Jrtice of Research and Development Laboratory
               Research Triangle Park, North Carolina 27711
                           EPA-600/7-77-139
                           _    u  n Q7T
                           DeCemDef 1977
ENVIRONMENTAL ASSESSMENT
OF SOLID RESIDUES FROM
FLUIDIZED-BED FUEL PROCESSING
Interagency
Energy-Environment
Research and Development
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 seven series.
These seven broad categories were established  to  facilitate further
development and application of environmental  technology.  Elimination
of traditional grouping was consciously planned to  foster technology
transfer and a maximum interface in related fields.  The seven 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

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-agehcy 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 systems.   The  goal of the Program
is to assure the rapid development of domestic  energy supplies in an
environmentally—compatible manner by providing the necessary
environmental data and control technology. Investigations include
analyses 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 environmental issues.

                            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 recommen-
dation for use.
This document is available to the public through the National  Technical
Information Service, Springfield, Virginia  22161.

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                                           EPA-600/7-77-139
                                            December 1977
ENVIRONMENTAL ASSESSMENT OF SOLID
      RESIDUES FROM FLUIDIZED-BED
                FUEL PROCESSING
                            by

                      Ralph Stone and Richard Kahle

                       Ralph Stone and Co., Inc.
                      10954 Santa Monica Boulevard
                      Los Angeles, California 90025

                       Contract No. 68-03-2347
                      Program Element No. EHB536
                     EPA Project Officer: Waiter B. Steen

                   Industrial Environmental Research Laboratory
                    Office of Energy, Minerals, and Industry
                     Research Triangle Park, N.C. 27711
                          Prepared for

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

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                                    ABSTRACT

    This report presents results for the first 15 months of an environmental assessment of
the solid residues generated by flufdized-bed coal combustion and oil gasification. Tasks
included a literature search, chemical and physical residue characterization,  laboratory
leaching studies, and testing of residues in various materials and agricultural applications.

    The literature search reviewed current fluidized-bed combustion technology, identi-
fied products in which residues might be used, and provided data on typical soil and
geologic conditions at the disposal sites being evaluated.  Laboratory tests included total
chemical characterization,  composition of acid-, base-, and water-soluble fractions,
cation exchanged capacity, BOD, temperature change from water addition, particle size
distribution, dry density, specific gravity, permeability, water-holding capacity, moisture
content, and small-scale column  leaching studies.

    Pilot-scale columns  simulated abandoned coal mines, dolomite and limestone quarries,
sanitary landfills,  soils ,and the ocean.  Water was added to columns on a prescribed
schedule and the resulting leachate was collected and analyzed for chemical constituents.
The data were used to assess the potential  for impact on water quality, and the capacity
of the disposal environment  to attenuate degradation.

    Product tests and preliminary market analyses were conducted for residue use in
concrete, asphalt, soil cement> and lime/fly ash aggregate.  Uses as acid mine drainage
neutralizer and agricultural soil conditioner/ fertilizer were also evaluated.

    This annual  report was submitted in partial fulfillment of Contract No. 68-03-2347
by Ralph Stone and Company, Inc., under the sponsorship of the U.S.  Environmental
Protection Agency.  This report covers the period from November 5,  1975 to December
31, 1976.   Further work  continues to be performed and will be summarized in future
reports.

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                                CONTENTS
                                                                             Page

Abstract
Figures
Tables
Acknowl edgments

   1.    Introduction                                                          1
            Background                                                        1
            Objectives                                                        5
            Scope of Work                                                     5

   2.    Summary                                                             8
            Introduction                                                        8
            Discussion                                                         8
            Continuing Investigations                                           9

   3.    Preliminary Results                                                   10

   4.    Fluidized-Bed Coal Combustion                                        14
            Introduction                                                       14
            Process Descriptions                                               14
            Once Through Operation                                           16

   5.    Residue Characterization                                              20
            Purpose                                                           20
            Residue Characteristics                                             20
            Chemical Composition                                              24
            Chemical Properties Tests                                          27
            Physical Properties                                                27
            Results                                                           37

   6.    Pilot Column Studies of Residue Disposal                                55
            Purpose                                                           55
            Simulated Sedimentary Environment Columns                         55
            Column Test Procedures                                            69
                                        ill

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                             CONTENTS (Cont.)
                                                                           Page

   7.    Reuse Potential for Fluidized-Bed Residues                            149
           Introduction                                                     149
           Overall Reuse Prospects                                          149
           Types of Coal Ash                                                153
           Coal Ash Utilization                                             153
           Specific Applications for Coal Ash                                159
           Specific Applications of Lime/Limestone Wet Scrubber Residues     182
           Potential Structural Materials Applications: Test Results             186
           Potential Agricultural Application of FBC Residues                 201
           Marketing Analysis Methodology                                  226
           Economic Analysis of Specific Applications                        229

References                                                                 235
Appendices                                                                 252

   A.   Laboratory Analytical Methods                                      252
   B.   Sample Data Sheet                                                  256
   C.   Column Leachate Concentrations                                     259
   D.   Characterization of Similar Residues                                 297
   E.   Description of FBC Units - Providing Residues                         307
   F.   Fluidized-Bed Oil Gasification                                      320
                                        IV

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                                    FIGURES
Number                                                                         Page
  1         Direct contact fluidized-bed stream generator                           15
  2         Once through pressurized fluidized-bed boiler power plant               17
  3         Laboratory-scale column leaching                                      25
  4         Temperature change from water addition to dry. residues                  29
  5         Temperature change from water addition to dry residues                  30
  6         Particle size analyses: coal combustion residues                          32
  7         Particle size analyses: oil gasification residues                          33
  8         Particle size analysis: pea gravel, granite bedrock, and large gravel      34
  9         Particle size analysis: silica sand and decomposed granite                35
  10        Particle size analysis: coal,dolomite,and limestone                       36
  11         BOD from residue water extracts                                        44
  12        Leaching characteristics of VFA and VSBM                              52
  13        Leaching characteristics of NJFA and  NJSBM                           53
  14        Leaching characteristics of EFA and ESBM                               54
  15        Simulated sedimentary environment: sea water                           56
  16        Legend for test column disposal environments                            57
  17        Sanitary landfill  test column                                           58
  18        Abandoned  limestone quarry test columns                                62
  19        Simulated sedimentary environment: dolomite quarry                     63
  20        Stratigraphic section of a typical coal  mine                             65
  21         Abandoned  coal mine test column                                       66
  22        Lysimeter construction and test column placement                        72
  23        Original location of representative soil samples                          77
  24        Typical test column  leachate collection system schematic                 82
  25        Outdoor columns leachate sampling apparatus                           84
  26        Drainage through limestone quarry columns                              85
  27        Drainage through dolomite quarry columns                               86
  28        Drainage through sanitary  landfill columns                              87

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                                     FIGURES (Cont.)
 Number
   29        Drainage through coal mine columns                                  8°
   30        Drainage through ocean disposal columns                              89
   31        Legend of typical columns for Figures 32 through 176                  103
 32-47     Test column leachate cumulative balances: chloride                   104
 48 - 63     Test column leachate cumulative balances: iron                       108
 64-83     Test column leachate cumulative balances: lead                       112
 84-103    Test column leachate cumulative balances: nickel                     117
104-123    Test column leachate cumulative balances: sulfate                    122
124 - 143    Test column leachate cumulative balances: zinc                       127
144 - 159    Specific conductivity and total  dissolved solid of  leachate from
                 columns 2 through 17                                          132
160-176    pH of  leachate from  columns 1-17                                  140
   177       Effect of freeze-thaw cycles on LCFA compressive strength             164
   178       Change of length with temperature for cured LFA  specimen             165
   179       Effect of curing time and temperature on LFA compressive strength      167
   180       Effect of curing time and temperature on LCFA compressive strength    168
   181        Effect of lime  content and curing conditions on LFA strength           170
   182        Effect of fly ash on LFA density                                     171
   183        LFA moisture correlation chart                                      174
   184        pH leachate for acid mine drainage                                  176
   185        Aerated or foamed cellular concrete production flow diagram          184
   186        Formed concrete production flow sheet                               185
   187        CS brick production flow diagram                                   187
   188        Concrete compressive strength tests: NJFA/VFA/  SBM after seven
                day cure                                                      195
   189        Concrete compressive strength tests: NJFA, VFA, VSBM after
                28-day cure                                                   196
   190        Concrete compressive strength tests: NJSBM,ESBM,EFA after
                7-day cure                                                    197
   191        Concrete compressive strength tests: NJSBM,EFA,ESBM after
                28-day cure                                                   198
                                        vi

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                                    FIGURES (Cont.)
 Number                                                                     Page
   192      Result of reaction between residues and emulsified asphalt             200
   193      Asphalt compressive strength tests: VSBM,NJSBM,ESBM after
                 29-hour cure                                                 202
   194      Asphalt campressive strength tests: VSBM,NJSBM,ESBM after
                 7-day cure                                                   203
   195      Asphalt comressive strength  tests: NJFA, EFA after 29-hour cure       204
   196      Asphalt compressive strength tests: NJFA7EFA after seven day cure     205
   197      Experiment 1 tomato plant growth: Exxon, New Jersey                 208
   198      Experiment 1 tomato plant growth: PER,Virginia                      209
   199      Experiment 2-A tomato plant growth                                 211
   200      Mean tomato plant height, experiment 2: VFA,FSFA,CFA             214
   201      Mean tomato plant height, experiment 2:  NJSBM,VSBM,NJFA        215
   202      Tomato plant growth vs. soil pH,experiment 2                        218
   203      Calcium content in digested tomato plant tissue: experiment 2          220
   204      Magnesium content in  digested tomato plant tissue: experiment 2       221
   205      Iron content in digested tomato plant tissue: experiment 2              222
   206      Manganese content in  digested tomato plant tissue: experiment 2       223
   207      Sulfate content in digested tomato plant tissue: experiment 2           224
   208      Zinc content in digested tomato plant tissue: experiment 2             225
   209      Distance to U.S. coal-fired power plants                            227
C-l-C-16   Chloride leached from Columns 2 through 17                         260
C-17-C-32  Iron leached from Columns 1 through  20                             264
C-33-C-£2  Lead leached from Columns  1 through 20                             268
C-53-C-72  Nickel leached from Columns  1 through 20                           273
C-73-C-92  Sulfate leached from Columns  1 through 20                           278
C-93-C-112 Zinc leached from Column  1 through 20                             283
C-113-C-130 pH  of leachate from  Column 1  through 20                          288
D-l
Concentration range and average of U.S. fly ash constituents
                                        vii
301

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                                   FIGURES (Cont.)
Number                                                                        Pqae
  E-l       FBC construction detail (side view)                                    309
  E-2       FBC construction detail (front view)                                   310
  E-3       Fluidized bed module: internal construction                            311
  E-4       FBM and regenerator flow diagram                                     312
  E-5       Section view of the integrated BVM/CBC unit                          314
  E-6       Bed material flow paths FBM,CBC regenerator                          315
  E-7       Pressurized FBC pilot plant, Linden,New Jersey                        316
  E-8       Exxon FBC unit                                                      319
  F-l       Low pressure fluidized bed oil gasification for power generation         321
  F-2       High pressure fluidized bed oil gasification for power generation        322
  F-3       Modes of operation,fluidized  bed oil gasification plant                 323
  F-4       Energy balances flow diagram                                         327
  F-5       Regenerative high-pressure oil gasification process                      328
  F-6       Esso,England oil gasification system                                   335
  F-7       Batch reactor                                                        336
                                        viii

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                                   TABLES
Number                                                                      Page
   1      U.S. Electric Generating Capacity                                   2
   2      U.S. Electricity Generation by Type of Fuel: 1970-1990               2
   3      Projected Annual Fuel Requirements: Steam Electric Power Plants        3
   4      Potential  U.S. Sulfur  Dioxide Pollution with No Abatement            3
   5      Sulfur Dioxide Abatement Processes                                   4
   6      Identification of Residues                                            6
   7      Environmental Impact Comparison of FBC Processes                    18
   8      Pilot Plant Operation for Characterized Residues                      21
   9      Characterization of Pope,Evans,and Robbins Bituminous Coal Samples   22
  10      Characterization of Pope,Evans, and Robbins Calcined Limestone
               Samples                                                       23
  11      Characterization of Exxon Miniplant Coal Samples                    23
  12      Stratigraphic Materials Simulated in Leaching Tests                   26
  13      Residue Cation Exchange Capacity                                   28
  14      Residue Acid Neutralization Capacity                                28
  15      Residue Physical Properties                                          38
  16      Permeability of Residues and Column Materials                        39
  17      Laboratory Characterization of Residues 1. Exxon  Miniplant,
               Linden,New Jersey                                             40
  18      Laboratory Characterization of Residues II. Pope,Evans, and Robbins,
               Alexandria,Virginia                                            41
  19      Laboratory Characterization of Residues III.  Esso,England              42
  20      Laboratory Characterization of Residues IV.  Esso,England              43
  21      Laboratory Leaching Tests: Granite  Bedrock                           45
  22      Laboratory Leaching Tests: Bituminous Coal                           46
  23      Laboratory Leaching Tests:  Dolomite                                 47
  24      Laboratory Leaching Tests: Limestone                                 48
  25      Laboratory Leaching Tests: "oO Silica Sand                           49
  26      Laboratory Leaching Tests: *16 Silica Sand                           50

                                         ix

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                                    TABLES  (Cont.)
Number
  27        Laboratory Leaching Tests: Claystone                                51
  28        Representative Thickness Sanitary Landfill Simulated in Test Columns  59
  29        Representative Thickness of Limestone and Dolomite Simulation
                Test Columns                                                  61
  30        Representative Thickness of Coal Mine Simulation Test Column        64
  31         Material Densities of Field Strata and Test Columns                   67
  32        Material Densities of Natural Strata and Test Columns                68
  33        Average Field Densities of Materials                                68
  34        Column and Residue  Identification                                   70
  35         Criteria Definition for Grading Analysis                             73
  36         Column Materials Grading Analysis                                 74
 37        Test Column Soils Characteristics                                   76
 38        Estimated Residential and Commercial Solid Waste Generation
                by Kind of Material and Product Source Category, 1971           78
 39        Sanitary Landfill - As Mixed Test Column                            80
 40        Materials in Test Column Layers by Weight                           81
 41        Complete Analysis of Los Angeles Owens  River Aqueduct (Fresh Water)
                Columns Test                                                  90
 42        Sea Water Analysis                                                91
 43        Residues Added to Columns                                         92
 44         Procedures for Sampling and Filling the Flooded Ocean Water Test
                Columns                                                      94
 45        Constituent Removal  by Ocean Disposal Column Strata                95
 46        Constituent Removal  by Limestone Quarry Column Strata              96
 47         Constituent Removal  by Dolomite Quarry Column Strata               97
  48         Constituent Removal  by Sanitary  Landfill Column Strata               98
 49         Constituent Removal  by Coal Mine Column Strata                     99
 50         EPA Proposed Regulations on Interim Primary Drinking Water
                Standards, 1975                                              10Q
 51        Surface Water Criteria for Public Water Supplies                    101
 52         Estimated Ash  Utilization Potential

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                                   TABLES (Cont.)
Number                                                                    Page
 53        Comparison of Ash Compositions                                    152
 54        Comparison of FBC Residue Compositions                             152
 55        Comparative Ash Production and Utilization, 1966 through 1972        154
 56        Ash Collection and Utilization, 1971                                156
 57        Known Miscellaneous Uses for Ash and Slag                          157
 58        Known Uses for Ash Removed from Plant at No Cost to Utility, 1971     158
 59        Development of Ash Production and  Use in the Economic Commission
               for Europe Region                                             160
 60        Density of Fly Ash Compared with Traditional Fills                   161
 61        Effect of Fly Ash Content on  LFA Strength and Durability             169
 62        Average Cement Requirements of Miscellaneous Materials             179
 63        Normal Range of Cement Requirements for B and C Horizon Soil        179
 64        Effect of Adding Zn and Varying the pH in the Soil on Zn Content
               and Yield Reduction of  Chard Leaves                           181
 65        Effects of Soil pH on Soybean Plants' Mineral Uptake                 181
 66        Potential Structural Materials Applications: Tests Performed            188
 67        Composition of Concrete  Test Cylinders                              189
 68        Diameter and Area of Concrete Test Cylinders: Seven-Day Cure        190
 69        Diameter and Area of Concrete Test Cylinders: Twenty-eight
               Day Cure   .                                                 192
 70        Results of Compressive Concrete Strength  Test After Seven Days        193
 71        Results of Compressive Concrete Strength  Test After Twenty-Eight
               Days                                                         194
 72        Asphalt Sample Compositions                                       199
 73        Planting Schedule for Agricultural Tests                              206
 74        Experiment 2-A: Tomato Plant Growth Results                        212
 75        pH of Soil  Residue Mixture                                         216
 76        pH of Soil  Residue Mixture After Crop 2 Harvest                      217
 77        Tomato Plant Digestion Analytical Results                           219
 78        Sludge Fixation  Costing Estimates                                   230
                                       XI

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                                   TABLES (Cont.)
Number
 79        Residue Value for Use in Concrete                                  23°
 80        Imputed Value of Residues in Asphalt Applications                   231
 81        Fluidized-Bed Residues as a Substitute for Calcium Carbonate in
               Peanut Growing                                              233
 A*-l       Soil Preparatory Methods                                          253
 A-2       Analytical Methods                                               254
 C-l       Variation in Coal Mine  Column Leachate Constituents                292
 C-2       Variation in Sanitary Landfill Column Leachate Constituents          293
 C-3       Variation in Dolomite Quarry Column Leachate Constituents          294
 C-4       Variation in Limestone Quarry Column Leachate Constituents         295
 C-5       Variation in Sea Water Column Leachate Constituents                296
 D-l       Common Minerals in U.S. Coals                                   298
 D-2       Chemical  Constituents of Coal Ash                                  298
 D-3       Coal Ash Solubility in Distilled Water                              299
 D-4       Mineral Phases Found in Coal Ash                                  299
 D-5       Physical Properties of Fly Ash from  Pulverized Coal Fired Plants      300
 D-6       Oxide Analyses of Incinerator Fly Ash from Typical Refuse            302
 D-7       Elemental Head Sample Analyses of Municipal Incinerator Fly Ashes   303
 D-8       Wet Chemical Analysis of Sludge Standards                          304
 D-9       Identification of APCS Sludge Standards                            305
 D-10      X-ray Analysis of APCS  Sludges                                   306
 E-l        Design Parameters: Exxon Miniplant                                319
 F-l        Atmospheric Pressure Oil Gasification Specifications                 324
 F-2        Specifications for Fluidized Bed Operation                          326-
 F-3        Gasification Product Compositions                                  329
 F-4       Environmental Impact Comparison                                  33T
 F-5        Advantages of Atmospheric Pressure Oil Gasification Over Stack
              Gas Wet Scrubbers                                            332
F-6        Summary of Experimental Results                                   334
                                       xii

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                                 ACKNOWLEDGMENTS

    The excellent support and direction provided by Mr. D. Bruce Henschel,  Program
Manager,  representing the U.S. EPA Industrial Environmental Research Laboratory,
Research Triangle Park,  North Carolina, is gratefully acknowledged.  We are equally
grateful to Mr. Richard A. Chapman under whose direction the work was performed.
Because Mr. Chapman is no longer with the program,  the work is continuing under the
direction of  IERL/RTP.

    We also acknowledge the information and close cooperation provided by Mr. William
T. Harvey and other Office of Fossil Energy officials of ERDA, Washington,D.C.; Mr.
Orus L. Bennett of the U.S. Department of Agriculture, Agricultural Research Service,
Morgantown, West Virginia; Dr. Stephen K. Seale of the Division of Chemical Products,
Tennessee Valley  Authority, Muscle Shoals, Alabamapand Mr. Jerome Mahoch of the
U.S. Army Waterways Experiment Station, Vicksburg, Mississippi.

    We appreciate the excellent cooperation, information and residue samples provided
by the following fluidized-bed pilot plant and Rivesville facility contractors; Messrs.
Robert Reid, Manager, Pope, Evans,  and Robbins,lnc., Alexandria, Va.;Dr. Ronald C.
Hoke, Exxon Research and Engineering Co., Linden,New Jersey; Dr. G.L. Johnes, Esso
Research Centre,  Abingdon, England; and Mr. H.f.  McCarthy, Allegheny Power Services
Corp., Greensburg, Pa.

    Technical review coordination for the contracted U.S. EPA fluidized-bed program
was provided by Mr.  Karl Landstrom with assistance from Messrs. David Sharp and K. T. Liu
of Battelle,  Columbus, Ohio.  Program review and data was provided by Dr. Harvey Abelson
of the Mitre Corp.
                                       xili

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                                  CHAPTER 1

                               INTRODUCTION


                                  Background
   Total electricity consumption in the United States is projected to increase at an
annual rate of 7 to 8 percent over 1970-1990.  The relative shares of coal, oil, gas,
and hydroelectric  generation are expected to decrease as nuclear sources come to
predominate.  These trends are shown in Tables 1  and 2.  However, the absolute
quantities of coal  and oil used should increase along with total consumption.  Projected
fuel usage  requirements are shown  in Table 3.

   Combustion of more coal and oil implies increased sulfur oxides generation, as
shown in Table 4.  This  may be aggravated by a projected increase in the average
sulfur content of coal burned, from the current 2.7 percent to 3.5 percent by the
year 2000.  Airborne sulfur compounds are associated with damage to human health,
vegetation, and materials. There  are many ways being researched to reduce sulfur
oxide emissions, as shown in  Table 5.

   One approach to alleviating the problem is to develop ways of burning high sulfur
fuels  without high-sulfur oxide emissions.   Among the options being researched are
fluidized-bed combustion of high  sulfur coal and fluidized-bed gasification of high
sulfur residual oils.  The EPA is evaluating two high  sulfur coal fluidized-bed combustion
pilot  plants. The  U.S.  Energy Research and Development Administration (ERDA) is
supporting  one small  scale and one large scale pilot plant.  One high sulfur residual oil
fluidized-bed reactor pilot plant is being  operated in England under an EPA international
agreement. In  these plants,  either pulverized limestone or dolomite bed material  is
admixed to the  coal or oil being burned.   The sulfur  in the  fuels reacts with the bed
material to form calcium and magnesium su I fates and,to some degree, sulfites and sul-
fides. Gaseous sulfur emissions are thus greatly reduced, but solid residues are increased,
These residues consist of calcium and magnesium oxides (from unreacted portions of
dolomite and limestone),  calcium and magnesium sulfur compounds, traces of unburned
coal and oil and their stack and bottom ash, and inert matter originated from natural
dolomite or limestone.

   The disposal of these residues is a matter of concern. For example, toxic substances
might be leached from the residues into ground or surface waters. This study was initi-
ated because there had been  no extensive  research into the environmental impacts of
the disposal of these  solid residues or the feasibility of their recovery.

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IMDLC 1 . U . -> . L
Type of Plant
Fossil steam
Nuclear steam
Steam subtotal
Hydroelectric - conventional
Hydroelectric - pumped storage
Gas turbine and diesel
Totals
Source: 159 .
TABLE 2. U.S. ELECTRICITY
Year Coal Oil
1970 46.4 11.8
1980 36.5 12.4
1990 26.7 8.0
1970(Actual)
%of
Capacity 7oj-a[
flO^Mw)
260 76
6 2
266 78
52 15
4 1
19 6
341 1 00

1980 (Projected) 1990 (Projected)
%of %°f
393 59
147 22
540 81
68 10
27 4
31 5
666 100

GENERATION BY TYPE OF FUFJ
Percent of Total
Gas
24.2
12.4
7.2
Generation
Nuclear
1.4
27.6
47.3
557 44
500 40
1 ,057 84
82 6
71 6
51 4
1,261 100

.1970-1990
Hydroejecfric
16.2
11.1
10.8
Source:  159,

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             TABLE 3.  PROJECTED ANNUAL FUEL REQUIREMENTS:
                           STEAM ELECTRIC POWER PLANTS
Fuel
Coal
Natural gas
Residual fuel oil
Uranium ore
Unit
106 kkg
9
10 cu m
106 bbl
kkg°
1970
292
185
331
6,800
1980
454
106
640
37,000
1990
635
118
800
115,000
 kkg of UgOn required to supply feed for diffusion plants without plutonium recycle.


Source: 158.
            TABLE 4.  POTENTIAL U. S. SULFUR DIOXIDE POLLUTION
                                 WITH NO ABATEMENT
                 Source
                                            Annual Emission of SO2
-
Power plant operation (coal and oil)
Other combustion of coal
Combustion of petroleum products
(excluding power plant oil)
Smelting of metallic ores
Petroleum refinery operation
Miscellaneous sources
Total
1967
13.6
4.6
2.5
3.4
1.9
1.8
27.9
1970
18.1
4.4
3.1
3.6
2.2
1.8
22.2
1980
37.3
3.6
3.5
4.8
3.6
2.4
55.2
1990
56.2
2.8
3.9
6.4
5.9
3.1
78.4
2000
85.7
1.5
4.6
8.7
9.5
4.1
114.1
a Includes coke processing, HLSO, plants, coal refuse banks, refuse incineration, and
  pulp and paper manufacturing.


Source; 160.

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 .   	 TABLE 5,  SULFUR DIOXIDE ABATEMENT PROCESSES

 1.   Precombustion processes
     a. Coal and oil cleaning
     b. Coal and oil gasification
     c. Fluldized bed gasification
 2.   Combustion processes

     a. Fluidized bed combustion
     b. Black, Sivalls, and Bryson

 3.   Limestone processes
     a. Wet scrubbing
     b. Dry removal

4.   Processes  for sulfur recovery from stack gases
    a.  Cat - Ox
    b.  WeUman-Lord
    c.  Esso-Babcock & Wilcox adsorbent
    d.  Formate scrubbing
    e.  Ammonia scrubbing
    f.  Westvaco char
    g.  Molten carbonate
    h.  Sodium bicarbonate adsorption
    i.  Modified Claus
    k.  Catalytic chamber
    I.  Ionics/Stone  & Webster
    m. Alkalized alumina

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                                      Objectives

    The general objective of this project was to assess the environmental  impact of the
disposal or the recovery of the residues which would be generated with widespread commercial
use of the fluidized-bed process for high sulfur coal combustion and gasification of high
sulfur residual oil.  Specific objectives were to:

    «  Determine  the  chemical and physical characteristics of the  residues from the
        fluid!zed bed process applied to coal and oil.

    •    Identify the leachate water pollution constituents and quantities resulting from
        land disposal of residues.

    •   Evaluate the potential effects of disposing the residues into different soi! and
        sedimentary environments and into the ocean.

    •    Investigate  the potential for recovery of the solid residues.

    •    Determine the needs for treating the residues and establishing methods for the
         disposal of such wastes.

                                   Scope of  Work                    ^

    Literature reviews, laboratory studies, and pilot test columns were used during Year 01
to determine the potential environmental impacts from disposal of solid residues from
fluidized-bed operations.  Residues from both the fluidized-bed combustion of high sulfur
coaiand fiuidized bed gasification of high sulfur residual oils were tested.  Residues
are being obtained from three pilot plants.  The residues received are identified in Table
6; the symbol  abbreviations shown will be used throughout the report in reference to the
three pilot plants.

     In general, the literature search provided information on the disposal and environ-
mental impacts of similar residues such as coal  ash or limestone SOX scrubber wastes.
Information on similar types of waste residues were obtained in laboratory and pilot test
reports.  From available sources, estimates were made of the conditions for and the levels
of pollutants anticipated from the residue wastes in  various environments.   Process descrip-
tions of material flows for plants generating residues were obtained.  Typical natural
conditions  were selected for our study work. The results of the literature  search were of
value in designing the specific limits and goals on the laboratory  and  column tests.

    The laboratory studies were used to duplicate a range of theoretical disposal environ-
ments on a small scale.  Residues were tested under controlled conditions; environmental
variables were controlled to duplicate many real conditions  that could affect the behavior
of the residues in natural environments. All leachate was collected and analyzed.

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                 TABIF6.   lOFNTlFirATIONJ OFRFSIDL1ES.
  Symbol
Residue
Source
 Nome of Residue
       Riot Plant
        location
CFA
FSFA

VFA

VSBM

NJFA
NJSBM
EFA
 ESBM
  Oil
  Oil

  Coal

  Coal

  Coal
  Coal
  Oil
  Oil
Cyclone fly ash         Esso; Abingdon, England
Fines,stack,regenerator, Esso; Abingdon, England
gasifier, fly ash
Virginia fly ash

Virginia spent bed
material
New Jersey fly ash
New Jersey spent bed
material
English fly ash
English spent bed
material
Pope, Evans,and Robbins;
Alexandria, Virginia
Pope, Evans,and Robbins;
Alexandria, Virginia
Exxon; Linden, New Jersey
Exxon; Linden, New Jersey

Esso; Abingdon, England
Esso; Abingdon, England

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Profiles of the residues for different disposal methods have been determined.  The results
of the laboratory studies were used to design the test columns.  Table 44 presents infor-
mation on the residues used in the laboratory and test column studies.

     The field work will attempt to verify the results of the laboratory and column studies
in natural environments.  To do so,  test plots will be constructed in the natural environ-
ments, and leachate monitoring probes and wells will  be installed.  Records will be kept
of environmental conditions, and leachate and groundwater quality will be monitored.
Analyses will be conducted to determine those disposal site factors which can minimize
adverse environmental impacts.

     Studies were also undertaken to determine the possibility of recovering and market-
ing the residues instead of disposing of them. Laboratory tests are being conducted to
determine the feasibility of using these residues for commercial products.  These tests
compare the properties of materials produced using residues with those made with conven-
tional raw materials.  A preliminary market study was initiated to determine the market
potentials for the residues and their finished products.

     Concurrent with the product feasibility task, an evaluation of requirements for treat-
 ing residues was initiated to establish whether treatment can enhance product use or is
 required for disposal.  The disposal needs for liquid wastes was also investigated in terms of
 environmental impacts.

    The Rivesvilie,West Virginia field test area was selected by first identifying potential
sites from literature, from our company knowledge, and from the  EPA.  Mail and telephone
contacts were used to help screen candidate sites for local  conditions and cooperation.  A
preliminary two-day visit was made to the Rivesville area.  The preliminary visit reviewed
available facilities and transportation requirements.

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                                      CHAPTER 2

                                      SUMMARY
                                       Introduction

     The overall purpose of the proposed work is to determine the environmental impact of
 the disposal of residues from the fluidized-bed combustion of high sulfur coal, and fluidized-
 bed gasification of high sulfur residual oil.  The specific objectives to be achieved are to
 determine:
 1 .   The characteristics of the solid, sludge, and liquid residues from the fluidized-bed
     processes applied to coal and oil.

 2.   The leachate constituents and quantities from land and ocean site disposal of the
     residues.

 3.   Other potential environmental  effects from disposing the residues into alternative land
     and water sites.

4.  The potential for  utilizing solid residues for manufacture of commercial products and for
    other
5.   Pretreatment requirements for the residues, prior to their disposal.

                                        Discussion

     Literature reviews, laboratory tests, and field studies are being used to determine the
environmental  impacts of disposal of solid and liquid residues from fluidized-bed operations.
Residues from fluidized-bed combustion of high-sulfur coal and fluidized-bed gasification
of high-suffur residual oils are being tested.  Residues were obtained from three pilot plants;
two ere supported by the EPA, and one Is supported by  ERDA.  The three plants
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    A comprehensive program of residue characterization was initiated to determine the
chemical and physical properties of the six residues. The resultant physical property data
was used to hydraulically design 36-plus pilot test columns.for leachate studies.  The resul-
tant chemical property data was used as a  baseline for the leachate tests and also to identify
constituents for which the test column leachate  would be analyzed.

    The laboratory studies were used to duplicate, on a small scale, eight disposal environ-
menlv toal mine, dolomite and limestone  quarries, ocean, sanitary landfill, and sand,clay
and sHt soils.  Environmental variables were controlled to duplicate as many
real world conditions as possible that would affect the behavior of the residues in natural
environtnentE.  All leachate was collected, and analyzed.  rVecise analytical profiles of
the residues and their disposal conditions were established.

     Large scale field test programs were postponed when it proved impossible to obtain
sufficient quantities of residues. To compensate, an expanded program of pilot scale  test
columns,  laboratory columns, and product testing was initiated.  When additional residues
became available, the data obtained from the aforementioned studies will be used to design
and monitor the large scale field leachate tests.

    Studies were undertaken to determine the possibility of recovering and marketing the
residues instead of disposing of  them.  Bench  tests investigated using residues in the manufac-
ture of certain commercial products.  Work is in progress using residues in soil cement,  lime-
fly ash-aggregate and Iime--fly  ash-cement-aggregate mixtures, and as load bearing fill.
Tests were completed using residues in concrete and asphalt.  These tests compared the pro-
perties of the recovered product with that  produced using conventional raw materials.  A
preliminary market study was performed to establish the market potentials for the residues
and their finished products.

     Concurrent with the product feasibility task, an evaluation of requirements for treating
residues was made to see if pretreatment can  enhance product use or is required for disposal.

     Potential use of the spent residues as soil conditioners for agricultural purposes was
investigated.  Mixtures of fly ash and bed material with soil have produced a variety  of
crops (tomato, spinach,  lettuce, corn, and sorghum).  Acidic soils may contain high levels
of aluminum and manganese which are easily  soluble and sometimes believed to be toxic
to crops; however, it has been known  for a long time that an  increase in pH will decrease
the uptake of heavy metals. Lime is presently used to help increase the pH but the residues
would presumably replace  the lime.

                                Continuing Investigations

     The work planned for  the second  and third  years includes  continuing the following:
long-term leaching in the  36 test columns, and completion of  product testing of residue use
as a cement substitute and as a  soil  conditioner.

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                                     CHAPTER 3
                                PRELIMINARY RESULTS

     The fly ash and fluidized-bed residue materials used in the study were from pilot plants
 operated by Exxon, Linden, New Jersey; Pope, Evans, and Robbins,Alexandria,Virgin!a;
 and Esso, in England.  For brevity they are referred to in this chapter as Exxon,  PER, and
 Esso.

     The following results are based on partial information and may change when the work,
 which is still in progress, is completed:

  .   1.   A comprehensive review of literature indicated that no historical environmental
 data existed on coal fluidized-bed combustion and  oil gasification,  other than progress re-
 ports on the various pilot plants and technologies currently under development.

     2.   No full-scale commercial fluidieed-bed power plant is at present operating in the
 world.

     3.   Extensive literature  describing oonventioncrl coal and oil combustion residue,
 physical and chemical characteristics, their ultimate disposal, and recovery alternatives was
 found.    Similarly, considerable literature on lime and magnesium sludge residues and
 their reuse in various applications was found.

     4.   The literature review and data developed  from over 200 different sources during
the first year for this project report indicated the following differences between fly ash
from fluidized-bed combustion and conventional coal and oil-fired combustion*.

     •    Residues from fluidized-bed combustion (FBC) are derived from spent stone and
         fly ash, and differ from conventional coal combustion dolomite or lime scrubber
         sludges and fly/bottom ashes.

     •    Fluidized-bed combustion normally produces  solid residues, whereas conventional
         combustion scrubbers produce liquid  sludges as well as some bottom ash solids.

     •    Test fluidized-bed fly and bottom ash samples wece dry,  whereas conventional
         combustion plant ashes are wetted to quench burning coals and to cool the residues.

     •    The FBC residue samples had higher specific gravities (weights) than conventional
         fly ash, and thus would not be as suitable for use in lightweight concrete and
         structural fills.

     •    The FBC fly/bed test residues had been recirculated and  hence contain  less organic
         material compared to conventional unrecirculated residues.
                                          10

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     5.  Results of laboratory mixing/leaching tests for residue characterization showed water
soluble fractions in Exxon fly ash were higher than acid soluble fractions for boron and mag-
nesium, and higher than base soluble fractions for nitrate.  Water soluble fractions in Exxon
spent bed material were higher than acid soluble fractions for sulfate, boron, lead, magnesium,
and sodium, and higher than base soluble fractions for nitrate,  aluminum, calcium,  copper,
manganese, and molybdenum.

     Water soluble fractions in  PER fly ash were higher than acid soluble fractions for sulfate,
boron, lead, and sodium, and higher than base soluble fractions for nitrate, calcium, copper,
magnesium, manganese, molybdenum, and nickel. For PER spent bed materials, the  water
soluble fractions exceeded acid soluble fractions for sulfate,  boron, and sodium, and exceeded
base soluble fractions for nitrate, aluminum, boron, calcium, copper, magnesium,  manganese,
and molybdenum.

     All the constituents in the Esso fly ash  except chloride, nitrate, and phosphate  were
less in the water soluble fraction than in the acid soluble fractions.  The water soluble
fraction exceeded the base soluble fraction  for chloride, nitrate, phosphate, aluminum,
calcium, chromium,  iron,  lead, manganese, mercury, molybdenum, silver, and zinc Ions.
For the Esso spent bed material, the acid soluble fractions exceeded the water soluble frac-
tions for all the constituents except sulfate, boron, mercury, and molybdenum, and the
water soluble fractions exceeded the base soluble fractions for all the constituents except
sulfate, aluminum, arsenic, beryllium, magnesium, and  zinc.

     Cyclone fly ash  water soluble  fractions were  less than acid soluble  fractions for all
constituents and exceeded base soluble fractions for nitrate, aluminum,  calcium, iron,
magnesium, manganese, molybdenum, silver,  and zinc.  Esso fines, stack fly ash water solu-
ble fractions exceeded acid soluble fractions for chloride,"boron, and molybdenum, and ex-
ceeded base soluble fractions for nitrate, arsenic, boron, cadmium, calcium, kon, lead, mag-
nesium, molybdenum, and silver.  Due to a shortage of residues for analysis, some acid and
base soluble fractions were not determined.

     6. BOD tests to  determine the biochemical rate of decomposition of residue water
soluble extracts in a standard solution of glucose and peptones were compared with a control
standard solution. The solutions with added residues showed a lag time of two days during
which  BOD  was inhibited, and the BOD increased so that the 5-day oxygen demand samples
were nearly as  high as the control sample.  The results indicated that the leachates contain
constituents which can act as temporary inhibitors to microorganism growth in the wastewater
containing biodegradable organic compounds.

     7. Laboratory bench-scale leaching tests run in 6 1/2 cm diameter x 21 cm length
vessels to evaluate column strata granular materials indicated the following principle
dissolved constituents:

   •   Granite bedrock: sulfate, sodium, and traces of  arsenic.

   •   Bituminous coal:  sulfate, arsenic, calcium, and sodium.


                                          11

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   •   Dolomite: sulfate, arsenic, sodium, and traces of boron and potassium.
   •   Limestone: sulfate, sodium and traces of arsenic, cadmium, potassium and lead.

   •   Silica sand (number 60): sulfate, sodium, chloride, and traces of potassium.

   •   Silica sand (number 16): sulfate, sodium, chloride, potassium, and traces of
       magnesium, lead and calcium.
   •   Claystone: sulfate, sodium, arsenic, chloride, and traces of calcium, lead, and
       magnesium.

   8.  High rate leaching tests were developed for the laboratory bench-scale residue vessels
and provided the following principle dissolved constituents:
   •   Fluidized bed sample residues leached sulfate and chloride anlons, and calcium,
       magnesium, iron, sodium, and potassium cations in significant concentrations.
       Many trace elements were also leached in relatively low concentrations.
   •   Chloride, sodium, and potassium were nearly completely extracted from the sample
       residues after six times the residues' weight in water had leached through the residue.

   «   Calcium and sulfate were leached at relatively constant high concentrations after
       residues had  received six times their weight in water.

   •   Residue feachate contained nickel, lead and iron compounds concentrations ex-
       ceeding the U.S.  EPA recommended permissable levels for drinking water supplies.

   •    Sulfate content in the residue leachate exceeded the noted recommended standard.
        However, sulfate may combine with calcium to form gypsum, or with lead to form
        lead sulfate.  Both of these sulfate compounds are relatively insoluble and thus will
        reduce the leaching of calcium and lead.

   •   Acid water increased the leaching of heavy metals.

   9.  Cation exchange capacities (CEC)  of the Esso and Exxon spent bed materials were
 equal at 1.9 CEC meq per 100 grams of residue.  PER fly ash and spent bed materials were
 2.4 CEC meq per 100 grams of residue.  Exxon fly ash was 0.5 and Esso fly ash was  13.6
 CEC meq per 100 grams of residue.

  10.  Acid neutralization capacities varied from 2.6 equivalents per kg for PER spent bed
 material  to 78.1 for  Esso fly ash, probably due to different ratios of calcium to sulfur in
 these materials, as received.

  11.  Exothermal reactions occurred after wetting all of the "as received" residues except
 Exxon fly ash.  The exothermal  reactions were attributed largely to  lime slaking upon addi-
tion of water.  Residue slaking temperatures were measured as high as 240°C(Exxon  spent
bed material).

  12. The  fluidized  bed fly ash particle sizes were fine (similar to a type of sandy silt) and
the composition was unchanged  by slaking. The spent bed material particle s?zes,as received,

                                         12

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were similar to sand and became even finer after slaking.  Oil gasification residue particle
analyses.fell within a narrow band corresponding to a typical sand with fines.  The exception
was unslaked Esso spent bed materials whose particle size distribution corresponded to a
typical sand.

  13.  The specific gravity values for Exxon and PER fly ashes (2.6 - 2.8) were in the range
for normal soils.  Esso fly ash specific gravity at 2.02 was less than for normal soils.  The
spent bed residues partly entered into solution after water was added; thus, their specific
gravity was difficult to determine accurately.

  14.  The residues "as received" had zero moisture content.

  15.  Water addition will likely change  the dry densities of all the residues tested except
the PER fly  ash.  Esso residue densities decreased significantly in dry density (by 37 - 49 per-
cent dry weight)  and Exxon spent bed material  increased significantly (by 48 percent) after
water  addition.

  16.  The ability of dry residues to hold moisture, termed their water holding capacity,
ranges between 0.44 and 0.98 grams of water per gram of dry sample.

  17.  Pilot test column simulation  indicated that the residue leachate had the following
characteristics i
   •   A highly  alkaline leachate resulted from coal mine,  dolomite quarry, limestone
       quarry,and ocean environments.
   •   A neutral leachate resulted from the landfill environments due to the neutralization
       of alkaline residue leachate by acidic landfill leachate.

   •    High initial  peak concentrations of sulfate occurred in all environments.

   •    Soluble chlorides in residues were  readily leached without attenuation in all of the
       column strata materials.
   •   Concentrations of mercury in sea water leachate may be an order of magnitude
        higher than concentrations found in leachate from other land-type conditions.
   •    Sea water leached iron from the residues more rapidly than fresh water did.
   •    Slight attenuation of zinc in residue leachate may occur in the column strata.

   •   Total dissolved solids were leached in decreasing quantities with the increasing
       passage of water.

  18.  Residues can  be  used as a conditioner for soils that are acidic,  high in heavy metals,
or deficient in trace metals.  Residues are a marketable source of calcium or magnesium and
are a substitute for lime or gypsum to raise soil pH.

  19.  Substitution of residues in portland  cement concrete mixtures could save about $0.50
per kkg of equivalent strength concrete.

                                           13

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                                     CHAPTER 4

                         FLUIDIZED-BED COAL COMBUSTION

                                   Introduction

     In fluid! zed-bed combustion, a granulated bed material (limestone or dolomite) en-
 compasses the pulverized burning coal. The bed and fuel are fluidized by combustion air.
 The calcareous bed materials absorb sulfur oxides, reducing their emission into the environ-
 ment.  The process generates large quantities of dolomite or limestone materials, magnesium
 or calcium sulfate, ash and some unburned coal.  This sorbent material may be either re-
 generated for repeated SO  removal, or removed from the plant for disposal.
                         J{
     There have been two approaches to steam generation using fluidized-bed boilers.  One
 method uses direct contact between the inert fluidized, heated stone particle bed and the
 heat transfer surfaces (boiler tubes) to produce steam.  An example of a fluidized-bed
 steam  generator with direct contact heat transfer is shown in Figure 1.  The hot flue gas,
 after ash  removal, can generate additional heat.   In boilers without direct fluidized-bed
 contact,  hot off-gases generate all the steam by conventional fashion.

     The start-up of an atmospheric fluidized-bed boiler  requires heating a portion of the
 bed  to 400  C to ignite the injected coal.  After ignition, the  temperature of the bed rises
 unfil the  energy released in the bed equals the energy absorbed by the boiler tubes plus
 that in the hot gases leaving the bed, and the system achieves thermal equilibrium.
 Excellent heat transfer and high heat capacity is maintained in a fluidized-bed boiler at
 uniform temperature, typically in the range  of 800 to 900  C.

     High heat-transfer coefficients between the fluidized-bed  and immersed steam genera-
tion  surfaces reduce the steam tubing requirements, and also permit operation at tower and
more uniform bed temperatures.  The lower temperatures  reduce NO emissions and slag,
and decrease equipment corrosion.                                x

                               Process Descriptions

     There are two fluidized-bed combustion modes, with either complete or partial com-
bustion of the fuel.  In the complete combustion mode (also called one-step or excess
oxygen combustion), oxygen in excess of the stoichiometric quantity required to burn the
fuel  is fed to the fluidized bed. The oxygen reacts with sulfur, forming sulfur dioxide,
which  in turn reacts with the calcium or magnesium in limestone or dolomite (hereafter
simplified to refer only to the calcium):

     CaCO3 +  S  + 3/2 O2 —*   CaSO4  + CO2.

     In the second mode (called two-step or  oxygen deficient combustion), I ess than the
stoichiometric amount  of oxygen is added to the fluidized bed.  This results in the formation
of calcium sulfide (CaS) which can be  converted to SO_ and  CaO  by roasting it in air or in

                                         14

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                                                        Flue
  Fuel Injection Pipes
  Fluidized Bed
           Air Distribution Grid
                                                             Boiler Tubes
                 Figure 1.  Direct contact fluidized-bed steam generator.
Source: 104.

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 oxygervor to CoCCL and H S by reaction with water and CO,.  SO2 or HjS can be
 converted to sulfur fn a  Claus plant) or to r^SO .  (in an acidplant).

     The three basic types of plant operation tor the fluidized-bed combustion of coal are:
 0) once-through (high or low pressure), (2) one-step regeneration (high or low pressure),
 and(3) two-step regeneration (high-pressureonly).

 Once-Through Operation^

     Once-through operation with pressurized  fluid-bed combustion (Figure 2) is quite
 simple.  Calcium sulfate and other compounds are produced in the bed in a stable form
 which requires disposal.  The cost of the process is minimized by operating with maximum
 sorbent utilization.

     Table 7 compares possible alternative fluidized bed combustion plant sorbent processes.
 The once-through use of limestone or dolomite sorbent  results in greater amounts of
 waste residues than if these residues were regenerated and recycled;  however, with the
 present state-of-the-art, residues regeneration appears to  be uneconomical.  Approximately
 7 times, by-weight, of raw crushed dolomite is needed for each unit of coal burned in
 a fluidized bed unit. Table 7 indicates that the fluidized bed process generate^ by
 weight, about 3 times as much spent bed residue as fly ash,  and the total quantity of
 fluidized bed residues represents the total of the original dolomite or limestone sorbant
 plus the solid ashes from  the burned coal and the chemical combination of sulfur and
other reaative materials.  The total weight of residues from the fluidized bed combustion
 process noted in Table 9  is estimated to be 1,958 kkg/day versus the total input of 195
plus 1,410 kkg/ 1 hour of coal and dolomite respectively.
                                        16

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Source: 104.
                                                        Electrical
                                                       Generator
                                              Particulate
                                               Removal
                                               Waste
                                               Residue
                                                          Steam
                                                         Turbine
                                       Fluidized Bed
                                          Boiler
 Heat Recovery
(Boiler Feed Water)
 Condensor
                                                                                                    Stack
                                                                                               Electrical
                                                                                               Generator
                                                               11  Boiler Feed
                                                                    Water

=i Circula-
    tion
   Water
                                           Heat Recovery
                                             (Flue Gas)
            Circulation Water
               Discharge
                          Figure  2.   Once-through pressurized fluidized bed boiler power plant.

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                     _IAPLE 7:    COMPARISON .OF FBC SORBENT PRQCEilEL
                                               One Step - 10 atm         One Step-
                   !mpact                    1%  S02      2%S02       10%S02    Tw°Step     Once Through

   	           Ab      Bb     Ab    Bb    Ab     Bb     Ab     Bb     Ac     Bd
   Energy         e
     Plant heat rate  (kcalAwhr)            2,600  2,700  2,470  2,550 2,360  2,390 2,460  2,520  2,330  2,290

     Plant energy cost (milIs/kwhr)           13.88  14.61  13.21   13.67 13.13  13.59 13.94  14.67  13.45  12.30

   Raw materials
     Total coal input (kkg/nr)                  221      229    211     216   202    205    212    218    195    195

     Dolomite input (kkgAr)                   940     940    940     940   940    940    940    940  2,830  1,410

     Methane input (103 cum  /day)at STP      790     103    75      97    69     90    0      0      0     0

oo  Plant  residues
     Spent bed material (kkg/day)              807     698   807     698   807    698    980    970  2,450 1,490

     Ash output9                             531      549   508     518   485    492    510    522    468    468

     Sulfur output (kkg/day)                   143     149   137     141   124    125    139    141      0      0

     Sulfur removal  efficiency11 (%)            90     90    90      90    85     85     90     90     94     94

   Increase in U.S. coal production relative
    to once through operation for total con-
    version to regenerative FBC processes (%)  13«3   17.3    8.1   10.5     3.8   4.9    9.0  11.7

   U.S. limestone/dolomite production re-
   quired for complete conversion to fluid-
    ized  bed combustion (%of  present total)      10     10    10     10     10    10     10    10      30    15


                                                    (continued)

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                                                    TABLE 7
       a
         Bases For analysis:
         195,000 kg/hr coal feed to boilers
         4.6% sulfur by weight in coal
         boiler sulfur removal efficiency = 95%
         dolomite utilization in boiler = 30% (regenerative systems)
         dolomite utilization after regeneration = 10%
         dolomite make up rate = 1 moleCa/moleS  (regenerative systems)
         dolomite cost = $ll/kkg
         coal at  $1.79/106 kcal
         methane at $3.17/106 kcal
       .sulfur recovery efficiency = 90%
         Column A for disposal before regeneration, Column B for disposal after regeneration.
^       At 3.0  moles Ca  mole S  dolomite make up rate and 31.6% utilization in boiler.
-o       At 1,5moles Co/mole S  dolomite make up rate and 63.3% utilization in boiler.
       - Includes methane input.
         Other materials for regeneration processes include process water, chemicals, and/catalysts.
       ? 1.0% ash in coal.
         Sulfur removal efficiency is lower for the one-step process at 1 atmosphere pressure because the process tail gas is
         incinerated rather than recycled to the boiler.

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                                     CHAPTER 5

                            RESIDUE CHARACTERIZATION

                                      Purpose

       The purpose of this subtask was to determine the chemical and physical properties of
FBC residue samples and the materials used in pilot-scale column studies.  This provided a
preliminary screening of potential environmental effects and direction of subsequent efforts.
Results were used in planning and conducting the pilot-scale column studies of residue
disposal, and in testing residue commercial and agricultural applications.

                              Residue Characteristics
       The chemical composition of ash and spent bed material is dictated, to a large
extent, by the composition of the bed material and the fuel.  Natural materials are largely
impure, and both coal and oil as well as limestone and dolomite contain traces of most
metals. Concentrations will vary depending on local  sources.  Combustion and other high
temperature reactions produce ashes and spent bed material containing many of these trace
metals. The specific chemical  composition of a given ash or  spent bed material is depen-
dent on the  combustion parameters, the fuel,and the bed material; and as a result, the
composition of ash and bed material varies widely.

        All of the residue samples available to us were from the pilot plant test runs and
may not be representative of future production runs.  Where possible, we have attempted
to determine the actual pilot plant test operating conditions and acquired analyses of the
raw fuel and sorbent feeds. Given this latter information, it should be  possible to relate
our test results to future production conditions.  Table 8 lists  the residues analyzed in the
laboratory and their test run conditions.

