SEPA
United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/7-78-107
June 1978
Environmentat
Assessment of
Solid Residues from
Fluidized-bed Fuel
Processing:
Final Report
Interagency
Energy/Environment
R&D Program Report
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide-range of energy-related environ-
mental issues.
EPA REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Government, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/7-78-107
June 1978
Environmental Assessment of Solid Residues
from Fluidized-bed Fuel Processing:
Final Report
by
Ralph Stone and Richard L. 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: Walter B. Steen
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
ABSTRACT
This report presents the results for an environmental assessment of the solid residues
generated by fluidized-bed coal combustion and oil gasification. Tasks included a litera-
ture 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, identified
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 ex-
changed capacity, BOD, temperature change from water addition, particle size distribu-
tion, dry density, specific gravity, permeability, water-holding capacity, moisture con-
tent, and small-scale column leaching studies.
Pilot-scale columns simulated limestone and dolomite quarries, sanitary landfills, aban-
doned coal mines, the ocean, and soils. Water was added to each column 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 final report was submitted in fulfillment of Contract No. 68-03-2347 by Ralph Stone
and Company,Inc., under the sponsorship of the United States Environmental Protection
Agency. This report covers the period from November 5, 1975 to December 31, 1977.
ii
-------
CONTENTS
Page
Abstract ^
Figures v
Tables ^
Acknowledgments xv
1. Introduction 1
2. Summary 7
Introduction 7
Technical Approach 7
3. Conclusions 9
4. Recommendations 14
5. Fluidized-Bed Coal Combustion 15
Introduction 15
Process Descriptions 15
6. Residue Characterization 20
Purpose 20
Residue Characteristics 20
Experimental Procedures 24
Results 28
7. Pilot Column Studies of Residue Disposal 53
Purpose 58
Simulated Sedimentary Environment Columns 53
Pilot Test Column Construction 74
Leachate Sampling and Analyses 88
Columns Operation During Sampling 97
Results and Statistical Evaluation 98
8. Comparison of the Residue Characterization and
Leaching Methods 159
iii
-------
CONTENTS (Cont.)
Page
9. Reuse Potential for Fluidized-Bed Residues lo7
Introduction 167
Overall Reuse Prospects 167
Types of Coal Ash 168
Coal Ash Utilization 171
Specific Applications for Coal Ash 178
Specific Applications of Lime/Limestone Wet Scrubber Residues 200
Potential Structural Materials Applications: Test Results 205
Potential Agricultural Application of FBC Residues 216
Marketing Analysis Methodology 248
Economic Analysis of Specific Applications 251
References 257
Appendices 274
A. Laboratory Analytical Methods 274
B. Sample Data Sheet 278
C. Characterization of Similar Residues 281
D. Description of FBC Units - Providing Residues 291
E. Fluidized-Bed Oil Gasification 304
Glossary and Abbreviations 321
iv
-------
FIGURES
Number page
1 Direct contact fluid!zed-bed stream generator 16
2 Once through pressurized fluidized-bed boiler power plant |g
3 Laboratory-scale column leaching 25
4 BOD from residue water extracts 35
5 Leaching characteristics of NJFA and NJSBM 37
6 Leaching characteristics of VFA and VSBM 33
7 Leaching characteristics of EFA and ESBM 39
8 Temperature change from water addition to dry residues 49
9 Temperature change from water addition to dry residues 50
10 Particle size analyses: coal combustion residues 51
11 Particle size analyses: oil gasification residues 52
12 Particle size analyses: pea gravel, granite bedrock, and large gravel 53
13 Particle'size analyses: silica sand and decomposed granite 54
14 Particle size analysis: coal, dolomite, and limestone 55
15 Legend for test column disposal environments 61
16 Abandoned limestone quarry test columns 63
17 Simulated sedimentary environment: dolomite quarry 64
18 Sanitary landfill test column 69
19 Stratigraphic section of a typical coal mine 71
20 Abandoned coal mine test.column 73
21 Simulated sedimentary environment: sea water jc
22 Original location of representative soil samples 77
23 Simulated sedimentary environment: sandy, clayey and silt soils
test column 73
-------
FIGURES (cent.)
