceeding health-
      or ecology-based MATE values for individual  parameters and MATELEi
      values for land disposal actually determined for the solid waste .  . 84

 29.  Discharge severities for constituents in coal utilization solid
      wastes exceeding health- or ecology-based solid waste MATE values   . 86
 30.  MATEwEi values measured for leachates, based on ecological
      effects and bioassay data  ..................... 87

 31.  Constituents in leachates exceeding health- or ecology-based
      water MATE values for individual parameters  ............ 88

 32.  Discharge severities for constituents in leachates from coal solid
      wastes exceeding health- or ecology-based water MATE values  .... 89
 33.  Constituents in leachates from coal utilization solid wastes
      exceeding proposed U.S. EPA toxicant extraction procedure standards. 91

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                              ACKNOWLEDGMENTS
     We gratefully acknowledge the U.S. Environmental Protection Agency, Fuel
Process Branch, Research Triangle Park, North Carolina, for partial support
of this work under Contract no. 68-02-2130: Characterization of Coal and Coal
Residues.  We are also indebted to the Peabody Coal Company, Freeburg, Illi-
nois; to Hydrocarbon Research Inc., Trenton, New Jersey; and to Pittsburg and
Midway Coal Mining Co., Fort Lewis, Washington, for supplying us with samples.

     The authors are indebted to G. V. Smith, C. C. Hinkley, H. Twardowska,
and M. Saporoschenko of Southern Illinois University, Carbondale, for Mb'ss-
bauer spectroscopic analyses of the samples.  The authors also wish to thank
the Analytical Chemistry Section of the Illinois State Geological Survey
under the direction of Dr. R. R. Ruch, and S. J. Russell, Dr. H. D. Glass,
and T. M. Johnson for assistance in portions of this research.

     The authors also wish to acknowledge N. Dean Smith, U.S. Environmental
Protection Agency; and G. L. Kingsbury and Bob Truesdale, both of Research
Triangle Institute, whose comments and suggestions have served to improve the
manuscript.

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                                  SECTION 1

                                INTRODUCTION
      Because  of  the oil  and  natural gas  shortages  in recent years, much has
 been  written  about finding alternate energy  sources.  Since coal  is so abun-
 dant  in  the United States, it  is an important energy alternative; however,
 many  of  our coal  reserves cannot be directly processed  for energy production
 if the government enforces strict  compliance with  the Clean Air Amendments of
 1977.  Technologies do  exist,  however  (or  at least are  being developed), that
 produce  clean fuel from coal by removing the environmentally hazardous
 materials  from the coal, and/or by converting the  coal  into oil and gas
 .products.

      No  less  than 13  low/medium-BTU and  nine high-BTU gasification systems
 are being  considered  for commercial and  government agency support.  An addi-
 tional 19  major  liquefaction processes are being considered for commercial
 development.   In addition to the major coal  conversion  techniques, there are
 many  other coal  processing methods that  clean the  coal  before  it  is used for
 energy production.

      Although the quality of fuels produced  by  these techniques is improved,
 the accessory elements  from  the coal are concentrated in the waste streams
 from  the process plant.  These waste products need to be characterized before
.environmentally  acceptable methods for their disposal can be developed.
 Emerson  (1978),  for example, itemized  15 waste  streams  from liquefaction pro-
 cesses.   Included in  this list were five solids: particulate coal, ash and
 slag  residues, char,  spent catalyst, and spent  absorbents.  These wastes are
 as different  as  the processes  that produce them; their  nature  depends upon
 the variables of the  conversion techniques.  The nature of the wastes also
 strongly depends upon the feed coal—and coal itself can be highly variable
 within any particular seam.

      Until recently,  research  has  emphasized the characterization of airborne
 contaminants. Several  investigators,  however—including Cavanaugh and Thomas
 (1977);  Spaite and Page (1978); Cavanaugh, Corbett, and Page  (1977); and
 Somerville and Elder  (1978)—have  characterized the waste streams from low/
 medium-BTU gasifiers.  Filby,  Shah, and  Sautter (1978)  characterized the
 trace elements in solid wastes from the  Solvent Refined Coal  (SRC-I) lique-
 faction  process. Sinor (1977) determined  that  the flow rate of Ni, As, Cd,
 and Pb from a Lurgi gasification plant may be as high as several  pounds per
 hour.  Because of the large  quantities of  raw materials consumed, large quan-
 tities of accessory elements may be discharged  even though they may be
 present  in the whole  coal in low concentrations.

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     The estimated quantities of solid wastes produced from coal  conversion
vary widely, but all  are high.  Sather et al. (1975) estimated that a com-
mercial coal gasification plant with a capacity of 250 million cubic feet of
gas per day will use about 8 million tons of coal  and generate about 2.3 mil-
lion tons of ash and dry refuse per year.  Other investigators (Seay et al.,
1972; Asbury and Hoglund, 1974) have estimated that the amount of residue
generated by a single gasification plant would occupy an area of 625 acre
feet per year; in 20 years the residue would cover 1,250 acres to a depth of
10 feet.  In another report, van Meter and'Erickson (1975) estimated that
400,000 tons of slag or ash would be produced annually by a 250 million scfd
gasification plant.  These estimates, however, do not include the wastes gen-
erated from coal pretreatment processes.  Jahnig (1975) calculated that
4,804 tons of refuse per day would result from the pretreatment of coal
before its use in the Bi-Gas high-BTU gasification process.

     Detailed characterization of the wastes produced from coal conversion and
processing is justified because of the volume of wastes produced and their ex-
treme variability.  Characterization alone, however, is insufficient to deter- .
mine acceptable disposal methods.  The accessory and trace elements present  may
or may not be in a form that allows mobility; therefore,  it is necessary to de-
termine which elements can be leached from the wastes under which circumstances.

     Sun et al. (1978) and Stone and Kahle (1977) have run leaching tests on
wastes from fluidized-bed gasifiers, but most research has been done on
wastes other than those from coal conversion processes.   Wewerka et al.  (1978)
have done extensive leaching tests on bulk refuse samples from the  Illinois
Basin under a wide variety of testing conditions.  Chu, Krenkel, and Ruane
(1976), Theis (1975), and Natusch et al. (1977) tried to  determine which con-
stituents could be leached from fly ashes.  The solubility of trace and other
accessory elements in gasification ashes and slags  is important, but has not
yet been investigated thoroughly.  Data on fly ashes and  slags produced  in
coal-fired furnaces may not be pertinent because the gasification ashes and
liquefaction residues are produced under different conditions—namely, at
high temperatures and pressures, and usually in a reducing atmosphere  rather
than in an oxidizing one.  Thus, significant alterations  in the mineralogy
and solubility of the accessory elements in ash can effect the potential of
these elements as pollutants.

     Severe contamination could also result from the disposal of refuse from
coal that was cleaned before combustion or conversion.  It is well  known that
when the pyritic minerals in* this refuse are exposed to air and oxidizing
conditions, iron sulfates and acids are produced (Singer  and Stumm, 1969;
Smith, Svanks, and Halko, 1969; Jones and Ruggeri,  1969).  Garrels and
Thompson (1960) concluded that the rate of oxidation was  chiefly a function of
oxidation-reduction potential (Eh), and was independent of total Fe content.
Similarly, Bell and Escher (1969) found that the production of acidic  iron
salts from pyrite was an almost immediate response to the atmospheric  gas
composition in contact with the water.  Reversing the gases from air to
nitrogen caused the acid formation to decrease, and reversing the gases from
nitrogen to air caused the acid formation to increase.  There is also  some
evidence that  oxidation  of Fe (II) can be affected by the catalytic
responses of trace constituents such as copper (Stauffer  and Lovell, 1969).

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     These results have far-reaching implications for those proposals that
recommend using alkaline gasification ashes to neutralize acid mine refuse,
or those that recommend disposing of ash and refuse together as landfill  in
strip mines.  Probably, accessory elements in the ash and refuse will be  ex-
tracted by the acid solution; trace elements may actually catalyze the forma-
tion of additional acid.

     Characterizing the solid wastes and determining the Teachable consti-
tuents that may be generated are important first steps in determining the
potential pollution hazards from the disposal of these wastes.  Furthermore,
it is necessary to determine the fate of the soluble constituents upon dis-
posal and the effect of leachates that are generated from the wastes upon
biota.
PURPOSE AND EXPERIMENTAL DESIGN

     The purpose of this study was to investigate the potential pollution
hazards of eleven selected coal solid wastes.  This study is part of ongoing
research by the Illinois State Geological Survey into the characterization of
coal and coal residues (Ruch, Gluskoter, and Kennedy, 1971; Ruch, Gluskoter,
and Shimp, 1973; Ruch, Gluskoter, and Shimp, 1974; Gluskoter, 1975; and Glus-
koter et al., 1977).  The eleven wastes chosen for this study included:
three Lurgi gasification ashes from runs employing three different feed coals;
two liquefaction residues—an SRC-I dry mineral residue and an H-Coal vacuum
still bottom mineral residue; a high-sulfur and low-sulfur coal-cleaning
refuse sample; a high- and low-temperature char; and a fly ash and bottom ash
(slag) from a coal-fired power plant.

     Listing detailed descriptions of all the available coal conversion and
processing technologies is beyond the scope of this investigation; such
descriptions are available elsewhere (Braunstein, Copenhaver, and Pfuderer,
1977; Parker and Dykstra, 1978).  To understand the nature of the waste
samples studied, however, we have included descriptions of the technologies
used to produce these solid waste samples.

     To determine the potential pollution hazards of the solid wastes, the
study was divided into six stages:

1.  Mineralogical characterization of the feed coals and the solid wastes.
2.  Chemical characterization of the solid residues.
3.  Determination of the soluble constituents of the wastes.
4.  Application of equilibrium solubility models to determine mineral phases
    controlling the aqueous solubility of the major ionic species.
5.  Identification of the interactions between earth materials and leachates
    generated from the wastes, as would occur in a disposal environment.
6.  Determination of the acute toxicity of the generated leachates by con-
    ducting 96-hour static bioassays using fathead minnow fry.

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                                 SECTION 2

                                CONCLUSIONS
1.  Chemical  and mineralogical  characterization of solid wastes from coal
    utilization processes showed that they had a wide range of chemical  and
    mineral composition.

2.  Characteristics of the feed coal  and process operating variables affected
    the mineral transformations that  occurred during processing and the
    character of the solid wastes generated by a given process.

3.  Thermochemical solubility modeling demonstrated that similar mineral
    phases controlled the aqueous solubility of many major, minor,  and trace
    ionic species for all of the solid wastes.

4.  Many metastable mineral phases—such as iron, aluminum, manganese, and
    silicon oxides and hydroxides—must be considered when predicting
    environmental impact during the initial leaching of coal  solid  wastes.
    Trace metal adsorption on or coprecipitation with these oxides  and
    hydroxides is a probable control  on the trace metal concentrations in
    coal-waste leachates.

£.  The chemical constituents in the  leachates were highly attenuated by all
    the soils, and the soil properties, rather than the chemical composition
    of the leachates, dominated the degree of attenuation.  Elution of Mg,
    and in some cases Mn, from the soils could have the greatest potential  for
    contaminating waters as a result  of land disposal of coal  solid wastes.

6.  Approximately one-half of the leachates generated from the eleven coal
    solid wastes at their natural pH  levels were acutely toxic to young  fat-
    head minnow fry.

7.  Several acidified leachates were  very toxic (LC-50 <1.0 mL/100  ml) and
    required large amounts of dilution (>1:100) to ensure survival  of the
    minnows during 96-hour bioassay.

8.  The acute toxicity of leachates equilibrated under anaerobic conditions
    did  not significantly differ from the acute toxicity of similar leach-
    ates equilibrated under aerobic conditions.

9.  The degree of a leachate's toxicity and the amount of dilution  necessary
    to ensure survival of the minnows during a 96-hour bioassay was largely a
    function of the pH and total ion  concentration of the leachate.

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10.   Some of the leacheates contained concentrations  of  Al,  B,  Ca,  Cd,  Cu,  Fe,
     K, Li, Mn, Ni,  Pb, S04, Sb,  and Zn  that may  be hazardous to  biota.

11.   The SRC liquefaction residue,  along with the fly ash and slag, for which
     the natural pH  leachates were  acidic,  produced the  leachates most  toxic
     to fathead minnow fry in this  study.

12.   Complex chemical, mineralogical, biological, and soil  attenuation
     factors must be integrated on  a case-by-case basis  to correctly assess
     the environmental impact of land disposal of solid  wastes  from a given
     coal utilization process.

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                                 SECTION 3

                              RECOMMENDATIONS


     The potential environmental and economic consequences caused by the dis-
posal of the solid wastes generated by even one large-scale coal  utilization
facility are impressive because of the sheer magnitude of the wastes gener-
ated.  The major solid wastes are the refuse from coal cleaning;  the ashes,
slags, and chars from conversion processes; and the sludges from  stack
scrubbing and water cleanup.  Clearly, careful planning is needed to mitigate
adverse effects on the environment; however, planning can be effective only
when there is an adequate data base.

     The data base should contain information on the qualitative  and quanti-
tative characterization (both chemical and biological) of coal solid wastes.
This information should include:

1.   Quantitative determination of the accessory elements contained in the
     wastes
2.   Determination of the solubility of the accessory elements under a
     variety of environmental conditions
3.   Establishment of the effects of coal characteristics and process oper-
     ating variables on the character of the solid wastes generated by a
     given process
4.   Determination of methods for recovering economically valuable metals
     from the solid wastes
5.   Determination of the ultimate fate of waterborne pollutants  resulting
     from solid-waste materials
6.   Characterization and quantification of both the acute and chronic
     biological toxicity and public health hazard associated with pollutants
     from coal solid wastes

     Research should be conducted to improve and validate environmental
goals, such as the Multimedia Environmental Goals (Cleland and Kingsbury,
1977).  The goals should be aimed at protecting the integrity of the environ-
ment within realistic bounds.

     The energy demands of the nation necessitate the large-scale construc-
tion of coal gasification, liquefaction, and scrubber plants.  The conversion
process designs are at the pilot and demonstration plant stages of develop-
ment; more plants will undoubtedly be built within the next decade.  On a
scale this large, there are few precedents that could be used to  predict the
environmental impact of the disposal of waste products.

-------
     Through proper planning, valuable trace elements can probably be
recovered from many wastes.   We need basic and applied research to formulate
those strategies and disposal options necessary to avoid the serious
problems that could appear suddenly in large-scale operations.  Furthermore,
the research must be begun soon so that the data will be available for the
planning of the initial  large-scale coal  conversion facilities.

-------
                                 SECTION 4

             SOLID WASTES FROM COAL CONVERSION AND UTILIZATION


     Descriptions of the more than 40 coal conversion technologies being
studied for possible commercial development are contained in various techni-
cal literature; however, this study only contains descriptions of the Lurgi
gasification and H-Coal and SRC-I liquefaction processes.

     Both types of conversion processes—liquefaction and gasification—are
meant to increase the hydrogen-to-carbon ratio of the coal  and remove
environmentally hazardous materials from the feed coals.   Natural gas is com-
posed of 75 percent carbon and 25 percent hydrogen by weight, with traces of
environmentally unacceptable constituents (Linden et al., 1976).   On the
other hand, petroleum is 83 to 87 percent carbon, 11 to  15  percent hydrogen,
and up to 4 percent oxygen, nitrogen, and/or sulfur (Ellison, 1967).  Clean
coal is approximately 75 percent carbon, only 5 percent  hydrogen, and 20 per-
cent additional constituents, including pyrite and organic  sulfur (Linden
et al., 1976).  Thus, it is necessary to either increase the amount of
hydrogen or decrease the relative quantity of carbon if  coal is to be con-
verted to a product containing useful quantities of oil  or gas.


LURGI GASIFICATION

     There are two classifications of gasifiers, low/medium-BTU and high-BTU.
In order to synthesize gas from coal, three ingredients  are needed: carbon,
hydrogen, and oxygen (Braunstein, Copenhaver, and Pfuderer, 1977).  Coal and
steam provide the carbon and hydrogen respectively.  In  low-BTU processes,
air is the combustant, and the raw gas has a heating value of 150 to 300 BTU/
scf.  For medium-BTU gasifiers, pure oxygen produces a raw gas with a heating
value of 300 to 400 BTU/scf.  Most low- and medium-BTU gasifiers can be up-
graded to a high-BTU system (900 to 1,000 BTU/scf) by addition of a methana-
tion step.  The latter process produces a gas of pipeline quality that can
fill commercial and residential needs.  The low- and medium-BTU gasifiers are
now primarily used on site for industrial purposes.  Gasifiers can be further
subdivided by the type of reaction bed used: fixed, fluidized, and entrained
beds.  Braunstein, Copenhaver, and Pfuderer (1977) give  a detailed discussion
of the reactor types.

     The Lurgi gasification process has been commercially available since
1936 (Cavanaugh, Corbett, and Page, 1977); currently, 60 commercial plants
use this process.  The Lurgi is a fixed-bed, pressurized gasifier that oper-
ates with either air or oxygen and steam.  Figure 1 shows a process schematic,
and a material balance for gas production is given in Table 1.  With the

                                      8

-------
                                                                                     COAL LOCK GAS
           fO ASH DEWATERING
             AUD TRANSFER'
                                                                                            CRUDE GAS TO
                                                                                            'SHIFT CONVERSION
                                                                                               CRUDE GAS TO
                                                                                               GAS COOLING
Figure 1.  Flow scheme for gas production from the Lurgi process {Sinor, 1977).
          TABLE  1.  MATERIAL BALANCE FOR  CAS PRODUCTION FROM  Till- LURCl  PROCESS (SINOR, 1977)
Stream number 4.1 It, 2 4.3 4.4
component Ibs/hr Ibs/hr l.bs/hr Ibs/hr
CO 2
H2S
C2H,,
CO
H2
Ch\
C2H6
N2 + Ar 10,275
02 460,365
Total dry gas 470,640
Water . ' 314,950 1,783,540
Coal (MAP) 1,250,300 1.9,639
.Ash 373,220 373,220
Naptha
Tar oil
Tar
Crude phenols
NH,
4.5 4.6
Ibs/hr Ibs/hr
1,333,502
13,538
.1.2,273
611,677
84,859
193,007
19,730
.11,861
—
2,280,447
++ 1,394,960
—
—
20,005
11,993 28,007
65,811 6,630
.1.73 8,272
15,978
4.7
Ibs/hr
729,157
'7,403
6,710
334,464
46,401
105,537
10,788
6,485
—
1,246,945
762,764
—
—
10,939
15,314
3,999
4,991
9,640
4.8
Ibs/hr
604,345
6,135
5,563
227,213
38,458
87,470
8,942
5,376
—
1,033,502
632,196
—
—
9,006
12,693
3,315
4,136
7,989
     TOTAL
                  1,938,480   1,783,540    470,640   '192,859     77,977   3,757,489    2,054,592  1,702,897

-------
fixed-bed process, the coal is supported on a grate and the gases are passed
through the coal, with the hot product gas exiting from the top of the
reactor.  The product gas is scrubbed to remove particulate matter and is
eventually desulfurized, and the hydrogen sulfide is converted to elemental
sulfur (Braunstein, Copenhaver, and Pfuderer, 1977).  The solid ash falls
through the grate of the fixed bed and is removed.

     Noncaking coals need no pretreatment except for sizing.  Caking coals
such as those from the eastern United States cannot be used in the Lurgi pro-
cess unless the system is modified so that the coal bed can be agitated to
prevent agglomeration.  During 1973 and 1974, the American Gas Association
and the Office of Coal Research studied the performance and suitability of
various American coals for gasification by the Lurgi process.  Four different
coals were sent to Scotland, where they were gasified in the full-scale
modified gasifier at Westfield.  The solid ashes from gasification of three
of the feed coals were analyzed for this investigation.  The feed coals
included Illinois Herrin (No. 6) and Harrisburg (No. 5) Coals, and a Montana
Rosebud seam coal.
LIQUEFACTION: H-COAL AND SRC-I

     Coal conversion technologies termed liquefaction can produce not only a
liquid fuel  but also gaseous or solid products, and in some cases a low-
melting solid fuel.  There are two basic liquefaction processes, pyrolysis
and dissolution.

     Pyrolysis processes yield only low volumes of liquid fuel., along with
large quantities of char, that would require further refinement.  It is
doubtful that pyrolysis systems will become a major source of petroleum
(Epperley and Siegel, 1974).

     Liquefaction by dissolution involves dissolving crushed coal in a sol-
vent, filtering out the ash, and treating the liquid by hydrocracking.  Once
the solids are removed, the liquid can be catalytically upgraded.  The solid
ash can be used as fuel or for the production of hydrogen for the system.
Hydrogen is used to remove the organic sulfur from the product that is not
removed along with the ash.

     Dissolution processes can be divided into three types: (1) systems that
use neither catalyst nor hydrogen; (2) systems that use hydrogen but no cata-
lyst; and (3) systems that use both hydrogen and a catalyst.  The Solvent-
Refined Coal (SRC) process is of the second type, whereas the H-Coal process
employs both a catalyst and hydrogen.

     The SRC-I process (fig. 2) produces a solid fuel containing less sulfur
than the original feed coal and little or no ash regardless of the feed coal.
The solvent-refined coal has a melting point of 300° to 400°F, and a heating
value of approximately 16,000 BTU/lb.  The SRC process can be divided into
five steps:
                                     10

-------
    SLURRY MIX TANK
         any MINERAL RESIDUE
             SAMPLE
                                    i FUEL ro sot


Figure 2. SRC process schematic (White and Zahradnik, 1976).
 1.
 2.


 3.


 4.
The ground coal  is mixed  with a solvent that  is derived  from the process
through a preheater  to  a  dissolver maintained at 800°  to 900°F and 1000
to 2000 psig.  Approximately 90 percent of the organic material 'in,the
coal is dissolved.

The excess hydrogen  is  separated and cleaned  by acid-gas absorption to
remove hydrogen  sulfide.
                                                                       i
The slurry is filtered  to remove the undissolved solids, which are then
washed with a light  solvent and dried.

The solvent is recovered  from the filtrate by flash-distilling in a
vacuum.
 5.   The distillation results in  four  fractions: a light liquid  by-product, a
     wash solvent, a process solvent that can be recycled for use  in  the
     slurry,  and a heavy residual  product oil, termed solvent-refined coal.
                                       11

-------
     In September 1976, we received a quantity of dry mineral  residue from
the Pittsburg and Midway Coal Mining Co.  solvent-refined coal  pilot plant at
Fort Lewis, Washington, for analysis.  A Kentucky No. 9 feed coal was being
used at the time the sample was obtained.  The point in the process from
which the sample was taken is indicated in figure 2.

     Dissolution by the H-Coal process requires slurrying the crushed coal
with a heavy recycled oil, mixing it with hydrogen, and treating it in an
ebullated bed reactor at about 850°F and 2500 psig (fig. 3).  The H-Coal pro-
cess employs a cobalt-molybdate catalyst that is kept in an ebullated state
by the upward flow of the coal suspension and by hydrogen bubbles (Braunstein,
Copenhaver, and Pfuderer, 1977).  Hydrogen needed for the process comes from
the slurry oil, which circulates through the reactor to maintain a constant
temperature.  Sulfur and ammonia are recovered from the gas taken from the
top of the reactor, and the unused hydrogen is treated and returned to the
dissolution process.  The raw oil product is flashed down to low pressure,
with the vapors distilled in an atmospheric distillation unit and the liquid
distilled under vacuum.

     Either a light synthetic crude oil or a heavy synthetic fuel oil can be
produced by this process, depending upon the temperature and pressures
involved.  Because of the difficulties in separating the solids, the process
is more applicable to production of a crude oil.  Hydrocyclones, centrifuges,
magnetic separators, and filters are all, for a variety of reasons, less than
100 percent efficient.

     The solid waste sample used in this study was an unfiltered vacuum still
bottom (fig. 3) from the H-CoalR PDU at the Hydrocarbon Research Inc.,
Trenton, New Jersey, laboratory.  At the time, the PDU was producing a fuel
oil product from an Illinois Herrin (No. 6) feed coal.


ADDITIONAL COAL SOLID WASTES

     In additional to the solid wastes collected from the conversion pro-
cesses, six solid wastes from other forms of coal processing and utilization
were studied.  These included a fly ash and water-quenched bottom ash (slag)
from a pulverized coal-fired power plant; the Illinois Herrin (No. 6) Coal
was the power plant feed coal.  Also, two coal-cleaning refuse samples—a low-
sulfur and a high-sulfur gob—were analyzed.  Again the Illinois Herrin
(No. 6) Coal was the source.

     The final samples were a medium-temperature char (1200°F) and a high-
temperature char (1800°F).  Both of these were prepared from the Illinois
Herrin (No. 6) Coal using an electrically heated movable wall  coke oven oper-
ated by the Illinois State Geological Survey in Urbana, Illinois.  The medium-
temperature char was prepared according to the American Society of Testing
Materials standard method for testing the expansion or contraction of
coal by the sole-heated oven (ASTM, 1973).  Jackman et al. (1955) present a
detailed discussion of the Survey's pilot coking plant and the procedure for
making the high-temperature char.
                                      12

-------
                                                                                     HYDROCARBON CAS.
                                                                                     HYDROGEN SULFIOC
                                                                                     AND AMMONIA TO
                                                                                     S£PAHATION AND
                                                                                     SULFUR RECOVERY
                                                                                                                                    DISTILLATE
                                                                                                                                    TO FUPT^E"
                                                                                                                                    REFlMING
                                                                                                                                    VACUUM STILL BOTTOM
                                                                                                                                    MINERAL .RESIDUE
                                                                                                                                          SAMPLE
Figure 3.  H-Coal process schematic (White and Zahradnik, 1976).