        Tables9through 11 give available analyses of  coal and  limestone feeds provided
by some of the experimental plants. The composition  of fossil fuels used in these experi-
ments varied widely.  The percentages of sulfur in the coal ranged from 0.75 to 4.46, and
in the coke about 1.28 (on a dry basis).  Venezuelan  No. 6 oil was used in the Esso gasi-
fier; and the sulfur  content was about 2.5 percent. Unfortunately, not  all  the experimen-
tal  plants providing residues were able to provide complete chemical analysis or other des-
scriptive information about the  raw materials that were used.

        The  composition of the limestone used for the fluid!zed-bed combustion tests varied.
The percentage of calcium in the  PER limestone was 36, and 47.5 for  Greer and Germany
Valley, respectively.  Available data showed that the sulfur  content of the limestones was
0.3 percent for Greer and 0.15 percent for the  Germany Valley limestones.  Magnesium,
iron,  aluminum and silicon were other important constituents  in the limestones.  Probably
both limestone and coal contained several trace metals, but available data showed only
Titanium (0.89 percent in the coal used for the  PER plant).
                                          20

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                   TABLE 8.
PILOT PLANT OPERATION FOR THARACTERI7ED RESIDUES
Residue Source
Pope, Evans &
Robbins
Alexandria, Va.
Fly ash
Spent bed material
Exxon Miniplant
Linden, N. J.
Fly ash
Spent bed material
Esso CAFB
Abingdon, England
Cyclone fly ash
Fines, stack fly ash
Spent bed material
Run Temp.
No. C


N.A* 815 to
870


30.4 835
(avg.)



10 860 to
950

Excess Air _ , T
Vol.% Fu6lType
High sulfur
bituminous
18 coal
Sewickley,
Pa.

16.1 Illinois
N6


No. 2
N.A,a heating oil
Venezuela

Sulfur _ , e , . Ca/S molar Flue SOo
... Bed Sorbent r , .. „__ *•
% feed ratio ppm
Calcined
limestone
4 to 4.5 Germany Valley Variable Variable
& Greer,
W. Va.

42 to 4.8 Grove 3.7 894
limestone



2.5 LimeBCRl359 1 (avg.) 200
U.S.A.

a N, A. = Not Avail able.

-------
         TABLE 9.  CHARACTERIZATION OF POPE, EVANS, AND ROBBINS
Constituent
Ash
Volatiles
Fixed carbon

Pyritic sulfur
Sulfate sulfur
Organic sulfur
Total sulfur
Carbon
Hydrogen
Nitrogen
Sulfur
Silicon
Iron
Aluminum
Calcium
Magnesium
Potassium
Sodium
Titanium
Oxygen

Coal
17.44
37.31
45.25
100.00
3.04
0.18
1.24
^736
67.56
4.80
0.93
4.46
4.08
2.48
1,80
0.63
0.10
0.38
0.10
0.09
12.59
100.00
*
Coke
27.82
0.00
72.18
100.00
0.00
0.29
0.99
1.28"
76.18
0.00
0.00
1.28
6.51
3,96
2.87
1.00
0.16
0.61
0.16
0.14
11.3
100.00
Ash
100.0
0.0
0.0
_ , - x
100.0
0.0
1.0
0.0
1.0
0.0
0.0
0.0
1.0
23.4
14.2
10.3
3.6
0.6
2.2
0.6
0.5
43.6
100.0
*
 Calculated values.


Source; 186.
                                    22

-------
         TABLE 10. CHARACTERIZATION OF POPE, EVANS, AND ROBBINS
                       LIMESTONE SAMPLES (percentage bv weiahrt

        Constituent               Greer Limestone      Germany Valley Limestone
    Calcium carbonate                75.0                   98.3
      (CaCO )
           o
    Magnesium  carbonate               4.0                     0.5
      (MgC03)
Ferric oxide (Fe0O«)
t. O
Alumina (ALO«)
Silica (SiO2)
Sulfur (S)
0.75
3.3
9.5
0.3
0.2
0.5
0.6
0.15
Source:  186.
     TABLE 11.  CHARACTERIZATION OF EXXON MINIPLANT COAL SAMPLES
Constituent
Moisture
Ash
Volatiles
Carbon
Hydrogen
Nitrogen
Oxygen
Chlorine
Sulfur
	 xt. — _ — _
As Analyzed
3 3
9.95
10.00
67.71
4.77
1.17
9.19
0.05
4.20
w- —T — -—• v™ r— — —
Dry
„_
10.26
10.31
69.81
4.92
1.21
9.47
0.05
4.33
After ignition

__
__
77.79
5.48
1.34
10.55
0.06
4.83
Source; 187.
                                   23

-------
                               Chemical Composition

      The preliminary chemical  tests of the residue samples consisted of: 1)  characteriz-
 ation after hydrofluoric acid digestion; 2) determination of their water, basic, and acid
 soluble fractions, and 3) determination of their sequential water leaching characteristics.

      Total Residue Characterization.   The total chemical compositions of the residue
 samples were determined after hydrofluoric acid digestion placed appropriate constituents
 into solution.  One gram residue samples were digested according to the procedure out-
 lined in the American Society of Agronomy's  Methods of Soil Analysis,  1965, p.  1019.
 The only significant departure from this procedure was the use of nickel instead of platin-
 um utensils; therefore, total nickel analysis was not performed.  The digestate was diluted
 to 100 ml.  All analyses of the digestate were conducted according to EPA  Methods for
 Chemical Analysis of Water and Wastes and Standard Methods, (14th ed.).  Appendix A
 of this report gives methods and  references for each analysis.  Analytical results are pre-
 sentedjJiereiriafter,in  the report.

      Soluble Fraction Analysis, The solutions to be analyzed were prepared by placing
 100 g samples of  each type of residue^as received/in a flask and adding either 250 ml of
 distilled water, 1.0 N NaOH, or 1.0  N HNOg in accordance with EPA-recommended
 procedures as further  described in Appendix A.  After mixing for twenty-four hours, the
 solutions were filtered and the filtrate analyzed to determine the acid, base and water
 soluble fractions  of the residues, as well as pH, COD, BOD, and TDS0 All analyses were
 conducted as for  the total characterization procedure,  and are cited in Appendix A.

      The BOD5  analyses were performed on the water extracts and on  distilled water
 samples.  The extract and distilled water samples contained 6.5 percent of  a nutrient
 solution of glucose, peptone,  calcium chloride, magnesium sulfate, ammonium chloride,
 sodium phosphate, potassium phosphate, and ferric chloride.

      Bench-Scale Leaching Tests.  Preliminary bench-scale leaching tests were conducted
 on residue samples prior to the construction of the pilot-scale test columns. The purpose of
 these tests was to estimate the long-term leaching characteristics of the residues.  Two
 hundred and fifty gram samples of each residue were placed in 30.48-cm high, 5.08-cm
 ID plastic columns.  Figure 3 . illustrates the  column operations. The water was added at
 the rate of 250 ml per leaching cycle.   Leachate was collected by gravity percolation
 once a week for six weeks.  Analyses were performed on  the leachate by the methods in-
 dicated in Appendix A.

      Laboratory-scale leaching studies were  oho con ducted on the various stratal materials
used in the large-scale test columns.  Table  12 lists the types and quantities of materials
 tested.  Three 250 ml  leaching cycles were done using  the procedures described above.
Chemical analyses were conducted to determine the quantities of various constituents
leached out of these materials over time.  These values were then used to help establish
background or baseline concentrations of leachate constituents analyzed in  the pilot-scale
columns.  Accelerated small-scale column leaching was also developed to simulate 52
                                       24

-------
Figure 3.   Laboratory-scale column leaching,
                   25

-------
TABLE 12.  STRATIGRAPHIC MATERIALS SIMULATED IN LEACHING TESTS
Stratigrophic
Unit
Sandstone
Sandstone
Claystone
Dolomite
Limestone
Granite bedrock
Simulant
Material
*16 Silica sand
#60 Silica sand
#60 Silica sand
clayr (kaolin)
Coarse meal grade dolomite
Coarse meal grade limestone
Granitic pea - gravel
Decomposed granite
Quantity (g)
300
300
240
60
300
300
225
75
     • Bituminous coal
Coarse ground lump
 bituminous coal
                                                       100
                             26

-------
separate 250 ml leaching cycles in a period of several weeks.  The results of these tests
were not available at the time that this interim report was prepared.


                               Chemical Properties Tests

Cation  Exchange  Capacity

      The cation  exchange capacities of the  residues and column materials were measured to
indicate the amount of interchange that could occur as a result of leachate water moving
through the various solids in the test columns.  The existing cations were replaced with
sodium  ions in an acetate solution.  The sodium ions were then replaced by ammonium ions
in the acetate solution.  The concentration of sodium ions in the ammonium acetate  was
measured next and converted to cation exchange capacity in milliequivalents per 100 g of
original dry material. A detailed outline of  the procedure is given in Appendix A.   The
residue cation exchange capacity data are shown in Table 13„

Acid Neutralization Capacity

      The test involved dissolving a weighted amount of residue in distilled, deionized
water.  As measured quantities of 12N HCL were added, the pH was monitored until the
neutral value was reached. The results were calculated to equivalents of 1 N HCL
required to neutralize one kg of residue.  These results are presented in Table 14 .

Heat Release

      One feature of some of the pilot plant  residues, as received, has been their extreme
exothermal  activity upon addition of water.  The apparent cause was lime slaking:

      CaO +  H2O   —>•  Ca(OH)2 +  heat.

Slaking of the sodium, potassium and magnesium oxides also probably contribute some heat
release, as well.  Temperature changes were recorded for the addition  of 3.8 I water to
13.6 kg, and are shown  in Figures  4 and  5  •

                                   Physical Properties

Residue Preparation

      Residue samples to be slaked were covered with water and allowed to react.  When
all activity had ceased, the slaked samples were dried in an oven at approximately  103  C
for 24 hours.  Unslaked residue samples were used as received without  further drying, since
moisture content was already about zero.
                                         27

-------
                          CO LUMNMATERj AL jgAILQJJ^£MM
 Material °                                 CEC meq/lOOg residue
   EFA                                            13.6
   ESBM                                          1 .9
   VFA                                            2 .4
   VSBM                                          2 .4
   NJFA                                          0.5
   NJSBM                                         1 .9
   Limestone                                       0.6
   Dolomite                                        1 .9
   Bituminous Coal                                 2.7
   Claystone/Sand, 4:1                              7.2
   Decomposed Granite                             26.6
   #1 6 Silica Sand                                  1.4
   #60 Silica Sand                                  2.8
Residues were slaked before determining CEC.
Residue
Source
Exxon Miniplant
Pope, Evans, and
Robbins
Esso, England
Type
Fly Ash
Spent Bed Material
Fly Ash
Spent Bed Material
Fly Ash
Spent Bed Material
Neutralization Capacity
(equivalentsAg)
17.5
26.0
8.8
2.6
78.1
35.5
                                    28

-------
                                                            220  C after 1000 sec
                                 Time (min)
Figure 4.   Temperature change frorn water addition to dry residues.

-------
CJ
o
             60




             55



             50



             45
§
lu
55^35
             30



             25




             20
             10
                  4812 1620
                               40
                                                                                   EFA
100
120
                  60          80

                       Time (min.)


Figure  5  .  Temperature change from water addition  to dry residues.

-------
Parti cl e Si ze An al ysi s

      The procedure used complied with ASTM D422. A 500 gm sample of each slaked
and unslaked residue was sieved, using fhe number 4, 10,  20,  40,  80,  TOO,  and 200
sieves.  No hydrometer analyses were performed on spent bed materials because some portion
of the residue was soluble, which would substantially alter the results.   Hydrometer
analyses were conducted on slaked samples only  for the fly ashes.  The  results from the
hydrometer and the sieve analyses were plotted together, and are presented in  Figures
6 and 7 .    Additionally, the sieve analyses for column strata material are shown  in
Figures  8 through 10.

Specific Gravity

      Specific gravity measurements were made for test residues to  establish their physical
characteristics for aggregate or other possible uses. The method used was that  shown in
ASTM D854, except that step  6.2 was changed from a period of partial  vacuum to a period
of vigorous shaking.  This did  not affect the results.  Specific gravity values were not
obtained for the spent bed materials, as some portions were soluble and this phenomenon
interfered with the ASTM D654 type analysis.

Moisture Content
      Procedures in ASTM D2216 were followed, using the residues as received (see
Table?,).

Degree of Saturation

      Degree of saturation was obtained by substituting into the formula:

                         _ _ _ WG _ ,  where

                           ~
      W =  moisture content                     V   =  ™it weight of water
                                                  w
      G =  specific gravity                      ,     _    .     . ,    -
             r           '                      I/   -  unit weight of residue
      Results are shown in Table 7  .              ' d

 Loose Dry Density

      The dry density of each residue, both slaked and unslaked, was  determined by pour-
 ing the  dried residue into a 100-ml  beaker. The difference between the empty and filled
 weights of the container was  divided by the known volume to yield the loose dry density
 value, which is shown in Table 7 .
                                           31

-------
                                                           Legend

                                                     o   NJFA,  unslaked
                                                    O  NJFA,  slaked
                                                    A  NJSBM, unslaked
                                                     A   NJSBM, slaked
                                                    D  VFA, unslaked
                                                     D   VFA, slaked
                                                    O  VSBM,  unslaked
                                                     O  VSBM,  slaked
1.0
  0.1
Diameter (mm)
0.001
     Figure 6 .  Particle size analyses: coal combustion residues.

-------
co
  100


   90


   80


   70

2oO
•4-

| 50

_£-
fo 40
^c

   30


   2Q


   10

    0
                                                                                           Legend

                                                                                    O  CFA, unslaked
                                                                                    O  CFA, slaked
                                                                                    A  EFA, unslaked
                                                                                    A  EFA, slaked
                                                                                    D  ESBM, unsld«jd
                                                                                    D  ESBM, slaked
                                                                                    O  FSFA, unslaked
                                                                                    o   FSFA, slaked
                              1.0
                                                  0.1
                                                  Diameter (mm)
0.01
.001
                                   Figure 7  . Particle size analyses «  oil gasification residues.

-------
o>
"5
 100


  90


  80


  70


  60


  50
140
  30


  20


  10


   0
                                              Legend

                                              o Granitic Pea Gravel—Composite Sample
                                              D Granite Bedrock (pea gravel to decomposed granite in a 3:1 ratio)
                                              O Granite Bedrock (small gravel to decomposed granite in a 1:1 ratio)
                                              O Large Gravel—Composite Sample
                 Figure  8
                                               Diameter (mm)
                              Particle size analysis:  pea gravel, granite bedrock, and large gravel.

-------
                                                        Legend
                                                            o  Silicasand1 (#60)
                                                            A  Silica sand (#16)
                                                            O  Decomposed granite
               1.0                               0.1
                             Diameter (mm)
Figure 9  . Particle size analysis:silica sand and decomposed granite.
0.01

-------
CO
O*
                                                                   Legend

                                                                   o  Bituminous Coalu-Composite Sample
                                                                   D Wiite Marble (Dolomite)—Composite Sample
                                                                   A  Limestone—Composite Sample
                                                                                                             0.01
                                                         Diameter (mm)
                               Figure 10  «  Particle size analysis? coal, dolomite, and limestone.

-------
Water-holding Capacity

   Water-holding capacity was determined for the slaked residues only.  A sample of slaked
and dried residue was placed in a funnel lined with  filter paper, covered with water, and
allowed to drain under the force of gravity.  The sample was covered to  prevent evaporation,
and allowed to stand until there was no further water drainage for a five-minute period. Then
the wet sample was weighed, dried at approximately 103° C for 24 hours, and reweighed.
The difference between the wet and dry weights  was equal to  the water held  in the sample.
This was divided by the dry weight of the sample to  give the water-holding capacity of the
residue.   Results of the  water-holding capacity tests are presented in Table 15.

Permeability

    Data was obtained following the procedure described in the Standard Method of Test for
Permeability of Granular Soils (Constant Head).   The results of the tests  for residue perme-
ability are shown on Table 16.

                                      Results

Chemical Composition

    Laboratory mixing tests wherein residue was added to water to characterize their total
soluble fractions are presented in Tables 17 through  20.  BOD results are also shown  graphically
in Figure 11. Results of the laboratory bench-scale leaching  tests are given  in Tables 20
through 26 and Figures 12 through 14.

    The procedures  followed in these tests do not give absolute values, but rather data for com-
parison of residues. The molecular states (types of compounds) of the analyzed elements were
not determined.  Comparison of the laboratory mixing test characterization analyses and bench-
scale small column leaching tests was a basis for planning the longer-term pilot-scale tests
(Chapter 6) which simulated field  conditions more closely.  The laboratory tests indicated that
major leachate constituents of the residues were  high in total  dissolved salts consisting of sulfate
and chloride onions, and calcium, magnesium, iron, sodium, and potassium cations. Many
trace metals were also present in low concentration, which would nevertheless be high enough
to cause concern if they were leached into the environment.

    Comparison of results for soluble  fractions showed that pH  will undoubtedly influence the
quality of the leachate.  In the bench-scale experiment, some elements (chloride, sodium,
potassium) were leached readily, and were almost completely extracted by the time  tap water
equivalent to six times  the weight of the residues had leached through.  On the other hand,
calcium  and sulfate were leached  in relatively constant,  high concentrations which  had not
diminished by the end of six water addition cycles.

    Sulfate content in leachate exceeded the recommended maximum for drinking water supply.
Sulfate is also of interest as it may combine with calcium to form gypsum or with lead as lead
sulfate.   Both of these compounds are relatively insoluble, and so leaching of calcium and lead
may be reduced.

-------
CO
00
Residue Specific
Type Gravity0
(g/cc)
VFA 2.65
VSBM c
NJFA 2.71
NJSBM c
EFA 2.02
ESBM c
CFA 2.72
FSFA 3.11
Moisture
Content13
(%drywt.)
0
0
0
0
0
0
0
0
Degree of
Saturation"
(%dry wt.)
0
o
0
0
0
0
0
0
Dry Density
Before After
1 Slaking*3 Slaking
(g/cc) (g/cc)
0.76
0.92
0,74
0.73
1.46
1,36
1.09
1.18
0.76
0,97
0,65
1,08
0.83
0^7
0.78
0./6
»
Water- holding
Capacity
IB H2o \
y g Residue /
0.66
0.50
0.74
0.44
0.70
0.98
0.76
0.78
               , Alter slaking.
                As received.
               c Not obtainable/ as some portion of the material in question enters into solution.

-------
         TABLE 16  .   PERMEABILITY OF RESIDUES AND COLUMN MATERIALS
                                        ~       Hydraulic Conductivity K
                  Description	(cm/sec)   	
Residue                                                        ^
   PER Virginia fly ash                                 1.9xlO~3
   PER Virginia spent bed material (slaked)               1.9 x 10~4
   Exxon New Jersey fly ash                            6.4 x 10_2
   Exxon New Jersey spent bed material (slaked)          3.7 x I0_g
   Esso, England fly ash (slaked)                        1.6 x 10_ «•
   Esso, England spent bed material  (slaked)              6.8 x 10

Column Material                                                -
   Limestone (granular)                                 1.0xlO_2
   Dolomite (granular)                                 5.9 x 10 «
   Bituminous Coal (granular)                            6.1 x 10 „
   Sanitary landfill                                     7.0 x 10~_3
   Claystone (4:1, #60 sand to clay)*                    1.64 x 10~
   Sandstone (#60 sand)                                3.2 x 10~2
   Sandstone ^16 sand)                                7.4 x 10,,
   Clayey loam (3:1 #60 sand  to soM)*                   1.1 x 10~2
   Silty loam (3:1 #60 sand to soil) *                     1.0 x 10[4
   Sandy loam                                         1.6x10_o
   Granite bedrock  (3:1 p-gravel to decomposed granite)*  5.2 x 10_9
   Gravel                                             8.2 x 10"

*
 By weight
                                        39

-------
          TABLE 17.  LABORATORY CHARACTERIZATION OF RESIDUES
                     1.  EXXON MINIPLANT, LINDEN, NEW JERSEY
Constituent
pH
Total dissolved solids
COD
BOD
Chloride
Nitrate
Phosphate
Sulfate
Aluminum
Arsenic
Beryllium
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Silver
Sodium
Zinc
Water
Soluble
9.3
2,124
45.6
f
— i
NDd
27
4
1,190
— _
ND
—
0.61
ND
1,805
— -
—
ND
2.5
10
—
ND
~
24
ND
22
ND
Fly Ash
Acidb
Soluble
j-*
e
_—
— _
ND
--
182
5,300
—
62.5

ND
0.2
34,600
__
—
78.4
7.7
ND
—
69
—
440
0.2
400
8.0
Basec
Soluble
13.0
—
--
__
5.76
3
6.3
26,000
—
22.5
—
0.88
0.2
ND
—
—
1.6
6.0
2,360
—
ND
—
__
0.4
—
0.5
Spent Bed Material
Water Acid Base°
Soluble Soluble Soluble
12.2
4,188
51.4
-J
ND
26
ND
1,900
0.06
5.0
ND
0.64
ND
6,017
—
0.5
ND
2.4
95
0.025
12
0.5
32
0.02
89
ND
6.6
—
—
—
ND
—
1.5
1,000
0.26
30.0
ND
ND
0.5
96,754
—
K07
7.6
1.4
ND
0.95
278
7.7
248
0.6
ND
1.0
13.0
— —
—
—
8.42
ND
ND
17,400
ND
18.7
ND
0.97
0.2
ND
— •
0.12
1.8
5.9
3,200
ND
ND
0.75
—
0.3
—
0.2
, All concentrations in mg constituent/kg residue, dry weight after shaker test.
b
  l.ON
* 1.0 N NaOH.
  None detected = ND.
f — Analysis not performed.
  See Figure 11.
                                   40

-------
          TABLE 18.  LABORATORY CHARACTERIZATION OF RESIDUES4
               POPE, EVANS, & ROBBINS, ALEXANDRIA, VIRGINIA
Constituent
PH
Total dissolved solids
COD
BOD
Chloride
Nitrate
Phosphate
Sulfate
Aluminum
Arsenic
Beryllium
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Silver
Sodium
Zinc
Water
Soluble
12.2
4,212
104.6
t
NDd
2
ND
1,600
ND
2.5
ND
0.5
ND
540
—
0.025
0.5
1.6
96
0.025
10
0.25
33
0.08
145
0.08
Fly Ash
Acidb
Soluble
4.1
e
—
__
ND
—
2
1,050
1.2
32.5
ND
ND
0.5
32,000
—
0.92
11.0
1.3
1,940
0.87
247
7.7
276
0.7
ND
1.1
Base
Soluble
12.9
—
—
_M
6.21
ND
ND
17,400
ND
20.0
ND
0.83
0.2
ND
—
ND
1.7
7.1
10
ND
ND
ND
—
0.3
—
1.0
Spent Bed Material
Water Acidb BaseC
Soluble Soluble Soluble
12.2
4,064
57,8
T
ND
28
ND
1,640
0.06
5.0
ND
0.82
ND
750
—
0.5
0.1
1.1
22
0.025
11
0.5
63
0.08
178
ND
6.1
—
—
__
ND
~
ND
1,050
0.26
32.5
ND
ND
0.5
32,000
—
1.07
6.6
1.5
22
0.95
272
7.7
276
0.8
100
0.3
12.9
—
—
__
22.83
7
ND
32,500
ND
17.5
ND
0.72
0.3
ND
—
0.12
2.2
7.6
ND
ND
7
0.75
—
0.4
—
0.4
,  All concentration in mg constituent/kg residue, dry weight after shaker test.
b l.ON HNO3.
j 1.0 N NaOH.
  None detected = ND.
® — Analysis not performed.
 See Figure 11.
                                     41

-------
           TABLE  19. LABORATORY CHARACTERIZATION OF RESIDUES
                              III.  ESSO, ENGLAND
Constituent
pH
Total dissolved solids
COD
BOD
Chloride
Nitrate
Phosphate
Sulfate
Aluminum
Arsenic
Berry Ilium
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Silver
Sodium
Zinc
Water
Soluble
12.2
5,266
132
f
11,200
24.5
6.0
4,380
0.25
ND
ND
ND
ND
4,500
1.75
ND
1.0
0.075
1.0
0.075
81
1.25
52
0.20
245
0.15
Fly Ash
Acid1*
Soluble
2.4
e
116
—
5,000

2.0
2,625
1.75
0.05
ND
0.325
0.075
70,000
14.2
2.25
7.0
ND
1.3
0.75
180
8.0
232
0.68
270
0.3
BaseC
Soluble
12.9
—
98
—
10,000
NDd
1.0
24,310
ND
ND
42
ND
0.05
316
ND
ND
0.25
ND
1.0
0.025
NO
1.5
~
0.15
—
0.025
Spent Bed Material
Water Acic^ BaseC
Soluble Soluble Soluble
12.1
6,214
68
f
8,200
12
1.9
3,380
0.25
ND
ND
0.63
0.05
4,750
1.5
0.5
1.7
0.17
1.0
0.1
0.8
0.25
ND
0.08
40
0.15
10.8
—
68
~
12,500
__
1.9
250
1.25
0.1
50
ND
0.28
75,000
13.5
2.0
6.0
ND
1.3
0.6
ND
7.5
ND
0.72
45
0.30
12.9
—
59
—
10,280
9.4
0.6
4,625
1.0
ND
114
0.52
ND
60
ND
ND
ND
ND
1.0
ND
ND
ND
—
ND
—
ND
,  All concentrations in mg constituent/kg residue, dry weight after shaker test.
&1.0NHNO3.
d
1.0 N NaOH.
None detected = ND.
f —Analysis not performed.
f See Figure 11.
                                     42

-------
           TABLE 20.  LABORATORY CHARACTERIZATION OF RESIDUES
                                 IV.  ESSO, ENGLAND
Constituent
pH
Total dissolved solids
COD
BOD
Chloride
Nitrate
Phosphate
Sulfate
Aluminum
Arsenic
Beryllium
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Silver
Sodium
Zinc
Water
Soluble
12.1
3,808
197.6
—
199.5
11.8
1.87
1,280
0.25
0.1
ND
ND
ND
510
—
ND
0.46
0.5
7
0.075
17
1.25
56
0.04
300
0.03
Fly Ash3
Acid Base
Soluble Soluble
	 6.T 	
	 g
—
—
210.6
-_
—
2,000
1.75
3.7
ND
ND
0.18
32,000
—
2.25
5.23
5.2
16
0.75
229
8
356
0.53
800
0.13
12.9
—
—
—
354.6
NDf
—
11,300
ND
0.3
42
0.13
0.01
ND
—
ND
0.25
0.7
ND
0.025
ND
1.5
f
ND
—
ND
Water
Soluble
12.0'
4,380
ocO *5
^w^ • O
—
160.7
10.6
0.35
1,680
—
0.1
—
0.43
OjOl
520
—
—
0.43
0.6
5
—
12
—
62
0.03
200
ND
FlyAsh6
Acidb
Soluble
1 6.4 "
—
—
—
77.6
~
—
2,190
—
3.4
—
ND
0.18
32,000
—
—
4.78
5.3
13
—
2.7
—
276
0.50
200
0.10
Base0
Soluble
13.0
—
—
—
388.0
2.6
—
3,260
—
ND
—
0.07
ND
ND
—
—
ND
0.1
ND
—
ND
—
—
ND
—
ND
? All concentrations in mg constituentAg residue, dry weight after shaker test.
b 1.0NHNQ3.
d
  l.ON NaOH.
  Cyclone fly ash.
  Fines, stack fly ash.
f None detected = ND.
? — Analysis not performed.
  See Figure 11.
                                    43

-------
 0)
1
 O
 o
 CO
300
285
270
255
240
225
210
195
180
165
150
135J
120
105
 90
 75
 60 -
 45 ~
 30 -
 15 -.
 0
                  Legend
                   * Standard (Control)
                   * NJSBM
                   * VSBM
                   o CFA
                   o NJFA
                   o FSFA
                   • VFA
                       1
        See Table 6  for explanation of
        letter code.                    Rgure
                                                 Day
                                                BOD from Residue water ejctracf;.

-------
         TABLE 21.    ,  LABORATORY LEACHINGbTESTS: GRANITE BEDROCK
M
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Cblcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.2
NDa
ND
34.0
2.5
—
ND
1.0
ND
ND
ND
—
ND
72.0
ND
Total Volume of Leachate (ml)
500
8.8
ND
ND
10.0
ND
—

ND
ND
ND
ND
ND
ND
60.0
ND
750
8.9
ND
—
2.5
0.8
ND
ND
ND
ND
ND
ND
ND
ND
64.0
ND
a ND - None detected.
  Water percolated through the bench scale residue sample.
 Mg/l except as noted.
                                  45

-------
       TABLE 22.  LABORATORY LEACHING TESTSfa:  BITUMINOUS COAL
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.0
ND°
ND
232.0
2.5
—
ND
3.6
ND
ND
ND
ND
4.0
80.0
ND
Total Volume of Leachate
500
8.8
ND
ND
42.0
5.0
—
—
0.3
ND
ND
ND
ND
ND
56.0
ND
(ml)
750
8.8
ND
—
10.0
2.5
ND
ND
0.9
ND
ND
ND
ND
1.0
64.0
ND
  ND - None detected.
  Water percolated through the bench scale residue sample.
c Mg/l except as noted.
                                    46

-------
Constituent
PH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.6
NDa
ND
9.0
0.8
—
ND
2.2
ND
0.1
ND
ND
8.0
103.0
ND
Total Volume of Leachate (ml)
500
8.8
ND
ND
3.0
0.8
—
—
0.1
ND
ND
ND
ND
ND
61.0
ND
750
9.2
ND
ND
ND
0.8
0.6
ND
ND
ND
ND
ND
ND
ND
60.0
ND
 ND - None detected.



Water percolated through the bench scale residue sample.




 Mg/l except as noted.
                                     47

-------
           TABLE 24.  LABORATORY LEACHING*3 TESTS;  LIMESTONE
Constituent
PH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.5
NDa
ND
10.0
ND
—
0.01
ND
ND
0.6
ND
ND
3.0
74.0
ND
Total Volume of Leachate
500
8.8
ND
ND
19.0
1.6
—
—
ND
ND
ND
ND
ND
ND
68.0
ND
(ml)
750
8.9
ND
—
6.0
1.6
0.7
0.01
ND
ND
ND
ND
ND
1.0
63.0
ND
a ND - None detected.



  Water percolated through the bench scale residue sample.



  Mg/l except as noted.
                                   48

-------
         TABLE 25,   LABORATORY LEACHINGb TESTS; *60 SILICA SAND
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.0
75.0
ND
123.0
ND
—
0.01
ND
ND
ND
ND
ND
3.0
168.0
ND
Total Volume of Leachate (ml)
500
8.8
NDa
ND
30.0 .
ND
—
—
ND
ND
ND
ND
ND
ND
77.0
ND
750
9.1
ND
—
5.0
1.6
ND
ND
ND
ND
ND
0.7
ND
2.0
70.0
ND
-. - ._ 	 „ . - - i
ND - None detected.
Water percolated through the bench scale residue sample.
Mg/l except as noted.
                                   49

-------
•• ""— •- — — '
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
10.0
9.0
ND
103.0
0.8
—
ND
3.7
ND
0.2
ND
ND
50.0
245.0
ND
Total Volume of Leachate (ml)
500
8.8
NDa
ND
12.0
ND
—
—
ND
ND
ND
0.03
ND
ND
68.0
ND
750
8.8
ND
—
7.0
ND
0.025
ND
ND
ND
ND
ND
ND
ND
62.0
ND

ND - None detected.



Water percolated through the bench scale residue sample.




Mg/l except as ioted.
                                     50

-------
           TABLE 27.  LABORATORY LEACHING*3 TESTS; CLAYSTONE
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.2
65
ND
141.0
0.8
__
ND
0.4
0.1
ND
0.1
ND
ND
161.0
ND
Total Volume of Leachate
500
8.8
ND°
ND
9.0
1.6
ND
—
ND
ND
ND
ND
ND
ND
97.0
ND
(ml)
750
9.0
ND
—
2.5
1.6
ND
ND
ND
ND
ND
ND
ND
ND
71.0
ND
 ND - None detected.
 Water percolated through the bench scale residue sample.
C Mg/l except as noted.
                                    51

-------
X
4-
§2 1,000
>£
1 "g 500

I °
D a\
U —
Cl
- - lt0
x'X'
- / ^-. — — 0.5
/ ,-•
- / ^ *
. .»*
iiiiifi
Fe
x
t/'
^ 	 —
/* ^^,*^*
x*" ^••*"^P
»^«^*
^•T 1 1 L I J S
0246 0246
Leachate ratio (I/kg) Leachate ratio (I/kg)
£
O O)

0) i> ^
> ,5,
*" _ j
| "o 2
u <»
Hg

100

50
-
__. —1 . =^~^=- vt= I 1
Ni*

- . ^
/'
/-/
- ^"^
^ i i i i i it
0246 0 50 100 200 300
Leachate ratio (I/kg) Leachate ratio (I/kg)
£
o 'ro 20
3^

1 •§ i-.o
i-5 0.5
D 0

Pb
12,000

^ 9,000
s>^ 6,000
* ^^
- sfS^ 3,000

^* : i t i ! i L
S04


,S'
'•?'"''
.•^"'^
i ^"**
***\ \ IIS i 1
0246 0246

x
£
|| 0.2
([} C
'S "S O-1
i 8
u
Leachate ratio (I/kg) Leachate ratio (I/kg)
Zn
Legend
x£ 	 — — VFA
^f' 	 	 VSBM
S' Notes
>r Leachate ratio = Water : Residue
0      2     4     6
      Leachate ratio (I/kg)
              Figure  12.  Leaching characteristics of VFA and VSBM.
                                52

-------
JX
|| 300
5l
.0 ~° 200
11 100
u .£
Cl
-
^---" 0.15
' ^"*" ^. 0.10
V^.-"""^ 0.05
Fe
_
-
rt«T"-"-T "T " T" " T~ i i
o
 D _C


U j>
      2.0
246
Leachate ratio  (I/kg)

                 Hg
                                                  0
         246
         Leachatt ratio (I/kg)
                                               100
50
         0246
               Leachate ratio  (I/kg)

   #>\
       "100"' 200 '  300 '
        Leachate  ratio (I/kg)
£.
"^
!"
•j-
D
U
.z-
4-
C
O
T^
Cumulative c

^2.0
> 1.5
:f i-o
-i 0.5
D
(D
(
|o.08
Jo. 06
J 0.04
§0.02
Pb
12,000
9,000
.^'^ 6/ooo
.<^^^ 3,000

s
^
&
^
- s'
s*\ i i it i i
D24'6 0246
Leachate ratio (I/kg) Leachate ratio (I/kg)
Zn Legend
^_ 	 NJFA
x^ 	 NJSBM
/
/ 	 Notes
/ _. — • 	 . . . Leachate ratio = Water :
^«— *f 1 1 1 I II
S04






Residue
          0246
                Leachate ratio (I/kg)
                       Figure  13 .  Leaching characteristics of NJFA and NJSBM.
                                        53

-------
c
o
3

15

10
5

CI
/ 15
/
• / 	 10
V^'"" 5
(s i i i t i i t

x
X

•/.'-'
^- "1 i f r !
Fe




J !
0     50     100    150
       Leachate ratio (I/kg)
              50     100    150
                Leachate ratio (I/kg)
                                                         50    100    150
                                                         Leachate ratio (I/kg)
x
o "TO
% j? 300
1^ 2°°
i-S 100
§ o
u "
Hg
200
150
100
Ni
-
. *
- / .'*
X1 i i i i t it
0 50 100 150 0 50 150 250
Leachate ratio (I/kg) Leachate ratio (I/kg)
£
«*••
§5 20
§n is
1 "S 10
e-C
_ D 5
-* <1>
Pb
200
150
" X"''^'-" 100
-/^•"' 50
4*'\ iii> I i
so4
-
; /' ' ^
^*\ ii ttii
0 50 100 150 0 50 100 150

•^
g 1? 4.0
^ 3.0
12 2*°
|1 i.o
u ">
Leachate ratio (I/kg) Leachate ratio (I/kg)
Zn
Legend
	 EFA
/ ^> 	 ESBM
/ ,'' Note
- *'£'' Leachate ratio = Water : Residue
/>
JS 1 1 I t 1 II
                      Figure  14,  Leaching characteristics of EFA and ESBM.
                                         54

-------
                                      CHAPTER 6

                   PILOT COLUMN STUDIES OF RESIDUE DISPOSAL

                                        Purpose

      One purpose of this sludy was to evaluate the possible impacts of residue disposal
into different locations. The first step in this evaluation was to simulate likely disposal
locations on  a pilot scale.  This allowed testing under defined conditions and control of
physical variables which might affect the behavior of the residues in natural environments.
The following section discusses the real world and simulated disposal locations that were
evaluated.

                        Simulated Sedimentary  Environment Columns

 Ocean  Disposal

      Actual location.  Residue wastes could be disposed into the ocean in many ways
which include dumping the  wastes into the open ocean, piping the wastes in the form of a
slurry onto the ocean floor (or a submarine canyon), or using the residues to build land or
islands.

      Test Column. The ocean disposal test column is more representative of a filled land
type disposal in the ocean where only the tidal portion of the residue would be flushed by
sea wafer for an extended period of time (also waves and land drainage can cause some
flushing).  The *60 sand used in the test column represents the deposited sandy base over
which the residues might be placed when filling begins (see Figure 15; for legend see
Figure  16).

Sanitary Landfills

      Actual Location.  Sanitary landfills are made of materials (a mix of ash residues and
solid waste)  and lifts of soil placed on natural ground or other inert material.  Sanitary
landfills may be built with 3m of mixed refuse to 003m of soil fill/lift), i.e.
 ~  90 percent solid waste and  ~ 10 percent cover soil. The residue to trash percentage
combination  may vary.  Both residues and refuse landfills can generate leachate when
saturated with water.

      Test Column. The test column simulated an arbitrarily selected real  world landfill
environment  where a brown  municipal type solid waste mixture was placed on  a sequence
of sedimentary strata overlying granite bedrock  (see Figure 1 8).  Organic solid waste  and
ash residues were separated for residue reclamation  after leaching tests.  Assuming a depth
of 30m  below the land surface for the water table,  each column represented the conversion
factors  for the thicknesses of the replicated real world strata materials as shown  in Table 28
The scale coefficients  of approximately 1:12 were chosen to conveniently replicate the
strata in the  test column assuming  a 30.5 m depth to groundwater.  Relatively impermeable

                                         55

-------
           20 cm
  oo
   E
   o
   £
   u
£
o
    u

   00
•III
                    Collection

                     Lysi meter
                                       Freeboard
                                       Residues
Sandstone (#60 sand)
Sandstone (*16 sand)



Gravel
Figure 15 »  Simulated sedimenj-ary environment: sea water test column.



                        56

-------
     BITUMINOUS COAL
     (coarse ground lump bituminous coal)
     CLAY STONE
     (clay and "oO silica sand)
      DOLOMITE
     (coarse meal grade dolomite)
      GRANITE BEDROCK
     (granitic P-gravel and decomposed granite)
      SOIL HORIZON A
      (sand, silt and clay loams)
     SOIL HORIZON B
      (sand, silt and clay loams)
      LIMESTONE
      (coarse meal grade limestone)
      SANDSTONE
          mesh silica sand)
      SANDSTONE
      (^60 mesh silica sand)


      SANITARY LANDFILL
      (solid waste)
Figure  16 .  Legend for test column disposal environments.
                        57

-------
          20cm
                            Freeboard
                            Residues
                            Sandstone (^ 16 sand)
                            Sanitary landfill
                            Claystone


                     ol lection
                     Lysimeter

                            Sandstone (#60 sand)

                            Sandstone pi 6 sand)


                            Granite bedrock
                            Sandstone (#16 sand)
                            Gravel
Figure 17.  Sanitary landfill test column.
                       58

-------
         TABLE 28. REPRESENTATIVE THICKNESS SANITARY LANDFILL
                        SIMULATED IN TEST COLUMNS
Material
Residue
Solid Waste0
Claystone
Sandstone
Granite Bedrock
Representative
Stratum
Thickness (m)
5.79
7.62
0.91
8.54
7.62
Column Layer
Thickness (m)
0.46
0.61
0.29
0.67
0.61
Scale ,
Coefficient
1:12.6
1:12.5
1: 3.1
1:12.8
1:12.5
,  No decomposition before leaching began in first 20 columns, "fresh" solid waste used.
  Excludes admixed *60 sand.
, Includes admixed *60 sand from claystone layer.
  Thickness of strata  in  field to thickness of simulated strata in test column (a ratio).

Source:  Ralph Stone and Company,  Inc. files.
                                      59

-------
materials, such as claystone, were "diluted" with sand to increase their permeability, thus
resulting in  reduced scale coefficients. Obviously, standard claystone is so impervious
that without the increase in permeability provided by the standard Ottawa sand, there would
have been no significant column leachate.  In nature, however, there is slow water move-
ment and leaching through the claystone.   Hence, the test columns replicated an accelerated-
type leachate test of what could occur in nature.

Limestone and Dolomite Quarries
      Actual Location.  An abandoned limestone quarry might contain 20 to 40 percent
 limestone; the remaining unquarried limestone could normally be left because it was of
 poor quality, had a high cost of mining, or for other reasons.  The sedimentary sequence
 which would be associated with the quarry would probably consist of a series of limestone,
 shale, and sandstone beds.  This type of strata occurs in varying percentages relative to
 each other.  No "typical" section below a limestone or dolomite quarry exists.  It might
 be all sandstone, all shale, or  a combination of any of the three types of strata.  For this
 reason,an arbitrary "topical" sequence was selected from a real world quarry as shown in
 Table 29.

      Test Column.    The  test  columns represent a configuration in which residues would
 be deposited in an abandoned quarry pit and underlain by the thickness of strata shown in
 Table; 28 (assuming a depth to groundwater table of 30 m).  In this  30 m section, below
 the residues there would be 14.2 m of limestone, 1.6 m of claystone, and 14.2 m of
 sandstone.  (See Figures 18 and 19.)  Again, claystone was admixed with sand to increase
 permeability, thus, resulting in lower scale coefficients.

 Coal  Mine.

      Actual Location.  An abandoned coal mine would be underlain by a sequence of
 shale, sandstone, limestone, and minor coal seams - the sequence  being predominantly
 shale (see Figure,20).  Disposal of residues would be in an abandoned mine underlain by
 similar strata.

      Test Column.  The test column represent an abandoned coal mine which is underlain
 by the thicknesses of strata, 'as shown in Table 30 and Figure 21 (assuming a 30 m depth to
 groundwater).

 Ratios of Densities
      Ratios of densities shown in Table 31  are calculated by comparing the densities of
materials as they exist in the columns with  densities of materials as they could exist in  the
field.  The densities of materials in the test columns were calculated using the actual
weights of materials added, divided by the amount (height) of column filled up (see
Table 32).  Densities of typical earth materials in the field were determined from various
sources (see Table 33..  Comparison of Tables 31 and 32 indicate that the actual densities
of materials placed in the columns were less than may exist under field conditions.
                                        60

-------
            TABLE 29.   REPRESENTATIVE THICKNESSES OF LIMESTONE. &
                      DOLOMITE SIMULATION TEST COLUMNS

Material
Limestone
Claystone
Sandstone
Limestone Quarry
Representa-
tive Stratum ^
Thicknesses (m)
14.2
1.4
14.2
Dolomite Quarry
Scale (a)
Coefficient
15.7
3.9C
15.7
Material
Dolomite
Claystone
Sandstone
Representa-
tive Stratum
Thicknesses (m)
14.2
1.4
14.2
Scale (a)
Coefficient
15.7
3.9<=
15.7
a Thickness of layer in field to thickness of simulated layer in column.
  Excludes odd-mixed *6X) sand.
 , As mixed, includes sand with clay in column, for increased permeability.
  Includes add -mixed *60 sand from claystone layer.
Source: 30, 49,  106.
                                     61

-------
            20cm
 u

o
CO
 o
o
"t
 E
 u
 E
 y
o*
-
-------
            E
            u

           o
           CO
            E
            o
         E
         u
            E
            u
                    20 cm
IS
IS
               Freeboard
                                   Residue
                                   Sandstone (^60 sand)
in
•M
itm,
                                   Dolomite

                    wm
                                   Claystone
                             Collection

                             Lysimeters
                                   Sandstone (*^60 sand)
                Sandstone
                            san
                                                  d)
                                   Gravel
Figure ¥9.  Simulated sedimentary environment: dolomite quarry test column,
                              63

-------
                TABLE 30, REPRESENTATIVE THICKNESS OF COAL

                           MINE SIMULATION TEST COLUMNS
    Mr,ter; I      Representative Stratum    Column Layer     _  .             a
    Material          TL-  i     /  \         TL- i     / \      Scale Coefficient
                     Thickness (m)         Thickness (m)
Bituminous Coal
Limestonei
Claystone
Sandstone
9.45
7.32
2.13
11.58
0.611
10.46
0.551
10.73
15.5
15.8
3.9
15.8
k Thickness of layer in field to thickness of simulated layer In column.

  Excludes odd-mixed $60 sand.

  Includes odd-mixed ^60 sand from claystone layer.
Source:  106.
                                     64

-------
                                             Limestone
            Coal
=£=£• Meters
^f 1.83
•^x-^-
X 	 tK
HE
,=£?!

§s^=-
} 1 I _L

0.3
0.6
"0.46
0.15
1:P
v/.o
0.-6
                        1-^. _T
                                  1 .52
                                 0.76
                                 ,0.3
                                 0.18

                                 1.40
                          gfe.   0.02
                                 0.15

                        fe-§:8§
                        ^^f^  0.015
                          S   °»92
                                 0.30
                                 1.83
                                             Shale
Limestone
                                             Shale
                                                Ugend
                                                 Lim»»ton»
    Siltsloneor
     sondstone
    Coal
  •J- R«d and grt«n
  ._   shole
    Black shale
 Figure 20:     Stratigraphic section of a typical coal mine.
Source:    106.
                                          65

-------
         20cm
 £
 u
 £
 u
 E
 u
 E
 u

o-
 E
 o
        •SK£^
        *$$*£>
        ',£.•'•&.! y
                          F reeboard
                          Residue
                          Sandstone (# 16 sand)
                          Bituminous coal
                         Claystone
       Sandstone (#60 sand)
Collection

Lysimeters


       Limestone
                          Sandstone (#60 sand)
                          Sandstone (#16 sand)
                          Gravel
  Figure 21.. Abandoned coal mine test column,
                   66

-------
ON
XI
'" 	 " L" J 	 - ' 	 	 -• - 	 - - 	 	 ~
Material
In Column
Limestone
Dolomite
P-Gravel
#16 Silica
#60 Silica
Claystone
Granite Bedrock
Solid Waste
Bituminous Coal
Density
(g/cc)
1.76
1.51
2.16
1.56
1.56
1.44°
1.82
0.63
0.89
Material
in Field
Limestone
Dolomite
Granodiorite
'Sandstone
Sandstone
Shale
Granodiorite
Sanitary Landfill
Bituminous Coal
Density
(g/cc)
2.71
2.85
2.72
2.32
2.32
2.42
2.72
0.594
1.25
Ratio
Column: Field
1 ;54: 1
1.89:1
1 .26: 1
1 .49: 1
1 .49: 1
1 .68: 1
1 .49: 1
1 .06:1
0.71:1
of Densities
Field: Column
1:0.65
1:0.53
1:<0.79
1:0.67
lrO.67
1:0.60
1:0.67
1:0.94
1 :1 .40

        Includes admixed #60 sand.

-------
TABLE 3 2.
Material
P-Gravel
#16 Silica Sand
# 60 Silica Sand
Clay: Sandb
Limestone
Dolomite
Granite Bedrock
Solid Waste
Coal
Clay w/out Sand
.Sandstone
1 :3 by weight
Granodiorite
eNot available
MATERIAL
Wt. Added
(Kg)
12.2
5.4
6.4
27.2
97.7
22.2
23.6
50.3
25.9
43.1
34.9
12.2
17.2
5.55

TABLE 33
DENSITII
Height
(cm)
18
6
9
55
200
49
52
91
46
91
61
61
61
12.25

ES OF NA1
IURAL bIKAIA
Test Column
Area Volume
(cu cm)
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16
314.16

*. AVERAGE FIELD
Material
Granite
Granodiorite
Sandstone
Shale
Limestone
Dolomite
Sanitary Landfill





















5,654.88
1,884.96
2,827.44
17,278.8
62,832.0
15,393.8
16,336.3
28,588.6
14,451 .4
28,588.6
19,163.76
19,163.76
19,163.8
3,848.5

, AINU ICil v-v
Density
(a/cc)
2.16
2.86
2.26
1.57
1.55
1.44
1.44
1.76
1.93
1.51
1.82
0.63
0.89
1.44

^LU/VIINJ
Density of
Field Rocks
(a/cc)
N.A.e
2.32°
2.32
2.32
2.32
2.42°
2.42
2.71
2.71
2.85
2.72d
0.594
1.25
2.42C

DENSITIES OF MATERIALS
Average
2
2
2
2
2
2
0
Field Densities
(g/cc)
.667°
.716°
.32°
.42°
.71b
.85b
.594








Source: 51.
Source:  98.
                                       68

-------
      The materials in the test columns were prepared by granulation and hence have
greater surface area exposed for chemical reactions than the natural rocks.  In the field the
natural rocky materials would have less surface area exposed to water percolating through
the strata.  The amount of surface  area exposed in  the field per meter of strata is a variable
depending on porosity, capilarity and the extent of fractures and/or permeability for each
material. No simple  comparison can therefore be made of surface area exposed per meter
of column material versus the surface area exposed per meter of sfraium in the field.

                             Column Test Procedures

Column Construction

      The test columns were made  from plastic PVC pipe (20.3 cm ID) cut to 3.05 m lengths.
For each simulated disposal environment^tratigraphic  configurations were developed during
the literature search and scaled to fit the columns.  Table 34 identifies the columns con-
structed by number code, environment, and residue type tested.  The simulated environment
was marked  on  the column, as were locations for layer interfaces, observation ports and
soil moisture (lysimeter) ports.  The lysimeter and observation ports (2.54 cm diameter)
were drilled in the column sides.  A 1,59-cm port was drilled in the center of the PVC
bottom cap for each column  and a  plastic drain spout was glued in place. The  columns
were washed clean, dried, and the bottom cap was glued to the pipe; finally/the columns
were bracketed to the wall in a vertical position.

      Filter paper (20.3  cm  diameter, *1 qualitative) with a plastic screen above (20.3 cm
diameter) was placed in the  bottom of the column.  These items were installed from the
top and their location adjusted  with a long pole to obtain their correct position.  The
columns were then ready for partial filling.

Lysimeter Assembly

      A porous ceramic cup  (1-bar) was attached to a 30.5 cm length of polyethylene
tubing (1.27 cm ID).  The ceramic cup and 3 to 5 cm of the tubing were then covered with
a 0.64 cm layer of *200-mesh silica sand, applied in a thick slurry.  The Iysimeters used
an absorbent cotton sock to hold the fine sand  during and after placement in  the test
columns.  Figure22 illustrates the lysimeter assembly and its placement in the columns.