Number
24 Lysimeter construction and test column placement
25 Outdoor columns leachate sampling apparatus
26 Drainage through limestone quarry columns
27 Drainage through dolomite quarry columns
28 Drainage through sanitap/ landfill columns
29 Drainage through coal mine columns
30 Drainage through ocean disposal columns
31 Typical test column leachai-e collection system schematic
32-37 Constituents leachated From test columns: NJFA
38-43 Constituents leached from test columns: NJSBM
44-49 Constituents leached from test columns: VFA
50-55 Constituents leached from test columns: VSBAA
56-61 Constituents leached from test columns: EFA
62-67 Constituents leached from test columns: ESBM
68 Effect of freeze-thaw cycles on LCFA compressive strength
69 Change of length with temperature for cured LFA specimen
70 Effect of curing time and temperature on LFA compressive strength
71 Effect of curing time and temperature on LCFA compressive strength
72 Effect of lime content ana' curing conditions on LFA strength
73 Effect of fly ash on LFA density
74 LFA moisture correlation chart
75 pH leachate for acid mine drainage
76 Aerated or foamed cellular concrete production flow diagram
77 Formed concrete production flow sheet
78 CS brick production flow diagram
79 Concrete compressive strength tests: NJFA,VFA,VSBM after seven
day cure
80 Concrete compressive strength tests: NJFA,VFA,VSBM after
28-day cure
Page
85
87
88
90
91
96
93
27
117
118
120
121
123
124
182
183
184
185
188
189
192
194
202
203
204
212
213
Vi
-------
FIGURES (Cont.)
Number Page
81 Concrete compress!ve strength tests: NJSBM,ESBM,EFA after
7-day cure 214
82 Concrete compressive strength tests: NJSBM,EFA,ESBM after
28-day cure 215
83 Result of reaction between residues and emulsified asphalt 218
84 Asphalt compressive strength tests: VSBM,NJSBM,ESBM after
29-hour cure 219
85 Asphalt compressive strength tests: VSBM,NJSBM,ESBM after
7-day cure 220
86 Asphalt compressive strength tests: NJFA,EFA after 29-hour cure 221
87 Asphalt compressive strength tests: NJFA, EFA after 7-day cure 222
88 Experiment 2-A tomato plant growth 226
89 Mean tomato plant height, experiment 2: VFA,FSFA,CFA 229
90 Mean tomato plant height, experiment 2: NJSBM,VSBM,NJFA 230
91 Tomato plant growth vs soil pH, experiment 2-A 233
92-95 Experiment 2A: analytical results of calcium, magnesium, sulfate,
and manganese 236
96-99 Experiment 2B: analytical results of calcium, magnesium, cadmium,
and copper 238
100-103 Experiment 2B: analytical results of iron, manganese, zinc, and
silver 239
104-107 Experiment 3: analytical results of calcium, magnesium,cadmium,
and copper 243
108-111 Experiments 3 and 4: analytical results of iron,lead,calcium, and
magnesium 244
112 Distance to U.S. coal-fired power plants 249
C-l Concentration range and average of U.S. fly ash constituents 285
D-l FBC construction detail (side view) 292
D-2 FBC construction detail (front view) 293
D-3 Fluidized bed module: internal construction 295
vii
-------
FIGURES (Cont.)