-------
                                  SECTION 5

                 MINERALOGICAL AND CHEMICAL CHARACTERIZATION
                          OF THE COAL SOLID WASTES
     The first stage in determining the potential  pollution hazards of coal
solid wastes was a complete characterization of the wastes, including both
chemical and mineralogical analyses. These analyses are necessary to predict
the total amounts and forms of constituents that could become available to
the environment upon disposal.  By determining the mineralogy of the feed
coals, it is also possible to determine what changes take place during coal
utilization.
ANALYTICAL PROCEDURES

     Eleven solid wastes were analyzed chemically (over 60 constituents were
determined) and mineralogically.  In addition, 88 supernatant solutions gen-
erated by making 10 percent slurries of the solid wastes were analyzed for
over 40 constituents and properties.  An additional  360 solutions were col-
lected from a soil attenuation study, and these were analyzed for 10 princi-
pal constituents.  The supernatant solutions and the solutions from the soil
attenuation study will be described later in this report.

     The methods used to characterize the solid wastes were instrumental
neutron activation analysis, neutron activation analysis with radiochemical
separation, optical emission spectrochemical analysis (direct reading and
photographic), atomic absorption analysis (flame and graphite furnace modes),
x-ray fluorescence analysis, and ion-selective electrode procedures.  A
detailed discussion of sample preparation, detection limits, and procedures
for these techniques can be found in Gluskoter et al. (1977).

     Chemical analyses of the supernatant solutions, and of solutions from
the soil attenuation experiments, were done by atomic absorption using flame
and cold vapor methods, by ion-selective electrode,  and by colorimetric
techniques.  The U.S. Environmental Protection Agency's "Methods for Chemical
Analysis of Water and Wastes" (1974) was used as a reference for these
techniques.  Parameters measured by electrode included pH, oxidation-reduction
potential, specific conductance, chlorides, fluorides, and sulfide.  Ferrous
iron, sulfate, orthophosphate, and boron were determined colorimetrically.

     The mineralogical characterization employed x-ray diffraction, optical
and scanning electron microscopy, and 57Fe Mbssbauer spectroscopic analysis
(Bancroft, 1973).  The x-ray diffraction and scanning electron microscopy


                                     14

-------
techniques are explained in detail  in Russell  and Stepusin (1979).   The pro-
cedures involved in Mb'ssbauer spectroscopic analysis have also been cited in
other literature (Smith et al.,  1978).


MINERALOGICAL CHARACTERIZATION

     Samples of the eleven wastes were analyzed by x-ray diffraction for
mineralogical characterization and by Mossbauer spectroscopic analysis for
determination of the iron species (table 2).  Three feed coals were also
characterized by x-ray diffraction:  the Illinois Herrin (No. 6) Coal, the
Harrisburg (No. 5) Coal, and the Montana Rosebud seam coal.   The two Illinois
coals were also analyzed by Mossbauer spectroscopy.

     Using techniques applied in previous studies of coal (Smith et al.,
1978), ash (Hinckley et al., 1979), and oil shale (Cole et al., 1978), the
Mossbauer parameters were analyzed for the iron species in the coals and coal
solid wastes (table 3).  Each iron absorption was described in terms of
Lorentzian curves with three parameters: isotope shift (S), quadrupole
coupling constant (E), and  internal  magnetic field, when present (M).

     Usually, the major iron-containing component in the Illinois No. 6 Coal
was pyrite with a small amount of Fe+2 present in illite (Saporoschenko
et al., 1979).  Because this was a washed sample, some of the soluble iron-
containing minerals such as  sulfates may have been removed.  Sulfates in coal
are primarily oxidation products of pyrite that are formed when coal is ex-
posed to moisture and the atmosphere.

     In comparison, the major iron species in the Illinois No. 5 Coal was
also pyrite, but ferrous sulfate rather than illite iron species were found.
X-ray diffraction analysis,  however, does show the presence of some illite in
the coal.

     The Rosebud coal exhibits two additional ferro-minerals—melanterite and
goethite.  This coal, however, was not studied with Mossbauer spectroscopy.

     Spectra of Lurgi ash samples derived from the Illinois No. 5 and No. 6
Coals were very similar.  Computer fitting of both spectra yielded seven
multiplets that were assigned to six different iron species.  These species
were separated into two groups.   The first group, iron oxides, included hema-
tite, magnetite, and goethite (Hinckley et al., 1979; Dezsi and Fodor, 1966).
All of these compounds had  six line Mossbauer spectra characterized by mag-
netic hyperfine splitting.   They accounted for 59 percent of  the iron in No. 5
Coal ash and 56 percent in  the No. 6 Coal ash.  The second group contained
the remaining three species, one ferric and two ferrous.  These three species,
which gave two line spectra, were iron ions in silicate and mullite.

     Assignment of a Mossbauer absorption to an iron silicate species is a
nonspecific  identification  because isotope shifts and quadrupole coupling con-
stants vary widely for these species  (Bancroft, Maddock, and  Burnes, 1967).
Iron silicate isotope shifts vary from 0.0  (measured vs. iron foil) to 0.5 mm/
sec for Fe+3, and from 1.0  to 1.4 mm/sec for Fe+2.  Quadrupole coupling

                                      15

-------
  TABLE 2.  MINERAL COMPOSITION OF COALS AND COAL SOLID WASTES
Rose- No. 6
bud (washed)
Nonferro
Sphalerite
Quartz
Calcite
Dolomite
Anhydrite
Bassinite
Gypsum
Kaolinite
Expandable
clay
Feldspar
Wallastonite
No. 5
(washed)
Fines
(slurry)
Refuse"
(h'igh-S
gob)
Refuse
(low-S
gob)
Medium-
temper-
ature
char
High-
temper-
ature H-
char CoalR
Lurgi
ash
(No. 6
coal)
Lurgi
ash
(No. 5
coal )
Lurgi
ash
(Rose-
bud)
Water-
Fly SRC quenched
ash residue slag
minerals
	 -
X*
X
X
X
X
X
X

X
—
—
X
X
X
X
X
—
—
X

X
—
	 r
X
X
X
X
X
—
—
X

X
—
—
_
X
X
—
X
X
—
X

—
X
—
_
X
X
• —
—
—
	
X

—
X
—
X
X
X
—
—
—
-
X

—
X
—
_
X
X
—
X
—
	
—

—
X
—
_ |_
X X
. — X
— —
— —
— —
	 	
	 V

	 v
__ 	
— SEMf
_
X
—
—
—
—
	 .
—

—
X
—
_
X
—
—
—
—
—
—

—
X
—
__
X
—
X
—
—
	
—

—
X
—
_ 	 -
XX —
— — —
— — —
V 	 	
— — —
_ — —
— X —

— X —
— — —
— — —
Ferro minerals
Pyrite
Pyrrhotite
Illite^
Mullitet
Melanterite
Fe+2silicate
Hematite
Goethite
Magnetite
Hydra ted
ferrous
sulfate
Ferrous
carbonate
X*
—
X
—
X
—
—
X
—


—

	
MX§
—
X
—
—
—
—
—
—


—

—
MX
—
MX
—
	
—
	
—
—

it
MX I'

—
MX
—
MX
—
	
—
	
—
—


—

—
MX
—
MX
—
	
—
	
—
—

II
MX"

—
X
—
MX
—
	
—
— .
—
—


—

M
MX
MX
MX
—
	
—
	
—
—


MX

—
MX —
MX MX
MX* —
— —
	 	
• — —
	 	
— —
— —


MX MX

— —
__
—
—
MX
_
M
MX
M
M


—

—
___
—
—
MX
_J_r
M
MX
M
M


—

—
	
—
—
MX
	
M
MX
M
M


—

—
	 L 	 	
— MX —
— — —
— — —
	 	 —
M — M
MX — —
M ' — —
M — —


— MX —

- — — —
  *X-ray analyses.
   Scanning electron  microscope.
  *X-ray diffraction  cannot  distinguish  between valence states of iron.
  c
   M=M6ssbauer  analysis.
  "Anhydrous.
I   Spinel  group  hercynite.

-------
constants for iron silicates vary from 0.0 to 1.0 mm/sec for Fe+3,  and from
1.5 to 3.0 mm/sec for Fe+2.   The assignment means that silicate species are
known to be present from x-ray and/or elemental  analysis, that the  assigned
absorption is described by isotope shift and quadrupole coupling parameters
that fall within the above ranges, and that these parameter values  do not
correspond to those of other known species.

     Analysis of the Lurgi ash from Rosebud coal revealed that the  oxides
hematite, magnetite, and goethite were also present.   This ash was  similar to
the ashes mentioned above, but differed in two.important respects.   First of
all, 65 percent of the iron was present as oxide—a greater proportion than
was present in the other two Lurgi ashes.  Secondly,  the oxide component
assigned to goethite in the Rosebud Coal ash had a smaller magnetic field
parameter than the goethite in the ashes from Illinois No. 5 and No. 6 Coals.
Dezsi and Fodor  (1966) observed Mossbauer multiplets  for goethite character-
ized by small magnetic field parameters; they ascribed this to lattice imper-
fections.  Consequently, since the nature of the lattice modifications are
not known, this species is best described as goethite-like.

     Nonoxide species were also similar to the other  ashes in the study.
Iron was distributed in mullite and silicate lattices.  All of these species
were insoluble because spectra of the ash as slurries in distilled  water were
essentially unchanged.  In such an experiment, absorptions caused by soluble
species are expected to show reduced or zero intensity in the wet sample.

     The magnetite species in the three Lurgi ashes were not identified in the
x-ray diffraction analyses because hematite, feldspar, and mullite—which
interfere with the principal magnetite peaks—were present.  Thus,  the two
techniques complement each other and allow identification of mineral species
that could not be identified by one method alone.

     The Lurgi ash samples included in this study are similar to the ashes
derived from other oxidative processes (e.g. combustion), such as those ob-
tained  from a conventional power plant  (Hinckley et al., 1979).

     The liquefaction residues were also characterized mineralogically
(tables 2 and 3).  The major iron compound in the H-CoalR sample identified
from the Mossbauer spectrum was hexagonal pyrrhotite  with a small amount of
hydrated ferrous sulfate.

     Pyrrhotite  spectra in the H-CoalR sample was unusual; magnetic parameters
determined from  this spectrum do not include the value 228 KOe found in both
monoclinic and hexagonal pyrrhotite.  Furthermore, a  magnetic parameter value
around 310 KOe was found in all of the samples containing pyrrhotite.  This
last value is characteristic of troilite, and suggests that the pyrrhotite in
these materials  is a mixture of troilite and iron-rich pyrrhotite (Schwarz
and Vaugham, 1972; Novikov et al., 1977).  X-ray analysis, however, indicates
only pyrrhotite  to be a component.

     X-ray diffraction and Mossbauer analysis for the SRC-I dry mineral resi-
due indicated that pyrrhotite was present  (Keisch, Gibbon, and Akhtar, 1977/
1978; Jacobs, Levinson, and Hart, 1978), along with hydrated ferrous sulfate.

                                      17

-------
TABLE 3.  MOSSBAUER PARAMETERS FOR IRON SPECIES IN COALS AND COAL SOLID WASTES
Assignment
                                S(mm/sec)
E (mm/ sec)
M(KOe)
                                                                                      Fe*
No. 6 coal (washed)
Pyrite
Illite Fe+2
No. 5 coal (washed)
Pyrite
Ferrous sulfate
No. 6 coal slurry (fines)
Pyrite
Illite Fe+2
Refuse (high-sulfur gob)
Pyrite
Illite Fe+3
Illite Fe+2
Ferrous sulfate
Refuse (low-sulfur gob)
Illite fe+i
Illite Fe+3
Illite Fe+2
Iron carbonate
Medium-temperature (650 C) char
Pyrrhotite
Pyrrhotite
Pyrrhotite
Pyrrhotite
Pyrite
Illite Fe+2
Ferrous sulfate (hydrated)
fiigh-temperature (990°C) char
Pyrrhotite
. Pyrrhotite
Pyrrhotite
Pyrrhotite
Pyrite
Spinel group-hercynite
Ferrous sulfate (hydrated)
H-CoalR
Pyrrhotite
Pyrrhotite
Pyrrhotite
Pyrrhotite
Ferrous sulfate (hydrated)

0.305(8)
1.26 (3)

0.304(1)
1.18 (2)

0.311(1)
].24 (2)

0.306(1)
0.407(4)
1.06 (2)
1.171(7)

0.20 (1)
0.17 (3)
1.256(4)
1.38 (2)

0.788(8)
0.74 (1)
0.735(8)
0.73 (1)
0.36 (1)
0.999(9)
1.24 (1)

0.769(9)
0.758(9)
0.727(7)
0.76 (1)
0.34 (])
1.013(9)
1.32 (1)

0.78 (1)
0.82 (1)
0.79 (1)
0.75 (1)
1.24 (2)

0.622(1)
2.79 (2.)

0.618(1)
2.92 (3)

0.652(1)
2.66 (4)

0.616(1)
1.142(4)
2.64 (4)
2.956(8)

0.88 (2)
0.32 (9)
2.56 (2)
1.59 (4)

-0.230(4)
-0.04 '(1)
0.100(9)
0.24 (1)
0.634(2)
2.39 (2)
2.56 (2)

-0.172(9)
-0.05 (1)
0.066(9)
0.13 (1)
0.634(5)
2.26 (3)
2.44 (5)

-0.146(6)
0.048(9)
0.048(9)
0.144(8)
2.59 (3)




















315(2)
305(3)
274(4)
251(4)




313(2)
304(3)
277(4)
247(5)




311(6)
301(5)
287(5)
268(4)


99.8
0.2

95.9
4.1

94.2
5.8

88.0
6.9
2.4
2.6

29.0
24.6
29.3
. 17.0

7.8
16.0
9.0
10.0
48.0
7.4
3.0

9.7
12.3
10.0
11.2
49-3
4.5
3.0

51.8
7.8
7.6
30.2
2.6
                                        18

-------
         TABLE 3.   Continued.
Assignment
Lurgi ash (No. 6 coal)
Hematite
Magnetite
Magnetite
Goethite
Fe+3 mullite
Fe+2 mullite
Fe+z silicate
Lurgi ash (No. 5 coal)
Hematite
Magnetite
Magnetite
Goethite
Fe+3 mullite
Fe+2 mullite
Fe+2 silicate
Lurgi ash (Rosebud)
Hematite
Magnetite
Magnetite
Goethite
Fe+3 mullite
Fe+2 mullite
Fe+2 silicate
Fly ash power plant
Hematite
Magnetite
Magnetite
Unassigned
Goethite
Fe+3 silicate
Water-quenched slag
Fe+4 silicate


Fet2 silicate

SRC residue
Pyrrhotite
Pyrrhotite
Pyrrhotite
Pyrrhotite
Pyrite
Ferrous sulfate (hydrated)
S (mm/ sec)

0.366(6)
0.273(6)
0.609(4)
0.658(4)
0.35 (3)
1.13 (2)
0.98 (2)

0.369(6)
0.268(6)
0.606(8)
0.64 (4)
0.37 (2)
1.111(5)
1.000(6)

0.366(6)
0.274(6)
0.62 (2)
0.65 (8)
0.36 (3)
1.128(8)
1.03 (1)

0.363(4)
0.322(4)
0.515(9)
0.542(9)
0.50 (3)
0.99 (3)

0.190(7)
0.609(8)
1.064(6)
1.029(5)
1.078(5)

0.713(7)
0.750(9)
0.743(5)
0.693(9)
0.370(6)
1.25 (1)
E (mm/ sec)

-0.194(5)
0.004(2)
0.004(2)
-0.03 (2)
0.78 (3)
2.80 O)
.1.89 (2)

-0.194(5)
0.004(2)
0.004(2)
-0.05 (5)
0.70 (4)
2.76 (9)
1.9 (1)

-0.180(5)
0.004(2)
0.004(2)
-0.02 (2)
0.80 (3)
2.79 (1)
1.98 (2)

-0.204(5)
-0.04 (2)
-0.02 (1)
-0.06 (3)
-0.02 (1)
2.02 (2)

0.754(9)
1.028(2)
2.106(8)
1.562(1) '
2.628(1)

o'.ii (i)
0.09 (2)
0.09 (1)
0.14 (2)
0.70 (1)
2.62 (2)
M(KOe)

511(2)
486(3)
453O)
383(4)




511(2)
487(2)
453(3)
385(3)




511(2)
486(2)
453(3)
346(6)




508(3)
483(3)
456(3)
429(6)
381(5)








302(6)
290(5)
268(4)
239(7)


Fe*
(%)

25.4
7.9
13.0
10.2
16.5
3.6
23.6

21 .2
8.7
13.8
8.8
11.7
5.0
24.8

25.2
9.3
11.1
11.1
12.4
8.7
14.4

13.0
18.2
10.8
10.7
10.4
9.9

2.8
12.0
27.9
40.0
17.3

16.8
11.8
35.6
16.4
9.4
9.9
*Percentages are approximate values based on calculated areas of the absorption curves;  they are
 relative to the iron species within each sample—not from one sample to another on a quantitative
 basis.
S = Isotope shift.
E = Quadrupole coupling constant.
M = Internal magnetic field (when  present).
                                                19

-------
Mbssbauer parameter values for pyrrhotite in this sample were different from
those of the H-CoalR and the chars in that they fell  within ranges character-
istic of the natural pyrrhotite from Sudbury in Ontario, Canada, which is
often used as a standard of reference.

     Sphalerite, calcite, anhydrite, and clay minerals were also identified
in the H-CoalR residue by x-ray diffraction.  Wollastonite (CaSi03), unde-
tected by x-ray diffraction, was found by a scanning  electron microscope with
an energy-dispersive x-ray analyzer in polished and'etched samples of heavy
minerals.  Pyrrhotite, quartz, and clay minerals were identified in the SRC-I
mineral residue by x-ray diffraction.

     Mbssbauer spectra of coarse refuse from a preparation plant using low-
sulfur, Jefferson County Illinois (No. 6) Coal indicated that two ferric and
two ferrous iron species were present.  The two ferric and one of the ferrous
species were assigned from the Mbssbauer parameters to illite; the remaining
ferrous species was assigned to an iron carbonate.  X-ray diffraction data
revealed traces of pyrite and melanterite in this sample, although it was
not found in the Mbssbauer analysis (tables 2 and 3).

     The principal iron compound in the gob from high-sulfur No. 6 Coal was
pyrite.  The compound with the next highest percentage of iron was a ferric
species which, together with one of the ferrous species, was assigned to
illite.  Ferrous sulfate was present in smaller quantities than the other
species.

     A coal slurry (fines) from the washing plant contained pyrite and illite.
Nearly 6 percent of the iron found in the slurry was associated with illite,
whereas only 0.2 percent of the iron found in the washed coal was associated
with illite.  Although hydrated ferrous sulfate was found in the slurry by
x-ray diffraction analysis, it was not found by Mbssbauer spectroscopy—
perhaps because oxidation occurred during the time between the two analyses.

     Results of Mbssbauer and x-ray diffraction analyses of the medium- (650°C)
and the high- (990°C) temperature chars indicate that pyrite was the principal
iron compound in both chars (tables 2 and 3).  Iron was found at concentrations
of 46.8 percent and 49.3 percent, respectively, in the form of pyrite. Consid-
erable concentrations (42.8 percent and 43.2 percent) of the iron was found in
the form of pyrrhotite (Smith et al.,1978; Montano, 1977). In the low-tempera-
ture char, 7.4 percent of the iron was found in illite, whereas 4.5 percent
of thejron was found in spinal (Hinckley et al, 1979) in the high-temperature
char. Both x-ray diffraction analysis and MOssbauer spectroscopy showed the
presence of hydrated ferrous sulfate in both chars. X-ray diffraction analysis
of the two chars also indicated the presence of two calcium compounds—calcite
and anhydrite—in the low-temperature char that were not present in the high-
temperature char, but were evident in the Illinois No. 6 feed coal.

     Fly ash from the power plant was different from the Lurgi ashes.  For
example, the oxide mixture contained more components more uniformly distrib-
uted than the Lurgi ashes.  Fly ash contained only two mullite and silicate
species; this difference was accentuated by an additional feature.  In the
                                      20

-------
Lurgi ashes, ferrous iron (Fe+2) accounted for 36 to 43 percent of the iron;
whereas in the fly ash, ferrous  iron accounted  for only 24 percent of  the  iron.

     The contrast between water-quenched molten bottom ash and fly ash sam-
ples was dramatic.  The bottom ash contained no oxides.   Species in the
bottom ash were silicates (glasses); although four were identified (table 3),
the relatively broad linewidth parameters suggested that more were probably
present.  Furthermore, most of the iron in the bottom ash was present as
ferrous rather than ferric ions.  The Fe+2/Fe+3 ratio in bottom ash was 35.4,
whereas in the fly ash and Lurgi ashes, the ratio ranged from 0.3 to 0.7.

     Comparing the mineralogy of the coal solid wastes with that of the feed
coals revealed that several chemical reactions took place during processing
and conversion.  For example, in the H-CoalR process, a small amount of
quartz and calcite reacted to form wollastonite.  More importantly, nearly all
the pyrite in the feed coal was converted to pyrrhotite in the solid waste.
This occurred at temperatures lower than one would expect, based on data con-
cerning reactions of pure iron sulfides at equilibrium conditions.  These
reactions could have occurred in the slurry preheaters or in the liquefaction
process reactors.  The pyrite-to-pyrrhotite conversion might have been a
result of the cobalt-molybdate catalyst (which converts organic constituents
to a fuel oil product in the H-CoalR process), but the effect of the catalyst
on the mineral -interactions is not known.  For example, in the SR'G process,
the change from pyrite to pyrrhotite also occurred without a catalyst; the
SRC process does not use a catalyst.

     In the two liquefaction processes studied, nearly all the pyrite in the
feed coals was converted to pyrrhotite in the solid residues.  This could have
been caused by intimate association of the hydrogen in the liquefaction
system with the pyrite in the coal slurry.  Established phase relationships
in closed systems cannot be directly applied to mineral matter in the lique-
faction processes because of the undefined interactions of the components and
the removal of vapor from the system during reactions.  Mineral reactions must
be deduced, therefore, from a thorough study of the coal mineral matter before
and after coal conversion.

     During the Lurgi gasification process, the pyrite in the feed coal was
converted to hematite; this indicates that an oxidation process occurred
during conversion.  A similar change from pyrite to hematite took place in the
power plant fly ash.  The Fe+2/Fe+3 ratios in the fly ash suggest that the
oxidizing conditions in the power plant were more extreme than the conditions
in the Lurgi process.  Furthermore, hematite and magnetite are closely related
substances.  At high temperatures, magnetite is the more stable oxide; whereas
below  1388°C, hematite is more stable (Deer, Howie, and Fussman, 1962).

     Ferrous iron present as magnetite, therefore, reflects the ash's temper-
ature history.  On the other hand, ferrous iron present in silicate glasses
more likely reflects oxidizing conditions.  Ferrous iron was present  in all
samples in substantial amounts  (%25 percent); thus, the Fe+2/Fe+3 ratio deter-
mined by Mbssbauer spectroscopy may be a useful factor to consider when
following process conditions.


                                      21

-------
     The two  chars were similar  mineralogically  in that both contained pyrite
and pyrrhotite,  which indicated  that an incomplete conversion occurred upon
heating.
          TABLE 4.  MAJOR ELEMENTAL COMPOSITION AND ASH CONTENT OF THE SOLID WASTES
Solid wastes
Element
Al
Ca
re.
K
Mg
Na
S
Si
Ti
Ash
content
*Source:

Lurgi
No. 5
(%)
9.6
2.3
15.1
1.3
0.4
0.2
0.5
24.6
0.6
96.3*

Sather

Lurgi
No. 6
m
10.8
1..7
"!.'!
2.1
0.4
•1.3
1.5
19.4
0.5
98.7


ELEMENTAL CONSTITUENTS
8.5
4.4
1 '-.
1.3
0.5
0.6
0.1
22.3
. 0.4
99.6


OF THE
High- Low-
temp, temp.-
c ha r e ha r
(%) m
1.8 1.4
0'. 5 0.6
. i' ' . '
0.3 0.4
2.9 0.8
<.l 0.9
2.9 2.6
4.0 5.0
<.l 0.4
16.8 15.2


SOLID WASTES
Low-S High-S
refuse refuse
(%) (%)
0.7
2. 1

1.7
0.4
0.4
0.5
26.1
0.8
85.5



5.6
::.8
;• . c
1.0
0.2
0.2
10.9
14.5
0.5
65.2






Element
B
Ba
Ce
Cl
Cr
F
Mn
Sr
Zn
Zr


Lurgi
No. 5
(mg/kg)
465
760
107
80
171
<10
2014
275
1500
185


Lurgi
No. 6
(mg/kg)
355
950
140
100
212
<10
1859
370
400
170


Lurgi
Rosebud
(mg/kg)
810
3900
105
205
55
300
929
1500
31
251



H-Coal
(mg/kg)
300
40
16
1000
28
100
77
30
71
—
Solid


wastes

Fly
SRC ash
(mg/kg) (mg/kg)
100
400
200
400
100
500
155
600
13
100
200 •
500
57
28
100
100
465
200
6-2
200

Bottom
ash
(slag)
(mg/kg)
—
490
100
100
130
133
380
310
560
200

High- Low-
temp, temp.
char char.
(mg/kg) (mg/kg)
400 300
100 66
22 24
200 400
29 25
92 100
77 57
13 <10
48 42
36 28


Low-S
refuse
(mg/kg)
200
400
100
700
78
900
310
79
500
200


High-S
refuse
(mg/kg)
9
300
92
300
45
1105
310
100
300
100
                                        22

-------
CHEMICAL CHARACTERIZATION               TABLE 6.  CHEMICAL COMPOSITION OF TOO FLY ASH
                                                SAMPLKS FROM THE SAME POWER PLANT
                                                COLLECTED IN DIFFERENT MONTHS
      Knowing  which  constituents are
present  in  the  solid  wastes and in
;what  concentrations is necessary to
predict  the maximum release of con-
stituents during disposal; there-
fore, the chemical  composition of
the solid wastes was  determined for
over  60  constituents.