Column Material Preparation

      Standard particle size analyses were performed on all materials added to the columns
(see Figures 6  through 10).  Detailed grading analyses were employed in the column design:
1) to prevent erosion and clogging (piping of finer material through coarser
materials); 2) to provide  sufficient permeability to  allow leaching; and 3) to  assure
classified reproducible grain sizes  and materials.  Table 35 presents the criteria used, and
Table 36 summarizes the  results of the grading  analysis.
                                        69

-------
TABLE 33. COLUMN AND RESIDUE IDENTIFICATION
Column
No. Environment
1


2


3
4
5
6
7
8
9
10


11
12
13
14
15
16
17
18
19
20
Ocean


Limestone


Limestone
Limestone
Limestone
Dolomite
Dolomite
Dolomite
Dolomite
Landfill


Landfill
Landfill
Landfill
Coal mine
Coal mine
Coal mine
Coal mine
Ocean
Ocean
Ocean
Operating Conditions of Test Runa
Residue
VSBM


NJSBM


VSBM
NJFA
VFA
VSBM
NJSBM
NJFA
VFA
VFA


VSBM
NJFA
NJSBM
VSBM
NJSBM
NJFA
VFA
NJFA
NJSBM
VFA
No. Date
NAb NA "


19.7 8-28-75


NA
19.7 8-28-75


19.7 8-28-75
19.7 8-28-75

NA NA



19.7 8-28-75
19.7 8-28-75

19.7 8-28-75
19.7 8-28-75

19.7 8-28-75
19.7 8-28-75

Average
Temperature Fuel Type
843 Sewickley
coal

905-910 Champion
coal
(eastern)







843 Sewickley
coal











Excess Bed
Air Sorbent
18 Germany
Valley
limestone
9.4 Grove
limestone








18 Germany
Valley
limestone










Ca/S Average
mfr Flue SO2
(ppm)
Variable Variable


2.5 360









Variable Variable












               (continued)

-------
                                             TABLE 33 (Cont.)
Operating Conditions of Test Runa
Column Average Excess Bed Ca/5 Average
No. Environment Residue No. Date Temperature Fuel Type Air Sorbent mfr Flue SO~
(°C) (%) (PPm)
21 Ocean EFA NA 11-10-75 890 #2 oil 5-10 BCR 1359 lime 1 200
22 Ocean ESBM
23 Limestone EFA
24 Limestone ESBM
25 Dolomite EFA
26 Dolomite ESBM
27 Landfill EFA
28 Landfill ESBM
29 Coal mine EFA
30 Coal mine ESBM
31 Sandy loam EFA
32 Sandy loam ESBM
33 Clay loam EFA
34 Clay loam ESBM
35 Silty loam EFA














36 Silty loam ESBM I














i














i














i














1 \




























\















a
,  Operating conditions at the pilot plant test site.
  NA - Not available.

-------
                            Porous Ceramic Cup

                            #200Mesh Silica Sand
                            Cotton Cover
                            Column Material
                                     Test
                                     Column Wall
                                         Rubber Stopper
                                           Polyethelene Tubing
Figure 22.  .  Lysimeter construction and test column placement.

                           72

-------
.,	TABLE 35.   CRITERIA DEFINITION FOR GRADING ANALYSIS

               Objective                               Criteria °'b

 1)  Prevention of erosion and clogging            t>     (filter)
    (piping of finer material through               —	,—^—  < 4 to 5
    coarser material)                             D85  (SOll)

 2)  Permeability sufficient to prevent the          D     (filter)
    buildup of large seepage forces                -	•>—qr—  >4 to 5
                                                L>15   isoii;

                                                D
 3)  Approximately parallel  grain size              50    filter)    ^5
    curves                                       D^ri   feoil)  ~
   D  = diameter such that x percent of material is finer.
 b  X
   filter = layer above, soil = layer below.

 Source: 25,154.
                                         73

-------
^\FIIter
Soil ^v.
Limestone
Dolomite
#16 Silica
Sand
#60 Silica
Sand
P-Gravel
Coal
Claystone 4:1
Granite
Bedrock 1:1
Granite
Bedrock 3:1
#16
Limestone Dolomite Silica
Sand
2 Marg.0' b
2Marg.
2 2
2 2Marg. 2Marg.
222
2 2Marg.

2Marg.
2
#60
Silica
Sand
2
2
2

2
2
o.k.
2
2
n /-. i ,~i /-i i. Granite Granite
P-Gravel Coal Cloystone _ , _ , ,
4.^ Bedrock Bedrock
1:1 3:1
2 Marg. 2
1 2
o.k. 2 22
1,3 2 Marg. 2Marg. 3
2
o.k. 2

o.k.
o.k.
,a Numbers indicate grading analysis criteria definition shown in Table 34  .
b
  Marg. = Marginal.

-------
      Most of the column fill materials were usable when delivered.  However, due to the
impervious characteristics of the extremely fine-grained claystone, it appeared that a
100 percent claystone layer would not permit leachate drainage.   Permeability tests were
performed on several different sand to clay mixtures.  The mix that provided a reasonable
permeability check had about  a 3:1 by weight ratio of *60 mesh silica sand to clay.
Homogeneous mixing was done in 5 to 10 kg quantities which were more easily handled.
The granite material also required mixing in a ratio of 3;1 granitic pea gravel to decom-
posed granite by weight to  achieve the desired permeability.

      The top soils used in  the soil columns represented common agricultural disposal en-
vironments; sampJes were  obtained in the field according to the desired classification and
the local in-situ locations were established from the USDA-Soil Conservation Service
report Soils of the Malibu Area.  Silty clay loam from the Castaic series was selected for
the silty loam test soil  type. Clay from the Cropley series was used for the clay loam test
soil, and very fine sandy loam from the  Huerhuero series  for the sandy loam test soil.
Table 37 shows the soil characteristics and Figure 23 indicates the locations from which
these representative soil samples were obtained.

      The silty and clay loams were admixed with *60 mesh silica sand to achieve satis-
factory leachate drainage.  A 4:1 sand-to-soil mixture by weight was used.  The clean
silica sand admixtures were used as a permeable, relatively inert "filler," which allowed
leachate movement through the simulated sub-surface environment.

      The sanitary landfill  materials were mixed according to the refuse percentages shown
in Table 38, following typical "as disposed " quantities.  The "as mixed" percentages
varied slightly, and are shown in Table 39.

Column Filling

      The columns were filled with materials to simulate  various strata in  the quantities
shown in Table 40 and according  to the  depths established during the  literature search
(Figures 15 to 21). Care was  taken to add the bottom pea gravel layer slowly to avoid
damage to the columns' bottom filter and screen.  Column interface level depths were
measured with a weighted string held from the top or through an observation port.   The
placed  layers were checked to ensure that there was a level  thickness from the center of
the column  to the  circumference.

      During column filling the leachate collection lysimeters were placed as shown in
Figure24, with the lysimeter generally located in the layer above the collection tube open-
ing.  Filling of material was stopped just below the opening and the lysimeter lowered on a
nylon string. The tube was threaded through the hole, and a rubber stopper was placed on
the tube and secured in the hole.  The height of the lysimeter was adjusted with the string
which was then tied to a bar across the top of the column.   Column filling was then
resumed.  When the lysimeters were covered to a depth of 15 cm or more,  the string was
cut.
                                        75

-------
                 TABLE 37.   TEST COLUMN SOILS CHARACTERISTICS
      Series
 Horizon (cm)
Characteristics
Castaic                   A         Dry color grayish-brown or light brownish-gray to
  Clay                   0-25      light yellowish-brown or light olive-brown.
  Loam                              Textures are silty clay loam.  Noncalcareous with
  Soil                               reactions from slightly acid to moderately alkaline.
                                    Moderate fine granular structure; hard, sticky,
                                    and plastic.
                          B         Dry color very pale brown or pale yellow to yellow
                        25-71      and light olive brown.  Textures similar to horizon
                                    A with up to 30 percent (by volume) shale fragments.
                                    Calcereous with reactions  from neutral  to moderately
                                    alkaline.  Weak fine granular structure; hard, sticky,
	and plastic.	

Cropley                   A         Dry color of dark gray and very dark gray.  Tex-
  Silty loam             0-36      tures of clay to silty clay.  Reaction is neutral to
  Soil                               mildly alkaline.   Medium  angular blocky structure;
                                    very hard, very sticky, and very plastic.

                          B         Colors are dark gray, gray, dark grayish-brown,
                       36 - 96      grayish-brown, olive-brown,  and yellowish-brown.
                                    Texture ranges from clay to clay loam. Calcareous
                                    in the lower section, with reaction from mildly to
                                    moderately alkaline.  Coarse  angular Wocky struc*
	ture; very hard, very sticky, and very plastic.
Huerhuero
  Sandy loam
  Soil
   A        Colors are grayish-brown, light brownish-gray,
  0-10      pale brown, and brown.  Textures are fine sandy
             loam to loam.  Reaction is medium acid to neutral.
             Fine granular massive structure; slightly hard,  non-
             sticky and non-plastic.

   B         Colors are dark brown, dark yellowish-brown, brown
 10-64      and strong brown.  Texture is sandy clay to clay,
             with up to 15 percent gravels in the lower portion.
             Reaction is neutral to moderately alkaline and cal-
             careous in the lower portion.  Medium to coarse
             angular blocky structure; very hard, slightly sticky,
	and slightly plastic.	
                                          76

-------
' "Source:"
    PA CI^IC     O CEA N
              i              i
          LFGEND

  1	J  Clay loam
          Sandy loam

          Silly loam
   0.5              1.0km
Scale* 7.7 cm = 1.0 km
      1 cm = 0.13 km
         Figure 23.   Original location of representative soil samples.

                                77

-------
           TABLE 38,  ESTIMATED RESIDENTIAL AND COMMERCIAL SOLID WASTE GENERATION
— 	 	 	 	 	 UJ 	 IXIINL-/ v^r iv\f* I CM/-VI — MIMIJ rnv juii\.. i .-tunny. r v.^irvnv
Product Source Categories ,
"As Generated" Basis (kkg x 10 )
Materials C _ «
 O JJ
Z •<
Paper 9.3
Glass
Metals
Ferrous —
Aluminum
Other non-ferrous
Plastics tr
Rubber and leather
Textiles tr
Wood
Non-.food product 9.3
52 ?
a> .£
C CD
'•§"8 1
§° 1
u °-
18.5
10.1
5.5
4.9
0.5
0.1
2.3
tr
tr
1.6
38.0
V) 4A f-
~O 
-------
Product Source Categories ,
"As Generated" Basis (kkg x 10 )
Materials
Food waste
Product totals
Yard waste
Miscellaneous
inorganics
Total waste
i.il s 1 ,
§• o ,E .c o> o
D_ u) t! D"" 3 *Z3
i/i v O •*- C -* ^
£ 0 S> CD U ^

u
c
a
"oL
Q.
Furniture
and
Furnishings
Clothing and
Footwear
As

-------
            TABLE 39.  SANITARY LANDFILL TEST COLUMN-AS,MLXED_
    Materials
                                        Percent
                Description
Paper


Glass
Metals

Plastics
                         8.39


                         2.27
                         2.15

                         0.86
Rubber and Leather
Textiles
                         0.59
                         0.23
Wood                    0.77
Non-Food Product Total   15.26
Food Waste               3.18
Product Total            18.44
Yard Waste               3.40
Miscellaneous Inorganics   0.39
Total                    22.23
37.7   Shredded newspaper and shredded
       paper.

10.2   Broken bottles,  colored and clear.
 9.7   Cut-up tin cans,
       cans and cut wire.
 3.9   Shredded plastic trash bags and
       miscellaneous plastics from trash.
 2.7   Cut-up shoes.
 1.0   Shredded drapes and rags.
 3.5   Cut-up wood crates.
68.7
14.3   Miscellaneous  household food
                                          15.3   Miscellaneous yard waste.
                                           1.7   River gravel and silica sand.
                                         100.0
                                        80

-------
                          TABLE 40. MATERIALS IN TEST COLUMN LAYERS BY WEIGHT
00

Column Layers in . .
Oj r AJ-I'J.' Limestone
rder of Addition _
Quarry
Pea gravel (.95 cm)
Pea gravel (.64cm) 12.2°
Silica sand #1 6 5.4
Silica sand #60 27.2
Clay: #60 sand 1:4 22.2
Limestone 50.3
Dolomite
Granite p-gravel: decomposed
granite 3:1
Silica sand #16
Silica sand #60 4.1
Clay: #60 sand 1 :4
Solid waste
Bituminous coal
Soil horizon B
Soil horizon A
Silica sand #16
Average Weight
Dolomite Ocean
Quarry Disposal

12.2° 12.2°
5.4 5.4
27.2 97.7
22.2

43.1


4.1






per Layer
Sanitary
Landfill

12.2°
5.4




34.9
6.4
16.8
14.1
12.2



8.2
by Column Type (kg)
Coal Sandy Clay Loam: Silty Loam
Mine Loam sand 1:4 sand 1:3
11.3 11.3 11.3
12.2° 6.4 6.4 6.8
5.4
13.2

25.9



4.1
23.6

17.2
80.5 88.9 76.9
17.9 15.0 12.5
5.4
     Columns 21-30 contain 6.8 kg of 0.95 cm gravel covered by 5.4 kg of 0.64 cm gravel.

-------
    Lysimeter
      Tube
  Leachate
  Bottom
Drain Collection
    Bucket
                                            Collection Flask
                                            1/4"    Polyethelene Tubing
                                                Y Connector
      To Vacuum Pump
Moisture Trap
     Figure 24, . Typical test column leachate collection system schematic.

                             82

-------
      For the soils tett columns, the leachate lysimeters were left attached to the string
for several  days while the columns were washed with tap water and the simulated strata
compacted. A detailed diagram of the lysimeter construction and placement is given in
Figure 24.  After filling the test columns, the external leachafe collection tubing and
flasks, connectors and manifold were added, as shown in Figure.25.

Sample Bottle  Labeling

      Each lysimeter had its own sample collection flask, labeled with the appropriate
identifying column number and lysimeter letter. All lysimeters, drains, and columns were
identified sequentially from the bottom of the column up, starting with A as the bottom
drain for all the columns.  Leachate sample collection bottles were placed and labeled
as follows in the typical example:

      Column  number, column  abbreviation, lysimeter letter, and lysimeter location =

              2 LQ-C-top lysimeter

Column Washing

      Before adding the residues, the strata materials in each column were leached with
tap water to ensure washed compacted strata and to establish the base-line column leachafe
quality and flow quantity. Tap water was added daily for at least two weeks, or until the
 chemical analysis revealed a nearly constant or zero level of leached constituents.  Results
of the baseline analyses are given  in  Figures 32 - 196. To determine the flow rate
characteristics of each column, the drains were kept open for two days until there was no
further leachate flow into the drain.  7.6 liters of tap water were added at the top, and the
rate of water leached for each  time period was measured over a period of 27 to 30 hours.
In column 14, the residue solidified, in situ, and the water was perched over the top layers.
This column was repacked with a sand mixture to eliminate the percolation obstruction.
All the columns were  successful in percolating water. The column percolation  data are
shown in Figures 26-30 .   Analyses of fresh and sea water used for column washing are
shown in Tables41  and42 .  Reduction in percolation rates occurred over the 15 months of
leaching.

 Residue Preparation and Addition

      In  laboratory studies, it was found that when  some residues  reacted with water, a large
amount of heat was released.   To avoid heat damage to the columns, weighed amounts of
residues were  first placed in an inert container to which water had been added so as to
slake and dissipate the heat of reaction.  Filter paper (20.3 cm diameter, *1 qualitative)
was placed in  the  columns above the stratum materials before residue addition. The amounts
of fluidized-bed combustion residues added to each column are shown on Table 43 ,
                                         83

-------
         "ۥ
         i
Figure 25 .  Outdoor columns (eachate sampling apparatus.
                           84

-------
    7500 -


    7000 -


    6500 -


    6000 -


    5500 -


    5000 -


5  4500 -
 V.
 0>
|  4000 -
Cfc.
 O

I*  3500 -
 o

°  3000 -


    2500 -


    2000 -


    1500 -


    1000 -


     500
3 after
 residue added
                I      I      I      I      I       I      I      I      I      I
               200   400   600   800   1000   1200  1400   1600  1800  2000
                                      Time (minutes)
                Figure  26  .  Drainage   through limestone quarry columns.
                                      85

-------
   7500  -

   7000  -

   6500  -

   6000

   5500

   5000

5 4500
 i_
 o
S 4000 -J
•I"  3500
3000 ~


2500 -
2000 -

1500 -

1000 -

500
' ' //
\ I /
\ \ :
' / J
•' / //
1 / ••
f '• /
• it /
/ f /
i /
1 1/
>f
nt
'dJ




Legend
Column
A

^«- ~» ««• «M* •«• «•• — — y
0

	 9







Number




fter residue
added
                 ITII      I      I       i      1      T7I
               200   400   600   800   1000   1200  1400  1600  1800   2000
                                      Time (minutes)
                  Figure  27  .     Drainage through dolomite quarry columns.
                                     86

-------
    7500 -

    7000 -

    6500 -

    6000 -

    5500 -

    5000 -

5f  4500 -
 i_
 
-------
                   Legend
 0>
"6
7500


7000


6500


6000


5500


5000

4500

4000
                             Column Number
£   3500
 o

°   3000

    2500


    2000


    1500


    1000


     500
                I      I      I      I      i      I      i      I      1      I
              200    400  600   800   1000   1200  1400  1600  1800   2000
                                     Time (minutes)
                 Figure  29 •  Drainage through coal mine columns.

-------
7500 -•
7000 -
6500 -
   .»•
    • •
                                   x
X"





^
1
«*-
O
X
•4—
o
3
















6000 -


5500 -
5000 -
4500 -
4000 -


3500 -


3000 -

2500 -
•
2000 -

1500 -


•
1000 -

1

XX ' -^
' / ' /'
• / / /
/ ///
i ///
! /// ^-^
•'/// /x
// / X
// / /
. / /
1 / '
' /
I/ /

1 / / Legend
I-* m Column Number
t/ / 1
'/ / 18
I/ .!

/
• ««
/ 20
f
/ . i r, • i
y 1 .. . . . i atf.er residue
•If added
/
t i./
500" f fir
LJf
o
           200   400   600   800   1000   1200  1400  1600  1800  2000
                                  Time (minutes)
             Figure 30    . Drainage through ocean disposal columns.

                                  89

-------
TABLE 41 . COMPLETE
ANALYSIS OF LOS ANGELES OWENS RIVER AQUEDUCT
(FRESH WATER) COLUMNS TEST
Analysis 1975-1976 Averages
Spec. El ec. Cond.
(Kxl06)
TDR (Calc.)
Total Hardness (CaCOg)
Color (apparent)
Turbidity (units)
Temperature (°C )
pH
Saturation index
Stability index
Calcium
Magnesium
Sodium
Potassium
Alkalinity (CaCO3)
Sulfate
Chloride
Nitrate (NO3)
Boron
Carbon dioxide
Fluoride
Iron
Oxygen (dissolved)
Silica
BOD5
COD
Nitrogen, TKN (as N)
Nitrogen (ammonia)
Nitrogen (nitrite)
Nitrogen (nitrate)
299

184
79
8
3.2
14.5
7.95
-0.30
8.55
24
5.0
30
32
109
20
13
0.8
0.34
3
0.52
0.09
8.9
22
1.7
4
0.10
<0.01
<0.001
0.18
Analysis
Aluminum

Antimony
Arsenic
Barium
Bismuth
Bromide
Cadmium
Chromium
Copper
Cyanide
Detergents (MBAS)
Gallium
Iodide
Lead
Manganese
Mercury
Molybdenum
Nickel
Phenol
Phosphate (PO4)
Selenium
Silver
Tin
Titanium
Tungsten
Vanadium
Zinc
Zirconium

1975- 1976 Averages0
0.07

<0.01
0.02
0.1
0.003
<0.1
<0.002
0.01
0.06
<0.01
<0.05
<0.0002.
0.01
0.01
<0.01
<0.0001
0.005
<0.0009
<0.001
0.16
<0.002
<0.02
0.0005
0.002
<0.07
0.002
0.01
<0.0003

  Chemical results m mg/l, except as noted.
 bTotal dissolved residue = Anions + Cations + COg + HCOl/2 + SiO .

Source:  185.
                                       90

-------
                  TABLE 42.   SEA WATER ANALYSIS
  A.  GENERAL:  DITMAR'S VALVES FOR THE MAJOR CONSTITUENTS, 1940
 	  (Values in. Grams Per Kilogram.  /100)	
    Constituent
                                      1940 Valves
                         Cl = 19
Chlorine
Bromine
Sulfate
Carbonate
Bicarbonate
Fluorine
Boric Acid
Magnesium
Calcium
Strontium
Potassium
Sodium
Total
18.980
0.065
2.649
0.071
0.14
0.001
0.026
1.272
0.400
0.013
0.380
10.556
34.553
55.04
0.19
7.68
0.21
0.41
0.00
0.07
3.69
1.16
0.04
1.10
30.61

           B.  PARTIAL ANALYSES OF COLUMNS TEST SEA WATFR
                                   1975-1976 Averages
Constituent
Sulfate
Iron
Zinc
Nickel
Mercury
Lead
Cl = 19°/00
.0032
.00052
.00003
.001
.0000105
.00044
%
.00931
.0015
.0001
.003
.00003
.0013
1
 Source 190.
                               91

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                 TABLE 43.   RESIDUES ADDED TO COLUMNS
      Residue Type
Quantify Added
    (kg)
         Remarks
Pope, Evans, & Robbins
Virginia  Fly Ash

Pope, Evans, & Robbins
Virginia  Spent Bed Material
    9.07
   13.61
slaked with 3.81 water over
two days.


unslaked weight.
Exxon Miniplant
New Jersey   Fly Ash
   13.61
Exxon Miniplant
New Jersey   Spent Bed Material   9.98
Esso Gasifier Plant
England  Fly Ash               11.34
Esso Gasifier Plant
England  Spent Bed Material      6.35
unslaked weight.
                        slaked with 7.6 I water over
                        two days, slaked (dry) weight,
                        Equivalent unslaked weight,
                        8.7  kg.
                        slaked with 3.8 I water over
                        one day, unslaked weight.


                        slaked with 3.8 I  over one
                        day, unslaked weight.
                                     92

-------
Water Addition
    Tri-weekly (every Monday, Wednesday, and Friday afternoons), potable water was
added to all columns, except for the ocean disposal columns which received sea water.
All clamps on drains were closed before the fresh or sea water was added, and the water
was retained in the columns through the next sampling day. Ideally, 7.6 liters of water
were added  each time.  However, some columns gradually reduced their drainage after
several months so that they received less than 7.6 liters at the top of the column.   Pro-
cedures for the sea water columns were changed after six months to investigate leaching
in a flooded environment; i.e., the sea water columns were kept saturated except for
partial surface drainage which allowed the addition of fresh sea water.  The purpose of
the flooding test was to simulate the addition of a residual landfill into an ocean environ-
ment rather  than in the former tidal  prism environment.

Leachate Sampling
    Leachate samples from the column drains and lysimeters were collected to measure
the results of the previous day's water addition.  See Table 44 for discussion of ocean
water test column procedures. Every Monday morning, sampling was started after emptying
the lysimeter collection flasks containing weekend drainage.  With a vacuum pump  set at
a vacuum of about 1,760 cm of water, 5 to 6 hours of collecting time normally provided
sufficient sample for analysis. All column lysimeters were sampled simultaneously using
the interconnected  tubing and flask systems linked to the vacuum pump (See Figure 24 above).

    After the vacuum pump was started, a collection container was placed beneath each
drain tube and the drain valve was opened. At the end of the day, the amount collected
in the container was noted  and the sample was taken.  Equal amounts of daily samples were
composited to make up one weekly sample of 250 ml.  If there was insufficient sample at the
end of the day, pumping was maintained until the amount needed for analysis was obtained.
After sampling all outlet valves for  the leachate,  drains were closed to prepare for the next
water addition.
    Next, the leachate containers  were rinsed clean with tap water to avoid contamination
of the next sample.  Notes were made in a daily log regarding routine activities or  varia-
tions in the  usual procedures and noted observations.

 Leachate Analysis
    The composite  samples were analyzed for pH, sulfate, chloride, iron,zinc,
nickel, lead, specific conductivity, and total dissolved solids.  During the first 25  weeks
of column operation, weekly composites were analyzed; thereafter,  the frequency of labora-
tory analysis was reduced to once for each two-week period, and after 32 weeks, to once
for each four-week period.  See Tables 45 through 51  for results of these analyses and
drinking water standards. Figures 31 through 159 give results of studies of leachate versus
total volume of water applied. Figures 31 through 143 also show the total grams of consti-
tuents in the columns before the leachate sampling was initiated.  Figures 160 - 176
illustrate the change in pH with the total volume of water applied.
                                          93

-------
      TABLE 44. PROCEDURE FOR SAMPLING AND FILLING THE FLOODED
                              OCEAN WATER TEST COLUMNS          	
1.    Filled columns initially with ocean water.

2.    Collected leachate samples from opened lysimeters per original procedure (at 8:00 A.M.
      on Monday, Wednesday, and Friday).

3.    Closed leachate lysimeter valves at 9:00 A.M.

4.    Shut off the leachate valves which provided sufficient sampling amounts.

5.    In the afternoon, refilled the column with the same amount of ocean water as was
      gravity or vacuum leached.

6.    All other routine compositing and analytical procedures were maintained. '
                                        94

-------
TABLE 45 . CONSTITUENT REMOVAL BY OCEAN DISPOSAL COLUMN STRATA
Column Layer
Column 1
Water
Residue
Sandstone
(Upper)
Sandstone
(Lower)
Drain
Column 18
Water
Residue
Sandstone
(Upper)
Sandstone
(Lower)
Drain
Column 19
Water
Residue
Sandstone
(Upper)
Sandstone
(Lower)
Drain
Column 20
Water
Residue
Sandstone
(Upper)
Sandstone
(Lower)
Drain
Sulfate
ga %b

1100
360

360

360
100

1100
1000

1000

1000
100

1100
370

370

370
100

1100
850

850

850
100
Iron
g %

0.540
0.950

0.950

0.500 47
53

0.540
0.740

0.740

0.180 76
24

0.540
0.270

0.270

0.240 11
89

0.540
0.220

0.220

0.220 47
53
Zinc
g %

0.052
0.052

0.032 38

0.032
62

0.052
0.052

0.052

0.052
100

0.052
0.052

0.052

0.052 28
72

0.052
0.047

0.047

0.034 28
62
Nickel
g %

0.700
0.700

0.350 50

0.350
50

0.700
0.700

0.700

0.700
100

0.700
0.700

0.550 21

0.550
79

0.700
0.700

0.550 50

0.550
50
Mercury
g %

1.500
1.500

1.500

1.500
100

1.500
1.500

1.500

1.500
100

1.500
1.500

1.500
--
1.500
100

1.500
1.500

1.500

1.500
100
Lead
g %

0.750
0.440

0.440

0.440


0.750
0.220

0.220

0.220


0.750
0.150

0.150

0.150


0.750
0.150

0.150

0.150








100







100







100







100
ag = Grams of constituent in leachate leaving column layer (or applied in tap water).
k%= Percent removal of constituent in leachate from residue layer.

                                       95

-------
   TABLE 46. .  CONSTITUENT REMOVAL BY LIMESTONE QUARRY COLUMN STRATA
Sulfate
Column Layer"
ga %b
Column 2
Water
Residue
Limestone
Claystone
Sandstone
Drain
Lysimeter loss
Column 3
Water
Residue
Limestone
Claystone
Sandstone
Drain
Column 4
Water
Residue
Limestone
Claystone
Sandstone
Drain
Column 5
Water
Residue
Limestone
Claystone
Sandstone
Drain

10
450
130 71
100 7
100
22


10
375
220 41
170 13
170
46

10
330
280 15
280
280
85

10
310
220 29
170 16
170
55

0
0
0
0
0



0
0
0
0
0


0
0
0
0
0


0
0
0
0
0
—
Iron
g %

.055
.055
.028 49
.028
.028
51


.055
.055
.045 18
.045
.045
82

.055
.055
.027 51
.027
.027
49

.055
.055
.025 55
.025
.025
45


0
0
0
0
0



0
0
0
0
0


0
0
0
0
0


0
0
0
0
0

Zinc
g %

.002
.027
.018 33
.018
.018
67


.002
.013
.007 46
.007
.007
54

.002
.019
.009 53
.009
.009
47

.002
.013
.007 46
.007
.007
54
Nickel
g %

0.
0.
0.
0.
0.



0.
0.
0.
0.
0.


0.
0.
0.
0.
0.


0.
0.
0.
0.
0.


000
070
045 36
025 -c
025
9
55

000
084
040 52
040
040
48

000
104
05448
054
054
52

000
104
050 52
050
050
48
Msrcury
g %

0.000
0.130
0.130
0.130
OclSO



0.000
0.225
0.225
0.225
0.225


0.000
0.370
0.370
0.270
0.270


0.000
0.190
0.190
0.190
0.190


0
0
0
0
0
100


0
0
0
0
0
100

0
0
0
37 o
0
63

0
0
0
0
0
100
Lead
g %

.000
.042
.042
.028
.028



.000
.035
.035
.035
.035


.000
.026
.026
.026
.026


.000
.032
.032
.032
.032





33

67







100






100






100
°g = Grams of constituent in leachate leaving column layer (or applied in tap water).
"%= Percent removal of constituent in leachate from residue  layer.
c  = Difference in quantities is due to removal of constituent in lysimeter leachate,
     not in column material.
                                    96

-------
TABLE  47.  CONSTITUENT REMOVAL BY DOLOMITE QUARRY COLUMN STRATA
Column Layer
Column 6
Water
Residue
Dolomite
Claystone
Sandstone
Drain
Lysimeter loss
Column 7
Water
Residue
Dolomite
Claystone
Sandstone
Drain
Column 8
Water
Residue
Dolomite
Claystone
Sandstone
Drain
Column 9
Water
Residue
Dolomite
Claystone
Sandstone
Drain
Sulfate
ga %b

10
380
200
200
200



10
420
320
180
180


10
360
300
250
250


10
300
150
150
150




47


53




24
33

43



17
14

69



50


50

0
0
0
0
0



0
0
0
0
0


0
0
0
0
0


0
0
0
0
0

Iron
g %

.055
.055
.045 18
.045
.045
82


.055
.055
.038 31
.038
.038
69

.055
.055
.044 20
.044
.044
80

.055
.055
.044 20
.044
.044
80
Zinc
g %

0.003
0.038
0.029
0.017
0.012



0.003
0.023
0.013
0.007
0.007


0.003
0.018
0.007
0.005
0.005


0.003
0.019
0.008
0.008
0.008




24
21

32
23



43
26

31



61
11

28



58


42
g

0.
0.
0.
0.
0.



0.
0.
0.
0.
0.


0.
0.
Nickel
%

000
103
03368
033
033
32


000
070
036 49
036
036
51

000
104
Q. 042 40
0.
0.


0.
0.
042
042
60

000
104
0.047 55
0.
0.

047
047
45
Mercury
g %

0.
0.
0.
0.
0.



0.
0.
0.
0.
0.


0.
0.

000
145
145
145
145
100


000
500
500
190 62
190
38

000
270
0.270
0,
0.


0.
0.
0.
0.
0.

,240 11
240
89

000
180
180
140 22
140
78
Lead
g %

0.000
0.056
0.056
0.056
0.056
100
.

0.000
0.050
0.050
0.050
0.050
100

0.000
0.036
0.036
0.025 31
0.025
69

0.000
0.018
0.018
O.Ofl 39
0.011
61
     Grams of constituent in leachate leaving column layer (or applied in tap water),
    = Percent removal of constituent in leachate from residue layer.
     Difference in quantities is due to removal of constituent in lysimeter leachate,
     not in column material.

                                        97

-------
              CONSTITUENT REM(
                                                               COLUMN STRATA
Column Layer
Column 10
Water
Residue
Landfill
Claystone
Granite
Drain
Column 1 1
Water
Residue
Landfill
Claystone
Granite
Drain
Lysimeter loss
Column 12
Water
Residue
Landfill
Claystone
Granite
Drain
Lysimeter loss
Column 13
Water
Residue
Landfill
Claystone
Granite
Drain
Sulfate Iron Zinc
ga °/J> g % g %
10
330
50
50
50


10
370
160
135
135



10
440
120
75
75



10
470
50
50
50



85

15



57


36
7



73
6

17
4



89


11
0.0025
0.0045
0.0045
0.0045
0.0045
100

0.0025
0.022
0.022
0.018 18
0.018
82


0.0025
0.007
0.007
0.006 14
0.006
86


0.0025
0.008
0.008 38
0.005
0.005 25
37
Nickel
g %
0.000
0.105
0.032 70
0.024 8
0.024
22

0.000
0.105
0.050 52
0.040 10
0.040
38


0.00
0.10
0.06 40
0.040C
0.040
27
33

0.0025
0.065
0.042 20
0.035 11
0.035
69
Mercury
g %
0.000
0.125
0.125
0.095 24
0.095
76

0.000
0200
0.200
0.150 25
0.150
75


0.00
0.275
0.275
0275
0.275
100


0.000
0.165
0.165
0.125 24
0.125
76
Lead
g %
0.000
0.018
0.018
0.013 28
0.013
72

0.000
0.070
0.070
0.054 23
0.054
77


0.000
0290
0.290
0.190 34
0.190
66


0.000
0.019
0.0195
0.0105 41
0.0105
59
ag = Grams of constituent in leachate leaving column  layer (or applied in tap water).
°% = Percent removal of constituent in leachate from residue layer.
c =  Difference in quantities is due to removal of constituent in lysimeter leachate, not
     in column material.
                                        98

-------
Column Layer
Column 14
Water
Residue
Bitum. coal
Claystone
Limestone
Sandstone
Drain
Lysimeter loss
Column 15
Water
Residue
Bitum. coal
Claystone
Limestone
Sandstone
Drain
Lysimeter loss
Column 16
Water
Residue
Bitum. coal
Claystone
Limestone
Sandstone
Drain
Column 17
Water
Residue
Bitum. coal
Claystone
Limestone
Sandstone
JDrain
Sulfate
a b
g %

5
370
180
115
115
115



5
450
225
180
125
125



5
350
250
250
250
250


5
300
200
200
200
200




51
18


31




50
10
12

28




29

Iron
g %

0
0
0
0
0
0



0
0
0
0
0
0



0
0
0
0

.055
.055
.035 36
.035
.035
.035
64


.055
.055
.023 58
.023
.023
.023
42


.055
.055
.030 45
.030 '
0,030

71



33



67
0


0
0
0
0
0
0

.030
55

.055
.055
.022 60
.022
.022
.022
40
Zinc
g %

0.
0.
0.
0.
0.
0.



0.
0.
0.
0.
0.
0.



0.
0.
0.
0.
0.
0.


0.
0.
0.
0.
0.
0.


003
020
020
020
012 40
012
60


003
023
023
Oil 52
004 30
004
18


003
026
026
026
007 73
007
27

003
018
018
018
005 72
005
2$
WW/^U-tiQlLXi.
Nickel
g %

0.000
0.104
0.038
0.038
0.026
0.026



0.000
0.070
0.042
0.042
0.028
0.028



0.000
0.103
0.048
0.048
0.038
0.038


0.000
0.102
0.080
0.080
0.040
0.040




63

12

25




40

20

40




53

10

37



22

39

39
-\*vuuixu3-3,
Mercury
g %

0
0
0
0
0
0



0
0
0
0
0
0



0
0
0
0
0
0


0
0
0
0
0
0


.000
.190
.190
.080 58
.080
.080
42


.000
.125
J25
.090 28
.090
,090
72


.000
.135
.135
.110 19
.110
.110
81

.000
.180
.180
.150 17
.150
.150
83
JKMIM
Lead
g %

0.000
0.075
0.075
0.048 36
0.034 8
0.028 — c
35
21

0.000
0.033
0.033
0.033
0.022 33
0.011 **
33
33

0.000
Oj024
0.024
0.024
0.013 46
0.013
54

0.000
0.023
0.023
0.023
0.020 13
0.020
87
ag = Grams of constituent in leachate leaving column layer (or applied in tap water).
b % = Percent removal of constituent in leachate from residue layer.
c   = Difference in quantities is due to removal of constituent in lysimeter leachate,not in
     column material.

-------
            TABLE 50  .  EPA PROPOSED REGULATIONS ON INTERIM
                      PRIMARY DRINKING WATER STANDARDS,  1975
          Constituent or characteristic
    Value
Reason for standard
Physical
   Turbidity, units

Chemical, mg/l
   Arsenic
   Barium
   Cadmium
   Carbon chloroform extract
   Chromium,hexavalent
   Cyanide
   Fluoride
   Lead
   Mercury
   Nitrates as N
   Selenium
   Silver

Bacteriological
   Total coliform, per 100 ml
  0.05
  1.0
  0.01
  0.7
  0.05
  0.2  ,
1.4-2 A
  0.05
  0.002
 10
  0.01
  0.05
                    Aestheti c
   Toxic
   Toxic
   Toxic
   Toxic
   Toxic
   Toxic
   Toxic
   Toxic
   Toxic
   Toxic
   Toxic
   Cosmetic
                    Disease
Pesticides, mg/I
Chlordane
Endrin
Heptachlor
Heptachlor epoxide
Lindane
Methoxychlor
Toxaphene
2,4-D
2,4,5-TP

0.003
0.0002
0.0001
0.0001
0.004
0.1
0.005
0.1
0.01

Toxic
Toxic

Toxic
Toxic
Toxic
Toxic
Toxic
Toxic
  Five mg/l may be substituted if it can be demonstrated that it does not interfere with
.disinfection.
  Dspendent upon temperature:  higher limits for lower temperatures.

Source:  162.
                                     100

-------
TABLE 51  .  SURFACE WATER CRITERIA FOR PUBLIC WATER SUPPLIES
Constituent or characteristic
Microbiological:
Total col i form
Fecal colifonn
Inorganic chemicals: (mg/l)
Ammonia
Arsenic
Barium
Boron
Cadmium
Chloride
Chromium, hexavalent
Copper
Dissolved oxygen

Iron (filterable)
Lead
Manganese (filterable)
Nitrates plus nitrite
pH (range)
Selenium
Silver
Sulfate
Total dissolved solids
(filterable residue)
Uranyl ion
Zinc
Organic chemicals: (mg/l)
Carbon chloroform extract (CCE)
Cyanide
Methyl ene blue active substances
Oil and grease
Pesticides:
Aldrin
Chlordane
DDT
Dieldrin
Endrin
Heprachlor
Heptachlor epoxide
Lindane
Methoxychlor


Permissible criteria
1
10, 000/1 00 ml
2, 000/1 00 ml1

0.5 (as N)
0.05
1.0
1.0
0.01
250
0.05
1.0
4 (monthly mean)
3 (individual sample)
0.3
0.05
0.05
10 (as N)
5.0-8.5
0.01
0.05
250
500

5
5

0.15
0.20
0.5
Virtually absent

0.017
0.003
0.042
0.017
0.001
0.018
0.018
0.056
0.035
(continued)
101
Desirable criteria
i
100/1 00 ml
20/1 00 ml'

0.01
Absent
do
do
do
25
Absent
Virtually absent
Near saturation

Virtually absent
Absent
do
Virtually absent
Narrative
Absent
do
50
200

Absent
Virtually absent

0.04
Absent
Virtually absent
Absent

do
do
do
do
do
do
do
do
do



-------
                              TABLE 51  (continued)
        Constituent or characteristic          Permissible criteria      Desirable criteria
f-
Organic chemicals:
Pesticides: (Cont.)
Organic phosphates plus carbamates
Toxaphene
Herbicides:
2,4-D plus 2,4,5-T,plus 2,4,5-TP
Phenols
Radioactivity:
Gross beta
Radium-226
Strontium-90


2
o.r
0.005

0.1
0.001

1,000
3
10



do
do

do
do

100
1
2
  Microbiological  limits are monthly aruithmetic averages based upon an adequate number
  of samples.  Total coliform limit may be relaxed if fecal coliform concentration does not
  exceed the specified limit.
2
  As parathion in cholinesterase inhibition,  it may be necessary to resort to even lower
  concentrations for some compounds or mixtures.

Source: 72.
                                           102

-------
                        -10
                        11
                        20
                        21
                        [30
                       ,50
 Influent (Water or Sea Water)
  Residue
  Lysfmeter Leachate
-^(Columns 10-13)
                              Lysimeter Leachate
                              (Columns 2-17)
   Lysimeter Leachate
   (Columns 1-20)
                       j 51   Drain Leachate

      00 - Baseline leachate  =  column drainage without residue
Figure 3].   Legend of typical columns for Figures 32 through 176.
                  103

-------

30
i
u
1 20
"o
10

Total Cf
Figure 32 so
Column 2
Limestone •_
NJSBM i 20
/ 10,11,20,21, 30,31,40,41 j?
O
10
00
200 400 600 800 1,000 1,200 1,400

-Total Cl _„ 00
Figure °y
Column 3
Limestone
VSBM
.10,20,21,30,31,40,41
- /
S r , , nA lit.
200 400 600 800 1,000 1,200 1,400
Total omount of water applied and leached (1) ,..,,,,„,
Total amount of water applied and leached (1)
30
O .
•*"• u
i/i
| 20
D)
i.
10

Figure 34
-To'Qlcf Column 4
... 30
Limestone
NJFA
u
I 20

10,11,20,21,30,31,40,41 ~
jS 10
/ 00
Figure 35
-Tofal cf Column 5.
Limestone
VFA

.

10,11,20,21,30,31,40,41
- /
/, ^^ 	
            200     400     600      300     1,000   1,200    1,400
                            Totol amount of woter cppliod gnd leached (I)

Note;  See Figure 3]     for further  legend explanation.
200     400    600     803     1,000    1,200   1,400
               Totol amount of wafer applied and Uached (I)
                             Figures  32   ~   35  ,  Test column leachate cumulative balances: Chloride.

-------
o
Oi
         u
         i
         I
                                      Figure 36
                                      Column 6
                                      Dolomite
                                       VSBM
10,20,21,30,31,40,4V
                    200
                  Total CI
400     600      800     1,000    1,200    1,400
         Total amount1 of water applied and leached (1)


   ,10,20,21,30,31,40,41

          Figure 38
          ColumnS
          Dolomite
            VSBM
                              oo
                     200     400     600     600     1,000    1,200   1,400
                                    Total amount of water cpplted and loathed (I)
                                                    15
u
I10
0)
                                                      Jotal Cf
                                                                               15 -
                                                                               10 -
                                                                                        200
                                                                                    Total C!
                              Figure  37
                              Column 7
                              Dolomite
                               NJSBM
                         .10,20,21,30,31,40,41
                                                                                                   00
                   400     600      BOO     1,000   1,200    1,400
                           Total amount' of water applied and leached (I)

                             Figure  39
                             Column  9
                             Dolomite
                               VFA
                 710,20,21,30,31,40,41
                                                                                               00
                                                                                                       -1.
                                                                                                               JL
                                                                                                                       J_
                                                                                                   _L
                                                             200      400     600      800     1,000    1,200    1,400

                                                                             Total amount of water applied and leachcJ (I)
       Note;  See Figure  31   for further legend explanation.
                                      Figures   36   -   39 ,  Test column leachate cumulative balances; Chloride.

-------
O
O
          i
          6
o
vt

O
"5
"o
                                10,20,21,30,31,4(0,41
Figure 40
Column 10
Landfill
  VFA
                                      oo
200     400     600      800     1,000    1,200    1,400
                Total amount of wator applied and leached (I)


            10,20,21,30,31,40,41

                 Figure   42
                 Column  12
                 Landfill.
                   NJFA
                     200     400     600      800     1,000    1,200    1,400

                                     Total amount of water applied and leached 0)
                                                                               10
                                                                            o
                                                                            I
                                                                                15
                                                                             n  10
                                                                             o
                                                                                           10,20,21,30,31,40,41

                                                                                                  Figure  41
                                                                                                  Column 11
                                                                                                  Landfill
                                                                                                   VSBM
                                                                                                              oo
                                                                                         200     400     600      800     1,000    1,200   1,400

                                                                                                        Total amount of water applied and leached (I)
                                                                                                    10,20,21,30,31,40,41
                                                                    Figure   43
                                                                    Column 13
                                                                    Landfill
                                                                      NJSBM
                                                  200     400     600      800     1,000    1,200   1,400

                                                                  Total cmouc.t of watec applied end leaehed (!)
       Note;     See Figure 31   for further legend explanation.
                                      Figures  40-43,  Test column  leachate cumulative balances: Chloride.

-------
     30
  U

   E

   I20

  z
   o
     10
         Total Cl
       30
    U



    S  20
    u>

    "5
    •5
       10
          Total C!
                200
30
Figure 44
Column 14 <_
Coal mine g 20
VSBM |
o
10,20,21,30,31,40,41,50,51
10
00
•^4 	 I-TT- 1 1 1 I.I
400 600 800 1,000 1,200 1,400
_ Total Cl"
Figure 45
Column 15
Coal mine
NJSBM
10,20,21,30,31,40,41,50,51
/

^
^_ 	 -M ,
200 400 £00 800 1,C€3 1,200 1,400
Total amount of woter epplied and leached (1) Toha! amounf of wafer ^P1^ ond leac*led (1)
Figure 46 3Q
Column 16
Coal mine •_.
NJFA »
S20
10,20,21,30,31,40,41,50,51 |
v' »S
10
	 I 	 ',.,1,00 , iiij
400 600 800 1,000 1,200 1,400

jotai ci" Figure 47
Column 17
Coal mine
VFA
10,20,21,30,31,40,41,50,51

200 400 600 BOO 1,000 1,200 1,400 "
                               Total amount of water applied end leached (I)
                                                                                               Total amount of water applied and leacVied (I)
Note:   See Figure  31   for further legend explanation.
                              Figures  44-47  .  Test column leachate cumulative balances: Chloride.

-------
o
00
           0.15
        2  0.10
           0.05
                Total F« I99g
           0.15
           0.10
           0.05
                Total Fe 950g
      Figure   48
      Column 2
      Limestone
 10,20   NJSBM
21,30,31,40,41
                                 00
                                             _L
                      200     400     600      800     1,000   1,200    1,400

                                      Total amount of water applied and leached (I)
                                   10,20
                               21,30,31,40,41
      Figure    50
      Column 4
      Limestone
       NJFA
                     200     400     600      800     1,000    1,200    1,400

                                     Total amount of water applied and leached (I)


      Note;   See Figure  31    for  further legend explanation.
                                                                                0.15
                                                                              S  0.10
                                                                              G>
                                                                                 0.05
                                                                                     Total Fe 128g
                                                                                 0.15
                                             I  °-10
                                                                              ,2
                                                                                 0.05
                                                                                     _Total Fe 996g
     Figure  49
     Column 3
     Limestone
10'20   VSBM
 21,30,31,40,41,50,51
                                                                                                                                  JL
                                                          200      400
   600      800     1,000    1,200    1,400
    Total amount of water applied and leached (I)

     Figure 51

     Column 5
     Limestone
  10,20
                                                                                                21,30,31,40,41
                                                          200     400     600      800     1,000    1,200   1,400

                                                                          Total amount of water applied and leached 0}
                                      Figures 48   -51  .     Test column Ieachate cumulative balances: Iron.

-------

0.3
£.
I
I 0.2
"s
a
H-
0.1
Total Fe 128g
Figure 52
Column 6
Dolomite
VSBM
10,20
.^^' 21,30,31,40,41
200 400 600 800 1
Total amount of water
0.15
V
U-
fe 0.10
~Q
3
0.05

.Total Fe 950g
10,20
/ .21,30,31,40,41
// Figure 54
// Column 8
// Dolomite
// NJFA
f i ,1 - °° -
200 400 600 800 1





,000 1,200 1,400
applied and leached (!)




,000 1,200 1,400
                                                                        0.15
                                                                      6
                                                                      s  o.io
                                                                        0.05
Jotal Fe 199g
                                                                        0.151 Total Fe 96g
                                                                        0.10
                                                                        O.C5
                         Figure  53
                     0,20 Column 7
                         Dolomite
                          NJSBM
                 21,30,31,40,41
                                                                                                 ., 00
                                                                                  200     400
                     600      800     1,000   1,200    1,400

                      Total amount of wafer applied and leached (I)
                                                                                                  10,20
                                                                                                 21,30,31,40,41
                        Figure 55
                        Column 9
                        Dolomite
                          VFA
                                                                                               oo
                               Total amount of water applied and leached (I)
       200     400    600      800     1,000   1,200    1,400

                       Total amount of water applied and leached (I)
.Note:   See Figure  31   for further  legend explanation.
                                Figures 52   -   55  .  Test column leachate cumulative balances; Iron.

-------
    0.3
  £ 0.2
    0.1
        Total Fa 128g
          Figure   56
          Column 14
          Coal mine
           VSBM
                             10,20
                   21,30,31,40,41,50,51
                             00
    0.15
    0.10
    0.05
              200
        _Total Fa 950g
400     600      800     1,000   1,200    1,400

        Total amount of water applied and leached (I)
          Figure  58
          Column 16
          Coal  mine
    10.20   NJFA
              200     400     600      800     1,000   1,200  ,  1,400

                              Total amount of water applied anel leached (I)
                                                                        0.15
                                                                        0.1
                                                                     2
                                                                      o
                                                                        0.05
                                                                            Total Fa 1998
                                                                     £
                                                                     o
                                                                        0.15
                                                                        0.10
                                                                        0.05
                                                                                  200
                                                       Total Fa 96g
          Figure 57
          Column 15
    10,20  Coal mine
            NJSBM
                                                                        20,21,30,31,40,41,50,51


                                                                               00
400     600     800     1,000   1,200    1,400

        Total amount of water applied and leached (1)
                                                                                                    Figure  59
                                                                                                    Column 17
                                                                                                    Coal mine
                                                                                              10,20
            VFA
                                                             200     400     600      800     1,000   1,200    1,400

                                                                            Total cunovnt of water applied and lecwhad (t)
Note:  See Figure  31   for further  legend explanation.
                               Figures  56   -  59  ,  Test column leachate cumulative balances: Iron,

-------
    3.0
    2.0
 O
 £
    1.0
            Total Fa 123 g
    1.5
 O

 1
    i.o
    0.5
 20,21,30

  Figure 60
  Column 1
  Ocean
    VSBM
              200     400
             Total Fs 199 g
600      SCO     V,000    1,200   1,400
 Total orr.ounr of water applied and leached (!)

  Figure   62
  Column 19
  Ocean
    NJSBM
                         20,21,30
               200     400     600     800     1,000    1,200    1,400
                              Total amount of water applied and leached (I)
                                                                        1.5
                                                                        1.0
                                                                     O
                                           0.5
                                                   Total Fe 950 g
                                                                        1.5
                                                                        1.0
                                         I
                                                                        0.5
                                                                                       20,21,30
                                                                                  200     400
                                                                                Total Fe 926 g
   Figure 61
   Column 18
   Ocean
     NJFA
600      800     1,000    1,200    1,400
 Tetal amount of vrtrter applied end leached (1)


   Figure  63
   Column 20
   Ocean
    VFA
                                                     200    400     600     800     1,000    1,200   1,400
                                                                     Total cmounr of water applied and leach&d (I)
Note:  See Figure 31    for further legend explanation.
                               Figures   60 -   63  .  Test column leachate cumulative balances:  Iron.