Number Pa9e
D-4 FBM and regenerator flow diagram
D-5 Section view of the integrated BVM/CBC unit 298
D-6 Bed material flow paths FBM,CBC regenerator
D-7 Pressurized FBC pilot plant, Linden, New Jersey
D-8 Exxon FBC unit ' 303
E-l Low pressure fluidized bed oil gasification for power generation 305
E-2 High pressure fluidized bed oil gasification for power generation 306
E-3 Modes of operation, fluidized bed oil gasification plant 307
E-4 Energy balances flow diagram 31 1
E-5 Regenerative high-pressure oil gasification process 312
E-6 Esso,England oil gasification system 319
E-7 Batch reactor 320
viii
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TABLES
Number
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 Comparison of FBC Sorbent Processes 19
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 Mi nip I ant Coal Samples 23
12 Stratigraphic Materials Simulated in Leaching Tests 26
13 Total Digestion Characteristics of Fluidized-Bed Residues 29
14 Soluble Salt Extraction Characterization of Residues I. Exxon Mini-
planf,Linden,New Jersey 31
15 Soluble Salt Extraction Characterization of Residues II. Pope,
Evans, and Robbins, Alexandria, Virginia 32
16 Soluble Salt Extraction Characterization of Residues III. Esso,
Great Britain 33
17 Soluble Salt Extraction Characterization of Residues IV. Esso,
Great Britain 34
18 Laboratory Leaching Tests: Limestone 40
19 Laboratory Leaching Tests: Dolomite 41
20 Laboratory Leaching Tests: Bituminous Coal 42
21 Laboratory Leaching Tests: Claystone 43
ix
-------
TABLES (Cent.)
Number
22 Laboratory Leaching Tests: #60 Silica Sand 44
23 Laboratory Leaching Tests: #16 Silica Sand 45
24 Laboratory Leaching Tests: Granite Bedrock 46
25 Residue Acid Neutralization Capacity 47
26 Residue Cation Exchange Capacity ' 47
27 Residue Physical Properties 56
28 Permeability of Residues and Column Materials 57
29 Column and Residue Identification 59
30 Representative Thickness of Limestone and Dolomite Simulation
Test Columns 62
31 Estimated Residential and Commercial Solid Waste Generation
by Kind of Material and Product Source Category, 1971 65
32 Sanitary Landfill - As Mixed Test Column 68
33 Representative Thickness Sanitary Landfill Simulated in Test Columns 70
34 Representative Thickness of Coal Mine Simulation Test Column 72
35 Test Column Soils Characteristics 76
36 Criteria Definition for Grading Analysis 80
37 Column Materials Grading Analysis 81
38 Material Densities of Natural Strata and Test Columns 82
39 Materials in Test Column Layers by Weight 83
40 Residues Added to Columns 86
41 Complete Analysis of Los Angeles Owens River Aqueduct (Potable 94
(Water) Columns Test 94
42 Constituents Present in Sea Water 95
43 Analyses of Sea Water Applied to the Test Columns 9O
44 Summary of Fluidized Bed Combustion Column Contents 99
45 Variation in Limestone Quarry Column Leachate Constituents IQO
46 Variation in Dolomite Quarry Column Leachate Constituents ]Q3
47 Variation in Sanitary Landfill Column Leachate Constituents ]Q4
48 Variation in Coal Mine Column Leachate Constituents ]Q5
-------
TABLES (Cent.)
page
49 Variation in Ocean Column Leachate Constituents 106
50 Variation in Sandy, Clayey, and Silty Soils Column Leachate
Constituents 107
51 Constituents Removed by the Test Columns: NJFA 109
52 Constituents Removed by the Test Columns: NJSBM 110
53 Constituents Removed by the Test Columns: VFA HI
54 Constituents Removed by the Test Columns: VSBM 112
55 Constituents Removed by the Test Columns: EFA 113
56 Constituents Removed by the Test Columns: ESBM 115
57 EPA Interim Primary Drinking Water Regulations, 1975 and Water
Quality Criteria for Beneficial Uses 127
58 Recommended Maximum Concentrations of Trace Elements in
Irrigation Waters 131
59 Comparison of Limestone Column Leachate Constituents with Water
Quality Criteria for Municipal Water Supplies 132
60 Comparison of Dolomite Column Leachate Constituents with Water
Quality.Criteria for Municipal Water Supplies 133
61 Comparison of Sanitary Landfill Column Leachate Constituents
with Wafer Quality Criteria for Municipal Water Supplies 134
62 Comparison of Coal Column Leachate Constituents with Water
Quality Criteria for Municipal Water Supplies 135
63 Comparison of Sandy,Clayey, and Silty Soils Column Leachate
Constituents with Water Quality Criteria for Municipal Water
Supplies 136
64 Leachate Analyses of the Test Columns from the NJFA 138
65 Leachate Analyses of the Test Columns from the NJSBM 140
66 Leachate Analyses of the Test Columns from the VFA 142
67 Leachate Analyses of the Test Columns from the VSBM T44
68 Leachate Analyses of the Test Columns from the EFA T46
69 Leachate Analyses of the Test Columns from the ESBM 150
70 Leachate Analyses of the Test Columns 154
XI
-------
TABLES (Cent.)