      Generally, nine constituents
were  found  in concentrations
greater  than  1000 mg/kg, or 0.1 per-
cent  of  the solid wastes  (table 4).
These were  Al,  Ca,  Fe, K, Mg, Na,
S,  Si, and  Ti.   Another group of
minor constituents  was found in
concentrations  generally greater
than  100 mg/kg, but less than
1000  mg/kg  (table 5).  These in-
cluded B,  Ba, Ce, Cl, Cr, F, Mn,
Sr, Zn,  and Zr.  Another 20 ele-
ments were  found in concentrations
less  than 100 mg/kg (tables 7 to 17).

      Correlation of the chemical
characterization of the wastes
from  this  study with characteri-
zations  from  other  investigations
is  difficult.  The  problem arises
from  the variability in the feed
coals and  the process parameters
used—that  is,  changes in temper-
ature and  pressure  will affect the
fate  of  constituents and the
nature of various waste streams.
jable 6  shows the chemical analy-
sis of two  fly  ashes collected at
different  times from the same coal-fired power plant.  Although  there  are
minor differences throughout, the major discrepancy is in  the sulfur values.
Whether  the reduction in sulfur is caused by the use of a  low-sulfur coal,
or  a  cleaning process for coal pretreatment, or a change in operating
conditions, is  unknown.

Constituent
Al
As
B
Ba
Be
Ca
Cr
Co
Cu
F
FeTotal
K
La
Mg
Mn
Mo
Na
Ni
STotal
Se
Si
Sr
Ti
Zn
Zr
Fly ash I*
(mg/kg)
73,600
46
—
490
16
•Jh.100
130
25
140
133
134,400
20,900
34
3,500
380
67
13,200
160
14,900
16
194,300
310
5,100
560
200
Fly ash II
(mg/kg)
87,376
33
600
700
10
.'•'...1 1
100
23
80
300
147,212
17,268
51
4,100
387
10
5,527
54
800.
6
226,925
200
5,096
600
200

*Fly ash I was used in the solubility, attenuation,
 and toxicity studies.
                                       23

-------
                                  SECTION 6

                   AQUEOUS SOLUBILITY OF COAL SOLID WASTES


     Leaching experiments have long been used to determine the soluble con-
stituents of waste materials; however, research has only recently begun to
focus on the importance of the vast array of variables inherent in these
techniques (Ham et al., 1978; Wewerka et al., 1978).  Three principal  vari-
ables influence the design of a leaching experiment: (1) the duration  of the
leaching period; (2) the type of system to use—static or flowthrough; and
(3) which experimental  parameters will be set—e.g. temperature, pH, aerobic
or anerobic.  Because of the number of variables, the leaching experi-
ment can be designed to suit the field situation that the investigator wishes
to simulate.

     A short shake test, which the U.S. EPA recommends for algal and static
bioassays (1977), will  put only the readily soluble salts into solution.  A
long-term test (over several months) would be more likely to allow equili-
brium conditions to develop.  Similarly, a long-term batch reactor test would
permit the equilibration of large volumes of leachate.  A column study, how-
ever, would allow for a more complete investigation of the rates of consti-
tuent solubility under the more variable conditions that would occur in a
field situation.  For example, the column test can be designed to study the
different flow rates and volumes, along with the wetting and drying that
simulates rainfall.

     A variety of experimental parameters exist; the parameters chosen depend
upon the field conditions to be simulated.  These parameters include the size
of the solid waste particles, the type of atmosphere (aerobic vs. anerobic)
in which' the system will be kept, the temperature of the leaching system, the
method of'agitation, and the use of a natural vs. adjusted pH for the  system.

     To determine the soluble constituents of the eleven coal solid wastes,
large-volume, static leaching tests were used.  This involved making 10 per-
cent (weight to volume) slurries of solid waste and distilled water in 2%-
and 5-gallon glass carboys.  The subsequent bioassay and attenuation studies
to be conducted with the leachates necessitated large volumes of leachate
and rapid attainment of equilibrium.  To attain equilibrium rapidly, the
wastes were initially ground to pass through a 28-mesh sieve.  This insured
uniformity among the wastes, which in turn promoted a more rapid equilibrium
than if larger sized particles were employed.  The 10 percent slurry simu-
lated a ponding type of disposal; it also facilitated attaining equilibrium
conditions more rapidly than if higher percentage slurries were made,  and
made it easier to stir the large volumes of heavy slurries.


                                     24

-------
     Duplicate series of four slurries were made -for each solid waste.  One
slurry from each set was allowed to equilibrate to its natural pH, while the
other three slurries in the set were adjusted by adding either nitric acid or
sodium hydroxide to pH values over the range of 2 to 12.  Over a period of
3 to 6 months, the slurries were stirred daily and their pH monitored or
readjusted when necessary to a specified value.  When a constant pH was
attained, it was assumed that chemical equilibrium had been reached.  Pre-
liminary studies conducted with the Lurgi ashes indicated that over 90 per-
cent equilibrium was attained within one week.

     Out of the two sets of slurries for each waste, one was equilibrated
under an argon  (oxygen- and C02-free) atmosphere, and the other under an air
atmosphere.

     Probably the single most important factor affecting the solubility of
the accessory elements in the coal solid wastes is pH.  Many coal wastes con-
tain sulfide minerals that can acidify upon exposure to air.  Heavy metals
contained in solid wastes disposed of in acidic strip or underground mines,
are potentially more soluble than metals in wastes disposed of under neutral
or alkaline conditions.  To study the effect of pH on leaching of consti-
tuents from the wastes, it was desirable to maintain a range of pH levels in
the slurries.

     The oxidation-reduction potential (Eh) is also an important factor
affecting the solubility of minerals  (Garrels and Christ, 1965).  When solid
wastes are buried underground or in water-saturated materials, anaerobic
(oxygen-deficient) conditions usually develop.  Studies of the effects of Eh
and pH on the solubilities of coal solid wastes could produce data that would
allow the prediction of potential pollution hazards or, on the other hand,
could predict which conditions would  be optimum for extraction of the poten-
tially valuable elements in the wastes.


RESULTS OF SOLUBILITY ANALYSIS

     The supernatant solutions  (leachates) from the equilibrated slurries
were analyzed for 43 constituents.  These concentrations plus the solid ash
chemical characterizations are given  in tables 7 through 17.  Any values given
with a less-than symbol (<) represent concentrations that could not be
detected by the technique used for the analysis.

     Seyeral generalizations can be made about the soluble constituents gen-
erated from the solid wastes.  As^ would be expected, the highest metal con^
          5_p_er-_.a ny-pa r_t.i c ular~was±e_were_fomicJLin the most acid supernatant
^solutions.  A comparison of all the acid solutions shows that four consti -
tuents are at relatively high  levels compared to recommended water quality
criteria  for all the waste solutions.   (The recommended water quality criteria
•were  based on values for the most sensitive likely use of the water recommended
'.by  the U.S. EPA  in 1972.)  These four constituents were Al , total Fe (both Fe+2
•and Fe+3), Mn, and Zn.  The range of concentrations of these constituents was
6 to  510, 2 to 3000, 1 to 31 ,  and 0.3 to 110 mg/L respectively.
                                      25

-------
TABLE 7.   CHEMICAL COMPOSITION OF LURGI ASH AND SLURRY SUPERNATANT SOLUTIONS OF THE ASH
          FROM AN ILLINOIS NO. 5 COAL AT SEVERAL pH'S
Chemical composition of
10", shirt
Air
(mg/L)
Constituents
Ag
Al
Au
As
B ,
Ba
Be
Br
Ca
Cd
Ce
Cl ,
cool
MCE?
Cr
Co
Cu
Cs
Eu
F
FeTotal
pe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu .
Mg
Solid ash
(mg/kg)
<.4
95,506
<.001
11
465
760
15
<1 .0
22,571
<1.6
107
80
—
—
171
36
50
10
1.7
<10
151,016
—
23
13
64
.05
12,867
49
31
1.1
3,618
pH
8.25*
	
<0.3
— •
<1 .0
5.0
<0.1
g/L)
PH..
9.57
^__
<0.3
	
<1 .0
5^5
<0.1

-------
TABLE 7.   Continued.
Chemical composition of 10% slurry supernatant
Air
(mg/L)


Constituents






























EC
Eli
A
1 .
Mn
Mo
Na
NH,,
Ni
Pb
P
PC*
Rb
STotal
S'2
SO,,
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Yb
Zn
Zr
(mmhos/cm)
(electrode
N.ltUtMl |>ll

Solid ash
(mg/kg) 8
2,014
61 <0
2,152 35
- 12
195
182
218
— <
180
5,400
500
8,400 623
2.8
23
<2 <
245,653 34
8.2
— <1
275 1
0.9
- <0
19 .
6,415 <0
4.2 <0
13
172
2.2
3.0
1,500 '
185
- 1
mv) — +266
of suponut.aut .

PH
.25*
.05
.3


.03
.1
—
.01
—
—
	

.2
—
•2

—
.0
.3
—
.5
—
.5
.4
—
	
—
—
.03
—
.10



pH
8.09
.30
<0.3
36
14
.06
.1
—
<.01
—
—
	
665
.4
—
<.2
23
—
<1 .0
1.8
—
<0.5
—
<0.5
<0.4
—
__
—
—
.12
—
2.15
+273


pH
6.05
4.2
<0.3
36
11
.40
.2
—
<.01
—
—
	
670
.6
—
<.2
24
—
<1 .0
2.1
—
<0.5
—
<0.5
<0.4
—
_
—
—
16.5
—
2.75
+357


pH
3
9
<0
42
3
1


<



492


<
125

<1
2

<0

<0
<0




110

5
+440


.09
.0
.3


.37
.2
—
.01
—
—
	

.7
—
•2

—
.0
.8
—
.5
—
.5
.4
—
	
—
—

—
.40



pH
10.88*
.01
<0.3
32
12
.03
.1
—
<.01
— •
—
	
650
.4
—
<.2
30
—
<1 .0
1.3
—
<0.5
—
<0.5
<0.4
—
__ _
. —
—
.01
—
1.13
+60


Argon
(mg/L)
pH
9.57
.04
<0.3
32
10
.01
.1
—
<.01
—
—
	
480
.4
—
<.2
14
—
<1 .0
1.8
—
<0.5
—
<0.5
<0.4
—
__ _
—
—
.01
—
2.10
+133


PH
6.25
15.9
<0.3
36
15
.14
.1
—
<.01
—
—
	
300
.5
—
<.2
18
—
<1 .0
2.0
—
<0.5
—
<0.5
<0.4
—
__
—
—
6
—
2.70
-28


pH
4.14
27.5
<0.3
38
16
.74
.1
	
<.01
—
—
^_
210
.9
—
<.2
88
—
2
2.5
—
<0.5
—
<0.5
<0.4
— '
	
—
—
65
—
5.40
+180


                                               27

-------
TABLE 8.  CHEMICAL COMPOSITION OF LURGI  ASH AND SLURRY SUPERNATANT SOLUTIONS  OF  THE  ASH
          FROM AN ILLINOIS NO. 6 COAL AT SEVERAL pH'S
Chemical composition of 10% slurry supernatant
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl .
COD£
MCEf
Cr
Co
Cu
Cs
Eu
F
FeTotal
Fe + 2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
Solid ash
(mg/kg)
<0.4
108,121
<.001
3
355
950
12
<1.0
16,652
<1.6
140
100
_
—
212
34
57
11
1.9
<10
143,780
—
26
7.0
6.1
.05
14,611
47
42
1.5
3,739
PH
7.55*
_
<0.3
—
<1.0
4.0
<0.1
<.02
—
290
.02
_
<25
2
28
<.02
<.05
.01
—
—
.31
.06
.03
—
—
—
<.0002
42
—
1.8
—
10.5
PH
5.10
_
2
—
<1.0
4.5
<0.1
<.02
—
480
.03
_
<25
2
28
.02
.05
.02
—
__
.30
.19
.11
—
—
—
<.0002
49
—
1.9
—
14
PH
3.82
_
14
_
<1.0
4.5
<0.1
.01
_
400
.03
	
<25
2
0
.05
.08
.13
—
—
.09
.24
.10
—
—
—
<.0002
51
—
2.0
—
15
PH
2.68
—
132
—
<1.0
5.5
<0.1
.03
—
570
.06
_
<25
81
23
.12
.19
.73
—
—
.04
560
533
—
—
—
<.0002
26
—
2.0
—
22
PH
8.82*
__
<0.3
—
<1.0
4.5
<0.1
<.02
—
440
.01
	
<25
2
10
.01
<.05
.01
—
—
.51
.06
.13
—
—
—
<.0002
39
—
1.6
—
9.5
Argon
(mg/L)
PH
7.20
_
<0.3
• —
<1.0
3.0
<0.1
<.02
—
370
<.03
	
<25
2
3
.01
<.05
.05
—
—
.34
.11
.05
—
—
—
<.0002
43
—
1.8
—
11
PH
5.35
_
<0.3
—
<1.0
4.5
<0.1
<.02
—
430
.02
_
<25
16
6
.06
<.05
.01
—
—
.16
101
no
_
—
—
<.0002
48
—
1.9
—
13.5
PH
3.79
n-i-
92
—
<1.0
8.0
<0.1
.01
_
500
.05
^
<25
140
4
.16
.17
.05
—
—
.02
880
864
—
—
—
<.0002
61
—
2.1
—
23
                                               28

-------
TABLE 8.  Continued.
Chemical composition
of 10% slurry supernatant
Air
(mg/L)
Constituents
Mn
Mo
Na
NHi,
Ni
Pb
P
PO,,
Rb
STotal
S'2
SO-
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode
Solid ash
(mg/kg) .
1,859
30
1,929
—
89
45
87
—
162
6,100
1,500 .
8.100
4.2
29
<1
229,946
8.21
—
370
1.1
—
21
6,295
4.6
17
184
1.5
2.9
400
170
—
mv) —
PH
7.55*
.45
<.03
34
17
.03
.1
—
<.01
—
—
<.2
820
.2
—
<.l
5
—
<1.0
1.8
—
<0.5
	
<0.5
<0.4
—
—
—
	
.12
—
.1.17
+223
PH
5.10
1.94
<.03
37
8
.13
.1
—
<.01
—
—
<.2
943
.3
—
<.l
29
—
<1.0
1.9
—
<0.5
—
<0.5
<0.4
—
—
—
	
5.5
—
1.50
+246
PH
3.82
2.7
<.03
38
12
.23
.1
—
<.01
—
—
<.2
808
.3
—
<.l
60
—
<1.0
2.1
—
<0.5
—
<0.5
<0.4
—
—
—
___
12
—
1.95
+407
pH
2.68
3.8
<.03
40
11
.50
.2
—
<.01
—
—
<.2
338
.6
—
<.l
130
—
<1.0
2.9
—
<0.5
	
<0.5
<0.4
—
—
—
.__
17
—
5.60
+349
PH
8.82*
.11
<.03
32
10
<.07
.1
—
<.01
—
—
<.2
730
.3
—
<.l
4
—
<1.0
1.5
—
<0.5
	
<0.5
<0.4
—
—
—
	
.01
—
1.20
+109
Argon
(mg/L)
pH
7.20
.W
-.03
37
10
.04
.1
—
<.01
—
—
<.2
735
.3
_
<.l
9
	
<1.0
1.7
—
<0.5
__
<0.5
<0.4
—
	
—
	
.11
_
1.39
+161
pH
5.35
». . 3
-.03
37
10
.14
.1
—
<.01
—
—
<.2
700
.3
—
<.l
27
_:
<1.0
1.9
—
<0.5
_
<0.5
<0.4
—
__
—
	
6.5
__
1.80
+102
pH
3.79
.!./
-.0.!
40
17
.42
.2
—
<.01
—
—
<.2
710
.5
—
<.l
120
, -—
<1.0
2.6
—
<0.5
^
<0.5
<0.4
—
—
—
T._L^
20
—
5.20
+243
*Natural pH of supernatant.
 Chemical oxygen demand.
*Methylene chloride extractable organics.
                                              29

-------
TABLE 9.   CHEMICAL COMPOSITION OF LURGI ASH AND SLURRY SUPERNATANT SOLUTIONS OF THE ASH
          FROM A ROSEBUD COAL AT SEVERAL pH'S
Chemical composition of
IDS slurry supernatant
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
ci t
COD;
MCET
Cr
Co
Cu
Cs
Eu
F
FCTotal
fe«
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
Solid ash
(mg/kg).
<.4 .
101,188
.007
22
810
3,900
4.3
<1.0
60,106
<1.6
105
205
—
—
55
5.0
49
3
1.0
300
60,059
—
24
8.2
12
.03
5,230
47
65
.5
21,531
pH
8.44*
_
<0.3
—
<1.0
26.9
<0.1
<.02
—
210 1
.02
	
<25
<1.0
26
.01
<.05
<.04
—
—
8.0
.01
.03
—
—
—
<.0002
11
—
.05
—
35
PH
8.14
_
<0.3
—
<1.0
23.2
<0.1
<.02
—
,100 1
.02
_
<25
2
11
.05
.08
.02
—
—
9.8
.19
.11
—
—
—
<.0002
8
—
.58
—
165
pH
4.95
_
7
—
<1.0
29.9
<0.1
<.02
	
,250 2
.06
_—
<25
2
16
.09
.12
.04
—
	
5.2
.15
.05
—
—
—
<.0002
14
—
.79
—
270
PH
3.13

510
—
<1.0
51.2
<0.1
.08
—
,050
.06
„ -
<25
45
41
.14
.20
.54
_
	
0.3
300
275
	
' 	
	
<.0002
31
	
1.40
—
410
pH
11.05*

<0.3
—
<1.0
19.8
<0.1
<.02
	
300
<.02
	
<25
11
—
.01
<.05
<.04
__
	
4.5
.02
.06
—
	
_^
<.0002
11
_^.
.36
	
.9
Argon
(mg/L)
PH
8.76

0.3
—
<1.0
24.3
<0.1
<.02
-»L
830 1
.02
	
<25
7
—
.03
.09
.02
	
—
9.9
.06
.06
—1
_
—
<.0002
9
__
.55
	
160
pH
5.26

5
—
<1.0
30.3
<0.1
<.02
— _
,170 1
.03
	
<25
12
16
.06
.10
.03
	
	
3.6
86
59
_
__
^
<.0002
18
_
.77
	
260
PH
3.43

420
	
<1.0
60.7
<0.1
.07
	
,900
.03
_
<25
no
	
.20
.23
.09
	
..
.25
670
633
.„
__
—
<.0002
34
_
1.40
_
440
                                               30

-------
TABLE 9.  Continued.
Chemical composition of 10% slurry supernatant
Air
(mg/L)
Constituents
Mn
Mo
Na
NH,,
Ni
Pb
P
PO,,
Rb
s
Total
S'2
SO,,
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (rnmhos/cin)
Eh (electrode
Solid ash
(ing/ kg)
929
29
74
—
5
38
2,095
—
46
5 400
** >HUU
1,100
6,000
12
15
<3
225,739
66
—
1,500
1.7
—
26
6,475
2.0
8.0
30.8
5.4
1.8
31
251
—
mv) —
PH
8.44*
.04
.4
10
13
<.07
<0.1
—
<.01
—


___
530
.4 .
—
<.3
7
	
<1 .0
3.4
—
<0.5
	 	
<0.5
<0.4
___.
• —
—
„_
<0.2
^
.95
+216
PH
8.14
1.06
<.03
14
14
.05
.2
_
<.01
_


.;.
585
1.0
	
<.3
22
___
<1 .0
g!o
— .
<0.5
^
<0,5
<0.4
_
	
	
	
0.3
_
4.3Q
+182 ;;
pH
4.95
16.2
<.03
16
19
.22
.3
_
<.01
_


_
567
1.2
	
<.3
55
	
2
14
—~
<0.5
._
<0.5
<0.4
_
—
-i-
_y.__
0/9

6.70
+259
pH
3.13
26.5
<.03
34
22
.50
.4
Ljn_
<.01
.-r--


_
295
1.3
	
<.3
75
	
3
26
' 	
<0.5
• _
<0.5
<0.4
_^_
	
—
' _
1.5
-.__
13.2
+320
pH
11.05*
.02
.6
10
13
<.07
.1
	
<.01
	



455
.3
	 ,
<.3
10

<1 .0
4J
1_
<0.5
_
<0.5
<0.4
.__
_
—
_
<0.2
, 	
.91
+45.05
Argon
(mg/L)
PH
8.76
.97
.8
11
18
.04
.2
	
<.01
	



472
.9

<.3
16

1
9.2

<0.5

<0.5
<0.4
_____
_ _
—

.02
	
4.10
+134
pH
5.26
lb.7
-.03
26
17
.17
.2
	
<.01
	



410
1.1

<.3
54

2
14

<0.5

<0.5
<0.4

___
—

.58

6,50
+130
pH
3.43
""uo
- . 0..
32
25
.54
.4

2.38


^~

383
1.2

< 3
94

2
26

.5

<0.5
<0.4

	
__

1.3

14.0
+251
*Natural pH of supernatant.
 Chemical oxygen demand.         -    .
*Methylene chloride extractable organics.
                                              31

-------
TABLE 10.   CHEMICAL COMPOSITION OF H-COAL LIQUEFACTION  UASTE  AND  SLURRY SUPERNATANT SOLUTIONS
           OF THE WASTE AT SEVERAL pH'S
Chemical composition of 10% slurry supernatant
Air
(mg/L)
Solid ash
Constituents (mg/kg)
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl .
CODT
Cr
Co
Cu
Cs
Eu
F
Fe
Total
pe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
0.
17,253
l!
300
40
1.
6.
7,862
<.
16
1,000

27.
4.
14
1.
0.
100
23,662

—
4.
4.
0.

2,490
9.
—
0.
844
16
01
5
8
7

4



5
45

7
69




6
9
86
05

8

24

PH
8.83*
3.0
11.0
—
110
<.03
	
75
15
<.02
<.l
<.05
—
—
1.00
<. 1

<.l
—
—
—
<.0002
1.4
—
<.01
—
0.5
pH
8.16
13.0
—
175
<.03
	
71
9
<.02
<.l
<.05
—
—
1.15
<. 1

<.l
—
—
—
<.0002
1.4
—
.01
—
0.6
pH
5.01
11.6
—
380
<.03
—
67
9
<.02
<.l
<.05
—
—
0.60
14

11
—
—
—
<.0002
2.1
—
.02
—
2.7
3
5
13

497
<

75
15

<
<


0
31

29



<
2



4
PH
.14
.5
.6
.1
.01
—

.03
—


.03
.1
.05
—
—
.86
.5

.5
—
—
—
.0002
.8
—
.02
—
.0
pH
11.31*
1.5
11.0
—
133
<.03
__
78
24
<.02
<.l
<.05
—
—
0.70
< 1

<.l
—
—
—
<.0002
1.2
—
<.01
—
0.6
Argon
H/L)
pH
8.50
12.2
—
155
<.03
—
70
8
<.02
<.l
<.05
—
—
1.20
<. 1

<.l
—
—
—
<.0002
1.5
—
.01
—
0.8
PH
5.53
1.5
12.9
—
425
<.03
• —
75
2
<.02
<.l
<.05
—
—
0.85
6.5

.9
—
—
—
pH
2.30
5.7
15.0
—
487
<.03
—
64
24
.05
<•?
<.05
—
—
0.84
90

90
—
—
—
<.0002 <.0002
2.0
—
.02
—
3.0
2.5
—
.02
—
4.0
                                               32

-------
TABLE 10.  Continued.
Chemical composition of ^Q% slurry supernatant
Air
(mg/L)
Constituents
Mn
Mo
Na
NH*
Ni
Pb
P
PO*
Rb
Total
S"2
SO*
Sb
Sc
. Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode
Solid ash
(mg/kg)
77
6.4
619
—
21
32
44
—
16
18,000
300
600
1.2
4.1
3.0
39,641
2.3
'0.6
30 ,
0.17
<0.1
3.5
1,019
1.7
5.7
33
4.4
1.0
71
— •
—
mv) —
PH
8.83*
<.02
<. 2
6.7
9
<.07
<0.1
—
<.025
—
—
<.2
65!5
<.4
—
<.5
<1
—
<1 .0
.20
—
<.5
—
<.6
<.4
—
<.5
—
	
.01
—
.44
pH
8.16
.04
<.2
7.0
6
<.07

-------
TABLE 11.   CHEMICAL COMPOSITION OF SRC LIQUEFACTION WASTE AND SLURRY  SUPERNATANT SOLUTIONS
           OF THE WASTE FROM A KENTUCKY COAL AT SEVERAL pH'S
Chemical composition of 10', slurr
Air
(mg/L)

Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
COD'1'
Cr
Co
Cu
Cs
Eu
F
FeTotal
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
Solid ash
(tng/kg)
.16
67,529
—
74
100
400
11
5.4
7,933
1.3
200
400
—
100
32
100
5.8
3
500
135,169
	
15
18
2.36
.08
8,717
97
—
0.78
60
PH
10.21
	
4.0
—
<1.0
3.6
<0.1
<.01
—
237
<.03
	
35
81
<.02
<0.1
<.05
—
—
0.44
<.l
<.l
—
—
—
<.0002
5.2
—
.02
—
0.6
PH
6.35*
	
<.5
—
•
-------
 TABLE  11.   Continued.
Chemical composition of 10'.' slurry supernatant
Air
(mg/L)
Constituents
Mn
Mo
Na
NHu
Ni
Pb
P
PO,
Rb
STotal
s-2
SO,,
Sb
Sc
Se
Solid ash
(mg/kg)
155
21
1,461
—
14
59
1,004
—
62
82,400
3,600
9,600
8.2
15
20
Si 110,930
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode mv)
17
6.2
600
.51
1.3
14
1,799
9.3
7.8
112
3.2
4.1
13.2
100
_
.
pH pH
10.21 6.35*
<.02 .93
<.2 c.2
340* 9.0
9.0 10
<.07 <.07
•- . 1 -: . 1
— —
<.025 <.025
— —
— —
•c.2 <.2
1,030 1,025
<.4 
-------
TABLE 12.   CHEMICAL COMPOSITION OF FLY ASH AND SLURRY SUPERNATANT SOLUTIONS  OF  FLY  ASH
           FROM AN ILLINOIS NO. 6 COAL AT SEVERAL pH'S
Chemical composition of 10',". slurry supernatant
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
CODr
Cr
Co
Cu
Cs
Oy
Eu
F
FeTotal
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Solid ash
(mg/kg)
<1.8
73,600
—
46
600
490
16
<3
26,100
<1.9
57
28
—
130
25
140
11
9.3
1.6
133
134,400
—
51
15
3.9
0.05
20,900
34
—
0.5
PH
8.82