-------


0.06
i
0 0.04
1
0.02
Total Pb 0.4 g
x 20, 21, 30
/ Figure 64 °-w
/ Column 2 ^
/ Limestone » o 04
/ NJSBM |
//31, 40,41
// °-02
f 00,10
Total Pb<0.453g

20,21,30,40,41 . ,_
/Figure 65
Column 5
Limestone
VFA
i mJ10 i r t t
""20"' 400 600 800 lW 1,'aOO •!% »JO 400 600 SOO 1,000 1,200 1,400
Total amount of water typllcd and leached (!) Tota! amount of water °PfUe
-------
                             20,21,30,31,40,41

                               Figure  68
                               Column 6
                               Dolomite
                                 VSBM
  0.06
£
E
   0.04
   0.02
        Total Pb 0.544g
                      20,21,30
                   31,40,41
Figure 70
Column 8
Dolomite
  NJFA
               200     400     600      800     1,000    1,200    1,400

                               Total amount of water applied and leached (I)
                                        0.15


                                      £
                                      *A

                                      1 0.10
                                      "5
                                        0.05
                             600      600     1,000   1,200    1,400

                              Total amount of watar applied ond leached (I)
                                                                            -Total Pb 0.4 9
                                                                       0.06
                                    £
 °> 0.04

I
   0.02
                                                                                   200
                                                                             Total Pb 0.453g
                              20,21,30,31,40,41
                                 Figure 69
                                 Column 7
                                 Dolomite
                                   NJSBM
                                                                                                 00,10
                                                                  600      800     1,000   1,200    1,400

                                                                   Tofol amount of water applied and leachea* (!)
          Figure  71
          Column 9
          Dolomite
20,21,30     VFA
                                                  200     400     600      SOO     1,000    1,200   1,400

                                                                  Total amount of wat«r applied and leached (I)
Note;   See  Figure  31   for further legend explanation.
                                Figures 68   -   71  .  Test column leachate cumulative balances: Lead,

-------
    0.03
    0.02
    0.01
         Total Pb 0.453g
                           Figure  72
                           Column 10
                           Landfill
                             VFA
                             50.10
                                      _L
     0.3
   £


   I
   *P
   •5
0.2
     0.1
               200     400
       Total Pb 0.544
              20,21,30
1,40,41
                                             _L
                                                     _L
                         600      800     1,000    1,200   1,400

                          Total amount of water applied end Uoched (I)
Figure  74
Column 12
Landfill
  NJFA
                       .   00.10
                              600      800    1,000    1,200    1,400

                               Tofal omovnt of water applied jond.leached (I)
                                                                       0.10 -
                                                                       0.05
                                                                             Total Pb 0.68g
                                                                                  Figure  73
                                                                                  Column 11
                                                                                  Landfill
                                                                                   VSBM
                                                                200     400    600      800     1,000    1,200   1,400

                                                                                Total amount of water applied and leached (I)
                                                                 O
                                                                         0.03
                                                                         0.02
                                                                         0.01
                                                                                Total Pb 0.4 g
                                                                                       20,21,30
                                                                                       11,40,41
Figure 75
Column 13
Landfill
  NJSBM
                                                                                                          j_
                                                                              2CO     400     600      SCO     1,000   1,200    1,4CO

                                                                                              Total amount of water applied and leached (1)
Note:  See Figure  31  for further  legend explanation,
                                Figures  72   -  75   .  Test column leachate cumulative balances:  Lead.

-------
0.15


£ 0.10
i
o
"5
*~ 0.05


Total Pb 0.68 g _. —,
Figure 76
Column 14
Coalmine °-°°
VSBM \
§
-20,21,30 <5 0.04
f 1
" -//t^ °'°2
^^X><50,51
KS 00,10
Totol Pb 0.4 g
Figure 77
Column 15
Coal mine
20,21,30,31,40 NJSBM
/
/
/'/41, 50,51
//
/S 00,10
200 400 600 800 1,000 1,200 1,400 200 400 600 300 1,000 1,200 1,400
Total amount of wafer applied and leeched (1) Total amount of water applied and leached (1)

0.03
£
J0.02
"75
&
0.01
Total Pb0.5449 F19Ur6 78
Column 16
Coal mine
10 ir A °'°0
NJFA
X20,21, 30,31,40 £
- f | °'04
/ 1
/ 	 --41,50,51 (2
~ If 0.02
{^_ 	 , 	 J10'10 ,
Total Pb 0.45 g Figure 79
Column 17
Coal mine
VFA

^^20,21,30,31,40
/^-~" 41 ,50, 51
f 00,10
200     400      600     800     1,000    1,200   1,400
                Total amount of water applied and leached (I)
                                                                                200     400    600      £00     1,000   1,200    1,<00
                                                                                               Total amount of water applied and leached (I)
Note:  See Figure  31   for further legend explanation.
                             Figures 76   -   79 .  Test column leachate cumulative balances« Lead.

-------
CS
1.5

Q_
in
£
O 1 *0
O)
"a
"o
t—
0.5

0.6
£
g
o
01 0.4
1
0.2
- Total Pb 0.68 g r. __ 1.5
Figure 80
Column 1
Ocean t
VSflM g,1'0
20,21,30,31 -
jr t-
er °PPlied and Ie0ched (l)
Total Pfa0.4g
Figure 82
Column 19
Ocean °-6
NJSBM i
i
o 0.4
20,21,30,31 5
/^TO °'2
Total Pb0.4533
Figure 83
Column 20
Ocean
VFA
_
20,21,30,31
^"*f^ i OCl i i i i
                     200     400      600     800     1,000    1,200    1,400
                                    Total omount of wafer applied and leached (I)
200     400      600     800     1,000    1,200    1,400
                Total amount of water applied and ieacfied fl)
        Note:   See Figure   31  for further  legend explanation,
                                 Figures    80-   83   ,  Test column leachate cumulative balances;  Lead,

-------
    0.3
 I 0.2

 I
    0.1
         Total Is unknown
                 Figure 84
                 Column 2
                 Limestone
                   NJSBM
                21,3031,40,41

                      ,-00-lQ  I	L
                                             J_
                                                    JL
     0.3
   Z
    ,0.2
     0.1
         Total is unknown
200      400     600      800     1,000    1,200   1,400
                Total amount of .water applied and leached (1)

                 Figure 86
                 Column 4
                 Limestone
                   NJFA
                        1,30,31,40,41
                              ,  00,10  ,
              200     400     600      800     1,000    1,200   1.4CC

                              Total amount oF water applied and leached (I)


Note:  See Figure 31.   for Further legend  explanation.
                                                                        0.3
                                                        k> 0.2
                                                                        0.1
                                                                            Total It unknown
                                Figure 85
                                Column  3
                                Limestone
                                 VSBM
                                                                                             21,30,31,40,41
                                                                             00,10
                                                                        0.3  -
Z
a

I  °'2
                                                                        0.1
                                                                                  200     400
        Total is unknown
600      800     1,000   1,200    1,400
 Total amount of water applied and leeched (I)


    Figure  87
    Column 5
    Limestone
     VFA
                                                                            21,30,31,40,41
                                                                    200     400     600      800     1,000    !,200   1,4CC

                                                                                    Total amount of water applied ant/ leached (I)
                               Figures 84 - 87,        jest column ieachate cumulative balances: Nickel.

-------
            0.15
         0
         ~o
         '5
            0.10
            0.05
                    Total Is unknown
                               20
Figure 88
Column 6
Dolomite
  VSBM
                              21,30,31,40,41
                                00,10
                       200     400     600      800     1,000    1,200   1,400

                                       Total amount of water applied and (cached (I)
                                                                               0.15
                                                                              w
                                                                              I  0.10
                                     o
                                     o
                                                                                0.05
                                                                                    Total Ni
                                                                                                20
Figure 89
Column 7
Dolomite
  NJSBM
                                                                21,30,31,40,41
                                                                                                                  _L
                                                                                                                                          i
                                                 100	400     600      800     1,000    1,200    1,400

                                                                  Total amount of water applied and leodud (I)
00
               0.15
               0.10
               0.05
                     Total Is unknown
Figure  90
Column 8
Dolomite
  NJFA
                                   21,30,31,40,41
                                       00,10
                         200     400     600  ""800"    1,000    1,200    1,400

                                         Total amount of water applied and leached (I)
                                                                                   0.15
                                                                                   0.10
                                                                                   0.05
                                                                                           Total it unknown
 Figure  91
 Column 9
 Dolomite
  VFA
                                                              21,30,31,40,41
                                                                                                                 00,10,
                                                     200      400     600      800     1,000    1,200    1,400

                                                                     Total amount of water applied and leached (I)
          Note:  See Figure  31   For further legend explanation,
                                         Figures  88 - 91.       Test  column leachate cumulative balances:  Nickel.

-------
•o
                                             Figure 92
                                             Column 10
                                             Landfill
                                               VFA
                           , 40, 41 ,50,51
                                      00,10
             °-3 -
              0.1
                      200
                    Total is unknown
                                             -l_
                                     600      800     1,000    1,200   1,400

                                      Total amount of water applied and leeched (I)
Figure  94
Column 12
Landfill
  NJFA
                            21, 30,31 ,40,41

                                  00, 10
                       200     400     600    800     1,000    1,200    1,400
                                       Total amount of water applied and Uached (I)
                                   0.3
                                 \
                                 I
0'2
                                                                                 0.!
                                                                                       Total Ii unknown

                                                                               0.10-

Figure  93.
Column 1 1
Landfill
  VSBM



                                                                                          200    400
                                                                                        Total Nt
                                                            600    800     1,000    1,200    1,400
                                                             Total amount of water applied and leached (I)
                                                                                              20
                                                                                             31, 40,41
                             Figure ?5
                             Column 13
                             Landfill
                               NJSBM
                                                       00,10
                                            200    400     600     800      1,000   1,200    1,400
                                                            Total amount of water applied and leached (I)
          Note :  See Figure  31  for further legend explanation.
                                   Figures   92-95.       Test column leachate cumulative balances: Nickel,

-------
  0.15
o> 0.10
  0.05
        Total Is unknown
                 20
                                                                          Total Is unknown
                     Figure  96
                     Column  14
                     Coal mine
                        VSBM
                         JXi.i 10
                                   JL.
                                                  _L
            200     400
600      800     1,000    1,200   1,400

 Total amount of water applied and leached (I)
   0.15
   0.10
   0.02
       - Total Nt
                  20
        Figure  98
        Column  16
        Coal  mine
         NJFA
200      400     600      800     1,000   1,200    1,400

                Totql amount of water applied and leached (I)
                                                                     0.15
                                                                      0.15
                                                                       Figure  97
                                                                       Column 15
                                                                       Coal mine
                                                                         NJSBM
                                                                                       21,30,31,40
                                                                                           5W.\ 10	i
                                                                               200     400     600      800     1,000   1,200    1,400

                                                                                               Total amount of water applied and leached (I)
                                                                                       21,30,31,40
                                                                                      Figure  99
                                                                                      Column 17
                                                                                      Coal  mine
                                                                                                OC,10
                                                     200
                                                                                               600      800     1,000    1,200    1,406

                                                                                                Total amount of water applied and leached (I)
Note:  See Figure 31   for further legend explanation.
                                   Figures 96 - 99.       Test column leachate  cumulative balances: Nickel,

-------
   3 ~
   1 -
 0
Total Ni 3
Figure 100
Column 1
Ocean z
VSBM I
o
I
*~ i
^^^^--—'20,21,30,31
200 400 600 300 1,000 1,200 1,400
Total amount of voter applied and leached (1)
Total It unknown
Figure 102 3
Column 19
Ocean ~
NJSBM | 2
0
"o
f.
.,, 20,21,30,31 1
^^^^ . 00. ,
200 400 600 800 1,OCO 1,200 1,400

Total is unknown
Figure 101
Column 18
Ocean
S 20,21,30,31
;S
S/
^-^^l
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Total Is unknown _. • no
Figure lOo
Column 20
Ocean
VFA

^- 20,21,30,31
^^•^^^^

    1 -
                           Total amount of water applied and leeched (!)
230     400     600     800     1,COO    1,20C    1,400
               Total amount of wa»er applied end leached (I)
Note:   See Figure 31   for further legend explanation,
                            Figures  100-103,    Test column leachate cumulative balances: Nickel.

-------
to
NJ
             600
           8
           CA
           J400
           o
           o
             200
                              Tt>tolSO4't200g
                          20            Figure 104
                                        Column 2
                                        Limestone
                                          NJSBM
200     400     600      800     1,000    1,200   1,400
                Totol amount of water applied and leached (!)

      Total SO4 953 g
                Figure 106
                Column 4
                Limestone
                  NJFA
                       200     400     600      SOO     1,000   1,200    1,400

                                       Total amount of water applied and leached (I)
                                                         300
                                                                                200
                                                                                100
   600
o*
IS)
|  400

                                                                                200
     Total SO4  3344 g
20             Figure  105
              Column 3
              Limestone
               VSBM
                                                                                                 400
                                                                                                   21,30
           600      800     1,000   1,200   1,400
            Total amount of water applied and leached (1)

           Total SO4 499g
             Figure  107
         20  Column 5
             Limestone
               VFA
                                                                                            '31,40,41
                                                                                                             10
                                                                                                               00,
                                                                  200     400    600      800     1,000    1,200   1,400

                                                                                  Total amount of wars' applied ant) leached (I)
          Note:  See Figure  31   for further  legend explanation.
                                       Figures  104-107.     Test column leachate cumulative balances: Sulfate.

-------
CO
1500


"
•a
t2 500
1,500
•»

X
I i.oco
^*
p
6

500-


Total SO° 3,3448
Figure 108
Column 6
Dolomite
VSBM
s 20

/
/ ^> 21,30,31,40,41
^•^_._, _ 	 1_— 	 i i i i i
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Total SO° 953g
4 Figure 110
Column 8

Dolomite
NJFA


20
J/
XX1' 30
X^VW. 41
Xfl .. , _»00'«> ,
1,500

"sT
1 i,coo
1

1
500



600

8
E
e 400
en
^
l2
200

                                                                         Jofo! SO^  1,200g
                                                                                                 Figure ]Q9
                                                                                                 Column 7
                                                                                                 Dolomite
                                                                                            20     NJSBM
             200     400     600      300     1,000   1,200   1,400
                             Total amount of water applied and leached (I)


Note:  See Figure 31    for further legend explanation.
                                                                                                00,10
                                                                               200     400     600      800     1,000   1,200    1,400

                                                                                               Total amount of vrater applied and leeched (I)
                                                                          Total S0° 493g
                                                                                                 Figure Ill-
                                                                                                 Column 9
                                                                                          ,JO     Dolomite
                                                                                                   VFA
                                                                                        200     400     600      600     1,000   1,200    1,400

                                                                                                       Total amount of woter applied and leached (\)
                              Figures  108-111,.    Test column leachate cumulative balances: Sulfate.

-------
K)
             600
         2   400
             200  -
                 Totol SO* 499g
Figure 112
Column 10
Landfill
  VFA
                         —21,30,31,40,41,50,51   10
                        1       '  i-     i  i,  , -,r
     200     400     600      800     1,000    1,200   1,400

                     Total amount of water applied end leached (I)
Total SO^  953g
Figure 114
Column 12
Landfill
  NJFA
                                               io00
                                       i J=r ss =& uu
                       200     400     600      800     1,000    1,200    1,400
                                       Total amount of water applied and leachad (I)

         Note:  See Figure  31   for further  legend explanation.
                                                                   Total SO  3,344g
                                                                                           Figure  113
                                                                                           Column  11
                                                                                           Landfill
                                                                                             VSBM
                                                                                 .200  -
                                                                                                        i	i
                                                                                           200     400     600      800     1,000    1,200    1,4

                                                                                                           Total amount of water applied and leached (I)
                                                                                 600  -
                                                                              s
                                                                              §>  400
                                                                                 200
                                                                                     Total SOj l,200g
                                                                                           Figure  115
                                                                                           Column  13
                                                                                           Landfill
                                                                                             NJSBM
                                                                               21,30,31,40,41
                                                                       -L_u^_—=1™-- = = == ^e 00
                                                                          200     400     600      SCO     1,000   1,200    1,400

                                                                                         Total amount of water applied and leached (I)
                                        Figures  112-115,     Test column leachate cumulative balances:  Sulfate,

-------
NJ
Ol
                 Total SO~ 3,344g
             300
          "o*
           8 200
          O

          I
              100
                                        Figure. 116
                                        Column 14
                                        Coal  mine
                                         VSBM
                       200     400     600      800     1,000    1,200    1,400

                                       Totol omount of water applied and leeched (I)
                           20
                   n 16
            Coal mine
              NJFA
21,30,31,40,41,50,51
                                      00,10
                        200
4CO     600
               800
                                                      1,000    1,200   1,400
                                       Total amounrof water cppllod and leoehcd (I)

          Note:   See Figure  31   for further legend explanation.
                                                300
                                             'sT
                                                                                200
                                                                                100
                                                                                 300
                                                                                 20°
                                                  100
                                                          Total SO4  l,200g
                                                             20
                                                                                Figure  H7
                                                                                Column  15
                                                                                Coal mine
                                                                                  NJSBM
                                                                                                      00,10
                                                                                                 400
                                                                         600     800     1,000    1,200    1,400

                                                                          Total cmounf of water applied and leached (I)
                                                                                                 20
                                                                Total SOT 499 g
                                                                      4     Figure  119
                                                                            Column 17
                                                                            Coal mine
                                                                              VFA
                                                                     21,30,31,40,41,50
                                                                  400
                                                                             600     300     1,000    1,200    1,400

                                                                              Total amount of water opplled and leeched (!)
                                        Figures 116 - 119.     Test column  leachate cumulative balances: Sulfate.

-------
   1500  -
  Total SO4  3,344g
         10
                                   20,21,30,31
                               Figure 120
                               Column 1
                               Ocean
                                 VSBM
                           00
              200     400    600      800     1,000  " 1,200   1,400

                             Total amount ef water applied and leached (I)
P
o
   1500
   1000
   500
Total S04l,200g

         •10
Figure  122
Column 19
Ocean
  NJSBM
                       20,21,30,31
                           00 .
             200     400     600      800     1,000    1,200    1,400

                             Total amount of water applied and leached (I)
                                                                      1500  -
                                              Total SO4- 953 g
                                                                                       20,21,30,31
                                                                                         Figure  121
                                                                                         Column 18
                                                                                         Ocean
                                                                                           NJFA
                                                                       200     400     6CO      800     1,000   1,200    1,400

                                                                                       Total amount of water applied end leoched (I)
                                                                      1500 • -
                                                                   •6*
                                                                      1000
                                                           a

                                                          1
                                                                       500
                                                                                         20,21>30,31
Figure 123
Column 20
Ocean
  VFA
                                                                                        400
                                                                                      600      800     I.,000   1,200    1,400

                                                                                       Total amount of water oppltod and leached fl}
Note:  See Figure  31  for further legend explanation.
                               Figures   120 - 123,    Test column leachate cumulative balances: Sulfate.

-------
o
•
   0.06
   0.04
   0.62
          Total Zn 0.53 g
20
   Figure 124
"21 Column 6
   Dolomite
     VSBM
              200     400
   0.06
   0.02
        Total Zn 0.82 g
       600      800     1,000    1,200   1,400
        Total amount of water applied and leached (I)


           Figure  126
           Column 8
           Dolomite
             NJFA
             200     400
                                                          1,400
       600      800     T7000    1,200

        Toto) amount of water applied and leached (I)
0.06
                                                  S 0.04
                                                 O
                                                                        0.02
                                                                               Total Zn 4.7 g
                                                                      0.06
                                                                    5 0.04
                                                                      0.02
                                                                                   200
                                                                           Total Zn 0.735 g
Figure 125
Column 7
Dolomite
  NJSBM
                                                             400     600      800     1,000   1,200    1,400

                                                                      Total amount of water applied and leocheo' (i)
                                                                       Figure  127
                                                                       Column 9
                                                                       Dolomite
                                                                         VFA
                                                                      21,30,31,40,41

                                                                             0
                                                                                200
                                                                          800     1,000    1,200    1,400

                                                                   Total amount of water applied end leached (I)
 Note:  See Figure  31   for further  legend explanation.
                                Figures  124 - 127.      Test  column leachate cumulative balances: Zinc.

-------
to
00


0.03
c
N
g
ro 0.02
o
i—
0.01







0.06
c
N
a
J> O.C4
"3
i2
0.02



Total Zn 0.735 g - _- . ..
Figure 1*0 "•'J
Column 10
Landfill N
VFA | o.io
"5
~ j°

0.05
-
20,21,30,31,40,41,50,51
2
0.01
20,21,30
^*~Z*~~~ 11 i^ft i fC\ — C0,10
^•s;^ i i i \ i
Total Zn 0.53g
Figure 129
Column 1 1
Landfill
vsm



«
20,21,30
	 • ' ij i in 11
^ZZ^^W M/10
s^~-—l 	 1 	 i 111!
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Total Zn 4.7g
Figure 131
Column 13
Landfill
NJSBM

-


^20,21,30
-X^«- 31 -j°^_^io
/^^^^^^==^~"^
J»i^s!ga^T i 1 ' 	 T i . — 1 — ^ 	 1 	 !_ 	 	
                       200     400     600      600     1,000   1,200   1,400


                                       Total amount of water applied and leached (I)
200     400     600     800


               Total amount of water applied and leached (1)
         Note;   See Figure 3V for further legend explanation.
                               Figures  128 -  131.   Test column I each ate cumulative balances:  Zinc,

-------
s>
S3


0.06

"5
i
O 0.04
2
,2
0.02


Total Zn 4.7 g
Figure 1 32
Column 2
Limestone °-°6
NJSBM £
,20 1
/ 0 °.°4
// x-21, 30,31,40,41 |
/ S 0.02
x ^^*
XX 10
r. 	 rrt-— — ~~lT~00 1 tit!
200 400 600 800 1,000 1,200 1,400
Total Zn 0.58 g
Figure 133
Column 3
Limestone
VSBM


-. 20
^^^\_^— - 21 ,30,31 ,40,41
^^-'^~^-— 	 ?JT10
200 400 600 800 1,000 1,200 l,4uO
Total amount of water applied and leached (1) ^ ^^ ftf ^^ ^.^ and |Mehcd fl)

0.06

iQ
I 0.04
o
1
0.02



Total Zn 0.82 g
Figure 134
Column 4 o.o6
Limestone ,5
NJFA 1
& 0.04
"o
°
jr 0,02
x/ ^x'2'.3°.3'i'«5,41
./^^^^ 10

Total Zn 0.735g
Figure 135
Column 5
Limestone
VFA
-

J»
^^^21,30,31,40,41
^ 	 -10
<^~*~r^i r M l 	 1 	 (10 i i i i i
^ *fif-.. '.T1 	 r?r 	 ^ 	 Ar.-~ -T ' „ 	 T^SR. 200 400 6co aoo 1,000 1,200 1,00
                     200     400    600      800     1,000   1,200   1,400


                                    Total amount of water applied and leached (I)




        Note;   See Figure   31  for further  legend  explanation.
Total amount of water applied and leached (I)
                                      Figures  132 - 135,      jest column leachate cumulative balances: Zinc,

-------
0.06
i5
$ 0.04
~
£
0.02


c 0.06
N
!£ 0.04
o
3

0.02

Total Zn 0.58g
Figure 136
Column 14 0 04
Coal mine
VSBM I
J 0.04
1
^•20,21,30,31,40 Q>02
/\^>~ 41 ,50,51
200 400 600 800 1,000 1,200 1,400
Total amount of water applied and leached (1)
Total Zn 4.7 9
Figure 137
Column 15
Coal mine
NJSBM
-
f 20,21,30
- /
X^^Sl^-p--10 .
'HjorTi39  ,  Test column leachate cumulative balances:Zinc.

-------

0.3


(5 0.2
i
o
"o
"o
" 0.1




Total Zn 0.58 g

0.4
Figure 140
Column 1
Ccean fi 0.3
VSBM §
^ 20,21 2
X^ 1 0.2
^X"^ ,2

s^^ 30,31
x<^-^^^^ o.i
^^\ , 00 , i i 	 1 	
200 400 6CO 300 1,000 1,200 1,400
T«*«i nmntmf t\f \wnfc1" acolied ond leached (1)
Total Zn 0.82 g r. « j»
H Figure 141
Column 18
Ocean
N1FA




^^ 20,21,30,31
^^^-^"^
^^^^
^^^ 10
' .11 .••riWri i -!„ 	 1 00 , . .'
lOTQl QTuOUnr Oi wcic* 4^»j*nvw wn« t*.™^ — \ i — — • -^ ^~*m^m^^^^^^
200 400 600 300 1,000 1,200 1,400
0.3


*o.i
O

"5
.2
0.1


_ Total Zn 4.7 g
Figure 142
Column 19
Ocean ,g Q ,
NJSBM 1
o
M.
^X 20,21,30,31 1
^X^^
^X^"^ 0-05
^'^———2 oo
r^Tr 	 -TTV^n...-^ ._sa=i 	 1 	 1 	 I 	 t
200 400 600 800 1,000 1,200 1,400
T**-t — *....* _(.,._.. » 	 !! 	 i 	 i i 	 i 	 i m
Total amount of water applied and leached 0)
Total Zn 0.735 g
Figure 143
Column 20
Ocean
VFA


/20,21
/
// 30,31
.^^ — 10
•" -'• 	 ' , rri *" l i j 	 ,
200 4°0 600 800 1,000 1,200 1,400
                          Total amount of water implied and leached (I)
                                                                                            Total amount of water applied and leeched (I)
Note:,  See Figure 31   for further legend explanation.
                           Figures  140-143.    Test column leachate cumulative balances: Zinc.

-------
    4000
    3000
 o
 _3
 u  2000
  •
 00
     1000
                        O 21  (S.C. = 8,500)   Figure 144

                       O 31   /41            Column 2

                                              Limestone
                        1
                f
 I
i
                                                                             a
                                                           
                                                           cu
                                                           fr
200      400        600       800


     Volume of Wafer Applied (lifers)
                                                          1000
                                                                     - 3
                                                   -  2

4000
^ 3000
o
_Q
E
^ 2000
u
i/»
1000
Figure 145
Column 3
Limestone __
-
— —
— «.

— —
1 ! 1 ! I f ! f I r I
                                                                           8.
                                                                           ft-
                                                                      - 1
                  200
         400
600
    800
1000
                          Volume of Wafer Applied (liters)

NOTE:  See Figure 31 for further legend explanation.


Figures 144 and  145,  Specific conductivity and total  dissolved solids of leachate from

                            Columns 2 and 3 - Limestone quarry.
                                     ir?

-------

4000


-£ 3000
o
"i
^ 2000
u
u-.
1000
_ Figure 146 —
Column 4
__ Limestone •__
_
,21
-
j *\.
A -
i/ \ '
J \^41
-^

•* * ^**
_ . —
200 400 600 800 1000
3
o1
o_
VI
t/t
O
<
2 1
El
to
^

1

Volume of Water Applied (liters)

4000


>« 3000
o
~i
3.
~ 2000
u
in
1000
Figure 147
Column 5
,_ Limestone _
,21

'
" /31
- / _
/ /\
- LS \
\41
I 1 1 1 I ! ! 1 ! 1 1
200 400 600 800 1000
3
o1
si
a
4
§L
tf
HI
^
I ~

                           Volume of Water Applied
NOTE:  See Figure 31 for further legend explanation.

Figures 146  and 147.  Specific conductivity and total dissolved solids of leachate from
                            Columns 4 and 5 -  Limestone quarry.

                                       133

-------


4000

,_^
"> 3000
J§
H
^i
U 2000
to

1000

Figure 148 ~
' Column 6
- Dolomite' —


- —
A/41
IV
1
' 031

— —
—
1 I 1 1 1 ! 1 ! ! 1 1
3
•H
O
cf
H
<"
2 8.
£.
al
t/>
S

1


200 400 600 800 1000
Volume of Wafer Applied (liters)
9000
8000

7000
^6000
£
"> 5000
Jg
E
a 4000
u
to* 300°
2000


1000

\/21 Figure 149
"~ Column 7
y Dolomite ~
/
/

_
«•

—

XV41
X
^
«•
o 31
l*J v 1
I 1 1 I 1 ! 1 I 1 I 1
5
g
«L
4|

a.
3 ^

51
in
{Q*
2 o

1



                    200      400        600       800       1000
                           Volume of Water Applied (liters)

NOTE:  See Figure 31 for further legend explanation.

Figures  148and 149.  Specific conductivity and total dissolved solids of leachate from
                             Columns 6 and 7 - Dolomite quarry.
                                       134

-------
4000

^
< 3000
(/>
JB
3:
"7 2000
u
t/1
1000

4000


,| 3000
1
^ 2000
U

1000
Figure 150 —
Column 8
- Dolomite: —

fl\

\/TV.4I
-•• —
i i i i i i i i I r !
200 400 600 800 1000
Volume of Water Applied (liters)
- Figure 151 "~
Column 9
- Dolomite —

- ' —
MM ^"
- -
_. _
/21
- n /
J^\
i f '"n 1^1 i i i i r i
200 400 600 800 1000
3
o
ff
0
in
O
2 i
51
>
1


3
£
D
VI
2 1
51
^
, ^


Volume of Water Applied (liters)
NOTE: See Figure 31 for further legend explanation.
Figures 150 and!51 . Specific conductivity and total dissolved solids of leachafe from
Columns 8 and 9 - Dolomite quarry.
          135

-------
4000
"i"
o
E 3000
=3.

(J
v>" 2000
1000


4000
-f 3000
51
e
u
w 2000

1000
Figure 152
Column 10
~" Sanitary landfill

_ —
~ ""

^™ • ^"«
-31 — 21
1 1 1-1 1 1 1 I ! | 1
200 400 600 800 1000
Volume of Water Applied (liters)
Figure 153
Column 1 1
"~ Sanitary landfill "~
_ —


-.
51
1 i i i i i i i i f i
200 400 600 800 1000
3
o
£L,
Dissolved
CN
to
~
I


3
0*
•M*
2 j?
i
o_
?
1 ^17

                            Volume of Water Applied (liters)
NOTE:  See Figure 31 for further legend explanation.

Figures 152 and 153 .  Specific conductivity and total dissolved solids of leachate from
                            Columns 10 and 11  - Sanitary landfill.

                                        136

-------
4000

1=
"| 3000
E
4 2000
00

1000
*~ Figure 154
Column 12
~~ Sanitary landfill ~


— ••
31
1
- I
V
_\51 2"
i i i i i i i I 1 ' f
3
sL
o
i.
?
i ~

    4,000
  J3,000
  CO
  ^
  E
    2,000
  VJ
    1,000
200       400       600       800


         Volume of Water Applied (liters)



                  Figure 155

                  Column 13

                  Sanitary landfill
                                                             1000
                                                                             8.
                                                                             o
                                                       2  r
                                                          a.
                                                          CO
                   200       400      600       800       1,000

                         Volume of Water Applied (liters)

NOTE:  See Figure 31 for further legend explanation.


Figures 154 and 155.  Specific conductivity and total dissolved solids of leachate from

                            Columns 12  and 13- Sanitary landfill.
                                         137

-------


4000



§ 3000
^V^
trt
"i
a.
~ 2000
u
in
1000

~ Figure 156 ""
Column 14
Coal mine ""

„_

-


O31
21 ©
A51'41
I 1 1 I 1 1 1 ! 1 ! !
3

— i
cT
i.
in*
2 1
ft
Q_
£
El
t»
_
1 *"""*

    4000
,0  3000

I
 3.

T  2000
    1000
200       400       600       800

       Volume of Water Applied (liters)



                Figure 157
                Column 15
                Coal mine
                                                            1000
J	I
I
                         I
                                                   I
                                   o
                                   3-
                                                     2
                                                                           ' (A
                                                                            8
                                                        CD
                                                        a.
                  200       400       600       800
                         Volume of Water Applied (liters)


 NOTE:  See Figure 31 for further legend explanation.

 Figures 156 and 157.  Specific conductivity and total dissolved solids of leachate from
                             Columns 14 and 15 - Coal mine.
                                       138

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4000

IT
< 3000
J?
•-U
£
a.

~ 2000
u
t
tn
1000

Figure 158
Column 1 6
- Coal mine -1
—
031
MB M^

^™ •»

A
- \ /JU41 H
\^\
^51
—
! 1 1 ! 1 ! ! 1 1 i !
3

c^
S1
LJ
O
»•
VI
8
9 <
*• n>
a.
^

ol
to
to"

1 "


200 400 600 800

8000

7000

--6000
J 5000
34000
u
oo* 3000
2000

1000
0.0
Volume of Water Applied (liters)
Figure 159
Column 17 —
- Coal mine
A ; 31
/
' M
-
-

I
\ V 21
.^^
» i 1 I 51 I i i I I r 1


5.0 5,
ET
40 M*
8
^~
8.
3.0 £
El
u«
20^-
*. 9 W -^

1.0


200 400 600 800 1000
                            Volume of Water Applied (lifers)
NOTE:  See Figure  31 for further legend explanation.
Figures 158 and 159.  Specific conductivity and total dissolved solids of leachate from
                            Columns 16 and 17 - Coal mine.
                                        139

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5  L
                                        Figure 160
                                        Column 1
                                        Ocean
            200
400
                                     600       800       1,000   1,200
                                       Volume of Water Applied (liters)
Note: See Figure 31  for further legend explanation.
1,400     1,600
                          Figure 160 o pH of leachate from Column 1  -Ocean.

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                         Figure 161
                         Column 2
                         Limestone
   51
                      200       400        600
                  Volume of Water Applied (liters)

NOTE:  See Figure 31 for further legend explanation.
                               80U
                                                           Figure  162
                                                           Column 3
                                                           Limestone
6
5
A
-
_.
I t t 1 1 t 1 1
                                                    Volume of Water Applied (liters)
Figures 161 and 162.  pH of leachate from Columns 2 and 3 - Limestone quarry,

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S3
                          Figure 163
                          Column 4
                          Limestone
                                                    00,10
                    200      400       600       800
                   Volume of Water Applied (liters)

    NOTE:  See Figure 31 for further legend explanation.
                                                                   13

                                                                   12

                                                                   11

                                                                   10
5.  8
    7

    6

    5

    4
                  Figure 164
                  Column 5
                  Limestone
                           41
                                                                                           00,10
               200       400        600      800
            Volume of Water Applied (liters)
                         Figures 163, and 1.64 .  pH of leachate from Columns 4 and 5 - Limestone quarry,

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CO
                           Figure 165
                           Column 6
                           Dolomite
                         200        400       600      800
                     Volume of Water Applied (liters)

    NOTE:  See Figure 31 for further legend explanation
       Figure 166
       Column 7
       Dolomite
    200      400       600
Volume of Water Applied  (liters)
800
                        Figures 165 and  166. pH of leachate from Columns 6 and 7 - Dolomite qua-ry.

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         13

         12

         11

         10
                       Figure 167
                       Column 8
                       Dolomite
11
                               00710
                     200       400       600
                Volume of Water Applied (liters)
NOTE:  See Figure 31  for further legend explanation.
                 800
Figure 168
Column 9
Dolomite
13
12
11
10
9
o. 8
7
6
5
A
-, 11
- A
• /w"
MA
fN Jf V,,
^^^~"_J 00,10
-
-
1 ! I t 1 1 1 1
                                      Volume of Water Applied (liters)
                    Figures 167 and 168,  pH of leachate from Columns 8 and 9 - Dolomite quarry.

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                         .Figure 169
                         Column 10
      Figure  170
      Column 11
13
12
11
10
9
8
7
6
5
4
banitary landfill
13
12
11
10
9
^ 	 41 8
/-x^X^-31 a
—£ 	 5|
/ 00,10
-^ 6
5
i i i i i i r 1 4 . • • 	
Sanitary lanarm
-
-
-
«.
nn 1 r»
-—• 	 UU, I U
*~ ^^-" — 51,41,31
^21
i i i I t i i i
200 400 600 800 " 200 400 600 800
                  Volume of Water Applied (lifers)

NOTE:  See Figure31 further legend  explanation.
Volume of Water Applied (liters)
                   Figures 169 and  170.  pH of leachate from Columns 10 and 11 - Sanitary landfill.

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          13 r-

          12

          11

          10

           9
           8
           6

           5  r-
              31,21
                        Figure 171
                        Column 12
                        Sanitary landfill
00,10
                     •51,41
                      200       400       600       800
                      Volume of Water Applied (liters)

NOTE:  See Figure 31 for further legend explanation,
14

13

12

11

10

 9


 8
                                                       R0ure 172
                                                       Column 13
                                                       Sanitary landfill
                                                                     • 11
                                                                     •00,10
                                                                    51
                                             /  /
                                                      200       400       600       800
                                                      Volume of Water Applied (liters)
                   Figures 171 and 172. pH of leachate from Columns 12 and 13 - Sanitary landfill.

-------
                        Figure 173
                        Column 14
                        Coal mine
                      200      400       600
                  Volume of Water Applied (liters)

NOTE:  See Figure 31 for further legend explanation.
800
                           Figure  174
                           Column 15
                           Coal mine
    200       400       600
Volume of Water Applied  (liters)
                   Figures 173and  174. pH of leachate from Columns Hand 15 - Coal mine.

-------
00
Figure 175
Column 16
Coal mine
13
12

11
10

9
a 8
7
6
5
4
-
• .11


A
-

^
_
/)
//
nl
Ml//
w
n


\


j^fj ^ 21 --31
-
—
i i i \ fiti
                          200      400       600
                    Volume of Water Applied (liters)

   NOTE:  See Figure 31  for further legend explanation.
800
                                                                                   Figure 176
                                                                                   Column 17
                                                                                   Coal mine
                                                                                           11
                                                                                             21
     200      400       600
Volume of Water Applied (liters)
                     Figures 175and 176.  pH of leachate from Columns 16 and 17 - Coal mine.

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                                    CHAPTER 7

               REUSE POTENTIAL FOR FLUIDIZED-BED RESIDUES

                                   Introduction

    Coal  and oil combustion generate large quantities of residues.  In 1972, for example,
approximately 30 million kkg of coal residues were produced.  Residue quantities are
projected  to increase substantially during the period 1970-90, primarily as a result of
increased  power demand.   During that period, the electric utility industry is predicted to
increase its consumption of coal by 100 percent and of oil by 150 percent.    Residue
quantities are likely to  increase more than proportionately for several reasons.  First, as
supplies of low-ash fuel are depleted, greater use will be made of higher-ash fuels.  Second,
more stringent pollution control regulations will result in fewer emissions to the environment
and therefore greater solid waste process residue quantities.  Third,  fluidized-bed coal
combustion and oil  gasification methods may be adopted by a significant portion of the
industry.  Both once-through and regenerative limestone/dolomite fluidized-bed systems
generate substantially more residues than conventional systems, although the increase is
greatest with once-through systems.   Preliminary work suggests that once-through systems
are favored by current economics: the projected expense of regeneration (less the value of
recovered sulfur products) appears to be greater than the saving from reduced limestone con-
sumption.   For coal boilers, once-through fluidized-bed systems should generate a minimum
of 50 percent more  residues than do conventional coal-fired power plants.

    This chapter evaluates possible residue application areas and the market prospects for
fluidized-bed residues. The following topics are considered:

    •  Overall reuse prospects for fluidized-bed residues.

    •  Review of applications for conventional coal ash and lime/limestone wet scrubber
       residues.

    •  Evaluation of specific,  feasible reclamation applications of residues in concrete,
       asphalt, agriculture (soil amendment), soil cover (strip mines and  landfills),  soil
        cement, pozzolan  cements (LFA and LCFA), acid mine drainage treatment, and
       road ice control.

    •  Preliminary assessment of market potential for residue applications.

                               Overall Reuse Prospects

    The history of reuse for conventional coal ash provides an insight into what the utiliza-
tion prospects for fluidized-bed residues might be.  Relatively little of the conventional
ash generated has found its way into productive use—about 16 percent in  1972.  Until about
1968, the ash utilization rate had been increasing rapidly, moving from 2 percent in 1955
to 17.5 percent in 1968.    Since then, however,  the rate has remained relatively constant,

                                            149

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although in total quantities reuse has continued to increase.  The utilization rate has re-
mained low even though many technically sound applications have been developed which
potentially could absorb more than the annual quantities generated." Table52 presents
estimated maximunvtechnically feasible,utilization potentials.  Although many reuse applica-
tions exist, it is not likely that the utilization rate will consume the available supply in the
near future.

     Factors other than technical feasibility also influence  actual utilization.  These factors
include:

     •  Technical complexity of the application.   Potential users are less likely to adopt a
        new residue material if it is significantly more complicated, or if it requires major
        changes in production methods.

     •  Reliability of the new raw residue process or product.

     *  Sufficient information about the potential application.

     •  Existence of a reliable source of supply for residues or residue-based products.

     •  Uniformity and quality of the residue or residue-based product.

     Given favorable conditions in the above areas, a potential user's decision will  be
based on the relative prices of conventional and residue materials, transport,  and any
necessary preprocessing of the residues over that required for  the competing conventional
material.  A potential user will  adopt that application which reduces his production costs
and maintains desired product quality.

   ,v In comparing the magnitude of the technically feasible applications of conventional ash
wfth actual utilization, there are indications of substantial economic and other impediments
to greater  increased use.  Many of these barriers may  be overcome in time, but unless
further reuse incentives are provided, most of the increased residues generated for 1970-90
will not be reused, but instead,will require disposal.  This conclusion must be modified for
fluidized-bed residues, however, since their composition and characteristics are substan-
tially different from those of conventional combustion ash residues. This is illustrated in
Tables 53 and 54, which compare the composition  of conventional coal ash, modified ash
(MFA), and fluid!zed-bed ash.  Lime or dolomite modified fly ash is generated by flue  gas
desulfurization (FGD) systems (e.g., wet limestone scrubbers) and fluidized-bed com bus tors.
Since differences affect the suitability of a residue for a given application, it is difficult to
predict the successes or failures of FBC residue applications.  The FGD residues (particularly
those from  dry systems) are quite similar to fluidized-bed residues.  Hence, the reuse poten-
tial of FGD and fluidized-bed residues may be compared with some reliability.

     There  is considerable literature on applications for residues from conventional caa I
combustion, from municipal waste incineration,  and from lime-limestone scrubbing (fre-
quently used for air pollution control on coal-fired generating units).  In addition,  there is

                                           150

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    TABLE  52. ESTIMATED ASH UTILIZATION POTENTIAL (10  kkg/yr)
Maximum
Utilization
Use Technically
Feasible

1970
Utilization
Estimated
Utilization
1971
Conditions

Potential
Improved
Utilization
Fly ash concrete (structural,
mass and concrete products)        9-14
Lightweight aggregate              12
Raw material for cement clinker     12
Bricks                              9
Filler in bituminous products       1-2
Base stabilizer for roads(^Pa)
Agriculture and land  recovery
(AP)                             —
Control of mine subsidence and    > 1
fires
Structural fill for roads
construction sites,  land,
0.49
0.19
0.15

0.12
0.10
0.01
 AP - annual production.
Source: 130.
3.2
0.5
0.23

0.68
0.3
0.68
  5.4
  2.7
>0.9
reclamation, etc. (AP)
Others
Total
0.29
0.15
1 .50
0.5
0.23
6.3
                                   151

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          TABLE 53. COMPARISON OF ASH COMPOSITION (%)
Constituent
Coal
Ash
SiO2 49.10
ALO 16.25
Fe0O_ 22.31
2 3
Ti02
CaO
MgO
Na20
K2O
S03
c
H2O soluble

1.09
4.48
1.00
0.05
1.42
0.73
2.21
2.51
TABLE 54.
Constituent

Fe2°3
CaO
MgO
S03
H2O soluble

Exxon
9
13
0
5
0
Lime Modified Dolomite Modified Lignite Ash
Ash Ash
30.85
13.70
11.59

0.68
33.58
1.49
1.12
0.71
2.20
1.12
22.11
30.81
12.54
10.72

0.42
17.90
14.77
0.72
0*99
8.09
1.76
—
32.60
10.70
10.0

0.56
18.00
7.31
0.87
0.68
2.60
0.11
8.55
COMPARISON OF FBC RESIDUE COMPOSITIONS
Ash Composition (%
Miniplant Pope,Evans and
.99 15.71
.44 4.9
.61 0.32
.81 4.56
.21 0.42
)Q
Robbins Plant






Esso, England
Gasifier
0.02
10.5
0.07
6.22

 These values do not sum to 100 percent. The remainder is primarily silicon dioxide with
 traces of unburned carbon and metal oxides.

Source: 42.
                                      152

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literature for proposed or experimental uses.
                                   Types of Coal Ash

    There are three types of residues collected from coal combustion: fly ash, bottom ash,
and slag. Fly ash is the ash collected from the stack effluent; bottom ash and slag are the
residues collected from the bottom of the boiler.  Whether these bottom residues are an  ash
or a slag depends on the design of the particular boiler.  For any specific boiler unit the fly
ash and bottom ash  will have a .(similar chemical composition, except that the bottom ash
will be lower in carbon content.
     Physically, fly ash consists of finely divided spheroids of siliceous glass ranging from
1 to 50 microns in diameter.  Some of these spheroids are considerably finer than portland
cement,  and a minor fraction consists of larger,  irregularly shaped particles, some opaque
and some transparent or translucent.  Carbon  is present chiefly  in the form of irregularly
shaped particles of coke.  Depending upon the type of coal and combustion conditions,
the carbon content of fly josh in the United States ranges from less than 1 to more than 20
percent.  The physical and chemical characteristics of fly ash emitted from any combustion
chamber depends on the  type of combustion equipment and  its design; the combustion  or
firing rate; the oxygen ratio, burning characteristics, and particle size of the coal; varia-
tions in steam load, draft, and combustion controls; and operator skill.   About 70 percent
of the  coal ash residue is collected as fly  ash.

     The bottom ash is collected either as  an ash or slag depending on the particular boiler
design.  The ash is grey  to black in color, quite angular, and has a porous surface.  The
slag particles are normally black, angular particles having a glass appearance.  The bottom
ash particles have an average particle diameter size of 2-1/2 millimeters and  an  average
specific  gravity of  about 2.5. When  there are reuse markets for fly ash,  it is handled dry by
a pneumatic  system, stored in silos or bins on the plant site,  and then transported in closed
tank trucks or rail cars.   Slags to be  sold  are pumped from quench tanks  below the boiler
to draining bins and then are generally stored in piles until marketed.  Bottom ash and slag
are granular  materials and lend themselves to mechanical handling schemes.

     Pulverized coal-fired units are "wet" or  "dry" bottom,  with the amount of fly ash and
bottom residue in each related to furnace  design and the pulverization level, volatile
matter, and ash content  of the coal. In the wet bottom design, up to half of the total
ash can be trapped within the furnace as ash or slag; however,  bottom ash in "dry" bottom
units amounts to only 20-25  percent of the total  ash.

                                  Coal Ash  Utilization

United States.

     Table 55 compares ash generation and use; in 1972 only about 16 percent of  the ash

                                            153

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en
      	TABLE 55.  COMPARATIVE ASH PRODUCTION AND UTILIZATION, 1966-1972	

        *°kdkUgC)ti0n       1966        1967         1968         1969         197°        1971         1972
       Fly ash         15,533,855    16,701,139  17,974,729   20,234,314   24,074,886  25,175,333  28,855,791
       Bottom ash       7,317,065     8,283,915   6,585,446    7,295,595    8,972,920   9,125,341   9,682,256
       Boiler slag       —            —          2,317,466    2,739,954    2,541,455   4,509,421   3,430,664
       Total          22,850,920    24,985,053  26,877,641   30,269,863   35,589,261  38,810,095  41,968,711
Utilization
Total (kkg)
Fly ash (%)
Bottom ash (%)
Boiler slag (%)
Total (%)
1966
2,767,520
7.9
21.0
—
12.11
1967
3,442,507
8.2
25.0
—
13.78
1968
4,711,932
9.6
25.0
57.8
17.53
1969
4,814,215
8.13
25.0
57.8
15.90
1970
4,622,704
8.13
18.63
39.06
13
1971
7,805,163
11.7
16.03
75.21
20
1972
6,872,381
11.4
24.3
35.3
16.3
   Source:

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and slag produced found application (11.4 percent of the fly ash, 24.3 percent of the bottom
ash, and 35.3 percent of the boiler slag). Ash collection and utilization for a typical year
(1971) are shown in Table 56; estimated 1976 ash generation is included for comparison. The
main applications were as an additive to cement,  a fill material for road and other construc-
tion,  and a filler in asphalt mix.  The "miscellaneous" use category was  also quite large;
Table 57 lists some of the applications aggregated under that heading.  It can be  inferred
that a large quantity of residues was removed at no cost to utilities and found its way into
useful applications.  Some of these applications (and known quantities) are listed in  Table 58.

    Yearly fluctuations in coal ash used suggest that the  trends are influenced by market
factors; thus, valid projections for future consumption are difficult to make.  Boiler slag
has been found useful in increasing the skid resistance of  asphalt pavement.  The  use of coal
ash as a raw  material in the manufacture of portland cement is another application where
usage has increased in the past several years.  Recent research results indicate that
large quantities of coal ash could also be effectively used for agriculture and land reclama-
tion products.  The use of coal ash as  a raw material  in the manufacture of portland cement
is another application where usage has increased in the past several years. Recent research
results also indicate that large quantities of coal ash  could also be effectively used for
agriculture and land reclamation products.  The use of coal ash for lightweight aggregate
initially looked promising, but in the  last few years its use has;declined.

     Effective utilization of coal ash requires that the ash satisfy the technical specifications
for the application and be economically competitive.  Ideally, any production or utilization
process should  be  located close to the source  of raw material; that is, at  the power plant.
However, this  is not always possible.  Thus, transporting coal ash to where it is to be used
is a major economic factor.  Using trucks, fly ash can be transported from a source at an
average 1976 cost of $0.04 per kkg/km (18 to 27 kkg per truck).  The cost of loading and
unloading is  about $2.00 per truck load. Furthermore, trucks can be expected to operate
with maximum  economy only to a range of about 150  to 175 miles, depending on road con-
ditions. This enables the trucker to get to his destination, unload, and return in  the same
day,  avoiding  any overtime or stayover.

     Fly ash  used in cement and concrete applications competes with natural raw materials
and cement industry products.   Its use is hampered by the fact that 1976 freight rates for
shipping fly  ash are about 20 percent higher than for  the  natural products. This is because
of tariffs that give an advantage to natural or virgin materials over secondary materials.

Europe.

     In 1971, the Federal Republic of Germany was using 79 percent of its total ash produc-
tion of 6,500,000 kkg, France was using 65 percent of its production of 4,185.000 kkg, and
the United Kingdom was using 54 percent of its production of 10,370,000 kkg.  ^  The prin-
cipal uses of the coal ash were in road construction,  compacted concrete, and construction  site
fills.
                                         155

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Ash utilized:
Mixed with raw material before forming
cement clinker
Mixed with cement clinker or mixed with
cement (pozzolan cement)
Partial replacement of cement
Concrete pjtoducts
Structural concrete
Dams and other massive concrete
Lightweight aggregate
Fill material for roads, construction
sites, etc.
Stabilizer for road bases, parking areas,
etc.
Filler in asphalt mix
Miscellaneous
Total
Ash removed at plant site at no cost to utility
but not covered in categories
listed under "ash utilized"
Total ash utilized
Ash removed to disposal areas at company
Fly Ash (kkg)
94,550
15,001
160,725
1 68,256
64,784
162,294
329,663
33,511
133,953
89,633
1 ,252,370
1 ,698,938
2,951,308
22,224,448
Bottom
Ash (kkg)
NAa
NA
32,094
NA
NA
12,648
484,156
7,149
2,570
431 ,299
969,916
492,514
1,462,430
7,663,065
Boiler
Slag (kkg)
83,440
NA
68,551
NA
NA
NA
2,384,924
44,964
74,118
388,305
3,044,302
346,346
3,390,648
1,117,941
  expense
Total ash collected                          25,175,756   9,125,495  4,508,589
Estimated 1976 ash production                 33,561,352  10,651,580  2,284,060
  Not applicable.

Source:  31.
                                  156

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      TABLE 57.  KNOWN MISCELLANEOUS USES FOR ASH AND SLAG

Oil well cementing                           Oil well drilling
Mine fire control                             Industrial testing
Mine subsidence control                       Vanadium recovery
Neutralization of acid mine drainage           Ice control
Cleaning abrasive                             Outdoor school tracks
Spontaneous combustion control                Asphalt shingles
Highway bridges                              Sandblastingg.it
Test caps                                     Filler for glass
Refrectory add mix                            Filler for fertilizer
Insulating cement                             Filler for paint
Grouting                                     Filler for plastics
Snow sanding                                 Dike repair and buildings
Pipe coating                                  Drainage filter
Foundries                                    Aggregate
  sand                                       Landfill
  manufacturer products                       Agriculture
Chemical products                            Dust control
Poz-O-Paca                                  Seal coating
Sewage treatment plants (filtration)            Roofing granules
Substrate course (heavy construction)           Railroad base
Ready mix                                    Mineral wool production


  A pozzolan.
Sources: 1,2,4,23,26,29,31,33,34,37,40-42,46,50,53,54,59,68-70,80-82,
        96, 101-103,110,111,114,116-118, 126,128-131,139,140,143-154,
         167,189.
                                157

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TABLE 58.  KNOWN USES FOR ASH REMOVED FROM PLANT
rvi i>iv^ <-^-J i i^-» .
Application
Manufacturing cement
Mine fire control
Antiskid winter roads
Building blocks and fill material
Experimental soil condition
Miscellaneous fill material
Airport pavement
Soil stabilization
Fertilizer filler
Rubber filler
Vanadium recovery
Dust control
Asphaltic wear course aggregate
Total
J, 1 1 U 1 1 1 f \ II 1
Fly Ash (kkg)
46,900
75,250

NAb
23
433,567
14,697
4,568
1,198
269
181
NAp
NAP
693,916
Bottom Ash
(kkg)
NApa
35,325
161,775
13,373
NAp
31 ,534
NAp
NAp
NAp
NAp
181
10,237
NAp
252,425
Boiler Slag
(kkg)
NAp
NAp
150,714
NAp
NAp
208,105
NAp
NAp
NAp
NAp
NAp
NAp
1,932
360,751
  Not applicable.
  Not available.