Number l!2g£
71 Comparison of Four Methods for Determining the Leaching
Characteristics of NJFA 160
72 Comparison of Four Methods for Determining the Leaching
Characteristics of NJSBM
73 Comparison of Four Methods for Determining the Leaching
Characteristics of VFA 1 62
74 Comparison of Four Methods for Determining the Leaching
Characteristics of VSBM 1 63
75 Comparison of Four Methods for Determining the Leaching
Characteristics of E FA 164
76 Comparison of Four Methods for Determining the Leaching
Characteristics of ESBM 165
77 Estimated Ash Utilization Potential 169
78 Comparison of Ash Compositions 170
79 Comparison of FBC Residue Compositions 170
80 Comparative Ash Production and Utilization, 1966 through 1972 172
81 Ash Collection and Utilization, 1971 173
82 Known Miscellaneous Uses for Ash and Slag 174
83 Known Uses for Ash Removed from Plant at No Cost to Utility, 1971 176
84 Density of Fly Ash Compared with Traditional Fills 177
85 Development of Ash Production and Use in the Economic Commission
for Europe Region 179
86 Effect of Fly Ash Content on LFA Strength and Durability 186
87 Average Cement Requirements of Miscellaneous Materials 196
88 Normal Range of Cement Requirements for B and C Horizon Soil
89 Effect of Adding Zn and Varying the pH in the Soil on Zn Content
and Yield Reduction of Chard Leaves 198
90 Effects of Soil pH on Soybean Plants' Mineral Uptake 199
91 Potential Structural Materials Applications: Tests Performed 206
92 Composition of Concrete Test Cylinders 207
93 Diameter and Area of Concrete Test Cylinders: Seven-Day Cure 208
XII
-------
TABLES (Cont.)
Number page
94 Diameter and Area of Concrete Test Cylinders: Twenty-eight
Day Cure 209
95 Results of Compressive Concrete Strength Test After Seven Days 210
96 Results of Compressive Concrete Strength Test After Twenty-Eight
Days 211
97 Asphalt Sample Compositions 217
98 Planting Schedule for Agricultural Tests 224
99 Experiment 2-A: Tomato Plant Growth Results 227
100 pH of Soil Residue Mixture 231
101 PH of Soil Residue Mixture After Crop 2 Harvest 232
102 Experiment 2-A: Tomato Plant Tissue, Chemical Analyses 235
103 Experiment 2-B: Tomato Plant Tissue, Chemical Analyses 237
104 Experiment 3: Spinach Tissue, Chemical Analyses 241
105 Experiment 4: Lettuce Tissues, Chemical Analyses 246
106 Sludge Fixation Costing Estimates 252
107 Residue Value for Use in Concrete 253
108 Imputed Value of Residues in Asphalt Applications 254
109 Fluidized-Bed Residues as a Substitute for Calcium Carbonate in
Peanut Growing 256
A-l Soil Preparatory Methods 275
A-2 Soil Tests 275
A-3 Analytical Methods 276
C-l Common Minerals in U.S. Coals 282
C-2 Chemical Constituents in Coal Ash 282
C-3 Coal Ash Solubility in Distilled Water 283
C-4 Mineral Phases Found in Coal Ash 283
C-5 Physical Properties of Fly Ash from Pulverized Coal Fired Plants 284
C-6 Oxide Analyses of Incinerator Fly Ash from Typical Refuse 286
C-7 Elemental Head Sample Analyses of Municipal Incinerator Fly Ashes 287
C-8 Wet Chemical Analysis of Sludge Standards 288
xiii
-------
TABLES (Cont.)