0.62
—
<1.0
40
<0.1
<.02
—
130
<.03
_
<25
3
<.02
<.05
<.04
—
—
—
1.5
<.05
<0.1
—
—
—
<.0002
36.0
—
0.15
—
PH
7.97
_
<0.3
—
<1.0
46
<0.1
.026
—
435
<.03
_
<25
1
<.02
<.05
<.04
—
—
—
1.4
<.05
<0.1
—
—
—
<.0002
10.2
—
0.24
—
PH
4.08*
_
62.6
—
<1.0
58
<0.1
.052
—
508
0.39
_
<25
. 5
<.02
0.31
0.20
—
—
—
2.5
13.5
9.0
—
—
—
<.0002
1.4
—
0.53
—
pH
2.74
_
419.0
—
<1.0
62
<0.1 •
.094
—
879
0.57
_
<25
10
1.94
0.44
0.84
—
—
—
0.16
155
87
—
—
—
<.0002
10.8
—
0.55
—
PH
9.98

4.12
—
<1.0
44
<0.1
<.02
—
401
<.03

<25
4
<.02
<.05
<.04
—
—
—
1.2
<.05
<0.1
—
	
—
<.0002
56.0
—
0.11
—
Argon
(mg/L)
PH
7.08

<0.3
—
<1.0
52
<0.1
<.02
—
449
<.03

<25
1
<.02
<.05
<.04
—
—
—
0.72
<.05
<0.1
	
	
—
<.0002
17.0
—
0.41
—
pH
4.26*

32.6
—
<1.0
57
<0.1
.043
—
506
0.25

<25
17
<.02
0.25
<.04
—
—
—
3.0
no
92.5
	
	
—
<.0002
1.1
—
0.60
—
pH
2.52

406.7
—
<1.0
64
<0.1
1.03
—
872
0.51
_
<25
43
1.91
0.50
0.95
—
—
—
0.13
270
210
	
	
—
<.0002
16.1
—
0.66
—
                                               36

-------
TABLE 12.  Continued.
Chemical composition
of 10% slurry supernatant
Air
(mg/L)
Constituents
Mg
Mn
Mo
Na
NH,,
Ni
Pb
P
PC*
Rb
STotal
s-2
SO*
Sb
Sc
Se
Solid ash
(mg/kg)
3,500
380
67
13,200
—
160
110
873
—
170
14,900
—
—
3.5
20
16
Si 194,300
Sm
Sn
Sr
Ta
Te
Th .
Ti
Tl
U
V
W
Yb
Zn
7.r
EC (iimihos/cnt)
Eh (electrode
7.7
11
310
1.2
2.0
12
.5,100
1;2
<12
230
6
2.6
560
200
—
niv) —
pH
8.82
0.28
.03
3.5
367}
<0.1
<.07
0.15
—
<.01
—
—
—
3,650
<0.4
—
<0.5
1.33
—
<1.0
0.27
	
<0.5
—
<0.5
<0.4
	
<0.5
—
—
.05
	
6.0
+158.9.
PH
7.97
33.0
0.44
2.0
281}
<0.1
<.07
0.15
—
.06
—
—
—
3,150
<0.4
—
<0.5
4.0
—
<1.0
0.16
—
<0.5
—
<0.5
<0.4
	
<0.5
—
—
.03
_ n
4.5
+215.5
PH
4.08*
46.1
9.14
<0.3
195
<0.1
1.31
0.15
—
<.01
—
- —
—
2,350
<0.4
—
<0.5
35.0
—
<1.0
2.0
_
<0.5
—
<0.5
<0.4
__
<0.5
—
—
20
	
3.27
+354.1
PH
2.74
53.9
10.0
<0.3
220
<0.1
1.77
0.20
—
1.2
—
—
	
3,100
<0.4
—
<0.5
95.5
—
<1.0
3.15
_
<0.5
	
<0.5
<0.4
	
1.25
—
—
15
_
7.09
+474.1
pH
9.98
0.05
<.01
6.0
415f
0.1
<.07
0.15
	
<.01
—
—
	
4,950
<0.4
—
<0.5
2.0
—
<1.0
0.55
_
<0.5
	
<0.5
<0.4
	
<0.5
—
—
.01
	
7.41
+46.8
Argon
(mg/L)
PH
7.08
40.9
2.25
2.0
271t
<0.1
<.07
0.15
_
<.01
—
—
	
3,250
<0.4
_
<0.5
6.67
—
<1.0
0.16
_
<0.5
___
<0.5
<0.4
	
<0.5
—
—
0.33
	
4.36
+200.3
pH
4.26*
44.9
9.16
<0.3
185
0.2
1.45
0.25
__
<.01
—
—
	
2,250
<0.4
—
<0.5
22.7
—
<1.0
1.58
_
<0.5
—
<0.5
<0.4
_
<0.5
—
—
16
_
3.27
+263.5
PH
2.52
54.3
10.4
<0.3
230
0.3
1.87
0.25
^
3.0
—
—
___
3,450
<0.4
—
<0.5
93.5
	
<1.0
3.48
_
<0.5
	
<0.5
<0.4
_
3.0
—
	
19
_
7.63
+390.1
 *Natural  pH of supernatant
  Chemical  oxygen demand.
 •N.iOII iiddoil for pH adjustment

-------
TABLE 13.   CHEMICAL COMPOSITION OF WATER-QUENCHED SLAG AND SLURRY SUPERNATANT SOLUTIONS
           OF THE SLAG FROM AN ILLINOIS NO.  6 COAL AT SEVERAL pH'S
Chemical composition of
Air
•(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
• Br
Ca
Cd
Ce
Cl
CODf
Cr
Co
Cu
Cs
Eu
F
6Total
pe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
Solid ash
(mg/kg)
.80
84,571
—
2.7
200
500
2.4
0.6
43,668
<2
100
100
—
100
17.5
40
14.5
1.83
100
137,267
—
12
0.33
6.88
.01
13,365
53
—
.87
5,066
PH
8.82
_
<.5
	
<1.0
<.5
<0.1
•c.Ol
—
7.0
<.03
_
<20
13
<.02
<.l '
<.05
—
—
.07
.68
<. 1
—
—
— .
•c.0002
2.0
—
<.01
—
0.6
pH
7.40
_
•c.5
	
<1.0
<.5
<0.1
<.01
—
9.5
•c.03
_
<20
13
<.02
<.l
<.05
—
—
.03
.17
•c.l
—
—
—
•c.0002
2.0
—
<.01
—
1.3
pH
3.81*
_
5.5
	
<1.0
<.5
<0.1
<.01
—
17.5
<.03
_
<20
10
<.02
<.l
.20
—
—
.04
.60
•c.l
—
—
—
< . 0002
3.0
—
.01
—
2.2
PH
2.83

41.0
	
<1.0
<.5
<0.1
<.01
—
33.5
•c.03

<20
9.4
<.02
<.l
.32
	 .
	
.02
10.5
1.8
—
—
—
<-0002
7.2
—
.03
__
4.0
lO'.V. slurry supernatant

pll
9.94

•c.5
	
<1 0
<.5
<0.1
•c.Ol
—
5.0
<.03

<20
20
<.02
<.l
•c.05
	
	
.06
.55
<.l
—
—
—
<.0002
1.9
—
<.01
	
0.2
Ar
pll
8.30

<.5
	
<1 0
<.5
<0.1
•c.Ol
—
9.7
<.03

<20
10
<.02
<.l
<.05
	
	
.04
.15
<.l
—
—
—
<.0002
2.0
	
<.01
	
0.9
gon
/LJ ..
pll
5.65*

<.5
	
<1 0
<.5
<0.1
<.01
—
12.0
•c.03

<20
8.4
<.02
<.l
<.05
— .
—
.02
12.2
11.0
—
—
—
<.0002
2.6
	
<.01
__
1.4

PH
3.09

35.5
	
<1 0
0.6
<0.1
!02
	
31.0
<.03

<20
29
.06
•c.l
.13
	
	
.04
140
125
—
—
—
<.0002
11.8
	
.03
	
3.8
                                              38

-------
TABLE 13.   Continued.
Chemical composition
Solid ash
Constituents (mg/kg)
Mn
Mo
Na
NH,,
Ni
Pb
P
PO,
Rb
- S
Total
S'2
SO,
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode mv)
465
2.8
5,935
—
57
20
786
—
100
1,100

100
1,200
4.2
20
<3
222,934
10.8
3.7
200
1.2
2.1
22
4,436
<4
7.7
56
2.5
1.7
62
200
—
—
Air
(mq/L)
pH pH pH
8.82 7.40 3.81*
.03 .06 .78
< . 2 < . 2 < . 2
98* 44t 2.'i
6.0 9.0 . 8.0
<.07 <.07 .13
<.l <.l <.l
— — —
<.025 <.025 <-025
— — —
_ 	 __

< . 2 < . 2 < . 2
97.5 10K5 80.5
<.4 <.4 <.4
— — —
<.5 <.5 <.5
7 7 14.5
— — —
,; 1 . 0 < 1 . 0 < 1 . 0
< . 02 < . 02 .04
— — —
<.5 .-..5 <.5
_ . _ _
•' . 6 < . 6 < . 6
< p 4 < . 4 < . 4
— — —
< . 5 < . 5 < . 5
— — —
_ _ _
.02 <.01 .18
— — —
0.55 0.33 0.32
+244.3 +305.3 +462.1

pH
2.83
.95
< . 2
4.9
9.0
.32
<.l
—
<.025
—
	

<.2
iog!o
<.4
—
<.5
38
—
<1.0
.14
—
<.5

<.6
<.4
—
<. 5
—
_
.28
—
1.00
+527.4
of 10% slurry supernatant
Argon
(mq/L)
pH pH pH
9.94 8.30 5.65*
.03 .05 .60
< . 2 < 2 < 2
45* 20* l.'e
14 8.0 11
<.07 <.07 <.07
<.l <.l < 1
__ 	 __
.11 <.025 <.025
— — 	
	 	 _

<.2 <.2 <.2
50.5 52.5 51 '.0
< . 4 < . 4 .< . 4
— 	 	
<.5 <.5 <.5
9 5.5 8
: — 	 	
< 1 . 0 < 1 . 0 < 1 . 0
<.02 <.02 <.02
— — 	
<.5 <.5 <.5

'' . 6 < . 6 < . 6
< 4 < 4 < 4
— — —
< . 5 < . 5 < . 5
_ _ _
- - . -
<.01 <.01 .02
	 	 	
0.24 0.18 1.64
+89.9 +186.3 +310.3


PH
3.09
.85
< 2
4^8
10
.13
< 1
	
<.025
	


<.2
28!5
<.4
	
<.5
31.5
	
<1.0
.16
— _
<.5

< .6
<.4
—
<.5
—
_
.28
	
1.26
+362.1
*Natural pH of supernatant.
^Chemical oxygen demand.
      added for pH adjustment.
                                               39

-------
TABLE 14.   CHEMICAL COMPOSITION OF CHAR (1800°F)  AND SLURRY  SUPERNATANT  SOLUTIONS  OF THE
           CHAR FROM AN ILLINOIS NO.  6 COAL AT SEVERAL pH'S
Chemical composition
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
COD1"
Cr
Co
Cu
Cs
Eu
F
FeTotal
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
. Lu
Mg
Solid ash
(mg/kg)
.20
17,147
—
3.7
400
100
1.3
1.3
4,574
<0.5
22
200
—
28.9
4.5
14
3.1
0.68
92
23,951
	
4.4
2.0
1.13
.01
2,656
8.4
—
0.2
603
PH
8.05*

<-5
—
<1.0
2.8
<0.1
<.01
—
93
<.30
_
<20
41
<.02
<0.1
<.05
—
—
1.60
<.l
<.l
	
	
—
<.0002
2.0
—
.03
	
1.8
PH
6.17

<.5
—
<1.0
2.2
<0.1
<.01
—
327
<.30

<20
6.8
<.02
<0.1
<.05
—
—
0.88
.35
<.l
	
	
	
<.0002
2.8
—
.05
	
3.0
PH
4.33

<.5
—
<1.0
2.5
<0.1
<.01
—
340
<.30

<20
60
<.02
<0.1
<0.05
—
—
0.64
250
230
	
	
	
<.0002
4.0
	
.06
	
3.5
pH
2.46

27.0
—
<1.0
3.3
<0.1
<-01
—
370
<.30

<20
190
.06
0.25
<.05
—
—
0.10
1,250
1,140
__
___
	
<.0002
8.6
	
.08
	
4.8
of 10°£ slurry supernatant

PH
7.45*

<.5
	
<1.0
2.4
<0.1
<.01
	
no
<.30

<20
31
<.02
<0.1
<.05
	
	
1.90
.15
<.l
	
	
	
<.0002
1.4
	
.03
	
1.7
Argon
(mq/L)
pH
7.26

3.0
	
<1.0
2.8
<0.1
<.01
	
280
<.30

<20
16
<.02
<0.1
<.05
	
— _
1.85
<.l
<-l
	
— '
—
<.0002
2.0
_
.04
	
2.5
pH
4.95

31.5
	
<1.0
3.0
<0.1
<.01
i 	
333
<.30

<20
30
<.02
<0.1
<.05
	
	
1.50
100
98
	
	
	
<.0002
4.2
—
.05
_„.,
3.6
PH
3.03

	
	
	
3.5
<0.1
<.01
	
357
<.30

<20
71
.04
<0.1
<.05
	 •
	
1.50
415
400
	
	
	
<:0002
9.4
—
.08
	
6.0
                                              40

-------
TABLE 14.  Continued.
Chemical composition
Solid ash
Constituents (mg/kg)
Mn
Mo
Na
NHu
Ni
Pb
P
PO,,
Rb
sTotal
s-2
SO*
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode mv)
77
4.1
953
—
20
12
87
—
26
28,700
1,400
300
0.44
4.8
4.1
40,015
1.9
0.9
13
0.33
0.1
5.8
959
2.6
2.0
20
0.63
2.0
48
36
—
—
Air
(mg/L)
pH pH pH
8.05* 6.17 4.33
.28 2.78 4.45
<.2 <.2 <.2
3.' 5 let e.'o
9.0 12 12
<.07 <.07 <.07
<.l .15 .2
— — —
.025 .025 .025
— — 	
— • — —
<.2 <.2 <.2
100 219 69.' 5
<.4 <.4 <.4
— — —
<.5 <.5 <.5
4 4.3 7
— — —
<1 .0 <1 .0 <1 .0
.22 .42 .50
— — —
<.5 <.5 <.5
— _ ~ __
<.6 <.6 <.6
<.4 <.4 <.4
— — —
<.5 <.5 <.5
— — —
___ 	 __
<.01 .04 .38
— __ _
0.56 1.76 2.62
+140.1 +195.8 +251.7

PH
2.46
5.00
<.2
s'.s
13
.20
.15
—
1.95
	
—
< .2
106.5
<.4
	
<.5
27.5
—
<1 .0
.68
—
<-5
_
<.6
<.4
—
<.5
—
_
.90
	
6.00
+353.3
of 10% slurry supernatant
Argon
(mq/L)
pH pH pH
7.45* 7.26 4.95
.58 1.80 2.52
< 2 <.2 <.2
3.0 4.'o 6.'l
11 8.0 11
<.07 <.07 <.07
<.l .15 .15
— — —
.025 .025 .025
	 	 	
— — —
<.2 <.2 <.2
77 73 33.'?
<.4 <.4 <.4
	 	 	
<.5 <.5 <.5
5 6.5 20
— — —
<1 .0 <1 .0 <1 .0
.28 .40 .54
— — —
<.5 <.5 <.5
_ _ _
<.6 <.6 <.6
<.4 <.4 <.4
	 	 	
<.5 <.5 <.5
_ _ _
_ _ _
<.01 .02 .25
_ _ _
0.60 1.41 2.18
-1.5 +66.9 +159.9


PH
3.03
4.85
<.2
8.4
18
<.07
.15
—
1.80
	
—
<.2
30.7
<.4
	
<.5
34
—
<1 .0
.64
—
<.5
_
<.6
<.4
	
<.5
—
_
.62
_
3.39
+188.6
*Natural  pH of  supernatant.
^Chemical oxygen demand.
*NaOH added for pH adjustment.
                                              41

-------
TABLE 15.   CHEMICAL COMPOSITION OF CHAR (1200°F)  AND SLURRY  SUPERNATANT  SOLUTIONS  OF  THE  CHAR
           FROM AN ILLINOIS NO. 6 COAL AT SEVERAL pH'S
Chemical composition of
10% slurry supernatants
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
COD7
Cr
Co
Cu
Cs
Eu
F-
FeTotal
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
Solid ash
(mg/kg)
.
13,601
—
f
300
66
1.
4.
6,075
0.
24
400
— '
24.
3.
11
3.
t
100
5,860
—
4.
1.
1.
•
3,321
8.
—
,
7,598
51


17


2
0

4



5
4

4
40



4
2
08
01

1

2

PH
9.71
_
2.18
—
<1 .0
11
<0.1
<.02
—
2.0
<.03
^
72
5
<.02
<.05
<.04
—
—
0.64
.08
<0.1
—
—
—
<.0002
5.5
— .
<.01
—
<.01
7

<0

<1
10
<0
<

207
<

72
2
<
.<
<


0
<
<0



<
3



0
pH
.19*
—
.3
—
.0

j
!02
—

.03
—


.02
.05
.04
—
—
.05
.05
.1
—
—
—
.0002
.7
—
.03
—
.13
PH
3.81
_
7.18
—
<1 .0
9.1
<0.1

-------
TABLE 15.  Continued.
Chemical composition of 10% slurry supernatants
Air
(mg/L)
Constituents
Mn
Mo
Na
NH,,
Ni
Pb
P
P0»
Rb
ST .
Total
s-2
SO,,
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th -
Ti
Tl
U
V
VI
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode
Solid ash
(mg/kg)
57
3.5
8,636 .
—
12 .
8
87
—
23
25,800

900
1,600
.38
2.4
3.3
50,490
1.9
3.5
<10
.3
1.3
4.9
4.318
2.6
1.8
21.8
.63
1.2
42
28
—
mv) —
PH
9.71
<.01
<0.3
22. 4t
<0.1
<.07
<0.1
—
<.01
—
_

	
655
<0.4
—
<0.5
3.33
— •
<1.0
<.03
—
<0.5
^
<0.5
<0.4
—
<0.5
—
	
.02
—
2.56
+134.3
PH
7.19*
.57
<0.3
11.0
<0.1
<.07
<0.1
—
<.01
—
_^

	
500
<0.4
—
<0.5
5.00
—
<1.0
0.55
—
<0.5
_
<0.5
<0.4
—
<0.5
—
	
.02
—
1.04
+258.0
pH
3.81
3.2
<0.3
16.5
<0.1
0.16
<0.1
—
<.01
—
	

	
955
<0.4
—
<0.5
23.0
—
<1.0
0.68
—
<0.5
__
<0.5
<0.4
—
<0.5
—
_
0.59
	
1.42
+362.6
pH
2.67
4.3
<0.3
27.5
0.1
0.34
0.15
—
<.01
, —
	

__
200
<0.4
—
<0.5
48.7
—
<1.0
0.93
—
<0.5
_
<0.5
<0.4
—
<0.5
—
_„_
1.0
__
3.71
+491.2
PH
9.72
<.01
<0.3
21.5$
<0.1
<0.7
<0.1
—
<.01
—
	

__
530
. <0.4
—
<0.5
3.33
—
<1.0
<.03
	
<0.5
_- -
<0.5
<0.4
—
<0.5
—
_
<.02
^
3.16
+83.5
Argon
(mg/L)
PH
7.63*
.34
<0.3
10.0
<0.1
<0.7
0.15
—
<.01
—
	

__
170
<0.4
—
<0.5
4.33
—
<1.0
0.49
	
<0.5
__
<0.5
<0.4
—
<0.5
—
^_
.08
^
0.75
+181.0
PH
4.09
3.1
<0.3
16.0
<0.1
0.19
0.15
—
<.01
—
	

_ _
860
<0.4
—
<0.5
19.3
—
<1.0
0.74
_
<0.5
^_
<0.5
<0.4
—
<0.5
—
^_
0.28
_
1.42
+321.1
PH
2.42
4.3
<0.3
26.0
0.1
0.34
0.30
_
0.15
—
_

__
175.
<0.4
—
<0.5
48.3
—
<1.0
0.90
__
. <0.5
__
<0.5
<0.4
	
<0.5
—
^_
0.66
_
6.32
+358.2
 *Natural  pH  of  supernatant
  Chemical  oxygen  demand.
       added  for pH  adjustment.
                                               43

-------
TABLE 16.   CHEMICAL COMPOSITION OF HIGH-SULFUR CLEANING WASTE  (GOB) AND SLURRY SUPERNATANT
           SOLUTIONS OF THE GOB FROM AN  ILLINOIS  NO.  6 COAL AT SEVERAL pH'S
Chemical composition of
10% slurry supernatant
Air
(mg/L)
Solid ash
Constituents (mg/kg)
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
ci
CODf
Cr
Co
Cu
Cs
Eu
.F
FTotal
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
.
56,522
—
13
9.
300
2
1.
28,159
<1.
92
300
—
45.
10.
29
9.
1.
1,105
86,157
—
11
1.
3.
.
9,962
43
—
.
1,869
20



3


2

4



3
3

6
2




2
24
02



34

PH
8.34
	
<0.3
—
<1 .0
<0.5
<0.1
<.02
—
21.8
<.03
	
28
7
<.02
<.05
<.04
—
—
1.40
<.05
<0.1
—
—
—
<.0002
11.4
—
.03
—
.09
7

<0

<1
<0
<0
<

480
<

28
5
<
<
<


0
<
<0



<
11



0
pH
.45*
—
.3
—
.0
.5
j
!02
—
2
.03
—


.02
.05
.04
—
—
.47
.05
.1
—
—
—
.0002
.9
—
.07
—
.95
PH
3.43
' —
4.7
—
<1 .0
<0.5
<0.1

-------
TABLE 16.  Continued.
Chemical composition
of 10% slurry supernatants
Air
(mg/L)
Constituents
Mn
Mo
Na
NH,,
Ni
Pb
P
PO.,
Rb
c
Total
S'2
SOu
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
'Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode
Solid ash
(mg/kg)
310
3.2
2,419
—
48
55
829
—
100
108,800

76,100
13,500
.2
9.1
12.6
145,490
6.9
3.3
100
.8
.6
13
4,668
8.2
2.9
35.3
2.5
2.1
300
100
—
mv) —
PH
8.34
<.01

-------
TABLE 17.   CHEMICAL COMPOSITION OF LOW-SULFUR CLEANING WASTE (GOB)  AND SLURRY SUPERNATANT
           SOLUTIONS OF THE GOB FROM AN ILLINOIS NO.  6 COAL AT SEVERAL pH'S
Chemical composition of
10% slurry supernatant
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
COOT
Cr
Co
Cu
Cs
Eu
F-
Fe
• Total
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
Solid ash
(mg/kg)
.30
97,008
—
68
200
400
3
3.2
21,227
1.8
100
700
—
78
13
36
15.2
1.5
900
24,813

—
19
4.1
7.94
.05
17,102
50
—
.42
3,859
PH
9.19
—
4.4
—
<1.0
1.0
<0.1
<.02
—
4.6
<.03
—
30
10
<.02
<.05
<.04
—
—
1.7
1.1

<0.1
—
—
—
<.0002
4.5
—
<.01
—
.02
PH
7.79*
	
<0.3
—
<1.0
<0.5
0.72
<.02
—
568 2
<.03
	
28
6
<.02
<.05
<.04
—
—
.94
1.08

<0.1
—
—
—
<.0002
17.8
—
.07
—
0.79
PH
3.50
	
8.53
—
<1.0
<0.5
2.54
<.02
—
,287 2
.08
__
28
12
<.02
.45
.28
—
—
2.2
10

2.3
—
—
—
<.0002
29.0
— •
.16
—
80.0
pH
2.54
	
29.0
—
<1.0
<0.5
1.90
.034
—
,595
.09
	
34
26
.06
.64
1.68
—
—
1.9
130

52
—
—
—
<.0002
38.0
—
.26
—
119.7
PH
9.24
	
0.62
—
<1.0
1.0
<0.1
<.02
—
4.6
<.03
	
30
4
<.02
<.05
<.04
—
—
1.7
1.2

<0.1
—
—
—
<.0002
3.0
—
<.01
—
.05
Argon
(mg/L)
pH
7.21*
	
<0.3
—
<1.0
<0.5
1.64
<.02
—
943 1
.04
	
28
9
<.02
<.05
<.04
—
—
1.1
.08

<0.1
_
—
—
<.0002
20.0
—
.09
—
30.0
PH
4.88
	
<0.3
—
<1.0
<0.5
1.82
<.02
—
,973 2
.08
	
28
11
<.02
.27
<.04
—
—
1.1
2.2

0.5
—
—
—
<.0002
25.0
—
.15
—
68.7
PH
2.43
	
57.0
—
<1.0
<0.5
2.54
.034
—
,784
.09
—
34
61
0.13
.48
1.34
—
—
.48
360

285
—
—
—
<.0002
40.0
—
.33
—
138.9
                                               46

-------
TABLE 17.  Continued.
Chemical composition of 10X slurry supernatant*'
A1r
(mg/L)
Constituents
Mn
Mo
Na
NH*
N1
Pb
P
PC-
Rb
s
"Total
s-2
SO,
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th
T1
Tl
U
V
W
Yb
2n
Zr
£C (mmhos/cm)
£h (electrode
Solid ash
(mg/kg)
310
<1
3,635
—
55
55
1,397
—
200
5,100

4,600
400
2.7
15.2
3.3
261,380
8.0
7.2
79
1.2
2.2
20
8,298
8.0
3.1
39.8
2.9
4.3
500
200
_
mv) —
PH
9.19
.02
_
485t
<0.1
<.07
.15
• ' —
.08
—


__
43
,<0.4
_
<0.5
19.3
—
<1.0
.03
. —
<0.5
_ .
<0.5
<0.4
_
<0.5
—
^
.16
.»
.74
+122
PH
7.79*
.59
__
245
1.8
<.07
.15
—
.04
—


__'
96
<0.4
—
<0.5
13.7
—
<1.0
2.60
—
<0.5
__
<0.5
<0.4
_
<0.5
—
.^
<.01
_
4.4
+189.8
PH
3.50
1.2.6.
_
250
3.9
.69
.40
—
14.5
_


—
73
<0.4
_
<0.5
64.6
_
<1.0
7.06
_
<0.5
^
<0.5
<0.4
_-
<0.5
—
	
• 27
^
9.3
+314.1
pH
2.54
24.4
.
250
4.5
1.06
.50
_
3.0
__


L
67
<0.4
_
<0.5
96.2
	
<1.0
8.00
	
<0.5
nm^
<0.5
<0.4
^
<0.5
—
_
1.55
mi^
12.1
+404.7
PH
9.24
.07
_
5051=
<0.1
<.07
<0.1
_
.06
.^


_ r
24
<0.4
-
<0.5
15.0
_
<1.0
.03
^
<0.5
«.
<0.5
<0.4
„
<0.5
—
_
2.25
^^^
.71
+53.4
Argon
(mg/L)
PH
7.21*
2.06
_
260
1.8
<.07
.20
—
2.75
„-. •


_
60
<0.4
^
<0.5
25.3
_
<1.0
3.70
_
<0.5
__
<0.5
<0.4
^
<0.5
' —
^^
.06
• _
5.4
+168.4
PH
4.88
9.9
__
245
4.0
.33
.40
_
3.25
_


--i-i-
49
<0.4
_ _
<0.5
55.0
_
<1.0
6.83
	
<0.5
	
<0.5
<0.4
—
<0.5
—
••••
.12
__
8.5
+210.4
PH
2.43.
30.7
	
255
4.9
.85
.70
_
44.0



__
45
<0.4
	
<0.5
116.5

<1.0
9.12
__
<0.5
	
<0.5
<0.4
	
<0.5
—
_
1.40
__
12.5
+319.8
 *Natural  pH of supernatant
  Chemical  oxygen  demand.
       added for pH adjustment
                                              47

-------
     Calcium values exceeded the recommended  levels  for  all  but the slag acid
leachate; however, although several of the calcium concentrations  were in the
range of 1000 to 2000 mg/L, they did not  present the environmental   hazard that
the four constituents mentioned.above do.  Additional  trace  metals were found
in some of the most acid leachates  at concentrations slightly above the recom-
mended levels for certain water types.  They  were not found  in solution at
detectable concentrations in the intermediate acid leachates (pH 5.5 to 4.0).
Boron was present in amounts exceeding the recommended level  for irrigation
water (0.75  mg/L) in all but two of  the most acid leachates,  and  over the entire
pH range in eight of the slurry sets.  The current assessment of boron's ef-'
feet on the environment, however, leaves  some question as  to whether the
boron concentrations found in this  study  are  hazardous to  the environment.