 Source; 31.
                         158

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    About 22 percent of the total amount of ash used was employed in road construction,
mainly in France and the  United Kingdom.  Eighteen percent of the total was used in con-
crete. Construction filler accounted for about 28 percent of the total  used.  Miscellaneous
uses included coal mine fire control, addition of fly ash to foundry sand, use as a compo-
nent of blasting compounds for cleaning metal surfaces, manufacture of acoustical  block,
pesticides, soap, etc. Table 59 gives the figures for hard coal and lignite ash production.
and utilization in Europe  and the United States in  1967, 1969, and 1971.  Annual fly ash
production in the United Kingdom is approximately  10 million kkg. The  low density ash is
useful for road fill, especially when embankments have to be constructed over poor ground
support such as compressible alluvial clay or silt.  In such situations,  excessive road founda-
tion weight could produce settlement beyond  allowable limits and may even produce a com-
plete failure of the subsoil foundations.

     In England the wet weight of fly ash per compacted  cubic meter is between 1.17 and
1.44  kkg/m  depending on the source and moisture  content of the material. This compares
"avorably with the weight of traditional (British) fill material. Table 60 gives a comparison
of fly ash densities with other traditional fill  materials.

     The stability of fly ash is such that it is now being used in Great Britain behind bridge
abutments,  etc.  Fly ash,  being pozzolanic, has both a high angle of shearing resistance
and high cohesion.  The relatively high shear strength of fly ash together with  its low density
suggests  its use as a support  .edge for selected filling behind earth retaining structures.
Being both granular and porous,  it is also an excellent drainage medium.  Because of its
self-hardening properties, there is little settling in  the compacted fly ash.   Being light and
fine, fly ash can be readily transported without special equipment, even in confined areas.

     Fly  ash is being  used throughout the United Kingdom and other European countries for
load-bearing structural fills at industrial, schools, and other sites since it has excellent load-
bearing  and foundation strength. Furthermore, because of its low density and self-harden ing
capacity, fly ash makes an ideal stabilized sub-foundation support for buildings built on un-
stable ground.  Because it is self-hardening,  fly ash is ideal for trenching, as deep neat
trenches can be excavated using minimal trench supports.  An ash fill, after hardening,  is
excellent material for trimming and so  it is ideal for excavating pad foundations, manholes',
utilities, etc. Small to medium-sized  rollers of the vibrating type can compact fly ash
adequately.  Ash is inert and alkaline.  Although tests have demonstrated few adverse effects
on cast iron,  lead,copper, PVC, or glazed stoneware pipes embedded in ash fills, it is im-
portant to remove soluble salts from new ash to prevent electrolytic metal corrosion or water
pollution.

                            Specific Applications for Coal Ash

This section considers the following specific application  areas for coal ash:

    •  Concrete

    • Stabilized bed construction

                                          159

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                         TABLE 59 .DEVELOPMENT OF ASH PRODUCTION AND USE IN THE
Os
o

Ash Source
i
Hard coal
Europe
U. S. A.
Total
Lignite
Europe
U. S. A.
Total

Production
(103 kkg)

27,250
27,500
54,750

21,370
400
21,770
1967
Amount
(103kkg)

12,477
3,744
16,221

1,380
6
1,386

Use
%of
Production

45.3
13.6
29.6

6.4
1.5
6.4

Production
(103 kkg)

35,710
31,661
67,371

23,017
NAb
23,017
1969

Use
Amount % of
(103 kkg) Production

13,630
4,862
18,482

1,278
N A
1,278

34.8
15.3
27.5

5.5
N A
5.5

Production
(103 kkg)

59,922
42,781
102,703

36,353
449
36,802
1971

Use
Amount % of
(103 kkg) Production

15,983
8,604
24,587

1,658
18
1,676

26.7
20.1
23.9

4.6
4.1
4.6

     0 The UN Economic Commission for Europe (ECE) is composed of 32 countries in the European geographical region and
       the U.S.A.  Its purpose is to present economic collaboration among all those countries.
     b  NA - Not available.
     Source:  132.

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    TABLE 60. DENSITY OF FLY ASH COMPARED WITH TRADITIONAL FILLS

                   Material                           Compacted Density
                                                        (kkg/cu m)

PFA                                                   1.1  - 1.3
Limestone                                              1.6-2.0
Burnt colliery shale                                      1.7 - 2-0
Sand                                                <2.10
Clay                                                <1.77
Hoggin (sand/clay)                                    < 2.14
Chalk                                               <1.75

Source:  137.
                                     161

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     •  Fill material

     •  Agriculture and reclamation

     •  Brick manufacture

     •  Water quality improvement

     •  Miscellaneous

 Current and experimental applications are considered.

 Concrete.

     The addition of fly ash to concrete can improve its strength, resistance to sulfate
 attack, workability, and permeability; it may also help control shrinkage and evolution
 of Kent during setting.  Fly ash concrete reportedly clings less tenaciously to form  and
 retains sharper comers and details,  thus enhancing the concrete's architectural value.

     Fly ash is valuable in cement and concrete primarily because it is a pozzolan.
 Pozzolans are siliceous-aluminous materials that have little or no cementitious value
 theB»seJves,lxit, in finely divided form and in the  presence of moisture, are able to react
 chemically with calcium hydroxide and other alkaline earth hydroxides to form compounds
 that harden. Fly ash in concrete also acts as a mechanical  filler supplementing or re-
 placing fine |s@Rd) aggregate.  Its spherical shaog impaaves the workability of the plastic
 concrete and the ease with which it is finished.   In domestic sewers, concrete is frequently
 exposed to  attack by sulfuric acid formed through the contact of hydrogen sulfide with wet
 surfaces. Addition of fly ash to concrete mixes can materially increase a concrete's resis-
 tance to sulfurJc acid attacfe.

     Mast fly ash concretes require more air-entraining agent to achieve a similar air con-
 tent to  that required for regular concrete.  Entraining agent requirements for a constant air
 content increases with the percentage of fly ash and  its carbon content present as a replace-
 ment for portland cement.

     Specifications fvr fly ash in concrete, bituminous pavement, and light-weight aggregate
should be a performance type, expressed in terms of desired  characteristics for the final
product.  Specifications are primarily based on experience with particular fly ashes since
some fly ash may not comply with  a given specification for producing an acceptable product.

     The economy of using fly ash  depends almost entirely on its quality, generation, location,
and cost relative to cement,  although there may be economic advantages from reduced pouring
and finishing time compared to standard  concrete.  Significant savings in using fly ash can
result when  large quantities of concrete  are involved.


                                            162

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    There are some materials handling problems associated with the use of fly ash in concrete.
Low viscosity, for instance, may cause problems in feeding and weighing, and the extreme
fineness of fly ash can lead to air pollution and other problems, such as poor insulating
properties of concrete used in electrical  boxes and switches.  Proper design of feeders and
scales and the installation of dust-collecting systems can eliminate these problems.

Stabilized Bed Construction.

    The use of granular material in base and sub-base construction for road and airfield
pavements runs into billions of kkg per year.  Because of the vast quantities of materials
used for this type of construction, an attractive and promising method for utilizing fly ash
is provided.  There has also been a substantial increase in the use of lime fly-ash aggregate
(LFA) and lime-cement fly-ash aggregate (LCFA) mixtures in pavement construction during
recent years.  Many state and federal agencies have expanded their specifications to in-
clude LFA and  LCFA as acceptable paving materials.  Based on their properties, great po-
tential markets can be developed for the use of LFA and LCFA materials  in paving construc-
tion.

     LFA mixtures are blends of  aggregate,  lime, fly ash, and water which, when compacted
to a relatively  high density, produce hard surface paving materials; LCFA contains concrete
in addition  to the materials in LFA.   Aggregates which can be successfully used in LFA and
LCFA mixtures  cover the entire  spectrum, including sands, gravels, crushed stones, and
several types of slag.  Typical proportions are 2-1/2 to 3-1/2 percent lime and 10 to 25
percent fly  ash, depending on the gradations of the aggregates.  When cement is  used
in the LCFA mixtures, the ratio of lime to cement is usually 3:1 or 4:1.  The optimum fly
ash content for a particular mix is the quantity needed to achieve maximum density in the
compacted mixture,  that is,  fill the voids in the aggregate  lime content. The optimum
content can be established by trial batch procedures for desired strength  and durability
characteristics.

     Important properties of paving materials are durability, dimensional stability, strength,
and stiffness. The standard test for durability of LFA and LCFA mixtures is the cyclic
freeze-thaw ASTM C593 designated test.  Figure 177 shows the pattern of strength loss and
gain of a typical LCFA material during alternate periods of freezing and thawing.  As the
curing period for the materials increased, the loss in strength decreased until ultimately the
material showed a gain in strength,  even during the cycle freezing and thawing period.
When the latter condition exists, durability of the material is improved.  All paving materials
in which the aggregate particles are bound together with binders such as cement,  asphalt,
or lime fly-ash change dimensions with temperature and moisture conditions.  Good pave-
ment performance requires that the coefficients of linear thermal expansion of the layers be
limited to less than 10  .  If large dimensional changes occur, the pavement will crack
excessively, permitting the infiltration of water and foreign material into the pavement with
a concomitant failure in pavement performance.   Dimensional changes of a typical LFA
material under varying moisture and temperature conditions are shown in Figure 178-   As a
general rule, the coefficients of linear thermal expansion for hardened LFA and LCFA
materials can be taken as 5 x 10  ,  or about the same as portland cement concrete.

                                          163

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                                                                 26   28
    Legend
        Period of constant 49*t temperature
        Period of ten freeze-thaw cycles
Source; 23
   Figure 177.  Effect of freeze-thaw cycles on  LCFA compress!ve strength.
                                164

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           60
           40
        0)
        H
        S.20
        D)

        
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     The higher the compressive strength,the better the quality of the LFA mixture.  The
strength of LFA and LCFA are time and temperature dependent.  Some time and temperature
versus strength relationships for typical LFA and LCFA mixtures are shown in Figures  179
and  ISO,/ respectively.  Data in Table 61 shows how the strength and durability of the well-
gcnded  aggregate vary with the fly ash content.

     Figure  181 shows the effect of lime content on compressive strength of LFA mixtures;
Figure  182shows the effect on density of LFA mixtures.  LCF and LCFA mixtures have an
excellent performance record as paving materials.  One of the best examples of the use of
LFA and LCFA materials for pavement construction is at the Newark, New Jersey airport.
A recent survey of the Newark airport facilities found the primary runway and taxiway system
to be in excellent condition. LFA and LCFA materials are also being used extensively by
the  Port Authorities of New York and New Jersey in the rehabilitation  and upgrading of the
pavements at  Kennedy International Airport.  Still, the application and marketing of fly ash
as paving materials has not been fully exploited.  The paving material market is tremendously
large, and with additional effort on a national level it appears that this market could absorb
a substantial portion of all fly ash produced.

Fill  Material

     Most fly  ash applications require substantial capital investment in  processing equipment,
and  time to develop markets. Using ash as a fill material, however, offers the advantage
of minimum processing costs and a large existing market.  The important material properties
when considering fly ash as a fill material are its grain size, density, compaction charac-
teristics, shear strength, and permeability.

     The compacted dry density of fly ash is usually in the range of 1 to 1.5 g/cu  cm, which
is a  high weight when compared with most conventional fill materials; the optimum moisture
content is normally in the range of 18 to 30 percent by weight.  The permeability of  compacted
fly ash  is low, typically in the range of 10~3 to 10"^ cm per minute.  This is quite adequate
for a homogenous, compacted fill  material.  Apart from slight solubility in water, fly ash is
chemically very stable, and there is little deterioration on exposure to  the atmosphere.  Also,
since the small soluble content is partially fixed after participation in the pozzolanic action,
leachate water passing over or through fly ashfill  will pick  up  somewhat lower quantities of
soluble chemicals.  Strength characteristics are enhanced by the pozzolanic action,  and there
is a  gradual increase of strength with time,  as with portland cement.

     Fly ash's  low unit weight and low compressibility help to reduce differential settlement
between the approach embankment and the structure itself.  Fly ash has also been used as
structural fill  to retain slurry at Grossblidergtroff Station of the Houilleres du Bassin Lorraine
(HBL) in eastern France.  Fly ash fill dams were constructed in the valley and the area be-
hind them was then filled  with water from a small  tributary stream of the Soar river.  Waste
ash from the generating station was later filled to reclaim land.
                                           166

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        120
    E
    o
   _C
    "a>
         90  -
         60
    I
    o
   u
         30
                                    40          60
                                    Curing Time (days)

    LFA Components (%)
     Lime—2.5
     Fly Ash—10
     Aggregate—87.5

   Source: 23.

Figure 179.  Effect of curing time and temperature on LFA compressive strength.
                                  167

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      120
   E
   u
   0>
        90  -
   I    60

   £
   Q.

   O
   (J
       30
           0
10
20       30        40


    Curing Time (days)
60
Source:  23.




Figure 180.  Effect of curing time and temperature on LCFA compressive strength.
                                168

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TABLE 61.  EFFECT OF FLY ASH CONTENT ON LFA STRENGTH AND DURABILITY

Fly Ash
Aggregate Content (%)
Type
Crushed stone
(well graded)

Slag
(uniformly sized)

10
12
15
20
24
28
Compressive
Strength
(kgf/sq cm)
33
56
79
46
54
61
Durability
Weight Compressive
Loss (%) Strength
(kgf/sq cm)
100
23
45
100
58
10
0
49
69
0
3
58
  All samples contain 3 percent lime.




Source: 23.
                                   169

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 E
 u
,g"   70
 f
 to
      35
 U
                      36 Days at 21°C
                                       8

                               Lime Content (%)
12
 Source:  23.



Figure 181 , Effect of lime content and curing conditions on LFA strength.
                              170

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       100
   IS1
   C
   
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    The major risks with compacted fly-ash fills are ash erosion (both internally and ex-
ternally) and liquefaction.  Internal erosion can be controlled by a properly designed
drainage and filter system to ensure that fine material is not carried out of the dam as a
suspension in seepage water.  External erosion due to wind,  rain, and wave action can
be controlled by suitable cover vegetation on the  downstream slope and slope protection
on the upstream slope.

    Liquefaction is the sudden decrease in the shear  resistance to almost zero  caused by
collapse of the structure of the material  associated with a sudden but temporary increase
in the pore pressure.  Liquefaction can be prevented  by avoiding the following conditions:

    •  Material gradation typically in the fine sand/coarse silt range

    •  Shock loadings

    •  Loose material with large percentage of voids

    •  High water table or excess pore water pressure

Soil Stabilization

    The degree of stability in a soil (wet or dry) refers to its ability to resist deformation
under repeated or  continuing loads. Treating the  soil to improve deformation  resistance
and strength is called stabilization. 34 A variety of stabilization methods are available;
however, no one method is best for all soil types because each soil differs markedly in its
properties and reactions to different stabilization methods.  LFA and LCFA mixtures are  two
materials which have been successfully used for soil stabilization in many applications,  and
there  is a developed technology concerning their use.


    When compacted to high densities,  the proper combination of lime,  fly ash,  aggregate
and water dries into a stable, hard, continuous slab which can be used as the subbase or base
for bituminous or concrete paving. The amorphous glassy materials in fly ash react to form
complex silicates and aluminate which in turn react with the calcium hydroxide and  magne-
sium oxide in lime to form a cementitious matrix.  The difference between LCFA and LFA
mixtures is in the addition of cement, which gives the LCFA material more strength.

    Aggregate. The type of material to be stabilized is an important parameter in LFA/LCFA
design.  For this purpose, five categories can be identified: clays, silty soils,  sandy soils,
coarse granular soils, and other fill (pozzolanic materials).  Treatment of clays depends
greatly on the chemical composition and particle size of the material.  The sodium-calcium
ion balance is an important factor affecting pozzolanic strength.  In practice, ratios of 5-9
percent lime and 10-25 percent fly ash are used in clay soils.

    Silty soils composed of less than 10-12 percent clay can be stabilized with lime alone,
or with a lime/fly ash ratio of about 1:2. Silty soils containing greater amounts of clay
require larger percentages of fly ash.
                                           172

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    Sandy soils almost always need the addition of fly ash to promote stabilization because
of their coarseness.  Sandy soils containing silt and clay (10-30 percent) may be stabilized
by lime alone if the clay is sufficiently pozzolan.  However, addition of fly ash will pro-
duce better results.  Lime-fly ash ratio of  1:5 are  common for sandy soils alone,  but grada-
tion will improve strength and durability.

    Coarse soils generally need little (2-4 percent) or no lime to meet stability requirements
for base courses. The strength of mixes containing clay or caliche can be further enhanced
by the addition of fly ash (lime/fly ash ratios of 1:5 are appropriate).  Materials such as
scoria, cinders, chert, or water-cooled slag have been used in LFA/LCFA compositions with
strengths approaching that of portland cement being reported.  Fly ash iot only contributes
to the natural pozzolanic qualities of the above mixtures, but also improves the gradation
which results in greater strength.

    Lime. Dolomite limes (quicklime and monohydrate) result in 30 percent stronger products
than calcitic limes, except in kaolinitic material  where the strengths  are about the same.
Currently, it is  believed that the MgO in dolomitic limes acts as a catalyst in the soil-lime
reaction.  Calcium to mg ratios of 1:1 and 2:lare optimal (magnesium must be in the oxidized
state), and most commercial dolomitic monohydrate limes are within these limits. No opti-
mum ratio  of lime to fly ash has been found which satisfactorily stabilizes all soils.  As the
lime to fly ash ratio is not very critical, and lime is 5 to 10 times more costly than fly  ash,
it is desirable to use mixtures which maximize the percentage of fly ash.

    Moisture.  To obtain maximum strength in the  hardened  product the moisture content of
the LFA/LCFA mixture must be near optimum.   Optimum moisture content varies depending
on the lime/fly ash ratio.  In general, the moisture content which results in the maximum
bulk density of the  lime-fly ash mixture is slightly higher than that needed for the maximum
hardened strength.  The carbon content  and fineness of the fly ash, as well as the floccula-
ting effects of the lime,  all affect moisture content.  Determining the optimum moisture
content for a particular mix of lime,  fly ash, and  aggregate can be facilitated by preparing
a figure similar to Figure  183. In this case, limits of 50:50 soil-lime,50:50 soil-fly ash,
and 100 percent aggregate were selected.  Laboratory analysis determined the optimum
moisture concentrations for these limits to be 29.2, 17.9/and 16.7, respectively. Inter-
mediate moisture concentrations are scaled off as shown from 18 to 28 percent.  The approxi-
mate optimum moisture content can then be read for any soil mix within the original limits.

    There are two questions which remain to be answered with respect to fluidized-bed
residues in LFA and LCFA soil stabilization mixtures.  First, do they work as well as con-
ventional fly ash? Second,  because of the limestone  content and the pozzolanic action
of the residues, can some of the lime and/or cement be replaced by the fluidized-bed
residues?  Work is in progress to answer these questions.

Neutralization of Acid Mine Drainage

    Acid mine drainage (AMD) annually causes millions of dollars of  environmental damage.
Polluted water taken by downstream users for industrial, agricultural, or potable

                                         173

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29.2
                                 Soil  (%)
               Figure 183.  LFA moisture correlation chart.
                                     174

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applications may require additional pretreatment; fish and vegetation may be killed,
agricultural land damaged, and an area's recreational value reduced.  The problem arises
when mining activities expose pyrites and marcasites to the oxygen in the air.  In the
presence of moist air, sulfuric acid is formed.  Every kg of iron sulfide exposed has the
potential to produce as much as 1.6 kg of sulfuric acid.  The extent of the pollution
damage depends on how much sulfide oxidation has occurred and how much acid has been
released into the environment.

     There  are two basic approaches to dealing with AMD: prevent its formation or prevent
it from contaminating ground or surface waters.  One approach which has been tried ex-
perimentally is to collect the acid as it forms and pump it to storage and treatment facilities,
where it is neutralized with lime or other chemicals before discharge.  This is an expensive
alternative,  especially if taken to its ultimate end of a treatment plant for every coal mine,
operating or abandoned.  Since the formation of acid is initiated by oxygen, attempts have
been made to prevent contact between the sulfides and air or water.  Mines have been
sealed to prevent water infiltration or exclude air, but results have not been promising.

     Work  has been done with using conventional coal fly ash residues for reclamation of
surface-mine spoils.    The residues provided nutrients needed by the soil, served as a
conditioner, and their alkakinity  has reduced the AMD.  Our preliminary analysis suggests
that fluidized-bed residues could  be used to neutralize AMD,  both from strip and subsurface
mines.  Neutralization capacity varies widely with the type of residue (see Figure 184).
Potential use for AMD control will therefore depend partially on the characteristics of the
specific residues available.

     The marketing potential of fluidized-bed residues for AMD is difficult to determine.
Residues used in this way are not directly part of the mining production process.  If this
application proves feasible, the demand for residues would depend primarily on environ-
mental regulations—the more restrictions placed on AMD and the more stringent the re-
quirements on strip-mine reclamation, the higher the demand.  Power producers must, as
part of their normal production process,  dispose of the residues generated.  They will dis-
pose of them by the least expensive means.  The assumption of a zero f.o.b.  price at the
power plant for the residues would not be likely  to hold for AMD application.  The large
quantities of residues required plus their low return to the mine owner suggest that the
power plant would need to contribute some or all of the freight charges.

     In general, residues would most likely be used for AMD control where the mine
site is as close or closer than the landfill site. The mine could be expected to pay the cost
of spreading the residues and perhaps some of the transport  costs, and  special environmental
protection  measures and other costs would  likely be incurred by a landfill operator, but not
by  the mine operator.  Thus, it is likely that fluidized-bed residues could be economically
shipped somewhat farther for AMD neutralization than for landfilling.

     The market potential for fluidized-bed residues will  thus be primarily determined,
assuming the application is technically feasible and there are significant regulations con-
cerning AMD,  by i'..3 location  of mine sites relative to power plants.  Residues from
                                             175

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X
 Q.
14
13
12
n
10
 9
 8
 7
 6
 5
 4
 3
 2
 1
                                                                        Legend
                                                                     • Control
                                                                     0 VFA
                                                                     0 VSBM
                                                                     D NJFA
                                                                     D NJSBM
                                                                     A CFA
                                                                     A FSFA
          I   I  I  I   I  I   |  I   I	!
                                  I	I   I  I  I   I  I   I  I  1   I
                                            I   I  I  I
     0 1020304050
                          100
150
200
250
300
350
                                           ml H2O
                        Figure 184. pH of leachate for acid mine drainage control.

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coal-burning plants will,at present,tend to be available only for eastern United States mines,
as most coal-fired power plants are now located in the East.  There are several areas in the
East where power plants and mining areas are in particularly  close proximity.   If fluidized-
bed oil gasification becomes widely adopted, many more mining areas will have a nearby
source of residues.

Soil Cement

    Soil cement is a mixture of soil,  portland cement, and water.  Compacted at optimum
moisture content and cured to hydrate the cement, soil cement forms a strong stable base
that is resistant to variations in moisture  and temperature.  Soil cementi typically have
modules of elasticities which range from  100,000 (for clayey soils with little cement) up
to 10° (for stronger mixtures), and are far more elastic than concrete.  Soil cement mix-
tures  are used for base courses under pavement, roadway shoulders, patching, ditch  and
channel linings, dam facings, and miscellaneous uses.

    In general, there are three types of  soil cement: compacted soil cement,  cement modi-
fied soil,  and plastic soil  cement.  Compacted soil cement contains the stoichiometric
amount of cement to harden the soil and  the stoichiometric amount of water to hydrate
the cement.  Cement-modified soil is an unhardened or partially  hardened mixture of soil
and cement.   Just enough cement and water are added to the soil to  change.its chemical
and physical  properties.  Addition of cement to soil  reduces the soil's plasticity and water
holding capacity, and increases its bearing value.  Plastic soil cement contains sufficient
water, at the time of placing,  to give the mix a consistency  similar to that of plastering
mortar.

    The surface of a  cured soil cement mixture is friable, hence  it cannot be used as a
running surface for motor vehicles without experiencing scuffing and pitting.  It is usually
overlaid with a layer of bituminous or concrete paving, the type  of covering determining
to some extent the type and thickness of  the soil cement sub-base.

    Soil cement  is an inexpensive paving material because of the three basic materials
needed.  Soil and water are either found at the site or transported only short distances.
The work  "soil" as used in "soil cement" means any combination of gravel, sand, silt,clay,
or filler (such as  cinders, shale, chat, etc.). The water used in soil cement preparation
serves two purposes: it aids  in compaction  by lubricating soil grains, and it is necessary
for cement hydration.

    Soil gradation is  an important factor in proper soil cement design.  Sandy and gravelly
soils with  about 10-35 percent silt and clay combined are the most desirable soil cement
aggregates and generally require the least amount of cement for satisfactory curing.   Coarse
soils containing 55 percent or more material passing the number four sieve also make good
soil cement aggregates. Sandy soils deficient in fines can make adequate soil  cement,
although the  amount of cement needed increases as the percentage of  fines decreases. Silty
and clayey soils also can be used to make satisfactory soil cement; however,  the higher the
clay content, the greater the amount of cement needed to provide adequate hardening.

                                          177

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Silty and clayey soils are sensitive to weather conditions (much more so than coarse or
well graded soils.

    The amount of portland cement needed to construct a suitable soil  cement pavement
depends on soil type and design load.  Any type of portland cement which complies with
ASTM or AASHTO specifications is satisfactory.  Types 1 and  1A,  normal and air-entrain-
ing portland cements are most commonly used.  Tables 62 and 63 show representative cement
concentrations for various soil types.

     When possible, the optimum amount of moisture to add to  a soil cement mixture should
be determined by a laboratory test, such as AASHTO T134 "Standard Method of Test for
Moisture-Density Relations of Soil-Cement Mixtures."  In general, sandy mixtures will
require approximately 22 I of water per sq m for a 15-cm compacted thickness.  Silty and
clayey  mixtures will require about 32 I of  water per sq m.  Experienced users can, within
practical limits, determine the optimum moisture content by test.  Soil  cement at optimum
moisture contains sufficient water to form a firm cast; when squeezed in the hand, water
cannot  be squeezed out.

     In  practice, soil cement is generally mixed ?n-s?tu or less commonly  away from  the
construction site and then trucked in.  In-place mixing is more economical; off-site mixing
is used  only when the quantity or quality of the aggregate at the site is not adequate
enough to meet the design standards. Mixing of the aggregate and cement can be either
on the ground (continuous mixing) or in a mixer (either traveling or stationary).   Mixers
provide a better control over the amount and blending of the components. Groundmixing
is cheaper and usually faster; it can be done using a dump truck or even by hand. Compac-
tion is usually done by rollers; however, in sandy soils or coarse soils lacking  in fines,
compaction must be done by vibration.

     Curing soil  cement mixtures have to be protected from the weather in order to prevent
moisture imbalance.  Bituminous coatings;  are generally used, but dirt,  straw, and paper
have all been successfully applied.

Agriculture and  Reclamation

    Residues can be used to eliminate acid type agricultural soils.   Soil pH is also an
important factor in c'etermining the solubility of many compounds such as  the concentration of
heavy metals present in  crops .  It had  been observed that in a strongly acid soi I, large
amounts of metals such as iron, aluminum, and manganese may come into solution and may be
adsorbed on  the surface  of the soil particle. Plants can easily take up metals in this form.   '
Soil with a safe toxic metal content atpH  7 can easily be lethal to most crops at pH 5.5.
However, it has also been found that an increase  in pH will  decrease the plant uptake of heavy
metals.  Application of sewage sludge or effluent irrigation may generally tend  to lower the
soil pH, and the addition of calcerous or magnesium compounds to soil can correct or eliminate
acidic soil conditions.

                                          178

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      Material _ Percent by Volume             Percent by Weight
Caliche
Chat
Chert
Cinders
Limestone screenings
Marl
Red dog
Scoria containing plus No. 4
material
Scoria (minus No . 4 material only)
Shale or disintegrated shale
Shell soils
Slag (air-cooled)
Slag (water-cooled)
8
8
9
8
7
11
9
12

8
11
8
9
10
7
7
8
8
5
11
8
11

7
10
7
7
12
Source:  189.
              TABLE 63.  NORMAL RANGE OF CEMENT REQUIREMENTS
                                FOR B AND C HORIZON SOILS0
AASHO Soil Group
A-l-a
A-l-b
A-2-4, A-2-5, A-2-6, A-2-7
A-3
A-4
A-5
A-6
A-7
Percent by Volume
5-7
7-9
7-10
8-12
8-12
8-12
10-14
10-14
Percent by Weight
3-5
5-8
5-9
7-11
7-12
8-13
9-15
10-16
  "A" horizon soils may contain organic or other material detrimental to cement reaction
  and may require higher cement factors.  For dark grey to gret A horizon soils, increase
  the above cement contents four percentage points; for black A horizon soils, six percentage
  points.

Source:  189.
                                       179

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   Related information on the effects of zinc level and soil pH on chard plants are shown
 in Table 64.  Inorganic zinc (and cadmium at one percent of the added zinc) was added
 to a sassafras sandy loam  soil and the pH was adjusted to 5.3, 6.4, or 7.2 in the metal
 amended soil.  The concentration of zinc uptake  in plants may be significantly reduced
 when the soil pH is increased by the addition of lime or other pertinent alkaline materials.
(A brief literature search identified previously published data and conclusions showing the
 same trace metal uptake improvement).

   Addition  of sulfur will reduce the soil pH.  The reduction of soil pH is directly pro-
 portional to  the quantity  of sulfur added.  Lowering the soil pH increased the concentra-
 tion of metals as shown in Table 65 and certain  other elements  such  as silicon, phos-
 phorus and potassium.

   At the Virginia Polytechnical Institute, other  field research on using fly. ash as* a
 fertilizer is seeking to determine (1) the plant nutrients  available in fly ash and (2) the
 effects of different fly ash application rates.  Research on revegetating several barren
 experimental sites has proven that fly ash could act as a neutralizing  agent, diluent,
 and soil conditioner to provide  needed  nutrients which enhance vegetation growth.84

   The U.S. Park Service, Washington,D.C., is testing sintered fly ash for use as an
 additive to soils subjected to continuous use (bicycle paths, camping  areas, hiking trails,
 picnic areas),  fa this application, sintered fly ash would be  added for its porosity and
 resistance to degradation.

 Brick Manufacture.

   Using fly ash as an additive  can  extend the life of a  clay or shale deposit; this is of
 particular value to brick  plants with limited raw materials supplies.  Extensive research
 on fly ash in brick has been done at the Coal Research Bureau of West Virginia University.
 This research has yielded tolerance  levels for many fly ash constituents which, when ex-
 ceeded, contribute to a poor quality brick.  These constituents include:  water soluble
 minerals, water soluble sulfur,  carbon, iron, and alkaline earths. The first commercial
 fly ash brick plant using the process developed at the  Coal Research Bureau is operating
 at Edmonton,Alberta.  The plant has a  design capacity of 35 million bricks per year.
 Economic studies currently underway indicate that the cost of the Coal Research Bureau
 process is less than that of the conventional  clay-brick manufacturing process. Several
 firms are currently examining the process for commercial exploitation.  Research  is under-
 way on coloring and texturing the brick, and on producing large size  bricks.

 Water Quality Improvement.

   Fly ash as a treatment miaterial for reclaiming  small eutrophic or algae-overgrown
 lakes is under study at Notre Dame  University. Fly ash can remove phosphates in the
 water and seal the bottom mud so that the release of pollutants is controlled.  A process
 for the removal of phosphates from water using fly ash has been developed at the  Poly-
 technic Institute,  Brooklyn,  N.Y.  When used for water treatment, fly ash will (1) increase

                                          180

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             TABLE 64. EFFECTS OF ADDING Zn AND VARYING THE pH
             IN THE SOIL ON Zn CONTENT AND YIELD REDUCTION
                             OF CHARD LEAVES
Added Zn
ppm
1.31
32.7
65.4
131.0
262.0
5.3
210
754
1058(7)°
2763(41)
2692(95)
Soil pHb
6.4
116
237
337(5)
765(9)
1678(22)
7.2
12
74
100
177
406(27)
  • Yield reduction in parentheses (%).
   g. Zn/g dry weight.

  Source: 191.
       TABLE 65. EFFECTS OF SOIL pH ON SOYBEAN PLANT'S MINERAL UPTAKE
Elements
in ppm
Fe
Mn
Zn
Co
Mo
Al
B
Ni
Si
P
K
Soil
7.4a
31
47
40
6.6
9.5
9.6
72
4.4
2000
4300
17,300
pH
6.1b
81
209
68
12.3
12.6
16.4
123.0
7.7
3800
6500
25,900
% Elements yield g 1 plant
Increase 7^a ^^
261.2 5.6 18.5
444.6 8.5 47.7
170.0 1.72 2.87
186.3
132.6
170.8
170.8
175.0
190.0
151.1
149.7
° No sulfur added.
b 10% sulfur added.
  P154619-5-1 soybean variety.

Source: 192.
                                   181

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the growth of floes, thus  enhance  settling,  (2) condition the waste sludge as a physical
aid to filtration,  (3) remove phosphates, and  (4) absorb organic molecules in solution.

 Miscellaneous.

    Industrial applications for the hollow, spherical, and extremely light-weight fly ash
 particles known as cenospheres are  being developed at Washington State University.  One
 application, known as "syntactic foam," is used to achieve buoyancy in deep ocean en-
 vironments.  Syntactic foam is formed by vacuum impregnating cenospheres with an appro-
 priate resin.  Research on aerospace applications of cenospheres is underway at the
 Grumman Aerospace Corporation.   From this  research, a closed pore insulation material
 for use on  the space shuttle has been developed.  A unique application using cenospheres
 in the production of a tape for fire  proofing and insulating high-voltage electrical cable,
 has been developed by the Quelcor Corporation.

             Specific Applications  of Lime/Limestone Wet Scrubber Residues

    "Modified fly ash,"  the solid by-product  from lime/limestone wet-scrubbing, is a new
 solid waste material which has different chemical and physical properties from regular fly
 ash.  Modified fly ash has little potential for mineral separation and benefication, and
 therefore, must be used in its  homogeneous state.  The Coal Research Bureau has developed
 several promising uses for modified  fly ash.  Several potential applications are considered
 below:

    *  Soil amendment

    •   Highway construction

    •  Aerated concrete

    •  Poured concrete

 Soil Amendments.

    Dried modified fly ash can be used as a soil amendment to increase  the calcareous
 component, and \ •> neutralize acid  soil.  Modified fly ash may also increase  the concen-
 trations of boron  and other trace elements, and also increase the  texture and drainage
 characteristics of soils.m Further research is needed to determine  if pollution would be
 created by water leacning.
 Highway Construction.

   Combustion Engineering participated in a  project with the Research and Development
 Division of the Federal  Highway Department  to study the use of residues as a highway con-
struction material. The program was part of the International Transportation  Exposition
 (Transpo '72} that was held from May 24 to June 4, 1972 at the Dulles Airport  in Washing-
ton, D.C.  To accommodate the 50,000 automobiles and 600 buses' arriving daily at the

                                         182

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exposition, a 49 hectare parking lot was constructed.  The Research and Development
Division of the Federal  Highway Administration used this opportunity to demonstrate the
recycling of waste products as highway construction materials.  The major portion of the
parking lot was paved with a mixture of modified fly ash and sulfate sludge from an acid
plant.
Aerated Concrete.

   Aerated concrete has been widely developed in  Europe.  Almost all new factory build-
ings in Sweden and West Germany are constructed, in part, using this material.  Aerated
concrete is a light-weight structural material consisting of small non-communicating gas
cells entrained in a calcium silicate matrix. A process flow sheet for the production of
aerated or foamed cellular concrete from modified ash is shown in Figure  .185 .  It is
necessary to add cement and a gas-producing agent to modified fly ash in making this
product. Commercial aerated  concrete varies from 0.3-0.8 g/cu cm in density, and has
a compressive strength of about  30-60  kgf/sq cm.

   Aerated concrete material can be sawed, nailed, drilled, screwed, or glued as wood,
but has the thermal and fire resistant properties of concrete.   Potential uses include non-
load-bearing walls,  sandwich construction with brick or concrete for insulating  purposes,
and.interior surfacing for exterior walls.  It can be formed in  any desired shape  or cut
from panels and is suitable for modular construction,

Poured Concrete.

   Figure 186 is a process flow sheet for the manufacture of poured concrete materials.
The  material is poured into molds for curing instead of being pressed as in the manufacture
of CS brick.   The resulting poured concrete block has a density of 1 J5 g/cu cm and com-
pressive strength of about 60 kgf/cu cm.  Modified ash does not require grinding or curing
prior to use in poured concrete.

   The advantages of producing autoclaved calcium-silicate products from limestone fly
ash include:

   • No SO~ capture or marketing problems would result as processing occurs below
      the temperature for sulfur dioxide regeneration.

   •  Little or no storage or curing time is required before use since structural materials
      produced are durable, pre-shrunk, and pre-strengthened.

   •  No exotic equipment is required for  production.

   •  Minimum pollution occurs at the plant since all  rejects  and process waters may be
      recycled.

   •  A potentially large market exists in low-cost housing or other construction.


                                            183

-------
                      Mech Precip - Dry Collected
                    Limestone Modified Fly Ash (92%)
8% Portland Cement
  Type I, Normal
            0.16% Aluminum Powder
                       Paddle Mixer (10 Minutes)
                            Pour into Molds
                         8 hours
Air Set
                         Autoclave, 16 hours
                         !»  16kgf/sq cm, 185C
                              Air Drying
                              (72 hours)
                                                         51% H20
                                                          @60C
    Source; 46.

    Figure 185.  Aerated or foamed cellular concrete production flow diagram,
                                184

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   Silica Sand
                          Wet Collected Limestone
                             Modified Fly Ash
                               (10% Slurry)
Dewater Ash to 58% H2O
Lime (CaO) 96% Pure
                            50% Ash+ 11% CaO
                                + 39% Sand
                               Paddle Mixer
                               (10 Minutes)
                             Pouring into Molds
                        24 hours Them
           al Set (HOC)
                            Autoclave, 16 hours
                           @ 16kgf/sq cm, 185 C
                                Air Drying
                                 (72 hours)
Source:  46.
              Figure 186.  Formed concrete production flow sheet.
                                     185

-------
Autocloved Products.

    Because absorbed sulfur dioxide is liberated when modified fly ash is heated, it is
necessary to find a technique for totally using  the ash which would either lock the sulfur
into the product or not require heating.  Autoclaving  has the advantage of locking sulfur
into the final product. The products with the greatest potential for using modified fly ash
are:

    •   Bricks and blocks

    •   Aerated or fo,amed concrete

    •   Concrete materials

    Calcium silicate (CS) brick production has been examined as a potential large tonnage
application of limestone modified fly ash.   Bricks produced by this method have the ad-
vantage of binding the sulfur  components within a calcium-silicate matrix.  These bricks
surpass the standards for conventional sand-lime brick.  Figure 187'is a process flow sheet
for the production of CS brick. Mixing  and humidity  curing are two important process
parameters in producing CS brick. Promising areas for using calcium silicate brick include
low-cost construction  materials,  interior walls, decorative walls, patios,  and thermal or
acoustic insulation.

                  Potential Structural Materials Applications: Test Results

    Several beneficial  materials applications for conventional coal-combustion residues
were discussed earlier in this  chapter.  Because of limited material,  it was not possible to
undertake a comprehensive structural testing program investigating all the possible uses of
fluidized-bed coal combustion residues;  several preliminary screening tests were run on
applications for the residues in concrete and asphalt.  These tests are listed in Table 66.
Concrete and asphalt are discussed separately below.  Tests are currently  being done  on
residue application in pozzolan cements, soil cement, acid mine drainage, and  load
bearing fill, which will be discussed in the final report.

Concrete.

    Procedure. The residue addition to concrete was tested for compressive strength.
Twenty batches of concrete were mixed, differing in the amount and type of residue added.
Two of the twenty were control samples in which no residues were added.   Four sample
specimen cylinders were made from each batch.  The procedure followed for making the
cylinders was ASTM CI92-69  ("standard method of making and curing concrete test speci-
mens in the laboratory");  the cylinders were approximately 5 cm in diameter by 10 cm in
length.  Table 67 gives the composition of each batch.  The mixtures are  considered
"rich mixes" because of the high cement content (approximately 15 percent).
                                          186

-------
                     Wet Collected Limestone
                   Modified Fly Ash (1% Slurry)
 Silica Sand
30 x 100 Mesh
Dewater Ash to
  34% H2O
                      50% Fly Ash+ 11% CaO
                         + 39% Silica Sand
                       Paddle Mixer (10 min)
                          @20.4% H2O
Lime (CaO)
 96% Pure
                          Slaking Reactor
                              (1 hour)
                          Forming Pressure
                          200 kgf/sq cm,
                            17.7% H2O
                         24-Hour Humidity
                       Storage: 95% Humidity
                              atSTP
                            Autoclave
                       8hr, 16kgf/sq cm, 185C
                            Air Drying
                             (72 hours)
             Figure 187«  CS brick production flow diagram;
                            187

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        TABLE  66  .  POTENTIAL STRUCTURAL MATERIALS APPLICATIONS:
                                   TESTS PERFORMED

	Application	Test Description	Method	

Concrete                    Compressive strength of cylindrical        ASTM C39
                             concrete specimens

Asphalt                     Compressive strength of bituminous        ASTM D1074
                             mixtures
                            Effect of water on cohesion of compacted  ASTM D1075
                             mixtures
Pozzolan cements
  LFA mixtures              Compressive strength of cylindrical con-   ASTM C-593
                             crete specimens
Soil cement                 Compressive strength of molded soil-       ASTM D1633
                             cement
Load-bearing fill             Classification for engineering purposes
                            Direct shear:  soil under consolidated      ASTM D3080
                             condition

  Reference numbers as found in 1974 Annual Book of ASTM Standards.  Philadelphia:
  American Society for Testing  and Materials (ASTM),  1974.
                                       188

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           TABLE 67.   COMPOSITION OF CONCRETE TEST CYLINDERS
Batch Type of,
No.a Residue
1 Control
2 VSBM
3
4
5 NJFA
6
7
8 VFA
9
10
1 1 Control
12 NJSBM
13
14
15 EFA
16
17
18 ESBM
19
20
Concrete Composition (% by weight)
Residue Fine Aggregate Portland Cement
0
5.2
15.8
25.0
5.3
15.7
25.0
5.2
15.0
24.7
0
5.3
15.2
25.7
5.2
15.2
25.1
5.3
15.2
25.1
71.5
64.8
53.6
41.0
64.7
53.4
41.0
63.7
51.0
40.5
71.5
64.7
53.7
43.2
64.8
53.7
41.0
64.7
53.7
41.0
15.2
14.9
14.7
14.0
14.9
14.7
14.0
14.6
14.0
13.8
15.2
14.9
14.7
14.7
14.9
14.7
14.0
14.9
14.7
14.0
Water
13.3
15.1
15.9
20.0
15.1
16.2
20.0
16.5
20.0
20.9
13.3
15.1
16.4
16.4
15.1
16.4
20.0
15.1
16.4
20.0
,  Two samples for each batch.
  Residue source code presented in Table 6.
                                   189

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     One sample from each batch was tested after curing for seven days; another , after
 twenty-eight days.  After curing, the cylindrical molds were removed and the diameter
 of the cylinders measured to obtain average cross-sectional area; the results are shown  in
 Tables 68 and 69.  Each cylinder was then capped to prepare them for the actual com-
 pressive strength tests.  The results of the tests are presented in Table 70 for the seven
 day curing and in Table 71 for the twenty-eight day curing.

     Results.  The results are shown graphically in Figures  188to 191, which plot compressive
 strength versus residue strength.  In general, the strength increased with curing time for
 all the fluidized bed residues. The only exception was the concrete containing more than
 about 18 percent by weight of EFA.  This was due to the unique property of the 7 day
 cured EFA.  Like the other residues, the strength of the concrete decreased from 5 to 15
 percent residue; however, at 25 percent residue content, the compressive strength had
 increased to a value higher than the concrete containing 5 percent residue.

     Optimum residue percentages varied widely.   Strengths increased with increasing
 residue concentration for fly (7 day cure) and spent bed materials from the Exxon, New
 Jersey,  pressurized msnipiant. On the contrary, with the exception of VFA (28 day cure)
 and the  EFA (7 day cure)F strengths decreased with Increasing content of residues from the
 PER, Virginia atmospheric pressure unit and from the Esso gasifier.  The following concrete
 test specimens showed unconfined couipresslve strengths greater than the contra' specimens:
 5 percent VSBM/^ day cure; 5,! 5, and 25 percent VSBM/28 day cure; 5, 15, .and 25
 zmcetit  NJFA/28 Jay cure; and 5 percent VFA/28 day cure.  The 25 day NJFA/7 day cure
 material was nearly equal to the control.

 Asphait

     Procedure. Residues were tested as replacements for aggregate filler in asphalt.  Samples
 were made and tested for compressive strength following the procedures outlined in ASTM-
 D-1074; test cylinders were approximately 10 cm in diameter and length.  Residue contents
 tested were 0, 20, 45,  82, and 92 percent of aggregate volume (measured by weight from
 specific  gravities). The aggregate conformed to State of California Department of Trans-
 portation 3/8-inch maximum gradation specifications.  To simplify  handling and to lower
 test cost, emulsified asphalt (SS-1 H) was used in concentrations of 8 to 13 percent by weight..
 Compression tests were also performed for samples containing portland cement, lime or
 hydrochloric acid additives.  Table 72 summarizes the sample compositions.

     All  residues were slaked before being added to the asphalt mixtures. Unslaked residues
 produced poor results, particularly the Exxon spent bed material. Reactions between the
 residue and the emulsified asphalt resulted in a  significant decrease in density. In some
 cases, expansion of the  residue was enough to completely disintegrate the test specimen
 which resulted in a crumbly pile of aggregate and partially coated residue (See Figure  192).

     Samples were subjected to a compacting load of 17,199 kg for two minutes. Samples
were then measured and coded, and those that were within 10.16 + 0.64 cm in  length were
cured in  an oven at 60 ± 3°C.  One sample of each composition was cured for 29 hours and
one for 7 days.
                                         190

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     TABLE  68 .  DIAMETER AND AREA OF CONCRETE TEST CYLINDERS:
                                 SEVEN-DAY CURE
Batch
No.°
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

b
5.37
5.45
5.61
5.77
5.45
5.37
5.53
5.77
5.77
5.61
5.40
5.24
5.40
5.40
5.40
5.40
5.40
5.32
5.40
5.40
Diameter
b
5.77
5.77
5.77
5.77
5.77
5.85
5.69
5.45
5.45
5.53
5.32
5.24
5.40
5.40
5.40
5.40
5.40
5.32
5.40
5.40
(cm)
c
5.69
5.85
5.69
5.37
5.77
5.85
5.69
5.45
5.45
5.53
5.40
5.40
5.24
5.24
5.24
5.32
5.16
5.24
5.32
5.32

c
5.45
5.45
5.69
5.77
5.61
5.37
5.61
5.69
5.77
5.61
5.32
5.40
5.24
5.24
5.24
5.24
5.24
5.24
5.32
5.32
Average
Diameter
(cm)
5.57
5.63
5.69
5.67
5.65
5.61
5.63
5.59
5.61
5.57
5.36
5.32
5.32
5.32
5.32
5.34
5.30
5.28
5.36
5.36
Average Cross-
sectional Area
(sq cm)
24.37
24.89
25.43
25.25
25.07
24.72
24.89
24.54
24.72
24.37
22.56
22.23
22.23
22.23
22.23
22.40
22.06
21.90
22.56
22.56
,  Two samples for each batch.
  First sample of the batch; two diameter measurements taken to minimize effect of
   random irregularities.
° Second sample of the batch; two diameter measurements taken to minimize effect of
   random irregularities.
                                    191

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          TABLE 69.  DIAMETER AND AREA OF CONCRETE TEST CYLINDERS:
                               TWENTY-EIGHT DAY CURE
Batch
No.a
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

b
5.29
5.45
5.37
5.37
5.29
5.45
5.29
5.29
5.45
5.45
5.32
5.40
5.32
5.40
5.40
5.40
5.40
5.40
5.40
5.40
Diameter
b
5.29
5.45
5.37
5.37
5.29
5.45
5.29
5.29
5.45
5.37
5.32
5.40
5.32
5.40
5.40
5.40
5.40
5.40
5.40
5.40
(cm)
c
5.45
5.21
5.45
5.37
5.45
5.29
5.45
5.45
5.29
5.37
5.40
5.24
5.32
5.24
5.24
5.24
5.24
5.16
5.24
5.24

c
5.45
5.21
5.37
5.37
5.45
5.37
5.45
5.37
5.29
5.37
5.40
5.24
5.32
5.24
5.24
5.16
5.32
5.24
5.24
5.24
Average
Diameter
(cm)
5.37
5.33
5.39
5.37
5.37
. 5.39
5.37
5.35
5.37
5.39
5.36
5.32
5.32
5,32
5.32
5.30
5.34
5.30
5.32
5.32
Average Cross-
sectional Area
(sq cm)
22.65
22.31
22.82
22.65
22.65
22.82
22.65
22.48
22.65
22.82
22.56
22.23
22.23
22.23
22.23
22.06
22.40
22.06
22.23
22.23
,  Two samples for each batch.
  First sample of the batch; two diameter measurements taken to minimize effect of
  random irregularities.
  Second sample of the batch; two diameter measurements taken to minimize effect of
  random irregularities.
                                     192

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                   TABLE 70.    RESULTS OF COMPRESSIVE CONCRETE STRENGTH TEST
                                              AFTER SEVEN DAYS
CO
Batch No.
1
2

3
4
5
6
7
8

9
10
11
12

13
14

15
16
17
18
19
20
Type of
Residue0
Control
VSBM



NJFA


VFA



Control
NJSBM




EFA


ESBM


Residue
Content
(%)
0
5.2

15.8
25.0
5.3
15.7
25.0
5.2

15.0
24.7
0
5.3

15.2
25.7

5.2
15.2
25.1
5.3
15.2
25.1
Cross-Sec-
tional Area
(sq cm)
24.37
24.89

25.43
25.25
25.07
24.72
24.89
24.54

24.72
24.37
22.56
22.23

22.23
22.23

22.23
22.40
22.06
21.90
22.56
22.56
Max Load
Before Fail-
ure (kg)
3,856
4,763

3,175
2,948
3,402
3,629
3,856
2,948

2,495
2,268
3,855
2,041

2,494
2,721

3,175
1,814
3,401
1,587
1,361
1,134
Time Load
Applied
(sec)
2.0
1.8

1.6
1.8
1.8
1.5
1.5
1.6

1.5
1.4
20
20

10
10

10
10
17
7
10
10
Strength
(kg/sq cm)
158.2
191.4

124.9
116.8
135.7
146.8
154.9
120.1

100.9
93.1
170.88
91.81

112.40
122.40

142.83
80.98
154.17
72.47
60.33
50.27
Fracture
Description
Conical , diagonal
Vertical and less
diagonal
Conical, diagonal
Diagonal
Conical , diagonal
Vertical, diagonal
Diagonal
Conical with small
vertical
Diagonal
Diagonal
Conical , diagonal
Diagonal , vertical
conical
Diagonal, vertical
Diagonal, vertical,
shearing
Diagonal, vertical
Diagonal, vertical
Diagonal, vertical
Diagonal, vertical
Diagonal
Diagonal, vertical
     Residue source code presented in Table 6.

