DoE
EPA
United
   nt of EOGI t]\
            LA 7831 PR
US Environmental Piott-i tmn Agrnc\
Office of Rfsciiic'h .UK! Developmenl
Industrial Environmental    EPA 600 779-144
HI-SIMP h I aborator\      June 1979
Researi h Ti langle P.iri> NC ? 7/11
         Trace Element
         Characterization
         of Coal  Wastes
         Third Annual
         Progress Report

         Interagency
         Energy/Environment
         R&D Program Report

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                 RESEARCH REPORTING SERIES


Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination  of traditional  grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

    1. Environmental Health Effects Research

    2. Environmental Protection Technology

    3. Ecological Research

    4. Environmental Monitoring

    5. Socioeconomic Environmental Studies

    6. Scientific and Technical Assessment Reports  (STAR)

    7. Interagency Energy-Environment Research and Development

    8. "Special" Reports

    9. Miscellaneous Reports

This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND  DEVELOPMENT series. Reports in this series result from the
effort funded  under  the 17-agency Federal  Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects;  assessments of, and  development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
                        EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products  constitute endorsement or recommendation for use.

This document is available to the public through the National Technical Informa-
tion Service. Springfield, Virginia 22161.

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                                                        DoE LA-783I-PR
                                                    EPA-600/7-79-144
                                                              June 1979
                                                                      UC-90i
       Trace  Element  Characterization
                    of Coal  Wastes  -
          Third Annual  Progress Report
             October 1, 1977 to September 30, 1978
                                by
            E. M. Wewerka, J. M. Williams, L E. Wangen, J. P. Bertino,
             P. L. Wanek, J. D. Olsen, E. F. Thode,* and P. Wagner

                      Los Alamos Scientific Laboratory
                         University of California
                      Los Alamos, New Mexico 87545
                An Affirmative Action/Equal Opportunity Employer

               EPA/DoE Interagency Agreement No. IAG-D5-E681
                       Program Element No.lNE825
EPA Project Officer: David A. Kirchgessner
      Industrial Environmental
        Research Laboratory
  Research Triangle Park, N.C. 27711
DoE Project Officer: Charles Grua
   Division of Environmental
     Control Technology
   Washington, D.C. 20545
   'Short-term Visiting Staff Member. Department of Management, New Mexico State University,
   P.O. Box 3DJ, Las Cruces, NM 88003.
                            Prepared for

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

                               and
                     U.S. DEPARTMENT OF ENERGY
                 Division of Environmental Control Technology
                        Washington, DC 20545

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                                  CONTENTS


ABSTRACT  [[[  I

EXECUTIVE SUMMARY [[[  1

SUMMARY OF TASK PROGRESS .................................................  4

TASK PROGRESS DESCRIPTION .................................................  7
      Task  1. Environmental Control Technology for Trace Elements in the
              Drainage From High-Sulfur Coal Preparation Wastes ...................  7
      Task 2. Identify Trace Elements of Environmental Concern in High-Sulfur
              Coal Preparation Wastes From the Appalachian Region  ................ 40

PERSONNEL  [[[ 44

APPENDIX A.   Column Leaching of Calcined Refuse ................................ 4(5

APPENDIX B.   Preliminary Cost Comparisons for Selected Environmental Control
                Options for Contaminated Coal Refuse Drainage ..................... fifi
APPENDIX C.   Column Leaching Studies of Limestone/Refuse Mixtures .............. (i.r>

APPENDIX D.   Column Leaching Studies of Lime/Refuse Mixtures .................. 76

APPENDIX E.   Program Code for Determining the Cost of Alkaline
                Neutralization of Coal Waste Drainages ............................. 82

REFERENCES [[[ 84


                                    TABLES
I.        Effect of Calcining on Trace Element Retention
         From Plant B Coal Refuse	  8


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       V.        Trace Element  Leachability of a High-Sulfur Coal
                 Refuse Sample  Calcined at 1000°C 	11

       VI.       Conditions of Preleaching Experiments Conducted
                 on a High-Sulfur Coal Refuse Material	12

       VII.       Elemental Analyses of Leachates From Preleaching
                 of Plant B Coal Refuse 	13

       VIII.      Effectiveness of Leaching Agents at Removal of
                 Trace Elements From Plant B Coal Refuse	14

       IX.       Effectiveness of Ferric Sulfate Treatment on Iron Removal
                 From Coal and  Coal Waste  	15

       X.        Analyses of Jemez  Limestone  Used in Neutralization
                 Control Technology Experiments 	17

       XI.       Description of Dynamic Leaching Studies of
                 High-Sulfur Refuse/Limestone Mixtures	17

       XII.       Results of Experiments Using Eleven  Sorbents  for pH Control and Trace
                 Element Attenuation for an Illinois Basin  High-Sulfur Coal
                 Refuse Leachate 	23

       XIII.      Comparison of Capabilities of Eleven  Sorbents  to Elevate pH and to
                 Attenuate Thirteen Trace Elements in Illinois Basin Coal
                 Refuse Leachates	24

       XIV.      Trace Element  Analyses of Soil/Refuse Leachate
                 Equilibrations	25

       XV.       Batch Attenuation  of Trace Elements in  Coal
                 Refuse Leachates by Soils	26

       XVI.      Results From a  Column Leaching Experiment With
                 Calcite-Coated  Illinois Basin Coal Refuse 	28

       XVII.     Analyses for the Control of Refuse Drainage by
                 Alkaline Neutralization	31

       XVIII.     Experiment Identification and  Catalog Description of Resins Used in
                 Bio-Rad's  Ion-Exchange  Experiments on  High-Sulfur Coal Refuse Leachates ..32

       XIX.      Summary  of pH, TDS, and Trace Element Compositions Resulting  From
                 Ion-Exchange Treatment of a  High-Sulfur Coal Refuse Leachate	33

       XX.       Trace Element  Analyses on Reverse Osmosis
                 Experiments	35
VI

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XXI.      Alkaline Neutralization/Permanganate Oxidation of
          Contaminated Coal Refuse Drainage	37

XXII.     Matrix Grid Summary of Environmental Control Options
          for Contaminated Coal Refuse Drainage	38

XXIII.    Matrix Grid Summary of Environmental Control Options
          for Contaminated Coal Refuse Drainage	39

XXIV.    Mineral Compositions of Coal Refuse Samples	40

XXV.     Trace Element and Mineral Content of Coal Waste
          from Appalachian Plant  G	42

XXVI.    Trace Element Compositions of Coal Refuse Samples  	43

XXVII.    Static Leaching of Low-Sulfur Appalachian
          Plant G Waste	43

XXVIII.   MEG/MATE Analyses of Plant G Coal Refuse Leachate	46

A-I.       Experiment Identification for Dynamic Leaching
          Studies of Calcined Refuse	46

A-II.      Analyses for Dynamic Leaching Studies of
          Calcined Refuse, Experiment No. GL-12  	47

A-III.      Analyses for Dynamic Leaching Studies of Calcined
          Refuse, Experiment No.  GL-18	48

B-I.       Landfill Growth and  Mass Flow of Water Through Waste
          Pile During 20-Yr Active Life of Pile	60

B-II.      Lime  Requirements for Various Treatments of Coal Waste	61

B-III.      Fly Ash Demand Requirements for  Codisposal Treatment of
          Coal Waste	61

B-IV.      Costs of Various Drainage Treatment/Prevention Processes  	62

B-V.      Annual Costs of Various Drainage Treatment/Prevention Processes	63

B-VI.      Net Present Value of Costs for Various Drainage
          Treatment/Prevention Processes 	64

C-l.       Experiment Identification for Dynamic Leaching Studies of
          Limestone/Refuse Mixtures  	65

C-II.      Analyses for Dynamic Leaching Studies of Limestone/Refuse
          Mixtures,  Experiment No. GL-12	66
                                                                                         VII

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 C-III.      Analyses for Dynamic Leaching Studies of Limestone/Refuse
           Mixtures, Experiment No. GL-14	(57

. C-IV.      Analyses for Dynamic Leaching Studies of Limestone/Refuse
           Mixtures, Experiment No. GL-15	68

 C-V.      Analyses for Dynamic Leaching Studies of Limestone/Refuse
           Mixtures, Experiment No. GL-16	69

 C-VI.      Analyses for Dynamic Leaching Studies of Limestone/Refuse
           Mixtures, Experiment No. GL-17	70

 D-l.       Experiment Identification for Codisposal of Lime
           and Coal Wastes	76
 D-ll.      Analyses for Dynamic Leaching Studies of Lime/Refuse
           Mixtures, Experiment No. CTWT-11-1 (Control)	76

 D-lll.     Analyses for Dynamic Leaching Studies of Lime/Refuse
           Mixtures, Experiment No. CTWT-11-2 (0.5 wt% Lime)  	77

 D-1V.     Analyses for Dynamic Leaching Studies of Lime/Refuse
           Mixtures, Experiment No. CTWT-11-3 (1.5 wt% Lime)  	77

 D-V.      Analyses for Dynamic Leaching Studies of Lime/Refuse
           Mixtures, Experiment No. CTWT-11-4 (3 wt% Lime) 	78

 D-VI.     Analyses for Dynamic Leaching Studies of Lime/Refuse
           Mixtures, Experiment No. CTWT-11-5 (10 wt% Lime) 	78

                                      FIGURES

 1.         Leachate pH and TDS versus leachate volume for  column
           leaching study of limestone/refuse mixtures	18

 2.         Leachate pH and TDS versus leachate volume for  column
           leaching study of lime/refuse mixtures 	'20

 3.         Iron levels  in aqueous streams of a reverse osmosis system	36

 4.         Leachate pH and TDS versus leachate volume for  column
           leaching study of Plant G refuse	45

 A-1.       The pH, TDS, and trace element  concentrations for dynamic leaching
           experiments with calcined refuse 	49

 C-l.       The pH, TDS, and trace element  concentrations for dynamic leaching
           experiments with limestone/refuse mixtures	71

 D-l.       The pH and trace element concentrations for dynamic
           leaching experiments with lime/refuse mixtures	79

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            TRACE ELEMENT CHARACTERIZATION OF COAL WASTES
                      THIRD ANNUAL PROGRESS REPORT

                       October 1, 1977 to September 30, 1978

                                        by

            E. M. Wewerka, J. M. Williams,  L. E. Wangen, J. P. Bertino,
               P. L. Wanek, J. D. Olsen, E.  F. Thode, and P. Wagner


                                   ABSTRACT

         In 1978, we performed laboratory experiments to investigate the efficacy
       of several control options for treating coal wastes at the preparation plant or
       during disposal. Our research revealed that calcining is one of the more ef-
       fective and permanent means of treating high-sulfur coal wastes before dis-
       posal to decrease, quite dramatically,  the release of environmentally un-
       desirable pollutants into the drainages from disposal sites. Another promis-
       ing control method is codisposal of the coal wastes with lime or limestone to
       neutralize  the  acid  drainage  and  retain soluble aqueous contaminants
       within the waste site. Other experiments have examined the feasibility of
       using natural sealants, such as clays, soils, calcite, and cements, to isolate
       the disposal site from its immediate environment. The various tradeoffs for
       these control options are discussed in terms of contaminant reduction, com-
       plexity, permanency, and cost.
         We have begun an assessment of coal preparation wastes from the Ap-
       palachian region. Based on the work we have done on refuse from a single
       plant,  it is clear that coal wastes  containing a low percentage of pyrite
       (<1%) generate worrisome amounts of acid drainage. Our experimental
       results show that the  trace  elements of environmental  concern  in the
       leachates from  these low-sulfur wastes are aluminum,  manganese, iron,
       nickel, and copper  when their concentrations are in  excess of the En-
       vironmental Protection Agency's recommended Minimum Acute Toxicity
       Effluent (MATE) values.
                            EXECUTIVE SUMMARY

  The mineral wastes from coal preparation and coal mine development constitute a major en-
vironmental problem in the United States.1 More than 3 billion tons of these materials have ac-
cumulated thus far and are increasing yearly at the rate of more than 100 million tons. In an ef-
fort to produce cleaner coals and also to upgrade their environmental acceptability, the level of

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waste production is expected to increase markedly with increased use of coal, possibly doubling
in the next decade. In addition to being large volume wastes, these coal preparation discards pre-
sent problems of serious environmental concern. Of the nearly 5000 coal waste dumps, half pose
some type of health, environmental, or safety problem. One of the growing environmental con-
cerns is the effect that trace metals in the waste dump drainages will have as they collect in the
surrounding streams and soils. In acknowledging this latter concern, the Department of Energy
(DOE) and  the Environmental  Protection Agency  (EPA) have jointly sponsored,  since 1975,
research at the Los Alamos Scientific Laboratory (LASL) to evaluate the trace element problem
and to determine and recommend corrective measures.
  The overall objectives of the LASL research program are to assess the problem of trace element
contamination in coal waste drainages  and to  identify  suitable control technologies. More
specifically these are to
    • assess the nature and magnitude of trace elements in the effluents from coal preparation
      wastes,
    • identify the chemistry of the trace  constituents of environmental  concern,
    • identify and experimentally verify effective  environmental strategies to control the release
      of hazardous constituents, and
    • analyze the tradeoffs associated with the different control technologies and recommend
      control measures or  necessary  research  development and demonstration  (RD&D)
      programs.
  To understand why coals and coal preparation wastes release elements in the amounts they do,
we have studied the levels and releases  of elements from a low-sulfur Appalachian  coal area
where the mineral drainage is not highly visible and from high-sulfur Illinois Basin areas where
mineral drainage has long been  recognized as a severe problem. Both types of wastes are com-
posed primarily of clay minerals, quartz, iron sulfides, and calcite. Low-sulfur Appalachian
wastes differ from the high-sulfur Illinois wastes by having <1% iron sulfide minerals (pyrite and
marcasite) as compared to 20-30% for the latter. Some 55 elements have been identified and un-
doubtedly there are more.  The most abundant  of these (aluminum, iron, and silicon) form the
major  minerals.  The trace  constituents are probably present as minor  minerals  (even  as
microparticles), components of residual coal, or substituents in the major minerals. A number of
elements that are generally considered to be environmentally sensitive are present in significant
quantities (>30 Mg/g of waste). These elements of concern include aluminum, arsenic, cobalt,
copper, fluorine, iron, lead, manganese, nickel, and zinc. Although the relative amounts of some
of the trace  elements are small, the absolute quantities available in a large waste  dump have
grave consequences when they are released by natural processes into the surrounding environ-
ment.
  The  high-sulfur (high-pyrite) wastes from the Illinois Basin, when exposed to air and water,
produce highly acidic drainages (pH ~ 2 to 4). Even low-sulfur (low-pyrite) Appalachian wastes
produce acidic drainages (pH ~ 4) though the total amount of acid is much less. Our experiments
to simulate  the intermittent rainfall and weathering to which coal waste dumps are subjected
have revealed that alternate oxidation and leaching of the pyrite in the waste is a most effective
way to regenerate acid leachates continuously. We have demonstrated experimentally that inter-
mittently leached coal wastes pose a far greater pollution threat, in both quantity and time, than
do those wastes that are always submerged in water or are isolated from air, water, or both in
some manner.
  Acidic leachates in coal waste dumps are very efficient in dissolving or degrading many of the
minerals present and releasing the elements associated with them. Last year, we reported that
aqueous  leachates  from  high-sulfur  Illinois  Basin coal  wastes  contained  nine  elements
(aluminum,  cadmium, cobalt,  copper, fluorine, iron,  manganese,  nickel,  and zinc) in  en-
vironmentally hazardous concentrations. More recently, we have analyzed leachates from a low-
sulfur Appalachian coal waste by the EPA's Multimedia Environmental Goal/Minimum Acute

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Toxicity Effluent (MEG/MATE) system for classifying potentially hazardous contaminants and
have found that six elements (aluminum, copper, iron, manganese, nickel, and zinc) were present
in levels of possible environmental concern. The severity of contamination caused by the low-
sulfur waste, however, is much less pronounced than that caused by the high-sulfur waste.
  From our studies and from information about actual dump drainages, it is evident that similar
and suitable control technologies to prevent environmental degradation by the release of acid and
trace elements are needed for both high-sulfur and low-sulfur coal preparation wastes, as the dif-
ference in waste types is more a matter of degree than of kind.
  Control strategies for expedient and environmentally acceptable disposal of coal preparation
wastes fall into three logical categories.
  I.    Alter the waste structure to produce an environmentally acceptable waste.
  II.   Dispose  the  waste in  a  manner that will  produce an  environmentally  acceptable
       drainage.
  in.  Collect and treat the  contaminated drainage from disposed, but untreated, waste.
Category I eliminates the source of the problem by immobilizing or removing I lie potential pollut-
ants from the waste. The second category could be implemented by retaining the pollutants in
the dump, providing back-up safeguards (if necessary), and monitoring the dump to insure en-
vironmentally acceptable containment. A properly devised and monitored disposal scheme in
Category II could provide I'or  an orderly release of environmentally acceptable levels of pollut-
ants. This category also recognizes that an acceptable, environmental control can be found
without the need to completely destroy or alter the waste itself. In the third alternative, one could
isolate the dump, let it generate pollutants as it would, collect the contaminated drainage, and
remove the pollutants from the drainage before releasing the water into the local waterways. This
strategy is the least desirable from an environmental viewpoint because it is nearly impossible,
with such large volumes of wastes and extensive drainage areas, to insure that the pollutants will
not inadvertently escape into the environment in unacceptable quantities. Our studies show that
the release of pollutants is certainly extensive enough that monitoring and treatment of such
drainages will be required for  many years and perhaps for centuries. All three control strategies,
when viewed in terms of the tradeoffs among their economic impact, technical complexity, and
overall effectiveness, have good and bad features and no single strategy is obviously more promis-
ing than  the other two.
  Two methods that immobilize or remove metal pollutants from coal wastes (Category I) are
calcining and preleaching, respectively. Our laboratory results on calcining show that heating the
waste to 800-1000° C releases the acid-producing sulfur and causes mineralogical transformations
that seal the remaining trace pollutants in the residue. Leachates from such calcined residues
have no trace element concentrations of concern. Unlike calcining, preleaching with oxidizing
agents has not been very fruitful.
  Building environmentally acceptable, controlled pollutant-release coal waste dumps (Category
II) has many possibilities. Codisposing the waste with neutralizing agents or sorbents and sealing
the surfaces of the waste particles have been investigated experimentally.  Small  particle
limestone,  lime, certain  types  of clays and soils, and industrial  wastes, such as fly ash and
alkaline sludges, have all shown promise as neutralizing agents when codisposed with highly
acidic coal wastes in our laboratory testing. Encapsulating the wastes in cement is also effective
in preventing trace element releases. This method of contaminant release control has the poten-
tial of rendering coal wastes nonhazardous under the provisions of the Resource Conservation and
Recovery Act (RCRA). Such a possibility plus the effective attenuation of trace elements already
demonstrated in laboratory-scale  codisposal experiments make  this method  look especially
promising.
  The third environmental control strategy, collection and treatment of contaminated coal waste
discharge, is largely the  application of well-known commercial water pollution control methods.

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Of the various controls we have considered for this purpose, alkaline neutralization of these acid
drainages  appears to have the best potential  as an effective and economical method. Higher
technological methods that we have investigated, such as ion exchange and reverse osmosis, have
better potential for polishing partially purified water than as a primary treatment.
  Making a selection from among the various  control options is by no means a straightforward
matter. The applicability of any of the control strategies must be evaluated in terms of the perti-
nent tradeoffs.  For example,  coal  refuse calcining has  excellent potential for preventing the
release of trace elements from coal refuse piles and is a one-time treatment, but it is expensive.
Alkaline neutralization, on the other hand, is low in cost. However, all the effluent from a given
dump will have to be treated, and when the acid-regeneration capability of the high-sulfur waste
is considered, the acid effluent from a given refuse pile might have to be treated for upwards of a
hundred  years. Taking  several of the more  important factors into consideration, we have
generated a comparison of several of the control options in the form of the following grid. (More
comparisons are made in the main body of the report.) The options seem to  be  choices  based
primarily on economics (favoring drainage treatment) and commitment to responsibility (favor-
ing immobilization). A blend of the factors may make Category II (waste pile construction) a
favorable compromise.


             COMPARISON OF ENVIRONMENTAL CONTROL OPTIONS

                                                               Alkaline
                 Parameter       Calcining    Codisposal   neutralization
              Cost                    High       Moderate       Low
              Effectiveness            Good       Good           Good
              Complexity             High       Moderate       Moderate
              Treatment duration      Short      Short           Long
              Permanency             Good       Uncertain       Poor

  In summary, our laboratory studies that have examined in detail the sources of trace elements
in coal waste drainages, the mechanisms of their release,  and their fate upon  weathering and
leaching  have allowed us to understand the problem sufficiently well to address the key en-
vironmental control technology issues effectively. A substantial portion of our future efforts will
be directed at identifying the most promising control options, demonstrating more clearly their
utility, and analyzing the balances between their advantages and disadvantages. To broaden the
scope of our work, we will also include further studies on high-sulfur coal wastes from the Ap-
palachian region. These studies will define the potential of trace elements in these wastes to lead
to undesirable environmental impacts and will identify the control technologies appropriate to
mitigate  those of environmental concern.

                          SUMMARY OF TASK PROGRESS

  The objectives of this ongoing research program are to assess the potential for environmental
pollution from trace elements released by the drainages from coal cleaning wastes and to identify
necessary environmental control  technologies for this  type  of contamination.  This report
describes the technical accomplishments in each of the main research areas of  the program for
the period October  1, 1977  to September 30, 1978.
  The research activities in this program are broken down into major tasks and subtasks as listed
in the Task Breakdown chart.
  Task 1—Environmental Control Technology For Trace Elements in the Drainages From High-
Sulfur Coal Preparation Wastes—is divided into three subtasks. The first of these (Subtask 1.1)

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                                     TASK BREAKDOWN


                  TRACE ELEMENTS CHARACTERIZATION  AND REMOVAL/RECOVERY

                               FROM COAL AND COAL  WASTES
 ENVIRONMENTAL CONTROL TECHNOLOGY
 FOR TRACE ELEMENTS  IN THE DRAINAGE
 FROM HIGH SULFUR COAL PREPARATION
 WASTES
               TASK 1
       1.1 ASSESS TECHNOLOGY TO
           PREVENT TRACE  ELEMENT
           RELEASES FROM  NEWLY
           PRODUCED REFUSE MATERIALS
       1.2 ASSESS TECHNOLOGY TO
           CONTROL OR REDUCE TRACE
           ELiaiENT CONTAMINATION OF
           REFUSE DRAINAGE
       1.3 DEFINE OPTIONS FOR
           CONTROLLING TRACE ELEMENT
           RELEASES IN THE DRAINAGE
           FROM COAL REFUSE
                                                                   TASK 2
IDENTIFY TRACE ELEMENTS OF
ENVIRONMENTAL CONCERN  IN HIGH
SULFUR COAL PREPARATION WASTES FROM
THE APPALACHIAN REGION
      2.1 ASSESS TRACE  ELEMENT
          STRUCTURE AND MINERALOGY
          IN REPRESENTATIVE REFUSE
          SAMPLES
      2.2 DETERMINE ENVIRONMENTAL
          BEHAVIOR OF THE TRACE
          ELEMENTS IN REFUSE
          SAMPLES
ia a laboratory investigation of various options for treating coal refuse materials either at the
preparation plant or during disposal to reduce subsequent releases of harmful trace elements dur-
ing waste dump weathering and leaching. Among the potential methods that we investigated this
year are calcining and preleaching of the refuse before disposal and applying neutralizing agents,
adsorbents, and sealants to the dump itself to prevent contaminated drainage.
  One of the more promising control strategies under investigation in the program is calcining.
High-temperature heat treating of the  refuse materials is used to remove volatile, acid-forming
constituents and to chemically immobilize potentially toxic trace elements in the fused matrix of
the refuse. In these researches, we have studied the changes in both the chemical and physical
characteristics of the calcined refuse and the teachabilities of the trace elements that remain in
the calcined mass. Our research has revealed that refuse calcining is technically one of the  more
effective and permanent  means of treating  high-sulfur coal  wastes  to eliminate subsequent
releases of acidic or contaminated drainage from refuse disposal sites.
  Refuse preleaching  has  been studied to explore the feasibility of pretreating high-sulfur coal
refuse materials with  aqueous leaching agents before disposal to remove some or all of the en-
vironmentally active trace elements and acid-forming constituents. Among the leaching agents
that we investigated for this purpose were (1) water, (2) mixtures of water and oxidizing agents,
such as ferric salts and hydrogen peroxide, and (3) an oxidizing acid, nitric acid. Only the strong
oxidizing acid appears to hold promise for removing a substantial proportion of the contaminants
of concern through preleaching of the  refuse samples that we studied.