     Sulfate was the dominant anion in solution with concentrations that
ranged as high as 5000 mg/L.  Sulfate, however, along with Cl, K,  and  Na,
showed no pH dependency in their solubility.

     Nonetheless, the most easily leached constituent does not always  possess
the greatest potential for pollution.  Although, under acid  conditions, many
constituents exceeded the U.S.  EPA  recommended  levels, it  was felt that those
that exceeded the recommended levels over the entire pH  range had  the  greatest
potential for pollution. Table  18 lists those constituents that were found to
exceed the recommended levels over  the pH range studied  (including both aerobic
and anaerobic solutions), and under the laboratory conditions described
earlier.  Also included in
table 18 is a summary of the pH
ranges for the supernatant solu-       TABLE is.
tions for each waste along with
the natural (unadjusted) pH for        	
both the aerobic and the
anaerobic series. .
                                       Sample
ELEMENTS WITH CONCENTRATIONS EXCEEDING
RECOMMENDED WATER QUALITY LEVELS UNDER
THE LABORATORY TEST CONDITIONS


          •	Natural pH	

    pH range  Air  Argon  Constituents
   .  The two most important fac-
tors affecting the solubility of
minerals were probably the pH and
the redox potential.  The solid
waste that has the lowest pH
value would also pose the great-
est potential threat to the
environment.  Indeed, the power
plant slag and fly ash natural
leachates appear to present
greater hazards because of their
dissolved constituents than the
natural pH leachates from the
other wastes.  The experimental
conditions described above, how-
ever, may not have been as condu-
cive as natural conditions to the
development of naturally acid pH's
for several of the other wastes,
such as the gob samples.
Lurgi Ash
(111. #6 Coal)

Lurgi Ash
(111. #5 Coal)

Lurgi Ash
(Rosebud Coal
Mont.)
SRC

H-Coal
Char (1200°F)
Char (1800°F)

Low-sulfur gob
High-sulfur gob
Slag
Fly ash
8.


10.


11.


10.

11.
9.
8.

9.
8.
8.
10.
8-2


9-3


1-3


2-2

3-2
7-2
1-2

2-2
9-2
8-2
0-2
.7


.1


.1


.9

.3
.4
.5

.4
.5
.8
.5
7.


8.


8.


6.

8.
7.
8.

9.
7.
3.
4.
6


3


4


4

8
2
1

2
5
8
1
8


10


11


7

11
7
7

9
7
5
4
.8


.9


.1


.5

.3
.6
.5

.2
.4
.7
.3
B,
Mn,
SO,,
B,
NHi,
Sb
B,
K,
Pb,
B,
Mn,
B,
B
B,
NH,,
Ca,
NHi,
, Sb
Ca,
, Pb

Ca,
Mo,
SO,,
Ca,
NH'I,
Ca,

Ca,

Cd
»

K,
1

Cd
, K,
Pb,

•Mn,
so,,,

, F,
NH,,,
»
Fe
»
Sb
*
SOi,
NHi,

Mn


t

None
K,
NH,,
B,
NH,,,

Ca,
SO,,


SO,,
                                     48

-------
     There is reason to believe that using 10 percent slurries in large
volumes may prohibit complete oxidation of the iron sulfides in several of
the solid wastes because of oxygen's slow diffusion rate through water.
Complete oxidation would result in sulfuric acid production and a lowering of
pH, along with a subsequent increase in constituent solubility for those
wastes containing an appreciable amount of pyrite.   Under different experi-
mental conditions, therefore, the natural pH's of some of the waste leachates
may be greatly decreased. It was felt that pH adjustment to the low values in
table 18 helps to simulate the acid conditions that may develop under different
environmental conditions.

     Comparison of the constituent concentrations of the two sets of slurries
for each waste was difficult because the sets were equilibrated to slightly
different pH values for the air and argon slurries.  Although it was
attempted to pair the pH values between the sets of slurries, the values
often varied by as much as 0.5 pH units.  The iron concentrations were in-
structive in cases where the acid pH's were similar: generally, the leachates
equilibrated under argon exhibited higher concentrations of iron (predomi-
nantly ferrous iron) in solution—especially at the intermediate acid pH
level (5.5 to 4.0).  Undoubtedly this was caused by the lack of available
oxygen in the slurries equilibrated under argon.  Similar results could be
expected for several other metals present.

     Table 18 also indicates that the soluble constituents found in solid
wastes were similar for the same treatment  no matter which feed coal was
used; i.e., the three Lurgi ashes yielded nearly the same major soluble con-
stituents for all three feed coals.  The same was true for the two liqui-
faction wastes.  The Illinois No. 6 Coal was used in both the Lurgi and
H-Coal processes, but quite different soluble constituents were derived from
the wastes.  The Cd, K, Mn, Na, Pb, SO.,, and Sb found in the Lurgi ash leach-
ates indicated that they were more soluble than those same constituents from
the H-Coal residue under the conditions used.
                                     49

-------
                                 SECTION 7

                      EQUILIBRIUM SOLUBILITY MODELING
                  OF THE LEACHATES FROM COAL SOLID WASTES


     The application of equilibrium solubility models can lead to useful  in-
sights into the chemistry of aqueous systems.  Equilibrium models provide, at
a minimum, boundary conditions within which questions may be framed.   For
example, a typical environmental problem solved by equilibrium models is  that
of predicting what is the highest concentration of a given constituent that
can be achieved in solution before precipitation occurs with a given  solid
phase.  Solutions to such problems can be sueful in developing a "worst case"
scenario for a given pollutant that is leaching from a solid waste, by
setting the upper boundary for concentrations of the pollutant that will  have
to be dealt with under a given set of conditions.

     The results of applications of solubility models to environmental prob-
lems must be interpreted carefully.  For example,  it is not uncommon  to find
large discrepancies in literature values for the solubility products  of some
mineral phases.  The value of the solubility product may depend on the direc-
tion of approach to equilibrium, the use of well-defined crystals versus  pre-
cipitation, and phenomena such as phase transitions, aging, colloid formation,
and differences in particle size.  These factors,  along with slow attainment
of equilibrium and the fact that impure minerals are found in nature  as
opposed to the pure minerals used to determine solubility constants,  may
obscure solubility relationships and their application to practical environ-
mental problems.

     Important factors controlling the solubility  of mineral phases include
pH, the redox environment of the system, the oxidation state of the mineral
components, the concentration and speciation of individual inorganic  and
organic ions and complexes in solution, and the ionic strength (total soluble
ions).  Applying the results obtained from solubility models to real  environ-
mental conditions requires considerable caution; nevertheless, assuming that
the activities are calculated correctly and that the equilibrium constants
are numerically factual, these models should accurately predict the solubil-
ity of an ion under a given set of conditions for  a long list of solid phases.


EQUILIBRIUM SOLUBILITY MODEL

     Explaining the aqueous chemistry of a complex system such as the leach-
ates from coal conversion solid wastes is diffucult.  Possible complexation,
ion pair formation, and the effects of organic components on the formation of


                                     50

-------
organo-metallic  complexes hinders the description  of these systems.  On the
other hand,  it  is  still  important to examine  these systems and account for
their soluble components, and we progress  if  we  prepare diagrams showing  the
relations of the known aqueous species to  the mineral  solid phases.

     Solubility and mineral stability diagrams were prepared according to
Garrels and  Christ (1965).  The thermodynamic solubility model used in this
study (WATEQF)  considered the speciation of 115  aqueous inorganic ions and
complexes and computed saturation data for over  100 minerals.  The theory of
the model and its  computer implementation  have been discussed previously  by
Truesdell and Jones (1973; 1974) and Plummer, Jones, and Truesdell (1976).

     The stability relations of the iron oxides  and sulfides in water were
plotted as a function of Eh and pH in figure  4.   Data from the leachates  of
the eleven wastes  and a pyrite standard, equilibrated under the same
                   01   23456789  10
                                         pH

Figure 4. Stability relations of iron oxides and sulfides in waste at 25° C when Fe*2
      10~3M (native sulfur field excluded).
                                                      II   12
                                                               14

                                                       10  M, and the sum of sulfur species is
                                      51

-------
conditions as the solid wastes, were also plotted.   Some explanation of
figure 4 may help to interpret the data.   The upper and lower limits of water
stability are shown; they mark the upper and lower  boudaries of the Eh and
pH of concern.  Thus, water decomposes into oxygen  gas at Eh and pH values
above the upper boudary; water decomposes into hydrogen gas at the lower
boundary.  Eh and pH values outside this range, therefore, are not normally
of concern when interpreting the aqueous chemistry  of natural systems.

     The solid lines between solid phases such as hematite and magnetite mark
the boundaries of mineral stabilities.  Data points falling within these
regions indicate that the samples are within the stability field of that
particular mineral.  Most of the data points in figure 4 fall within the
hematite stability field.  This is reasonable because x-ray diffraction
showed hematite to be present in most of the samples; however, magnetite and
pyrrhotite were also shown to be present in some of the solid wastes.  The
diagram illustrates that these two minerals are unstable in these systems
and, given sufficient time, they will decompose to  other mineral phases.

     Data points that fall on or near a boundary line, such as the pyri.te
standard (fig. 4), indicate that a solution is in simultaneous equilibrium
with the various solid phases described by the boundary.  The pyrite used in
this study was a technical grade material that contained impurities in the
form of hematite and magnetite; thus it is reasonable that the solution
would be in equilibrium with these three mineral phases, and that the elec-
trodes used in the measurements were operating properly.

     The boundaries between solid phases and aqueous species (such as between
hematite and the aqueous Fe+2 ion) serve as true "solubility" boundaries;
they are a function of the activity of the ion in solution.  Two such bound-
aries are shown in figure 4—one for 10~6M, and another for 10~2M Fe+2aq.
The 10~6M boundary is chosen by convention, on the  premise that if an
ion's activity in equilibrium with a solid phase is less than 10~6M, the
solid will be immobile in that particular environment.  This  convention  was
developed largely from experience but seems to correlate well with natural
geologic systems (Garrels and Christ, 1965).  The 10"2M boundary was chosen
because it corresponds to the upper limit of Fe+2 concentrations measured in
the leachates from the solid wastes.

     The boundary between two aqueous species such as the Fe+2 and Fe+3 ions
is drawn where the concentration of each ion is equal; thus the labeled
areas are those where the particular ion is dominant, even though small con-
centrations of other ions may also be present.

     The 10~6M boundaries of the metastable minerals maghemite and freshly
precipitated ferric hydroxide are drawn as broken lines.  Maghemite and
ferric hydroxide are unstable with respect to hematite, pyrite, and magne-
tite, and given sufficient time, they will convert to the thermodynamically
stable minerals.  However, maghemite and ferric hydroxide are clearly of
more than transitory existence in natural environments and warrant considera-
tion as mineral phases that probably control iron concentrations during the
initial leaching of solid wastes, which is probably the environmentally
critical period.

                                     52

-------
      The data plotted  in  figure 4 indicate that amorphous  ferric hydroxide is
 probably a control on  iron  concentrations in the leachates at pH values less
 than 7.  Indeed, computations  of ion activity products  for the leachates
 agree with the solubility constant for the amorphous  ferric hydroxide in the
 acid solutions.  The mineral  phases that were identified  through chemical
 equilibrium modeling as contributing to the control of  the ionic composition
 of the leachates were  summarized (table 19).

      Iron concentrations  tended to drop below detectable  levels in the alka-
 line solutions.  These low  concentrations were predicted  by the solubility
.modeling, and they support  the interpretations given  in the mineral stability
 diagram (fig. 4).

      The plot of the data in figure 4 shows that the  Eh-pH relations of the
 alkaline leachates are not  being controlled by equilibria between minerals
 given on the diagram.   Figure 5 shows the aqueous  stability relations of the
 manganese oxide-carbonate system.  The manganese oxides and carbonates are
                                            very likely in  equilibrium in the
                                            alkaline leachates, whereas the
                                            acid leachates  fall in the aqueous
                                            Mn+2 ion field— facts that are sup-
                                            ported by the computations of the
                                            ion activity  products for the man-
                                            ganese minerals (table 19).  These
                                            computations  showed that the alka-
                                            line solutions  were generally in
                                            equilibrium with the manganese
                                            oxides or carbonate on whichever
                                            boundary the  particular data points
                                            shown  in the  diagram fell.  The
                                            acid leachates  were undersaturated
                                            with respect  to the various manga-
                                            nese minerals (fig. 5).  Thus, it
                                            appears  that  manganese oxides are
                                            controlling the Eh-pH relations of
                                            the alkaline  leachates and the
                                            metastable, freshly precipitated
                                            ferric hydroxide is controlling the
                                            Eh-pH  relations in the acid leach-
                                            ates.
  + I.2-1
   1.0-
  +0.8-

'  +0.7-

  +0.6-

_ +0.5-

I +0.4-

§ +0.3-
  +0.2-

  +0.1-
-0.2-
  -0.4-
  -0.6-
  -0.8-
                               Hausmannite
                                 Mn,0
                        Rhodochrosite
                            MnCO.,
    • Lurgi-l B
    • Lurgi-l 6
    A Lurgi-Rosebutl
    • H-Coal
    » SRC-I
    O Fly ash
    D Bottom ash
    O High temperatui
    O Medium temperaluic char
    * High S refuse
    9 Low S refuse
              e chat
     01  23456
                      7
                     pH
                        8  9  10
                                  12 13 14
 Figures.  Stability relations of manganese oxides and carbon-
        ates in water at 25°C when total carbonate species
        isio"3M.
                                                 The solubilities of gypsum and
                                             anhydrite exerted a dominant
                                             influence over calcium and  sulfate
                                             concentrations in the leachates at
                                             all  pH levels, with the exception
                                             of the H-Coal, bottom ash,  high-
                                             temperature char, and low-sulfur
                                             refuse leachates (fig. 6).  Whereas
                                             theS6 Achates W6re all
                                             Saturated With respect tO
                                             gypsum still provided the upper
                                        53

-------
            TABLE  19.   MINERAL  PHASES  CONTRIBUTING  TO  THE  CONTROL  OF  THE  IONIC COMPOSITION OF-LEACHATES FROM COAL UTILIZATION SOLID WASTES
en
-p.
Lurgi
111. #5
Mineral
Magnesite
Dolomite
Calcite
Stronti-
anite
Rhodo-
chrosite
Anhydrite
Gypsum
Barite
Fluorite
Fluor-
apatite
Hydroxy-
apatite
Strengite
Manganese
phosphate
Magnetite
Hematite
Maghemite '
Goethite
Amorphous
Fe(OH}3
Pyrolusite
Birnessite
Nustite
Bixbyite
riausmanite
Manganite
Amorphous
Al(OH),
Diaspore
Boehmite
Amorphous
Si02
Quartz
Formula
MgC03
CaMg(C03)2
CaC03

SrC03

MnC03
CaSO,,
CaSOu-2H20
BaSO,,
CaF2

Cas(POj3F

Ca5(POi,)3OH
FePO,,-2H20

MnHPOu
Fe30,,
Fe203
-Fe203
FeOOH

Fe(OH)3
Mn02
Mn02
Mn02
Mn203
Mn30,,
MnOOH

A1(OH)3
A100H
A100H

Si02
Si02
Base

EQ
EQ

EQ

EQ
EQ
EQ
EQ


SS

SS



SS
SS
SS
SS

-SS
SS
EQ
EQ
SS
SS
SS





EQ
EQ
Acid







EQ
EQ
EQ








SS
SS
SS
SS

EQ








SS
EQ

EQ
SS
Lurgi
111. #6
Base




EQ


EQ
EQ
EQ


SS

EQ



SS
SS
SS
SS

SS
EQ


EQ
SS
EQ





EQ
EQ
Acid







EQ
EQ
EQ








SS
SS
EQ
SS

EQ







EQ
SS
SS

EQ
SS
Lurgi-
Rosebud
Base
EQ
SS
EQ

SS

EQ
EQ
EQ
EQ
EQ

SS

EQ



SS
SS
SS
SS

SS
EQ
EQ
EQ
SS
SS
SS





EQ
EQ
Acid







EQ
EQ
EQ





SS

EQ
EQ
SS
EQ
SS

EQ







EQ
SS
SS

EQ
SS
H-Coal
Base
EQ
EQ
SS

EQ




EQ
EQ

SS

SS



SS
SS
SS
SS

SS
EQ
EQ
EQ
SS
SS
SS


EQ
EQ



Acid








EQ
EQ








EQ
SS
SS
SS

EQ












EQ
SRC
Base
EQ
SS
SS

SS

EQ
EQ
EQ
EQ


SS

EQ



SS
SS
SS
SS

SS



EQ
EQ
EQ


EQ
EQ


EQ
Acid







EQ
EQ
EQ





EQ

EQ
EQ
SS
EQ
EQ

EQ











EQ
EQ
Fly
Base

EQ
SS

EQ

EQ
EQ
EQ
EQ
EQ

SS

SS



SS
SS
SS
SS

EQ
EQ

EQ
SS
EQ
EQ


SS
EQ

EQ
EQ
ash
Acid







EQ
EQ
EQ





EQ


EQ
SS
EQ
SS

EQ








EQ
EQ

EQ
SS
Bottom
ash High-temp.
(slag) char
Base
EQ
EQ
EQ

EQ

EQ


EQ


SS





SS
SS
SS
SS

SS
EQ
EQ
EQ
SS
EQ
EQ


EQ
EQ

EQ
EQ
Acid









EQ








EQ
SS
EQ
SS










EQ


EQ
SS
Base


EQ

EQ

EQ


EQ
EQ

SS




EQ

SS
SS
SS

SS



EQ
EQ
EQ


SS
EQ

EQ
EQ
Acid















EQ

EQ

SS
SS
SS

EQ









EQ

EQ
EQ
Medium-
temp.
char
Base


EQ

SS

EQ

EQ
EQ


SS




EQ
SS
SS
SS
SS

EQ
SS
EQ
EQ
SS
SS
EQ


SS
EQ

EQ
EQ
Acid







EQ
EQ
EQ





EQ


SS
SS
EQ
SS

EQ








EQ


EQ
SS
High-
sulfur
refuse
Base


EQ

EQ


EQ
EQ
EQ


SS





SS
SS
SS
SS

SS
EQ


EQ

EQ


EQ
EQ


EQ
Acid







EQ
EQ
EQ





EQ

EQ

SS
EQ
SS










EQ


EQ
SS
Low-
sulfur
refuse
Base

EQ
EQ

EQ

EQ


EQ
EQ

SS

EQ


EQ
SS
SS
SS
SS

EQ
EQ

EQ
EQ
EQ
EQ


SS
EQ

EQ
EQ
Acid









EQ
EQ




SS

EQ
EQ
SS
SS
SS













EQ
SS
           EQ = Equilibrium.

           SS = Supersaturation.

-------
                2-
              O 3
              in
              a.
                6-
• Limit I [>

• Luifii I 6

A Lurcji Rosebud

• H - Coiil

* SRC I

O Fly iish

Q Botiom ush
                     Medium ti:mp<;r;iUin! chili

                     Hi(|h S ll!lllU!

                     LnwSiofiiM!
                                              SUPERSATURATED
                                     UNDERSATURATED
                                    4     3
                                      pCa'2
Figure 6. Calcium sulfate equilibria of leachates from coal utilization solid wastes.
boundary for prediction  of calcium and sulfate concentrations.   This is sig-
nificant for the H-Coal  residue, because it contained  high  concentrations of
sulfur, but had low water-soluble sulfur levels, for all  the sulfur species
considered.  This  illustrates the need for information on mineral  forms in
the solid waste, in addition to chemical analysis of the  waste.

     The three Lurgi  ashes, the medium-temperature char,  and the SRC-I resi-
due were generally in equilibrium with gypsum, whereas the  fly ash and high-
sulfur cleaning refuse were in equilibrium with anhydrite.   The exceptions in
these samples were those at high pH, where Ca concentrations in solution were
limited by CaC03 equilibria.

     The calcium carbonate equilibria of leachates from the eleven solid
wastes in contact  with air are shown in figure 7.  Calcium  concentrations in
the acid leachates were  usually controlled by gypsum and  anhydrite equilib-
ria; they appear as a vertical line independent of carbonate activity.  Cal-
cium concentrations in highly alkaline solutions in contact with atmospheric
carbon dioxide should be controlled by calcite solubility.   The data plotted
in figure 7 indicate  that leachates with pH values between  7.0 to 7.5
were undersaturated with respect to calcite, whereas those  leachates with pH
values greater than 7.5  were generally supersaturated  with  respect to calcite.
                                      55

-------
o-

1-


2-

3-

4-


5-

6-

7-

8-


9

10

11

12


13

14


15

16

17

18

19

20
                                                 SUPERSATURATED
                         UNDERSATURATED
                      • Alkaline leachates

                      o Acidic leachates
                                         pCa+:
                                               0

                                             ISGS 19/9
Figure 7. Calcium carbonate equilibria of leachates in contact with air from coal utilization solid wastes.
     Other researchers have noted that calcite  is  more soluble when the  Mg
ion is present, which was the case in these  leachates.  Hassett and Jurinak
(1971) found  that  calcites with low levels of Mg  increased in solubility.
Similarly, Berner  (1975)  showed that incorporation of Mg within the calcite
crystal caused the resulting mangnesian-calcite to be considerably more
soluble than  pure  calcite.  Furthermore, Akin and  Lagerwerff (1965) demon-
strated that  Mg and SOi, enhanced the solubility of calcite.  It seems, there-
fore, that the mixed-salt system occurring in these leachates yields  a cal-
cium carbonate mineral with higher solubility than either pure calcite or
aragonite.  Using  the solubility product for pure  calcium carbonate minerals
to predict the calcium concentration of the  alkaline leachates could  result
in error by underestimating the true Ca concentrations.
     Figure 8  shows  the silicon dioxide and  aluminum hydroxide solubility
equilibria.  Most  samples fell within the  range  of Si solubilities  that  a
expected from  amorphous glass and quartz.
                          range
                           This
is consistent with  the
                         are
                                       56

-------
                                       SUPERSATURATED
Figure 8. Silicon dioxide and aluminum hydroxide solubility equilibria of le.ichates from coal utilization solid wastes.
experimental design, which  employed glass carboys as the equilibration vessel,
and in which quartz was  identified in all the solid wastes.  Clearly, amorphous
SiOa is not the most stable phase, and silica concentrations,  after long
periods of time, would probably be controlled by alumino-silicate minerals or
quartz.