-------
        TABLE 71. RESULTS OF COMPRESSIVE CONCRETE STRENGTH TEST AFTER TWENTY-EIGHT DAYS
Batch No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Type of
Residue0
Control
VSBM


NJFA


VFA


Control
NJSBM


EFA


ESBM


Residue
Content
(%)
0
5.2
15.8
25.0
5.3
15.7
25.0
5.2
15.0
24.7
0
5.3
15.2
25.V
5.2
15.2
25.1
5.3
15.2
25.1
Cross-Sec-
tional Area
(sq cm)
22.65
22.31
22.82
22.65
22.65
22.82
22.65
22.48
22.65
22.82
22.56
22.23
22.23
22.23
22.23
22.06
22.40
22.06
22.23
22.23
Max Load
(kg)
3,629
4,763
4,536
3,856
5,443
5,670
5,897
4,536
2,948
2,722
5,443
2,722
3,175
3,856
3,629
2,495
1,361
3,629
1,814
1,134
Time Load
Applied
(sec)
3.0
2.5
2.5
2.5
3.5
3.0
3.0
4.0
2.0
3.0
8.0
10.0
6.0
8.0
7.0
5.0
3.0
6.0
5.0
5.0
Strength
(kg/sq cm)
160.2
213.5
198.8
170.2
240.3
248.5
260.4
201.8
130.2
119.3
241.0
122.4
142.8
173.5
163.2
113.1
60.8
164.5
81.6
51.0
Fracture Description
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Conical and diagonal
Residue source code presented in Table 6.

-------
       300>-
       250h
    y
    o- 200
     D)
    g>   150h
NO   tO
     2
     E  lOOh
         50H
          0
Legend

^  Control
A  NJFA
O  VFA
D  VSBM
    5
10               15              20
      Residue Content (% by weight)
25
30
                Figure 188. Concrete, compressive strength tests: NJFA,  VFA, VSBM after seven day cure,

-------
   300
   250
£-
 O)
   200
   150
0)
(D
cL
o
U
   100
    50
     0
                   Legend
                   •  Control
                   A  NJFA
                   O  VFA
                   D  VSBM
                                                         I
                                                                        I
                                        10
                                                                                        25
                   Figure 1-89
                        15              20

             Residue Content (% by weight)

Concrete compresslve strength tests: -NJFA, VFA, VSBM after 28-day cure,
30

-------
                                                                   Legend

                                                                • Control
                                                                <3> NJSBM
                                                                *  ESBM
                                                                ®  EFA
50
                                  I
1
1
                                  10
                               25
                                30
                            15              20

                    Residue Content (% by weight)

Figure 190. Concrete compresstve srrength tests: NJSBM/ESBM^EB^after seven day cure.

-------
        300
        250
     £ 200
    I
     CD
     £  150
O    0)
00    >

        100
    U
         50
 Legend

•  Control
A  NJSBM
Q   EFA
D   ESBM

      I
                                                             I
I
                                            10              15               20
                                                 Residue Content (% by weight)
                                                                      25
                                30
                          Figure 191 . Concrete compressive strength tests:  NJSBM, EFA, ESBM after
                                      28 day cure.

-------
            TABLE 72. ASPHALT SAMPLE COMPOSITIONS
Number
of
Samples
12
24
24
24
4
24
4
24
4
24
68

Asphalt
8
8
8
8
8
8
8
8
8
8

Sample Composition ,
i
Aggregate
92
72
47
..
82
MM
82
*mmm
92
—

Percent by Weight
Fly Ash or
Bed Material
—
20
45
92
•MM
82
—
82

Other
Components
— .
—
«.
—
10 cement
10 cement
10 lime
10 lime
0;24V7*HCL
91.76-85 0

.24-7* HCL

Depending on type of residue
                                199

-------
Figure  192  .  Result of reaction between residues and emulsified asphalt,
                               200

-------
   Results.  In most cases, substitution of fluidized-bed combustion residues for aggregate
did not have a significant beneficial or adverse effect on asphalt compressive strength
(see Figures 193 through 196).  In several cases, test specimens containing New Jersey spent
bed material showed significantly increased strength (e.g., specimens 7 day  cure/90 per-
cent residue, 29 hour cure/45 percent residue).  In some instances a major reduction in
strength occurred (e.g., 7 day cure/82 percent NJFA),.

   Samples showed large increases in strength when other treatment additives (portland
cement,  lime or hydrochloric acid) were also included.  Replacement of 10 percent  by
volume of residues with portland  cement increased strength from 200 to 300 percent.
Replacement with  lime similarly increased compressive strength.  The strength increase
was more than with comparable cement samples when short curing times were used, but
less than for comparable cement samples following longer curing times. Neutralization
of residue pH with hydrochloric acid also resulted in some increased sample compressive
strength.

                  Potential Agricultural Application of FBC Residues

    Plants, to complete their life  cycle successfully, require some trace zinc, copper,
iron, manganese,  boron,  chlorine, and aluminum, as well as large quantities of oxygen,
carbon,  hydrogen, nitrogen, phosphorus, potassium, magnesium, and calcium.  The former
group of elements  is called the micronutrients and the latter, the macronutrients.  Any
material which contains these nutrients in plant-available form has potential  value as a
soil conditioner.  Fly ash and spent bed material contain most of the micronutrients and
some of the macronutrients in plant-available form,  as shown in Tables 17 to 20,  which
present the  results of residue chemical characterizations.  Residues,  because of composi-
tion and particle size, may be a  good soil conditioner with  considerable nutritive value.

    Residues could  also be used as liming material to reduce  soil acidity. Soil acidity
develops in humid regions  (such as the eastern United States) where the calcium and
magnesium may  be gradually leached; it is accelerated by crop removal and cultivation.
Soil pH is a major determinant of plant growth.  Most plants grow best between the range
of 7.0 to 7.5, hence both high and low pH's may be detrimental.

    In acid soils, large amounts of iron, aluminum, manganese, copper, zinc, and boron
may enter into solution and be adsorbed on the surface of the soil particles in a form that
plants can readily assimilate.  High levels of soluble manganese, iron,  aluminum, and
boron may be toxic to crops, but liming can  correct this condition.  In contrast, molybde-
num is more soluble in alkaline soils than in  acid soils, and thus uptake of this micronu-
trient may be increased with liming.  However, if soil has a pH greater than 8.0, most of
the trace elements are fixed in the soil matrix and are unavailable to plants.

   The potential for residue agricultural applications was evaluated  in a series of small-
scale plant growth tests.  Table 73 presents the test schedule.
                                         201

-------
ro
                                                                              Legend
                                                                       •  Control
                                                                       A  VSBM
                                                                       O  NJSBM
                                                                       D  ESBM
                              20
30
40        50       60       70
    Residue Content (% by weight)
80
90
100
                Figure 193.   Asphalt compressive strength tests: VSBM, NJSBM, ESBM after 29 hour cure,

-------
        lOOr-
         80
      E
      o
         60
8
      O)
      .1  40
      I
      u
         20
 Legend

•  Control
A  VSBM
O  NJSBM
D  ESBM
                                                          I
                                                 I
                                     J
                    10
           20
30
40       50       60       70
    Residue Content {% by weight)
80
90
100
                    Figure :194^  Asphalt compressive strength tests:  VSBM, NJSBM,  ESBM after seven day cure.

-------
         100
                                                                                      Legend
                                                                               •  Control
                                                                               O  NJFA
                                                                               O  EFA
          80
cr
tsi

O)
          60
8
       O)
       (U
                                                             I
                                                                I
                                       I
                     10
                        20
30
40        50       60        70
     Residue Content (% by weight)
80
90
100
                     Figure 195 .   Asphalt compressive strength tests:  NJFA/ EFA after 29 hour cure.

-------
          100,-
                                                                     Legend
           80 -
                             • Control
                             O NJFA
                             O EFA
        E
        u
           60
s
        U)
        >  40
        U)
        0)
         _
        E
        c
        U
           20
                                                                       1
                                                _L
                       10
20
30
40        50       60       70
     Residue Content (% by weight)
80
90
100
                       Figure 196-.    Asphalt compressive strength tests:  NJFA, EFA after seven day cure.

-------
                    TABLE 73  PI ANTING SCHEDULE FOR AGRICULTURAL TESTS
No.a'b
1
2
Date
Planting
3 March 1976
12 June
of
Harvesting
7 May
29 July


Tomato
c
Tomato
Residue Weight
(g/400 g of soil, dry wt.)
75,150,225,300
2.5,12.5,25.0,37.5
Remarks
Completed
Completed
  Numerals refer to a given set of pots in which crops are being planted sequentially; letters refer to specific rotation
,    in any given set of pots.
  Six residues were tested (CFA,  FSFA, VFA, VSBM,NJFA, and NJSBM), with one set of pots for each residue type,
    and one set as a control.  1,000 cu cm pots were used.
  Cherry tomato.

-------
Experiment 1.

   Procedure. Small plastic pots (10.26 by 10.26 by 10.26 cm with about 1.061 cu cm
volume were filled with a commercial poiting mixture (SupersoiS). The average weight of
potting mixture used was about 400 grams.  The pots were too small to permit the test
plants to complete their entire life cycle.  Residues were mixed into the potting mixture
at application rates of 75, 150,  225, and 300 grams per pot, which corresponds to field
application rates of 67.2,134.4, 201.7, and 268.9 kkg per hectare.   Six residues were
tested: CFA,  FSFA, VFA, VSBM,  NJFA, and NJSBM (these are identified in Chapter 1,
Table 6). There were two control  pots, and  a total of 50 pots used.  Fertilizer was surface-
applied to each  of the soil/residue (and control) mixtures: one gram of ammonium sulfate
as* a source of nitrogen and one gram of monobasic  potassium phosphate as a source of
phosphate and potassium.  These fertilizers were applied in two equal doses of 0.5 grams
each.  The first  application was made two  weeks after planting, and the second four weeks
after planting.

   Germinated cherry  tomato seeds were planted (3 March 1976); each pot was subsequently
thinned to one plant per pot.  There were two replications for each residue application rate;
this  was donee to reduce the impact of genetic and environmental variability on the test
results.  The tomato plants were irrigated once a week.  The plants were harvested on
May 7,  1976.

   Results.  The results are shown In Figure 197 and 198,   (T. represents the lowest applica-
tion rate and T, the highest).  No pictures are shown of  CFA or FSFA because the tomato
plants did not grow at all in those fluid!zed-bed oil gasification residues. The very high
soil  pH produced by the  residues significantly suppressed root development for all residues
at all application rates.   Also, plant growth was significantly less for the test plants than
for the  controls, and higher application rates were associated with reduced growth.  From
this experiment  it was concluded that (1) there are differences among the six residues in
their effects on  plant growth,  and (2) at these high application rates there is a significant
negative impact on plant growth and root development.  Based on these conclusions,  a
second  experiment was devised to test the impact of lower  application rates (below 35 kkg
per  hectare).

 Experiment 2.

   Procedure.   This experiment was identical to the previous one, except as noted.
Application rates were 2.5, 12.5, 25.0, and 37.5 grams per pot, corresponding to field
application rates of 2.2, 11.2,  22.4, and 33.6 kkg per  hectare.  Three replications were
performed for each application rate, and two controls. There were seventy-four pots used
in total.  Fertilizer was  applied as above and the plants  were irrigated once per week, with
the  exception that of the first three weeks when exceptionally warm  weather required
irrigation twice per week.  Planting occurred on 12 June 1976, and harvesting on 29 July
1976.   Above-ground plant tissues were digested and analyzed using  the procedures out-
lined in Appendix A.


                                         207

-------
          Exxon, New Jersey fly ash
     Exxon, New Jersey spent bed material
Figure  197. Experiment 1, tomato plant growth
                    208

-------
           PER, Virginia fly ash
 PER, Virginia, and Exxon, New Jersey fly ash
Figure  198. Experiment l^omaro plant growth .
                     209

-------
   Results.  Photographs taken of the plants just before harvesting are shown in Figure 199.
The impact of residue application on plant growth is given quantitatively in Table 74 and
graphically in Figures 200 and 201 .  Table 74 presents the wet and dry weight and the
ratio of wet to dry weight.

   The results show a significant improved growth response at application rates of 2.2 and
11.2 kkg per hectare for CFA,  FSFA, VFA,  and NJFA  residues. For these same residue
types,  growth was repressed at 22.4 and 33.6 kkg per hectare application rates.  There
was a significant positive growth response at all application rates for the VSBM, and
NJSBM residues.  Percent dry weight increased from 5 to 80 percent for all residue types
for application rates of 2.2 and 11.2 kkg per hectare. For CFA, percent dry weight
decreased significantly at a 22.4 kkg per hectare application rate.

   The potting mixture used in the experiments had a high ievel of humic acid and, con-
sequently, a low pH (about 5.5).  Since the fly ash and spent bed residues are quite alka-
line, adding them to the potting mixture raised soil pH (as  shown in Tables 75 and 76).
The effect on plant growth plotted against soil pH is presented in  Figure 202.  The figure
shows growth improvements (in comparison to the control) when pH was in a range from
6.2-7.8.  This improvement is almost certainly at least partially the result of the residues
having increased the pH to more optimal values.

   The biodegradatlon of the  residue materials by soil microorganisms may also have re-
leased micronutrienfs for plant uptake.  If the pH adjustment mechanism were beneficial,
one would expect it would make little difference what type and source of fluidized-bed
residue were used.  But,  as Figure 2Q2 shows, there is considerable variability in results
for a given pH.  Since the various residues differ substantially in  chemical composition,
it may be  tentatively assumed that this dispersion reflects differences in the availability
and quantity of nutrients that were provided  to the plants in the residues.

   Results for chemical analyses of plant tissues are given in Table 77, and graphically
in Figures 203  fe 208»   Tomato plants grown on residue-treated soil showed significantly
lower concentrations of analyzed heavy metals than the control plants.  This effect is
undoubtedly pH-related,, For the most part,  sulfate  concentrations were not significantly
different for treated and control plants.   Exceptions were FSFA/lL, VFA/T., NJFA/T9/
and NJSBA/VX, Lj, and T^.  There was no significant difference in the concentration
of magnesium between the control and residue-treated vegetation except for NJFA/X-.
All residue-treated vegetation (except VFA/TJ showed significantly higher concentrations
of calcium, which is associated with Improve*!cell turgidity.  Although the calcium con-
centration was higher in the treated plants, they did not show signs of a toxic calcium
level.

   From this experiment, it appears that residues applied at reasonably  low concentrations
increased the soil pH and therefore restricted the uptake of heavy metals by plants, and
even reduced their concentration En plant tissues.   Excessive concentrations of heavy metals
in plants utilized for direct or indirect human consumption are undesirable;  specifically
any food with an increased cadmium metal content is considered  dangerous for human

                                       210

-------
 Control
             '1        '3

        PER, Virginia fly ash
               Control  T    T.   1    T
                              2.    o    4

              PER, Virginia spent bed material
Control  T
    Exxon, New Jersey fly ash
                                              Conh-ol  T,    T2    T3
        Exxon, New Jersey spent bed material
  Control T
           ,
Esso, England cyclone fly ash

                  Figure 199.
           Control   T
             Esso, England fines, stack fly ash

Experiment 2-A, tomato plant growth.
                                     211

-------
TABLE  74.   EXPERIMENT 2-A: TOMATO PLANT
             GROWTH RESULTS
Application
Treatment Rate
Code0 (kkg/ha)
Control 0
CFA 2.2
11.2
22.4
33,6
^ FSFA 2.2
to
11.2
22.4
33.6
VFA 2.2
11.2
22.4
33.6
VSBM 2.2
11.2
22.4
33.6


*,"
31
30
34
15
5
33
27
19
14
36
37
36
43
43
39
35
35

Plant Height
«2B
28
30
33
20
16
35
35
22
9
43
43
43
37
45
40
35
43

(cm)
|3
*»-O
17
29
35
11
13
41
36
19
8
45
45
47
43
40
41
36
37
(continued)
Mean
Height
(cm)
25.3
29.6
34.0
15.3
11.3
39.6
32.6
20.0
10.3
41.3
41.3
42.6
42.3
42.6
40.6
35.3
' 38.7

Green
Weight
of Shoots
(9)
40.0
31.1
57.5
11.4
5.3
62.0
55.0
15.0
13.0
48.8

60.2
64.3
64.4
61.6
28.3
40.0

Dry
Weight
of Shoots
(g)
3.5
4.9
5.2
0.7
0.5
5.5
4.7
1.4
0.9
5.6

6.3
4.2
6.4
5.7
1.9
3.7

Ratio of
Dry to Wet
Weight
8.75
16.55
15.29
4.57
9.43
13.88
14.41
7.01
8.73
13.55

10.46
6.53
9.93
9.25
6.71
9.25


-------
                                                   TABLE 74 (Cont.)
CO
Treatment
Code
NJFA



NJSBM



Application
Rate
(kkg/ha)
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6

Rb
Rl
43
33
10
5
37
45
43
37
Plant Height (cm)
R2b
36
40
8
8
39
43
45
32

R3b
39
34
3

42
44
37
30
Mean
Height
(cm)
39.3
37.0
7.0
6.5
39.3
44.0
41.6
33.3
Green
Weight
of Shoots
(g)
55.1
38.7
3.9
4.8
35.6
35.2
75.9
33.6
Dry
Weight
of Shoots
(g)
5.4
3.4
0.3
0.4
3.0
3.0
6.0
3.2
Ratio of
Dry to Wet
Weight
9.80
8.78
7.69
8.33
7.63
8.52
7.90
9.52
        i Residue source code presented in Table 6.
         Replicate

-------
 D)
"5

 8   20
15


10
                                                                             e
                D  VFA
                A  FSFA
                O  CFA
                                                                       I
                             10                  20                   30

                                        Residue Concentration (kkg/ha)

Q-See Table 6  for explanation of letter code.

                       Figure, 200.   Mean tomato plant height, Experiment 2: VFA, FSFA, CFA
                                                                                      40

-------
to
Cn
               45  r-
               40  -
               35  -
               30


               25
           §   20
               15


               10


                5
                  0
O  NJSBM
D  VSBM
O  NJFA
        10
                                                          I
                                                  I
        20                  30

Residue Concentration (kkg/ha)
40
          See Table  6  for explanation of letter code.


                        Figure 201 .  Mean tomato plant height: Experiment 2: NJSBM, VSBM, NJFA.

-------
Application
Treatment Code Rate
(kkg/ha)
Control
CFA



FSFA



VFA



VSBM



NJFA



NJSBM



0
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2 _
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6

R C
Rl
5.52
7.01
7.43
6.91
7.71
7.07
7.72
7.53
8.22
7.52
7.18
7.59
7.11
6.33
8.21
8.73
7.91
6.83
7.80
8.29
7.42
8.72
7.32
6.61
6.63
Soil
R/
5.62
7.23
7.22
7.72
7.62
7.01
7.51
7.72
10.32
8.49
6.82
7.81
7.83
6.91
7.26
7.51
7.75
6.50
7.69
8.51
8.50
7.62
8.01
8.11
6.42
PHb
*3C
5.55
7.20
7.32
7.70
7.81
7.20
7.73
8.20
9.73
7.62
7.64
6.48
6.31
6.81
7.56
7.92
7.72
6.42
7.25
8.21
6.81
6.91
7.68
8.39
7.42

Mean
5.56
7.14
7.32
7.44
7.71
7.09
7.65
7.81
9.42
7.87
7.21
7.29
7.08
6.68
7.67
8.05
7.79
6.58
7.58
8.33
7.57
7.75
7.67
7.70
6.82
,  Residue source code presented in Table 6.
  Soil and water mixed in 1:1 ratio.
  Replicate
                                         216

-------
     TABLE 76. pH OF SOIL RESIDUE MIXTURE AFTER CROP 2 HARVEST
Applicatioi
Treatment Code Rate
(kkg/ha)
Control
CFA



FSFA



VFA



VSBM



NJFA



NJSBM




2.2
' 11.2
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22,4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
2.2
11.2
22.4
33.6
n
R,°
6.7
6.73
7.54
7.17
7.13
7.21
7.80
8.04
8.33
7.14
6.34
7.15
6.76
5.90
7.36
7.82
7.31
7.27
7.75
8.30
6.20
6.24
6.81
7.66
7.35
Soil
R2°
7.1
6.70
6.90
7.60
7.80
7.20
7.60
8.00
7.50
7.60
7.10
6.80
6.30
6.60
6.64
6.71
7.33
6.70
7.0
8.0
6.50
6.12
7.13
7.10
7.60
PHb
R3°
6.9
7.30
7.10
7.40
8.20
6.80
7.40
7.00
8.50
7.40
6.90
7.20
6.20
6.40
7.33
7.43
7.42
7.30
7.0
7.70
6.50
6.21
6.82
6.90
7.50

Mean
6.90
6.91
7.18
7.39
7.90
7.07
7.60
7.68
8.11
7.38
6.78
7.05
6.42
6.30
7.11
7.32
7.35
7.09
7.25
8.00
6.40
6.19
6.92
7.22
7.45
.Residue source code presented in Table 6,
 Soil and water mixed in 1:1 ratio.
 Replicate
                                     217

-------
CO
          45
          40
          35
          30
       o
      r 25
       CO
         20
          15
         10
                                          I
I
                  Legend

                  •  VFA
                  A  VSBM
                  O  NJFA
                  O  FSFA
                  D  NJSBM
                  •  CFA
I
                           6789
                                              Soil pH
                       Figure 202..  Tomato plant growth vs. so?l pH, Experiment 2.
                            10

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TABLE 77.  TOMATO PLANT DIGESTION ANALYSIS RESULTS FROM EXPERIMENT 2
Treatment
Control
CFAA,
CFAA2
FSFAA1
FSFAA2
VFAAT
VFAA3
VFAA4
VSBMA1
VSBMA2
VSBMA4
NJFAA1
NJFAA2
NJSBMA1
NJSBMA2
NJSBMAo
o
NJSBMA4
Ca
0.08
0.19
0.19
0.22
1.22
0.12
0.05
0.37
0.17
0.16
0.56
0.12
0.15
0.38
0.30
0.86
0.66
Mg
0.158
0.197
0.145
0.155
0.202
0.153
0.151
0.148
0.211
0.102
0.140
0.135
0.523
0.182
0.130
0.178
0.170
s%°<
1.65
1.50
1.00
0.60
4.30
1.40
0.80
2.30
1.60
0.50
1.90
0.90
3.75
2.60
1.60
3.70
3.40
Mn
ppm
68
93
14
3
14
18 .
17
6
N.D.
N.D.
N.D.
22
N.D.
16
10
12
N.D.
Zn
ppm
51
20
2
20
2
10
5
4
2
7
3
6
0.1
1
1
N.D.
4
Fe
ppm
130
90
N.D.a
N.D.
N.D.
90
30
30
N.D.
40
60
70
N.D.
20
20
N.D.
40
  N.D. = None detected.
                                 219

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to
S3
O
                                                              Legend


                                                              O  CFA

                                                              A  FSFA

                                                              O  NJFA

                                                              O  NJSBM
                                                              D  VFA

                                                              D  VSBM
                                    ]Q                    2Q                    30


                                                    Residue Concentration (kkg/ha)



                         Figure 203.  Calcium content in digested tomato plant tissue;  Experiment 2.

-------
K>
                                    10
    Legend
    O  CFA
    A  FSFA
    °  NJFA
    0  NJSBM
    D  VFA
    D  VSBM
20
30
40
                                                   Residue Concentration (kkg/ha)

                       Figure 204   Magnesium content in digested tomato plant tissue :   Experiment 2,

-------
K>
ro
          160


          140
I
       ,? •  80H
Legend
O  CFA
0  NJFA
2  NJSBM
D  VFA
D  VSBM
A  FSFA (T , T2/=Oppm)
                                                       20   ~                30

                                                 Residue  Concentration (kkg/ha)

                       Figure 205 .  Iron content in digested tomato plant tissue: Experiment 2.

-------
                  90 _
ro
10
CO
                                         10
Legend

D  VFA


O  CFA

A  FSFA


O  NJSBM


O  NJFA

D  VSBM(Tr
                                                                        T4=0ppm)
       20                    30



  Residue Concentration (kkg/ha)
40
                         Figure 206 .  Manganese content in digested tomato plant tissue:  Experiment 2.

-------
'10
                                                                  Legend
                                                                  O CFA
                                                                  A FSFA
                                                                    - VFA
                                                                  D VSBM
                                                                  Q NJFA
                                                                  O  NJSBM
                                                              20                    30

                                                       Residue Concentration (kkg/ha)
                            Figure 207.  Sulfate content in digested tomato plant tissue: Experiment 2,

-------
ro
K>
Oi
                                         Legend


                                         D  VFA


                                         °  VSBM


                                         Q  NJFA


                                         0  NJSBM

                                         A  FSFA

                                         O  CFA
                                      10
      20'                  30




Residue Concentration (kkg/ha)
40
                           Figure 208  .  Zinc content in digested tomato plant tissue: Experiment 2,

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consumption.  Soils containing low pH, high heavy metal levels, or deficiencies in trace
metals appear to benefit most from residue application.

                        Marketing Analysis Methodology

   The method of estimating the potential market for fluidized-bed residues in specific
applications involved converting data on prices of transport, residues, and conventional
materials into the cost-equivalent distance that residues could be economically  hauled,
and then using data on power plant locations to determine the geographical extent of the
potential market.  Figure 209  shows the location  of large coal-fired power plants  in the
United States  and adjacent areas within a 240 and 480 km range of the plant. The 240
km distance is shown because after approximately that location it may be more economical
to ship by rail. 54 The  480 km distance is shown  only for comparative purposes in order
to illustrate that increase in market area coverage may not be proportional to the  increase
in travel distance from power plants.  Established market patterns that are not easily disrupted,
price rfatio. changes as market penetration increases, and other factors could limit  pene-
tration .

   The value  attributed to residues for any given use should not be considered as the es-
timate of its market price. First, the residues have more than one possible use.  For each
use there will be a certain relationship between the demand for the residues and their
delivered price. The aggregate demand relationship for the residues will be the sum of
the demand functions for the different uses.  Second,  the willingness of sources  to supply
residues  at various prices would also influence their market price.  In other words, market
price is determined by the interaction of both  demand and supply conditions, not just by
use value.

   The most direct method of estimating the value of a substitute input to a production
process is to raipute its value from the cost of the inputs replaced by the  new input, hold-
ing the output constant. Suppose,  for example, that  1,000 kg of peanuts could be grown
on a given plot  using either 100 kg of ordinary lime (the conventional input) or  by using
200 kg of spent  bed material from a fluid!zed-bed power plant (the new input).  Suppose
further that the  delivered price for  ordinary lime  is $2 per kg and that there is no  established
market (and thus no price) for  the residues.  In this situation, the imputed value of the
residues would be $] oer kg (delivered),  based on 200 kg ($200) residue  equalling  TOO kg
($200) of lime as a so!  conditioner. This means that  if a market for residues were  es-
tablished, a rational producer would switch from  lime to residues if their delivered price
was less than $1  per kg.

   Sometimes  it  may not be possible to impute the value of the residues in a given  applica-
tion from the cost of the displaced inputs.  This would be the case if it cannot be  readily
determined how  much of which inputs can be replaced by a  unit of the new input at the
given output level.  In such as case, it may be possible to impute the value of the residues
from  their impact on output.  Several examples are given below to illustrate the method
and its pitfalls.

                                        226

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K)
*-J
        Legend

       •   Power plant site
           0-240 km from power plant

                  km from power plant
    Source:  54.
                                 Figure 209  .  Distance to large U.S.  coal-fired power plants.

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       If the experimental data available indicated that 200 kg of residues yielded 1,000 kg
 of peanuts and that the price of peanuts is $0.50 per kg, we could not conclude that the
 value of the residues is $2.50 per kg (1,000 x 0.50/200).  It is likely that, even without
 any residues, some peanuts would have been produced.  Suppose, then, that without any
 inputs 500 kg of  peanuts would  have been produced. Again,  this does not  imply that the
 value of the residues is $1.25 per kg (500 x  0.50/200)  since other inputs might be able
 to achieve  the same result (in this case 100 kg of lime).  Taking the example a bit further,
 suppose that 300 kg of residues  would yield 1,400 kg of peanuts.  The value of the extra
 output would be  $200 and the residues would still be replacing $200 worth of lime.  Could
 we conclude from this that the proper input value for the residues is $1.33 per kg? Perhaps,
 but only if  several restrictive conditions were shown (or assumed) to hold.   The imputed
 value would be wrong, for instance, if a higher  lime application rate could achieve the
 same yield. It would also be wrong if a third input (a source of sulfur,for example) could
 be used in conjunction with lime to achieve the  same yield.  This would be the case where
 the residues serve a function not served by the input being replaced.  The problem with
 imputations based on output changes is  that they may misrepresent the situation. The
 appropriate question with respect to any imputed value for an input is, whether or not a
 rational producer would adopt that input  if its price were less than the imputed value. If
 not,  then the imputed value is invalid.

   The delivered cost of standard quality  residues is a prime consideration to the potential
 user.  Most of the ash currently being reused is removed by  a broker (or the ultimate user)
 at no cost to the  utility.  In that situation, the price (or cost) to the user will represent
 charges for  (1) pick-up, (2) transport, (3) quality standardization, and (4)  profit to the
 broker.  For purposes of analysis, the broker profit will  be neglected,  although a fixed
 percentage  could be included  in the calculation. For many reuse applications it is im-
 portant that the chemical and  physical characteristics of the residues are standardized
 within reasonable limits.  Variations in residue parameters may limit its usability.  Ob-
 viously, for some applications, physical and chemical variations would be  significant; for
others they may make little difference.   For  certain uses it has been estimated that the
delivered price of fly ash assuming uniform quality could  be as high as $10 to $14 per kkg.

   Shipping costs will  affect the delivered prices for residues and virgin raw materials.
With widespread adoption of fluidized-bed processes, most areas of the nation (with the
possible exception of the West) will  have ready,  close-by access to residues,  in many
cases, access to residues may even be better than for alternative conventional raw materials.
Approximate truck transport costs are $0.04 per kkg/km (with 18 to 27 kkg per truck).
For short hauls, an extra charge of $1.00 for loading and the same charge for unloading
has been assumed.  As stated previously,  the maximum efficient range for truck transport
is  estimated to be about 240 km  (depending on road  conditions), since at that distance
the driver can get to his destination, unload, and return on the same day,  while avoiding
overtime and other costs for a  layover.  4 For rail transport, a car-lot is about 50-54 kkg
and transport cost about $0.02 per kkg/km,  plus  an  additional fee for shaking the car to
 complete unloading.  It should be noted that rail freight rates discriminate about 20 percent
against secondary materials (such as fly ash)  in comparison to primary materials.
                                        228

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   Although current practice provides zero-cost pickup of residues from some power plants,
it may be reasonable to assume that utilities must generally pay to have them removed.
The value of the fly ash to them is not zeio, but rather is less than zero by the unit they
have to  pay to dispose of the residues.  The cost of land disposal has been,  and is projected
to continue increasing in response to: (1) the impact of general  inflation on transport and
handling costs, (2)  increasing scarcity of acceptable,  close-by  landfill sites,  and (3) in-
creasing strict environmental regulations on waste disposal.  Disposal cost will vary from
place to place, but can generally range from  $3-6 per kkg.  Costs may be even higher if
special  treatment is necessary prior to disposal. For example, chemical fixation followed
by landfilling is one method of treatment for the residues from limestone flue-gas desulfurf-
zation systems.  The experience of several firms with that process is shewn in Table 78.

   Thus, certain applications not judged economically feasible  if the residue cost was
zero at  the power plant site may be acceptable if  the power plant paid for removal of the
residues.  Because of the difficulties  in estimating (1)  what the  utility would be willing to
pay for  residue removal, and (2) the cost of insuring adequate residue quality, in the re-
mainder of the analysis, it will  be assumed that these two factors balance one another and
that the residues are available at a zero cost.

                      Economic Analysis of Specific Applications

Concrete.

   Substantial research (discussed above) exists showing  that adding fly ash to concrete
can improve the characteristics of the concrete.  The fly ash can be used to replace aggre-
gate and, because  it is also a pozzolan, a portion of the portland cement.  Based on pre-
liminary research results,  concrete mixtures with approximately 5 percent residue content
dispiay  improved strength characteristics.  Table 79 compares the composition of the op-
timal  concrete mix  (as determined in  the testing program) containing residues to that of a
standard concrete mix (used as a control for the tests).  The table also estimates the cost
savings  from using residues as a partial substitute for aggregate and portland cement which
would result if residues were available at a free delivered price.  This saving would be
$0.50 per kkg of concrete. Since 53 kg of residues would be used in one kkg of concrete,
the imputed value of the residues would be $0.50/53 kg or about $0.01 per kg of residue.
This implies that a concrete producer would (all other  things equal) use the residues if their
delivered price were about $0.01 per kg or less.   To the extent that the improved character-
istics  imparted by the residues to the  concrete results in  a higher matket price for the
concrete, the producer may be willing to pay in excess of $0.01 per kg delivered for the
residues.  Assuming an imputed value of $0.01 per kg, a rail freight rate of $0.02 per
kkg-km, and a zero f .o.b. price for  the residues at the  power plant site, residues could
be rail-hauled a distance up to 472 km and remain competitive.  By truck they could be
economically transported about one-half that distance.

Asphalt.

   Coal ash has been  used  successfully as a replacement for aggregate in  asphalt for some

                                         229

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               TABLE 78 .  SLUDGE FIXATION COSTING ESTIMATES
                       All  values are condition and site dependent
Source
Commonwealth Edison
Company, Will County
Station




Duquesne Light Company,
Phillips Station
International Utilities
Conversion Systems, Inc.
Chemfix
Dravo Corporation
Cost
($Akg,50% solids)

6.50
9.41
5.78
11.00
5.50
7.98

1.65-2.75
5.50
1.65-3.30
Remarks

On-site disposal — vendor quote
Current estimate
Best experience
Worst experience
Target
Total disposal

On-site disposal
On-site disposal
Total cost to customer; includes pump-
ing to 10 mi
  Company Operation - on-site disposal; excludes capital costs.
              TABLE  79,    RESIDUE VALUE FOR USE IN CONCRETE
                      Composition (%)          Value ($Akq)a

                 Control       Residue Added  Control  Residue Added
Item
Cost Reduction
  ($Akg)
Concrete compo-
nent
Fly ash
Aggregate
Portland cement
Water
Total


0
71.5
15.2
13.3
100


5.3
64.7
14.9
15.1
100


0
3.55
8.02
0
11.57


b
3.21
7.86
0
11.07


0
0.34
0.16
0
0.50
  Based on a delivered cost (in Los Angeles) for portland cement of $52.78/kkg and for
,  aggregate of $4.96/kkg.
  Value of residue to be imputed from savings from its use  ($11.57 - $11.07 = $0.50/kkg).
                                       230

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time. For example,  the West Virginia Department of Highways has found that an asphalt
surface coating with  a thickness of 5 to 7.5 cm made from dry bottom-ash and emulsified
asphalt works satisfactorily and its cost is about half that of conventional asphalt.  The
low cost results, from two factors.  First, there is a large, readily available supply of coal
ash located conveniently throughout the state.  Second,  the technology required is simple
and the same as needed with conventional asphalt.  Ash is loaded into a portable con-
tinuous pugmili, frequently located at the power plant site, and mixed with a metered
amount of emulsified asphalt.  Then  it is either loaded directly on trucks or stockpiled for
future use.  The well-graded ash usually requires no additional blending.   Using emulsified
asphalt makes heating and drying unnecessary, thus eliminating the need for relatively
costly hot bins or dryers.

   Other examples of successful use  of coal-ash residues  in asphalt  could be cited. But
even though the technology appears  simple and sound, use in this application has remained
quite limited (approximately 180,000 kkg of residues in 1972)J3l  There does appear to
be a substantial potential market,  however.  In comparison to a delivered (Los Angeles)
price of aggregate of $4.96 per kkg, conventional coal-combustion residues could be
transported approximately 250 km by rail (at $0.02/kkg-km) or 125 km by truck  (at $0.04/
kkg-km) and be competitive.

   Little work has been done on limestone or dolomite modified residues.  Wet-collected
residues from flue gas desulfurization systems appear to have some promise in  asphalt
applications.  However,  if substantial dewatering or drying is required prior to use,  their
cost may be prohibitive.  Fluidized-bed residues are collected dry, and appear to have a
higher potential.  Preliminary tests were conducted to determine the technical feasibility
of using fluidized-bed residues in a mixture with emulsified asphalt.  The results indicated
that up to 92 percent of the aggregate could be replaced.  Table 80 shows the approximate
savings which could  be realized assuming a free delivered price for the residues, and 92
percent replacement. For any given transport distance (or delivered price for residues)
the net savings or costs per unit of asphalt can be easily calculated.

      TABLE 80.  IMPUTED VALUE  OF RESIDUES  IN ASPHALT APPLICATIONS
Item
Asphalt Component
Emulsified asphalt
Aggregate
Fly ash
Total
Composition (%r
_ t , Residue
Confrcl Added

8
92
0
Too

8
0
92
Too
Control

94.53
4.96
0
99749
($/kkg)a
Residue
Added

94.53
0
b
•HBWMW-v
94.53
Cost
Reduction
( $Akg)

0
4.96
0
4~96~
QBased on a delivered cost (an Los Angeles) for asphalt of $93.53/kkg and for aggregate of $4.96,

 Value of residue to be imputed from savings from its use.
                                       231

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Agriculture

    Fluidized-bed residues can improve crop growth and yield by (1) altering pH (the residues
are quite alkaline),  (2) improving soi! structure, (3) providing essential micronutrients
(Zn,Cu/Fe,Mn/B/Cl/AI)/  (4) providing sulfur, and (5) serving as a source for macro-
nutrients (O,C,H,N,P,K,Mg,Ca).  Thus, the residues can serve many functions as an
agricultural input.  The purpose of this analysis is  to estimate the value of the residues
for agricultural applications.  Because both the residues and many conventional agricul-
tural  inputs serve multiple functions,  it is sometimes difficult to identify the inputs which,
in a given  application, could be replaced by fluidized-bed residues.  Therefore, some of
the analysis below will be based on the value  of yield changes.

    Research currently being conducted at the  Virginia Polytechnic Institute and State Univer-
sity   has  indicated that fluidized-bed residues can be used as  a source of calcium for
large-seeded peanuts, at least partially replacing  application of calcium  carbonate.  The
impact of providing a calcium source  and a comparison between equal applications (980
kg/ha) of residue and calcium carbonate on yield were beneficial.  On the average,  both
had a positive impact on yield,with the calcium carbonate increasing yield by  17 percent
and the residue increasing it by 11 percent. However, at the given application rate, it is
implied that the delivered price of residues would  have to be significantly less  than that
for calcium carbonate to make up for  the lower yield obtained.  For example, the de-
livered price of calcium carbonate in Los Angeles,California, is about $13.60  per kkg.
Applying. 980 kg to one hectare would cost  $13.33 for the  material and result in (on the
average) an extra $84 of peanut production.   Because the residues, as a source of calcium,
are not as  good ess calcium carbonate  on an equal weight basis, the farmer would have to
be paid $72.11/kkg to accept residues to make it economical for him to do so.  Since this
payment is unrealistic, use of residues in this application cannot be predicted on the basis
of the field test results.

    However, one factor, transporting costs, suggests that such application could be economically
feasible. Although the calcium content of available calcium carbonate is about 40 percent,
in comparison to the residues' approximate 10  percent, a higher residue application, rate
may result  in matching yields achieved with calcium carbonate. For example, suppose
3,860 kg of residues per hectare could achieve the same yield as 980 kg of calcium car-
bonate per  hectare (this would equalize calcium content).   In this situation,the imputed
value would be $3.40 per kkg and, assuming the residues had a zero f.o.b.price at the
power plant, the economically feasible transport distance would be 170 km by  rail and 85
km  by truck. This is, of course, a hypothetical result and  more experimental work needs
to be  completed before the economic  feasibility of this application can be determined.

   Test pi lot Din Table 81 shows an improvement in yield for the spent bed material versus
the calcium carbonate. As discussed  above, the residues may fulfill several functions in
plant  growth. Apparently in Plot D,  a growth requirement is being met by the residues
                                        232

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 which calcium carbonate does not meet.  The value (relative to calcium carbonate) in
 this application is $250 for increased yield and $13 saved by replacing calcium carbonate,
 for a  total value of $263 per 980 kg. This represents an imputed value for the spent-bed
 material of $268 per kkg. However, there would likely be other inputs capable of filling
 the same need, and the proper comparison would be without that input.  There is some
 evidence that in certain types of soil the fluidized-bed residues will achieve higher yields
 than will ordinary limestone, even at equal application rates.  The VPI study identified
 "Woodstock loamy fine sand" as possibly being such a soil type.
                 TABLE 81.  FLUIDIZED- BED RESIDUES AS A SUBSTITUTE
                   FOR CALCIUM CARBONATE IN PEANUT GROWING
   Material Applied
                        Application Rate                Yield ($Aa)
                             (kg/ha)
                                                   B      C      D      E      Avg
Control                       0            1190   1097   1907   1225    1862     1457
Calcium carbonate          980            1420   1337   2109   1489    1894     1699
Spent bed material           980            1317   1151   2040   1739    1830     1615
Source:  84.
    Fluidized-bed ash and spent bed material are both quite alkaline and hence can be used
 to raise soil pH.  In that function, it is a substitute for slaked iime  (Ca(OH)2). The
 delivered price of slaked lime in Los Angeles is approximately $65 per kkg.  The amount of
 NJFA necessary to cause the  same pH adjustment as the slaked lime  has been estimated to be
 13.5 kg; for NJSBM the equivalent is 5.5 kg.  This corresponds to an imputed value for NJFA
 of $4.80 per kkg and  for NJSBM of $11.80 per kkg.  Again, assuming a zero f.o.b. price at
 the power plant, the NJFA residues could be economically transported 240 km, and the NJSBM
 residues 590 km by rail.  It should be stressed,  however, that these  calculations assume that the
 only function provided by either the residues or the slaked lime is pH adjustment. Since
 this is not the case, it would  be necessary to know the yield response for different types of
 soils and plants to draw firm conclusions on the economic feasibility of this application.  Each
 conclusion would be specific  for a given type of crop and soil condition.

    The market for pH adjustment materials is quite large. On an average, 675-900 kg/ha/year
 of limestone is needed to maintain optimal soil  pH in areas where large quantities of nitrogen


                                       233

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fertilizers are used. For several reasons, one of which is the expense of limestone, less
limestone is used than  is necessary for optimal yields.   It has been estimated that in the   .-
United States, about 80-90 million kkg of limestone could be used annually to advantage.
In those areas where the delivered price  of residues is significantly less than for limestone,
on an equivalent basis it can be expected that farmers would more nearly approach the
optimal level  of application.  The potential market for the residues is therefore substantially
greater than our projected generation rate of 2 to 12 million  kkg per year for 1995. As
discussed previously, however, there are also substantial impediments to large-scale
utilization for this purpose, such as transportation costs and the  need  for farmer education.
                                       234

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                                      REFERENCES

1.    Adams,L.M., J. P. Capp,and E. Eisentnout.  Reclamation of Acidic Coal-Mine
      Spoil with Fly Ash.  U.S. Bureau of Mines Report of Investigations 7504,Apr. 1971 .

2.    Amos,D.F. and J.D. Wright. "The Effect of Fly Ash on Soil  Physical Characteristics."
      In Proceedings of the Third Mineral Waste Utilization Proceedings.  Chicago: U.S.
      Bureau of Mines and I IT Research Institute, March 14-16, 1972, p. 95-104.

3.    Argonne National Laboratory.  A Development Program on Pressurized Fluidized-Bed
      Combustion.  Annual Progress Report, 1  July 1975 to 30 June 1976. Prepared for the
      U.S. Energy  Research and Development Administration and the U.S. Environmental
      Protection Agency.

4.    Argonne National Laboratory.  A Development Program on Pressurized Fluidized-Bed
      Coal Combustion. ANL/ES-CEN-F090  Monthly Progress Report, April 1976. Pre-
      pared for U.S. Energy Research and  Development Administration and U.S. Environ-
      mental Protection Agency.

5.    Argonne National Laboratory.  A Development Program on Pressurized Fluidized  Bed
      Combustion.  ANL/ES-CEN-F091. Monthly Progress Report, May 1976.  Prepared
      for U.S. Environmental Protection Agency.

6.    Argonne National Laboratory.  A Development Program on Pressurized, Fluidized-Bed
      Combustion.  Monthly Progress Report, June 1976. Prepared for the U.S. Energy
      Research and Development Administration and  the U.S. Environmental Protection
      Agency.

7.    Argonne National Laboratory.  A Development Program on Pressurized,Fluidized-Bed
      Combustion.  Monthly Progress Report, July 1976. Prepared  for the U.S. Energy
      Research and Development Administration and  the U.S. Environmental Protection
      Agency.

8..    Argonne National Laboratory.  A Development Program on Pressurized, Fluidized-
      Bed Combustion.  Monthly Progress Report, August 1976. Prepared for the U.S.
      Energy  Research and Development Administration and the U.S.  Environmental Pro-
      tection Agency.

9.    Argonne National Laboratory.  A Development Program on Pressurized,Fluidized-
      Bed Combustion.   Monthly Progress  Report, October, 1976.  Prepared for the U.S.
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131 .  Rossoff, J., and R.C. Rossi.  Disposal of By-Products  from Non-Regenerable Flue
      Gas Desulfurizatipn Systems: Initial  Report. EPA-650/2-74-037-a .  Prepared for
      Office of Research and Development, U.S.  Environmental Protection Agency.
      Washington: GPO, 1973.  (Environmental Protection Technology Series.)

132e  Secretariat, Economic Commisiion for Europe. Activities of the Economic   Commission
      for Europe in the Field of Ash Utilization.  Third Ash Utilization Symposium, Pitts-
      burgh, Pennsylvania, March 13-14,  1973.

133.  Selmezi,  J.G. and R.G.  Knight, "Properties of Powerplant Waste Sludges," Pro-
      ceedings; Third International Ash Utilization Symposium, Pittsburgh, Pa., March
      13-14, 1973.

134.  Shaver,R.G. "A Solvent-Refined Coal Process for Clean Utility Fuel."  In Gould,
      R.F., Pollution Control and Energy Nedds.  Washington, D.C.: American Chemical
      Society, 1973, p. 80-90.       " - -

135.  Simpson,  J.B. and J.E. Richey.  "The Geology of the Sanquhar Coalfield and Ad-
      jacent Basin of Thornhill." Memoirs of the Geological Survey, Scotland, March
      1936.                   — ~

136B  S!onaker,JsF. and JeW, Leonard.  "Review of Current Research on Coal in the U.S."
     JPjoceedings ; Third International Ash Utilization Symposium, Pittsburg, Pa., Marcn
                      "
137.  Smith, P.H.,  "Large Tonnage Use of PFA in England and Other European Countries."
      In Proceedings; Third Internationa! Ash Utilization Symposium, Pittsburgh, Pa., March
      13-14, 1973.

138.  Smith,R.H. "Inorganic Wastes Are a Virtually Untapped Source of Raw Material.",
      Resource Recovery and Energy .Review, 2(4): 14-16, July/August 1975.

139.  Sorg, Thomas J., and Thomas W. Bendixen.  "Sanitary Landfill." In C.L. Mantel I.
      Solid Wastes. New York: John  Wiley & Sons, Inc. 1975, p. 71-114.

140.  Spicer, T.S. and P.T.  Luckie.  "Operation Anthracite Refuse."  In Proceedings of
      the Second Mineral Waste Utilization Symposium. Chicago; U.S. Bureau of Mines
      and I.I.T.  Research Institute, March 18 and 19, 1970, p. 195-204.
                                        246

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141.  Staff of Research and Education Association.  Pollution Control Technology. New
      York: Research and Education Association, 1973,  p. 432-433.

142.  Personal Communication.  R.M. Statnick,U.S.EPA, North Carolina,to Dr. Art Levy,
      Battelle Memorial  Institute,  Columbus,Ohio, March 17, 1976.

143.  Sullivan, G.D. "Coal  Wastes." In Proceedings of the First Mineral Waste Utilization
      Symposium. Chicago: U.S.  Bureau of Mines and  I.I.T. Research Institute, March
      27 and 28, 1968, p. 62-66.

144.  Taylor, W.C. "Experience in the Disposal and Utilization of Sludge from Lime-Lime-
      stone Scrubbing Processes." Combustion.  Oct. 1973,  p. 15-23.

145.  Tennessee Valley Authority.  Processing Sludge: Fluidized Bed Solids Characteriza-
      tion. EPA-IAG-D5-0721 .  Quarterly Progress Report, Jan 1 to March 31, 1976 .
      Prepared for U.S.  Environmental Protection Agency. April 1976.

146.  Tennessee Valley Authority.  Processing Sludge; Fiuidized Bed Solids Characteriza-
      tion. Quarterly Progress Report No. 2, April 1 to June 30, 1976.  Prepared for the
      U.S. Environmental Protection Agency.

147.  Tennessee Valley Authority.  Processing Sludge; Fluidized Bed Solids Characteriza-
      tion. Quarterly Progress Report No. 3, July 1  to September 30, 1976. Prepared for
      the U.S. Environmental Protection Agency.

148.  Tennessee Valley Authority and Office of Agriculture and Chemical Development.
      Processing  Sludges from Lime/Limestone Wet Scrubbing Processes for Disposal or
      Recycle and Studying Disposal of Fluidized Bed Combustion Waste Products. Quarter-
      ly Progress Report, Chattanooga, Tennessee. January 20,  1976.

149.  Environmental and Energy Conservation Division,  The Aerospace Corporation.  Treat-
      ment and Disposal  of Flue Gas Cleaning Wastes from Utility Power Plants; Research
      and Development Status.  Prepared for the Officeof Research and Development,U.S.
      Environmental Protection Agency, March  1976.

150.  Timms,  Albert G., and William E. Goriet.  "Use of Fly Ash in Concrete." Public
      Roads,  Vol. 29,  No. 6,  February 1957.

151.  Transportation Research Board.  Bituminous Emulsions for Highway Pavement.  Prepared
      for Federal Energy Administration. Washington,D.C.: 1975.

152.  Troxell, George Earl,  Harmer E. Davis, and J.W. Kelly.  Composition and Proper-
      ties of Concrete.   2nd ed., McGraw-Hill Pub. Co., Inc.,  New York, 1956.

153.  TRW Systems  Group. Recommended Methods of Reduction, Neutralization, Recovery,
      Or Disposal of Hazardous Waste. Volume  IV. EPA-670/2-73-053 d. Prepared for U.S.
      Environmental Protection Agency. Aug. 1973.

                                      247

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15.4.  U.S. Army Corps of Engineers, "Drainage and Erosion Control-Subsurface Drainage
      Facilities for Airfields," Part XIII, Chap. 2, Engineering Manual, Military Con-
      struction .  Washington, D.C., June 1955, p. 15.

155.  U.S. Department of Commerce.  Energy Research Needs.  PB-207 51 6. National
      Technical Information Service, Oct. 1971,  p.  Ill 1-IV65.