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    Several methods were considered to treat coal refuse during disposal to prevent the release of
  trace contaminants during subsequent waste dump weathering or leaching by surface or ground
  water. These included codisposal of the refuse material with neutralizing agents or trace element
  adsorbents and the application of watertight sealants to all  or parts of the waste dump mass.
  Especially promising among these techniques is the codisposal of high-sulfur refuse with lime or
  limestone to neutralize acid drainage in situ and retain aqueous contaminants within the refuse
  disposal site.
    Our research has shown that the codisposal of attenuating agents or sorbents, other than lime
  or limestone, with acidic coal refuse materials also has good potential for reducing  or abating
  trace element contamination of disposal site drainage. Many natural materials, such as certain
  types of clays and soils, and many industrial wastes, such as fly ash or alkaline sludges, have con-
  siderable capacity to attenuate contaminated refuse'drainage, and often  they are available in
  large and accessible quantities near refuse disposal sites. Some of our research  during  the year
  was directed at assessing the effectiveness of various attenuating agents for reducing the trace
  element and acid compositions of coal refuse leachates.
    Another area of control technology that we are addressing  is to seal the refuse pile, dump, or
  burial site to prevent the intrusion of air or water. The concept of sealing has  overtones in all
  aspects of coal waste (and other waste)disposal. Sealants can be used  for existing refuse piles and
  dumps and for near surface and underground burial of wastes.  A variety of sealant scenarios, with
  an emphasis on clays, soils, calcite, and various cementing agents (Portland and silicate  cements
  and polymers) as sealing agents, are being considered, and  we  have begun laboratory experi-
  ments to test some of these materials.
    The second portion of this task (Subtask 1.2) was the assessment of environmental controls to
  reduce or attenuate undesirable trace elements  in the drainages from  coal refuse dumps. Our at-
  tention in this area was given to pollution abatement techniques that have proved effective for
  treating acid mine drainage. These techniques include alkaline neutralization, ion exchange, and
  reverse osmosis. We have also initiated studies on the effectiveness of using a variety of sorbents,
  such as clays, soils, and solid coal combustion by-products, on high-sulfur coal refuse leachates.
    Alkaline neutralization was  shown to be the  most effective  and least costly of  the  refuse
  drainage  treatment options that we studied. Ion exchange and reverse osmosis both proved to be
  technically feasible methods for reducing the  contaminants in refuse drainage to acceptable
  levels; however, the necessity to further treat the solutions for acidity sharply reduces the accept-
  ability of these methods. This and the known tendency of ion exchange and reverse osmosis to
  overload or plug  when the contaminant or suspended solid contents  are high lead us to believe
  that these techniques might be most applicable as secondary treatment methods to clean up the
'  effluents  from some other primary control process.
    The last portion of this  task  (Subtask  1.3)  involves a discussion of the results and  major
  implications from the research that we have conducted thus far on control technologies  for trace
  element contamination of coal refuse drainage.  Included  in this section is a consideration of the
  relative costs, effectiveness, treatment duration, likely RCRA classification, and premanency of
  the most promising control method being studied.
    Our research this year has begun to classify the nature of the tradeoffs to be made among the
  various control options for the disposal of acidic coal refuse materials. The methods that poten-
  tially provide the most effective and permanent  means of abating trace element contamination of
  refuse drainage (notably calcining) are also the most costly and complex  methods to use. The
  control techniques that are designed to retain contaminants within the refuse disposal site, such
  as codisposal with various agents, are effective for attenuating the trace element compositions of
  refuse drainages  for at  least short durations, but some of these may lack permanence.  Accept-
  ability for nonhazardous RCRA disposal requirements is another questionable aspect.  Finally,
  the methods to treat  refuse  drainage  (alkaline neutralization and reverse osmosis) appear to be

-------
quite attractive because of their relatively low costs and effective trace element reduction. These
met hods, however, are fraught with potential problems, such as indefinite treatment duration,
possible contamination escape, and cost to meet RCRA permit and performance requirements of
a hazardous waste.
  Task 2—Identify Trace Elements of Environmental Concern in High-Sulfur Coal Preparation
Wastes From the Appalachian Region—was split into two subtasks. One (Subtask 2.1) involved
studies of the mineralogy and elemental composition of low-sulfur coal refuse samples collected
from the Appalachian area; the other (Subtask 2.2) concerned the aqueous leaching behavior of
these materials.
  The mineralogy of the low-sulfur refuse material is notably different from that of the Illinois
Basin that we studied  earlier. There is very little detectable pyrite or marcasite in the Ap-
palachian samples, whereas, these acid-forming minerals composed 20-30% of the Illinois Basin
materials.  Clay minerals and quartz represent about  60% of the detectable mineral composition
of the Appalachian samples.
  The elemental composition  of the Appalachian refuse is a reflection of its mineral  matrix.
Aluminum and silicon are by far the most abundant elements present in the refuse. From an en-
vironmental viewpoint, this low-sulfur Appalachian refuse was found to contain potentially
troublesome quantities  (>40 /ig/g of refuse) of aluminum, copper, iron, manganese, nickel, and
zinc.
  Static and dynamic leaching tests were conducted  on the Appalachian refuse material. These
studies were designed to simulate the weathering and leaching behavior of the refuse materials
and to yield data on those potentially troublesome trace elements that may be released into the
environment. An analysis of the data from the leaching experiments was made using Multimedia
Environmental Goals established by the EPA. This analysis identified aluminum, copper, iron,
manganese, nickel, and zinc as the elements of most  environmental concern in the Appalachian
refuse samples that we studied.
                         TASK PROGRESS DESCRIPTION

TASK 1-ENVIRONMENTAL CONTROL TECHNOLOGY FOR TRACE ELEMENTS IN
THE DRAINAGE FROM HIGH-SULFUR COAL PREPARATION WASTES

Subtask 1.1—Assess Technology to Prevent Trace Element Releases From Newly Produced
Refuse Materials

  The purpose of this subtask is to investigate in the laboratory the options available for treating
high-sulfur coal refuse materials, either at the preparation plant or during disposal, to prevent or
reduce subsequent releases of environmentally harmful  trace elements during waste dump
weathering and leaching. Such control technology could include chemical or physical processing
to remove the undesirable elements from the refuse; treating the refuse materials to immobilize
these elements; applying neutralizing agents, adsorbents, or sealants at the refuse dump site; and
burying, grading, and compacting the waste materials to control the flow of water and air through
refuse piles.
Calcining to Immobilize Refuse Constituents

  The possibility that the release of toxic trace elements into the environment can be controlled
by pretreatment of coal preparation wastes has been investigated experimentally. One approach

-------
that we are examining is calcining (high-temperature heat treating) of these materials to remove
volatile, acid-forming constituents and to chemically immobilize potentially toxic trace elements
in the refuse matrix. In these researches, we have studied the changes in both the chemical and
pliysical characteristics of the refuse and trace element mobilities that result from the heat treat-
ment. Our research has revealed that refuse calcining is technically one of the more effective and
permanent means of treating high-sulfur coal wastes to eventually completely eliminate subse-
quent releases of acidic or contaminated drainage from refuse disposal sites.
  Our  initial set of calcining  experiments  was performed using high-sulfur coal preparation
wastes from Illinois Basin  Plant B to determine the effects of heat treatment on the  elemental
composition of this type of refuse material. The sample was prepared by crushing the refuse to
-3/8 in. and calcining it in a quartz tube at 800 to 850°C in air  for 6 h. The calcined material,
which had partially agglomerated, was ground to -20 mesh for subsequent studies. The analysis
of the chemical and trace element composition of the calcined refuse sample showed a marked
decrease ir. the concentration of the volatile components in the refuse. Of particular interest was
the loss of sulfur that occurred as a result of the calcining. From an original concentration of 13.4
wt% sulfur in the noncalcined sample, the described sample treatment yielded a product that
contained only 0.7 wt% sulfur. Other volatile components whose concentrations were decreased
by the calcining were bromine, lead, and cadmium.  The complete elemental analyses for  the
calcined refuse sample appear in Table I.
                                        TABLE I
           EFFECT OF CALCINING ON TRACE ELEMENT RETENTION
                           FROM PLANT B COAL REFUSE
   Element    Level8     Retention (%)b
Element   Level"   Retention  (%)"
Na
Mg
Al
Si02
P
S
Cl
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
1 140
4 900
115 000
168 000
560
11 400
<100
24 500
1 900
20
5 490
120
100
190
190 000
70
110
73
                                90
                               120
                               120
                                80
                               140
                               110
                               100
                               100
                                90
                               100
                                80
                               110
                               140
                               100
                               130
Zn
Ga
As
Br
Mo
Cd
Cs
La
Ce
Eu
Yb
Lu
Hf
Ta
Pb
Th
U
300
29
110
<0.1
35
0.29
9
60
130
2
5
0.6
5
1.7
12
15
6
                          120

                           70
                          <5
                           40
                           40
                           80
                          100
                          110
                          100
                          100
                           90
                          100
                          120
                           20
                          100
                          140
 •l'".xprriini'iii:dly determined concent ration before cnlcinin;;. in purls per million.
 "Krnir ;i|i|inixiniii(ely ± .'((•% of vnlue.

-------
  Several sets of calcining and leaching experiments were conducted to determine optimal heat-
treatment conditions necessary to immobilize the potentially toxic trace elements in the refuse
matrix. These experiments were performed using high-sulfur coal preparation waste from Illinois
Basin Plant C. The waste was ground to -20 mesh and calcined in air at 600, 800, 1000, and
1200°C for 2 h.
  The effect of refuse calcining treatments on the mineral composition of the refuse is illustrated
by Table II, which delineates the changes in refuse mineralogy that occurred  at various
temperatures. The two most environmentally active species, pyrite (marcasite) and calcite, have
been transformed to high-temperature phases by 600°C. By 1000°C, even the clay minerals have
been converted to structurally indefinable aluminosilicates, and the samples have become fused
or sintered at particle surfaces. The x-ray diffraction analyses reported in Table n support the
concept that the mineralogical transformations thought to occur in coal waste burning (Table III)
have been effected  by heat treatment  in the range of 800  to 1000°C.
                                     TABLE II

             PRESENCE OF COAL REFUSE MINERALS AT VARIOUS
                           CALCINING TEMPERATURES
                                     TABLE III

              HIGH-TEMPERATURE MINERAL TRANSFORMATIONS
                         OF HIGH-SULFUR COAL REFUSE
                        Clays
Complex Aluminosilicates
                        Calcite     CaO + C02 (gas)
                        Pyrite
                          or        Fe,03 + S0a (gas)
                        Marcasite
                        Quartz     Quartz

-------
        Extensive studies of the trace element teachabilities of the calcined refuse samples have been
      conducted.* The effects of calcining temperature on leachate pH and total dissolved solids (TDS)
      content are seen in Table IV. Calcining to 600°C and higher results in leachates with elevated pH
      values. This is a consequence of the conversion of the acid-forming mineral species, pyrite and
      marcasite, to more stable oxide forms and the driving off of the sulfur. Calcining of the refuse also
      significantly reduced the general teachability of the material as evidenced by the reduced TDS
      values of the leachates.
        The success of calcining at reducing trace element releases during refuse leaching is illustrated
      by Table V, which lists trace element data from a comparison leaching test of calcined and un-
      cnlcined refuse samples. (More complete data are presented in Appendix A.) The refuse samples
      referred to in the table had been subjected to static leaching for 48 h. It is seen that the concentra-
      tions of the group of toxic elements listed are reduced in the leachates from the calcined refuse by
      as much as two orders of magnitude over the concentration in the uncalcined refuse leachates.
        Calcining acid coal refuse materials before disposal could produce  several beneficial effects.
      Foremost among these is the conversion of an active, highly  polluting waste material  into a
      chemically and geologically inert mass that can be easily and safely disposed almost anywhere
      with ordinary landfill practices. Thus, calcining presents a highly effective and permanent solu-
      tion to a most difficult waste control problem. As a corollary, the calcined refuse materials might
      be classified as  nonhazardous under the criteria developed in conjunction  with the  Resource
      Conservation and Recovery Act (RCRA). This circumvents the need to meet the cumbersome
      and costly permit and performance requirements that RCRA dictates for the disposal of hazard-
      ous wastes, a category into which most if not all untreated high-sulfur refuse materials will un-
      doubtedly fall. Lastly, there is high potential for the recovery of by-products in  connection with
      refuse  calcining  that does not exist for many other  control technology schemes.  Potentially
      recoverable products include sulfur, iron, and  aggregate materials.
        The major drawback for refuse calcining is the cost of constructing  and operating a calcining
      plant. Interestingly, most of this expense is for operation of the scrubber system that is necessary
      to remove sulfur oxide emissions from the calcining plant's gaseous effluents (see Table HI). With
      a scrubber system based on lime or mixtures of lime and limestone, calcining of high-sulfur coal

      'The calcined residues were statically leached (stirred with distilled water) for a period of 48 h using a ratio of 4 ml water
      to 1 g of calcined refuse, and pH and total dissolved solids values were determined.
                                            TABLE IV

                            EFFECT OF CALCINING TEMPERATURE
                         ON THE LEACHABILITY OF A HIGH-SULFUR
                                   COAL REFUSE MATERIAL"
                         Calcining      Sample      Leachate     Leachate
                        Temp (°C)    WtLoss(%)       pH      TDS(Wt%)


                        Uncalcined          -            2.9           1.4
                            600           23            5.9           0.2
                            800           23            6.2           0.3
                           1000           23            8.0           0.2
                           1200           23            8.0

                        "•JO-» siiinplus nl1 crushed  rel'use/100 ml H,0/-IS h.

10

-------
                                      TABLE V

                      TRACE ELEMENT LEACHABIL1TY OF A
                      HIGH-SULFUR COAL REFUSE SAMPLE
                                CALCINED AT l()00°Ca
                               Uncalcined Refuse   Calcined Refuse
                   Element          (ppm)              (ppm)


                   Al                100                   0.4
                   Fe                600                 <0.03
                   Mn                 5.8                 0.03
                   Co                  2.8               <0.01
                   Ni                  4.8                 0.01
                   Cu                  0.10                0.01
                   Zn                  2.8                 0.05
                   Cdb                68"                  0.3b

                   pH                 2.9                 8.0
                   TDS (%)            1.4                 0.2
                    •~)0-<{ .samples of crushed refuse/200 mi H,()/48 h.
                    "In purls per billion.
refuse materials may cost in the range of $3 to $5 or more per ton of cleaned coal (see Appendix B,
Table B-IV). Studies are now under way to seek methods to reduce the costs. Perhaps the most
straightforward way to reduce the cost of refuse calcining is to decrease the need to scrub sulfur
oxide from the process effluents. One way to accomplish this is through sulfur retention during
calcining by adding limestone to the refuse materials, as is practiced in the fluidized-bed com-
bustion of coal. The results from current research in this area suggest that the cost of calcining
can be reduced by one-half to two-thirds by using this sulfur retention technique.
  Other ways that the effective cost of calcining high-sulfur coal refuse  can be reduced have
already been touched upon. These include offsetting values for recovered by-products, such as
sulfur and iron, and what might best be termed as value added through the substantial savings
by not having to comply with the RCRA hazardous waste requirements. Both of these pos-
sibilities could aid substantially in decreasing the total cost of waste disposal based on a refuse
calcining concept as compared to less effective or less desirable control methods.
Refuse Preleaching to Remove Mobile Trace  Elements  or  Acid-Forming Constituents
Before Disposal

  The purpose of our research in this area was to explore the feasibility of pretreating high-sulfur
coal refuse materials with aqueous leaching agents before disposal to remove some or all of the en-
vironmentally active trace elements and acid-forming constituents. Among the leaching agents
that we investigated for this purpose were (1) water, (2) mixtures of water and oxidizing agents,
such as ferric salts and hydrogen peroxide, and (3) an oxidizing acid, nitric acid. Only the strong
oxidizing acid appears to hold promise for removing a substantial proportion of the contaminants
of concern.
                                                                                           11

-------
        Two basic types of experiments were conducted in this series. The first involved agitation of
      various aqueous agents (usually about 250 mi) with 50 g of crushed Plant B coal refuse (-20 mesh)
      at room  temperature.  The  apparatus for  this type of study normally consisted of a 500-mi
      Erlenmeyer flask equipped with an open 15-cm glass chimney or extension at the top of the flask
      to allow air to  enter yet retain the contents. The second type of preleaching experiment used
      similar ratios and  amounts of refuse and  leaching agents but  was conducted at elevated
      temperature.  The apparatus used here was a 500-m£, three-necked, round-bottomed flask equip-
      ped with a reflux condenser,  a heating mantle, and a gas delivery tube. Agitation was provided by
      a magnetic stirrer.  At the completion of the experiments, the solid and  liquid contents were
      separated by successive filtrations through Whatman Nos. 541 and 50 filter papers.
        A description of the experimental parameters maintained during  the preleaching experiments
      appears in Table VI. Note that Samples 1, 4, 6, and 8 are analytic controls used to evaluate the
      initial  compositions of various leaching  agents.
        The  elemental analyses of the various leachates resulting from the refuse leaching treatments
      appear in Table YD. In Table VEII, the experimental data are reported as the percent of each ele-
      ment that was removed from the solid refuse by the leaching treatments. (This latter representa-
      tion makes the interpretation of the experimental data somewhat easier.) In addition, the infor-
      mation in Table VIE has been arranged to reflect the effectiveness of the various leaching agents
      at removing iron (mainly as the  acid-forming  minerals, pyrite  and marcasite) from  the refuse
      samples. The interpretation of the data in Tables VII and VIE is complicated by the many
                                               TABLE VI

                        CONDITIONS OK PKKLEACU1NC EXPERIMENTS CONIH'CTKI)
                               ON A IIIGH-SULKUK COAL KEKLSE MATKKIAI.
         CTWT-9-   ml WATER
                                ml Fe**
                                               MISCELLANEOUS
                                              TIME(I)ays)   TEMP(°C)
             lc
             2
             3
             4C
             9
            10
            11
            12
            13
            14
            15
            16
            17
            18
            19

            20
            21
            22
250
250
250
250

240
227.5
212.5
212.5
162.5
250
225

237.5
240
250
           250  A
           250  A
           250  B
           250  B
           250
           250
           250
    C
    C
    C
250  C

12.5 C
12.5 C
12.5C
62.5 C
12.5C
10 ml 30% HA
10ml30%H,0,
25 ml tetrahydrofuran
25 ml absolute eihanol
25ml30%H20,
250 ml 0.1N NaOH + 1 g Na,COs
250ml0.1N NaOH + 1 g Na,CO,
+ 25ml30%H10,

10ml30%H,0,
->.V> ml IWV HNO,"
                              1
                              10

                              10

                              10

                              1
                              10
                                                  20
                                                  20

                                                  20
20
20
92
92
92
92
92
92
92
92
92

92
20
92
            •MiMipiTr > I" im'H"hiii--i'in wittiT
            »\ i- HIM-, ni.-l.ir hVjiSO.i,: It i^ n <)•_';, m,,|nr; C i> O.pjr. m
            •>.impli'- 1. l. ti. iuul S im> cnnimK
            d.\ ml h. Pi h lirr.ik jitter Si li JclHni"n
12

-------
KI.KMKNTAI. ANAI.YSKS OK I.KAOIATKS KHOM
  I'KKI.K/U HIM, OK PIJtlfT H fllAI. NKKIWK
Reaction
Tim.
Sample Ne. (P«yil
1 1
1
10
1
10
10


10 10
11
12
13
14
16
16
n
IB
19
20 1
21 1
22 2
Reaction
Temp Ft---
CO (Mole/1)'
20
20
20
20 0.01
20 0.01
20 006
20 0.05
20 0.2S
20 0.25
20 0.25
82
92 0.25
92
92 0.06
92 0.05
92 0.05
92 0.25
92
92
n o.os
20
92

Mite.
Added

_
_
_
-
_
_
-
-
-
_
HA
HA
TOP
ElOH
HA
N..CO.
N..CO. + HA
-
HA
HNO.
S.
Par
Wane pH
Prewel
S..1
Ye. 2.1
Ye. fi
,:i
Ye. .6
Ye> J
.2
Yei .1
Ye. .(I
Ye. .(>
Yd .0
Yn .H
Ye> .«
Ye. .11
Ye» .1;
Ye. .1
Yc. .H
4.1
Ye. 1.1
Ye. 2.0
Ye. CO
llullon
ameteiV
TD9
(*)

1.04
140
O/tt
1.60
2. SO
6i«
666
6.96
IJS
7.72
I.M
a.m
8.28
2.4'J
2.42
75fl
7.74
2.41
1.04
6.48

F Ma
PPM PPM
<0.2 0.7
9 1.1
If, 16
11.6 2
14 IB
l.'i IB
0.3 5
II 93
n 20
W 68
27 64
21 37
•n a
•£• 22
•ft 31
27 64
•JUBII*
•.1MW-
l.'i ZB.I
6.1 IVG
42 19 H

Al K
PPM PPM
<2 0.2
970 311
1100 ID
<3 0.4
1100 9
MOO 7
C2 0»
IOU1 17
IIUU 10
IOUO 220
2600 600
1100 240
IM» 400
I21U IfO
MCI) 22U
24011 SHO
<* 2UU
IU IM)
15.11) IHR
9UI W
mu Mm
Kiemrnl l«vel» Hrm
Ca Cr
PPM PPH
O.I <7
5H> S»
7» Km
II.H 
680 ff«l
6K> 
1 4«>
so an
670 U)1
670 IOU
760 l»n
690 7.V
SO 840
730 TfO
670 110
710 1400
490
G10
7:« 810
r£n 6.10
ffiHI I270U
oved From Waata1
Mo
PPM
<0.2
29
Xt
<0.2S
31
33
5
31
33
35
31
39
37
34
40
39
15
21
37.5
no.6
114

Ft' Co
PPM PPM

0.4 SI
0.4 88
<0.05 64

-------
                                                            TABUC VIIJ
                                     EFFECTIVENESS OK LEACHING AGENTS AT REMOVAL OK
                                             ELEMENTS FROM PLANT B COAL  REFUSE
Iron Leach
Effectiveness
Very Poor
Poor
Time (days)   Temp(°C)  Fe**'added
Fair
Excellent
     1
     1

     1
     1
     1
     1
     1
    10
    10
    10
     1
     1
     1
     1

    10
     1
     1
92
92

20
20
20
92
92
20
20
20
92
92
92
92

20
92
92

92
0.25N
0.05N
0.05N

0.01N
0.05N

0.05N

0.05N

0.25N
0.25N
0.25N
Element
Misc added
Na.CO,
Na,CO,/H,0,
H,O,
Cdiil n»l

THK-

Control


('(ml ml
EtOH
H,0,
H,0,


H,O,
HNO,
Fe
0.3
1.5
9.1
9.8
9.9
10.5
11.8
13.3
13.2
13.5
13.8
14.2
15.9
16.0
20.8
28.0
32.6
91.4
Ca
44.5
55.4
50.9
52.7
59.0
65.6
65.6
68.2
61.7
61.9
60.9
60.9
62.7
62.0
60.8
69.0
64.4
80.9
Co

-------
chemical conditions involved in the experiments. However, it is readily apparent that the most
effective preleaching agent is the strong aqueous oxidizing acid, nitric acid.
  Neither a weak base (sodium carbonate) nor water alone proved to be very effective at remov-
ing iron or most other trace elements from the refuse samples. Ferric ion, added as a leaching
agent in the form of ferric sulfate, proved to be a more effective agent for preleaching the refuse
samples. Refluxing of ferric (0.25JV) sulfate solution in the presence of crushed refuse material for
1 day (Sample No. 12) resulted in the removal of close to 30% of the total iron from the sample, as
well as considerable amounts of several other key trace elements. A review of the literature on
coal desulfurization with ferric ion' suggests that much greater pyrite (iron) removal efficiencies
can be obtained from the  refuse samples by increasing the ferric sulfate concentrations in the
leaching solutions to about IN (Table IX). Finally, by far the most effective preleaching agent for
removing iron and the several other environmentally important trace elements considered in this
investigation  was nitric acid solution (Sample No. 22). More than 90% of the total iron and about
50% or more  of the total cobalt, copper,  manganese, nickel, and zinc were removed by a 2-day
treatment of  the refuse  material with 8N nitric acid.
  Our research on preleaching of coal refuse materials to remove labile trace elements, the acid-
forming mineral constituents, or both is still at a rather early stage, and we do not yet possess suf-
ficient technical information on this potential control technology option to conduct a solid
economic assessment of it. In  a  properly designed control technology scheme in which the
leaching agent is recycled,  the use of nitric acid, for example, to preleach coal refuse could prove
to be economically viable,  especially considering the strong possibility for resource recovery of-
fered by this technique. Although more experiments are  needed before a final assessment can be
made, the usefulness of ferric ion solutions  to preleach  coal refuse materials  appears marginal
because of the relatively low extractabilities achieved for many of the elements of greatest en-
vironmental concern.
Addition of Neutralizing Agents to Discarded Refuse Materials

  Several methods are being considered to treat coal refuse during disposal to prevent the release
of trace contaminants during subsequent waste dump weathering or leaching by surface or


                                      TABLE IX

            EFFECTIVENESS  OF FERRIC SULFATE TREATMENT ON
                IRON REMOVAL FROM COAL AND COAL WASTE


                               Percentage of Iron (Pyrite) Removed
                                   Coal Waste              Coal
               Fe+++ Level (N)    0   0.05   0.25     0     0.4      O.i)
               92°C/24ha        4"    2"     18"    	
               H)0°C/6h         	    ~lc   33-43"   50-64d
               •See text for experiment description.
               "Observed value is 10% higher, but 10% is also soluble in water at
               •20°C!
               cRef. 1, p. 176.
               "Ref. l.p.67.
                                                                                            15