     The Al equilibria,  similar to the Fe and Si equilibria, were dominated
in the mid-acid and alkaline pH range by the amorphous hydroxide; a meta-
stable mineral phase was apparently controlling the solubility.   These
metastable mineral phases must be considered when estimating possible environ-
mental impact during the initial  leaching of coal conversion solid wastes.

     The aqueous chemistry  of other potential contaminants  were  examined
(table 19); and it was found, for example, through computation of ion activity
products for BaSO.,, that Ba concentrations in the leachates would never exceed
0.1 ppm, even in very  acid  solutions.  Fluoride concentrations in the

                                       57

-------
leachates seemed to be controlled by precipitation of fluorite (CaF2) and
fluorapatite (Ca5(PO.»)3F).  Phosphate levels in the alkaline leachates would
never exceed 1  ppb; this was indicated by the ion activity product calcula-
tions for fluorapatite and hydroxyapatite (Ga5(POtt)3OH).   In the acid leach-
ates, the precipitation of iron and manganese phosphates  apparently controls
the phosphate levels.

     The results of this study have several implications  concerning heavy
metals.  The data suggest that removal of trace metals such as Cd, Co, Cr,
Cu, Ni, Pb, and Zn from slurry pond leachates may be controlled by adsorption
on or coprecipitation with iron, manganese, and aluminum oxides and hydroxides.
Trace metals would continue to be removed this way for long periods of time
because the adsorptive capacity of the solid phase would  be continually
replenished by formation of new metal oxides in the leachates.  In any case,
partitioning between trace metals and solid phases must be considered when
evaluating trace metal mobility in these systems, and furthermore, sulfate,
hydroxide, and carbonate are the major inorganic ligands  that must be con-
sidered.

     Thus, application of thermochemical solubility models to the coal solid
waste leachates examined in this study has yielded some valuable insights
into the potential these wastes have for pollution.  Application of these
models has shown that, whereas the concentrations of chemical constituents
in the solid wastes and leachates varied over a wide range, similar mineral
phases controlled the aqueous solubility of many major, minor, and trace
ionic species for all of the solid wastes.
                                     58

-------
                                  SECTION 8

                  SOIL ATTENUATION OF CHEMICAL CONSTITUENTS
                     IN LEACHATES FROM COAL SOLID WASTES
INTRODUCTION

     When evaluating the potential  coal  solid wastes have for pollution, it is
important to consider where the soluble  constituents of the wastes go during
land disposal. Of primary  importance is the  characterization of the waste and
waste leachate and the soil or receiving medium;  these characterizations  can
be conducted by a number of laboratory  techniques and are not difficult to
determine.  What is more difficult to determine,  however, is the interaction
that takes place when the wastes or waste leachates and soils are brought
together, as in a simulated landfill condition.   The problems in duplicating
field conditions in the laboratory, as  is well known, stem from the nonsteady
state of physical parameters.   To determine the  long-term effects of disposal,
it is also desirable to understand the  physical,  chemical, and biological
mechanisms of constituent removal.

     This investigation includes an experimental  method designed to determine
soil-waste interactions, plus  a discussion of environmental problems that
could possibly result from the disposal  of coal  solid wastes.  Also included
is a technique for the prediction of constituent  migration distance.  A
detailed discussion of the mechanisms that remove hazardous elements from soil
applied wastes has been omitted since it can be  found elsewhere: in Fuller
(1977), Phillips and Nathwani  (1976), and Braunstein, Copenhaver, and Pfuderer
(1977).  We have included, however, a discussion  of these removal  mechanisms
as they apply to the wastes analyzed in  this investigation.


DISPERSED SOIL METHODOLOGY

     Soils are ideal media for waste disposal because their attenuating
behavior can render many of the hazardous properties harmless; then the wastes
can be eventually incorporated into the soil system  (Phillips and Nathwani,
1976).  Before disposal, however, it is desirable to have some idea of the
results of the soil-waste  interaction,  which will vary with wastes and soil
types.

     In the past, column leaching studies have determined the results of soil-
waste interaction.  There  are two principal difficulties with column leaching
studies: the long period   of time required, and the difficulty in simulating
                                      59

-------
field flow patterns.  For example,  it may  require  up to a year to obtain the
necessary data for soils with high  clay  contents,  and even sandy soils may
require several months.

     Farquhar and Rovers (1976) and Rovers,  Mooij, and Farquhar (1976) de-
signed a dispersed soil  (batch reactor)  methodology as an alternative tech-
nique.  They conducted  simultaneous experiments  using dulpicate soils and
wastes to examine dispersed  soil  and column  leaching techniques.  For the
latter, they used both  undisturbed  and  remolded  soil samples.   Their success
in comparing the use  of these two types  of soil  samples enabled them to
develop the dispersed soil  technique, which  represents a remolded soil.  Their
subsequent experimentation  illustrated  this, but not without the following
reservations and assumptions:  (1) the effects of lateral dispersion cannot be
measured;  (2)  intergranular flow  must  be assumed;  (3) no microbial activity  is
assumed because of  the short duration  of the dispersal soil motluM;  (-\]  thf
remolded  soil  column  must  be leached in conjunction with  the batch reactors  to
determine  the  degree  of attenuation caused by dilution by soil water; and
(5)  it is  difficult to accurately predict the attenuation of contaminants that
undergo retarded removal.

     The first two  factors  are  also true for column studies.  The inability  to
measure the effects of microbial  activity as an  attenuation factor is a  trade
off  for the short period of time  needed for the  dispersed soil experimentation.
The  last two factors  listed above,  however,  are  the most critical.  The  need
for  leaching a remolded soil  column simultaneous to the batch reactors would
result in  lengthening the  experimentation time.   An increase in the waste
solution to soil ratio in  the  batch reactors, however, would reduce the  impor-
tance of dilution by  soil  water as  an attenuation  mechanism.  Most waste
leachates  are  highly  complex systems and certain elemental components will be
selectively removed prior  to other  elements.  It is difficult to predict with
any  certainty  the degree of attenua-
tion of constituents  that  undergo
retarded removal, with a technique
that would not take an unreasonable
amount of  time.
EXPERIMENTAL  DESIGN

     A modified  version  of the  dis-
persed soil technique  developed by
Farquhar and  Rovers  (1976) was  used
to determine  the  behavior  of con-
stituents  in  the  aqueous super-
natant solutions  from  the  coal
solid wastes.

     Three sets  of five  1-liter
linear polyethylene  bottles  were
used as reaction  vessels (fig.  9);
each set was  used to study one  soil.
After the  soils  had  been brought to
Addition of waste effluent followed
  by slugs of desorption water
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          Aliquots for chemical analysis
Figure 9. Schematic diagram of dispersed soil methodology.
                                       60

-------
field capacity (moisture content), 700 ml or an equivalent volume of filtered
(0.45 ym Millipore) supernatant from the waste slurries were added.  Then the
vessels were shaken using an EquipoiseR Heavy-Duty Shaker at a rate of 265
oscillations per minute.  The shaking lasted for 1% hours, which was suffi-
cient time to develop equilibrium conditions (Rovers, Mooij, and Farquhar,
1976).  The samples were then filtered through Whatman #45 filters, and 60 ml
of the filtrate was filtered again through MilliporeR .45 micron pore size
membrane filters.  The 60 ml portion was withdrawn for chemical analysis, and
the remaining solution was transferred to the next reaction vessel in the
series.  A 60 ml sample was collected from each of the post-contact solutions.
This procedure was repeated to determine the constituents that could be de-
sorbed from the soils after mixing with the leachates.  This was accomplished
by passing distilled water through the reaction series.

     Three Illinois soils—Ava silty clay loam (sicl), Bloomfield loamy sand
(Is), and Catlin silt loam (si 1)—with a broad range of physical and chemical
characteristics, were collected and characterized (table 20).  Twelve waste
leachates were studied, including 10 of the 11 aerated natural (unadjusted)
pH supernatant solutions.  The Lurgi gasification waste using the Illinois
No. 5 Coal did not possess sufficient sample volume for analysis.  Also, both
of the acid-aerated liquefaction leachates, H-CoaU and SRCu, were studied to
assess the fate of their relatively high trace metal concentrations.

     The filtrates collected from this study were analyzed for 10 constitu-
ents: Al, B, Ca, Fe, K, Mg, Mn, Na, SO.,, and Zn.  These constituents were
chosen because they were the constituents present in the leachates in suffi-
cient concentrations to be potential pollution hazards after being leached
through  soil.  The filtrates collected from the two acid coal-liquefaction
leachates were also analyzed for: Be, Cd, Co, Cr, Cu, F, Ni, and Pb.


ATTENUATION RESULTS

      It  is difficult to make broad generalizations about varied, complex
systems  such as the waste leachate-soil mixtures.  One could say, however,
that the attenuation of constituents in each leachate was similar for each
soil type, although the degree of removal or elution of individual
 TABLE 20.  SOIL CHARACTERISTICS



Soil
Catlin
silt loam
Ava
silty clay loam
Bloomfield
loamy sand
Surface Organic
CEC area, Np carbon
pH (meq/100 g) (m2/g) (%)
7.1 18.1 . 10.1 4.73

4.5 13.1 28.3 1.18

5.7 0.8 1.7 0.21


Sand
m
11.6

2

82


Silt . Clay
(%> (%)
60.9 27.2

69.6 28.4

10 8

                                      61

-------
                                          TABLE 21.
SUMMARY 01" SOIL-ATTENUATION BEHAVIOR
OF CHEMICAL CONSTITUENTS IN LEACHATES
FROM SEVERAL" COAL SOLID WASTES
                                          Elements

                                          Al, B, Ca,

                                          Total Fe,

                                          Na*. SOi,, 7n



                                          Additional  trace metals

                                          K*

                                          Mg

                                          Mn
           Attenuated
           Variable

           Eluted

           pH-dependent variability
                                          *Eluted or steady at low concentrations  (<10 ppm).
constituents  varied with  soil  type
(table 21).   Most of the  constitu-
ents were  attenuated through  the
reactor  series; however,  because
of selective  removal, some  of the
constituents  for certain  wastes
were first eluted from the  soils
before undergoing attenuation.

     To  illustrate the rate of
attenuation or elution, figures 10
through  16 were drawn to  represent
typical  examples of constituent
behavior.   The figures depict the
constituent concentration vs.  the
soil leachate ratio, which  is the
grams of soil necessary to  remove
or elute the  indicated concentration of a  constituent from  one  milliliter of
leachate.   Also included  is the original supernatant concentration and a
recommended water quality standard (U.S. EPA,  1972) for comparison.   A figure
depicting  the additional  trace elements (Be,  Cd, Co, Cr, F,  Ni, and  Pb) that
were determined for the two acid-aerated liquefaction wastes  could not be
drawn because these elements  were removed  to  less than detectable concentra-
tions in the  first reaction vessel.

     Iron  and zinc were the two metals that were most often  present  in the
highest  concentrations in the waste leachates.   Figure 10 is  a  plot  of the
zinc concentration through  the leachate-soil  mixtures for the natural pH
leachate (pH  4.12) from the fly ash with an original zinc concentration of
20 ppm.   Figure 11 is a similar diagram for total iron for  the  most  acidic
SRC liquefaction residue  leachate (pH 3.5); in  this case, the original total
iron concentration in the leachate was 2962 ppm.
                         Supernatant concentration
                                                  Fly ash3
                                 Secondary drinking water standard

                                     Bloomfield Is
                                     ^"~~ -^        Ava sicl
                                  Soil leachate ratio, gm/mL


Figure 10. Zinc concentrations vs. soil/leachate ratio for fly ash3 (pH 4.12).
                                        62

-------
     Catlin soil proved to  be  the most efficient of the three soils tested  in
removing metals from solution.   This  is probably due to its higher cation-
exchange capacity and  its higher pH  (7.1).   The higher exchange capacity .of
the Catlin soil and its higher buffering ability enables it to neutralize
acidic leachates better than  the other two  soils, and in many cases,
precipitation of metal hydroxides will result.  Probably adsorption as well
as precipitation are significant for  the removal of metals in cases where  the
metal concentrations are  as high as  those described above.  Thus, the high
clay and organic content  of the Catlin soil would make it a better medium  for
adsorption than the other two soils.   Figures 10 and 11 illustrate the "worst"
cases for two metals that are found  throughout the supernatant solutions.   In
the other leachate solutions,  these  metals were either present in concentra-
tions too low for detection,  or they were attenuated during mixing in the
first reaction  vessel  to  concentrations too low for detection.  None of  the
metals mentioned above displayed any degree of elution from the soils.

     Because of their  selective removal, the behavior of the other constit-
uents measured  in the  attenuation  analysis was not as consistent or as easily
interpreted as  that of the  metals  discussed above.  From this investigation,
Mg and Mn emerge as having  the most  potential for pollution from land
disposal of the coal solid  wastes.   Both Mg and Mn undergo varipus degrees
of elution (negative attenuation),  depending upon the particular waste
leachate-soil mixture.

     Figures 12 and 13 are  plots of the elution of Mn through the reactor
series for two  of the  liquefaction  residue leachates.  Overall, the greatest
elution of Mn occurred in the liquefaction residue leachate-soil mixtures.
In a typical example (fig.  12), an  initial  flush of Mn from the soil is
followed by adsorption or reverse  exchange out of solution.  The trend  is
generally that  the more  acid the leachate-soil mixture, the higher the
               3000 H
             I
             2 2000-
               1000-
                       Supernatant concentration
                                                   SRC.,
(Secondary drinking water standard, 0.3 ppm)
                                                  •_ Bl,
                                  Catlin sil
                          I
                                   Soil leachate ratio, (|ni/ml_


Figure 11. Total Fe concentration vs. soil/leachate ratio for SRC4 (pH 3.5).
                                       63

-------
                                                     (Secondary drinking water standard, 0.05 ppm)
                                                            2             3
                                                  Soil  leachate ratio, gm/mL
Figure 12. Manganese concentration vs. soil/leachate ratio for SRC (pH 4.69).
                               Ill
                               12-
                               10-
E
a
a
c*
O p _
to .
c
03
1 >
at
O>
c
(O
01
5 4-
s


2-



n-
s
•r
/
/
/
/
/
K
/
/
f (Secondary drinking water standard.
/
1
/
j
I
1
;^
II *-—•»-. ^
// "~"^ 	 -^-I'El 	
//'
i/'.*..
•' ''-^ 	 • 	 Catlin sil
*^-- Supernatant concentration






0.05 ppm)









• ^


	 •
                                                    234567
                                                    Soil leachate ratio, gm/mL                15051979
Figure 13.  Manganese concentration «s. soil/leachate ratio for H-Coal (pH 3.10).
                                                             64

-------
concentration of Mn initially eluted.  A mixture  of  the  acid  H-Coal  leachate
with the Bloomfield soil, however, resulted  in  a  greater elution  of  Mn than
when the leachate contacted the other two  soils (fig.  13).  A similar
example is the acid SRC.,, where the  initial  leachate Mn  concentration is
5.4 ppm and the final Bloomfield elution was 108.2 ppm Mn.  The recommended
water quality level for Mn is 0.05 ppm  (U.S.  EPA), 1972).   The other mixtures
exhibit a pattern similar to that of figure  12, but  the  initial eluted Mn
concentrations are in the range of 0.5  to  4.0 ppm.

     An elution of Mg is observed for all  the leachate-soil mixtures with the
exception of the Bloomfield mixture  (fig.  14).   In several  cases, the increase
in Mg concentration is as high as 300 ppm.   These flushes of  Mg are  thought to
be caused by cation-exchange reaction in the soil.   The  flushes of minerals
have been found to cause increases in the  hardness of groundwaters around
waste disposal sites  similar to those envisioned for the disposal of coal con-
version wastes (Griffin and Shimp, 1978).

     The fate of boron in the coal wastes  is of interest because it  was found
to exceed the recommended water quality  levels  for irrigation water  in all of
the waste leachates,  except for the  water-quenched slag.  Boron's concentra-
tion ranges from 5 ppm to as high as 65  ppm  (Lurgi Ash,  Rosebud Seam Coal) in
the leachates.  Catlin soil, followed by Ava and Bloomfield respectively, was
the most efficient at removing boron (fig.  15).  Other researchers have shown
that boron is readily adsorbed by illite  (Harder, 1961;  and Couch and Grim,
1968), and that adsorption increases with  increasing pH  (Sims and Bingham,
1967).  Both of these factors favor  higher retention of  boron by Catlin soil
than the Ava and Bloomfield soils.
                                    2        3
                                  Soil leachate ratio, gm/mL
Figure 14. Mg concentration vs. soil/leachate ratio tor SRC IpH 3.5).
                                      65

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     In almost all of the  natural  pH supernatant solutions, calcium  and  sul-
fate are the dominant cation  and  anion in solution.  Over the pH  range  stud-
ied, S04~2 is the dominant sulfur species in solution (Garrels and Christ,
1965; Stumm and Morgan,  1970).   Because of the high concentrations of both
calcium and sulfate and  the rate  at which they are removed from solution,  the
precipitation of gypsum  (CaSO^-ZHzO) and/or anhydrite (CaSOO would  seem to be
an important attenuation mechanism.  Figure 16 plots the typical  case for  sul-.
fate attenuation with the  trend of Ava > Catlin > Bloomfield.  Adsorption  of
sulfate could also be occurring with the acid leachate-Ava mixture,  although,
because of the amount of sulfate  being removed (Bolt and Bruggenwert, 1976),
it is unlikely that this is the only mechanism.

     Figures 17 and 18 are combined plots of calcium and sulfate  behavior
through the reactor series.  The figures have been normalized by  using  C/Co
(the constituent concentration in each reaction vessel/the original  leachate
concentration) for the vertical axis.  The first plot indicates there is a
definite relationship between the removal of calcium and sulfate, which sup-
ports an interpretation  that  precipitation of gypsum is the dominant attenua-
tion mechanism.  The second graph, however, gives the more normal case  where
both constituents are removed similarly in the Ava mixtures, but  calcium is at
least initially eluted,  whereas sulfate is attenuated for the Catlin and
Bloomfield mixtures.  These samples indicate that in some situations, adsorp-
tion of sulfate by soil  appears to be the dominant attenuation mechanism.   It
is difficult to account  for precipitation of CaSOij for the last two  leachate-
soil mixtures because it was  impossible to account for the available Ca  from
the soils themselves.
               30-
                                               LURGI Rosebud,
                       -Supernatant concentration
                                                  Ava sicl
                        Irrigation water, recommended standard (0.75 ppm)
                                —(	,	 - r • -

                                 234
                                 Soil leachate ratio, gm/mL
Figure 15. Boron concentration vs. soil/leachate ratio for Lurgi-Rosebud (pH 8.4).
                                       66

-------
                                       •  Supernatant concentration
                                                                                     Fly ash.
                                         Secondary drinking water standard
                                                         ~\	1	1	r
                                                         2345
                                                           Soil leachate ratio, gm/mL
Figure 16.  Sulfate concentration vs. soil/leachate ratio for fly ash (pH 4.12).
                        I.O-
                        0.5-
                                                                   	  	S(V_8loomfie/d / Ca-Bloomfield
                                                                                                S04-Catlin

                                                                                               Ca-Catlin
                                                                   2                   3
                                                             Soil leachate ratio, gm/mL
    4

ISGS 1979
Figure 17. Ratio of concentration of Ca or SO4 in leachate after reaction with soil to the initial concentration vs. soil/leachate ratio.
                                                             67

-------
        1.5-1
        1.0-
       o
       u
        0.5
                                                      SOj-Catlin

                                                      S
-------
and the soil bulk density.   From this data,  the migration distance per unit
time can be computed.

     If it is assumed that: soil bulk density = 1.50 gm/cm3,  leachate volume
6 in./yr (15.24 ml/cm2 yr), and landfill  life = 30 years, then the migration
distance is computed to be:

    (0.75 gm/mL(15.24 ml/cm2 yr)(30 years)
    	—	 = 228 cm or 7.5 ft in 30 years
                  1.50 gm/cm3

     This calculation does not account for dilution by soil  water or waters
of infiltration, and interactions occurring in the soil  profile prior to the
subsequent waste additions reaching the leachate front.
                                     69

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                                  SECTION 9

                BIOASSAYS OF LEACHATES FROM COAL SOLID WASTES
INTRODUCTION
     The environmental data acquisition for a complete environmental  assess-
ment of coal-based energy technology includes physical, chemical, and bio-
logical analyses (Hangebrauck, 1978).  The preceding sections have comprised
the physical and chemical analyses of this investigation; this section com-
prises the biological analysis investigation of the potential pollution
hazard of coal solid wastes.

     If coal conversion processes are developed on a commercial  scale, they
will generate an enormous amount of solid waste (Braunstein, Copenhaver, and
Pfuderer, 1977).  The solid wastes from coal conversion plants will probably
be deposited in landfills and ponds (Talty, 1978).  Landfills are subject to
leaching; ponds could be contaminated and thus serve as potential sources of
pollution to other water resources such as groundwater and nearby streams.
Since the impact of coal solid wastes on aquatic biota has not been adequately
assessed, toxicity tests of the leachates generated from these wastes were
conducted with fathead minnow fry (Pimephales promelas].

     The purposes of toxicity tests were to determine: (1) if the leachates
from three Lurgi gasification ashes, an H-Coal liquefaction residue,  an SRC
liquefaction residue, two chars, a fly ash, a water-quenched slag, and two
gob samples were acutely toxic to young fathead minnows;  (2) how much dilution
was necessary to eliminate mortality caused by toxic leachates on a short-term
basis; (3) if the acute toxicity of leachates equilibrated under anaerobic
conditions differed significantly from similar leachates equilibrated under
aerobic conditions; and (4) which water-soluble constituents leached  from
these coal solid wastes were responsible for the toxicity.


MATERIALS AND METHODS USED FOR BIOASSAYS

     Ninety-six hour static bioassays of the leachates were conducted with
1- to 6-day-old fathead minnow fry, Pimephales pvomelas.   The fish were propa-
gated in the laboratory and in outdoor ponds at the Illinois Natural  History
Survey in Urbana, Illinois.  The leachates were obtained from the same vessels
used in the solubility and attenuation studies; they were filtered through a
0.45 ym pore size membrane filter  prior to the bioassays.

     The toxicity tests were divided into two phases: the screening procedure
and the LC-50 determination.  During the screening procedure, the young

                                     70

-------
fathead minnows were exposed to the "full-strength" leachates.   During the
LC-50 determinations, the minnows were exposed to "full-strength" leachates
diluted with soft reconstituted water that was prepared according to sugges-
tions in "Methods for Acute Toxicity Tests with Fish, Macro-invertebrates and
Amphibians" (Committee on Methods for Toxicity Tests with Aquatic Organisms,
1975).  The screening procedure enabled us to determine LC-50 values more
efficiently, since LC-50 determinations were not needed for leachates that
did not cause 50 percent mortality in the screening procedure.   Procedures
outlined in Litchfield and Wilcoxon (1949) were used for the LC-50 deter-
minations.

    •Ten young fathead minnows were placed into glass fingerbowls (115 x
45 mm) containing 200 mL of "full-strength" or diluted leachate.  Each bio-
assay was replicated.  Fish mortality data were collected at 24, 48, 72, and
96 hours after the bioassays were begun.  The test organisms were not fed and
the solutions were not aerated during the bioassays.  Since one-half of the
leachates were equilibrated under anaerobic conditions, all solutions were
aerated before the fish were added.  The bioassays were conducted at a con-
stant temperature (21 ± 1°C) and with a constant photo-period (16L-8D) in an
environmental chamber.  At the beginning and end of all bioassays, pH and
dissolved oxygen were measured with a Beckman pH meter and a YSI dissolved
oxygen meter.  Specific conductance was measured at the beginning of each
bioassay with a YSI portable conductivity meter.


RESULTS OF BIOASSAY STUDY

     The screening procedures were conducted to determine if the "full-
strength" leachates were acutely toxic.  To test the effect of pH on the
mortality of fathead minnows, bioassays were conducted utilizing buffered re-
constituted water ranging in pH from 4.9 to 11.0.  The results of the pH
experiment were similar to those of the screening procedures (figs.  19 to 23).
Many of the leachates and the reconstituted water were not acutely toxic to
young fathead minnows if the pH of the  solutions was between 6.2 and 9.0.
Low mortality  (5 to  20 percent) occurred, however, in 37.5 percent of the
neutral leachates, and mortality was greater than 20 percent in a Lurgi Ash
(111-5-6, pH = 7.1), H-Coal (HC-5, pH = 8.8), solvent-refined coal  (SRC-6,
pH =  7.3), and a low-sulfur gob  (LSR-2, pH = 6.9).  Total mortality occurred
in those  solutions with pH values less  than 6.0, and mortality was 50 percent
or higher in solutions with pH values greater than 10.0.