156.  U.S. Department of the Interior. List of Coa! Waste Banks. June 15, 1972,  p.  288.

157.  U.S. Environmental Protection Agency.  A  Solid Waste Estimation Procedure; Ma-
      terial Flows Approach. EPA/530/SW-147.  Washington, GPO, May 1975, p. 6.
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158.  U.S. Environmental Protection Agency.  Development Document for Proposed
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159.  U.S. Environmental Protection Agency. Economic Analysis of Proposed Effluent
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160.  U.S. Environmental Protection Agency.  Proceedings of Second international  Con-
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161.  U.S. Environmental Protection Agency.  Proceedings; Symposium on Flue Gas De-
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162.  U.S. Environmental Protection Agency.  Proposed EPA Regulations on Interim Pri-
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163.  U.S. EPA. Studies of the Pressurized Fluidized Bed  Coal Combustion  Process. EPA -
      600/7-76-011 .   September 1976.                            ~~

164.  U.S. Environmental Protection Agency. Water Quality Criteria.  EPA R3/73/Q33.
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165.  Vogely,  W.A. "The Economic Factors of Mineral Waste Utilization.11 In Proceedings
      of the First Mineral Waste Utilization  Symposium.   Chicago: U.S. Bureau of Mines
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                                       248

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166. Walker,  George W. The Calera Limestone in San Mateo and Santa Clara Counties,
     California.  California Division of Mines  Spec. Rep. 1-B, Dec. 1950.

167. Walker,  William H. "Monitoring Toxic Chemicals in Land Disposal Sites." Pollution
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168. Wen,C.Y.,R.C. Bailie,C.Y.Lin, and W.S. O'Brien.  "Production of Low BTU Gas
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     Washington,D.C.: American Chemical Society, 1974, p. 9-21T

169. Westinghouse Research Laboratories. Evaluation of the Fluidized Bed Combustion
     Process - Volume I. EPA 650/2-73-048A.  Prepared for the U.S. Environmental
     Protection Agency. Dec. 1973.

170. Westinghouse Research Laboratories.  Experimental and Engineering Support of the
     Fiuidizad Bed Combustion Program. 76-9E3-FBCOM-R1,  Monthly Progress Report,
     December 1975. Prepared for the United States Environmental Protection Agency.

171. W3sH~:;"hause Research Laborator?esc  Experimental and ^.^i^r'.sg Support of the
     Fiuidhed-Bed Combustion Program.   76~9E3--FBCOM-R^  'vb.;ivJ> °rogress Report,
     January  1976.  Prepared for the United States Environmental ?«;j*ec son Agency.

172. WesHnghouse Research Laboratories. Experimental', and %i^h...-  "  • ^-port of the
     Floidized-Bed Combustion Pmgmm.  76~9E3-FBCQM-R4l''^. K-,ty~K,'gress  Report,
     February 1976. Prepared for the United States Environmental <*Yofectk*n. Agency.

173. Westinghouse Research Laboratories.  Experimental and Enginepnng Support of the
     Fluidized Bed Combustion Program. 76-9E3-FBCOM-R5.  Monthly Progress Report,
     March 1976.  Prepared for the United States Environmental Protection Agency.

174. Westinghouse Research Laboratories .Experimental and Engineering Support of the
     Fluidized Bed Combustion Program.  76-9E3-FBCOM-R6. Monthly Progress Report,
     April 1976. Prepared for the United States Environmental Protection  Agency.

175. Westinghouse Research Laboratories.  Experimental and Engineering Support of the
     Fluidized-Bed Combustion Program.  68-02-2132.  Monthly Progress  Report,  May
     1976, Prepared for U.S. Environmental Protection Agency.

176. Westinghouse Research Laboratories. Experimental and Engineering Support of the
     Fluidized-Bed Combustion Program.  7th Monthly Progress Report, June 1976.
     Prepared for the U.S.  Environmental Protection Agency.

177. Westinghouse Research Laboratories. Experimental and Engineering Support of the
     Fluidized-Bed Combustion Program.  Monthly Progress Report, July 1976. Prepared
     for the United States Environmental Protection Agency.


                                     249

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1/8.  Westinghouse Research Laboratories. Experimental and Engineering Support of the
      Fluidized-Bed Combustion Program. Ninth Monthly Progress Report,, August 1976.
      Prepared for the United States Environmental Protection Agency.

179.  Westinghouse Research Laboratories.  Experimental and Engineering Support of the
      Fluidized-Bed Combustion Program.  Tenth Monthly Progress Report, September 1976.
      Prepared for the United States Environmental Protection Agency.

180.  Westinghouse Research Laboratories. Experimental and Engineering Support of the
      Fluidized Bed Combustion Program.  Eleventh Monthly Progress Report, October
      1976.  Prepared for the U.S. Environmental Protection Agency.

181.  Westinghouse Research Laboratories.  Experimental and Engineering Support of the
      Fluidized Bed Combustion Program.  Twelfth Monthly Progress Report, November 1976.
      Prepared for the U.S. Environmental Protection Agency.

182.  Westinghouse Research Laboratories.  Experimental and Engineering Support of the
      Fluidized Bed Combustion Program.  Thirteenth Monthly Progress Report, December
      1976.  Prepared for the U.S. Environmental Protection Agency.

183.  Wong^G.S* and A.D. Buck. Detection of Calcium Sulfates and Magnesium Oxide
      in Fly Ash by X-Ray Diffraction (Final Report).U.S. Army Engineer Waterways
      Experiment Station Miscellaneous Paper C-76-5.  Prepared for the Assistant Secretary
      of the Army (R & D)f Department of the Army*  June 1976.

184.  Yeager,K.E. "The Effect of Desulfurization Methods on Ambien; Air Quality." In
      Gould,  R.F, Pollution Control and Energy Needs,  Washington,D.C.: Arnorican
      Chemical Society, 1973, p. 48-68.

 185.  City of Los Angeles, Department of Water and  Power, Sanitary Engineering Division.
      "Complete Analyses of Major Los Angeles Water Sources,  1975-1976 Averages."

186. Personal communication.  Robert R. Reed, Pope, Evans and Robbins, Inc., to Ralph
     Stone, Ralph Stone and Company, Inc., March 23, 1976.

187. Personal communication.  R. C. Hoke, Exxon  Research and Engineering Co., to
     Ralph Stone, Ralph Stone and Company,  Inc., March 19, 1976.

188. Personal communication. M. Alphandary, Esso Research Centre, to Ralph Stone,
     Ralph Stone and Company, Inc., October 13,  1976.

189.  Portland Cement Association.  Soil-Cement  Laboratory Handbook.  Skokie, III.: 1971.
                                       250

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190. Sverdrup, H. V., Martin W. Johnson,  and Richard Fleming. The Oceans— Their
     Physic, Chemistry, and General Biology, (p. 166)  Prentice Hall, Inc., 1942.

191. Chaney, R. L. Crop and Food Chain Effects of Toxic Elements in Sludges and
     Effluents.  Proc. of the Joint Conference on  Recycling Municipal Sludges and
     Effluents on Land. Published: National Association of State Universities and Land-
     Grant Colleges, Washington, D. C.  pp. 129-143, 1973.

192. Procopiou, J., A. Wallace, and G. V. Alexander.  Microelement Composition
     of Plants Grown with Low to High Levels of Sulfur Applied to Calcaneous Soil in
     a Glass House. Plant and Soil, pp.. 44,359-365 (1976).
                                       251

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                                 APPENDIX A

                      LABORATORY ANALYTICAL METHODS

      Chemical analyses were performed on leachate from the laboratory-scale columns,
the pilot scale columns, and test cells.  Environmental Protection Agency methods
(Manual of Methods for Chemical Analysis of Water and  Wastes, EPA 625/6-74-003) were
used for all analyses.  The analyses performed, the methods used, and references for the
methods are shown in Tables A-l and A-2.

      To insure the validity of the test results, EPA-approved quality control procedures
were instituted.  The program involved co-analysis of a series of standards, duplicate
unknowns,  and spiked unknowns.  One duplicate was run for every four samples; where
there were  fewer than four samples, all were duplicated. Spikes were run on one of every
eight samples; for fewer than eight samples, at least one spike was run.  Standards were
scattered throughout the runs to maintain instrument calibration.  All reagents were  checked
for stability on a rotating basis which covered each reagent at least twice yearly.
                                       252

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                     TABLE A-l. SOIL PREPARATORY METHODS
               n                             * A I.L j                   Reference0
	Purpose  	        Method                 (page number)

Total Residue Characterization         Hydrofluoric and perchloric
                                      acid digestion                     1019

 Soluble Fraction Analyses            Water extraction                    935
                                     Acid extraction (1.0 N_
                                      nitric acid)                        935
                                     Base extraction (1.0 N_
                                      sodium hydroxide)                 935

 Cation Exchange Capacity            Sodium saturation                   899

 Tomato Plant Analyses                Wet digestion                         11
   American Society of Agronomy.  Methods of Soil Analysis, Part 2, Madison, Wisconsin^
 ,   1965; except as noted.
    Same as water extraction, except nitric acid  solution was substituted for dist'Hed water.
    Same as water extraction, except sodium hyc. ,,:
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TABLE A-2.  ANALYTICAL METHODS
Parameter
Metals
Aluminum
Arsenic

Beryllium
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Pofastum
Silver
Sodium
Zinc
Physical
Total Dissolved
Solids
Specific
Conductance

Inorganic
Boron
Chloride
Nitrate
PH
Phosphate
Sulfate
Organic
BOD
COD


RC°
X

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X


X




X
X
X
X
X
X

X

X

Performed on Reference6
LCL^ PCL° P D^ Method (page number)
X


X
X


X
X
X
X
X
X
X
X
X
X







X
X
X
X

X

X










X
X

X
X
X

X

X


X

X



X

X

X

Colorimetric
(Eriochrome cyanide R)
Colorimetric (Silver
diethyldithiocarbamate
Atomic Absorption
Atomic Absorption
Flame Emission
Atomic Absorption
Atomic Absorption
X Atomic Absorption
Atomic Absorption
X Atomic Absorption
X Atomic Absorption
Flameless Atomic Absorption
Atomic Absorption
Flame Emission
Atomic Absorption
Flame Emission
X Atomic Absorption


Gravimetric

Electrometric (platinum
electrode)

Colorimetric (Curcumin)
Titrimetric (Mercuric nitrate)
r Colorimetric (Brucine)
X Electrometric
Colorimetric (Ascorbic Acid)
X Turbidimetric

92
9
99
101
103
105
108
110
112
114
116
118
141
143
146
147
155


267

275


13
29
197
239
481 g
277
*
Manometric 1558h

X
X
Dichromate reflux
Low Levels
High Levels for Saline Samples

21
25
       (continued)
               254

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                                    TABLE A-2 (continued)
  RC - Residue characterization.
  LCL - Lab column leachate.
^ PCL - Pilot column leachate.
  PD - Plant digested sample.
  U.S. Environmental  Protection Agency.  Manual of Methods for Chemical Analysis of
  of Water and Wastes. EPA-625/6-74-003 .   Washington, D. C. Office of Technology
  Transfer, US EPA, 1974.
  Analyzed on 1:1 plant/distilled water mixture.
^ American Public Health Association, Standard Methods , Nth ed., Washington, D. C.,
h
  American Society of Agronomy.  Methods of Soil Analysis, Part 2. Madison, Wisconsin,
  1965.
                                       255

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                                  APPENDIX B
                              SAMPLE DATA SHEET
      SURVEY OF Pi LOT PLANTS USING FLUiDIZED BEDS FOR THE COMBUSTION OF
              COAL AND THE GASIFICATION OF HIGH-SULFUR FUEL OILS

We are conducting special studies for the U.S. EPA (Contract No. 68-03-2347; Project Officer,
Richard Chapman: 1346 Willow Road, Menlo Park, California 94025) on the residues from the
fiuldized bed combustion of coal and the gasification of high-sulfur fuel oils.  The purpose of
this questionnaire is  to provide us with basic design Information on the pilot plants covered by
the study to aid in our assessment of residue disposal Impacts. Please complete and return to:
                            Ralph Stone and Company,  Inc.
                            10954 Santa Monica Boulevard
                         Los Angeles, California  90025  USA
                         Phone: (213) 478-1501 and 879-1115
1 .   General Pilot Plant Characteristics
    a.  Name of plant:

    b.  Address:
    c.  Designer:

        Address:
    d.  Operating organization:

2.  Construction Information

    a.  General contractor:
    b.  Construction commencement date:

    c.  Construction completion date:

    d.  Start-up date:	
    e.  Total capital cost:	

3.  General Information

    a.  Number of employees required to operate pilot plant:

    b.  Number of operating days in 1975:	
    c.  Number of days shut down for maintenance,  process modification, etc.

    d.  Estimated annual operating cost:	^^
                                       256

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4.  Operating Information.  Please give design estimates rather than actual operating  values.
    Answer in listed units of measure, if possible; if other units are used, please specify them.
    a.  Bed volume (cu m):
    b.  Quantity of bed material (kg):
     c.  Average bed material feed rate (kg/m?n):
     d.  Average particle size of bed material (cm):
     e.  Mode of operation
        (1)  Number of stages:             	
         (2) (  )  Baich; (  ) continuous (check one)
         (3) (  )  Once through; ( ) regenerated (check one)
     f.   Coal  or oil feed rate (kg/hr):	
     g.   Air requirements  (scfm):	     	
         Fuel hydrogen requirements (scfm):
         Combustion efficiency:
         Power output (kwhr): 	
     k.   Heat released (Btu/hr):
     I.   Please describe number and types of flue gas control equipment (cyclones,  scrubbers,
         etc.).
    m.  Quantities and types of wastes produced.
         solid:
           fly ash:	
           spent bed material:  	____________
         liquid:
           type:	        ; quantity:
           type:    -	; quantity:
                                         257

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4.  Operating Information (cont.)
    n.  Describe handling and storage facilities used for the different kinds of wastes.
5.  Please provide a copy of the results of any analyses which have been conducted on the
    spent bed material and fly ash and copies of recent progress or other reports.

    Use the space below or an additional page for additional comments.

    Thank you for your generous cooperation.
                                        258

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                                  APPENDIX C
                     COLUMN LEACHATE CONCENTRATIONS

    Figures C-1 through C-130 present the amounts of chloride, iron, lead,
nickel, sulfate, zinc, and pH of leachate from the pilot test columns over a period of
eight months.  Tables C-1 through C-5 show the variation in leachate constituents from
residues in the coal mine, sanitary landfill, dolomite and limestone quarry, and sea
water columns.
                                      259

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!'20
T
IH
o
5 80

40








^120
1
fl>
5*

r5 so


40



Figure C-l
Column 2
Limestone
NJSBM
|120
a>
22
t
2 80

Xi 40
\ iV O /
\\J>£X/
1 I 1 \^ } !_...!_ 1 I J 1 J 1 J 1 1 J
Months 12
Figure C-3
Column 4
Limestone

% 120

4)

ft
-/•x 6 G0
I \
, \
"A"M /"' 40
il V' V
LJS. • \
iiit i"~Pi — r i i i i i i i i i i
Figure C-2
Column 3
Limestone
VSBM
-







^~,
, i i iV7"'r 1 i i i I I I 1 t I r -
Months 12
Figure C-4
Column 5
Limestone
VFA


^\

\
\
l
•Kl ^
! \
^i \
A \ \
/ ' \iir^a—
' I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Months 12 Months 12
Legend
Top lysimeter 	
Bottom lysimeter — — » 	 • 	
Top and bottom lysimeters 	 ± 	 A——
Drain 	 — 	
Figures  C-l  -  C-4. Chloride leachate from Columns 2 to 5. Limestone quarry.
                                 260

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                     Figure C-5
                    Column 6
                    Dolomite
                     VSBM
  120
 -g
 'i
 i5 80
  40
     ?i  i  i  i i  i  i  i  i  i
                          I  1  1  1  i t
                    Months     12


                   Figure C-7
                   Column 8
                   Dolomite
                    NJFA
-J20
I
   80

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1J120
J.
T>
J
u 80
   40
                       Figure C-9
                       Column 10
                       Landfill
                        VFA
                                                 ?120
                                                 T>
                                                 O
                                                   80
                                                   40
 '"V\
i  M
V''   x>\
 x. *    v*.^
                                                                      Figure C-10
                                                                      Column 11
                                                                      Landfill
                                                                      VSBM
                      Months
                                                                    Months
                                                                          i  i  i  i  i  i  t  i i
   120
•o

1  00
U
   40
                     Figure C-l 1
                     Column 12
                     Landfill
                      NJFA
                                                 80

                                                                    Figurs C-l 2
                                                                    Column 13
                                                                     Landfill
                                                                    NJSBM
                                                      1  1  1  1  1  1  1  1 f  !  1 I 1  1  1  1  1  1  1
                     Months   12
                                                                           12
              Top lysimeter   — —	
              Middle lysimeler	
              Bottom lysimeter —• — > —
              Drain         •	——-
                                       Legend

                                        Top, middle, and bottom lysimeters  —»—T—
                                        Drain and top and middle lysimeters  —O—0—
                                        Drain and middle lysimeters       —7—v —
         Figures C-9   -   C-12.  Chloride leached from Columns 10 to 13. Sanitary landfill,
                                         262

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  Pi 20
    40 '-
                      FigureC-13
                      Column  14
                      Coal Mine
                      VSBM
        J_l
                                                   CO
                                             Figure C-14
                                             Column 15
                                            Coal Mine
                                             NJSBM
                      Months
                           I  I  ) I  I  I  I  ii  1  I  LI  !  i I  I  I  I
                                      Months     12
  *
  6 80
    40
                      Figure C-15
                      Column 16
                      Coal  Mine
                      NJFA
          i  i  i  i  i   "
                            i  i  i
                                      i  i  i
                                           Figure C-16
                                           Column 17
                                           Coal Mine
                                           VFA
                      Months   12
                                                                     Months
Top lysimeter   	
Middle lysimeter —	
Bottom lysimeter —. — » —
Drain         	
             Legend
Drain ancl middle lysimeter
Top and middle lysimeters
Top and bottom lysimeters
 — v—v—  Drain and bottom lysimeter
—*—*—  Drain & top, middle & bottom
-~»—*—    lysimeters
            Figures C-13  -   C-16.  Chloride leached from Columns 14 - 17: Coal mine,
                                             263

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I  4.0
   2.0
                      Figure C-17
                      Column 1
                       Ocean
                       VSBM
               -o —o —
          I  I I  I  I  I  I  I 1  I  I  I  l_.i,.l_...l.. I
                     Months   12
I
   2.0
   1.0
                    FigureC-19
                    Columns 3 and 4
                    Limestone
                   VSBM and NJFA
                     I  I  I  I I I  I  I  I  I  !--.
                     Months   12
2.0
                                                1.0
                    Figure C-18
                    Column 2
                   Limestone
                    NJSBM
    Jl
   Hi
    M
     IT°r~?~i°"t  I  i..i__ i  i I  i  I  i  i  i  i
                                                2.0
                  Months  12


                  Figure C-20
                  Column 5
                  Limestone
                  VFA
    -0	o~~o —O—o— O	O -*- 0 ——
     II	I  I  I  I  I  1  I  I  I I  I  1  I  I  I  I
                                                                  Months   12
                                       Legend

                           BoHom lysimeter
                           Drain and top lysimcters
                           Top and bottom lysi meters
                           Drain and top and bottom lysimcters
     —a—o-
     	A	A-
     	O	O-
           Figures C-17  -   C-20.  Iron leached from Columns 1 to 5: Ocean and Limestone
                              quarry.
                                           264

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1.0
1.0
                Figure C-21
                Column 6
                 Dolomite
                  VSBM
  Months  12


Figure C-23
 Column 8
Dolomite
 NSFA
                  Months
        12
                                         I
                                          e 2.0
                                            i.o
                                          S. i.o
                                            0.5
                                                Figure C-22
                                                Column 7
                                                Dolomite
                                                 NJSBM
                                                              I I  I  I  I  I  I I  I  I  I  I
                                                             Months   12


                                                               Figure C-24
                                                                Column 9
                                                               Dolomite
                                                               VFA
                                                             Months   12
                                    Legend

                    Top and bottom lysimeters
                    Drain
                    Drain & top & bottom lysimeters
           Figures C-21   -  C-24.  Iron leached from Columns 6 to 9.  Dolomite quarry.
                                        265

-------
  0.5-
| 2.0 -
  1.0 -
Figure C-25
Column 14
Coal Mine
VSBM
i
| 2.0
1.0
' 1 1 1 1 mr-U-lm-L.r±-l 111 1 J J | _] I
Figure C-26
Column 15
Coal Mine
NJSBM
_
-
Months 12 Months 12
Figure C-27
Column 16
Coal Mine
NJFA
J.1.0
0.5
'•*TATi?r~f~^-»- 1 i i i i i i i i i t ]_
Figure C-28
Column 17
Coal Mine
VFA


f O— O— b«v.
' 1 1 1 1 V-P— t 1 I 1 1 1 1 1 1 1 1 1 1
Months 12 Months 12
                                            Legend

                          Middle lysimeter             	
                          Drain & top & bottom lysimefers  — o—-o —
                          Drain and middle lysimeter      — v—v —
                          Top and bottom lysimeter       — *— A —
                          Drain, lop, middle & bottom    —B—• —
                             lysimeters
              Figures C-25  -   C-28.  Iron leached from  Columns 14 to 17: Coal  mine,
                                                266

-------
I
- 8.0
  4.0
                   Figure C-29
                   Column 18
                   Ocean
                    NJFA
      nn
  2.0
                 Months     12


                  Figure C-31
                  Column 20
                  Ocean
                   VFA

                D — — D— -a —
       tiii
                     Figure C-30
                     Column 19
                     Ocean
                     NJSBM
J4.oh
                                             2.0
                                            •o
                                            34
      i  i.i i  i  i i  i  i  i..i  ii  t. 1.1. i  i i
                Months    12
                  Figure C-32
                  Column 1
                  Ocean
                  VSBM
                  Months   .  12
                 Months   12
                                      Legend
                          Drain              	
                          Bottom lysimetcr       —• — • —
                          Top lysimetcr         — — »— —
                          Drain and top lysirneter   —o—o~
                          Incoming water          0
         Figures C-29   -  C-32.  Iron and lead leached from Columns 18 to 20 & 1: Ocean.
                                      267

-------

1?
T)
8
0.2
0.1

1 0.2

0.1

Figure C-33
Column 2
Limestone
NJSBM
i
3 0.4
1 1 1 | 1 T'F^H 1 1 1 1 1 | 1 ! 1 I
Months 12
Figure C-35
Column 4
Limestone
NJFA
_>•>
•**
1
TJ
8 0.2
' 1 | 1 l 1 T=K-"-| i i 1 1 1 1 i | I | |
Figure C-34
Column 3
Limeston e
VSBM
-
- r.
J/| ^
' | i T-Ti^r^P1*!" i i I 1 1 | i l i i I
Months 12
Figure C-36
Column 5
Limestone
VFA


- ,^.-ON
f \ L III IT^i 1 1 1 1 1 1 r 1 l l 1
Months 12 Months 12
Legend
Top lysimeter _____
Bottom lysimeter — « — • —
Drain «_-_-«—_
Figures C-33  -   C-36. Lead leached from Columns 2 to 5: Limestone quarry.
                            268

-------

»w
•o
5
0.8
0.4
1
-i
0.4
Figure C-37
Column 6
Dolomite
VSBM
r «§- 0-8
t>
o
0.4
V i \ 1 1 1 FT— 1_ 1 . i 1 1 II i 1 1 II
Months 12
Figure C-39
Column 8
Dolomite
NJFA
1
0.2
/yv
W \ iV^f^^! 1 I 1 ! 1 ' ' 1 ' 1—
Figure C-38
Column 7
Dolomite
NJSBM
-
_ ^
-1 \
tt\ i i r^t=fei i i_.i t i i i i i i i
Months 12 '
Figure C-4Q
Column 9
Dolomite
VFA
-
-^
/t.-H-'-t— t~4"-t-=t 1 1 1 .1 1 1 1 1 l_l 1 1
             AAonths  12
                            Legend

                  Top lysimefer          	— —
                  Bottom lysimefer        	•	• —
                  Drain               	
Figures C-37   -  C-40.  Lead leached from Columns 6 to 9: Dolomite quarry,
                                  269

-------
* »
I
TO
J5
 0.2
 0.2
                   Figure C-41
                  Column 10
                  Landfill
                  VFA
                    i
                   Months  12
                  Figure C-43
                  Column 12
                  Landfill
                   NJFA
                  Monti*
                                    Legend

                              Top lysimeter
                              Middle lysimeter
                              Bottom lysimeter
 Figure C-42
  Column 11
 Landfill
 VSBM
                                             0.2
                                                               Months   12
Figure C-44
Column 13
 Landfill
NJSBM
                                                                    ' i  '
                                                              Months   12
                                                                               i .1.
          Figures C-41  -   C-44.  Lead leached from Columns 10 to 13. Sanitary landfill,
                                       270

-------




I

TJ
-§0.8



0.4


Figure C-45
Column 14
Coal Mine
VSBM
-



" f\
1 i
/M \
i'lfi \
iil \
I i \V s^
•VI V^---_- X.
/, , r«£E5=t=s ,11111
Months 12



s
]
0.2

Figure C-47
Column 16
Coal Mine
NJFA
>-
-
i^C'TrfV
m \\ i\
riv'H V
/^ '•LvArirar^ i i. .]_l_l_J_
Months 12





f
, E

•o
J
J0.4


0.2

1 , i i 1
Figure C-46
Column 15
Coal Mine
NJSBM
-



i\
l\
II
' W\
f^.f- — vf~\r~-. ^
L^v-^( , iTr", i i i I i I r t i i i
Months 12



|
1 0.4
0.2
1 1 i ? 1 	 	
Figure C-48
Column 17
Coal Mine
VFA
-
-
Mv\
\\
\ \ ,
„„;., 1^ ,11111,111
Months 12
Legend
Top lysimeter
Middle
Bottom
lysimeter 	
lysimeter "~
Figures C-45  -  C-48.  Lead leached from Columns 14 to 17: Coal Mine,
                             271

-------
                 Figure C-49
                 Column 18
                 Ocean
                  NJFA
i  i i  i  i  i I  i_ i  i i._.]..i  I i  i  i i  ;
            Months   12
                  Figure C-51
                  Column 20
                  Ocean
                  VFA
 1.2
.§0.
 0.4
       \  1  1 1  1  )  1 1  1  1  1 1  1  1 I  !  1  1
                                           °-8

                                          •o
                 Months  12
                                                         Figure C-50
                                                         Column 19
                                                         Ocean
                                                         NJSBM
                                                      i  i i  i  j  i i  i  i  i i i  i  i i
                                                          Months    12
                                                      Figure C-52
                                                      Column  1
                                                      Ocean
                                                       VSBM
                                   Legend
                    Top lysi meter
                    Bottom lysimeter
                    Drain
                                           « - « —
          Figures C-49  -  C-52.  Lead leached from Columns 18 to 20 and 1: Ocean,
                                     272

-------



i
1
0.8
0.4


|
3
V
2
0.8
0.4

Figure C-53
Column 2
Limestone
NJSBM
1
"o
u
2
0.8
~<~N A °'4
!U- X f i i t i i t i i i i i ii i i
Months 12
Figure C-55
Column 4
Limestone
NJFA
1
1
o
0.8
vfL
7 i Vf 1 1 1 1 i i 1 1 ! 1 L.J 1 1_!_L
Figure C-54
Column 3
Limestone
VSBM


-
j*A
!xi 1 1 1" 1 I 1 i 1 1 1 ! 1 1 i 1 1 1 1
Figure C-56
Column 5
Limestone
VFA



"A ^
T~f="'f' 'I ! 1 1 J 1 I I 1 1 1 | 1 1 1
             Months   '2
                                                                   12
                                 Legend
                        Top lysimeter       — — ~~
                        Bottom lysimeter     ~~    "~"
                        Drain             •
Figures C-53   -  C-56.  Nickel leached from Columns 2 to 5: Limestone quarry,
                                     273

-------

1
O
-B
2
0.8
0.4



«— >
"«
•8
Z

0.0
0.4


Figure C-57
Column 6
Dolomite
VSBM
!
.s
u
2
0.8
-fr
IK'."-
** 1 1 1 ! 1 till 1 1 ! 1 1 1 | | | 1 |:
Months 12
Figars C-59
Column 8
Dolomite
NJFA
^**
^
J-
"«J
•8
2

0.8

0.4
A^v-A-fl—
KV/^nr iC/t Vi i. i i i i i i i i i_i
Figure C-58
Column 7
Dolomite
NJSBM
-
-
-
/*!>.
£&£\ i i rT~i i i i i i i i i i i i
Months 12
Figure C-60
Column 9
Dolomite
VFA




/•"x
/ /s \ ^-,
-•'f' 1 1 T 1 l 1 ii i 111 1 ti r i 1
              Months  12
Months 12
                               Legend

                       Top lysimeter       	
                       Bottom lysimeter     	 	
                       Drain                    ~
Figures C-57  -   C-60. Nickel leached from  columns 6 to 9.  Dolomite quarry,
                                  274

-------


t~*
1
"
W ^LTT \ ^^^^J""*"
ri j rx^t'-F^Tr^ i i i I ] |_ i j | j |
Months 12
Figure C-63
Column 12
Landfill
NJFA
f
^.
— "5
•iS
z
0.8
0.4
A
j/', ,^p^^>-H i t 1 1 -LJ 1 1 1 1 1
Figure C-62
Column 11
Landfill
VSBM

-

-
f •*
l/^^^
v \ i^r i i i T^I i j i i i i i i i i i
Months 12
Figure C-64
Column 13
Landfill
NJSBM


-
-
/x .. 	 .._.
W T_-'-:^----
»T;\.I i^f-Trr-! i i i i i i i i i .i . i
Ki-_»L, 19
            Months  12
                                 Legend
                      Top lysimeter        	
                      Middle lysimeter      	
                      Bottom lysimeter      	•   •
                      Drain             	—
Figure C-61   -   C-64.  Nickel leached from Columns 10 to 13: Sanitary landfill,
                               275

-------


0.8
0.4



1
•^
Z
0.8
0.4




Figure C-65
Column 14
Coal Mine
VSBM
-8
z
0.£
"•^^
V\ ir'VT^4-"t— 1 i I 1 1 | 1 ' ' ' ' '
Months '2
Figure C-67
Column 16
Coal Mine
NJFA
1
"el
2
0.8
0.4
/•Cx^
^f^i^^/\^rfT/\ i • ' ' > j ' * * r
Months 1 2
Legend
Top lysimeter — —
Middle lysimeter 	
Bottom lysimeter 	 •
Figure C-66
Column 15
Coal Mine
NJSBM
- .
-
vx
^r^r^^,., ..it.,..,,
Months 12
Figure C-68
Column 17
Coal Mine
VFA





i/^^Q?
£1 i i i i iTS , i i i i i i . . i i
Months 12
	 . 	
Figures C-65  -  C-68.  Nickel leached from Columns 14 to 17: Coal mine.
                            276

-------
z
D.O -
 4.0 -
/w
/ 1 l^l 1 1 1
Figure C-69
Column 18
Ocean
NJFA
\
I ! 1 1 1 I 1 1 1 1 1 1 1
                                             c.o
                                             4.0
                                                                Figure C-70
                                                                Column 19
                                                                Ocean
                                                                NJSBM
                                                     _      ~..p._
                                                   1  i  i i  i  r i1 i  i  i  i  i
  8.0
  4.0
                   Months  12

                 Figure  C-71
                 Column 20
                 Ocean
                 VPA
                                           2.0
                                           1.0
        i	i i  I  i  I  i i  i  I  I  I  I  i I  i  t  I
                   Months   12
                                                             Months  12


                                                             Figure C-72
                                                             Column 1
                                                             Ocean
                                                             VSBM
                                                                                i  i
                                                                    12
                            Top lysimeter       	
                            Bottom lysimeter     	 	 -—
                            Drain            	
                            Incoming water         ©
       Figures C-69  -   C-72.  Nickel leached from Column 18 to 20 and 1. Ocean,
                                        277

-------
^3000
  2000
  1000
               Figure C-73
               Column 2
               Limestone
               NJSBM
c
t
  2000
  TOOO
              Figure C-75
              Column 4
              Limestone
              NJFA

fc_i
                                           2000
                                          .1000
                                                    Figure C-74
                                                    Column 3
                                                    Limestone
                                                    VSBM
                                               •/
                                              f\ i  i  i i  i  i  i t  i  i  i i  i  i i  t  i i
                                                                   12
                                          3000
                                    2000
                                    1000
            1  1  1 1 1  1 1  1  1 1  1  1  1 I  1
                    Months
                         12
                                                   C-76
                                                   Column 5
                                                   Limestone
                                                   VFA
                                               /-"TxT^:
                                              />    "-

                                               I  I  '  I '  I  I I  I  .1  I, I  I  I.  I !
                                                      Months  12
                                       legend
                            Top lysimeter
                            Bottom lysimeter
  Figures C-73 - C-76.  Sulfate leached from Columns 2 to 5: Limestone quarry.
                                      278

-------



1
^ 3000
H
2000

1000

Figure C-77
_ Column 6
Dolomite
VSBM



/ \
-jT-^y
' I 1 1 1 1 i 1 >1 1 1 ! 1 \ 1 I 1 I t |
                                              3000
                                              2000
                                              1000
                                                                Figure C-78
                                                                Column 7
                                                                Dolomite
                                                                NJSBM
                                                    \  I 1  1  1  1  1   1  1  I  !  1  1  I 1  I  1
2000
1000
                    Months  12


                Figure C-79
                Column  8
                Dolomite
                NJFA
                                             2000

        1  1  ! 1  1  I  1  1  1  1  1 1  1  1  1  1  1
         12


Figure C-80
Column 9
Dolomite
VFA
                   Montltt   12
  Months 12
                                     legend

                            Top lysimeter
                            Bottom lysimefer
                            Drain
                            Drain and bottom
                              lysimeter
Figures C-77 - C80.  Sulfate leached from Columns 6 to 9:  Dolomite quarry.

                                          279

-------
  400
  200  -
Figure C-81
Column 10
Landfill
VFA
V
2000
t^
vxA
i^J^TLl-^t^*^^ 1 1 1 I 1 1 T 1 1 T 1
Months 12
Figure C-83
Column 12
Landfill
NJFA
1
V
£
"3
*/»
2000
VTK
' -/_ . 1 *-V* — — TTJm» 	 1
f./w"^\
^< \ 1 ^f^""^1,,^,^} I 1 1 T 1 1 1 1 f | |
Months 12
Legend
T !•-•

Middle lysimeter — — 	
Bottom lysimeter —_.__..
Drain
Bottom and middle
lysimeter 	 X 	 X-
I Figure C-82
Column 11
Landfill
VSBM
-
-
ft
1' te£>o^"'
Y j | ^sfZ^»-^t^Ci"*^t -J t 1 I 1 I I I 1 t 1
Months '2
Figure C-84
Column 13
Landfill
NJSBM









-ri'-Vyy^vV-yriw y -jx*_j. i i \ \ \ \ \ \ \ \ \
Months 12



	




 3000 -
 2000 -
 1000 -  _
Figures C-81 to C-84.  Sulfate leached from Columns 10 to 13:   Sanitary landfill,
                                      280

-------
2000
1000
2000
1000
                Figure C-85
                Column  14
                Coal  mine
                VSBM
                                          |
           3000
                                             2000
                                             1000
                     i  ?
                            i  i  i  i  i
                              Figure C-86
                              Column  15
                              Coal mine
                              NJSBM
                                                                  1 1  1  I  1  1  I  1  1  1
               Figure C-87
               Column  16
               Coal mine
               NJFA
                                           „   3000
                                              2000
                                             1000
      i  i i  i  |
                 i
                     i  i  i i  i  i
i  i  i _L
                              Months  12


                             Figure C-81
                             Column  17
                             Coal mine
                             VFA
                  Months   12
                               Months  12
                                      Legend

            Top lysimefer    	      Top, middle, and bottom
            Middle lysimefer	
            Bottom lysimefer  	•	•	
            Drain         ————
          lysimeters
       Bottom and top lysimeters
       Figures C-85 - C88.  Sulfate leached from Columns 14-17:  Coal mine,
                                        281

-------
J.
 »  12000
  8000
  4000
                    Figure C-89
                    Column 18
                    Ocean
                    NJFA
       1  1  !  1 1  1  t  t 1  1  !  !  t  I 1  1  !  !
12,000
 8000
 4000
                    Months  12
                    Figure C-91
                    Column 20
                    Ocean
                    VFA
                                             3000
                                            2000
                                              1000
                                                                 Figure C-90
                                                                 Column  19
                                                                 Ocean
                                                                 NJSBM

                                                    i i  i  i  i  i i  i  i  i  i t i  i  t  i	i i  i
           i ii  i  i  i i  i  11  i i  t  i  i  i i
                    Months   12
                                                               Months   12
                                                                Figure C-92
                                                                Column  1
                                                                Ocean
                                                                VSBM
                                              3000-  -.
                                              2000 -
                                              1000
                                                           I  i  I  l l  1  I  l__l  1  t l  i  i
                                                                  Months  12
                                     Legend

                          Top lysimeter       	— — —
                          Bottom lysimeter     ^—•	•	
                          Drain           	.——
     Figures C-89 - C-92. Sulfate leached from Columns 18 to 20 and 1: Ocean.
                                       282

-------



io.s
5?
H
0.2
0.1




*«•
1
•* 0.3
2
N
0.2
0.1
Figure C-93
Column 2
Limestone
NJSBM
} 0.3
u
c
R
0.2
"^\ x- °J
/ / • \ X x
// \^ \
v' l \
^i Ir^^rl'^-t— ^=~i ! 1 1 1 ) 1 i 1 I I 1 	
Figure C-94
Column 3
Limestone
VSBM


o
- i
.' 1
>fcW^>4^>V^I I I 1 1 1 1 r
Months 12 ™"»» «
Figure C-95
Column 5
Limestone
VFA
!
o °-3
c
R
0.2
0.1
£*fxv3=ttr=v=fcz\ i i i I i i ' i ' i i






1 1 1 1

Figure C-96
Column 4
Limestone
NJFA
-
-
/T-r"t--i~l--t— • >~\ ill. !,., 1 !. .!,..
k^^lU, 19




till
                Months  12
                                    Legend
                        Top lysimcter
                        Bottom lysimeter
                        Drain
                        Top and bottom
                           lysimeters
Figures C-93   -   C-96. Zinc leached from Columns 2 to5 :  Limestone quarry,
                                        283

-------



1
o 0.3
c
tCi
N

0.2



0.1




Figure C-97
Column 6
Dolomite
VSBM





-
/\
/ i
i \
i \
n / A
I / A 1
\* / \i 	 -
f , •'S^— **• f f£ *V"^"^
£,?vrK/ FTT P-i i i i

^0.3
°°~^
a
c
R
0.2



0.1



1 1 ! I t 1 1 1
Figure C-98
Column 7
Dolomite
NJSBM





-




~t^"^
\
/ N
/-A~l. J-Af— Uj.OlA-1 1 1 1 t 1 1 1 1 1 1 1
Wo-*1* 12 Months 12


J 0.3
C
R
0.2
0.1



Figure C-99
Column 8
Dolomite
NJFA





/"V"'"x
/ •' *v
/ / \ N-
/ / \ V'v.
fr-^ — (— p-j-a^n-rofm | j |

^
f o-3
c
R
0.2
0.1


1 1 1 1 ( | f !
Figure C-100
Column 9
Dolomite
VFA



-
x-x\
"~/ \
' /ii
/V'T'T1'
'' i V i r^«»-.^=i i i i i i i i i i i i
              Months  12
                          Months  12
     Top lysimeter    	
     Bottom lysimeter  	 ——
     Drain	
Drain and top lysimeter         — — ——
Drain and bottom lysimefer      — —— 	
Figures C-97  -  C-100.  Zinc leached from Columns 6 to 9: Dolomite
                                                                              quarry,
                                   284

-------
•£ 0.3
o
H
0.2
0,1
 0.3 -
 0.2 ~
 0.1 -
                  Figure C-l 01
                  Column 10
                  Landfill
                  VFA
                                             V  0.3
                                                 0.2
                                                   0.1
                     ]  1  1  1  1  1  1 1  1    |
                                                                          Figure  C-l02
                                                                          Column 11
                                                                          Landfill
                                                                          VSBM
                   Months  12
Figure C-l 03
Column 12
Landfill
NJFA
•£ 0.3
u
c
R
0.2
0.1
Figure C-l 04
Column 13
Landfill
NJSBM
-
/Jf^r=r^^=f^y . II I 1 1 1 i I l 1 1
                    Months  12
                                                                   Months  12
             Top lysimeter    	
             Middle lysimeter	
             Drain          	
                                        Legend
                                              Bottom lysimeter
                                              Top, middle, and bottom
                                                 lysimeters
            Figures C-101   -  C-104.  Zinc leached from Columns 10 to  13: Sanitary landfil
                                          285

-------




J.
o 0.3
c
R
0.2
0.1


Figure
Column
C-105
14
Coal mine
VSBM






/ ^CV£\

Months





5 0.3
1
0.2
0.1





J 0.3


R
0.2
' 0.1

1 1 1 1 [ | 1 1 !
Figure C-106
Column 15
Coal mine
NJSBM





-
/ -jrTY_^
^^fr-,5^17 . . t i t i , i
12 Months 12
Figure C-107
Column
16
Coal mine
NJFA
"*
-
A
I'/vl
//--•YhrV-.
1/7 \VA \_ "^
V, , , V-£
-------
N

2.0
1.5

1.0



0.5




Figure C-109
Column 18
Ocean
NJFA
"
1.5
j.
0
— c
."•\ N '•"
.' \
\
- \ 0.5
/ \
/ X" "^v
// ^ss^
/i i i i i'5r=T=!rj i i i i i i i i i i i
Figure C-110
Column 19
Ocean
NJSBM
—
-



* \
/ \
- . \
1 \
I \
/s~^*. »»-.——
^i i r-r-T-r 1 "i i i i i i i i i i i i
Months 12 Months 12



0.6



0.4


0.2




Figure C-lll
Column 20
Ocean
VFA
|
*tT
c:
R2.0
/ \
1 1
i i
1 *
1 \ 1.0
"~ /
/ ^-_

/^/ ^v,^
^/ i. i i.i iT~i i J i i i i i i i i .i
Figure C-l 12
Column 1
Ocean
VSBM



-
' J
1 |
' I
/ \
/ \
/ ^ \
/./*\ 's.V
j£*£/ i V+^'l i ' J_ 1 J l i i i i L
                     Months  12
                                                                 Months   12
                                       Legend
                            Top lysimeter
                            Drain
          Figures C-109   -  C112.  Zinc leached from Columns 18 to 20 and 1:  Ocean.
                                         287

-------
   16
   12
x
O.
                    Figure C-113
                    Column 2
                    Limestone
                     HJSBM
v   2.
     V
            ,1_L.1._1_. .!_.! .1  1  I  -I—1 ..I--I—t—1-1
    12
I
a.
                    Montis  1 2


                  Figure  C-115
                  Column 4
                  Limestone
                  NJFA
      7°
      I  /•'
        llilltjiilllliJiiJ
                    Months  12
                                                12
                                             Q.
                                                                    Figure C-114
                                                                    Column 3
                                                                    Limestone
                                                                    VSBM
                                                  i  i  i  i i  i  i....i .I..-I...1 i  i.
                                                                Months  12
                                                                               .I—I..
                                               12
                                                                    Figure C-116
                                                                    Column 5
                                                                    Limestone
                                                                    VFA
                                                   !  1  1 1  !  1  L 1 1  1  .1  1  1  1  1 1  1  1
                                                                Months   I2
                                      legond

                           Top lysimeter      	
                           Bottom lysimeter    	  —~
                           Drain           	
         Figures C-113  -   C-116.  pH of leachate from Columns 2 to 5: Limestone quarry.
                                       288

-------
X
a.
-
Y**—
A
: \
\
^
iitii
Figure C-117
Column 6
Dolomite
VSBM

i i i i i i i i i i i i i
   12
                    Months  12
                  Figure C-119
                  CoJumn 8
                  Dolomite
                  NJFA
            |  I  I  l_ l._l  I  I I  I  I ...I-J-1—l—t
                    Month*   12
                                                12
                                                                      Figure C-11 8
                                                                      CoJumn  7
                                                                      Dolomite
                                                                       NJSBM
    il  |  I  III 11  ;  I  I  I I i  I  i _i_j
                 Months  12
12
                                            r
                                             D.
                       Figure C-120
                       CoJumn 9
                       Dolomite
                       VFA
                                                   i  i  i  t i  i  i  i  i  t  i  i i  i  i  i  i  i  i
                 Months  U
                                      Legend
                           Top lysimeter
                           Bottom lysimeter
                           Drain
                           Drain and bottom
                              lysimcter
      Figures C-117  -  C-120. pH of leachare from Columns 6 to 9: Dolomite quarry.
                                        289

-------
 12
12  -
                Figure C-121
                Column 10
                Landfill
                VFA
                                             12
                                           X
                                           a.
      I  I  i  I  i  I  i i  I  I  I  I  I  i I  i  i
                  Months  12

                FigureC-123
                Column  14
                Coal mine
                VSBM
                                                 Figure C-122
                                                 Column  11
                                                 Landfill
                                           VSBM,NJFA,NJSBM
                           j_J..J-L-L.'.J-J-Ti-J  I  I  I  I  i I  I
                                          Months  12
                                           X
                                           CL
                                             12
                 1_LJL
                  Months  12
                                               Figure C-124
                                               Column  15
                                               Coal mine
                                               NJSBM
                                          Months  12
                                                                            ,1  I,...I. .1 J
                                   Legend
           Top lysimeter     	
           Middle lysimeter	
           Bottom lysimeter   —. --
           Drain          	
     Figures C-121
                   Top and middle lysimeters       	*	*—
                   Top, middle, and bottom
                      lyiimeter               -^—*—— i —
                   Drain and top, middle, and
                      bottom lysimr.ters          	»	•—
-  C-124.  pH of leachate from Columns 10 - 15: Sanitary landfill
   and ocean.
                                      290

-------
   12
a
Figure C-125
Column 16
Coal mine
NJFA
        i  i  i  i  i
X
 a.
   12
  Months  12


Figure C-l 27
Column 18
Ocean
NJFA
          3— n— 0-°-
      J__l_L_JLJ_
  _ULJ__UU
                     Months
                           12
x
 a.
   12
Figure C-l 29
Column 20
Ocean
VFA
                                      _u
               _L_I_JL_L
                     Months  ] 2
X
Q.
                                                12
                                   r

                                 -n>o*"~c
                                                    Figure C-l26
                                                    Column 17
                                                    Coal mine
                                                    VFA
                                                    t  I I  I  I  I  I. I.. I.. l_l-i-J_(-J_L-L
                                                                 Months   12
                            X
                             a.
                                                12
                        Figure C-l 28
                        Column  19
                        Ocean
                        NJSBM
      |._.,l-.l-. lr I  I I  I.I  I  I  I 1  I  i  I  i  i
                   Months  12
                                                 12
                                            X
                                            CL
               ..!.. I. .1-1—i


                      Legend
                       Figure C-l30
                       Column 1
                       Ocean
                       VSBM
        i  ,i i  i  i  i  i i  i  i  i  i  i  i i  i  i
                    Months   12
                  Top lysirneter     	Drain and top lysimeter        -
                  Middle lysimeter	Drain and top and bottom
                  Bottom lysimefer   	»—-•	   lysimeters
                  Drain          	—


         Figures C-125 to C-130.  pH of leachate from Columns 16 to 20 and 1;
                           Coal mine and ocean.
                                         291

-------
          TABLE C-l . VARIATION  IN COAL MINE COLUMN LEACHATE CONSTITUENTS
to
rS
Residue
Type

NJFA
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
NJSBM
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
VFA
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
VSBM
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
S

min

700
375
700
—

870
140
90
240

30
280
40
30

80
160
40
30
=

max

1000
990
1000
1000

1250
1280
840
875

1000
1480
1125
1010

1000
1550
1250
1300
Cl

min

12
8
21
12

18
15
18
23

13
20
17
25

19
12
15
24
Range of Concentration
Fe Zn

max

103
60
47
57

63
70
80
60

80
80
39
76

110
96
83
90

min

0.10
0.10
0.10
0.10

0.05
0.05
0.05
0.05

0.03
0.03
0.03
0.03

0.05
0.05
0.05
0.05

max min

0.23 < 0.01 '
0.40 0.01
0.23 0.03
0.40 <0. 01

0.23 <0.01
0.30<0.01
0.25<0.01
0.23<0.01

0 10 0.01
0.25<0.01
O.KK0.01
0.10 <0.01

0.25 0.01
0.40 0.01
0.25 0.01
0.40 0.01

max

0.10
0.20
0.05
0.08

0.05
0.09
0.02
0.05

0.07
0.32
0.06
0.09

0.07
0.07
0.10
0.05
(mg/l)
Ni

min

0.02
0.07
0.04
0.12

0.01
0.01
0.02
0.16

0.06
0.10
0.07
0.03

0.02
0.15
0.04
0.08

max

0.20
0.34
0.17
0.14

0.17
0.12
0.39
0.20

0.09
0.35
0.30
0.20

0.22
0.32
0.20
0.12
Pb

min

0.02,
O.OT
0.02
0.02

0.06
0.02
0.04
0.02.

0.01
0.02
0.02
0.01

0.06
0.02
0.04
0.02

max

0.20
0.20
0.20
0.20

3.20
0.38
0.11
0.22

0.20
0.22
0.19
0.22

0.80
0.63
0.65
0.62
      See Table 6 for residue identification.

-------
          TABLE C-2.  VARIATION IN SANITARY LANDFILL COLUMN LEACHATE CONSTITUENTS
Isi
tS
Residue0
Type

NJFA
Top lysi meter
Middle lysi meter
Bottom lysi meter
Drain
NJSBM
Top lysi meter
Middle lysimeter
Bottom lysimeter
Drain
VFA
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
VSBM
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain


min

35
15
—
63

5
10
10
10

9
12
15
4

140
75
124
170
S04

max

1000
620
675
960

255
500
500
370

207
165
160
25

1365
1370
1250
1260
Range of Concentration
CI" Fe Zn

min

21
22
15
15

10
17
10
15

10
9
12
17

30
32
30
26

max min
ND
64
65
90
40
ND
120
58
87
80
ND
105
56
75
73
ND
120
117
110
115

max
ND
<0
<0
<0
<0
ND
<0
<0
<0
<0
ND

-------
         TABLE 03.  VARIATION IN DOLOMITE QUARRY COLUMN LEACHATE CONSTITUENTS
S3
Residue0
Type

NJFA
Top lysi meter
Bottom lysi meter
Drain
NJSBM
Top lysimeter
Bottom lysimeter
Drain
VFA
Top lysimeter
Bottom lysimeter
Drain
VSBM
Top lysimeter
Bottom lysimeter
Drain
so.

min

1000
ND
1000

165
420
240

35
490
130

300
400
130

max

1360
ND
1500

950
630
510

1100
1120
1280

1500
1100
1100
cf

min

—
ND
14

13
16
17

21
35
15

15
12
15

max

30
ND
60

107
100
95

80
80
80

120
106
96
Range of Concentration (mg/l)
Fe Zn Ni

min

0 ,01
0.01
O.Oi

0,01
0,01
0,01

0.01
0.01
0.01

0.01
0.01
0.01

max min

0,5 0.01
0,5 0.01
Q.5<0.01

0.3 0»02
0.3<0;0'1
0,3<0.01

O.K0.01
0.1 <0.01
0.1<0.01 .

0.5 0.02
0.5<0.01
0.5 0.01

max

0.09
0.09
0.01

0,1
0.02
0.02

0.05
0.12
0.09

0.18
0.02
0.07

min

0.22
0.06
0.02

0.08
0.05
0.13

0.12
0.08
0.13

0.12
0.13
<0.01

max

0.25
0.14
0.30

0.27
0.25
0.30

0.38
0.25
0.20

0.40
0.25
' 0.38
Pb

min

0.04
0.05
0.03

0.05
0.02
0.03

0.02
0.01
0.02

0.05
0.07
0.02

max

0.38
0.17
0.16

0.80
0.20
0.40

0.18
0.19
0.02

0.61
0.57
0.55
       See Table 6 for residue identification.