-------
      ground water. These include codisposal of the refuse material with neutralizing agents or trace
      element adsorbents and the application of watertight sealants to all or parts of the waste dump
      mass. Especially promising among these techniques is  the codisposal of high-sulfur refuse with
      lime or limestone to neutralize acid drainage in situ and retain aqueous contaminants within the
      refuse disposal site.
        One of the major conclusions from our earlier studies of the environmental behavior of coal
      refuse materials concerned the importance of pH in controlling trace  element releases during
      refuse leaching. In  all instances when leachate pH was maintained at or near the neutral point,
      only minimal amounts of trace elements weresolubilix.edby theleachates.Conversely, when ox-
      idative degradation of the pyritic materials in the refuse caused leachate acidities to build  up,
      substantial quantities of such environmentally troublesome elements as aluminum, cobalt, cop-
      per,  iron,  manganese,  and  nickel  were lixiviated. by the acid  leachates.''4 This marked
      dependence of trace element contamination on leachate pH suggested that a potentially fruitful
      means of preventing trace element releases from discarded refuse materials might be the addition
      of neutralizing agents to the refuse  before disposal to negate leachate acidity as soon as it is
      formed.
        Column leaching experiments that used mixtures of crushed limestone and high-sulfur refuse
      were conducted to test the effectiveness of this in situ neutralization concept and also to examine
      what effect the location of limestone application had on the results. The refuse was from Illinois
      Basin Plant B.  This refuse contains relatively large amounts of pyrite and marcasite but no
      detectable calcite. This combination represents a worst-case example of acid-forming potential,
      and in fact, our earlier studies showed that the leachates formed by passing water through a
      packed column  of this material were not  only highly acidic but were also highly contaminated
      with trace elements. Interestingly, the limestone itself contain" troublesome amounts of several
      environmentally sensitive elements  including copper,  iron,  lead, manganese, and zinc. The
      elemental  analysis of the limestone  used  is given  in Table X.
        The combinations of refuse and limestone incorporated into the leaching  studies are listed in
      Table XI. Crushed or powdered limestone was combined with the refuse or placed in the column
      in three different geometric arrangements: at the inlet (simulating a limestone layer placed on
      top of a  refuse pile),  at the outlet (simulating refuse disposed on top of a limestone layer), and
      limestone and refuse intermixed. These column leaching experiments were conducted by passing
      distilled water through the column packed with the refuse/limestone mixtures at a rate of 0.5
      mi/min. Periodically, samples of leachate  were collected at the column outlet, and pH, total dis-
      solved solids, and trace element compositions were determined. Leachate flow was interrupted
      once during several of the experiments (after a little more than 10 t had been eluted), and dry air
    . was passed through the packed columns for three weeks before recommencing leachate flow. This
      was done to explore contaminant regeneration in  the refuse/limestone mixtures.
        The overall effect of the various limestone additions to the refuse columns is illustrated by the
      behavior of the leachate pH shown in Fig. la. In general, it is seen that adding limestone to the
      acid refuse material was only partially successful in controlling leachate acidity. The pH values
      of the refuse/limestone leachates for experiments GL-14, 15, and 17 (where the limestone was in-
      termixed with the refuse or placed at the  column outlet) are  higher throughout than for refuse
      alone (GL-12). However, even in the best instance it took about 5 £ of water for 1300 g of refuse to
      reach neutrality. Placing the limestone layer on the inlet side of the  refuse column  (GL-16)
      resulted in no decrease in leachate acidity over the control system. This undoubtedly is due to the
      slow rate of dissolution of limestone in neutral solution (water).
        The effects of the various limestone additions on the TDS composition of the refuse leachates
      are depicted in Fig.  Ib. There is very little difference among the TDS values for any of the
      leachates. This most likely results from the fortuitous balancing of the constituents removed (by
      elevating the leachate pH) with those added by limestone dissolution (see Fig. la).
16

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                        TABLE X

       ANALYSES OF JEMEZ LIMESTONE USED IN
              NEUTRALIZATION CONTROL
              TECHNOLOGY EXPERIMENTS
        Element
            Level
            (Mg/g)
          Level
Element   (j/g/g)
Na
Mg
Al
SiOj
P
S
K
Ca
Sc
Cr
Mn
Fe
Cu
Zn
Ga
As
Br
                    120
                     0.34
                     0.41
                     3.4
                    220
                    <0.1
                    790
                    42
                     0.1
                    18
                    560
                     0.26
                    19
                    19
                    <0.5
                     0.6
                     0.3
  Rb
  Ag
  Cd
  Sb
  La
  Ce
  Sm
  Eu
  Yb
  Lu
  Hf
  Ta
  W
  Hg
  Pb
  Th
  U
<20
  0.3
  0.6
 <0.5
  0.4
 <0.8
 <0.2

 <0.3

 <0.2
 <0.5

  0.1
 82
 <0.2
  1.2
                         TABLE XI

   DESCRIPTION OF DYNAMIC LEACHING STUDIES OF
      HIGH-SULFUR REFUSE/LIMESTONE MIXTURES
Experiment No.  Limestone Location

    GL-12       (None-control)

    GL-14       Intermixed
    GL-15
    GL-16
    GL-17
         Layered at outlet
         Layered at inlet
         Layered at outlet
                                    Sample8
 1500 g refuse (-3/8 in.)

 1300 g refuse (-3/8 in.)
  220 g limestone (-3/8 in.)

 1300 g refuse (-3/8 in.)
  229 g limestone (-3/8 in.)

 1300 g refuse (-3/8 in.)
  221 g limestone (-3/8 in.)

 1300 g refuse (-3/8 in.)
  220 g limestone (-20 mesh)
•Illinois Basin Plant B refuse used throughout.
                                                                         17

-------
                                                                   LEGEW
                                                                 o = GL-12
                                                                    GL-14
                                                                                     (a)
                                                                                     (b)
6.0     9.0     12.0     15.0
       VOLUME  (liters)
                                                               W.O
21.0
24.C
                                           Fig. 1.
       Leachate pH and TDS versus leachate volume for column leaching study of limestone/refuse
       mixtures.
18

-------
  The trace element compositions for the leachates from the refuse/limestone mixtures were fol-
lowed throughout the experiment (Appendix C). Some elements, such as aluminum, chromium,
potassium, scandium, and vanadium, were apparently sensitive to leachate pH and, hence,
tended to precipitate from the refuse/limestone mixtures. (The exception was GL-16 where the
I>H remained low.) Other  elements, including cobalt, copper, iron (probably in ferrous slale).
manganese, and zinc were not apparently so highly pH-dependent in these mixtures; therefore,
there was little effect of the limestone addition on the leachate concentrations of these elements.
Unfortunately, most of the elements that we have identified as being of greatest environmental
concern (listed  in Ref. 3) fall into the latter category.
  In summary,  these experiments revealed that crushed limestone (-3/8 in.) is only moderately
effective in controlling the acidity of refuse leachates, largely, we believe, because of the slow rate
of dissolution of the limestone under the conditions of the experiments. During the year, we have
extended these  studies to include, as additives, more finely powdered limestone and limestone
I hut  bas been slurry-mixed with the  refuse. Both should be more effective (in a kinetic sense)
than the coarser dry-mixed limestone at controlling leachate pH and, indirectly, trace element
composition. Preliminary data from these later experiments, which will be tabulated and discus-
sed in future reports,  reveal that both the fineness of the limestone and the manner in which it is
mixed with the refuse are indeed  very important variables in determining the effectiveness of
limestone at controlling refuse leachate pH and trace  element composition.
  Our efforts involving the additions of powdered lime to high-sulfur refuse materials to control
leachate pH  and trace  element content proved to  be very fruitful. For these experiments,
powdered lime in varying amounts (3 to 50 g) was slurried in 150 mi of distilled water with 530 g
of -3/8-in., high-sulfur coal refuse from Illinois Basin Plant B. The resultant mixture was subse-
quently dried in air at50°C and recrushed to -3/8-in. particles. Four different lime concentrations
were used. The experiments are identified as  follows.

                                                Lime Level
                             Experiment No.        (wt%)

                                                     0
                                                     0.5
                                                     1.5
                                                     :j
                                                    10

  Column leaching experiments were conducted with about 500 g of each of the above samples to
determine the effects  of the lime additions. The refuse mixtures were packed into pyrex columns
40 cm long by 5 cm in diameter and subsequently were leached with distilled water at a flow rate
of 0.5 mi/min until more than 4 i of water had been passed through the refuse beds. Leachate
flow was interrupted once during the experiment at  the 4.2-.E point, and dry air was passed
through the column for 2 wk to test the acid-regeneration potential of the refuse/lime mixtures.
Tables and plots of leaching data, pH, and trace element analyses for  these experiments are com-
piled in Appendix D.
  Figure 2 shows pH and total dissolved solids  behavior as a function of lime addition. A consis-
tent pattern of the effects of the lime additions  emerges from these data. The add it ions of 0.5 and
1.5 wt% lime to  the acid refuse had only a small influence on leachate pH and trace element con-
centration because the acid neutralization provided by  these amounts of lime was overwhelmed
by the acid present in the refuse. The additions  of 3 and 10 wt% of lime, on the other hand, did in-
deed effectively counteract the acid properties of the refuse. The pH values of the leachates for
these mixtures were higher, TDS values were relatively low, and the trace element concentrations
were depressed.
CTW
CTW
CTW
CTW
CTW
'-11-1 (control)
'-11-2
'- 1 1 -:)
'-11-4
'-11-5
                                                                                            19

-------
                                                                LEGEND
                                                                "CTWT11-1
                                                                =»CTWT11-2
                                                              » = CTWT11-5
              0.0     1.0      2.0      3.0      4.0      5.0     6.0     7.0     8.0
                                    VOLUME  (liters)
                                                                                 (a)
                                                                                  (b)
                                         Fig. 2.
       Leachate pH and TDS versus leachate volume for column leaching study of lime/refuse mix-
       tures.
20

-------
  The mixture containing 3 wt% lime was especially interesting because a leachate pH of 7 was
maintained for nearly the entire duration of the continuous part of the leaching experiment (until
4.2 t  had been  passed through the column). The TDS values for this refuse/lime combination
were also very respectable (ranging downward from about 0.6 wt%), especially considering that
the dissolution of the lime itself adds substantially to the dissolved solids content of the solution.
By the end of the continuous part of the leaching experiment, concentrations of troublesome
trace elements,  especially iron and manganese, had been reduced to environmentally acceptable
levels. Regeneration of this refuse/lime mixture with air did tend to lower the leachate pH and to
elevate the trace element concentrations. However, we did not continue the study long enough
after the regeneration point to determine subsequent  behavior.
  The codisposal of alkaline agents, such as lime, with acidic coal refuse materials does appear to
be an attractive option for controlling trace element contamination of disposal area  drainages.
The technique is only moderately costly ($0.50 to $1.00 per ton of cleaned coal, see Appendix B)
and appears to  be a highly effective means of preventing the release of a contaminated drainage
from coal refuse dumps.  The technology for mixing alkaline agents with coal refuse materials
should be relatively simple and is immediately effective.
  There are also a few questionable aspects connected with the use of alkaline additives for coal
refuse materials.  One uncertainty involves the long-term effectiveness or permanency of the
method. Also, the durability and immobility of the alkaline additives over long geologic periods
must  be demonstrated. Another potential drawback of codisposing alkaline additives with high-
sulfur coal refuse materials concerns the RCRA classification of the resulting refuse/additive
mixtures. It is  not at all clear whether such a mixture would be classified as hazardous or
nonhazardous. As pointed out earlier, a hazardous RCRA designation could be quite costly for
the disposal site operator. Another somewhat negative aspect of refuse codisposal with alkaline
agents (as compared to refuse calcining, for example) is its low potential for by-product recovery.
The lack of such  potential, of course, negates the possibility of offsetting environmental costs
with recovered  product value.

Addition  of Sorbents or Attenuating Agents  to Discarded Refuse Materials

  The codisposal of attenuating agents or sorbents, other than lime or limestone, with acidic coal
refuse materials also has  great potential for reducing or abating trace element contamination of
disposal site drainage. Many natural materials, such as certain types of clays and soils, and many
industrial wastes, such as fly ash or alkaline sludges, may have considerable capacity  to at-
tenuate contaminated refuse drainage, and often these materials are available in large and acces-
sible quantities near refuse disposal sites. Some of our research during the year was directed at
assessing  the potential of various attenuating agents  for reducing the trace element and acid
compositions of coal refuse leachates  and thus at revealing the possible effectiveness of this class
of agents  as refuse dump additives.
  Our initial investigation into this area included a series of natural and man-made materials
collected from various parts of the country. In one set of experiments, acidic coal refuse leachates
were equilibrated with eleven solid sorbent materials to evaluate their trace element attenuation
capacities. The solids used were
             • CaCOj (standard)
             • Acid mine drainage treatment sludge
             • Bottom ash  from  a western power plant
             • Precipitator ash (fly ash)
             • Bottom slag from a midwestern  plant  burning  western coal
             • S03 scrubber sludge from a midwestern plant burning western coal
                                                                                            21

-------
                    • Alabama soil
                    • Illite clay
                    • Montmorillonite clay
                    • Kaolinite clay
                    • Sea sand  (two replicates).
         The experimental procedure consisted of shaking the solid with the coal refuse leachate* for
       15 h, measuring the pH, and analyzing the filtrate for trace elements. Companion experiments in
       which the solids were shaken with distilled water were carried out to evaluate the alkalinity of
       the sorbent and to determine its water soluble components. The pH values of the filtrates from
       the solid attenuating materials previously mixed with distilled water ranged from 5.8 (sea sand)
       to 11.2 (precipitator ash). The pH values of the filtrates from the refuse leachate/solid mixture
       ranged from  2.8 (sea sand) to 9.6 (precipitator ash). As a  general rule, the higher the pH,  the
       lower the trace element concentrations. Total dissolved solids are  not included in these discus-
       sions  because after equilibration,  the  soluble matter  of some sorbent  materials  artificially
       elevated the  TDS values  in the leachates.
         The results of these experiments are discussed with reference to Tables XII and XIII. Table XII
       has essentially  all the  data  pertinent to the experiments, including the liquid/solid ratios,  the
       measured pH values, and the trace element concentrations. In general,  Table XII is self  ex-
       planatory and points out the potential benefits of using some of the  coal combustion by-products
       and naturally occurring clays as a treatment for coal refuse drainages, even where the acid con-
       tent of the drainage is quite high. Table XIII lists in a more qualitative manner, the performance
       of the various sorbents with regard to leachate pH elevation and attenuation of the 13 trace ele-
       ments that we have identified as being of greatest environmental  concern in the Illinois Basin
       coal refuse effluents. We have isolated different sections in Table Xin to draw attention to some
       of the salient features.For example, because the solubilities  of Fe+3 and Al"13 are highly depend-
       ent on pl-l in acidic solutions, those sorbents that are most  effective in elevating the pH are also
       most effective in decreasing the concentrations of Fe+3 and AI+3.The results listed in Table XIII
       are quite striking and demonstrate clearly that 7 of the 11 soi-bents tested are ell et -live in control-
       ling the key leachate parameters.Cost analyses of various codisposal options, including lime and
       fly ash with and without limestone  modification,  are included in Appendix B (Table B-IV) and
       are favorable for several options.
         In another series of investigations, 14 subsurface soils from the Illinois Basin were tested to
       determine the ability of these materials to reduce the trace element and acid concentrations in
       contaminated coal refuse leachates. These soils represent a cross section of the types found in  the
       coal producing regions of the Basin. Soil properties ranged from noncalcareous to calcareous, un-
       weathered to weathered, low to high clay content, and  low to high cation-exchange capacities.
       Only one soil had appreciable organic content.
         The experimental procedure for this study involved a series of successive dilutions with each
       soil type. First, a moderately contaminated coal refuse leachate was agitated for about 16 h using
       a 5:1 leachate-.soil ratio (by weight) for each of the  noncalcareous  soils and a 10:1 leachate:soil
       ratio for the calcareous soils (see Table XIV). The latter condition was chosen because of the  ex-
       pected higher acid-attenuating capacities of the calcareous soils. (This first set of leachate/soil
       equilibrations is designated Leach Step  1 in Table XIV.) Fresh soil was  then added to  the
       filtrates from the first leach step, and the mixtures were again agitated for a 16-h period (Leach
       Step 2). This cycle of equilibration followed by fresh soil  addition was carried out as many as five
       times for some of the leachate/soil mixtures. This information, along with data on leachate  pH
       and trace elementcomposition, are shown in Table XIV. A qualitative assessment of the leachate
       attenuating capacities of each of the soil types appears in  Table  XV.

       *The coal  refuse  leachate had a pH of 2.6 and a strong yellow color, indicating that most of the Fe*1 had been converted
       to Fe*1.
22

-------
                        TABLE XII

RESULTS OK EXPERIMENTS USING ELEVEN SOHBENTS FOR pH
   CONTROL AND TRACK ELEMENT A'lTENUATION FOR AN
   ILLINOIS BASIN HIGH-SULFUR COAL REFUSE LEACHATE
                                         Element Levels Removed
Sample
0
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
24
Sorbent

AMI) Treatment
Sludge
Bottom Ash
Precipitator Ash
Illite
Montmorillonite
Kaolinite
Alabama Soil
CaCO.
Bottom Slag
SO, Scrubber
Sludi-e
Sea Sand
Sea Sand
Liquid/Sol PH
Liquid Ratio
Leachate
H,O
Leachate
H,0
Leachate
H,0
Leachate
H,0
Leachate
H.O
Leachate
H,O
Leachate
H,0
Leachate
H,O
Leachate
H,0
Leachate
H,0
Leachate
H,O
Leachale
H,0
Leachale
H.O

4
4
3
3
3
3
3
3
9
9
3
3
3
3
3
3
3
3
3
3
3
3
3
2.64
7.63
7.67
8.08
8.59
9.63
11.23
8.08
7.84
7.95
8.46
4.29
6.03
4.01
6.30
8.03
9.14
4.23
7.63
7.34
8.35
2.80
5.88
2.81
5.83
F
PPM
2.0
0.2
0.2
1.5
0.7
1.6
1.1
1.5
1.6
0.4
0.2
2.6
0.3
2.3
0.2
0.16
0.15
0.9
0.2
4.0
4.2
1.8
0.2
1.5
0.17
Na
PPM
108
82
5
150
36
163
49
145
22
770
106
6
90
5
102
11
102
2.5
125
25
95
95
Al
PPM
10
<0.5
<0.2
0.6
<0.2
<0.2
0.6
2
0.6
<0.5
7
21
13.5
0.4
10
<0.2

-------
                      TABLE XIII

  COMPARISON OK CAPABILITIES OF ELEVEN SOKBENTS TO
ELEVATE pH AND TO ATTENUATE THIRTEEN TRACE ELEMENTS IN
        ILLINOIS BASIN COAL REFUSE LEACHATES-
Sorbcnt pH
CaCO, EEE
AMD Treatment EEE
Sludge
Illite EEE
PrecipitatorAsh EEE
Montmorillonite EEE
Bottom Ash EEE
SO, Scrubber EEE
Sludge
Alabama Soil FF
Bottom Slag FF
Kaolinite FF
Sea Sand P
•EEE = > lOOx Reduction
GG = 10 to lOOx Reduction
FF = 3 to 10* Reduction
P = 0.5 to 3x Reduction
o = >2x Increase
Fe
EEE
EEE
EEE
EEE
EEE
EEE
EEE
GG
P
GG
P

Al Ni
EEE GG
EEE EEE
GG GG
GG GG
FF GG
EEE FF
EEE FF
P P
FF P
P P
P P

Mn
EEE
GG
GG
EEE
GG
P
P
o
P
o
P

Zn
EEE
GG
FF
GG
GG
GG
P
P
P
o
P

Co
GG
GG
GG
GG
GG
FF
P
P
P
P
P

Cr
P
GG
GG
0
GG
GG
FF
GG
GG
FF
P

Cu
FF
GG
GG
FF
FF
P
FF
P
P
0
o

F
GG
GG
P
P
GG
P
o
P
P
P
P

Cd Na
GG P
P P
GG P
GG P
FF o
FF P
0 P
P P
0 P
0 P
P P

K
P
P
o
P
P
P
o
P
P
P
P

Ca
P
o
o
o
FF
o
o
P
P
P
P


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                                                                                           TABLE XV

                                             HATCH  ATTENUATION OK TRACE  ELEMENTS IN  COAL  REFUSE LEACHATES  BY SOILS
                                                           Soil Parameters
Degree of Attenuation*
Soil Type
Till
Till
Till
Till
Loess
Till
Organic
Loess
Alluvium
Loess
Loess
Till
Alluvium
Loess
Soil No.
10
11
12
4
8
14
3
6
5
1
13
7
9
2
pH
8.2
8.2
8.2
8.2
8.2
8.5
8.1
8.1
8.3 '
7.6
8.0
7.9
7.7
5.6
COi(%)
15.1
13.4
9.2
8.6
8.3
7.7
6.8
5.8
1.6
0.7
0.4
0.3
0.2
0.0
CEC (meq/g)D
91
77
96
89
88
143
303
116
261
144
98
280
253
279
OM (%)c
0.4
0.9
0.2
0.9
0.3
0.2
7.3
0.4
0.7
0.3
0.2
0.3
0.6
0.5
pH Ko" Al Zn Ni Co Cr Cd Mn F Ca
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EEEE EEEE EEEE EEEE GG GG GG GG FF FF P
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EEEE EEEE EEEE EEEE GG GG GG GG FF P P
EEEE EEEE EEEE EEEE GG GG GG GG FF FF P
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-------
  The data in Table XV are ordered according to the percentage of titratable carbonate in each
soil. According to the effectiveness scheme used in the table, all of the soils with >1.6% carbonate
content are rated as fair (FF) to excellent (EEEE) in attenuating the toxic elements present in
the leachate. These results show that many alkaline soils do have a significant capacity to reduce
the trace element and acid contents of refuse drainages. This attenuating capacity appears to
function mainly on the strengths of these soils in controlling leachate acidity. The additional
question concerning whether the cation-exchange capacity (CEC) of each soil type has any major
bearing on the capacity of that soil to attenuate leachate contamination  is somewhat more dif-
ficult to answer based on the data that we have obtained thus far. It is significant, however, that
even those soils with essentially no acid-neutralizing capacity (Soils 2, 7, and 9) do attentuate
many of the leachate contaminants somewhat. This  observation lends credence to the postulate
that  both the  alkalinity  and  ion-exchange  capacity  are  important in determining  the
contaminant-attenuating properties of soils.
  Even  though  our work with soils as an environmental control medium for acidic, coal  refuse
leachates is still in its early stages, it is already apparent that soils as a group (especially alkaline,
unweathered soils) have great potential  for  this purpose because  of  their abundance  and
availability near coal refuse dumps. The results of our work this year were sufficiently encourag-
ing to suggest that a cost estimate for this form of environmental control technology be made. Us-
ing a  locally available soil with a 5 wt% titratable  alkalinity, we estimate the  cost per  ton of
cleaned coal to  permanently treat highly acidic coal refuse matter (by intermixing with the
refuse) to be in the range of $0.80 to $1.30, depending on the potential acidity of the refuse (see
Appendix B, Table B-IV). These costs would, of course, be lower if some of the more  highly
alkaline soils listed in Table XV were to be used and if the soils also had significant ion-exchange
capacity.
  Future studies in this area will be aimed at quantifying both  the total capacities and ion
specificities  of various soils during the attenuation of coal refuse leachates.  This will be done by
passing contaminated leachates through soil columns and by direct leaching  of mixtures of
various soils and acid refuse materials. The more promising control options will be scaled up to
better duplicate field  conditions.
Sealing Refuse From Air and Water

  In view of the overwhelming evidence that isolating high-sulfur coal refuse from air and water
will prevent the formation of acids and thereby the release of trace elements into the environ-
ment, one area of control technology that we are addressing is that of sealing the refuse pile,
dump, or burial site to prevent the intrusion of air or water. The concept of sealing has overtones
in all aspects of coal waste (and other waste) disposal. Sealants can be used for existing refuse
piles and dumps and for near-surface and underground burial of wastes.
   Various sealant, scenarios,  with an emphasis on clays, soils,  cnldte. and  various cementing
agents (Portland and silicate cements and polymers) as sealing agents, are being considered, and
we have begun laboratory experiments to test some of our ideas. One of the first experiments in-
volved slurrying crushed coal refuse (-3/8 in.) with 5 wt% lime in water and neutralizing the
alkaline mixture by bubbling  C02 through it until the pH was reduced to 7. This had the effect of
coating the coal waste particles in the slurry with limestone by the reaction CaO + COS = CaC08.
The effectiveness of the seal was tested by drying the particles, performing a column leaching test
on them, and measuring the pH and trace element compositions of the resulting leachates. The
results of this experiment are given in Table XVI. These data reveal that this method of coating
the refuse particles with a limestone film  was very successful in controlling both  the acid and
trace element compositions of the refuse leachates. The pH values of the emerging leachates were
maintained between 7.2 and 7.9 for the entire experiment,  and the criteria pollutants (iron and
                                                                                            27