      The mortalities that occurred during the screening procedures of the
natural pH leachates are listed  in table 22.  The natural pH leachates from
the Lurgi gasification process were not acutely toxic.  The aerobic natural
pH leachate generated from H-Coal liquefaction residue was relatively non-
toxic on  a short-term basis; however, HC-5, the natural pH leachate equili-
brated under anaerobic conditions, was  relatively alkaline (pH = 8.8), and
35 percent mortality occurred.  Total mortality occurred in the aerobic
natural pH leachate  from SRC dry mineral residue; this leachate was acidic
(pH = 5.6).  The natural pH leachate of SRC equilibrated under anaerobic con-
ditions (SRC-6) was  a neutral solution  (pH = 7.1); however, 40 percent
mortality occurred during the screening procedure.  The natural pH leachates


                                      71

-------
            100
             80-
         >•   60
         e
         o
             40
              20-,
                                •ana  o
• Illinois 5 -Air
O Illinois 5-Argon
• Illinois 6 - Air
D Illinois 6  Argon
 A RtWfltM.'.  A,'
 A Rosebud—Argon
 X Reconstituted water
                2.0
                        —i—
                          3.0
              4.0
                                                                                   11.0
Figure 19. Percentages of mortality of 1- to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
          to 24 leachates of different pHs generated from three Lurgi gasification ashes and 7 buffered solutions of reconstituted
          water.
             100
           o
              80-
               60-
               40-
               20
      §• m
 • H-Coal-Air
 O H-Coal-Argon
 • SRC-Air
 O SRC-Argon
 X Reconstituted water
                 2.0
                          3.0
                                    4.0
                                              5.0
                                                                                      9.0
                                                                                                10.0
                                                                                                          11.0
                                                              pH
Figure 20. Percentages of mortality of 1- to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
           to 16 leachates of different pHs generated  from SRC and H-Coal liquefaction residue and 7 buffered solutions of recon-
           stituted water.
                                                            72

-------
              100
               80-
               60-
            o
                40
                20
                    -B-
                                       -e—e*.
                  2.0
• Bottom slag-Air
O Bottom slag-Argon
• Fly ash-Air
D Fly ash-Argon
X Reconstituted water
                           3.0
                                     4.0
                                              5.0
                                                                                               10.0
                                                                                                         I 1.0
Figure 21. Percentages of mortality of 1-to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
          to 16 leachates of different pHs generated from a water-quenched slag and a fly ash and 7 buffered solutions of reconsti-
          tuted water.
               IOO
               80-
            >  60'
            o
               40-
                20-
                       -BH
                  2.0
•  HTC-Air
O  HTC-Argon
•  LTC-Air
D  LTC-Argon
X  Reconstituted water
                           3.0
                                     4.0
                                                                                     9.0
                                                                       10.0
                                                                                 II.O
 Figure 22. Percentages of mortality of 1-to 6-dayold fathead minnow fry {Pimephales promelas) resulting from 96-hour exposures
           to 16 leachates of different  pHs generated from high- and low-temperature chars and 7 buffered solutions of reconsti-
           tuted water.
                                                           73

-------
TABLE 22.  PERCENTAGES OF MORTALITY OF 1-TO-6-DAY-OLD FATHF.AD MINNOW FRY (i'lUKrHALZC ':~EC;-ZLAz)
         RESULTING FROM 96-110UU EXPOSURES TO THE NATURAL pH LF.ACHATFS OF .1.1 COAT. SOLID WASTES
Sample
BS-1
BS-5
ILL-5-1
ILL-5-5
ILL-6-1
ILL-6-5
HC-1
HC-5
SRC-2
SRC-6
KS-3
KS-7
FA-3
FA- 7
HSR-2
HSR- 6
LSR-1
LSR-5
HTC-1
HTC-5
LTC-2
LTC-6

Type
Gasification ash
Gasification ash
Gasification ash
Gasification ash
Gasification ash
Gasification asli
Liquefaction residue
Liquefaction residue
Liquefaction residue
Liquefaction residue
Water-quenched sing
Water-quenched slag
Fly ash
Fly ash
High-sulfur gob
High-sulfur gob
Low-sulfur gob
Low-sulfur gob
High-temperature char
High-temperature char
Low-temperature char
Low-temperature char

Atmosphere
Aerobic
Anaerobic
Aerobic
Anerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic

P
7.
8.
7.
7.
7.
7.
8.
8.
5.
7.
3.
5.
4.
4.
7.
8.
8.
8.
7.
7.
6.
8.

H
8
0
1
3
1
5
3
8
6
3
7
8
0
3
7
0
8
9
2
6
8
1

Mortality
0
0
0
0
0
0
15
100
100
40
100
100
100
100
5
0
15
15
0
0
5
0

from the water-quenched  slag and the fly ash from a coal-fired  power plant
were acidic  (pH  <5.8), and total mortality occurred in all  four leachates.
Low mortality  (<5  percent) occurred in the natural pH leachates generated
from the high-sulfur gob.   Both natural pH leachates generated  from the low-
sulfur gob were  relatively alkaline (pH values of 8.8 and 8.9), and low
mortality  (15 percent)  occurred in these solutions.  Low mortality (<5 per-
cent) occurred in  natural  pH leachates generated from the high- and low-
temperature  chars.

     Attempts were made  to decrease the mortality rate caused  by low pH by
neutralizing some  of the acidic leachate solutions with  sodium  hydroxide.
Total mortality  occurred in all neutralized solutions.   Since  all  the neu-
tralized solutions had specific conductance values greater  than 7.00 mmhos/cm,
it was postulated  that the exposures to relatively large total  ion concentra-
tions resulted in  "ionic shock." To test this hypothesis, several  solutions of
reconstituted water  of differing specific conductances were prepared using
NaCl; the results  of 96-hour static bioassays of these solutions are shown in
figure 24.   Total  mortality occurred in solutions with a specific  conductance
                                      74

-------
                100-
                80-
                60-
             o
                40.
                20-
•  HSR-Air
O  HSR-Argon
•  LSR-Air
D  LSR-Argon
X  Reconstituted water
                  2.0
                            3.0
                                      4.0
                                                                                      9.0
                                                                                                10.0
                                                                                                         11.0
Figure 23. Percentages of mortality of 1- to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
          to 16  leachates  of different pHs  generated from a high-sulfur gob sample and a low-sulfur gob sample and 7  buffered
          solutions of reconstituted water.
                                                    345
                                                Specific conductance (mmhos/cm)
 Figure 24. Percentages of mortality of 1 - to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
           to 7 buffered solutions of reconstituted water of different specific conductances adjusted with NaCI.
                                                           75

-------
greater  than 6.10 mrnhos/cm.   The high  total  ion concentrations were  probably
responsible for the total  mortality that occurred  in  the neutralized acidic
leachates.

     The LC-50 values were determined  to investigate  the relative  toxicities
of the leachates and how much dilution was necessary  to ensure their survival
during 96-hour static bioassays.  The LC-50 values, their 95 percent  confidence
intervals,  and the dilutions necessary to ensure survival  of the minnows are
listed in tables 23 to  27.  The pH values listed are  those of the  "full-strength"
leachates after aeration and prior to  dilution with reconstituted  water.  The
 TABLE 23.  THE LC-50 VALUES, THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
          NECESSARY TO ELIMINATF, MORTALITY FOR THREE LURCT GASIFICATION ASH LEACHATES OBTAINED
          IN 96-HOUR STATIC BIOASSAYS USING 1-TO-6-DAY-OLD FATHEAD MINNOW FRY C/'./'«£.'V//1WS
          PROI-1ELAS).
"" - .- ' ._.--.-__!_ . . _™_ -r- ._.___.___._, • . i. -!-._-. 	 . 	 , 	 -i _. -r -M. ._.-.— r i 	 "• 	 ' 	 l •
Sample
1*
2
3
4
5*
6
7
8
1*
2
3
4
5*
6
7
8
1*
2
3
4
5*
6
7
8
Atmosphere
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
pH
Rosebud
7.8
7.6
5.4
3.3
8.0
7.6
4.7
3.7
Illinois No.
7.1
7.0
6.1
3.0
7.3
7.1
6.0
4.4
Illinois No.
7.1
4.1
3.9
2.6
7.5
7.1
. 4.9
3.8
LC-50
(ml./ 100 mL)
>.100
>100
18.00 < 2.70
0.50 ' 0.13
>.100
>100
2. .10 :' 0.76
0.78 -.1. 0.16
5
>100
>100
11.00 ± 3.85
1.80 :' 0.61
>100
>100
40.00 ± 16.40
1.00 + 0.09
6
>100
8.60 ± 2.92
5.20 ± 0.99
6.40 i 0.90
>100
>100
10.00 ± 2.60
0.38 i- 0.01
Dilution for
0% mortality
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
:1
:1
:100
:769
:1
:1
:200
:250
:1
:1
:50
:166
:1
:1
:50
:200
:1
:43
:38
:1000
:1
:1
:26
:1000
  *Natural 'pH solutions
                                        76

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LC-50 value is the  statistically determined concentration of leachate at
which 50 percent mortality occurs.  There is an  inverse relationship between
toxicity and  the LC-50 value; for example, the LC-50 values for Rosebud-3
(BS3) and BSi, are 18.00 and 0.50, respectively (table 23).  Eighteen milli-
liters of 883 diluted  with 82 mL of reconstituted  water was as toxic as
0.50 mL of BSi, diluted with 99.5 mL of reconstituted water.  Leachates exhib-
iting greater toxicity, therefore, have lower LC-50 values than less toxic
leachates.  If,  in  the "full-strength" leachates,  less than 50 percent mor-
tality occurred, the LC-50 is reported as greater  than 100 mL/100 mL.

     Generally,  all  leachates were acutely toxic when acidic (pH <6.2).  With
increasing acidity,  toxicity also increased and  the LC-50 value decreased.
The LC-50 values of leachates equilibrated under aerobic atmospheres were not
significantly different from LC-50 values of similar leachates equilibrated
under anaerobic  atmospheres (p >.05, paired t-test).

     Natural  pH  leachates generated from Lurgi gasification ashes were not
acutely toxic; therefore, their LC-50 values were  greater than 100 mL/100 mL,
and no dilution  was  necessary to achieve 0 percent mortality (table 23).
 TABLE 24. LC-50 VALUES,  THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
         NECESSARY TO ELIMINATE MORTALITY FOR H-COAL AND SRC LIQUEFACTION LEACHATES OBTAINED
         IN 96-HOUR STATIC BIOASSAYS USING 1-TO-6-DAY-OLD FATHEAD MINNOW FRY (PIMEPHALES
         PROMELAS).
Sample
1*
2
3
4
5*
6
7
8

1
2*
3
4
5
6*
7
8
Atmosphere
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic

Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
pH
H-Coal
8.3
7.7
5.9
3.3
8.8
7.6
7.6
3.1
SRC-I
7.7
5.6
3.6
3.1
6.6
7.3
5.5
3.7
LC-50
(mL/100 mL)
>100
>100
39.00 ± 4.80
29.50 •': 8.85
>100
>100
>100
7.90 i 1.66

>100
21.00 :'. 3.36
16.00 i 2.72
0.36 ± 0.10
74.00 ± 6.22
>100
25.00 ± 2.75
0.26 ± 0.07
Dilution for
0% mortality
1:1
1:1
1:5
1:21
1:6
1:1
1:1
1:46

1:1
1:10
1:10
1:1000
1:2
1:1
1:7
1:2000
  *Natural pH solutions
                                       77

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TABLE 25.  LC-50 VALUES, THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
         NECESSARY TO ELIMINATE MORTALITY FOR LEACHATES GENERATED FROM BOTTOM SLAG AND FLY ASH
         OBTAINED IN 96-HOUR STATIC HIOASSAYS USING l-TO-f)-!)AY-O!.n KATIIKAD MINNOW FRY
        ' (PIMEPHALES PROMELAS).
Sample

1
2
3*
4
5
6
7*
8

1
2
3*
4
5
6
7*
8
Atmosphere

Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic.
Anaerobic
Anaerobic

Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
PH
Slag
8.0
7.6
3.7
3.3
7.7
7.1
.. 5.8
3.8
Fly ash
8.7
8.0
4.0
2.7
9.6
7.9
4.3
2.4
LC-50
(mL/100 ml.)

>100
>100
22.50 ± 4.28
8.00 ± 1.68
MOO
MOO
37.00 i 3.89
3.90 ! 0.55

>100
>100
9.00 ' 2.70
0.64 •' 0.08
80.00 :' 7.20
MOO
3.15 :>: 0.72
0.68 :' 0.12
Dilution for
0% mortality-

1
1
1
1
1
1
L
1

1
1
1
1
1
1
1
1

:1
:l
:28
:20
:1
:1
:5
:100
,
:l
:1
:100
:2000
:3
:1
:1000
:333
 *Natural pH solutions
     The aerobic  natural  pH leachate generated  from H-Coal  liquefaction resi-
due was not acutely toxic and therefore required  no dilution for 0 percent
mortality.  During  the screening procedure, total  mortality occurred in the
anaerobic natural  pH H-Coal leachate (table 22).  During the LC-50  determina-
tion, however,  40 percent mortality occurred  in the full-strength leachate,
and 30 percent  mortality occurred in a solution of 180 ml of HC-5 and 20 ml
of reconstituted  water.  The  LC-50 determination was made 9 months  after the
screening procedure was  performed, and apparently the  leachate had not
reached equilibrium at the time of the screening  procedure.  The  LC-50  value
for HC-5, therefore, was greater than 100 mL/100  mL, even though total mor-
tality occurred during the screening procedure  (table  24).  The aerobic nat-
ural pH leachate  generated from the SRC liquefaction residue had a pH of 5.6,
was acutely toxic,  and required a 1:10 dilution to eliminate mortality.  In
addition, we  estimate that 50 percent mortality would  occur in a solution of
21 mL SRC-2 and 79  ml reconstituted water (table  24).   The anaerobic natural
pH SRC leachate had an LC-50 value greater than 100 mL/100 mL, and required
less than a 1:1.5 dilution to eliminate mortality.

     The natural  pH leachate generated from the water-quenched slag and equil-
ibrated under aerobic conditions was relatively toxic  (LC-50 = 22.50 ± 4.28)
and required  a  moderate  amount of dilution (1:28)  to negate its toxicity.  The

                                      78

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 TABLE 26.  LC-50 VALUES, THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
          NECESSARY TO ELIMINATE MORTALITY FOR HIGH-SULFUR AND LOW-SULFUR GOB LEACHATES
          OBTAINED DURING 96-HOUR STATIC BIOASSAYS USING 1-TO-6-DAY-OLD FATHEAD MINNOW FRY
          (PIMEPHALES PROMELAS).
 Sample
Atmosphere
PH
                                                 LC-50
                                               (mL/100 mL)
                                                  Dilution for
                                                  0% mortality
   1*
   2
   3
   4
   5*
   6
   7
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
                                       LSR
7.9
5.4
3.8
8.9
7.7
6.6
>100
>100
57.00 •'; 2.28
 3.80 .'• 0.4V
>100
>100
96.00 ± 0.83
 2.1.5 ± 0.16
                                       HSR
1:1
1:1
1:3
1:50
1:1
1:1
1:1
1:100
1
2*
3
4
5
6*
7
8
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
8.
7.
3.
2.
8.
8.
3.
2.
1
7
5
7
0
0
9
6
>100 '
>100
41.00 ±
3.00 ±
>100
>100
56.00 ±
2.30 ±


2.
0.


2.
0.


87
62


52
14
1
1
1
1
1
1
1
1
:1
:1
:4
:67
:1
:1
:2
:67
  *Natural pH solutions
natural  pH slag leachate equilibrated  under anaerobic  conditions was  less
toxic  (LC-50 = 37.00  ±  3.89) and less  acidic than  the  aerobic leachate.   Both
natural  pH leachates  generated from  the fly ash were relatively toxic
(LC-50 <11.70) and required a dilution of 1:100 or greater to ensure  survival
during the bioassay.  The natural pH leachates of  the  two gob and  two char
samples  were not sufficiently toxic  on a short-term basis to establish LC-50
values and required little dilution  (<1:1.5) to eliminate mortality
(tables  26 and 27).

DISCUSSION OF BIOASSAY  RESULTS
     The potential hazard that coal  solid wastes pose  to the aquatic  environ-
ment lies in the relatively large concentrations of accessory elements in the
waste  and the possibility of acid formation.  Accessory elements could be
leached  from the solid  wastes by water in a slag pond  or water percolating
through  a landfill.   Pyritic minerals  in these solid wastes produce acid when
exposed  to air and water, and acid could lower the pH  of the pond  or  the pH
of the water passing  through a landfill.  Lowering the pH could increase the
leaching of potentially hazardous chemical  constituents or directly harm
organisms in the affected area.
                                        79

-------
TABLE 27.  LC-50 VALUES, THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
         NECESSARY TO ELIMINATE MORTALITY FOR HIGH-TEMPERATURE AND LOW-TEMPERATURE CHAR
         LEACHATES  OBTAINED  DURING 96-HOUR STATIC BIOASSAYS USING 1-TO-6-DAY-OLD FATHEAD
         MINNOW FRY (I'lMKI'HAW.
Sample
  1
  2*
  3
  4
  5
  6*
  7
Atmosphere
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
                                                LC-50
                                              (mL/100 mL)
                                      LTC
9.2
(,.8
4.2
4.0
8.8
8.1
4.6
3.8
                                      HTC
>100
>10()
12.00 '  1.30
 3.48 ±  0.48
98.00 i  2.00
>100
17.40 :'.  1.22
 1.03 ±  0.11
1*
2
3
4
5*
6
7
8
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
7
6
5
3
7
7
5
4
.2
.5
.4
.9
.6
.8
.4
.3
>100
>100
5.40 i
O.HO '
>100
>100
14.00 :>•
3.20 :'.


0.92
0. 1.8


1.54
0.20

                               Dilution  for
                               0% mortality
1:1
1: .1.
1:20
1:50
1:1
1:1
1:8
1:200

1:1
1:1
1:100
1:333
1:1
1:1
1:13
1:50
 *Natural pH solutions
     Three of the 11 natural  pH leachates  that were equilibrated under  aero-
bic atmospheres (SRC liquefaction residue, water-quenched  slag, and fly ash)
were acidic (pH <6.2).   Total  mortality  occurred during  the screening proce-
dures  of these acidic  leachates (table 22).   These acidic  leachates were
relatively toxic (LC-50  <25.00 ml/100 ml)  and at least a 1:10 dilution  was
necessary to ensure survival  during a bioassay (tables 24  and 25).
     Many factors probably contributed to  the acute toxicity of the acidic
leachates.   It has been  demonstrated (Griffin et al., 1978) that total  mor-
tality occurs when fathead minnow fry are  exposed to acidic reconstituted
water  (pH <5.9) for 96 hours.   Since the test organisms  were propagated.and
held in water having a pH  of  approximately 7.4 and then  experienced a rapid
change in pH, the mortality was partially  due to "ionic  shock."  A rapid
lowering of the pH disrupts the Na+/H+ exchange system of  fish and results
in a loss of sodium that can  cause death (Giles and Vanstone, 1976).  Some
of the acidic leachates  also  contained concentrations of Al, Cr, Cu, Mg, Ni,
and Zn, which under laboratory conditions  have been shown  to be acutely toxic
to fish (Brown, 1968;  Doudoroff and Katz,  1953; Eaton, 1973; McCarty, Henry,
and Houston, 1978; Pickering,  1974; and-Pickering and Cast, 1972).
                                        80

-------
    The natural  pH leachates generated from the H-Coal  liquefaction residue
and the low-sulfur gob were relatively alkaline (pH >8.3) and acutely toxic
during the screening procedure (table 22).   The organisms were propagated
and held in water having a pH of approximately 7.4; they experienced a rapid
change in pH during the bioassays.   Thus the mortality might partially be
caused by the rapid rise in pH, since 5 percent and 50 percent mortality
occurred in bioassays of reconstituted water with pH's of 9.2 and 10.0,
respectively.  The short-term acute toxicity of three of these four natural
pH leachates, however, was eliminated with  little dilution (<1:1.5), and
HC-5 required a 1:6 dilution to ensure survival during a 96-hour bioassay.

     Because of the complex chemical composition of the leachates and the
unknown synergistic and antagonistic effects of the chemical constituents
composing the leachates, it is not possible from these experiments to deter-
mine specifically which chemical constituents were directly responsible for
the observed mortality.  This point is illustrated dramatically by the
anaerobic leachates generated from SRC liquefaction residue.  The pH of the
leachate during the screening procedure was 7.3, yet 40 percent mortality
occurred.  In addition, none of the chemical constituents were present in
concentrations exceeding known acute LC-50  values.

     To determine more precisely which chemical constituents are responsible
for the toxicity of coal solid waste leachates, it is necessary to perform
additional chemical and biological  analyses.  Such analyses would include
the determination of organic compounds found in the wastes and leachates, as
well as bioassays of particular chemical constituents and mixtures of chemi-
cal constituents found in those leachates generated from coal solid wastes,
such as Al, Cd, Cu, Mg, and Ni.

     When coal solid wastes are disposed of in landfills, it is important to
investigate how the waste leachates interact with earth materials; the
results of our investigation of soil-leachate interactions were discussed
earlier in this report.  Unfortunately, because of the small amount of leach-
ate used in the attenuation study, we were  not able to conduct bioassays of
the filtrates; however, Al, Fe, K, Mg, and  Zn were present in large enough
concentrations to pose a hazard.  For example, the filtrates produced from
the acidified SRC leachate often contained  zinc in amounts higher than
0.87 mg/L, which was the LC-50 value for zinc using fathead minnows in soft
water, determined by Pickering and Henderson (1966).

     Filtrates from the two chars, the low-sulfur gob, the SRC liquefaction
residue, and the two Lurgi ashes tested often contained more than 5 mg/L of
potassium.  Although potassium is not acutely toxic to fathead minnows at
this concentration, it is acutely toxic to  other aquatic organisms such as
freshwater mussels (Imlay, 1973).  Even though several elements in the leach-
ates are attenuated by the soil, some are not affected; they may even be
eluted from the soil and could become a hazard to the aquatic environment.
The soil characteristics of a proposed disposal site for coal solid wastes,
therefore, and the location and access to nearby water resources should be
studied before the site is chosen.
                                     81

-------
     This limited biological  analysis of the potential  hazard of coal  solid
wastes consisted of acute static bioassays of the waste leachates using fat-
head minnow fry. It is considered very important to increase the scope of this
investigation to assess the environmental  impact of coal  solid wastes.
Several types of aquatic organisms should  be tested in  addition to fish,
although recommended safe levels for selected test fish such as the fathead
minnow, Pimephales promelas,  quite often provide protection to other aquatic
animals and plants (U.S. EPA, 1972).

     Patrick, Cairns, and Scheier (1968) made a comparative study of the
effects of 20 pollutants on fish, snails,  and diatoms and found that no
single kind of organism was most sensitive in all situations.  A literature
review by Braunstein, Copenhaver, and Pfuderer (1977) indicated that crusta-
ceans  (such as Daphnia magna} and phytoplankton may be  appreciably more sen-
sitive to trace elements than are insects  and fish.  Preliminary experiments
with Daphnia magna demonstrate that this zooplankter is more sensitive to SRC
liquefaction leachate than the fathead minnow fry.  A complete environmental
assessment of coal solid wastes should therefore include acute ecological
bioassays utilizing fish, zooplankton, phytoplankton, and possibly a detrito-
vore—suggestions that have also been made in a recent  EPA publication (EPA,
1977).

     Besides conducting acute bioassays with several types of organisms,
representing all major trophic levels, it  is also essential to conduct
chronic bioassays to assess the chronic effects of coal solid wastes.   Long-
lived  organisms such as fish might be harmed by long-term exposure (directly
or through the organism's food supply) to  chemical constituents leached from
coal solid wastes.  Reduced reproduction,  malformation, disease,'reduced
growth, or generally decreased ability to  compete with  other organisms could
result from long-term sublethal exposure to potentially hazardous chemical
constituents found in coal solid wastes.  It is important, therefore,  to in-
vestigate the accumulation and concentration of potentially hazardous  chemi-
cal constituents found in coal solid wastes by lower trophic levels, as well
as to  investigate the chronic toxicity of  coal solid wastes to long-lived
aquatic organisms.

     Finally, a battery of health effects  tests must be conducted on coal
solid wastes and leachates.  The EPA has recommended (for a level 1 assess-
ment)  that the wastes be tested for the presence of microbial mutagenicity,
rodent acute toxicity, and cytotoxicity.  The specific  tests include the Ames
Test,  the Rabbit Alveolar Macrophage (RAM) assay, the Human Lung Fibroblast
(WI-38) Assays, and acute toxicity bioassays with rats.  The tests detect a
broad  spectrum of potential health effects, are not as  costly as long-term
animal bioassays, and are relatively reliable (Smith, 1978).  With these tests
it is  possible to screen wastes, including coal solid wastes  and their leach-
ates,  for potential carcinogenicity, cytotoxicity, and  other detrimental
health effects.
                                     82

-------
                                  SECTION 10

               POTENTIAL POLLUTION HAZARD FROM COAL SOLID WASTES


     Evaluating the potential pollution hazard of coal  solid wastes involves
comparing the quantities of the wastes and their constituents with standards
for acceptable levels of these constituents in the environment.   Unfortu-
nately, no established standards exist that delineate which specific chemical
or mineralogical  compositions of coal  solid wastes pose potential hazards.
Similarly, no established standards exist that specify which concentrations
of chemical constituents in aqueous effluents from coal solid wastes will
cause significant environmental damage.  This section addresses  this problem
by comparing the chemical analyses of the solid wastes and leachates and the
bioassay data, with the Multimedia Environmental Goals (MEGs) (Cleland and
Kingsbury, 1977)  and the toxicant extraction procedure criteria  (U.S. EPA,
1978) for hazardous wastes.  Both MEGs and the toxicant extraction procedure
were sponsored or proposed by the U.S. EPA.


MATE VALUES FOR SOLID WASTES

     The effluent guidelines proposed in the MEGs are known as Maximum Acute
Toxicity Effluents (MATE).  A MATE value is a theoretical value  calculated  to
predict the maximum concentration of a constituent that will not have adverse
health or ecological effects after short-term exposure.  MATE is now a
defunct term that will be replaced by DMEG (Discharge MEG) in future publica-
tions (D. Kingsbury, 1980, personal communication).  MATELEi values were cal-
culated using equation 52 of MEGs Volume 1 (Cleland and Kingsbury, 1977,
p. 112).  They were based on ecological effects using the LC-50  data from
Section 9 of this report.

     Table 28 lists the MATE values for 50 inorganic constituents of solid
wastes disposed of on land.  Each constituent has two values: one based on
predicted adverse effects to health, the other based on predicted adverse
effects to soil ecosystems.  The table also lists the concentrations of those
constituents that were found to exceed their respective MATE values.  Also
listed are the MATELE1 values, representing the MATE values measured for the
solid wastes as a whole.