-------
              TABLE C-4.  VARIATION IN LIMESTONE QUARRY COLUMN LEACHATE CONSTITUENTS
NJ
NO
Ol
Residue
Type

NJFA
Top lysimeter
Bottom lysimeter
Drain
NJSBM
Top lysimeter
Bottom lysimeter
Drain
VFA
Top lysimeter
Bottom lysimeter
Drain
VSBM
Top lysimeter
Bottom lysimeter
Drain
S*

min

1030
1030
1190

—
200
800

500
700
875

980
750
750
4

max

1130
1100
1450

1000
500
450

1125
1250
1000

1680
1125
1000
a"

min

5
13
14

19
--
10

15
14
12

—
—
"

max

78
41
40

70
—
40

105
67
38

no
105
110
Range of Concentration (mg/l)
Fe Zn Ni

min

0.15
0.15
0.15

0.10
0.10
0.10

0.15
0.15
0.15

0.15
0.15
0.15

max min

0.25<0.01
0.25 0.01
0.25 0.01

0.10 0.02
1.50 0.01
0.10<0.01

0.25<0.01
0.25<0.01
0.25<0.01

0.25 0.01
0.25 0.01
0.25 0.05

max

0.01
0.1
0.08

0.10
0.10
0.025

0.012
0.012
0.01

0.05
0.17'
0.02

min

0.13
0.15
0.15

0.10
0.06
0.07

0.10
0.06
0.05

0.02
0.07
0.06

max

0.35
0.43
0.44

0.4
0.32
0.39

0.4
0.38
0.2

0.36
0.38
0.40
Pb

.min

0.025
0.025
0.025

0.025
0.037
0.60

0.02
0.025
0.025

0.05
0.10
0.04

max

0.37
0.16
0.37

0.14
0.2
1.8

0.2
0.19
0.18

0.6
0.78
0.25
          See Table 6 for residue identification.

-------
             TABLE C-5.  VARIATION IN SEA WATER COLUMN LEACHATE CONSTITUENTS
ro
Range of Concentration
Residue

NJFA
Top lysi meter
Drain
NJSBM
Top lysi meter
Drain
VFA
Top lysi meter
Drain
VSBM
Top lysi meter
Bottom lysi meter
Drain
50= Cf
min

3800
2500

1250
2450

1900
3400

1750
1500
1500
max min
ND
7000
8500
ND
2000
2550
ND
6300
6000
ND
3000
2300
2300
Fe
max min
ND
1

ND
0
0
ND
0
0
ND
0
0
0

.0
—

.5
.5

.5
.5

.5
.5
.5
max

5.5
0.5

1.4
1.4

1.5
1.5

3.4
3.4
2.8
Zn
min

0.05
0.06

0.15
0.05

0.12
0.02

0.15
0.1
0.05
max

0.90
0.60

0.90
0.17

0.42
0.12

1.80
0.40
0.40
(mg/l)

Ni
min

0.26
0.06

0.06
0.06

0.22
0.23

0.62
0.80
0.35
max

0.38
0.33

0.24
0.24

0.30
0.27

1.37
1.40
2.0


Pb
min

0.40
0.70

0.15
0.16

0.2
0.63

0.55
0.30
0.30
max

1.60
0.78

1.03
0.85

0.87
0.90

2.25
2.75
3.00
       See Table 6 for residue identification.

-------
                                  APPENDIX D
                  CHARACTERIZATION OF SIMILAR RESIDUES

                                   Coal Ash
    Cpal ash Is primarily an iron-aluminum-silicate material which contains lime,
magnesia, sulfur trioxide, sodium and potassium oxides, and carbon, as well as traces
of heavy metals. Although  the specific composition of a coal ash is mainly dictated
by the geology of the coal deposit and the operating parameters of the boiler unit, many
common minerals are present in U.S. coal.  A breakdown of these minerals is given in
Table D-l .  Table D-2 tabulates a more detailed  compilation of typical coal ash chemical
constituents. The soluble constituents of coal ash from distilled water are summarized
in Table D-3.

    During  combustion,  the inorganic minerals in the coal are subjected  to furnace
temperatures between 1400°C and 1700°C.  At these temperatures the minerals will
react to form muJIite,  quartz, hemmatite, and calcium-sulfate.  The distribution range for
these mineral phcses is compiled in Table  D-4.

    Fly ash generally occurs as fine spherical particulates ranging in diameter frorr  0.5/u
to lOOju, and having an average diameter of 7/u.  The color of fly ash will range from
light tan to  gray to black, depending on the iron  and carbon content.  The pH  of fly
ash will vary from 6.5 to 11 .5 and will average about 11.  A summary of the typical
physical properties of fly ash is presented  in Table D-5.  Figure D-l diagrams the con-
centration range of the major constituents in U.S. fly ash.

    The residue recovered from the bottom of a coal-fired boiler unit occurs as either
bottom ash or slag. These residues are typically composed of gray to black porous,
angular particles.  Depending on the type of boiler process used,  some particles will
have a glassy appearance.

    The fly ash modified by limestone or dolomite injection into boilers will have signifi-
cantly different composition from normal fly ash.  The ash compositions generated by the
combustion of bituminous coal and lignite coal are compared with the ashes obtained in the
limestone and dolomite injection processes in Table  53.

                           Municipal Incinerator Residue

    During  incineration, furnace temperatures are between 980 C  and 1100 C, with
flame temperatures at approximately 1400 C.  This process results in the reduction  of the
incinerated  refuse to 25 to 35 percent of its original  weight and to  less than 10 percent of
its volume.  The resultant residue after quenching is a wet, complex mixture of metal, glass,
slag,  charred and burned paper, and ash.   It is the ash that is important here because its
chemical composition is very similar to that of fly ash from coal-burning boilers.
                                       297

-------
                 ABLED=T_.__£QMMQbLMINERALS
Pyrite, marcasite - FeS2
Chalcopyrite - CuFeS«
Arsenopyrite - (FeS2 • FeAs«)
Stibnite - Sb2S3
Gypsum - CaSO4  •
Calcite - CaCO«
Quartz - SiO2
Siderite - FeCO,
                         (7)
Kaolinite - AI^O
Dolomite -CaMg(CO3)2
Apatite - Ca5(F, Cl, OH)
Mica-KAI2(Si, AI)301Q(OH)2
TABLE D-2 .
Constituents
Silica (SiO2)
Alumina (ALO_)
Ferric oxide (Fe«O_)
Calcium oxide (CaO)
Magnesium oxide (MgO)
Titanium dioxide (TiO«)
Potassium oxide (K«O)
Sodium oxide (Na«O)
Sulfur trioxide (SO )
Carbon (C)
Boron (B)
Phosphorus (P)
Manganese (Mn)
Molybdenum (Mo)
Zinc (Zn)
Copper (Cu)
Mercury (Hg)
Uranium (U)
CHEMICAL CONSTITUENTS OF COAL
Range
20-60
10-35
5-35
1 -20
0.25 - 4
0.5-2.5
1.0-4.0
0.4-1.5
0.1 -12
0.1 -20
0.01 -0.6
0.01 - 0.3
0.01 - 0.3
0.01 -0.1
0.01 -0.2
0.01 -0.1
0.0-002
0.0-0.1
ASH
Average
48
26
15
5
2
1
2
1
2
4
Trace
Trace
Trace
Trace
Trace
Trace
Trace
Trace
"Alkalies
                          Source:
                                      298

-------
      TABLE D-3.  CHEMICAL CONSTITUENTS OF COAL ASH	_
        Soluble Ions	Range (for 1 -1.7% dry solids)
          Co4"4"                             200 - 850 ppm
            r-t,,.y
          Mg                               185 - 400 ppm
          SO4~                             200 - 250 ppm
          K+                               Trace
          Na                               Trace
          PO4~                             0-5 ppm
          BG>3~                             0-10 ppm
Source: 128.
      TABLE D-4. MINERAL PHASES FOUND IN COAL ASH
Phase
Quartz
Mullite
Magnetite
Hematite
Glass
Percent
0-4
0-16
0-30
1-8
50-90
 Source:  126.
                            299

-------
  TABLE D-5.   PHYSICAL PROPERTIES OF FLY ASH FROM PULVERIZED
                             COAL FIRED PLANTS
 Constituents
  Unit
              Range
Range of particle size

Average percent passing No. 325 sieve (44/n)

Bulk density (compacted)

Specific gravity

Specific area/gram
microns

percent

kg/cu m
cu cm,
I/O
   0.5-100

   60-90

1,TOO-1,300

   2.1-2.6

3,300-6,400
Source:  69.
                                300

-------
ou


50


40
g
§
'•J5 30
4-
c

§8
U 20



10






II II
1
1
1
1
1 r
1
1 Range ~
1
1
! ' L
- i !
•
I

! r
i
1
1 1
• !
i i
1 i
* :
i i i i *
SiOo AI2Os FeoOo CaO MgO
fc ij
Constituent
1 1 1


_

1 |
1 / Average
t^
1

-



—



^

t
i
• ^ 4"
SOg Na2O Other Loss on
Ignitioi
Source: 34.
                      Figure D-l .  Concentration range and average of U. S. fly ash consfituents.

-------
In comparison, the fly ash is predominately 200 microns in size, and consists of wood and
paper ash,  aluminum foil, carbon particles, metal pins and wire, glass, sand, and iron
scale. A general analysis of the inorganic components found in fly ash is presented in
Table D-6.  A comprehensive elemental analysis for four different municipal incinerator
fly ashes is presented in Table D-7.  It has also been reported that small amounts of cad-
mium, lead, and mercury have been found in fly ash samples.

                        Sludge From Li me-Limestone Scrubbing Processes

   In Table D-8, chemical analyses of nine sludges collected from nine different lime-lime-
stone scrubbing processes are presented.  The nine different sources or conditions under
which these sludges were produced are listed in Table D-9. The results of an X-ray analysis
performed on these sludges are listed in Table D-10.
    TABLE D-6.  OXIDE ANALYSES OF INCINERATOR FLY ASH FROM TYPICAL REFUSE
               Component                               Total Oxide Content (%)
sio2
AI2°3
Fe2°3
CaO
MgO
Na2O
K20
TiCL
2
S0_
3
P2°5
ZnO
BaO

53.0
8.2
2.6
14.8
9.3
4.3
3.5
4.2

0.1

1.5
0.4
0.1
102.0
Source: 41.
                                          302

-------
                    TABLE D-7.  ELEMENTAL HEAD SAMPLE ANALYSES OF MUNICIPAL
                                INCINERATOR FLY ASHES (% by weight)
Sample
F-l
F-2
F-3
co F-4
CO
Sample
F-l
F-2
F-3
F-4
Ag
0.02
0.01
0.07
0.01

Ni
0.04
0.03
0.03
0.02
Al
11.63
11.03
13.31
11.51

P
0.76
0.63
0.60
0.63
Ba
0.11
0.09
0.23
0.11

Pb
0.50
0.40
0.26
0.38
C
5.16
0.68
0.42
11.18

S
0.47
0.40
0.51
0.32
Ca
5.23
6.09
4.25
4.16

SI
17.98
22.88
20.57
18.03
Cu
0.08
0.13
0.06
0.05

Sn
0.18
0.14
0.13
0.18
Cr
0.11
0.06
0.05
0.06

Ti
1.54
1.13
1.88
1.41
Fe
3.22
3.21
2.05
2.11

Zn
0.74
0.60
1.50
0.63

1
0
1
1


0
0
0
0
K Mg Mn
.66 0.99 0.40
.76 0.94 0.11
.12 0.99 0.07
.92 0.92 0.15

Au
.01
.01
.01
.01
Na
1.93
2.28
1.55
1.09





Source: 33.

-------
                    TABLE D-8.  WET CHEMICAL ANALYSIS OF SLUDGE STANDARDS0
STD 1
SiO2
AI203
Fe203
CaO
MgO
Na2O
CO
2 K20
TiO2
?205
CO2
SO2
S03
CaCO3
46
23
13
4
0
0
2
1
0
2

0
5
.7
.2
.7
.7
.9
.3
.6
.5
.3
.6
-
.8
.9
STD II
1.5
0.32
0.27
49.6
0.54
0.04
0.17
<0.02
0.05
29.2
11.7
3.5
65.7
STD III
30.7
6.6
8.6
22 .7
1.5
0.50
1.1
0.26
0.11
5.3
5.8
6.5
12.0
STD IV
0.79
0.05
0.18
42.5
0.10
0.03
0.05
<0.02
0.06
3.7
38.8
3.3
8.4
STD V
19.4
6.8
5.4
27.6
3.2
0.08
0.24
0.32
0.08
7.2
2.2
12.3
16.3
STD VI
1.1
0.01
0.09
52.5
0.52
0.02
0.14
< 0.02
0.13
36.6
6.3
0.5
80.6
STD VIA
27 .7
14.7
8.3
24.2
0.70
0.16
1.2
0.79
0.19
15.3
3.4
<0.1
34.7
STD VII
4.6
2.3
1.6
40.1
0.20
0.05
0.29
0.11
0.08
13.6
5.4
24.9
30.9
STD VIII
1.2
0.48
0.72
42.5
0.90
0.05
0.07
<0.02
0.06
11.5
24.1
8.4
26.1
STD IX
2.0
0.45
0.72
46.2
0.40
0.04
0.21
<0.02
0.07
24.4
13.7
4.4
55.4
a Standards are identified in Table D-9.
Source: 144.

-------
        	TABLE D-9.  IDENTIFICATION OF ARCS SLUDGE STANDARDS	
        Standard   	Description	

           I           Fly ash from Connecticut Light and Power Company's Devon Station.
           11          C-E sludge0—CaCOa •  150% of stoichiometric.  2,000 ppm SO2.
           Ill         Kansas Power and Light sludge.
           IV         C-E sludge—-Co (OH)2.  38% to 50% of stoic hiometric.  50 to 60%
                      SC>2 removal.  Slurry feed 830 liters/min.  Recycle 625 liters/min
                      with 210 liters/min blowdown.
           V          Union Electric sludge.
           VI         C-E sludge—CaCOg. 150% of stoic hiometric.  45 to 55% removal.
                      No recycle.
           VIA        Standard VI plus 50% Standard I (fly ash).
           VII         C-E sludge—300 to 325% of stoichiometric. 64% SO2 removal.
                      135 kg/hr fly ash. 250 kg CaCO3.
           VI11        C-E sludge—120 to 130% of stoichiometric  Ca(OH)2.  90.8% re-
                      moval. 450 liters/min Ca(OH)2 slurry underbed.  Inlet  SO2 860 to
                      840 ppm. Outlet SC^ 80 ppm.  65 kg/hr Ca(OH)2. No fly ash
                      addition.
           IX         C-E sludge—830 liters/min H2O spray. 125 kgAr lime feed.  150 C
                      reaction temperature.
a Sludge from the Combustion Engineering pilot plant.
Source: 144.
                                      305

-------
          TABLE D-10. X-RAY ANALYSIS OF APCS SLUDGES
 Standard	Major	Minor	Trace

    I         SiO2                 Fe0O0              CaCO^
Source: 144.
    III        Si00                 Fe304              3AI2O3-SiO,
                2                 CaCOs              Ca(OH)2
                                  2CaSO3-H2O         CaSO4
                                                     MgO
IV 2CsSO3-H2O
V SiO2
CaC03
VI CaCOs
VIA CaCO3
VII 2CaSO3-H2O
VIII 2CaSO3-H2O
IX CaCOs
—
CaSO4-2H2O
2CaSOs-H2O
SiO2
2AI2O3^2SiO2
CaCO3
CaCOs

Si O2
Ca(OH)2
2CaSOs-H2O
Fe304
3Al2O3-2SiO2
CaSO4
SiO2
2CaSOs*H2O
CaSO4
Fe203
2CaSOs*H2O
CaSO4-2H2O
SiO2
Ca(OH)2
Si 62
SiO2
CaSO4-2H2O
Fe203
Ca(OH)2
                             306

-------
                                   APPENDIX E

                             DESCRIPTION OF FBC UNITS
                                PROVIDING RESIDUES

                    Pope,  Evans, and Robblns Process (Alexandria, Virginia)

    The U.S. Energy Research and Development Administration supports one pilot-scale
and one full-scale fluidized  bed coal combustion unit operated by Pope, Evans, and Robbins
(PER). In an earlier project on the PER unit (spnsored by the National Air Pollution Con-
trol Administration), they monitored air pollution emissions from the fluidized-bed combus-
tion of coal under different  conditions to determine those most favorable for reducing SO2
emissions.  Major test variables and ranges were:

            Coal type                                  Medium and high sulfur
            Bed temperature                            815-1,038  C
            Bed depth                                  15-51 cm

            Bed material                                Sintered ash and limestone
            Flue gas oxygen content                     0.5-5.0%
            Superficial gas velocity                      1 .8-4.3 m/sec
            Sorbent type                                Dolomite 1337
                                                       Limestone 1359

            Sorbent state                               Raw, hydrated, and  precalcined

            Sorbent particle size                        7-325 mesh
            Fly-ash recirculation                        Full range (0-80%)
            Method of sorbent feed                      Pneumatic feed with the coal,
                                                       pneumatic feed remote from
                                                       the coal feed and premixed
                                                       with the coal

    Tests were conducted on both pilot-scale and full-scale test units. This study tested
residues from the full-scale unit located at Rivesville, West Virginia, only.

Fluidized-Bed Combustor  (FBC)

    The FBC tests explored  SO9 capture on a bench scale prior to a major expenditure of
resources in testing the  full-scale unit.  Flue gas analyses, sulfur balances, and bed particle
size versus time analyses were compiled for these tests.  Portions of the operation also tested
used salt addition for sorbent SO2 activity enhancement, and for combustion catalysis in a
once-through operation. The bench scale fluidized-bed combustor (FBC) contained a rec-
tangular bed with dimensions 30.5 by 40.6 cm.  The combustor was enclosed by an air
distribution grid at the bottom, and water walls around the periphery.   Side and front views
                                        307

-------
are shown in Figures E-l  and E-2.

    Air passed into a plenum below the grid, through the grid buttons, and into the com-
bustion chamber to fluidize the bed material and provide combustion oxygen. The bed
material generally consisted of sintered coal ash crushed and double -screened to a mesh size of
<8 to >14(or of limestone 1359 of mesh size  
-------
                                 Combusted Gases
 Water Wai led
     Column
  Fly Ash (fuel)
    Feed Scre
Start-up Coal
 Feed Screw
  Injection
  Air
  Fuel Injection
     Port
 Source:  124.
                                                          Welded Seam Duct
                                                              Sight Port
                                                             Water Cooled Hood
                                                               Light-off Burner Port
                                                               Thermocouple Ports
                                                                     Wall
                                                               Auxiliary Feed
                                                               Ports (2)
Plenum Chamber
                     Figure E^-l.  FBC construction detail (side view),
                                       309

-------
                          . Co
-------
CO
             FBM Gas
             Breeching
          Steam
           Drum
                Front Panel
           Ughtoff
             Burner
                                                              FBM  Exhaust
                                                                     A
                                                                    Vertical Coal-
                                                                    Feeder Inlet
 Additive or
  Ash Feed
Port (auxiliary)

 Air Plenum
                                                            .Fluidized Bed
                                                                          Header
                                                                                                          Down comers
          Source:124.
                       Figure  E-3,  Fluidized bed module: internal construction.

-------
      To FBM
        Dust
     Collector
    and Stack
GO
                                            CBC Flue, Gas to CBC
                                            Dust Collector and Stack
 Air
Heater
            Air
      Source: 121 .
                              BC (behind FBM)
                                                   Gas to Sample System
                                  FBM

                              o    o
                                           «—Greatly Exaggerated Separation-*-]

                                                  Connecting Slot
                       Gravity Bed Feed
                                        Inclined Screw

                                            Drop Leg
                                                                                                    Gas Outlet
Gas Cooler



X




X
LU
_«)
O.

t/1
p
E

2 .

V 1'
Bed Sample
£t
*~
i_
<
£
E
^.
C CN
6 ^
\J •
x 
-------
    An experimental carbon burn-up cell (CBC) was added to the FBM to raise the system
carbon burn-up from 90 percent into the 98-100 percent range, and to determine the
problems of operating with two distinct temperature zones (815° C in  the FBM and 1,038° C
in the CBC).  The CBC consisted of a chamber with a rectangular cross section (27  by 40
cm).  The uncooled insulated walls of the CBC were fabricated of 27  percent chromium steel.
The CBC was an integral part of the FBM and  was located at the back of the combustor under
the steam drum.  Figure E-5  is  the section view of the integrated FBM/CBC unit.  The CBC
operated continuously and burned the carbon-con tain ing fly ash from  the FBM.  Coal was
fed with the fly ash when ash alone could not maintain the desired  1,038-1,149° C bed
temperature.  Fly ash from the  CBC's own collector was also recycled during most tests.
CBC emissions of hydrocarbons  and< carbon monoxide were essentially zero. Figure E-6
shows the flow path of bed material for the FBM, CBC, and regenerator.

               Exxon  Research and Engineering's Process (Linden, New Jersey)

    The U.S. EPA (Office of Research and Development) sponsored a two-phase program
to investigate the feasibility of producing large amounts of heat at  low SO  emission levels
by burning coal under high pressure in a fluidized  bed of limestone.  The first  phase of the
program involved the design  and construction  of a  continuous f luidized-bed combustion/time
regeneration pilot unit—the  FBCR miniplant (shewn In figure E-7). Design parameters of
the process (mainly combustor and regenerator) are shown In Table E-l. The unit has been
designed to operate at pressures up to  10 atmospheres with a heat release rate of about 1.5
million  kcal per hour, equivalent to a power plant capacity of approximately 635 kilowatts.

    The combustor was constructed from a 61-cm.,  refrectory-lined pipe with a final 'nside
diameter of 30 cm.  It was designed with 5 flanged sections (each 0.9 m long), a bottom
plenum for air intake below the removable distributor plate,  and an upper bed expansion
section  containing the gas discharge outlet to the cyclones.  The regenerator was constructed
from a 46-cm pipe, refractory  lined to 13 cm  internal diameter.

    Fluidizing air to the  combustor and regenerator was supplied by a stationary compressor
with a capacity of 36.8 std cu  m/min.  Control valves and differential pressure transmitter
controlled the superficial bed velocities. In the combustor, the air passed through the
distributing grid and then the fluidized bed, to a heat exchanger for cooling,  and out
through two refractory-lined cyclones for participate removal. Air for the reducing-gas
regenerator was electrically  preheated.  The reducing gas from the  regenerator passed
through a ceramic distributor plate supporting  the regeneration bed, a refractory-lined
cyclone, and a heat exchanger before being discharged through a butterfly valve. Pressure
on the combustor and regenerator was kept the same by a differential pressure controlled by
positioning the butterfly valve  in the regenerator discharge line.

    Heat extraction and temperature control in the fluidized bed was accomplished by
boiling water in the vertical zones of the reactor.  Solids transfer between reactors and
discharge from the regenerator  was accomplished using a pulsed air  transport technique
controlled by pressure differentials across and  between the fluidized beds.


                                         313

-------
                                                        FBM Exhaust

                                             ,_	A	A   A  	_.
                                             *^v^ -»•• — — •»_ -> /• -,/ ^s^,'1? nr -^,-v- •• * - fT* - r*** • •* ^ f. •
                                                ••  •"    y — /  ,y f ^ •* ***. .f • *• ^  •(   v	•• r
CO
                                                                                                                     CBC
                                                                                                                     Exhaust
                                             P',., f-l  . P,, P NR  P . }>.   >T; . A« - P,
                                             ^i .^.'r^  i^1. u'\»  ^' •:>>.;  :-u..;ft-. :
I 0.2m    -t^
                                                                                                  ~T\. Insulation
                    Additive Ash
                   Port #1 (typical)
                                           Coal Feeder
                                           (partial view)
      2.5 x 5.1 cm

   Intercommunication  Slots
      Access Door
                     i
      Mushroom Feeder (fly ash)

      Air Distribution Grid
           Source: 124.
                                          Figure   E-5.  Section view of the integrated FBM/CBC unit.

-------
                                                                   Uncontrolled Flow
                                                                        Paths
                              FBM
                                                                   Controlled Flow Path
                          Key
Source: 12.4.
              Bed material may flow in both
              directions - via gravity, pressure
              difference, or diffusion.  Rates
              uncontrolled.
              Bed material can flow only in
              direction of arrow with  rate
              control.


Figure E-6.   Bed material flow paths: FBM,CBC and regenerator.

                       315

-------
     City Water     Cooling Water
CO
                                                                                               To Scrubber
                                                                                       in      uur
                                                                                       t        A    i
                                                                                     [ Heat Exchgngerk»*T*>  To
                                                                                                        Scrubber
                                                               Heat Exchanger]
                   Water FeedPump
                                                                                   Water Out
                                                                                    Water In
                       76 liters/min
                      4.2 kg/sq cm
                                                                                    *- Water Oul
                                                                                    —  Water In
Discard  \
             Limestone
               & Coal
                                                                                                         Fuel
                                                                                                        Storage
       Injection
         Air
               -a
          o
     Air Compressor
5.6 cu m*/mln @ 12.3 kg/sq cm
          -a
                •o
           Air Compressor
          39.2 cu m*/min
         8.8 kg/sq  cm (gauge)

          * At STP
          Source:  43.
                                                Legend

                              CS - Cyclone Separator    PF - Pulse Feeder
                              CV - Collector Vessel      RV - Refill Vessel
                              Figure  E-7*  Pressurised F&Cpilot plant,  Linden, New Jersey.

-------
      TABLL E-l   DESIGN PARAMETERS: EXXON MINI PLANT
           Parameter
 Unit
       Component

Combustor      Regenerator
Unit dimensions
  Height
  Internal diameter

Maximum operating conditions
  Temperature
  Pressure
  Superficial  bed velocity
  Heat released by combustion
  Cooling load

Maximum material rates
  Air
  Coal
  Limestone
  Natural gas
    U output
 cm
 cm
°C
 atm
 m/sec
 103 kcal/hr
 103 kcal/hr


 std cu m/min
 kg/hr
 kg/hr
 std cu m/min
 kg/hr
  71.10
  31.75

  927
  10
  3.05
  1,588
  907

  33.98
  218
  30.84
48.30
12.70

1,093
10
1.52
2.55
                 0.28
                 18.14
 Source? 43.
                                   317

-------
    The second phase of the program involved a study of the factors influencing the forma-
tion and the control of nitrogen oxides (NO ) in fluidized bed combustion. For these
studies, a 7.6 cm ID fluidized bed combustor and  two smaller electrically heated fixed
bed reactors were used. An automatic instrument  continuously measured NO,SO,,, and
O_ emissions. The operating factors that were studied included excess air level, rempera-
ture,  and bed composition.

    The 7.6-cm unit was modified to operate as a two-stage combustor,  in order to test a
reactor configuration that would yield low NO  emissions  by promoting the reduction of
NO by CO and then the reaction of NO with £t)_and lime.  Operating at substoichio-
metric conditions, the  NO-CO reaction was permitted and secondary air was added at a
higher point in the bed to complete the combustion and provide SO- for reaction with the
remaining NO.  A schematic diagram of the Exxon fluid bed combustion unit is shown in
Figure E-8.
                                        318

-------
CO
                                 Vent
   WTM
                                              Instrument Calibration By-Pass
Feeder
Scale
                                       Coal
                                       Hopper
                                     and Feeder
                                                           Cyclone and
                                                                 Filter

                                                                    Air
                                                                 Condenser
      Reactor
                                                                   Water
                                                                 Condenser
     N2    CO   SO2
        O2  NO  Air
                       Gas Rotameters
                                                                                 Refrigerator
                              T
                                                                             Condensate
Figure E-'8.. Exxon FBC unit.
                                                                             IR SO2
                                                                             Analyzer
                                                  IRCO
                                                 Analyzer
                                                                                                    I
                                                                                                             WTM
                                              NO Analyzer
                                                                                       WTM
                                              Polarographic
                                              O2 Analyzer
                                                   J
                                                                                                Intermittent
                                                                                                Gas Sampler
     Source: 43

-------
                                    APPENDIX F

                        FLUIDIZEDH8ED OIL GASIFICATION

                                    Introduction

     Fluidlzed-bed oil gasification provides the technology for utilizing high-sulfur residual
oils and asphalts for clean power generation.  Oil can be gasified at either atmospheric or
elevated pressure.  At atmospheric pressure, a  fluidized-bed gasifier provides clean fuel to
a boiler. At elevated pressure, the fuel goes to a combined-cycle gas and steam turbine
power plant. Power-cycle schematics for low and high pressure alternatives are shown in
Figures F-l  and F-2.

     Low and high pressure systems may use either once-through operation,  or regeneration
of the limestone or dolomite sorbent. The quality of waste material is minimized by keeping
the spent sorbent dry,  which makes it potentially suitable for other uses.

     The atmospheric (low) pressure process can be used to retrofit an existing boiler or as
a design feature on a new boiler., Capital  costs of a retrofit, once-through oil  gasification
system may  be 50 to 70 percent less than a  retrofit stack gas cleaning system.
                                              v
                                   Process Descriptions

Low-Pressure Gasification

     The gasiflcation/desulfurization operation can be accomplished by either the regenera-
tive or the once-through mode. Figure F-3 illustrates the major process streams and elements
of the two operational  modes.  The specifications assumed for design of a commercial plant
are shown in Table F-l .

Regenerative Operation

     The major components of the regenerative operation are the gasifier and  regenerator
vessels.  The gasifier Is an air-fluidlzed bed of lime operated at 870°C with  subtaichiometric
air fc20 percent of stoichiometric).  Heavy residual oil is injected into the gasifier vessel
where it cracks and is  partially cpmbusted to form a hot, low-sulfur gas. Hydrogen sulfide
produced during gasification  reacts with the lime to produce calcium sulfide and water:
     H2S + CaO	—CaS + H2O

The hot fuel gas is transported to the boiler burners where combustion is completed, and the
calcium sulfide is sent  to the regenerator.  The regenerator is an air-fluidlzed vessel operated
with a slight excess of air at  about 1,000 C.   Regeneration takes place by reaction of
oxygen with the calcium sulfide (spent lime) to give an SO~ rich  stream (of about 10 mole
percent $02) and a regenerated Hme having a slightJy decreased activity compared to that
of fresh lime:

    CaS + 3/2 O2	»-CaO + SO2

                                         320

-------
                      Cyclone
                                                                                   Stack Gas
                                    Hot Fuel Gas
CO
1-0
     Oil

Limestone
(CaCO3)
    Regenerated
      Limestone
        or  --_
    CaSGv
                                   1800-3600 kca I/cum*
                     Particulates
 Fluidized Bed
   Gasifier/
 Desulfurizer
1 Atm, 870 C
                            Spent
                           Limestone
                 Limestone
                 Processing
                for Reuse or
                  Disposal
                                                    7
                                              Booster
                                                Fan
                                                                           Conventional
                                                                             Boiler
Turbines
                                                                       Generator
     * AtSTP.
     Source:  104.
                          Figure FrK  Low pressure fluidized bed oil gasification for power generation,

-------
                             one
CO
ro
                                                                            Stack Gas
                                            Hot Fuel Gas
    Oil 	•

 Steam 	*

Lime-   	•
stone
(CaCOg)

Regenerated
 Limesjone
   or  __
         CaSC
         aAt STP.
      Source.  104.
                                        1800-3600 kca!/cu
   Fluidised Bed
    Gasifier/
   Desulfurizer
10-15atm, 870 C
                               Spent
                               Limestone
  Limestone
  Processing
 for Reuse or
   Disposal
                                                 High Temp.
                                                    Gas
                                                 Combustor
rteat
Recovery
Boiler
        Turbine
Generator
                                                                                                  Generator
                          Figure  F-2.  High pressure (I jidfzed bed oil gasification for power generation.

-------
                 Once-through Mode
                                          Stack Gas
         Combustion Air
                                                                          Combustion Air
Regenerative Mode

               Stack Gas


                    I
CO
to
CO
-*. 1. - J 	 ' 	 1 L--
Clean Fuel Gas Bo|ler
Final OH 	 1 ; 	 ^
! T
1
Clean Fuel C
r
i
1
^^

-* 	 Limestone Feed Lmieslone 	 ^ Gasifier
~ .c. ' Make-up
Gasifier r -«• 	
~* 	 Temperature
A Control Stream
1 f Spent
L 	 | ,S.penf Lime
i «S) (CaS) 1

j_ Sulfate AIr *" Reaen

Legend
	 Gas
CaSO4 Liquid Ca
n. , 	 Solid Feed D's
Disposal
— •• Solid Circulation
1 Regener
so2-
eratOT ~~Str«
S°4
3OSOI
Boiler
JOS
c.10| r\t\
Temperature
Control Stream
ated Lime
Rich ^ Sulfur
am Recovery

       Source: 104.
                          Figure  F-3 . Modes of operation, fluJdized bed oil gasification plant.

-------
  TABLE F-U ATMOSPHERIC PRESSURE OIL GASIFICATION SPECIFICATIONS
             Process Specifications
                         Design Variables
Sulfur Removal: 90-95%                            Boiler Size:  600 Mw
Fuel Oil:  3% sulfur by wt.;LHV = 9.81 x 10  kcal/kg  Load Factor: 40%, 80%
Limestone:  98.6% CaO yield                       Turndown: 4/1
        Parameter
              Operating Variables

Regenerative System       Once-Through System
Gasifier  temperature (C)        870
Regenerator (sulfate          1,000
  generator) temperature (C)

Limestone make-up rate       1  mole CaO/mole sulfur
Air/fuel naiio                20%of sta'chiometric
Limestone utilization         5% sulfur by wt.  In bed
Fluidization velocity (m/sec)  2.4
Minimum fluidizafion         0.9
  velocity (m/sec)

Particle sizes, avg. ( n )     2,000
Gasifier bed depth, static (m)  0.8 - 1.1
                        870
                        820
                       3 moles CaO/mole sulfur
                       20% of stoSchiometric
                       19% sulfur by wt. in bed
                       2.4
                       0,3
                       1,000
                       1.1 - 1.2
Source: 104.
                                     324

-------
The SO- stream is transported to a sulfur recovery system,  and the regenerated lime is re-
turned ro the gasifier along with an approximately stoichiometric amount of fresh make-up
limestone.

Once-Through Operation.  The elements of the once-through operation  are a gasifier vessel
and a sulfate generator,or a predisposal vessel.The operation of the gasifier is the same as
for the regenerative operation. The sulfate generator operates similarly to the regenerator but at
a lower temperature (   ~  800 C), so that the calcium sulfide from the gasifier is converted
to calcium sulfate rather than calcium oxide.  The dry calcium sulfate may be disposed of,
and the gas stream from the sulfate generator is sent to the gasifier. A limestone addition
rate of up to three times that used in rhe regenerative operation may be  necessary to achieve
sulfur removal of 90 to 95 percent.

High-Pressure Combined-Cycle Gasification

    The high pressure combined-cycle gasification process can be accomplished by either
once-through or regenerative operation. Table F-2 lists the factors specified for the con-
ceptual design of the high pressure fluid-bed oil gasification process.  Figure F-4  shows a
flow diagram of the energy balances for the high pressure fluid-bed oil gasification process.

Regenerative Operation.   The high pressure regenerative process shown  in Figure  F-5 consists
of a Ffuidized-bed gasifier/desulfurizer vessel, a limestone/dolomite regenerator, and a
sulfur recovery section.  Residual oil is injected into the gasifier vessel  and fluids zed-bed
of lime operated at 870° C with substoichiometric air (]4 to 25 percent of  stoichiometric).
This yields (by cracking, partial combustion,  and  hLS absorption by the limestone or dolomite)
a hot fuel gas of low energy value and sulfided lime or dolomite.  The gas is transported to
the combined-cycle plant where combustion is completed, and the suffided lime or dolomite
is sent to the regenerator.  The regenerator may be designed to produce  gas rich in FLS or
SO9  and regenerated sorbent with a decreased activity.  The SO« or \ij> stream is trans-
ported to a sulfur recovery system, and the regenerated sorbent is returned to the gasifier
along with a nearly stoichiometric amount of fresh make-up sorbent.

    The regeneration of calcium sulfide and the production of a high-sulfur gas for recovery
can be achieved by either of two processes, as follows:

     1)  Regeneration with CO^ and H2O to produce H2S:

         CaS + H20 + CO2 —* CaC03 +

    2)  Regeneration with air to produce

         CaS + 3/2 O2  —>  CaO + SO2

Table F«3 lists the gasification product compositions and fuel heat values for a high-pressure
fluidized-bed gasification system with limestone regeneration.
                                          325

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              TABLE F-2.  SPECIFICATIONS FOR  HIGH PRESSURE
                          FLUIDIZED BED OPERATION
          Item
               Specification
Plant electrical capacity
Capacity factor
Turndown ratio
Number of gasifier modules
Modes of operation
Gasifier pressure
Pressure of gas turbine
Sulfur removal
Residual oil
Gasifier temperature
Regenerator temperature
Sulfate generator temperature
Air/fuel ratios
Lime particle diameters
Regenerative lime utilization
Once-through lime utilization
Limestone make-up rate
Gasifier temperature control
Regenerator temperature control
Sulfate generator temperature
 control
Plant heat rate
250 Mw (PACE Plant)
70%
4/1
2
Regenerative or once-through
~ 15 atm
11 atm (11.6 kgf/sq  cm to turbine)
90-95%
3 wt % sulfur
870 C
600 Ca
930 C with once-through option
14 (minimum) & 25% stoichiometric
500-2000^1 average diameter
10%
35%
1 mole CaO/mole sulfur fed
Stack gas recycle, steam or water injection
Lime circulation rate; water injection
Excess air circulation (~200% excess)
2300 kcal/kwh (assumed for purposes of
material balances)
a With CO2/H2O regeneration; 1150 C with air regeneration*
Source: 104.
                                  326

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        Limestone/Dolomite 30 C

                          Steam

                         Water
GO
10
                                         Hot (870 C) Fuel Gas to
                                          combined cycle plant
Residual
Fuel Oil
             Fluidized Bed
            Oil  Gasification
                System
                                     Booster Com-   |
                                      pressor  Power |
                Energy Losses  (heat losses, carbon deposition,
                sensible heat of the flue gas, cooling water)


                 Limestone/bolomite (1000C)

                 Sulfur
    '   Auxiliary Power (cooling water pumping, oil pumping,
    j   solid circulation, compression for regeneration)


Booster Compressor


 Air from GT Compressor (air/fuel ratio = 14-25% of
  stoichiometric)
           Source; 104.
                              Figure F-4 . Energy balances flow diagram,

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           Clean Fuel  Gas to Combined
                  Cycle Plant
                                               Cyclone
                                                               Fines
                                                               Fines
                                                               Disposal      Disposal
                                                                                          H2S or SC»2 to
                                                                                         "Sulfur Recovery
                                                                            Cyclont
CO
10
00
  Make-up Sorbent

Temperature Control

    Residual Oil
               Pressurized Air from
             Gas Turbine Compressor
          Source: 104.
                                                 Oil
                                               Gasifier
Utilized Sorbent
                                                               Regenerated Sorbent
                                                                     Sorbent
                                                                     Disposal
                                           Booster
                                         Compressor
                          Sorbent
                        Regenerator
                                                                                     KLO and CO2 or Air
                                   Figure F-5  . Regenerative high-pressure oil gasification process.

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      TABLE .F-3. GASIFICATION PRODUCT COMPOS HiQMS
                                          Composition (% by volume)
              Gas
	_______	       14%A/F°	25% A/F

 N2                                       50.74             47.74
 H2                                         0.82              2.64
 CO                                       13.40              7.97
 C02                                        6.70              7.97
 H2O                                        0.00             20.56
 CH4                                        9.43              6.55
 C2H4                                     18.86              6.55
                                            0.05              0.02
 Low heating value (hot) (10^ kcal/cu m)         ~ 70              ~ 40

 QAir/fuel ratio.
 Source: 104.
                               329

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Once-Through Operation .   If a high sorbent make-up rate is required for the regenerative
processes and if high sorbent utilization can be achieved in  the gasifier, a once-through
system may be attractive.  A flow diagram of the once-through system was presented in
Figure E-4. Once-through operation would require conversion of calcium sulfide to calcium
sulfate before disposal of the sorbent.  The reaction is:

     CaS+2CL  — *•    CaSO,.
              £.              4

                        Process Environmental Comparison

     Table F-4 compares environmental factors for power generation by oil gasification (with
a conventional plant or with a combined-cycle steam and gas turbine plant) with the en-
vironmental effects of a conventional oil-fired power plant using limestone scrubbing.

     The spent sorbent from the fluidized bed oil gasification/desu If urieation process is dry
and granular ( ~ 6 mm). The composition is primarily calcium oxide and calcium  sulfide
with small amounts of calcium sulfate— the spent stone from  regenerative operation contain-
ing approximately 1 to 2 percent CaS and, from once-through operation, a projection of 30
to 80 percent CaS. Table F-5 lists some advantages of low-pressure oil gasification over
stack gas wet scrubbers.

     Preliminary indications suggest that the once-through operation  may be somewhat more
attractive to a utility than the regenerative operation.

                   Esso Research Center's Process (Abingdon, England)

CAFB  Pilot Plant

     The Chemically Active Fluid-Bed (CAFB) developed by Esso reduces sulfur oxide pollu-
tion while using high sulfur oil to produce power. The process uses a fluidized-bed of lime
particles to convert the oil into a hot, low sulfur gas ready for combustion in an adjacent
boiler. The process has the additional benefit of removing vanadium before the final com-
bustion states and thus eliminating a source of internal boiler corrosion.

     When oil is combusted under sub-stoichiometric conditions, the  sulfur is trapped by
lime as calcium sulfide:
H2S
         + CaO  — *   CaS +
CaS formed by the reaction of H_S and CaO in the gasifier fluid-bed is converted back to
CaO in a fluid-bed regenerator By contact with air:

     CaS + 3/2 O2  — *    CaO + SO2.

The amount of regenerated lime removed is made up by the addition of fresh limestone tovthe
combustor; sulfur is recovered during the regeneration process in several ways, such as con-
version to hLSO . or elemental  sulfur.
            2   4                       330

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                                    TABLE F-4.  ENVIRONMENTAL IMPACT COMPARISON
CO
CO
               Environmental  Factors
Conventional Oil-  Conventional Oil-Fired
Fired Power Plant   Plant with Atm-Pressure
with Limestone        Oil Gasification
Wet Scrubbing
                 Regenerative  Once-through Regenerative  Once-through
Combined Cycle Power Plant
           with
Pressurized Oil Gasification
Plant capital investment ($/kw)
Plant energy cost (mills/kwhr)
Limestone waste (kkg/day)
Water usage (kkg/day)
SO^ emission (kg/10 kcal)
NO emission (kg/106 kcal)
Particulate emission (kg/10 kcal)
325
13.1
440 (sludge)
450 (sludge)
0.63
1.44
0.04
Thermal emission (% of conventional plant) 100
Auxiliary power & fuel (% of plant
Plant heat rate (kcal/kwhr)
Land requirement
input) 4.0
2,400
large area for
disposal pond
310
12.7
80-160
0.63
0.29
0.04
~ 100
2.5
2,400
large area
300
12.5
450-730
0.63
0.29
0.04
-100
2.5
2,400
large area
180
9.7
80-160
0.63
0.29
0.04
— 50
7.5
2,400
more compact
plant
160
9.2
450-700
0.63
0.29
0.04
-50
5.0
2,300
power
     Basis:  635 Mw power plant @ 1973 costs; capitalization at 15%; residual oil at $1.79/10° kcal; gasification at air/fuel
            ratio of 20% of sroichiometric; limestone make-up rate of 0.5 to 1.0 times stoichiometric for regeneration  and 1.5
            to 3.0 times stoichiometric for once-through; for wet scrubbing a make-up rate of 1.2 times stoichiometric; NO
            emission for gasifier based on pilot plant measurements; combined cycle plant based on conventional gas-turbine*
            technology, advanced gas turbine conditions can  reduce plant costs and total emissions; gasification process con-
            sists of two independent gasifier modules.
     Source: 104.

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   TABLE F-5.  ADVANTAGES OF ATMOSPHERIC PRESSURE OIL GASIFICATION


	OVER STACK GAS WET SCRUBBERS	




1 .  Corrosion and fouling problems minimized in SO2 removal process and in boiler


     (minimum SO  and V)
                A



2.  No flue gas  reheat required.




30  Uses crushed limestone - no limestone pulverizing system needed.




4.  Simplified disposal - dry solids and no disposal pond.




5.  More compact system.




6,  Reduced  structural costs.




7.  Lower auxilary power requirement.




8.  Reduced  energy cost.




9.  Improved NO  control.
               /x



10.  Potential market for spent CaO






Source:  104.
                               332

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     The main unit of the CAFB process is the combustor and regenerator system, which is
made of an insulated steel shell  contained in a refractory concrete cast.  The gasifier and
regenerator are cavities in a single refractory concrete block.  The block contains other
cavities which make up the gasifier outlet "cyclones, the gas transfer ducfs, and transfer
lines through which solids circulate.  The gasifier product gas fires a 2,930 kw pressurized
water boiler.  The hot water is heat-exchanged through a forced convection cooling tower.
The rest of the system consists of the necessary  blowers, pumps, and instruments to operate
the gasifier,  regenerator, burner,  and solid circulation system.
Batch Reactor and CAFB Experiments

     Under contract to EPA's Office of Research and Development, Esso (England) investiga-
ted sulfur absorption and lime regeneration operating variables. The experimental equipment
used in the study consisted of two batch reactor units and the continuous CAFB pilot plant.
Changes were made to various sections between test runs as a result of experience, and to
achieve specific objectives. The oils used were heavy fuel oils from Venezuela crudes ob-
tained from the Amuary Refinery of the Crude Petroleum  Co. Pilot plant runs had employed
U.S. Stone BCR 1691 and  a U.K. limestone from Denbighshire.    Batch units had employed
the latter two stones, as well as  U.S. Stone BCR 1359.  A summary of the experimental
results appears in Table  F-6.

     Each batch unit contained a reactor,  air  and fuel systems, a flare for product gas
disposal,  and a gas sampling and analysis system, as shown in Figure  F-6.  The reactors were
made of stainless steel with a refractory lining. The lower section, which contained  the
fluid bed, was 17.8 cm (ID) by 84 cm high.  The reactors used in the original tests were
not fitted with cyclones and, therefore, were used  only in low gas velocity experiments.
The unit has no provision for temperature control other than by adjusting the quantity of
insulation around the reactor.  The insulation was arranged to permit the unit to operate
in the range of 800 to 900  C with air velocity of 1.2 m/sec and an excess air of over
30 percent to that required for combustion.

     When operating under combustion conditions and also during regeneration of bed
material, the gas from the bed was monitored  directly for CCL,CO, (X and for appropriate
information on combustion efficiency, sulfur removal efficiency, or sulfur release deduced.
During gasification, a portion of the product gas was burned in a sample flame located just
above the reactor,  and the combustion products were analyzed for SCU, O_, CO, and COj.
The desulfurizing efficiency of the gasifier was calculated from the analysis of the fully
combusted gas.  The first reactors were used in the initial fuel oil screening work; the two
later batch reactors were designed and constructed for studies of various operating modes.

     The upper section of the reactor was redesigned to permit installation of two internal
cyclones and to allow drainage of the cyclone for external sample  collection. Internal
cooling coils contained in the reactor allowed the  temperature to be controlled indepen-
dently of fuel and air rates.  The type of reactor used for these studies is shown in Figure F—7*
                                           333

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           TABLE  F-6, SUMMARY OF EXPERIMENTAL RESULTS
Batch Tests

    I.  Nearly 100% sulfur removal at 870 C, 20% air/fuel ratio, with limestone
        make-up rate of 1  mole CaO/mole of sulfur bed.
    2.  Nearly 100% of fuel vanadium removed.
    3.  About 20% of fuel sodium removed.
    4.  Clean product fuel is easily combustible with a luminous smoke-free flame,
    5.  Regeneration at 1000 C gives a 10% SC^-gas product and a regenerated
        lime having reduced activity.

Continuous Unit
    1 .  Results indicate superior behavior during continuous operation due to the
        improved temperature control.
        -  Lower air/fuel ratios, down to 17% of stoichiometric, have been
           demonstrated.
        -  90% sulfur removal has been demonstrated.

Source:  104.
                                334

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CO
CO
Oi
       Air


Propane (for
 start-up)


       Oil
                                                      CAFB Batch Reactor
  Fuel
Metering
  Pump
                                                                                           Sample Flame
                                    Fuel Injector
                                        Air
           Source;   53.
                                    Figure F-6. Esso,England batch reactor oil gasification system,

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                                                        Outgoing Gas Will
                                                          Be Burned Here
                                                                   External
                                                                   Cyclone
                                    Fuel Injection
Source: 53.
                                      Distributor

                                      Gas Preheater

                                      Air Supply
                       Figure F-7  -Batch reactor.
                                                        14cm   Bed
                                                         •*—  Datum
                              336

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                                TECHNICAL REPORT DATA
                          (Please read htuntctions on the reverse before completing)
  REPORT NO.
 EPA-
-77-139
                                                       3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
 Environmental Assessment of Solid Residues from
    Fluidized-Bed Fuel Processing
                                           5. REPORT DATE
                                           December 1977
                                           6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)

 Ralph Stone and Richard Kahle
                                           8. PERFORMING ORGANIZATION REPORT NO,
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Ralph Stone and Co. , Inc.
 10954 Santa Monica Boulevard
 Los Angeles, California  90025
                                           10. PROGRAM ELEMENT NO.
                                           EHB536
                                           11. CONTRACT/GRANT NO.

                                           68-03-2347
 12. 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 PE
                                           Initial; 11/75-12/76
                                                           PERIOD COVERED
                                           14. SPONSORING AGENCY CODE
                                            EPA/600/13
 15.SUPPLEMENTARY NOTES TERL-RTP project officer for this report is Walter B; Steen, Mail
 Drop 31, £19/541-2825.
 16. ABSTRACT
           The report gives results of the first 15 months of an environmental assess-
 ment of solid residues generated by fluidized-bed combustion (FBC) of coal and gasi-
 fication of oil.  Included are a literature search, c'lemical and physical residue char-
 acterization, laboratory leaching studies, and testing of residues in various materi-
 als and agricultural applications. The literature search reviewed current FBC tech-
 nology, identified products in which residues might be used, and gave data on typical
 soil and geologic conditions at the evaluated disposal sites. Laboratory tests included
 total chemical  characterization, composition of acid-, base-, and water-soluble fi-ac-
 tions,  cation exchange capacity, BOD,  temperature change from water addition, par-
 ticle size distribution, dry density, specific gravity,  permeability, water-holding
 capacity, moisture content, and small-scale column leaching studies. Pilot-scale
 columns simulated abandoned coal mines, dolomite and  limestone quarries, sanitary
 landfills, soils, and the ocean. Water was added to columns on a prescribed schedule
 and the resulting leachate was collected and analyzed for chemical constituents. The
 data were used to assess the potential for impact on water quality,  and the capacity
 of the disposal environment to attenuate degradation. Residue use was considered for
 concrete, asphalt, soil cement, and lime/flyash aggregate.
17.
                              KEY WORDS AND DOCUMENT ANALYSIS
                 DESCRIPTORS
                                           b.lDENTIFIERS/OPEN ENDED TERMS
                                                         COS AT I Field/Group
 Pollution
 Assessments
 Solids
 Residues
 Coal
 Fluidized-Bed
  Processing
          Combustion
          Fuel OH
          Gasification
          Water Quality
          Leaching
          Soils
          Geology	
Pollution Control
Stationary Sources
Environmental Assess-
  ment
Fluidized-Bed Combus-
  tion
Acid Mine Drainage
13B
14B
07D

21D

13H.07A
  21B
08G,08W
18. DISTRIBUTION STATEMENT
                               19. SECURITY CLASS (TinsReport)
                               Unclassified
                        21. NO. OF PAGES
                            350
 Unlimited
                               20. SECURITY CLASS (Thispage)
                               Unclassified
                                                                   22. PRKfr
EPA Form 2220-1 (9-73)
                             337

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