-------
      manganese) were controlled within acceptable limits. The other elements reported in Table XVI
      are greatly reduced in concentration as compared to their levels in leachates from untreated
      refuse materials. (See control sample in Table D-II.)
        Calcium carbonate coating of acid refuse materials is a promising method for controlling con-
      tamination of aqueous drainages. In practice a local self-contained unit could be designed to use
      this principle. The needed lime could be supplied from a small kiln, and the CO, and heat for
      drying the coated particles could also be produced by the kiln. Furthermore, coal fines or mid-
      dlings from thecleaningplantcouldconceivably be used as the principal fuel for the kiln.The ad-
      vantages of this combination in savings of energy and expense could be considerable.
        In other work in the area,  we have begun to investigate the feasibility of producing a concrete-
      like aggregate from  mixtures of Portland cement and crushed acid coal refuse.  The resulting
      product should be a marked improvement over the untreated refuse aggregate, including reduced
      permeability, acid-generating  potential,  and  increased  structural  integrity.  Several small
      cylinders (3.1 cm in diameter and 2.5 cm long) were produced using various proportions of mortar
      and -20-mesh refuse. Static leaching tests of several of these cylinders with distilled water for
      periods of up to 34 days revealed that the structure of the cylinders was not appreciably degraded
      by contact with  water. Furthermore, the pH of the leachates  ranged from about 9 to 11.5, sug-
      gesting that  trace element teachability  of the refuse would be substantially reduced.
        One problem with using commercial cements to produce refuse aggregates is the high cost of
      structural-grade cement. Therefore, we will begin to explore the possibility of producing cements
                                            TABLE XVI

                 RKSULTS FROM A COLUMN  LEACHING EXPERIMENT WITH
                      CALCITE-COATED ILLINOIS BASIN COAL REFUSE

                    Sample No."      1         2         4         11         17
Vol (I)
pH
TDS (%)
F
Na
Al
K
Ca
Cr (Mg/£)
Mn
Fe
Co
Ni
Cu
Zn
Cd (ng/t)
0.100
7.4
0.84
0.3
7
<0.5
7
900
<0.5
0.7
5
0.13
0.3
0.1
0.07
2
0.201
7.2
0.63
0.4
6
<0.5
8
870
1
0.5
2
0.12
0.2
0.1
0.07
1
0.697
7.9
0.34
0.3
2.5
<0.5
4
630
<0.5
0.2
0.4
0.06
0.2
<0.1
0.03
0.4
2.309
7.7
0.27
0.3
1
<0.5
2
540
<0.5
0.1
<0.3
0.05
0.1
<0.1
0.01
0.2
3.326
7.7
0.22
0.4
1
<0.5
1
480
<0.5
0.07
<0.3
<0.05
<0.07
<0.1
<0.01
0.3
                    •Kxperimumal conditions: 500 K of calcile-coated. -.'i/S-in. coal
                    refuse material was packed into a 5-cm-diam bv 40-cm-loiif! class
                    column. Distilled water was passed upward through the column
                    at a rale of 0.5 inl/inin. Kxcept where noted, element concentra-
                    tions are
28

-------
or cementitious materials from the refuse itself. This could involve the calcining of powdered
refuse and limestone mixtures or perhaps the treatment of the refuse to produce a pozzuolanic
material.
Subtask 1.2—Assess Technology to Control or Reduce Trace Element Contamination of
Refuse Dump Drainages

  The purpose of this subtask is to identify environmental controls to reduce or attenuate un-
desirable trace elements in the acidic drainages from coal refuse dumps. Our attention in this
area has been given to pollution abatement techniques that have proved effective in treating
acidic waste waters with compositions similar to coal refuse drainage. These techniques include
alkaline neutralization, ion exchange, reverse osmosis, and permanganate oxidation. We have
also initiated studies on the effectiveness of using a variety of sorbents, such as clays, soils, and
solid coal combustion by-products, on high-sulfur coal refuse Icachales. (Tin1 latter research was
discussed above in Subtask 1.1.) In these studies we are continuing to give greatest emphasis to
the control of the dozen or so trace elements that we have identified in our previous studies as be-
ing of greatest concern in  the  drainages from Illinois Basin coal refuse.
  During the year, we were able to initiate a small number of cooperative projects with commer-
cial organizations having expertise in  water treatment. We supplied the contaminated leachates
and performed the before and after chemical analyses, and the commercial organizations treated
the supplied solutions. Of the companies contacted, General Mills Chemical, Inc. (Minneapolis,
Minnesota) agreed to treat some of  our high-sulfur refuse drainage  solution using chelating
agents; Bio-Rad Laboratories,  Inc. (Richmond, California) used ion exchange; Carus Chemical
Co. (LaSalle, Illinois) used permanganate oxidation; and UOP Fluid Systems Div. (San Diego,
California) used reverse osmosis. Diamond Shamrock Chemical Co. (Redwood City, California),
a supplier of ion-exchange  resins, expressed an interest in our program and asked to be kept cur-
rent.
Treatment of Contaminated Refuse Drainage by Alkaline Neutralization

  Alkaline neutralization is used extensively to treat acid drainage from coal mines. Although it
is well known that alkaline neutralization is very effective in controlling the acid and overall salt
compositions of mine waste waters, the degree of control that this method exerts over some of the
more  highly leachable, toxic trace elements remains to be established. Elaboration of this latter
point  is the basis for the study that we conducted in this area.
  The experiments conducted were basically titrations in which limestone, lime, or lye (NaOH)
were  added to one liter of  contaminated refuse drainage (iron mostly in ferric state) until a
predetermined pH value was reached. The solutions (or slurries) were allowed to sit overnight
and then filtered, the pH values were measured, and the compositions of the resulting solutions
were analyzed. A brief description of the experiments follows.
            • Sample 0 was the  control.
            • Sample  5 was  prepared by  titrating with slightly more than the chemical
              equivalent of powdered  limestone (31.65 g). The limestone was assumed to be
              pure CaCOj and buffering effects were neglected.
            • Sample 6 was prepared by adding limestone (175 g) to one liter of waste water un-
              til there was no further pH change.
            • Sample  2 had  an  elevated pH by adding about  0.2  g of lime to the 35 g  of
              limestone used  initially.
                                                                                            29

-------
                  • Samples 4 and 1 both were neutralized using lime. The 14.5 g of lime in No. 4
                    produced a pH of 7.3, and the 17 g of lime in  No. 1 produced a pH of 10.7.
                  • Sample 7 was neutralized with concentrated NaOH to increase pH without hav-
                    ing the attendant calcium  salt precipitation problem.
        The results from these alkaline neutralization experiments  are seen in Table XVII and show
      the  effectiveness of this technique for decreasing trace element  concentrations in coal waste
      leachates. The pH values and iron contents of the treated leachates are within acceptable limits
      based on the 1977 EPA effluent limitation guidelines for coal preparation plants (Fe < 3.5 ng/ml>
      averaged over 30 days and pH 6-9). Manganese exceeds the acceptable level of 2.5 to 3 jug/m£
      averaged over 30 days in the limestone case, however. This is due to the dissolution of manganese
      from the limestone during the neutralization of the  leachate acid.
        As were many techniques discussed in this report, alkaline neutralization was shown to be an
      effective method for reducing or abating trace element contamination of coal refuse drainage.
      The projected costs for such a treatment are relatively low ($0.10 to $0.80 per ton of cleaned coal,
      see Appendix H. Table H-IV). Also the technique is relatively easy to apply, as evidenced by the
      large number of neutralization plants already in  operation to treat acid mine drainage.
        However, in spite of the low cost and ease of application,  alkaline neutralization has some
      rather considerable disadvantages.  For example, it never really treats the source of contamina-
      tion (that is, the refuse  itself), and hence,  its use in treating the drainage from the disposal site
      may be needed almost indefinitely. Also, although the standard refuse disposal practice involves
      burying the refuse on top of impermeable liners, such as clay, to channel refuse dump drainage
      into treatment areas, there is no assurance that drainage will  not eventually escape through or
      around  these liners and  thus negate the effectiveness of this method. Another consideration that
      may make alkaline neutralization  less attractive involves the costs associated  with meeting
      RCRA requirements. Most certainly, waste materials disposed of in a way that produces con-
      taminated  drainage will be classified as  hazardous. Thus the apparent low cost of alkaline
      neutralization may have to be tempered with additional costs needed to meet RCRA permit and
      performance requirements. Finally, there is little opportunity  for by-product recovery during or
      subsequent to neutralization treatment. Thus the potential for realizing economic gain in this
      way is quite low.
        Although alkaline neutralization  as a refuse  drainage treatment technique has some rather
      severe drawbacks, it is nonetheless widely used, highly accepted, and as this program has shown,
      very effective in controlling trace element contaminants. Undoubtedly, this method will continue
      to be used  widely in the near future to treat contaminated coal refuse effluents.

      Treatment of Contaminated Refuse Drainage by Ion Exchange

        Bio-Rad Laboratories treated some of our high-sulfur refuse drainage solutions by ion exchange
      and returned them to us for analysis. The treatment consisted of flowing 250 ml/mm of leachate
      in two  equal fractions over 25 cm8 resin  beds  (1.5 x 15 cm column) at  a  flow rate  of  about
      '2 ml/min.  Four resins were used, making eight samples in all. The first fraction of the leachate
      was  sufficient to swamp the two resins that were not strongly acidic. A second fraction of the
      leachate was too much for all the resins. In the best case, nearly 100 gal. of resin were needed per
      1000 gal. of refuse drainage.
        Table X VIII provides  the catalog description of the resins used and our experiment identifica-
      tion numbers. Table XIX is a summary of the results of the ion-exchange experiments. Trace ele-
      ment analyses for 14 of the more common trace elements of environmental concern in the Illinois
      Basin are tabulated for the original leachate and for the treated solutions. It is clear from the data
      in the table that the acidic cation-exchange resins (AG-50W-X8 and AG-MP-50) depressed the
      pH of the original solution to even lower values. These, however, were most effective in reducing
      the trace element concentrations.
30

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                                          TABLE XVII

                            ANALYSES FOR THE CONTROL OF
                 REFUSE DRAINAGE BY ALKALINE  NEUTRALIZATION"
Sample No.
NEUTRALIZING
AGENT
pH
TDS(%)
Na
Mg
Al
K
Ca
Sc
Ti
V
CT(ng/l)
Mn
Fe
Co
Ni
Cu
Zn
Rb
Ag
Cd(ng/l)
Cs
La
Ce
Sm
Eu
Tb
Dy
Pb^g/4)
Th
U
NONE
(CONTROL)
1.1
0.47
2.4
22
18
2.7
170

<0.4
0.11
15
3.6
820
2.0
3.2
0.53
3.9


18






0.07
13.5


                                 LIMESTONE
                                       7.1
                                       3.14
                                       3.8
                                      66
                                      <0.2
                                       4.3
                                    7700

                                      <0.4
                                      <0.01
                                       1.0
                                       6.4
                                       0.3
                                       0.82
                                       1.00
                                       0.20
                                       0.14
                                       4.6
LIMESTONE   LIMESTONE
                 + LIME
      7.4
      3.20
      4.8
     75
     <0.2
      8.4
   9300

     <0.4
     <0.01
      0.5
      4.4
      0.3
      1.1
      1.8
      0.19
      0.15
                                                      0.4
   6.6
   3.14
   3.8
  73
 <0.2
   3.9
8200

 <0.4
 <0.01
   2
   3.3
   0.4
   0.50
   0.72
   0.22
   0.08
                    <0.2
                                      <0.01
                                                     <0.01
                    <0.01
4
LIME
6.6
3.17
3.8
60
<0.2
3.5
8200

<0.4
<0.01
16
1.0
0.3
0.58
0.69
0.21
0.10


2.4





<0.01
°

1
LIME
10.7
3.07
4.0
30
<0.2
3.3
8000

<0.4
<0.01
62
0.1
0.3
0.23
0.32
0.22
0.04


<0.2





<0.01
°

7
NaOH
5.9
3.36
9400
22
<0.2
4.6
120
<0.01
<0.4
<0.01
1.5
0.07
0.06
0.05
0.05
0.01
0.02
<0.01
<0.01
0.6
<0.04
<0.5
<0.08
<0.02
<0.01
<0.01
<0.02
<0.01
'Values in fig/ml unless otherwise stated.

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                                          TABLE XVIII
EXPERIMENT IDENTIFICATION AND CATALOG DESCRIPTION OK RESINS USED IN UIO-KAD'S
        ION-EXCHANGE EXPERIMENTS ON HIGH-SULFUR COAL REFUSE LEACHATES
   Experiment IDfl   Dose
           Resin
Mesh Size
Resin Description
         831

         832
         811          1st     AG-50VV-X8     -200 to-400

         812          2nd    AG-50W-X8
                      1st      AC-MP-50

                      2nd      AG-MI'-frt)
         841          1st      AG-50I-X8

         842         2nd      AG-50I-X8

   •Leachate CTWT-8 was used.
                       -200 to-400
 1st     Chele.x 100     -100 to-200

2nd     Chelex 100
                        -20 to-50
               A strongly acidic cation exchange
               resin composed of nuclear sulf'onic
               acid exchange groups attached to a
               styrene divinylbenzene polymer
               lattice.
               A strongly acidic, macroporous cat-
               ion-exchange resin with nuclear
               sulf'onic acid exchange groups. The
               resin has an effective surface area
               approximating 35 mVdry g or 30-
               35% porosity.
               A chelating resin that is a
               styrene divinylbenzene copolymer
               containing iminodiacetate functional
               groups, structurally classed
               with the weak acid cation exchangers
               by virtue of its carboxylic acid
               groups.
               A mixed bed resin for deinnization
               with equivalent amounts of AG-50VV-X8
               H+ formand AG-1-X8OH- form.

-------
                                       TABLE XIX

                 SUMMARY OF pH, TDS. AND TRACE ELEMENT COMPOSITIONS
                 RESULTING FROM ION-EXCHANGE TREATMENT OF A HIGH-SULFUR
                                 COAL REFUSE LEACHATE"
   pH
   TDS(%)
   Al
   Ca
   Co
   Cu
   F
   Fe
   K
   Mn
   Na
   Ni
   Ti
   Zn

   •All r
                  INITIAL
                LEACHATE
AG-50W-x8
811
       812
AG-MP-50
821     822
                              Chelex 100
AG-501-xS
                             831
                                                                  832
                                                                          841
      iMcoiitrnliiins in
                   except where
                                                    842
1.8
3.26
540
170
400
7
160
0.15

600
28
15
8
17

27
0.85
2.62
<0.5
0.9
0.4
<0.05
no
<0.02
2.8
0.2
2.3
<0.02
2.6
0.08
<0.5
0.06
1.45
3.12
26
7.8
140
8
135
0.15
4.4
7550
23
13
17
13
<0.5
28
0.88
2.52
4
0.6
0.4
0.4
270
<0.02
3.3
36


12(



.2

)

.2

2.00
3.37
430
4.2
90
10
220
0.15
5.1
8190
3.3
15
48
15
1.2
31
2.68
3.15
110
290
70
0.3
220
<0.02
2.5
4820
30
0.3
33000
0.3
<0.5
0.3
2.54
3.99
820
360
650
16
410
0.06
6.3
7550
12
21
1170
21
<0.5
65
1.94
1.74
180
115
110
5
180
0.1
3.3
3910
17
8
11
8
<0.5
14
2.37
3.33
440
330
120
9
300
0.16
5.2
7370
0.04
14
9
14
<0.5
28
  These  experiments  are  preliminary in nature and  were designed to  demonstrate the ap-
plicability of this particular water cleaning technology to the problem of undesirable trace ele-
ment contamination of high-sulfur coal preparation waste leachates. Therefore, we did not at-
tempt to complete an economic analysis of this control option. Using data from the literature, we
estimate that the cost of treating acid refuse drainage with ion exchange would be in the area of
$0.29 per ton of cleaned coal (Appendix B, Table B-IV). It is recognized that should we pursue the
ion-exchange method for acid mine drainage and refuse leachate clean-up, we should also need to
consider  (a) the effect of solution pH control on trace element removal, (b) resin type, (c) resin
capacities, (d) resin regeneration, and (e) related items, such as capital and operational costs. It
is clear, however, that ion exchange can reduce concentrations of trace elements of environmental
concern in refuse leachates to acceptable levels (note Expt No.  811 in Table XLX), though the
need to further treat these solutions for acid greatly reduces the applicability of the method. This
and the known tendency of ion-exchange to overload or plug when the contaminant or suspended
solids contents are high lead us to believe that ion exchange might be most applicable as a secon-
dary treatment method to clean up the effluents from some other control process.
Treatment of Contaminated Refuse Drainage by Reverse Osmosis

  Reverse osmosis (RO) is a technique that is used widely to desalinate seawater and other types
of contaminated drainages produced by agricultural and industrial operations. In this method, a
series of semipermeable membranes or filters are used to segregate or isolate dissolved contami-
nants from the main volume of water. Separation is achieved by forcing water that is relatively
                                                                                            33

-------
      free of contaminants through the filter while retaining the contaminants in a concentrated liquor
      on the upstream side of the filter. This produces clean or product water and contaminated or re-
      ject water. There are many variables that can affect the performance of an RO water treatment
      system, including the composition of the contaminated water, the efficiency and selectivity of the
      filter material, and the number of times the water is passed through the filter bank.
        A series of preliminary, bench-scale experiments to test the effectiveness of RO at cleaning con-
      taminated refuse water were performed for us by UOP Fluid Systems Division. In these experi-
      ments, UOP used two types of RO filters designated as Filters 1 and 2 in Table XX. Filter 1 was
      UOP's RC-100, which is a poly(ether/urea) membrane, and Filter 2 was UOP's PA-300, which is a
      poly(ether/amide) membrane.  The initial feed solution (Sample 01) of contaminated refuse
      drainage was passed through each of these RO filters. The compositions of the respective product
      or treated waters from the first pass through each of the filter units are listed under Samples 02
      and 03 in  Table XX.  These data show  that both filters were  quite effective  at reducing the
      priority trace  elements in the  refuse leachates to  acceptable levels. Filter 1 appeared to be the
      better of the  two for this purpose, but a suspected break in Filter 2 probably negated its an-
      ticipated better performance.  (Note that as was the case for the ion-exchange studies that we
      conducted,  reverse osmosis did not appreciably  affect the  pH of the refuse  leachates.)  The
      analyses for the combined reject waters from the first passes through both membranes also are
      listed in Table XX (Sample 04).
        In the next  stage of the RO experiment, the reject water (now the feed solution) was split and
      passed through each filter type. This process was continued until the reject water had been  suc-
      cessively passed through each filter five more times. The  analyses for the  now highly con-
      centrated feed solution just before the seventh pass through the filters  (Sample 19) and the
      analyses of the cleaned or product water derived by RO from  this concentrated feed (Samples 20
      and 21) are in  the last three columns of Table XX. These latter data, of course, reveal the perhaps
      marginal effectiveness of the RO method at  treating highly concentrated waste leachates.  Here
      Filter 1 (the RC-100 membrane) still reduced I he concentrations oft rare coniaiiiinanis to accept -
      able levels, whereas the iron  and manganese levels ol  the product water from treatment with
      Filter 2 exceeded presently established point source levels. The reduction of iron content during
      the  first and  seventh passes through each membrane is depicted graphically in Fig. 3.
        An important consideration in the use of RO concerns the ratio of the final reject water  that
      will still need  further treatment before final disposal and the total amount of water treated. Peak
      recovery when placing six filters in series is 80-85%. Thus 15-20% of the original  volume of
      drainage will still need to be treated. The  magnitude of water is less, but all of the contamination
      is still present and still  needs  to be treated.
        The work that we have conducted thus far shows that RO, like ion exchange, can be quite effec-
      tive under some circumstances for treating trace element contamination in coal refuse drainage.
      RO  is marginally effective for highly concentrated leachates (Table XX) and is apparently quite
      susceptible to membrane fouling by suspended particulates and solids. In addition, it is neces-
      sary to further treat the effluents from  RO to reduce the acidity to acceptable levels. These  con-
      siderations suggest that RO,  like ion exchange, may function best as a  secondary  method to
      polish off effluents from the  alkaline neutralization  of acid  refuse drainages. Data in the
      literature suggest that the cost of using RO to treat coal refuse drainage would be in the range of
      $0.20 per ton  of cleaned coal  (Appendix B,  Table B-IV).
      Permanganate Oxidation to Treat Coal Refuse Drainage

        One of the problems with direct alkaline neutralization of coal refuse drainage to control trace
      contaminants is that some elements (notably, iron and manganese) are not precipitated from
34

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                                       TABLE XX

          TRACE ELEMENT ANALYSES ON REVERSE OSMOSIS EXPERIMENTS


  Sample No.0        01          02         03        04         19          20         21
Pass thru system
Process Position
Filter Type"
Cond (^imhos)
pH
TDS (%)
Al
Ca
Cd (ng/t)
Co
Cr
Cu
F
Fe
Mn
Ni
Zn
1st
Feed
-
5 090
2.38
0.55
174
230
102
0.8
0.19
2.0
4.1
235
73.7
2.1
7.4
1"
Product
1
1 780
2.39
<0.01
<0.1
7.4
<1
<0.01
<0.001
<0.01
0.1
0.08
<0.01
<0.01
0.01
I8t
Product
2
1 140
2.61
<0.01
0.7
4.6
<1.0
<0.01
<0.001
0.01
0.1
1.64
0.32
<0.01
0.04
I8t
Reject
1+2
-
2.36
0.73
206
280
110
0.9
0.26
2.5
4.6
298
86.6
2.6
8.8
Tth
Feed
-
21 600
2.02
4.54
1 390
1 480
680
6.4
1.8
20.7
9.9
2 020
620
23.3
58.3
nth
Product
1
4 710
1.93
0.02
<0.1
3.3
<1
<0.01
0.005
<0.01
0.1
0.22
0.02
<0.01
0.02
•7th
Product
2
3 280
2.15
0.05
8.9
7.9
5
0.05
0.03
0.16
0.3
17.8
4.4
0.16
0.46
•Concentrations reported as pg/ml unless noted otherwise.
"See text.