     The MATELE1 values indicated that eight of the 11  wastes were not acutely
toxic.  The remaining three had MATELEi values that indicated relatively low
toxicity.  On the other hand, the MATE values for the individual  chemical con-
stituents of the waste indicated that 20 of the 50 constitutents were present
in greater concentrations than their MATE values.  This implies  that these  20
elements are potential pollution hazards—a statistic that does  not agree well

                                      83

-------
     TABLE 28.  CONSTITUENTS IN COAL UTILIZATION SOLID WASTES EXCEEDING HEALTH- OR ECOLOGY-BASED MATE VALUES FOR INDIVIDUAL PARAMETERS
                AND MATELE1 VALUES FOR LAND DISPOSAL ACTUALLY DETERMINED FOR THE SOLID WASTE
CO
MATE*
Parameter
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
Cr
Co
Cu
F
Fe
Ga
Ge
Hf
Hg
K
La
Li
Mg
Mn
Mo
Na
Ni
Pb
Health
(mg/kg)
. 50
16,000
N
50
9,300
1,000
6
N
48,000
10
250,000
260,000
50
150
1,000
7,500
300
15,000
1,700
150
2
N
340,000
70
18,000
50
15,000
160,000
45
50
Ecology
(mg/kg)
10
200
N
10
5,000
500
11
N
3,200
0.2
N
N
50
50
10
.N
50
N
N
N
50
4,600
N
75
17,000
20
1,400
N
2
10
Lurgi
111. No. 5

95,506

11

760
15

22,571
1.6


171

50

151,016




12,867



2,014


195
182
Lurgi
111. No. 6

108,121



950
12

16,652
1.6


212

57

143,780




14,611



1,859


89
45
Lurgi
Rosebud H-Coal

101,188 17,253

22

3,900


60,106 7,862
1.6 0.4


55

49 14

60,059 23,662




5,230


21,531
929 77


5 21
38 32
SRC

67,529

74


11

7,933
1.3


100

100

135,169




8,717



155


14
59
Fly ash

73,600

46


16

26,100
1.9


130

140

134,400




20,900



380


160
110
Bottom
ash
(slag)

84,571



500


43,668
2


100

40

137,267




13,365



465


57
20
High- Medium-
temp, temp. High-S
char char refuse

17,147 13,601 56,522

13




4,574 6,075 28,159
0.5 0.4 1.4




14 11 29

23,951 5,860 86,157




9,962



77 57 310


20 12 48
12 55
Low-S
refuse

97,008

63


-. ' •

21, -227
1.8


78

36

24,813




17,102



310


55
55

-------
 TABLE 28.   Continued.
MATE* BnV-l-nm Uinh. Moftinm-
Parameter
P
Rb
s
Total
Sb
Sc
Se
Si
Sm
Sn
Sr
5 Ta
Te
Th
Ti
Tl
U
V
W
Zn
Zr
Health
3,000
360,000
N

1,500
160,000
10
30,000
160,000
N
9,200
15,000
300
130
18,000
300
12,000
500
3,000
5,000
1,500
Ecology Lurgi Lurgi Lurgi ash temp. temp. High-S Low-S
(mg/kg) 111. No. 5 111. No. 6 Rosebud H-Coal SRC Fly ash (slag) char char refuse refuse
0.1 218 87 2,095 44 1,004 873 786 87 87 829 1,397
N
N

40
N
5 . 16
N 245,653 229,946 225,739 39,641 110,930 194,300 222,934 40,015 50,490 145,490 261,380
N
N
N
N
N
N
160 6,415 6,295 6,475 1,019 1,799 5,100 4,436 959 4,318 4,668 8,298
N
100
30 172 184 30.8 33 112 230 56 35.3 39.8
N
20 1,500 400 31 71 560 62 48 42 300 500
N
MATE
    LEI
        values  measured for solid waste (mg waste/kg  soil)  are  as  follows: Lurgi No. 5: >2 x 106  (nontoxic);  Lurgi No.  6:  >2  x  106
(nontoxic); Lurgi Rosebud: >2 x 106 (nontoxic);  H-Coal:  >2 x 106  (nontoxic); SRC: 42,000; fly ash: 18,000; bottom ash: 45,000; high-
temp, char: >2 x 106 (nontoxic); medium-temp,  char:  >2 x 106 (nontoxic);  high-S refuse: >2 x 10s  (nontoxic); low-S  refuse:  >2  x  106
(nontoxic).
N = none.

*From ApjJehdix C
 model  changes.
                    Cleland and Kingsbury,  1977;  values  listed  here are  100 times those listed in Appendix C to reflect  January  1978


fMATELE1 (yg/g) = 0.002 x MATE^ (yg/L);  MATE^ (yg/L) = 100  x  LC5o(mg/L).

-------
TABLE 29.   DISCHARGE SEVERITIES FOR CONSTITUENTS IN COAL UTILIZATION SOLID WASTES EXCEEDING
           HEALTH- OR ECOLOGY-BASED SOLID WASTE MATE VALUES
MATE
Param-
eter
Ag
Al
Au
As
6
Ba
Be
Br
Ca
Cd
Ce
Cl
Cr
Co
Cu
F
Fe
Ga
Ge
Hf
Hg
K
La
Li
Mg
Mn
Mo
Na
Ni
Pb
P
Rb
s£otal
Sc •
Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Zn
Zr
Total
Health
(mg/kg)
50
16,000
N
50
9,300
1,000
6
N
48,000
10
250,000
260,000
50
150
1,000
7,500
300
15,000
1,700
150
2
N
340,000
70
18,000
50
15,000
160,000
45
50
3,000
360,000
N
1,500
160,000
10
30,000
160,000
N
9,200
15,000
300
130
18,000
300
12,000
500
3,000
5,000
1,500
Ecology
(mg/kg)
10
200
N
10
5,000
500
11
N
3,200
0.2
N
N
50
50
10
N
50
N
N
N
50
4,600
N
75
17,000
20
1,400
N
2
10
0.1
N
N
40
N
5
N
N
N
N
N
N
N
160
N
100
30
N
20
N
Lurgi
No. 5

478

1

2
2

7
8


3

5

3,020




• 3



101


97
18
2,180




8






40


6

75

Lurgi
No. 6

541



2
2

5
8


4

6

2,876




3



93


44
4
870




8






39


6

20

Lurgi
Rose-
bud H-Coal

506 86

2

8


19 2
8 2


1

5 1

1,201 473




1


1
46 4


2 10
4 3
20,950 440




8 1






40 6


1 1

2 4

Bottom High- Medium-

SRC Fly ash

338 368

7 5


2 3

2 8
6 9


2 3

10 14

2,703 2,688




2 5



8 19


7 80
6 11
10,040 8,730



3
4 6






11 32


4 8

28

ash temp. temp.
(slag) char char

423 86 68



1


14 1 2
10 2 2


2

4 1 1

2,745 479 117




3



23 4 3


28 10 6
2 1
7,860 870 870




7 1 2






28 6 27


2

3 2 2

High-S
refuse

283

1


t

9
7




3

1,723




2



15


24
5
8,290




5






29


1

15

Low-S
refuse

485

7




7
9


2

4

496




4



15


27
5
13,970




9






52


1

25

discharge
severity
6,054
4,531
22,805 1,033
13,152 12,020
11,155 1,463 1,100
10,412
15,118
Discharge severity = concentration/MATE
                                                86

-------
with the results generated by the MATELE1  values  for the wastes (that eight
were not acutely toxic).  It seems,  therefore,  that the MATE values for solid
waste disposal on land are perhaps conservative when applied to coal solid
wastes.

     The discrepancy between the estimated hazard based on MATE values for
individual chemical constituents and the measured toxicity of the leachates
seems to originate in the assumption (during  the  derivation of the MATE value)
that the solid waste is highly  soluble  in  water.   Coal  solid wastes are gen-
erally made up of materials of  relatively  low water solubility, this contra-
dicts the assumption and may be the  reason for  the overestimation of the
hazard for these particular wastes.

     Another method to further  evaluate the toxicity of the constituents is
comparing their discharge severities (concentration/MATE value).  After doing
so (table 29), it is clear that Al,  Fe, and P are predicted to have the most
potential for exceeding discharge limits and  posing environmental problems.


MATE VALUES FOR LEACHATES

     The MATE values for water  quality  of  the chemical  constituents measured
in the leachates from the coal  wastes are  given in tables 30 and 31.  The
tables also provide a listing of those  constituents in  the leachates that ex-
ceeded their MATE values for individual parameters (appendix C in Cleland and
Kingsbury, 1977), along with a  listing  of  MATEWE  values (Cleland and Kings-
bury, 1977, eq. 50, p. Ill), which are  based  on ecological effects and acute
bioassay data that were obtained using  the leachates from the wastes (Sec-
tion 9).
 TABLE 30.  MATEWE VALUES MEASURED FOR LEACHATES, BASED ON ECOLOGICAL EFFECTS AND BIOASSAY DATA
Leachate
Lurgi No. 5
Lurgi No. 6
Lurgi Rosebud
H-Coal
SRC
Fly ash
Bottom ash (slag)
High-temp, char
Medium- temp, char
High-S refuse
Low-S refuse
MATEWE value*
(yg/L)
>109
>109
>109
>109
2.1 x 10'
9 x 106
2.25 x 107
>109
>109
>109
>109
LC50 96-hr
(ppm)
>107
>107
>107
>107
210,000
90,000
225,000
>107
>107
>107
>107
Mortality, full
strength leachate
(«)
0
0
0
15
100
100
100
0
5
5
15
Dilution for,
no mortality
None
None
None
1:1
1:10
1:100
1:28
None
1:1 .
1:1
1:1
 *MATEWE  (pg/L) = 100 x LC50(mg/L)
  No mortality during 96-hour  bioassay.
                                       87

-------
TABLE 31.  CONSTITUENTS IN LEACHATES EXCEEDING HEALTH- OR ECOLOGY-BASED WATER MATE VALUES FOR INDIVIDUAL PARAMETERS
MATE*
Parameter
Al
As
B
Ba
Be
Ca
Cd
Cl
Cr
Co
Cu
F
Fe
Hg
K
oo Li
oo Mg
Mn
Mo
Na
NH,,+
Ni
Pb
P
s-2
SO,
Sb
Se
Si
Sn
Sr
Te
Ti
Tl
V
Zn
Health
(mg/L)
80
0.25
47
5
0.03
240
0.05
1,300
0.25
0.75
5.0
7.0
1.5
0.25
N
0.33
90
0.25
75
800
N
0.23
0.25
15
N
1,250
7.5
0.05
150
N
46
1.5
90
1.5
2.5
25
Ecology Lurgi Lurgi Lurgi
(mg/L) 111. No. 5 111. No. 6 Rosebud H-Coal
1 3.0
0.05
25 26.9
2.5
0.055
16 470 290 210 110
0.001 0.02 0.02
N
0.25
0.25
0.05
N 8.0
0.25
0.22
23 30 42
0.38 1.00 1.8
87
0.10 0.45
7
N
N
0.01 0.03 0.03
0.05 0.1 0.1
0.0005
N
N
0.2 0.4
0.25
. N
N
N
N
0.82
N
0.15
0.1 0.12
SRC Fly ash
62.6

58


415 508
0.39


0.31
0.20

1.0 13.5


0.53

0.93 9.14



1.31
0.15


2,350









20
Bottom High- Medium-
ash temp. . temp. High-S Low-S
(slag) char char refuse refuse
5.5




17.5 93 207 480 568




0.20

0.60 1.08




0.78 0.28 0.57 1.83 0.59



0.13
0.20 0.15
0.04

1,600









0.18
*From Appendix C (Cleland and Kingsbury,  1977).

-------
     The MATEwE values, which are the measured values of the  leachates, were
computed from  the LC-50 values for  the  aerobic natural pH leachates, (see
Section 9,  this report).  Eight of  the  11  leachates produced  a  low mortality
percentage  (<15 percent), whereas three of the leachates were highly toxic.
The toxicity of the leachates from  the  fly ash and bottom ash was  mainly
caused  by their acidity.

     Comparing the MATE^ values  of the leachates  to  the table of constituents
exceeding  individual MATE values and  to the discharge severities (table 32),
TABLE 32.   DISCHARGE SEVERITIES FOR CONSTITUENTS IN LEACHATES FROM COAL SOLID WASTES EXCEEDING
          HEALTH- OR ECOLOGY-BASED WATER MATE VALUES
Param-
eter
Al
As
B
Ba
Be
Ca
Cd
Cl
Cr
Co
Cu
F
Fe
Hg
K
Li
Mg
Mn
Mo
Na
NH,/
Ni
Pb
P
S'2
SO,,
Sb
Se
Si
Sn
Sr
Te
Ti
Tl
V
Zn
MATE
LurQ1
Health Ecology Lurgi Lurgi Rose-
(mg/L) (mg/L) No. 5 No. 6 bud H-Coal
80 1 3
0.25 0.05
47 25 1
5 2.5
0.03 0.055
240 16 29 18 13 7
.05 .001 20 20
1,300 N
0.25 0.25
0.75 0.25
5.0 0.05
7.0 N 1
1.5 0.25
0.25 0.22
N 23 12
0.33 0.38 3 5
90 87
0.25 0.10 4
75 7
800 N
N N
0.23 0.01 3 3
0.25 0.05 2 2
15 0.0005
N N
1,250 N
7.5 0.2 2
0.05 0.25
150 N
N N
46 N
1.5 N
90 0.82
1.5 N
2.5 0.15
25 0.1 1
Bottom
ash
SRC Fly ash (slag)
63 5

2


26 32 1
390


1
4 4

4 54 2


2

9 91 8



131 13
3


2









200 2
High- Medium-
temp, temp. High-S Low-S
char char refuse refuse





6 13 30 35






4




3 6 18 6




4 3


1










 Total  discharge
   severity
38    55
37
10
39
975
35
19
                                         53
                                         48
                                        89

-------
                      TABLE 33.  CONSTITUENTS  IN LEACHATES FROM COAL UTILIZATION SOLID WASTES
Parameter
Maximum
allowable
leachate
(mg/L)
Lurgi No. 5
Nat. pH Adj. pH
8.25 6.05
Lurgi No. 6
' Nat. pH Adj. pH
7.55 5.10
Lurqi Rosebud
Nat. pH Adj. pH
8.44 4.95
H-Coal
Nat. pH Adj. pH
8.83 5.01
        Primary drinking water

Arsenic          0.5
Barium         10.0
Cadmium          0.1
Chromium (VI)     0.5
Fluoride        14.0
Lead            0.5
Mercury          0.02
Nitrate        100.0
Selenium         0.1
.Silver          0.5
        Secondary drinking water

Chloride      2,500.0
Copper         10.0
Hydrogen
  sulfide        0.5
Iron            3.0                                                           14.0
Manganese        0.5                4.2            1.94           16.2            1.67
Sulfate       2,500.0
Total
  dissolved
  solids      5,000.0
Zinc           50.0
pH  (units)       5.5-9.5
        Irrigation water

Aluminum        20.0
Beryllium        0.5
Boron           2.0          5.0    6.8     4.0     4.5     26.9    29.9    11.0    11.6
Cobalt          5.0
Molybdenum        .05                                      0.4
Nickel          2.0

Nat. = Natural
Adj. = Adjusted


reveals that only Ca  and Mn consistently exceed their MATE values  for  most of
the  wastes.   Fly ash  leachate contains  the most constituents  that  exceed MATE
values, 13,  compared  to  only two each for the H-Coal  and the  two char  leach-
ates;  The measured MATE^ values  for the leachates  represent acute  toxicity,
whereas those elements exceeding listed MATE values  represent potential
chronic toxicity problems.  More data need to be collected and evaluated in
order to  validate the proposed MATE  values and the use of discharge  severi-
ties  and  acute toxicity  data as a  basis for predicting long-term environ-
mental effects.


      Another basis for evaluating  the potential hazard posed  by coal  solid
wastes is to compare  the concentrations of constituents in the leachates from
this  study with the proposed U.S.  EPA hazardous waste criteria (U.S.  EPA,
1978).  Before evaluating results, however, the two  extraction procedures
must  be compared.


                                        90

-------
EXCEEDING PROPOSED U.S. EPA TOXICANT EXTRACTION PROCEDURE STANDARDS

                    Bottomash   High-temp.    Medium-temp.     High-sulfur     Low-sulfur
_   SRC       Fly ash   (slag)      char          char          refuse        refuse
Nat. pH  Adj.pH  Nat. pH   Nat. pH  Nat. pH Adj.pH  Nat. pH  Adj. pH Nat. pH Adj. pH  Nat. pH  Adj.pH
  6.35   4.69    4.08     3.81    8.05   4.33   7.19    3.81    7.45    3.43   7.79    3.50
               0.39
        31.2   13.5                  250.0           4.75                       10.0
  0.93   1.38   9.14         '          4.45   0.57   3.20    1.83   14.7    0.59  12.6
               4.08     3.81


              62.6

  4.0    4.0   58.0             2.8     2.5    10.0    9.1
     The  procedure proposed  by  the EPA calls for  screening through a  3/8-inch
sieve, which  can be compared to the 45-mesh sieve  that was used in this  study.
The solid is  then shaken in  a volume of water that is  16 times its weight;  in
this study, the volume of water is nine times the  solid's weight.  In  the EPA ,
procedure,  the sample is adjusted  to pH 5.0 ± .1 with  acetic acid; in  this
study, the  pH was adjusted with nitric acid to several  values, many of which
were close  to 5.0.  The EPA  procedure calls for a  24-hour shaking period; this
study used  a  6-month equilibration.

     Clearly, the intent and the methods used for  the  two extraction  proce-
dures were  quite similar; however, they cannot be  directly compared.   The
effects of  using acetic acid compared to using nitric  acid, the effects  of the
differences in equilibration times, and the consequences of differences  in
final volumes is difficult to assess.  Nevertheless, the results obtained by
the two methods should be similar.  Table 33 presents  a tabulation of


                                        91

-------
constituents of the leachates from this study that exceeded the proposed
U.S. EPA maximum allowable effluent levels for primary and secondary drinking
water parameters and for irrigation water standards for short-term (less than
20 years) application.

     These results indicate that only Cd in the fly ash leachate exceeds the
primary leachate standard (10 times drinking water) and would thus be classed
as a hazardous waste by the proposed U.S. EPA criteria.  It is useful to com-
pare the secondary drinking water parameters and note that Mn and Fe fre-
quently exceed 10 times the drinking water standard level.  This occurs mainly
in the acidified leachates as compared to the natural pH leachates.  When
making these comparisons, the differences between our procedure and the EPA
procedure should be kept in mind, particularly the two differences in final
volume and in pH.

     Interestingly, boron exceeds the irrigation water standard in the leach-
ates from nearly all the coal wastes and at all pH levels.  This is a poten-
tially serious problem in the western states, where high levels of boron in
irrigation waters are a problem because of the toxicity of boron to plants.
This illustrates that the ecologically based MATE value for boron may need to
be lowered to be more consistent with irrigation water standards.

     Of the leachates obtained from the 11 coal solid wastes at their natural
pH level, only the fly ash leachate contained a significant level of acute
toxicity.  Whereas the acute toxicity of most coal ash leachates was low,
however, they were measured with only one species of organism, and the poten-
tial for long-term pollution that could cause chronic toxicities is unknown.
The elements in the leachates that exceeded the MATE values for water quality
and irrigation water standards may be a guide to potential long-term pollution
problems.

     The thermochemical modeling indicated several of the leachates were in a
mqtastable equilibrium.  For example, the pyrites and pyrrhotites in the coal-
cleaning and liquefaction residues will eventually oxidize to form an acidic
leachate, which would have a much higher acute toxicity than was measured at
its natural pH in this study.  The toxicity to be expected upon oxidation of
the metastable minerals would be more closely estimated from the bioassay and
chemical data from the acidified leachates.  Thus, all these chemical,
mineralogical, biological, and soil attenuation factors must be integrated
when assessing the environmental impact of land disposal of the solid wastes
from coal utilization processes.
                                      92

-------
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                                     98

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                                 APPENDIX

                           LIST OF PUBLICATIONS
Griffin, R. A., R. M. Schuller, S. J. Russell, and N.  F.  Shimp,  1979,  Chemi-
     cal analysis and leaching of coal conversion solid wastes,  in
     F. A. Ayer [ed.h Environmental aspects of fuel  conversion  technology
     IV: U.S. Environmental Protection Agency, EPA-600/7-79-217, Research
     Triangle Park, NC.
Griffin, R. A., R. M. Schuller, J. J. Suloway, S. J.  Russell, W. F.  Childers,
     and N. F. Shimp, 1978, Solubility and toxicity of potential pollutants
     in solid coal wastes, in F. A. Ayer [ed.], Environmental aspects  of
     fuel conversion technology III: U.S. Environmental Protection Agency,
     EPA-600/7-78-063, Research Triangle Park, NC.
Hinckley, C. C.,  G. V. Smith, H. Twardowska, M. Saporoschenko, R. H. Shi ley,.
     and R. A. Griffin, 1980, Mossbauer studies of iron in Lurgi gasification
     ashes and power plant fly.and bottom ash: Fuel, v. 59, p. 161-165.
Saporoschenko, M., C. C. Hinckley, G. V. Smith, H. Twardowska, R. H. Shiley,
     R. A. Griffin, and S. J. Russell, 1980, Mb'ssbauer spectroscopic studies
     of the mineralogical changes in coal as a function of cleaning, pyroly-
     .sis, combustion, and coal conversion processes:  Fuel, v. 59, p. 567-574.
.Schuller, R. M.,  R. A. Griffin, J. J. Suloway, 1979, Chemical and biological
     characterization of leachate from coal cleaning wastes, in J. D.  Kil-
     groe  ted.],  Coal cleaning to achieve energy and environmental goals:
     U.S. Environmental Protection Agency, EPA-600/7-79-098a, Research Tri-
     angle Park,  NC.
Schuller, R. M.,  J. J. Suloway, R. A. Griffin, S. J. Russell, and W. F.
     Childers, 1979,  Identification of potential pollutants from coal  con-
     version wastes, in Elements  in coal and potential environmental con-
     cerns arising from these elements: .Mini Symposium Series No. 79-06,
     Society of Mining Engineers  of AIME, Littleton, CO.
Shiley, R. H., S. J. Russell, D.  R. Dickerson, C. C.  Hinckley, G. V. Smith,
     H. Twardowska, and M. Saporoschenko, 1979, Calibration standard for
     x-ray diffraction analyses of coal liquefaction residues:  MDssbauer
     spectra of synthetic pyrrhotite: Fuel, v. 58, p. 687-688.
Smith, Gerard V., Juei-Ho Liu, Mykola Saporoschenko,  and Richard Shiley,
     1978, MBssbauer spectroscopic investigation of iron species in coal:
     Fuel, v. 57, p. 41-45.
                                     99

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                               TECHNICAL REPORT DATA
                         (Please read Instructions on the reverse before completing}
1. REPORT NO.
 EPA-600/7-80-039
                           2.
                                                     3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Chemical and Biological Characterization of Leachates
 from Coal Solid Wastes
            5. REPORT DATE
             March 1980
            6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
R. A. Griffin, R. M.Schuller, J.J.Suloway,
 N.F.Shimp, and W.F.Childers	
                                                     8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Illinois State Geological Survey
Natural Resources Building
Urbana, Illinois 61801
            10. PROGRAM ELEMENT NO.
            EHE623A
            11. CONTRACT/GRANT NO.

            68-02-2130
12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and Development
 Industrial Environmental Research Laboratory
 Research Triangle Park, NC  27711
                            PERIOD COVEREO
            14. SPONSORING AGENCY CODE
             EPA/600/13
is. SUPPLEMENTARY NOTES IERL_RTP project officer is N. Dean Smith, Mail Drop 61, 919/
541-2708.
16. ABSTRACT ,
          The report gives results of the chemical and mineralogical characterization
 of coal solid wastes. The wastes included three Lurgi gasification ashes, mineral
 residues from the SRC-I and H-Coal liquefaction processes, two chars,  two coal-
 cleaning residues, and a fly-ash-and-water-quenched bottom ash (slag) from a coal-
 fired power plant. Leachates generated from the solid wastes at eight pH levels and
 under two different gas atmospheres were analyzed for more than 40 chemical con-
 stituents.  Thermodynamic speciation of inorganic ions  and complexes in solution
 were modeled.  The modeling demonstrated that similar mineral phases controlled
 the aqueous solubility of  the major ionic species for all wastes. Adsorption and co-
 precipitation of trace metals with iron, manganese, and aluminum oxides and hy-
 droxides were thought to be  the likely controls on trace metal concentrations in the
 leachates.  A high degree of  attenuation of the leachate  constituents by soils was ob-
 served. Soil properties controlled the degree of attenuation to a greater  extent than
 did the chemical concentrations  of the leachates. Results of acute 96-hour static
 bioassays using fathead minnows identified mortality as being caused by  the com-
 bined effect of pH arid total ionic strength of the leachate.
17.
                             KEY WORDS AND DOCUMENT ANALYSIS
                DESCRIPTORS
                                          b.lDENTIFIERS/OPEN ENDED TERMS
                        c.  COSATI Field/Group
 Pollution            Bioassay
 Wastes              Ashes
 Coal                Coal Gasification
 Combustion         Coal Preparation
 Chemical Properties  Fly Ash
 Minerals            Slags
Pollution Control
Stationary Sources
Biological Properties
Chars
Coal Cleaning
13B

2 ID
21B
07D
08G
06A1
13H
                                  11B
                                  07A
18. DISTRIBUTION STATEMENT
 Release to Public
                                          19. SECURITY CLASS (TMi Report)
                                          Unclassified
                        21. NO. OF PAGES
                             110
20. SECURITY CLASS (Thispage)
Unclassified
                        22. PRICE
EPA Form 2220-1 (9-73)
                                       i nn

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