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               10000
                tooo  -
                o.oi   -
                           FEED
FILTER-1    FILTER-2     REJECT
                                             Fig. 3.
                      Iron levels in aqueous streams of a reverse osmosis system.
     solution in their lower oxidation states by merely adjusting the pH to the neutral point. To cir-
     cumvent this problem, acid drainage treatment facilities usually precede the neutralization step
     by some type of oxidation reaction to convert such components as Fe+l and Mn+l to higher oxida-
     tion states that precipitate from solution in the range of pH 5 to 6.
       During the year, Carus Chemical Company conducted several experiments for us in which per-
     manganate was used as an oxidizing agent to maximize the valences of the components in a con-
     taminated coal refuse leachate. The intent here, of course, was to increase the effectiveness of the
     alkaline neutralization of the resulting solution. The leachate used had a very high concentration
     of iron, over 50% of which was in the Fe+a state. The product water produced by the combined ox-
     idation/neutralization process  shows clearly that this method can be quite effective at reducing
     the trace elements in a contaminated refuse drainage sample to acceptable levels. (See Table
     XXI.)
       Because of the success with  neutralization alone, we do not have further experiments planned
     in this area.
      Chelating Agents to Control Trace Elements in Coal Refuse Drainage

       General Mills Chemical, Inc. participated with us in an investigation of the use of chelating
      agents to remove heavy metal contaminants from coal refuse drainages.  Our collaborators at
36

-------
pH
TDS (%)
Al
Ca
Cd
Cr
Co
Cu
Fe
Mn
Ni
Zn
Na
K
1.8
3.25
540
170
0.4
0.16
7
0.15
6600
15
17
27
8
28
                                     TABLE XXI

         ALKALINE NEUTRALIZATION/PERMANGANATE OXIDATION OF
                    CONTAMINATED COAL REFUSE DRAINAGE
                                      Starting       Cams
                        Parameter8   Solution   Sample No. 2b
                                                      6.92
                                                      0.45
                                                    <0.1
                                                    520
                                                    <0.001
                                                      0.002
                                                    <0.01
                                                    <0.01
                                                      0.055
                                                      0.36
                                                    <0.01
                                                      0.01
                                                     11.8
                                                    860
                           •Cnnrenl rat inns reported as mf.ll.
                           "pll adjusted to 7 with Ca(OH),.
General Mills treated a contaminated refuse leachate that we sent them with several commercial
and experimental chelating agents. We have not yet received the results of these experiments
from them. However, they have reported that because of the highly acidic leachates (pH ~ 2),
none of the agents tested were effective in reducing the metals content.
  No further experiments are planned in this area.
Subtask 1.3—Define Options for Controlling Trace Element Releases in the Drainages
From Coal Refuse

  The purpose of this activity is to assess the results and major implications stemming from the
research that we have conducted thus far on environmental control technologies for trace element
contamination of coal refuse drainages. Also in this subtask we will delineate those areas where
more work needs to be done, either to complete our understanding of the various environmental
options or to solve specific control problems.  The foregoing discussions have emphasized the
technical feasibility and some advantages, disadvantages, and tradeoffs that need  to be con-
sidered when choosing among environmental  control methods for preventing or treating con-
taminated coal refuse drainage. The major issues in this regard for many of the control methods
considered in this report appear in Tables XXII and XXIII. For the most part, the comparison
grid in the executive summary condenses the information discussed in the previous sections. Ar-
ranging the information in a grid illustrates the complexity involved in choosing from among the
various control  possibilities.
                                                                                           37

-------
                                            TABLE XXII

                 MATKIX GRID SUMMARY OF ENVIRONMENTAL CONTROL
                 OPTIONS  FOR CONTAMINATED COAL REFUSE DRAINAGE
         Parameter

     Cost"

     Effectiveness*1
     Likely RCRA
     Classification
                               Lime        Fly Ash        Soil
Calcining    Preleaching   Codisposal   Codisposal   Codisposal
high

excellent
     Process complexity      high

     Treatment duration"    short

     By-product potential    high

     Permanency            excellent
very high"

good

high

short

high

good'
moderate      mod. to high   moderate0

good          good          good

low           low           low
                            short
                            none
              short
                                          none
short
                                                         none
nonhazard
     "Kauri's IVoin ii hifjh of >-S"> (197S)/lon of cleaned coal lo a low of $0.'J()/lon of cleaned coal.
     "('MM be jiisiil'ied only by development olby-product  recovery  technology.
     cSiie specific.
     "Ability lo preveiil or abate conlaininaled drainage.
     ''Shori  means days to months.
     'Must be confirmed by further experiments.
        The relative costs of the control methods under consideration vary from quite high (perhaps as
      much as $5.00 per ton of cleaned coal for refuse calcining) to fairly low ($0.20 per ton of cleaned
      coal for alkaline treatment of refuse drainage). In general, the costs tend to reflect the complexity
      of the control processes. It is noteworthy that the most costly types of controls are also potentially
      the most permanent and environmentally desirable solutions to the refuse disposal problem. As
      indicated in the tables, several of the refuse drainage control methods that we are studying have
      some potential for by-product recovery. This factor could significantly reduce the overall pollu-
      tion control cost.
        Our research suggests that each of the control techniques listed in Tables XXII and  XXin  is
      quite effective over short  periods of time.  One of the major areas that remains to be defined for
      many of the methods under consideration is the long-term effectiveness or permanency of the
      proposed solutions. Answers to this question are being sought from scale-up experiments that
      more closely simulate actual waste dump conditions than the small scale laboratory experiments
      that we have been working with.
        The last item of importance on the tables concerns the possible constraints imposed by RCRA
      on the handling and disposal of coal refuse materials. Wastes  classified as hazardous by RCRA
      will involve a maze of paperwork and conformance to regulations that will be quite expensive to
      negotiate.  This  consideration alone may represent the singlemost important cost in refuse dis-
      posal. The RCRA posture with regard to large volume wastes is still being defined; consequently
38

-------
                                     TABLE XXIII

            MATRIX GRID SUMMARY OF ENVIRONMENTAL CONTROL
            OPTIONS  FOR CONTAMINATED COAL REFUSE  DRAINAGE
                 Parameter
   Alkaline      Reverse         Ion
Neutralization   Osmosis     Exchange
             Cost8
low
             Effectiveness"         good

             Process complexity    moderate

             Treatment duration0   very long

             By-product potential   none

             Permanency           poor
             Likely RCRA
             Classification
hazardous
moderate
                 some"
                 poor
moderate
good
high
very long
good
high
very long
              some"
              poor
hazardous     hazardous
             "Himjjes from n high of >$5 (1978)/ton of cleaned coal In a low of $0.20/1 on of dimmed coal.
             "Ability to prevent or abate contaminated drainage.
             c\'i'rv lon» means indefinitely.
             "Ky-product is potable water.
we  cannot yet  identify the probable RCRA  classification  for many of the waste treatment
schemes that we are studying.
  The nature of the tradeoffs to be made among the various control options for disposal of acidic
coal refuse materials is beginning to emerge. The methods that potentially provide the most ef-
fective and permanent means of abating trace element contamination of refuse drainage (calcin-
ing and preleaching) are also the most costly and complex methods to use. The control techni-
ques that are designed to retain contaminants within the refuse disposal site, such as codisposal
with various agents, are effective for  attenuating the trace element compositions of refuse
drainages for at least short durations, but some of these may lack long-term effectiveness. Accept -
ability for  nonha/.ardous RCRA disposal requirements is  another questionable aspect. Finally,
the methods to treat refuse drainage (alkaline neutralization and reverse osmosis) appear to be
quite attractive because of  their relatively low costs and effective trace element reduction, but
these are methods fraught  with other potential problems. These include  indefinite treatment
duration, possible contaminant escape, and cost to meet RCRA permit and performance require-
ments for hazardous wastes.
  Future work in this program will provide further elucidation of the technical feasibilities and
cost/benefit tradeoffs of these and other environmental control  options for contaminated coal
refuse drainage.
                                                                                            39

-------
      TASK 2-IDENTIFY TRACE ELEMENTS OF ENVIRONMENTAL CONCERN IN HIGH-
      SULFUR COAL PREPARATION WASTES FROM THE APPALACHIAN REGION

      Sub task 2.1—Assess  Trace Element Structure and Mineralogy in Representative Refuse
      Samples

        The emphasis  of this subtask is  to determine sufficient detail about the structure and
      mineralogy of selected samples of Appalachian Region refuse (and coal) to establish an under-
      standing of the trace elements of greatest environmental concern and to aid in the selection of ap-
      propriate  environmental control for  trace element contamination of refuse dump  effluents.
      Chronologically, there are several parts to this activity: sample selection and collection; trace ele-
      ment and mineralogical characterization of the bulk refuse samples; and detailed delineation of
      the mineralogy of specific trace elements  of interest.
      Sample Collection From Homer City Coal Cleaning Plant

        We are pursuing our originally stated intent, that of trying to obtain some samples from the
      new multistream coal preparation plant at Homer City, Pennsylvania. We have received formal
      approval from the Pennsylvania Electric Company (PENNELEC) for a visit to their facility to
      collect these samples. As soon as all the necessary details can be attended to,  we will proceed.
      Meanwhile, we have been characterizing the structure and behavior of a low-sulfur coal cleaning
      plant refuse from the Appalachian Region (Plant G).
      Structural Studies of Appalachian Region Coal Refuse

        We have completed our assessment of the bulk mineralogy and trace element compositions of
      several refuse fractions from Appalachian Plant G refuse. Average mineral compositions from x-
      ray diffraction analyses of three refuse fractions, two coarse and one fine, from this plant are com-
      pared with average values from similar analyses of Illinois Basin Plant B refuse in Table XXIV.
                                         TABLE XXIV

                  MINERAL COMPOSITIONS OF COAL REFUSE SAMPLES
                                           Plant Ga         Plant B"
                          Mineral       Average Wt %    Average Wt %
                       Kaolinite                11                7
                       Illite                    19                11
                       Quartz                  22                17
                       Pyrite/Marcasite         <1                26
                       Calcite                   1                0
                       Mixed Clay               6                17
                       Gypsum                  1                1

                       "I,mv.sulfur ri'l'use.
                       "Mijili-siiH'iir ri'fuse.
40

-------
The mineralogy of the Plant G refuse is notably different from that of the Illinois Basin refuse
materials that we have been studying. There is very little detectable pyrite or marcasite in the
Plant G refuse (<1 wt%), and the clay minerals and quartz represent over 60 wt% of the refuse
composition.  Small amounts of calcite and gypsum compose the remainder of the detectable
mineral matter in the refuse. Therefore,  the acid-generating potential of the Plant G material
should be very low. An unusually large fraction of the total mineral composition of the Plant G
refuse (20 to 25 wt%) was either microcrystalline or amorphous and could not be analyzed by x-
ray diffraction methods.
  The trace element analyses for the Plant G refuse samples are now complete, and those data
are tabulated in Table XXV. Using a portion of the available analytic data, we have compared
the trace element make-up of the Plant G refuse with that from a high-sulfur (Plant B) Illinois
Basin coal refuse. This is done in Table XXVI. Here it is seen that the most notable difference is
in the iron content, with Plant G having 2% and Plant B having 11%. This, of course, is a reflec-
tion of the low, iron sulfide mineral content in this sample of Appalachian coal waste. Except for
copper, the trace  elements are also lower for the Eastern coal. The relatively higher aluminum
and silicon values in the Plant G refuse reflect the higher clay and quartz concentrations. From
an environmental viewpoint, the Plant G refuse contains potentially troublesome quantities (>50
Mg/g of refuse) of aluminum iron,  manganese, nickel,  and zinc.
  The trace element/mineral associations of the Plant G refuse will be reported  next year.
Subtask 2.2—Determine Environmental Behavior of the Trace Elements in Refuse Samples

  The activities in this subtask are an extension of the environmental weathering and leaching
studies, which we conducted previously on Illinois Basin refuse.to selected samples of refuse from
the Appalachian Region. The purpose of the research in this subtask is (1) to develop an under-
standing of the environmental behavior of the trace elements in selected Appalachian  Region
refuse (and coals) under typical waste dump or storage conditions and (2) to identify the trace
elements of greatest environmental concern in these materials. This work, as well as our previous
work  on the leachability of Illinois Basin refuse, is directed toward defining the technology needs
for controlling or preventing trace element contamination of the aqueous drainage from the thou-
sands of refuse dumps, culm banks, and coal storage piles located in the Eastern and Midwestern
United States.
Environmental Assessment of a Low-Sulfur Refuse From the Appalachian Region

  Static and dynamic leaching tests have been conducted on the Plant G refuse material. These
studies were designed to simulate the weathering and leaching behavior of the refuse materials
and to yield data on those potentially troublesome trace elements that may be released into the
environment. We have identified aluminum, iron, manganese, nickel, and zinc as residing in the
Plant G refuse in quantities >50 ^g/g of refuse and therefore likely to be released in concentra-
tions high enough to be of environmental concern.
  Static leaching tests were performed on 50-g portions (-20 mesh) of Plant G refuse derived from
the two coarse fractions. These portions were leached with 200 m£ of water in a system open to air
and at room  temperature for periods of up to 42 days. The detailed  pH and trace  element
analyses of these samples appear  in Table XXVII. Note that the pH remained fairly constant
around 4 for the first 2 wk but at 42 days it had decreased to 3. This decrease  probably occurred
by a gradual  depletion of the small amount of neutralizing capacity naturally present in the
refuse material in the form of calcite.
                                                                                           41

-------
                                                          TABLE XXV


                                       TRACE ELEMENT AND MINERAL CONTENT OK COAL
                                             WASTE FROM APPALACHIAN PLANT C
                                 SAMPLE
                                                       140
                                                                        141
(1)
IDENTITY
LOCALE
DATE OBTND
PCT H20
PCT LTA
PCT ORIGNL
SIZE, KG
CHNS ANAL
NITROGEN
SULFUR
MINERALOGY
KAOLINITE
ILLITE
QUARTZ
PYRITE
CALCITE
MIXED CLAY
GYPSUM
SAMPLE
ELEMENT
(2)
LI PPM H A
EE PPM H A
B PPM L E
F PPM R 0
NA PCT H A
KG PCT H A
AL PCT H A
SI PCT R 0
P PPM R 0
CL PPM R N
K PCT H A
CA PCT H A
SC PPM R N
TI PCT R N
V PPM R N
CR PPM H A
MN PPM H A
FE PCT H A
CO PPM R N
HI PPM L E
CU PPM II A
ZN PPM H A
GA PPM R N
GE PPM L E
AS PPM H N
RB PPM H N
Y PPM L E
ZR PPM L E
MO PPM L E
CD PPM H A
SN PPM L E
SB PPM R N
CS PPM R N
LA PPM R N
CE PPM R N
SM PPM R N
EU PPM R N
TB PPM R N
DY PPM R N
YB PPM R N
LU PPM R N
HF PPM R N
U PPM R N
W PPM R N
PB PPM H A
TH PPM R 0
U PPM R 0

GOB A CORS
PLANT G
06/23/76
4.54
84.82
100.00
59.70

.28
.60

11.18
19.03
23.87
-1.00
1.03
7.47
1.52
40
RAW BASIS

119.00
3.00
56.00
600.00
.17
.52
9.56
20.20
160.00

2.07
.12
15.80
.73

87^00
93.90
jioo
55.00
43.00
72.00
22.20
-8.00
14.20
121.00
21.00
160.00
-8.00.
.20
-8.00

2-22
58.30
74.50
6.09
1.13
.80
5.82
2.83
.59
V.K

22.00
15.60
5.32
                                                                                          42
                      FN  GOb
                     PLANT  G
                 06/23/76
                      20.14
                      73.35
                     100.00
                      42.60
                        .16
                        .66
                      11.16
                      19.46
                      21.31
                      -1.00
                       1.92
                       6.29
                        .76
                                                                                          12

                                                                                     RAW'BASIS"

                                                                                        1 14.00
                                                                                          1.80
                                                                                         52.00
                                                                                        550.00
                                                                                           .12
                                                                                           .
                                                                                         20.10
                                                                                        150.00
                                                                   GOB B CORS
                                                                      PLANT G
                                                                   06/23/76
                                                                        U.60
                                                                       81.52
                                                                      100.00
                                                                       60.80
                                                                          .12
                                                                          .61
                                                                        11.31
                                                                        19.61
                                                                        19.76
                                                                        -1.00
                                                                          .19
                                                                        3.1§
                                                                        1.58
     41

RAW'BASIS*

   132.00
     2.60
    S6.00
   560.00
       . 11
       .57
     9.25
    20.45
   150.00

     2.05


       !67
   116.00
   104.00
    96.75
     2.05
    11.00
    46.00
    53.00
    69.00

    -8! 60
    20.30
   131.00
    19.00
   130.00
    -8.00
       .40
    -8.00
     2.95
     9.58
    52.40
    85.80
     5.50
     1.50
     1.56
     5.68
     2.46
       .56
     4.82
     1.14

    20:00
    15.80
     4.40
                                 •I'l.l'S OH MINI'S INDICATES VALUE GREATER OR LESS THAN THAT lilVKX. NTMHKHS li oil I.AHCKK

                                 AKK MKSH SIZES. OTHERS ARE IN INCHES.

                                 •I.K1TKKS INDICATE HOW SAMPLE WAS PREPARED AND ANAI.W.KD
                                   It-liAW SAMI'LK
                                   I.= I.OU TKMPKHATl'HE ASH
                                   H-HICII TEMPERATURE ASH
                                   N-NKl I'KON ACTIVATION ANALYSES
                                   A-ATOMIC ABSOKITION
                                   K- EMISSION SPKCTHOSCOPV
                                   0-OTHEK
                                                                                           .
                                                                                         17.00
                                                                                         -6.00
42

-------
                   TABLE XXVI

       TRACE ELEMENT COMPOSITIONS OF
              COAL REFUSE SAMPLES
                      Average   Average
           Element8   Plant Gb  Plant Bc
                                   5.1
                                   13.6
                                  144
                                   11
                                   30
                                   71
                                   35.4
                                  149
                                   94
Al (%)
Si (%)
Mn
Fe (%)
Co
Ni
Cu
Zn
As
9.2
20.2
97 '
2.0
12
49
48
69
17.7
           •Compositions reported as
           "l/iw-sulfur refuse.
           "Hijih-sullur refuse.
                                unless otherwise noted.
                   TABLE XXVII

        STATIC LEACHING OF LOW-SULFUR
          APPALACHIAN PLANT G WASTE
Sample No."
Time (Days)     0.01     1
                                      16
42
pH
TDS (%)
F
Na
Mg
Al
K
Ca
C.r( j/K/mtf)
Mn
Fe
Co
Ni
Cu
Zn
CdUK/mg)
3.9
0.10
1.4
18
240
29
90
580
49
6
15
1.5
3
3
4
30
4.3
0.13
2.0
20
250
25
130
810
7
7
16
1.5
4
1
5
31
4.3
0.09
2.3
29
270
28
135
850
9
8
16
2
4
1
6
27
4.1
0.10
2.6
25
260
40
170
840
7
8
11
2
5
2
7
46
3.0"
0.23"
3.1
29
320
280
165
960
300
12
31
3
6
6
15
25
•Viiliii's in
"Sw lext.
          . nf wnsle unless noted otherwise.
                                                                   43

-------
  Column leaching studies were also done on Plant G refuse, in which 500 g of material (-3/8 in.)
was packed into glass columns 5 cm in diameter by 40 cm long. Distilled water at a flow rate of 0.5
ml/mm was passed upward through the columns. For two samples (GL-23 and  GL-24), the flow
of water was stopped after approximately 3 liters had passed through, and the columns were al-
lowed to dry out. Intermittently, these aired columns were moistened during a 2-wk period to
simulate the wet and dry periods encountered by a refuse pile. At the end of the 2-wk period,
water flow was resumed as before until a total leach volume of 10 i had passed through the
column. The behavior of the material as reflected by the pH and the TDS values as a function of
water volume passed through the column is shown in Fig. 4. At no time did the pH reach the low
levels of the high-sulfur Illinois Basin refuse, but there was much more acid-generating capability
in the Plant G refuse than might have been anticipated from the low pyrite/marcasite content of
the material. It is possible that pyrite in an amorphous, subcrystalline form not detectable by x-
ray diffraction analysis is an active generator of acid. Perhaps a clearer understanding of the
acid-generating capacity  of this  refuse will come about as we continue  our  studies of trace
element/mineral associations.
  In an effort to assess which elements present in the Appalachian Plant G refuse are of en-
vironmental concern, an analysis of the data from the leaching experiments was made according
to the procedure described in Ref. 5. Using the (MATE) criteria established by  the EPA and in-
cluding a dilution factor (lOOX)indicative of the natural dilution of process effluents by surface or
ground waters, we determined an  adjusted MATE value. That value for  each element  was
divided into the leachate concentration of that element to ascertain the relative environmental
hazard of that refuse constituent. For this purpose elemental concentrations were chosen when
100 m£of water had passed through 500 g of waste. When a hazard factor is near or greater than 1,
the potential of an element to cause an environmental problem is signaled. Table XXVIII in-
dicates that the elements aluminum, copper, iron, manganese, nickel,  and zinc  are  of en-
vironmental concern in the Plant G coal refuse.
  Further evaluation of the environmental behavior of Plant G refuse will be included in future
reports on this project.


                                    PERSONNEL

  A large number of LASL personnel besides the authors participated in the programmatic effort
during the year. Their work  and contributions are gratefully acknowledged.
          Administrative Advisors: R. D.  Baker, R. J. Bard, and R. C. Feber
          Analytic Advisors: G. R. Waterbury and  M. E. Bunker
          Neutron-Activation Analyses: W. K. Hensley  and M. E. Hunker
          Atomic Absorption Spectrophotometry and Wet Chemisty: E. J. Cokal, L. E. Thorn,
            and W. H. Ashley
          Spectrochemical Analysis: 0. R. Simi, J. V. Pena, and D. W. Steinhaus
          Electron and Ion Microprobe: W. F.Zelezny,  N.  E.  Elliot,  W.  B.  Hulrhinson,
            W. 0. Wallace, R. Raymond,  and R. C. Gooley
          X-Ray Diffraction  Analyses: R. B. Roof
          Optical and SEM  Microscopy: R. D. Reiswig and L. S. Levinson
          Statistical Evaluation: R. J. Beckman

-------
   a
   if)
   (N
   s
   r^
   cp
      ii
>5      30
                             4-5      60      75
                             VOLIM!  (Liters)
                                                           LEGEND
                                                        o = GL-23
                                                        o = a-24
                                                        * = GL-25
                                                        o = a-26
                                                                          (a)
                                                                          (b)
120
                                 Fig. 4.
Leachate pH and TDS versus volume for column leaching study of Plant G refuse.
                                                                                45

-------
                                   TABLE XXVIII

                         MEG/MATE ANALYSES OF PLANT G
                              COAL REFUSE LEACHATE


ELEMENT
Ni
Fe
Mn
Cu
Al
Zn
Cd
Ca
Co
Mg
K
Cr
F
Na

LEACHATE8
LEVEL, PPM
3.8
50
10
4.8
90
7.2
0.033
320
1.9
250
26
0.12
1.4
16
PLANT G
ADJUSTED MATE"
VALUE, PPM
1
25
10
5
100
10
0.1
1 600
25
8 700
2 300
25
380
80 000

HAZARD
FACTOR0
4
2
1
1
0.9
0.7
0.3
0.2
0.07
0.02
0.01
0.004
0.003
0.0002
                  "Column leach; 100-ml aliquot; 500 g of refuse.
                  "lOOx MATE value for liquids.
                  cLeachate value/adjusted MATE value.
                                    APPENDIX A

                COLUMN LEACHING STUDIES OF CALCINED REFUSE


                                     TABLE A-I

              EXPERIMENT IDENTIFICATION FOR DYNAMIC LEACHING
                           STUDIES OF CALCINED REFUSE
                                                   Sample Size
                      Experiment No.     Sample"        (kg)

                          GL-12         Control         1.5
                          GL-18      Calcined refuse      1.5
                      •Minus 3/8 in. Plant B refuse used.
46

-------
                                        TABLE A-H

                           ANALYSES FOR DYNAMIC LEACHING
                               STUDIES OF CALCINED REFUSE
                                     Experiment No. GL-12

                                                   Sample No.
Parameter*
Vol (/)
pH
TDS(%)
Na
Mg
Al
K
Ca
Sc
Ti
V
CrOig/i)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Mo
Ag
CdOig//)
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
\V
Pb(ng/i)
Th
U
1
0.040
1.3
8.63
25
500
1600
51
530
3.0
<0.4
1.44
790
130
15000
36
51
10
76
<0.2
7.9
<0.04
<2
<5
<0.01
430
<0.04
1.3
5.3
0.83
0.35
0.47
0.14
0.25
0.05
<0.02
<0.05
0.04
1100
1.7
0.46
3
0.580
1.6
3.13
8
170
520
11
440
0.78
<0.4
0.71
420
19
5300
13
19
1.5
38
<0.2
1.3

<2
<4
<0.01
130
<0.04
0.60
1.4
0.34
0.11
0.02
0.08
0.11
0.02
<0.02
<0.05
<0.04
210
0.34
0.31
4
1.290
2.1
1.02
4
43
130
13
260
0.14
<0.4
0.42
85
8
1700
4
8
<0.9
13
<0.2
0.58
<0.04
<2
<9
<0.01
85
<0.04
0.26
0.53
0.12
0.03
<0.1
0.03
<0.03
<0.01
<0.02
<0.05
<0.04
60
0.04
0.19
7
2.365
2.2
0.55
3
29
61
6
210
0.03
<0.4
0.21
38
3
930
3
3
<0.06
6
<0.2
0.65
<0.04
<2
<1
<0.01
35
<0.04
<0.5
0.44
0.06
0.02
<0.1
0.43
<0.03
<0.01
<0.02
<0.05
<0.04
45
<0.02
0.01
8
3.345
2.5
0.08
1
7
7
4
52
<0.01
0.16
0.04
<4
0.7
200
0.4
0.7
<0.07
1
<0.2
0.08
<0.04
<2
<1
<0.01
4
<0.04
<0.5
0.09
<0.02
<0.01
<0.1
0.04
<0.03
<0.01
<0.02
<0.05
<0.04
12
<0.02
<0.01
10
4. 175*
2.6
0.11
1
28
4
3
47
<0.01
<0.4
0.04
<5
0.5
170
0.2
0.5
<0.09 -
1
<.2
0.07
<0.04
<2
<1
<0.01
19
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
0.02
<0.03
<0.01
<0.02
<0.05
<0.04
51
<0.02
<0.01
18
7.735
1.7
3.87
3
56
450
4
230
0.77
<0.4
0.38
260
7
7600
4
7
4
11
<0.2
2.8
<0.04
<2
<1
<0.01
41
<0.04
0.2
1.1
0.19
0.08
<0.1
0.12
<0.03
0.02
<0.02
<0.05
<0.04
110
0.43
0.14
20
8.290
1.8
1.87
1
30
230
5
140
0.31
<0.4
0.16
160
4
3300
2
5
1
6
<0.2
0.56
<0.04
<2
<1
<0.01
30
<0.04
0'2
1.0
0.14
0.04
<0.1
0.03
<0.03
0.01
<0.02
<0.05
<0.04
30
0.15
0.06
23
9.855
2.2
0.33
0.9
4
22
4
35
0.01
<0.4
0.07
13
0.9
650
0.4
0.9
<0.09
1
<0.2
0.1
<0.04
<2
<1
<0.01
22
<0.04
<0.5
0.2
<0.02
<0.01
<0.1
0.01
<0.03

-------
                                                     TABLE A-II1

                                        ANALYSES  FOR DYNAMIC LEACHING
                                           STUDIES OF CALCINED REFUSE

                                                  Experiment No. GL-18

                                 Level in                             Sample No.
Parameter*
Volt/)
pH
TDS(%)
Na
Mg
Al
SiO,
P
K
Ca
Sc
Ti
V
CrUg/J)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Mo
Ag
Cd^g/J)
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
\V
PbOig//)
Th
U
Material0
(ppm)



1140.
4900.
115000.
168000.
560.
24500.
3200.
29.3
5490.
118.
100000.
191.
190000.
69.9

73.
296.
28.6
108.
<0.1
371.

<0.1
290.
15.8
98.6
229.
29.6
3.21


8.68
1.11
8.48
1.66
8.15
12000.
25.4
9.55
1
0.060
3.9
1.91
350.
940.
170.


2300.
590.
0.08
<0.4
0.17
55.
75.
680.
7.
7.
<0.08
10.
<0.2
0.13
0.1
3.57
<1.
<0.01
7.
0.09
1.92
2.35
0.66
0.19
<0.1
0.40
0.13
0.02
<0.02
<0.05
<0.04
10.
<0.02
0.64
2
0.155
3.8
1.48
260.
710.
85.


1600.
610.
0.03
<0.4
0.09
14.
61.
610.
5.
5.
<0.08
4.
<0.2
0.08
<0.04
2.11
<1.
<0.01
0.5
0.04
0.87
1.57
0.30
0.14
<0.1
0.31
0.06
0.02
<0.02
<0.05
<0.04
14.
<0.02
0.27
3
0.765
4.1
0.57
67.
1780.
3.


710.
690.
<0.01
<0.4
<0.0l
2.
16.
180.
0.5
0.6
<0.02
0.2
<0.2
<0.02
<0.04
<2.
<0.2
<0.01
0.9
<0.04
0.14
0.39
<0.02
0.02
<0.1
0.05
<0.03
<0.0l
<0.02
<0.05
<0.04
<5.
<0.02
0.01
6
2.795
5.7
0.03
2.
4.
<0.1


13.
45.
<0.01
<0.4
<0.01
<1.
0.3
3.
<0.02
<0.05
<0.02
<0.01
<0.2
<0.02
<0.04
<2.
<0.2
<0.01
0.04
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<5.
<0.02
<0.01
19
13.740
4.9
0.06
7.
8.
<0.8


33.
58.
<0.01
<0.4
<0.01
<8.
2.
25.
0.8
1.7
<0.17
3.
<0.2
<0.02
<0.04
<2.
<1.
<0.01
3.
<0.04
<0.5
0.85
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<42.
<0.02
0.01
26
18.630
5.7
0.01
1.
0.5
<0.1


2.
3.
<0.01
<0.4
<0.01
<3.
0.1
2.
<0.05
<0.1
<0.05
0.1
<0.2
0.03
<0.04
<2.
<1.
<0.01
<0.05
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<13.
<0.02
<0.01
                   "Values in n$Jmt unless otherwise stated.
                   "\Vaier How was stopped at 4.01. air was passed through the column Tor 4 wit. then water flow was resumed.
48

-------
1.°.
                                          LEGEND
                                          = CL - IB
                                          = GL-12
               2.50   3.75   5.00   6.25    7.50
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                                                       Fig.  A-l.
       The pH,  TDS, and trace element concentrations for dynamic leaching experiments with
       calcined refuse.
                                                                                                                         49

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50

-------
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a
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                   2.50    1.75    5.00    6.25    7.50     B.75    10.01
                          VOLUME  (liters)
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                                                       VOLUME  (liters)
9-

a
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                                                       VOLUME  (liters)
                                                               Fig. A-l.  (cont)
                                                                                                                                                     51

-------
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                    2.50    3.75    5.00   6.25    7.50
                           VOLUME  (liters)
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52

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-------
                                   APPENDIX B

   PRELIMINARY COST COMPARISONS FOR SELECTED ENVIRONMENTAL
     CONTROL OPTIONS FOR CONTAMINATED COAL REFUSE DRAINAGE
                                 INTRODUCTION

  Our assessment of environmental control technology for Illinois Basin coal cleaning wastes has
proceeded to the point where a preliminary cost comparison of various pollution-abatement alter-
natives is in order. Cost data on many of the options are scattered throughout the literature, but
they lack a consistent time base (constant-dollar figures) and the vital relationship between solid
waste composition and pollutant concentration in the leachate. This latter information  is
available in our  FY 1977 Annual Report8  and provides the link for an across-the-board com-
parison.
                                    BASE CASE

  To provide a consistent basis for comparison, which could be related to existing data, three
hypothetical coal cleaning plants were postulated. For purposes of comparison, all were assumed
to have the same production capacity, ratio of waste to cleaned coal, landfill disposal area, and
annual rainfall. Also, the active life of the waste disposal site was considered to be the same. To
take advantage of published data on costs of landfill disposal, values for these parameters, other
than rainfall,  were  selected  from the National Academy  of Science/National Academy of
Engineers (NAS/NAE) Mine Waste Disposal Report (Ref. 6, pp. 78-79). They were
            • production—2 070 00 tons/yr cleaned coal,
            • solid  waste sent to disposal pile—621 000 tons/yr,
            • disposal area—250 acres, and
            • active life of disposal area—20 yr.
An average annual rainfall of 35 in./yr was arbitrarily selected. The time base was selected as
March 31, 1978, the latest date for which engineering cost indexes were available.1
                              GENERAL GUIDELINES

  Costs for complete process operations must be based on a knowledge of the size and design of
equipment, labor requirements, electric  power needs, cost  of  consumable materials,  and
material-handling requirements. The amount of information accessible for each of the seven en-
vironmental control processes considered here varied a great deal in relevance and detail. In some
instances, a so-called conceptual engineering design was required. In others, proportioning of
capacities, updating of the costs, or both was all that Was required or feasible. These variations
are explained under the heading for  each process.
  These guidelines were followed consistently.
  (1) A capital recovery factor of 0.2588 was used to convert capital costs to an annualized basis.
     This is consistent with the NAS/NAE report (Ref. 6, p. 139) and takes into account a  10%
     depletion allowance  and normal straight-line, 10-yr depreciation, but no investment tax
     credit. If anything, it overstates the annualized capital charges.
  (2) The above annualized capital charges were lumped together with all other annual charges
     to calculate $/ton  of coal and for discounting  in calculating present value  data.
                                                                                         55

-------
      (3) All discounted cash flow computations, sinking-fund computations, etc. were performed us-
         ing  standard tables for 10% discrete compound interest and the appropriate time span
         (usually 20 years).8
      (4) A delivered  cost of lime of $45.00/ton was used uniformly in all calculations. The price of
         lime is a widely varying quantity, presently ranging from $32 to $42/ton in bulk quantities,
         FOB.' Transportation charges vary also, but the $45/ton price is an average for hauling and
         unloading over a distance of some 50 to 60 miles.
      (5) For all pretreatment and pile treatment options a net weight fraction (nwf)  of FeS, was
         calculated from  the following relationship."

         [(Pyrite wf +  Marcasite wf)/119.9 - 5X (Calcite wf/100)]X 119.9 =  nwf FeS2.      (B-l)

         The waste from hypothetical Plants A, B, and C, corresponding to Illinois Basin Plants A,
         B, and C, had the following net weight fractions of FeS8: 0.184, 0.260, and 0.294, respective-
         ly. Lime requirements were calculated by multiplying the above figures by 0.937; this
         yielded tons of lime required for complete neutralization of the acid generated by these sul-
         fides in one ton of waste.
                   DATA SOURCES AND COMPUTATIONAL PROCEDURES
      Alkaline Neutralization of Coal Refuse Drainage and Clarification of Effluent

        Lime neutralization cost data for acid drainages appear in various prior reports, one of which is
      the Brown's Creek, Lost Creek Pollution Abatement Study (Ref. 10, p. 83).  However, the infor-
      mation is insufficient to permit wide variation in the parameters of effluent flow and iron con-
      centration in determining plant capital and operating costs. Therefore a plant design based on a
      reactor-clarifer (Ref. 11, pp. 19-51), which returns the slurry precipitate to  the active pile, was
      evaluated. Cost was estimated from the clarifier settling area and 1955 standard cost data (Ref.
      12,  p. 69) that was updated according to  standard proportioning procedures.*
        Because  it  was thought desirable to  evaluate a wide  variety of input  data  and system
      parameters, a  computer program was prepared to determine the size and cost of a neutralizer-
      clarifier for a variety of leaching conditions from piles of coal cleaning wastes. All costs above the
      base landfill disposal case are calculated, with the exception of costs for retaining, impounding,
      and channeling the pile effluent from rainwater  percolation. These must be considered in any
      posttreatment process but are very site specific so that no realistic "average  figure" seems credi-
      ble. The following paragraphs serve as documentation for the computer program called LAND-
      FIL (listed in Appendix E), as well as detailing design and cost calculation methods and assump-
      tions for the lime neutralization posttreatment.
        Input data to the computer program are (1) parts per million of Fe+> and Fe+> in the effluent;
      (2) annual rainfall in the area of the pile, in inches; (3) area of the active pile, in acres; and (4)
      fraction of rainfall absorbed by the pile.  This last figure was  assumed to be 0.9999 for an un-
      covered pile and 0.3333 for a soil-covered, grassed-over pile.
        Lime requirement was calculated from stoichiometry assuming 1.5 moles of acid generated per
      mole of iron in the effluent. This is a reasonable average figure according to the literature (Ref.
      14, p. 5). However, the calculation was made more conservative (that is, inclined in the direction
      'The standard proportioning procedure was to multiply the standard cost by the ratio (March 1978 value):(year of com-
      putation value) of the appropriate category in the Chemical  Engineering Plant Cost Index or the Marshall & Swift
      Equipment Cost Index.'-"
56

-------
of higher lime use) by using Ca(OH)s for the weight of lime in the neutralization reaction. The re-
sulting figure of 1.2406 X 10"4 pounds of lime per cubic foot of effluent per ppm of iron was used in
the calculation of lime demand for each set of initial conditions.
  Clarifier area  was calculated from  the Coe and Clevenger formula" using the largest area
calculated from settling-rate data. The  solids were assumed to settle to 12% of the original
volume before being removed  as  underflow from the clarifier. The rationale and method of
calculation are explained in detail in Ref. 15. Total dissolved solids were assumed to be eight
times the iron concentration and to this was added the lime requirement for calculation of solids
in clarifier underflow. The cost of the clarifier was determined by linearizing the two major por-
tions of the standard cost curve (Ref. 12, p. 69). This approximation is reasonably good in the
ranges 100-1000 sq ft and 1000-8000 sq ft of clarifier surface. For output in excess of 8000 sq ft the
calculated cost is clearly too low, especially because more than one clarifier would be needed in
such high ranges. However, in the  worst case of active pile application studied, the requirement
of 8000 sq ft was not reached until after seven years had passed so that discounting the future cost
of additional clarifiers tends to offset the low-cost prediction.
  Clarifier underflow is returned to the active pile by a pipeline assumed to be 1500 ft in length
with an effective hydraulic  head of 250  psi. The computer program sizes the pipe and pump
depending on flow volume and calculates the cost of pipe, pump, and the pumping energy ac-
cording to standard formulas using a maximum velocity of 1 ft/s* (see Ref. 11, pp.  6-45 and Ref.
16,  pp. 92 and 177).
  Operating costs consisted of labor costs plus power costs. Power was calculated for the clarifier
and the slurry pump. Labor was estimated at $40.00/day for a part-time operator/maintenance
man;  this estimate  may  be  too low.
  Output of program LANDFIL provides information on  the calculated  lime requirement in
tons/day,  clarifier area in sq ft, annualized capital cost in dollars, and annual operating cost (ex-
clusive of lime) in dollars. As previously mentioned, the output also included annual cost of lime.
The program was run for each of the 20 yr for  each of the three hypothetical  plants,  using
laboratory data on ppm of iron versus the total water-to-waste ratio as input. For year one, a 12.5-
acre uncovered pile is assumed. For years  2-20, covered piles increasing by 12.5 acres per year are
calculated and first year lime costs are added because there is always 12.5 acres of open pile being
worked. This provides a precise lime cost and slightly understates the annual operating cost.
Average figures for each  of the four 5-yr periods were calculated. Finally, a sinking-fund pay-
ment, applied to each year of operation,  was calculated from the average cost for the last 5 yr
(highest  average annual costs). The sinking fund was calculated at a 10% rate of  return to
provide the necessary trust fund corpus at the end of the 20-yr active live. Annualized  total cost
and cost per ton of  cleaned coal were obtained by summing annualized capital  cost, annual
operating cost,  annual lime cost, and annual  sinking-fund payments.
Ion Exchange and Reverse Osmosis Costs to Treat Refuse Drainage

  Time did not permit careful cost analysis of more expensive reverse osmosis and ion-exchange
posttreatment options. However, Source 62062 in the Brown's Creek and Lost Creek study (see
Ref. 11, pp. 83-87) was found to be roughly comparable to Plant C in effluent composition,
though differing in flow volume. For a preliminary comparison of costs, it was deemed sufficient
to use the ratios of costs derived from the earlier study. The cost estimates for these two processes
should be considered only as very crude approximations.

'Through errors, the velocity and cost were calculated for different wall thicknesses of pipe. Velocity was calculated for
thin-wall 5s-pipe, and cost was calculated for the thicker wall 40 st-pipe corresponding to the assumed pressure. In some
instances this may result in a pumping energy cost that is  5 to 10% too low. This cost is only a small proportion of the
total cost however.
                                                                                              57

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     Codisposal of Lime and Coal Refuse

       Costs for directly adding 25 and 50% of stoichiometric amounts of lime needed if all the pyrite
     -was converted to acid were calculated on delivered lime cost only. Because of its fine particle size,
     it was assumed that the lime would not add appreciably to the bulk of the pile but would fill the
     voids between the waste material. Only a negligible amount  of energy and labor above that
     already devoted to pile construction would seem to be required.  There is good theoretical reason,
     based on the comparatively small exposed surface of pyrites in coal  waste piles, to believe that
     even less lime may serve to deactivate or neutralize the  acid-leaching processes.
     Codisposal of Fly Ash and Coal Refuse

       Capp and Adams have reported successful attempts to reclaim the surface of spoil banks and
     coal waste piles for vegetative propagation by large additions of alkaline, power-plant fly ash."
     The amount varied with conditions of the waste and overburden, but the authors stated that the
     fly ash they used had about one-twelfth the neutralizing capacity of limestone. This unmodified
     fly  ash therefore had  one-eighteenth the neutralizing capacity of lime.  We also  considered
     limestone-modified fly ash, which was assumed to have one-twelfth the neutralizing power of
     lime.
       Two scenarios for fly ash use were considered. In the first, the power plant was located 15 road
     miles from the coal cleaning plant; in the other it was within 1500 ft of refuse landfill. In both
     scenarios, it was assumed that no market existed for the fly ash. It was assumed that (based on
     the base-case costs) the cost to the power plant for disposal to landfill was $1.50/ton of fly ash.
     Truck loading charges  were set at $2.00/ton for the first scenario. To this was added a hauling
     charge of $1.80/ton,  an unloading  charge of $0.50/ton, and an additional operating cost of
     $0.50/ton; a total  of $4.80/ton of fly ash added to the pile for the first scenario. For the second
     scenario, it was assumed that the power plant would deliver the fly ash with its own conveyer
     system to the landfill area, without charge. The only charge would be $0.50/ton of fly ash for ad-
     ditional operating expense at the landfill. This results from the very large additional volume of
     material that must be distributed and compacted. More machines, fuel, and labor are necessarily
     required for any of the  fly-ash scenarios than for straight wastefill. Calculations of the cost were
     made only for one level of addition, namely, fly ash equivalent in neutralizing power to direct ad-
     dition to the pile of 25% of the  theoretical amount of  lime needed.
     Codisposal of Local Soils With Coal Refuse Materials

       The model system used was a soil with alkalinity corresponding to 5% by weight of CaCO,. It
     was assumed that the worst case of oxidation before disposal would be 10% of the FeS8 content.
     Calculations  were made for sufficient soil to negate 11% oxidation. For the three plants (A, B,
     and C) in the study the mass-of-soil per mass-of-waste ratios were 0.678,0.957, and 1.082, respec-
     tively. In other words, burying coal cleaning waste from Plant A would require 0.678 tons of a 5%
     alkaline  soil to neutralize any acid formed before disposal and to immobilize or attenuate any
     further reaction  or release of metal  ions from one ton of waste. The costs would be somewhat
     lower if the soil was more highly alkaline; however, a certain minimum amount would be required
     to attain the densification and compaction that is deemed essential to this process. Therefore, the
     Plant A costs given are probably about as low as one might expect  for any plant, regardless of the
     soil alkalinity.
58

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  Mixing soil with waste during the disposal process would have the advantage of filling the voids
between the larger refuse particles with small particles of soil. On a volume basis, the theoretical
maximum ratio required for this purpose would be approximately 0.68 soil/waste. In practice,
this theoretical maximum would never be reached, so very good densification should be possible
with a 50 to 75 wt% addition. One could expect the permeability of the resulting mixture to be
much lower than that of normally compacted waste alone. The combination of the neutralizing
and immobilizing power of the soil, together with the lowered permeability, could be sufficient to
prevent significant ground-water pollution.
Calcining to Immobilize Refuse Contaminants

  Pretreatment by calcining to approximately 1000°C is an attractive method for immobilizing
the labile contaminants in coal refuse materials. The landfill requirements and cost would not
change much from those of uncalcined refuse materials because the calcined mass and scrubber
slurry (sulfur dioxide removal from the calciner effluent) would occupy about the same disposal
volume as the original coal cleaning waste. Another important point is that an amount of lime
proportional to the FeS8 present in the refuse would be required for sulfur dioxide removal from
the stack gases. Optionally, half  the lime in the scrubber may be replaced with limestone.
  For calculational purposes, we  assumed that the heat of combustion of the residual coal and
the pyrite and marcasite constituents in the refuse would be sufficient to maintain operating
temperature in the kiln once the  temperature was reached using auxiliary fuel to heat the kiln.
The assumption was based upon the high thermal efficiency of modern kilns but may not hold if
the heat  of fusion of the glassy materials formed is substantial.
  Capital costs  were approximated  only roughly.  Based  on  20 days/yr of  operation, the
throughput of waste would require three rotary kilns of commercial maximum size for Plant A
and four for Plants B and C. Baghouse and sulfur dioxide scrubbers account for the remainder of
the major equipment items. Capital cost was estimated at $7 000 000 for Plant A, $8 500 000 for
Plant B and $9 000 000 for Plant C.  However, these costs could be 50%  or more low without
significantly affecting the ultimate cost figures because the lime for sulfur dioxide neutralization
is two-thirds or more of the total cost.  However, if a combined limestone/lime  neutralization
system is used, annual and unit  costs may be significantly reduced.
  Calcining costs depend on the  proportion of sulfur immobilized  in the residue  and also upon
calcining temperature. The predicted costs given are the minimum that might be expected. They
could be  50 to 100%  higher, depending upon the ultimate process chosen.

Water Flow Through Waste Landfill  Pile

  The magnitude of the annual volume of leach water from the landfill may be observed from the
calculated data in Table B-I. To compare this with our laboratory column teachings, consider
that 4 129 125 tons of water  are predicted to flow through the pile by the 20th yr and 12 420 000
tons of water will have accumulated in the pile, which means that the cumulative flow in the 20th
yr is equivalent to only 220 mi of leach water having passed through a laboratory column packed
with 1500 g of coal cleaning waste. After the pile is complete, the cumulative flow increases at a
rate of 17.7 mt/yr so  that the two-liter mark, a point at which we find the leachate still loaded,
corresponds to about 100 yr after the pile has ended its active life.
                                                                                          59

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      Lime/Waste Ratio Required for Various Control Processes

        The lime/waste ratio for various processes is shown in Table B-H Note that the posttreatment
      will require considerable additional lime beyond the 20-yr active life, but this amount has not
      been calculated. The amount of fly ash needed for codisposal neutralization of waste acidity is
      given in Table B-ffl.


                                   CONTROL OPTION COSTS

        Tables B-IV, B-V, and B-VI present total cost data for 8 control processes and 13 total varia-
      tions, in different forms. Table B-IV compares each on a basis of unit cost in dollars per ton of
      cleaned coal shipped. Table B-V presents the same data in terms of annual coats over the 20-yr
      working life of the disposal area. Costs in Tables B-IV and B-V include charges for treatment re-
      quired after the active life of the pile has expired. Table B-VI compares the options  in terms of
      net present value of cost, calculated at 10% cost of capital. To the person unfamiliar with the ter-
      minology of finance, these figures may be considered as the total number of dollars  that would
      need to be paid in a lump sum in 1978 to assure pollution abatement for the  life of  the project
      (and beyond, if necessary).  Figures in  all three of these tables do not include the  basic cost of
      landfill, which is indicated  on each table, or the cost of sealing the disposal  site.
                                              TABLE B-I

                      LANDFILL GROWTH AND MASS FLOW OF WATEK THROUGH WASTE
                               PILE DURING 20 YR ACTIVE LIFE OF PILE-
Flow ThrouL'h Pile Cumula

Year
1
•_>
:t
•1
r,
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
(Tons of
Uncovered
49550
49550
49550
49 550
49550
49550
49550
49 550
49550
49550
49550
49550
49500
49550
49550
495.50
49550
49550
49550
49550
Water)
Covered
0"
16517
113 033
49 550
66066
82 583
99099
115616
132 132
148649
165 165
181 682
198 198
214715
231231
247 748
204 264
280781
297 297
313814
Annual Total
Flow (Ions)
49 5.50
66 066
82 583
99 (199
115616
132 132
148649
105 165
181 682
198 198
214715
231 231
247 748
264 264
280781
297 297
313814
330 330
346 847
363 363
Water Flow
(tons)
49 550
115616
198 198
297 297
412913
545045
693 693
&58 858
1 040 540
1 238 738
1 453 452
1 684 (i83
1932431
2 1966!)5
2 477 475
2 774 772
3 088 586
3418916
3 765 762
4 129 125
Waste
(tons)
621 000
1 2-12 000
1 863 000
2 484 000
3 105000
3 726 000
4 347 000
4 968 OIK)
5 589 000
6210000
683 1000
7452000
807301X1
8 694 000
9315000
9 936 (MX)
10557000
11 178000
11799000
12420000
live Data

Water/Waste
Mass Ratio
0.0797!)
0.09309
0.10639
0.11968
0.13298
0.14628
0.15958
0.17288
0.18618
0. 19947
0.21277
0.22607
0.23937
(1. 25267
0.26597
0.27920
0.29256
0.30586
0.31916
0.33246
Liters/1. 5kg
0.0532
0.0621
0.0709
0.0798
0.0887
0.0975
0.1064
0.1153
0.1241
0.1330
0.1418
0.1507
0.15%
0.1684
0.1773
0.1862
0.19.50
0.2039
0.2128
0.2216
     •Assumes 35 in.AT annual rainfall and '250 acres ultimate landfill area.
     •No covered portion in first year.
60

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                         TABLE B-II

            LIME REQUIREMENTS FOR VARIOUS
               TREATMENTS OF COAL WASTE
              Process
TON OF LIME/TON OF WASTE
Plant A   Plant B   Plant C
Calcining-Lime Neutralization
Calcining-Lime and Limestone Option
25% Lime to Pile
Lime Neutralization of Drainage—1st yr.
Lime Neutralization of Drainage—2nd yr.
Lime Neutralization of Drainage—10th yr.
Lime Neutralization of Drainage—20th yr.
0.1722
0.0862
0.0431
0.0003
0.0004
0.0010
0.0015
0.2433
0.1218
0.0609
0.0019
0.0025
0.0090
0.0229
0.2571
0.1377
0.0689
0.0001
0.0001
0.0004
0.0008
                         TABLE B-III

           FLY ASH DEMAND REQUIREMENTS FOR
         CODISPOSAL TREATMENT OF COAL WASTE8


                                 TON OF FLY
                              ASH/TON OF WASTE
         Type of Fly Ash    Plant A    Plant B   Plant C
        Unmodified          0.7758    1.0962     1.2402
        Limestone Modified    0.5172    0.7308     0.8268
        •Equivalent to case where 25% of the theoretical amount of lime is used.
                                                                          61

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                                           TABLE B-IV

           COSTS OF VARIOUS DRAINAGE TREATMENT/PREVENTION PROCESSES
                              Process
           Pretrcatment
           Calcining-(60% Fixation of S02)
           Calcining-( Li me- Limestone S02system)

           Codisposal
           25% of Theoretical Lime Requirement
           50% of Theoretical Lime Requirement
           Unmodified Fly Ash (Equivalent to 25% Lime)
             (Mine 15 mi. from power plant)
           Unmodified Fly Ash (Equivalent to 25% Lime)
             (Mine adjacent to power plant)
           Limestone-Mod. Fly Ash (Equivalent to 25% Lime)
             (Mine 15 mi. from power plant)
           Limestone-Mod. Fly Ash (Equivalent to 25% Lime)
             (Mine adjacent to power plant)
           Local Soils and Subsoils (Equivalent to 4% Lime)

           Effluent Treatment
           Lime Precipitation/Clarification
             (First live years of active pile)
           Lime Precipitation/Clarification
             (Last live years of 20-yr active pile)
           Reverse Osmosis
           Ion Exchange
           •All costs would lie added lo a basic landfill disposal cost of
           $0.-Hi/ton of cleaned coal shipped. All costs are adjusted to March
           1978 value. See text for assumptions and qualifications regarding
           cosi s.
           "Major cost is lor lime or limestone in scrubbing system.
           ''Major cost is lor transporting the fly ash. which is assumed lo be
           free.
           "Highly active waste.
Dollars/Ton of Cleaned Coal"
Plant A   Plant B    Plant C
 3.30"
 2.14"
 0.64
 1.28
 3.72C

 0.39

 2.48°

 0.25

 0.81


 0.08

  0.10
4.44b
2.80b
0.90
1.81
5.26C

0.55

3.5 lc

0.36

1.15


0.83d

1.11"
4.94b
3.08"
1.02
2.05
5.95C

0.62

3.97C

0.41

1.30
62

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                                TABLE B-V

               ANNUAL COSTS OF VARIOUS DRAINAGE
                TREATMENT/PREVENTION PROCESSES
                   Process
  Annual Cost ($k)/2.07 MM
Annual Tons of Cleaned Coal8

  Plant A   Plant B   Plant C
Pretreatment
Calcining-(60% Fixation of SO,)                    6826     9201      10219
CalcininK-(Lime-Limestone SO, system)             4420     5802       6375

Codisposal
25% of Theoretical Lime Requirement                1326      1872       2118
f)0% of Theoretical Lime Requirement              '2651     .'i 744       4 2.'!4
Unmodified Fly Ash (Equivalent to 25% Lime)        2312     3268       3G97
  (Mine 15 mi. from power plant)
Unmodified Fly Ash (Equivalent to 25% Lime)          240       340        385
  (Mine adjacent to power plant)
Limestone-Mod. Fly Ash (Equivalent to 25% Lime)     1542     2178       2465.
  (Mine 15 mi. from power plant)
Limestone-Mod. Fly Ash (Equivalent to 25% Lime)      161       227        257
  (Mine adjacent to power plant)
Local Soils and Subsoils (Equivalent to 4% Lime)      1677     2380       2681

Effluent Treatment
Lime Precipitation/Clarification                     172      1 725       106
  (First  five years of acti%'e pile)
Lime Precipitation/Clarification                     202      2292       121
  (I ,ast five years of 20-yr active pile)
Reverse Osmosis                                                       407
Ion  Exchange                                                         602
•The linsic landfill disposal cost, adjusted from 1974 to 1978 dol-
lars using the Marshall and Swift Equipment Index for Mining, is
S()(i2 000 per year. All costs are adjusted to March 1978 values.
See text for assumptions and qualifications regarding costs.
                                                                                    63

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                                         TABLE B-VI

                NET PRESENT VALUE OF COSTS FOR VARIOUS DRAINAGE
                          TREATMENT/PREVENTION PROCESSES


                                                Net Present Value of Cumulative Cost"
                                                                 ($k)
                             Process
Plant A   Plant B   Plant C
           Pretreatment
           Galcining-(60% Fixation of S02)
           Calcining-(Lime-Limestone S02 system)

           Codisposal
           25% of Theoretical Lime Requirement
           50% of Theoretical Lime Requirement
           Unmodified Fly Ash (Equivalent to 25% Lime)
             (Mine If) mi. from power plant)
           Unmodified Fly Ash (Equivalent to 25% Lime)
             (Mine adjacent to power plant)
           Limestone-Mod. Fly Ash (Equivalent, to 25% Lime)
             (Mine 15 mi. from power plant)
           Limestone-Mod. Fly Ash (Equivalent to 25% Lime)
             (Mine adjacent to power plant)
           Local Soils and Subsoils (Equivalent to 4% Lime)

           Effluent Treatment
           Lime Precipitation/Clarification
           Reverse Osmosis
           Ion Exchange

           "1'resent value of basic landfill operation, adjusted In March I9T8
           value, is $8 187 000. All costs arc adjusted to March 1978 value.
           See text for assumptions and qualifications regarding costs.
58 086
37614
 11 275
 23 550
 19679

  2 050

 13 120

  1 367

 14268



  1 568
79 299
49371
15932
31 865
27 807

 2 897

18539

 1 931

20 257


15981
86 965
54 251
18016
36 032
31 460

 3277

20 973

 2 185

22811
64

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                         APPENDIX C

COLUMN LEACHING STUDIES OF LIMESTONE/REFUSE MIXTURES


                          TABLE C-I

   EXPERIMENT IDENTIFICATION FOR DYNAMIC LEACHING
         STUDIES OF LIMESTONE/REFUSE MIXTURES
  Experiment No.  Limestone Location
                           Sample8
       C.L-12

       CL-14


       CL-l.r>


       CL-lfi
(None - Control)

Intermixed


layered at outlet


Layered at inlet


Layered at outlet
1500 g re fuse

1300 K refuse
 220 g limestone

1300 g refuse
 229 g limestone

1300 g refuse
 221 g limestone

1300 g refuse
 220 g limestone (-20 mesh)
  "Minus :t/8 inch Illinois Basin Plant B refuse used throughout;
  minus H/8 inch limestone unless noted.
                                                                          65

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                                                     TABLE C-I1

                                 ANALYSES FOR DYNAMIC LEACHING STUDIES OF
                                          LIMESTONE/REFUSE MIXTURES

                                                Experiment No. GL-12

Parameter*
Vol (t)
pH
TDS(%)
Na
Mg
Al
K
Ca
Sc
Ti
V
Cr(M(!/*)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Mo
Ag
Cd(ng//)
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Pb(ng/l)
Th
U

1
0.040
1.3
8.63
25
500
1600
51
530
3.0
<0.4
1.44
790
130
15000
36
51
10
76
<0.2
7.9
<0.04
<2
 in Mtl'ni/ unless otherwise slated.
           6\\'nier tlmv \vn> stopped ot this point, air was passed through the column lor -1 uk. then UMUT l
66

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Sample No.'
                                                     TABLE C-lll

                                  ANAI.YSKS FOR DYNAMIC l.KACHINC.1 STUDIKS (IK
                                           LIMESTONK/HEKUSE MIXTURES

                                                  Experiment No. GL-14

                                    6        8       11        18       19       21
                                                                                         25
26
         29
                  30
Vol (1)
pH
TDS (%)
Na
Mg
Al
K
Ca
Sc
Ti
V
CrOig/i)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Mo
Ag
Cd(*ig/l)
CB
La
Ce
Sro
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
PbUig/l)
Th
U
0.085
2.5
4.72
IB
630
810
0.37
590
1.4
' <0.4
0.48
. 320
48
8100
26
44
4.1
55
<0.2
0.40
<0.04
<2
<0.1
<0.01
320
<0.04
0.47
1.20
<0.02
0.10
<0.1
0.21
0.14
0.02
<0.02
<0.05
<0.04
30
0.47
0.27
0.195
2.6
4.62
12
430
730
1.2
730
1.1
<0.4
0.37
180
49
8500
24
43
2.4
49
<0.2
0.06
<0.04
<2
<0.1
<0.01
210
<0.04
0.93
<0.08
0.02
0.07
<0.1
0.18
0.10
0.03
<0.02
<0.05
<0.04
12
0.36
0.23
2.260
2.9
0.52
1.3
31
9
0.5
630
<0.01
<0.4
<0.01
4.5
4
660
1.8
3.1
<0.1
3.5
<0.2
<0.02
<0.04
<2
<0.1
<0.01
18
<0.04
0.10
<0.08
<0.02
0.08
<0.1
0.17
<0.03
<0.01
<0.02
<0.05
<0.04
9
<0.02
<0.0l
3.000
4.4
0.34
1
19
<0.5
0.5
570
<0.01
<0.4
<0.01
<5
2.4
305
0.5
1.4
<0.1
1.9
<0.2
<0.02
<0.04
<2
<0.1
<0.01
4.8
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<5
<0.02
<0.01
. 6.090
7.4
0.25
0.9
3.2
<0.5
0.7
550
<0.01
<0.4
<0.01
<6
0.28
3
<0.09
<0.23
<0.1
0.23
<0.2
<0.02
<0.04
<2
<0.1
<0.01
0.28
•C0.04
<0.5
<0.08
<0.02
<0.01

-------
                                                   TABLE C-IV

                                ANALYSES FOR DYNAMIC LEACHING STUDIES OF
                                         LIMESTONE/REFUSE MIXTURES

                                               Experiment No. GL-15
     Sample No.
                                                           11  .
                                                                    18
                                                                            19
                                                                                     22
                                                                                               27
                                                                                                         28
Vol U)
pH
TDS(%)
Na
Mg
Al
K
Ca
Sc
Ti
V
Cr(>ig//)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Mo
Ag
CdW/)
Cs
La
Ce
Sm
.Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Pb(ng/t)
Th
U
0.090
2.4
6.08
30
470
1000
0.4
920
1.8
<0.4
0.70
330
60
10400
30
50
7
70
<0.2
0.31
<0.04
<2
<2
<0.0l
330
<0.04
<0.5
3.2
0.06
0.17
<0.1
0.20
<0.03
0.03
<0.02
<0.05
<0.04
40
0.74
0.34
0.200
2.6
4.97
16
1940
590
48
970
1.0
<0.4
0.53
230
54
9200
27
48
3.2
54
<0.2
<0.02
<0.04
<2
<1
<0.01
200
<0.04
<0.5
1.1
0.31
0.11
<0.1
0.20
0.13
0.24
<0.02
<0.05
<0.04
170
0.43
0.21
1.650
2.6
0.43
0.8
24
40
3.2
370
0.08
1.11
0.09
24
2.4
610
1.6
2.4
0.32
3.2
<0.2
<0.02
<0.04
<2
<2
<0.01
16
<0.04
<0.5
0.25
<0.02
0.02
<0.1
0.02
<0.03
<0.01
<0.02
<0.05
<0.04
16
0.03
0.02
3.825
4.3
0.34
1
11
<2
5
830
<0.01
<0.4
<0.01
<16
1.5
180
1.3
1
<0.3
0.8
<0.2
<0.02
<0.04
<2
<2
<0.01
16
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
16
<0.02
<0.01
7.020
5.8
0.12
0.4
4
<0.4
2
260
<0.01
<0.4
<0.01
<4
0.4
66
<0.08
0.3
<0.1
0.3
<0.2
<0.02
<0.04
<2
<2
<0.01
0.8
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<8
<0.02
<0.01
U.lW
6.2
0.05
0.4
2
<0.4
2
96
<0.01
<0.4
<0.01
<1
0.2
22
<0.09
<0.2
<0.1
0.2
<0.2
<0.02
<0.04
<2
<2
<0.01
<0.09
<0.04
<0.5
<0.08
<0.02
<0.01
<0. 1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<9
<0.02
<0.01
14.395
3.6
0.94
4
24
39
8
680
0.03
<0.4
<0.01
<8
5
1400
2
4
0.5
8
<0.2
0.02
<0.04
<2
<2
<0.01
8
<0.04
<0.5
0.43
0.05
0.02
<0.1
0.01
<0.03
<0.01
<0.02
<0.05
<0.04
16
<0.02
0.01
14.915
4.7
0.77
2
17
0.8
7.5
780
<0.01
<0.-1
<0.01
<8
3
1100
2
2.5
<0.2
2
<0.2
<0.02
<0.04
<2
<2
<0.01
8
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
0.05
<0.03
<0.01
<0.02
<0.05
<0.04
<16
<0.02
<0.01
20.050
5.4
0.02
0.4
1.5
0.7
2
100
<0.01
<0.4
<0.01
<7
0.2
7
<0.2
<0.4
<0.2
<0.04
<0.2
<0.02
<0.04
<2
<2
<0.01
0.2
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<15
<0.02
<0.01
25.135
5.8
0.03
0.5
1
0.5
3
100
<0.01
<0.4
<0.01
<5
0.2
5
<0.1
<0.3
<0.1
<0.03
<0.2
<0.02
<0.04
<2
<1
<0.01
0.1
<0.04
<0.5
<0.08
<0.02
<0.01
<0.l
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<10
<0.02
<0.01
     •V»)ue.s in ti%Jml unless otherwise staled.
     B\\'nier (low wns slopped at thi? point, nir wn*. passed i
                                               the column lor I \
68

-------
                 TABLE C-V

ANALYSES FOR DYNAMIC LEACHING STUDIES OF
        LIMESTONE/REFUSE MIXTURES
             Experiment No. GL-16
 Sample No.*
Vol U)
pH
TDS(%)
Na
Mg
Al
K
Ca
Sc
Ti
V
Cr^g/J)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Mo
Ag
CA(itfi/t)
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Pb(xg/*)
Th
U
0.100
1.5
6.27
28
370
1100
38
640
2.35
<0.4
0.99
570
38
10700
24
40
7
56
<0.2
5.8
<0.04
<2
0.2
<0.01
300
<0.04
1.5
2.2
0.08
0.20
0.05
0.61
0.30
0.06
<0.02
<0.05
<0.04
900
1.1
0.38
0.300
1.5
5.88
17
350
1100
33
650
2.1
<0.4
0.80
660
37
7200
25
41
5
58
<0.2

<0.04
<2
0.6
<0.01
410
<0.04
1.3
2.6
0.68
0.19
0.10
0.49
0.15
0.05
<0.02
<0.05
<0.04
640
1.1
0.31
1.510
2.2
0.74
2.3
46
110
11
220
0.12
<0.4
0.28
76
5
1200
3
5
0.23
7.6
<0.2
0.39
<0.04
<2
<1
<0.01
34
<0.04
<0.5
0.37
0.03
0.03
<0.1
0.04
<0.03
<0.01
<0.02
<0.05
<0.04
53
0.03
0.06
2.815
2.5
0.34
2
18
36
4.5
122
0.02
<0.4
0.11
42
2
540
1
2
<0.06
3
<0.2
0.28
<0.04
<2
<1
<0.01
15
<0.04
<0.5
<0.08
<0.02
0.01
<0.1
0.04
<0.03
<0.01
<0.02
<0.05
<0.04
36
<0.02
0.01
  1 Values in fig/ml unless otherwise stated.
                                                                        69

-------
                                              TABLE C-VI

                             ANALYSES FOR DYNAMIC LEACHING STUDIES OK
                                     LIMESTONE/REFUSE MIXTURES

                                           Experiment No. GL-17
                      Sample No.'
13
        18
Vol(/)
PH
TDS(%)
Na
Mg
Al
K
Ca
Sc
Ti
V
CrOig//)
Mn
Fe
Co
Ni
Cu
Zn
Ga
As
Br
Rb
Mo
Ag
CdUg/J)
Cs
La
Ce
Sm
Eu
Tb
Dy
Yb
Lu
Hf
Ta
W
Pb(Mg/J)
Th
U
0.100
3.5
4.01
43
710
130
71
600
0.40
<0.4
<0.01
43
54
7800
27
43
<0.1
49
<0.2
0.04
0.12
<2
<1
<0.01
140
<0.04
<0.5
<0.08
<0.02
0.03
<0.1
0.24
<0.03
<0.01
<0.02
<0.05
<0.04
27
<0.02
0.07
2.040
3.8
0.51
2
39
<0.3
3
600
<0.01
<0.4
<0.01
21
5
480
2.4
3
<0.1
3
<0.2
<0.02
<0.04
<2
<1
<0.01
12
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
9
<0.02
0.01
3.530
4.5
0.31
1
10
0.5
10
630
<0.01
<0.4
<0.01
<5
2
150
0.5
1
<0.1
1
<0.2
<0.02
<0.04
<2
<1
<0.01
4
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
-
<0.02
<0.01
5.660
5.4
0.26
0.8
3
<0.3
2
580
<0.01
<0.4
<0.01
<3
0.6
61
0.3
0.3
<0.06
0.2
<0.2
<0.02
<0.04
<2
<1
<0.01
0.3
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
-
<0.02
0.08
9.435
6.5
0.19
1
4
<0.1
1.5
510
<0.01
<0.4
<0.01
<1
0.1
<0.5
<0.02
<0.05
<0.02
<0.01
<0.2
<0.02
<0.04
<2
<0.2
<0.01
<0.02
<0.04
<0.5
<0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<5
<0.02
<0.01
1 1 .590
7.2
0.13
1
3
<0.1
1.5
320
<0.01
<0.4
<0.0l
<1
0.04
<0.5
<0.02
<0.05
<0.02
<0.01
<0.2
<0.02
<0.0-1
<2
<0.2
<0.01
0.03
<0.04
<0.5
•C0.08
<0.02
<0.01
<0.1
<0.01
<0.03
<0.01
<0.02
<0.05
<0.04
<5
<0.02
<0.01
                       Values in us/ml unless otherwise stated.
70

-------
s.
                                   X
                                       LEGEND-
                                     ° =GL-12
                                     o = CL-u
                                     « = GL-15
                                     • =GL-16
                                     • -GL-17
                   9.0    12.0    15.0

                  VOLUME (liters)
                                    18.0
                                          21.0
                                                                                         a
                                                                                         5;
                                                                                                     lECEUD
                                                                                                     =CL-I2
                                                                                                    « -CL-16
                                                                                                    • =CL-17
                                                                                                \
                                                              6.0    9.0    12.0    15.0    18.0

                                                                   VOLUME  (liters)
                                                                                                              24.C
                                       LCCENO
                                     o-GL-12
                                     «=GL-16
                                     • -GL-17
             6.0    9.0   12.0   15.0   18.0

                  VOLUME  (liters)
                                                                                        LEGEND
                                                                                       a -GL-12
                                                                                       o = Cl-U
                                                                                       » - GL -15
                                                                                       • =CL-16
                                                                                       • -GL-17
                                                              6.0    9.0    12.0    15.0

                                                                   VOLUME  (liters)
6.0    9.0    12.0   15.0

     VOLUME (liters)

O-




"s-

n
CL.
O
(_)
0
O

Je
'o




p
L
t c
vV *-
'v\ 2
\%>. ^
VVV...F 5

H/ "-. ^
\ '"•-. -
"*
Xv -"""" "°


* ' * •
LEGEND
o- GL-12
o -GL-14
• -GL-15
.-CL-I6
»-CL-17

k
^^*^tJ
1
V,
\ '••-.
\ \
\ \
1__^ '""•• 	

' ' *
                                                                                VOLUME  (liters)
                                                  Fig.  C-l.
     The pH,  TDS,  and trace element  concentrations for dynamic  leaching experiments with
     limestone/refuse mixtures.
                                                                                                                 71

-------
                                         ,  \
                                                      LECCNO
                                                    • = CL-15
                                                    « =CL-16
                                                    • =GL-I7
                      6.0
                             9.0    U.O     15.0
                            VOLUME  (liters)
                                              LEGEND
                                            D.GL-I?
                                            o «CL-K
                                            « = CL-15
                                            . = CL-I6
                                            » = CL-17
              6.0     9.0    12.0    15.0     18.0
                    VOLUME  (liters)
                                                                                                                                      210
                                                     LECCNQ

                                                     = CL-1«
                                                     = GL-15
                                                     = GL-16
                                              LCCCNO
                                            o =GL-12
                                            o = CL-M
                                            • = GL -15
                                            « =CL-I6
                                            • =CL-i;
                      6.0     9.0     l?.0    15.0
                            VOLUME  (liters)
              6.0     9.0     12.0    15.0
                    VOLUME  (liters)
                                                                                                                                      21.0
                                                     IECENQ
                                                     =GL-12
                                                     = CL - »
                                                     - CL -15
                                                     =CL-I6
        0.0    JO     6.0     9.0     12.0     15.0     180    21.0    2<.C
                            VOLUME  (liters)
                                             LECCNO
                                           o -CL-12
                                           o = CL -14
0.0    J.O    6.0     9.0     12.0     15.0    18.0    71.0    2<.C
                    VOLUME  (liters)
                                                             Fig.  C-l.  (cont)
72

-------
                                    \
                                             LEGEND
                                           o=GL-12
                                           ooGL-14
                                           .oGL-15
                                           • =CL-I6
                                           • -CL-17
       3.0
6.0     9.0    12.0     15.0

       VOLUME  (liters)
                                                                        0.0
                                                                        a —
                                                                \
                                                                                                            LEGEND
                                                                                                          o-GL-12
                                                                                                          o=CL-14
                                                                                                          «=CL-I5
                                                                                                          • -CL-16
                                                                                                          • -GL-I7
                                                                             0.0
                                                                                                 9.0     12.0    15.0

                                                                                                VOLUME  (liters)
                                                                                                                             21.0
                                                                                                                                    24.C


a"" :
< ;


9:
'g;


c
u
\ fe
\ "
\ 5
\
\

lECEND
a =CL-I2
0 = GL - '4
« = CL - 16



H]


                                                                        a"
                                                                        Q.O.
                                                                                                                         UCENO
                                                                                                                         = a-i2
                                                                                                                         = CL - M
                                                                                                                       « = GL-1b
                                                                                                                       • • CL -16
       3.0
6.0     9.0     12.0    Ib.O    18.0

      VOLUME  (liters)
                                                                            0.0    3.0
                                                                                          6.0     9.0     12.0    15.0

                                                                                                VOLUME  (liters)
                                             LEGEND
                                            =GL-12
                                            = CL-U
                                            =GL-I5
                                            =GL-16
0.0    3.0    6.0    9.0    12.0    15.0    18.0     21.0    24 .C

                   VOLUME  (liters)
                                                               0.0    3.0     6.0     9.0     12.0    15.0    IB.O    21.0    24.C

                                                                                  VOLUME  (liters)
                                                      Fig. C-l.  (cont)
                                                                                                                                       73

-------
    E
    a
   O
                                                     LEGEND
                                                   o-GL-12
                                                   o = CL-14
                                                   . . CL-15
                                                   . -GL-I6
                                                   '-GL-17
6.0     9.0     12.0    15.0

      VOLUME  (liters)
                                                  18.0
                                                         21.0
                                                                24.C
                                                                                                            LEGEND
                                                                                                          o = GL-I2
                                                                                                          o -CL-14
                                                                                                          « = CL-15
                                                                                                          » = GL -16
                                                                                                         9.0     12.0    15.0

                                                                                                        VOLUME  (liters)
                                                                                                                                     21.0
                                                     LEGEND
                                                   "-CI.-I2
                                                   o-CL-14
                                                   .-GL-15
                                                   . -GL-16
                                                   • -GL-17
                                                                               CD o-
                                                                               a —:
                             9.0    12.0     15.0
                            VOLUME   (liters)
                                                  18.0
                                                         21.0
                                                                                                            LEGEND
                                                                                                          o -CL-12
                                                                                                          o -CL-14
                                                                                                          ' -GL-15
                                                                                                          • . GL-16
                                                                                                          • -CL-I7
                                                                                    0.0
                                                                                   9.0    12.0     15.0

                                                                                  VOLUME  (liters)
                                                     LEGEND
                                                   o - GL -12
                                                   o = CL - U
                                                   • » CL-15
                                                   • • GL-16
                                                   • -GL-17
                     6.0     9.0    12.0    15.0
                           VOLUME  (liters)
                                                                                                           LEGEND
                                                                                                         o = CL-12
                                                                                                         o -CL-I4
                                                                                                         • • CL-15
                                                                                                         . -GL-16
                                                                                                         •=CL-17
                                                                                   9.0     12.0     15.0
                                                                                  VOLUME  (liters)
                                                                                                                                           2<.C
                                                              Fig.  C-l.  (cont)
74

-------
                                     L.ECEND
                                   o-CL-12
                                   o=GL-M
                                   • -GL-I5
                                   • -GL-I6
                                   • . GL-17
                         LEGEND
                       o.CL-12
                       o-GL-14
                       • -GL-15
                       •-CI-16
                       « . Cl-17
3.0
              9.0    12.0    15.0
             VOLUME  (liters)
                                                                                 6.0
 9.0    12.0    15.0
VOLUME  (liters)
                                                                                                            18.0
             9.0    12.0    15.0

             VOLUME  (liters)
                                     LEGEND
                                   a-CL-12

                                   • -GL-15
                                   • -Gl-16
                                   '-GL-I7
                                                                .S:>
                                                               a.
                         LEGEND
                       o • CL -12
                       o-GL-U
                       • -GL-15
                       . -GL-16
                       ..GL-17
                                                                                                 ^


                                                                                                 I'l.
                                                                                60
 9.0     12.0     15.0

VOLUME  (liters)
                                                                                                                   2VO
                                     LEGEND
                                   o-a-12
                                   o oCL-M
                                   • -GI-I5
                                   ' -GL-I6
                                   • -CL-I7
             9.0    12.0    15.0
            VOLUME  (liters)
 9.0     12.0     15.0
VOLUME  (liters)
                                             Fig.  C-l.  (cont)
                                                                                                                            75

-------
                                     APPENDIX D

               COLUMN LEACHING STUDIES OF LIME/REFUSE MIXTURES

                                      TABLE D-I

                   EXPERIMENT IDENTIFICATION FOR CODISPOSAL
                              OF LIME AND COAL WASTES
                                  Weight of
                   Experiment No.  Waste (g)
   Amount of
Lime Added (%)a
CTWT-11-1
CTWT-11-2
CTWT-11-3
CTWT-11-4
CTWT-11-5
500
500
500
500
500
0 (control)
0.5
1.5
3
10
                   'Percentage based on waste. Lime added as slurry, then mixed and
                   dried. Mixtures leached with upward distilled water.
                                      TABLE D-II

                   ANALYSES FOR DYNAMIC LEACHING STUDIES OF
                               LIME/REFUSE MIXTURES
                               Experiment No. CTWT-11-1
                                       (Control)
  Sample No.0
       12
16
18
  'Concentrations in us/mi unless noted otherwise.
  "Water flow was stopped at this point, air was passed through the column for 2 wk, then water flow was resumed.
20
Vol(Jl)
pH
TDS(%)
F*
Na
Al
K
Ca
Cr (ng/t)
Mn
Fe
Co
Ni
Cu
Zn
Cd (jtg/£)
0.043
1.8
6.54
12
12
1200
4.6
380
610
34
13200
20
30
4
48
230
0.172
1.9
6.19
11
8.6
1100
2.4
370
560
33
12000
18
28
4
48
250
0.344
1.9
4.06
6.5 •
5.6
720
1.3
330
450
22
7790
12
18
3
29
170
1.026
2.4
0.56
1.8
1.1
74
1.1
100
90
3
1100
2
3
0.34
4
25
1.927
2.6
0.13
1.2
0.5
13
1.2
30
11
0.7
230
0.4
0.6
<0.02
0.9
4.6
3.581"
3.3
0.05
1.3
0.6
3
2.2
12
3
0.2
100
0.1
0.2
<0.02
0.3
1.4
3.963
2.2
0.34
0.7
3.6
42
5.2
60
30
1
700
0.7
0.8
0.5
1
7
4.206
2.4
0.18
0.7
2.1
21
3.5
31
7
0.5
380
0.3
0.4
0.20
0.7
2.5
76

-------
                                    TABLE D-III

                 ANALYSES FOR DYNAMIC LEACHING STUDIES OF
                              LIME/REFUSE MIXTURES
                              Experiment No. CTWT-ll-2
                                    (0.5 wt% Lime)
Sample No.*
                                                      12
16
18
20
Vol(/)
PH
TDS(%)
F
Na
Al
K
Ca
Cr (n%lt)
Mn
Fe
Co
Ni
Cu
Zn
Cd (tig/I)
0.055
2.1
5.40
9
4.0
790
1.4
450
480
33
10750
18
28
4
50
240
0.198
2.2
4.33
9
3.1
610
3.3
510
370
26
8300
14
21
3
35
200
0.396
2.3
2.89
5.6
1.9
420
0.4
490
280
18
5670
10
15
2
23
140
1.166
2.6
0.58
1.1
0.7
54
0.4
380
60
3
950
1.5
3
0.2
4
30
2.065
2.9
0.19
0.5
0.5
10
1.1
240
5
0.6
260
0.3
0.5
<0.02
0.9
5
4.237"
3.5
0.04
<0.2
0.4
0.8
1.1
60
2
0.2
75
<0.07
0.2
<0.02
0.3
1
4.658
2.2
0.55
1.2
2.3
47
2.6
250
50
2
1020
0.8
1
0.9
2
9
4.946
2.6
0.14
0.5
0.8
8
1.0
70
4
0.3
205
0.1
0.2
0.1
0.4
3
"\\'n(er flow
        ons in jjjj/rn£ unless noted otherwise.
        wn> slopped at this point, air was passed through the column for _ wk. then wnier llnw \v;i> resumed.
                                    TABLE D-IV

                 ANALYSES FOR DYNAMIC LEACHING STUDIES OF
                              LIME/REFUSE MIXTURES
                              Experiment No. CTWT-11-3
                                    (1.5 wt% Lime)
Sample No.*
                                                     12
                                                              16
                                                                       18
                  20
VolU)
PH
TDS(%)
F
Na
Al
K
Ca
Cr (tig/t)
Mn
Fe
Co
Ni
Cu
Zn
Cdfog/l)
0.048
2.6
1.72
5.9
7.6
380
1.3
510
140
21
2820
13
18
2
24
130
0.190
2.6
1.54
5.0
4.9
320
3.7
530
120
17
2330
11
15
1
20
110
0.332
2.7
1.19"
3.7
4.7
240
0.9
550
80
13
3720
8
11
1
16
90
1.064
3.0
0.49
1.6
1.3
55
0.6
500
8
4
540
2
3
0.2
4
30
1.944
3.2
0.29
0.6
1.1
24
1.0
400
<1
2
260
0.8
2
<0.02
2
20
3.759"
3.9
0.13
0.3
0.8
6
0.8
220
<1
0.4
105
0.1
0.4
<0.02
0.6
3
4.104
2.3
1.02
1.8
1.3
110
0.2
300
100
3
1980
1
3
2
6
45
4.387
2.6
0.37
0.6
0.5
34
0.2
170
30
1
710
0.4
0.9
0.35
2
4
      irnitiins in uglml unless noted otherwise.
      lnw wns stopped at this point, air was passed through the column lor - wk. iht-n w;iti*r t1<«w w;i* rt-
                                                                                                   77

-------
                                                    TABLE D-V

                                ANALYSES FOR DYNAMIC LEACHING STUDIES OF
                                             LIME/REFUSE MIXTURES
                                               Experiment CTWT-11-4
                                                    (3 wt% Lime)
                  Sample No.*
                                                  12
                                                                             16
18
•('nncemr.i'inns in mlmt unless noted oiherwise.
"Water llnw wa» stopped at this point, air was passed through ihe column lor 2 t
20
VolU)
pH
TDS(%)
F
Na
Al
K
Ca
Cr (M§//)
Mn
Fe
Co
Ni
Cu
Zn
Cd(Mgfl)
0.042
6.6
0.54
0.15
7.9
0.7
8.9
890
<1
3
120
0.7
1
0.04
0.5
5.4
0.168
6.3
0.48
0.15
6.4
<0.6
12.4
870
<1
2
120
0.6
0.9
0.04
0.4
4.0
0.336
6.5
0.37
<0.15
3.4
<0.6
6.1
780
23
2
69
0.4
0.7
0.04
0.2
2.0
1.125
6.8
0.27
<0.15
1.5
<0.6
5.3
700
3
1
14
0.2
0.3
0.03
0.1
0.6
2.076
7.4
0.24
<0.15
1.1
<0.6
3.5
620
2
0.6
7
0.2
0.2
0.02
0.08
0.4
4.2.W
7.9
0.15
<0.15
1.0
<0.6
3.0
380
<1
0.3
3
<0.07
0.1
0.02
0.07
0.6
4.562
2.8
0.73
4.8
4.9
180
7.9
550
19
12
700
8
12
0.9
14
100
4.830
3.0
0.45
1.6
2.0
54
8.2
540
6
5
300
3
4
0.2
5
32
                                                                                        n.s resumed.
                                                    TABLE D-VI

                                 ANALYSES FOR DYNAMIC LEACHING STUDIES OF
                                             LIME/REFUSE MIXTURES
                                                Experiment CTWT-11-5
                                                    (10 wt7t Lime)
               Sample No.*
                                                    12
                                                             16
  18
                                                                              20
Vol(/)
pH
TDS(%)
F
Na
Al
K
Ca
Ci(ns/l)
Mn
Fe
Co
Ni
Cu
Zn
Cd (MB//)
0.044
13.1
0.50
0.18
6.3
<0.5
3.8
1100
<1
<0.02
<0.1
0.05
0.1
0.03
0.02
<1
0.174
13.2
0.51
0.28
2.9
<0.5
1.8
1400
<1
<0.02
<0.1
0.05
0.1
0.04
0.03
<1
0.304
13.1
0.46
0.20
0.9
<0.5
1.7
1100
<1
<0.02
<0.1
0.1
0.1
0.02
0.02
<1
1.045
12.9
0.47
0.25
0.6
<0.5
1.2
1100
<1
<0.02
<0.1
0.1
0.06
0.02
0.02
<1
1.910
12.9
0.49
0.25
0.6
<0.5
1.7
1200
<1
<0.02
<0.1
0.05
0.08
0.03
0.03
<1
4.002"
12.6
0.28
0.12
1.6
<0.5
1.0
380
<1
<0.02
<0.1
<0.05
<0.03
<0.02
0.01
<1
4.297
10.7
0.36
<0.1
16
<0.5
3.3
920
<1
<0.02
<0.1
<0.05
0.05
0.03
0.02
2
4.563
11.4
0.15
<0.1
1.3
0.5
0.9
360
<1
<0.02
<0.1
<0.05
<0.03
<0.02
<0.01
<1
                •('I>MIciiJr.iii"M- in M/mt unless mned otherwise.
                *\V;iicr lluw wn> slopped HI this point, air wn> pas>ed ihrmixh ihe t
                                                              iliinui in
                                                                       »k. ilu
                                                                                        rotiined.
78

-------
I-
 USBfl
o - CTWTtM
o - CTWtn-2
• - CTWTn-j
• - CTWTn-4
» . CTWTff-5
              20    iO     40     SO

                     VOLLfcC (Liters)
                                       6O    70     80
                                                                                                            o . cTwrn-1
                                                                                                            o . CTWTII-2
                                                                                                            «-C7wtn-i
                                                                                                            • - CTWTn-4
                                                                                                            » - CTWTn-5
                                                                   00     K>
                                     2O    JO     40     SO    60
                                            VCLUiC (Liters)
                                                                                                               70    80
                                            LECOC
                                          o . CTWTn-l
                                          o . cTwrn-2
                                          • . CTWTn-3
                                          • • cTwrn-4
                                          • . CTWTII-5
  00    10
              20    JO    40     50     60
                    VOLLKE (Uters)
                                                   80
                                                               8
                                                                   \sssm
                                                                  o . CTWTD-I
                                                                  o . CTWTtl-2
                                                                  » • CTWTII-3
                                                                  « - CTWTtl-4
                                                                  • • CTWTH-5
                                                                   00     K)     20
                                           JO     40    SO

                                            VOLUKC (Liters)
                                                                                                         60    70    80
                                            \££BSt
                                          a ' CTWTn-l
                                          o . CTWTII-2
                                          • - CTWTH-3
                                          • - CTWTn-4
                                          » = CTWTn-s
              20    JO    4O     SO
                    VOLLKC  (Liters)
                                       60    70     80
                                                               I
                                                               5
                                                                "o-
                                                                  a . CTWTn-l
                                                                  o . CTWTH-2
                                                                  • - CTWTn-3
                                                                  • - CTWTtt-4
                                                                  » - CTWTn-b
                                     20    JO     4O     SO

                                            VOLUvE (Liters)
                                                                                                         60     70    80
                                                     Fig. D-l.
      The pH and trace element concentrations for dynamic leaching experiments with lime/refuse
      mixtures.
                                                                                                                      79

-------
     P:
                                                        CTWTn-1
                                                     a - CTWTD-2
                                                     4 - CTWTIt-3
                                                     • - CTWT11-4
                                                     » - CTWTD-5
       OOW     20JO*Oi06070
                            vai>€  (Liters)
                                                                                 00     ,»
                                                                                                                  ty.
                                        ttstc
                                       o . CTWTH-I
                                       o - CTWT11-2
                                       • - CTWT11-3
                                       • - CTWTtl-4
                                       » . CTWTI1-5
       20     30     40     SO"
              vOLU»e  (Liters)
                                                                                                                           60      70     80
       00     X)
                     2O     JO     «O     SO
                            VOLUKC  (Liters)
                                                 60      7O      BO
                                                                                                                                LEfiQfi
                                                                                                                              o - CT»fTn-1
                                                                                                                              o-CTWTH-2
                                                                                                                              » - CTWln-3
                                                                                                                              • - CTWTH-4
                                                                                                                              « - CTWTH-5
K)      JO     JO     4O     SO     6O
                      (Liters)
    p-
       00
                     20
                                           \
                                        b!
                                        $
                                                       . CTWTH-1
                                                        CTWln-2
                                                     • - CTWT1I-4
                                                     » » CTWTII-i
                            JO     40     SO
                            VOLL*£ (Liters)
                                                 60     70     80
                                      a -CTWTI1-I
                                      o . CTWTI1-2
                                      • . CTWTI1-3
                                      « - CTWTII-4
                                      • - CTWTII-5
                                                                                 OOI020J040S0607080
                                                           Fig.  D-l.  (cont)
80

-------
                                           \sssm
                                          a . ciwrn-i
                                          o . crwrn-2
                                          •. crwrn-3
                                          • • cTwin-«
                                          »« CTwin-s
0010?OJO*OS0607080

                   VCXUkC (Utes)
                                                                    OOI020M40M6070
                                                 Fig.  D-l. (cont)
                                                                                                                          81

-------
                                     APPENDIX E

            PROGRAM CODE FOR DETERMINING THE COST OF ALKALINE
                   NEUTRALIZATION OF COAL WASTE DRAINAGES
                              LASL Identification No. 1065.
              PRDGRRM L RHDF IL (I NPUT. OUTPUT. TRPE5= I NPIJT. TRPE6=OUTPUT^
              DIMENSION PPMFE(20> .PDLIME<20> .   TPYLIME<20> > TPDLIME (20'.' .
             1TPDTDS <20> ,PPILIME<6> . COSTLIM (20. 6) «TTPD<20> . CLRCOST <20::' •
             2DPCOST(20^.CHPCOST<20>.CLRRR<20>
        C     ;ET FLRG TD  1 FDR SIN'3LE  IRON  CDNC. FERDIN.  ELSE  0

              IF'HFLRG.GT.O '50 TO 10
              DnTR PPMFE'10..20..50..100..200..400..500..600..700..
             1900..1000..1100.«130G.»1500.«1700..1900.»2000.<2500.«3000.»3500.,
              GD TO  101
            10 RERIK5»991>PPMFE<'O
           101 RERD<5.. 992 '30 TO 12
            11 DD 15  1=1.20
            12 PDLIME(O=1.2406E-04»PPMFE(I>
              TPYLIME(I>=PDLIME=TPYLIME(D.'365.
            13 DO 14  J=l,6
              PPILIME(.J>=36.*3*J
            14 COSTLIM(I,J>=PRILIME(J>»TPYLIME(I>
        C»»»» PRILIME !S PRICE OF LIME DELIVERED  IN $'TON!COSTLIM  IS RNNURL
        C     COST OF LIME
              TPDTDS(I>=-3.»PPMFE(I>»CUFT*62.4x730.E09
        C»»»» TONS PER DRY OF TOTRL DISSOLVED  SOLIDS
              TTPD < I> =TPDTDS (I> -t-TPDLIME  SCLfiRR (I> =1 30. »TTPD (I>
              IF(CLRRfta>.LT.100.> CLRRR=100.
              IF(CLRRR.GT.1000.> GO TO 21
              CLRRBS=10000.-6.67*(1000.-CLfiRRa»
              '3D TO 22
           21 CLRRB3= 10000.+7. »-1000.')
           22 flDJCBS=CLRRBS»(235.x39.>
              235 IS MRR 1973 CHE COST INDEX -  CRN BE CHRNGED FOR LRTER USE
              VflR SLURRY IS GPM BOTTOM FLOU  FROM SETTLER
              SLURRY=1.70776E-06»CUFT
              CH=250.»SLURRY
              MRX TOTRL HERD OF 250 PS I HRS  BEEN RSSUMED FOR COST CRLC
              IF *3- 33*500.
              250.6 IS MRR 73 COST INDEX FOR PUMPS
              GO TO 302
          301 PUMPCST=<250.6'115>»3.33*(500.-»-4.5*<:CH-400.>*».63>
          302 IF(SLURRY.GT.7.67)  GD TD 401
              302 IS FDR 1.5 IN PIPE?401-2"»402-2.5"!403-3-?404-4";405-5"
              RSSUME 1500 FT TOTRL LENGTH OF PIPE
              DUM=1500»(264x115)
              PIPECST=2.2»DUM
              GD TD 409
          401 IF(SLURRY.GT.12.34> GD TO 402
              PIPECST=2.75*DUM
              GO TD 409
          402 IF(SLURRY.GT.17.97> GD TD 403
              PIPECST=3.3»DUM
82

-------
      GO TO 409
  403 IF GO  TD  404
      PIPECST=4.2»DUM
      GO TD 409
  404 IFCSUJRRY.GT.4iS.> GO TD 405
      PIPECST=5.2*DUN
      GD TD 409
  405 PIPECST=6.3*DUri
      MRITE<6'993'»  '
  409 PPCOST=PUMPCST+PIPECST
      DT 1 =2 . 36*RD JCBS1I>T2= 1 . 43»DT 1 $DT3= 1 . 35»DT2
      CLRCOST C I > =PPCOST+DT3
      HPPUMP=500. » 1'SLUP.RY '3960. > »1 . 33*HPCLfl=CLflPfi  ». 01 5
      EKI,JH=0.7457»
      DPCDST  =365. »40. +ELECDST
      CflPCQST < I > = . S533*CLflCDST < O
      IF(NFLftG.GT.O> GD TD 600
   15 CONTINUE
      i.JRITE<6»994->RflIN.flCRES.FRflflB
      i.JRITE<6.995>
      DD 500  1=1.20
      URITE<6.996)PPMFE »CLflRfl »CflPCDST(I> .DPCDST(D
  500 CONTINUE
      MRITE<6»997>  » J=l »6>
      URITE <6- 993) <  » J=l »6) « 1=1 »20>
      GD TD 399
  600 CONTINUE
      URITE <6»994)RHIN»ftCREStFRflftB
      IJRITE<6»995>
      MR I TE <6 • 996) PPMFE <1 > F TPDL I ME <1> > CLRRfl <1 > • CRPCOST <1 > • DPCDST < 1>
  350 CONTINUE
      URITE<6.897>
      URITE (6.997)  J) » J=l .6> » 1 = 1 » 1)
  399  REftD(5'990)NEXIT
        IF(NEXIT.GT.O) GD  TD  5
  900 CONTINUE
  990 FORMftTCIl)
  991 FDRMftT(FlO.O)
  992 FDRMflT<3x,*. FRftCTIDN RBSORBED: «-,2X»F5.-4'>
  995 FDRMRTdHO^PPM IRDN».Tl 1 »»TDNS LIMExDfiY»»T26«»CLftRIFIER flRER*.
     1T42.»RNN. CflP. CDiT»«T53.»flNN. DPER.  COST*)
  996 FDRMRT<3X»F6.0.T11.F3.4.T26»F10.2»T42»F10.2»T53»F10.2)
  397 FORflRT(lHO.»LIME COST flT VRRIDUS  PRICESt  SflME PPMS FE RS RBDVE*)
  993 FDRriflT<» ».6F10.2)
  997 FDRMflT
-------
      REFERENCES

       1. E. M. Wewerka, J. M Williams, P. L. Wanek, and J. D. Olsen, "Environmental Contamina-
         tion From Trace Elements in Coal Preparation Wastes: A Review and Assessment of the
         Literature," Los Alamos Scientific Laboratory report LA-6600-MS (August 1976).

       2. R. A.  Meyers,  Coal  Desulfurization  (Marcel Dekker  Inc., New York, 1977).

       3. E. M. Wewerka, J.  M. Williams, N. E. Vanderborgh, A. W. Harmon, P. Wagner, P. L.
         Wanek, and J.  D. Olsen, "Trace Element Characterization of Coal Wastes — Second Annual
         Progress Report, October  1, 1976-September 30,  1977," Los  Alamos  Scientific Laboratory
         report LA-7360-PR (also EPA-600/7-78-028a) (July 1978).

       4. E. M. Wewerka and  J. M.  Williams, "Trace Element Characterization of Coal Wastes, July
         1, 1975-June 30, 1976," Los Alamos Scientific Laboratory report LA-6835-PR (March 1978).

       5. E. M. Wewerka, J. M. Williams, and P. Wagner, "The Use of Multimedia Environmental
         Goals to Evaluate Potentially Hazardous Trace Elements in the Drainage From High-Sulfur
         Coal Preparation Wastes," in preparation.

       6. National  Academy of Sciences/National Academy of Engineers Committee, Underground
         Disposal of Coal Mine Wastes  (Washington: National Academy of Sciences, 1975) pp. 78-
         79.

       7. Annon.,  Chemical Ki^inemii-,'.  85, No.  12:7 (May 22,  1978).
      8. F. C. Jelen, Cost and Optimization Engineering (McGraw-Hill Book Co., New York, 1970),
         p. 440.

      9. Annon. "Key Chemical Lime," Chemical £ Engineering News, p.  10 (April 24,  1978).

      10. Ackenheil & Associates Geo. Systems, Inc., "Evaluation of Pollution Abatement Techniques
         Applicable  to Lost  Creek  and Brown's Creek Watershed, West  Virginia," Appalachian
         Regional  Commission report NTIS PB-242 722 (October 1973).

      11. R. H. Perry, etal., Eds.,  Chemical Engineer's Handbook, 4th ed. (McGraw-Hill Book Co.,
         New York,  1963).

      12. R. S.  Aries, et al.,  Chemical Engineering Cost Estimation  (McGraw-Hill Book Co., New
         York, 1955).

      13. P. M. Kohn, "CE Cost Indexes Maintain 13-Year Ascent," Chemical Engineering, 85, No. 11,
         pp.  189-190 (May  8, 1978).

      14. J. S.  Scott, and K.  Bragg, Eds., "Mine and  Mill Wastewater Treatment," Environmental
         Protection Service (Canada) report EPS3-WP-75-5 (December 1975).

      15. H. W. Cremer and T. Davies, Eds., Chemical Engineering Practice, Vol. :t.  Solid Systems
         (Academic  Press Inc., New York,  1957), pp.  259-283.
84

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16. H.  Popper,  Ed.,   Modern Cost-Engineering Techniques  (McGraw-Hill Book Co., New
   York, 1970). (Note: p. vi is essential for indexing costs.)

17. J. P. Capp and L. M. Adams, "Reclamation of Coal Mine Wastes and Strip Spoil With Fly
   Ash," Amer. Chem. Soc., Div. Fuel Chem. Preprints  15(2) (1971).
                                                                                        85

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                                       TECHNICAL REPORT DATA
                                 fPleost read tmuructiont on the revene before completing)
         1. REPORT NO.
         EPA-600/7-79-144
                                                             3. RECIPIENT'S ACCESSION NO.
        4. TITLE AND SUBTITLE
         Trace Element Characterization of Coal Wastes: Third
         Annual Progress Report
                               E. REPORT DATE
                                June 1979
                               6. PERFORMING ORGANIZATION CODE
          AUTHORS E.M.Wewerka, J.M.Williams, L.E.Wangen,
         J.P.Bertino, P.L.Wanek, J.D.Olsen, E.F.Thode,
         and P. Wagner	
                                I. PERFORMING ORGANIZATION REPORT NO.

                                LA-7831-PR
        9. PERFORMING OROANIZATION NAME AND ADDRESS
         Los Alamos Scientific Laboratory
         University of California
         Los Alamos, New Mexico 87545
                               10. PROGRAM ELEMENT NO.

                               INE825
                               11. CONTRACT/GRANT NO.
                               EPA Interagency Agreement
                                IAG-D5-E681
         1J. SPONSORING AGENCY NAME AND ADDRESS
         EPA, Office of Research and Development (*)
         Industrial Environmental Research Laboratory
         Research Triangle Park, NC  27711
                               13. TYPE OF REPORT AND PERIOD COVERED
                               Annual: 10/77 - 9A8	
                               14. SPONSORING AGENCY CODE
                                 EPA/600/13
        is. SUPPLEMENTARY NOTES Cogp0nsored by j^g  Project off leers ~.  D. A.Kirchgessner (EPA)
         and C. Grua (DoE). EPA-600/7-78-028 and -028a are earlier progress reports.
        16. ABSTRACT
                   The report gives third year results of a program to characterize the
         trace element content of coal waste.  In 1978 laboratory experiments were performed
         to investigate the efficacy of several control options to treat coal wastes at the pre-
         paration plant or during disposal. The research revealed that calcining Is one of the
         more effective and permanent means of treating high sulfur coal wastes before dis-
         posal to decrease, quite dramatically, the release of environmentally undesirable
         pollutants into the drainages from disposal sites.  Co-disposal of the coal wastes with
         lime or limestone to neutralize the acid drainage and contain soluble aqueous contam-
         inants within the waste site is also a promising control. Other experiments examined
         the feasibility of using  natural sealants (e.g. , clays, soils, calcite, and cements) to
         isolate the disposal site from its immediate environment.  The report discusses  the
         various trade offs for these control options in terms of contaminant reduction, com-
         plexity, permanency, and cost. An assessment of coal preparation wastes from the
         Appalachian region  has begun: work on refuse from a single plant indicates signifi-
         cant acid drainage,  even with coal wastes with a low percentage (< 1%) of pyrite.
         Experiments show that Al, Mn, Fe, Ni, and Cu ions are potentially of concern,  as
         their concentrations exceed certain Multimedia Environmental Goal (MEG) values.
                                     KEY WORDS AND DOCUMENT ANALYSIS
                        DESCRIPTORS
                                                 b.lDENTIFIERS/OPEN ENDED TERMS
                                                                         c. COSATi Field/Group
         Pollution
         Coal
         Waste Treatment
         Roasting
         Chemical Analysis
         Sulfur
Drainage
Calcium Oxides
Calcium Carbonates
Sealers
Pollution Control
Stationary Sources
Coal Waste
Trace Elements
Acid Drainage
13B
08G

13H
07D
07B
11A
         8. DISTRIBUTION STATEMENT
         Release to Public
                                                 IS. SECURITY CL
                                                 Unclassified
                                            31. NO. OF PAGES
                                               94
                    30. SECURITY CLAS
                    Unclassified
        EPA Form 1220-1 (I-T1)
86

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