Number Page
C-9 Identification of ARCS Sludge Standards 289
C-10 X-ray Analysis of ARCS Sludges 290
D-l Design Parameters: Exxon Miniplant 301
E-l Atmospheric Pressure Oil Gasification Specifications 308
E-2 Specifications for Fluidized Bed Operation 310
E-3 Gasification Product Compositions 314
E-4 Environmental Impact Comparison 315
E-5 Advantages of Atmospheric Pressure Oil Gasification Over Stack
Gas Wet Scrubbers 316
E-6 Summary of Experimental Results 3] 8
xiv
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ACKNOWLEDGEMENTS
The excellent support and direction provided by Mr. Walter B. Steen,Project Officer,
and Mr. D. Bruce Henschel,Program Manager, representing the United States Environ-
mental Protection Agency Industrial Environmental Research Laboratory, Research Triangle
Park, North Carolina, is gratefully acknowledged. We are equally grateful to Mr.
Richard Chapman, Project Manager, under whose direction the work was initially per-
formed. Because, Mr. Chapman is no longer with the program, the work was continued
under the direction of Mr. Walter Steen.
We also acknowledge the information and close cooperation provided by Mr. William T.
Harvey and other Office of Fossil Energy officials of Energy Research and Development
Administration, Washington,D.C.; Mr. Orus L. Bennett of the United States Department
of Agriculture, Agriculture Research Service, Morgantown,West Virginia; Dr. Stephen
K. Scale of the Division of Chemical Products, Tennessee Valley Authority, Muscle
Shoals, Alabama; and Mr. Jerome Mahoch of the United States Army Waterways Experi-
ment 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,Virginia; Dr. Ronald C.
Hoke, Exxon Research and Engineering Co., Linden,New Jersey; Dr. G.L. Johnes, Esso
Research Centre, Abingdon,England; and Mr. H.T. McCarthy, Allegheny Power Services
Corp., Greensburg,Pennsylvania.
Technical review coordination for the contracted United States Environmental Protection
Agency 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.
xv
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CHAPTER 1
INTRODUCTION
Total electricity consumption in the United States was projected to increase at an annual
rate of 7 to 8 percent over 1970-1990. The relative shares of coal,oil,gas, and hydro-
electric generation were 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 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 Environmental Protection Agency has been evaluating two high sulfur coal
fluidized-bed combustion pilot plants. The United States Energy Research and Develop-
ment Administration (ERDA) has been supporting one small scale and one large scale pilot
plant. One high sulfur residual oil fluidized-bed reactor pilot plant has been operating
in England under an Environmental Protection Agency international agreement. In these
plants, either pulverized limestone or dolomite bed material was admixed to the coal or
oil being burned. The sulfur in the fuels reacted with the bed material to form calcium
and magnesium sulfates and, to some degree, sulfites and sulfides. Gaseous sulfur emissions
were thus greatly reduced, but solid residues were increased. These residues consisted
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 originating from natural dolomite or limestone.
The disposal of these residues has been a matter of concern since toxic substances might
be leached from the residues into ground or surface waters. This study was initiated
because there had been no extensive research into the environmental impacts of the dis-
posal of these solid residues or the feasibility of their recovery.
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
fluidized bed process applied to coal and oil.
1
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ELECTRIC GENERATING CAPACITY
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)
nSCf *>°°f|
260 76
6 2
266 78
52 15
4 1
19 6
341 . 1 00
1980 (Projected) 1990 (Projected)
» **' M? ™
393 59
147 22
540 81
68 10
27 4
31 5
666 100
GENERATION BY TYPE OF FUEL
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
Hydroelectric
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
106kkg
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 UoO., 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.
-------
- TABLE 5. SULFUR DIOXIDE ABATEMENT PROCESSES
1 . Precombustlon processes
a. Coal and oil cleaning
b. Coal and oil gasification
c. Fluidized bed gasification
2. Combustion processes
a. Fluidized bed combustion
b. Black, Si vails, and Bryson
3. Limestone processes
a. Wet scrubbing
b. Dry removal
4. Processes for sulfur recovery from stack gases
a. Cat - Ox
b. Wellman-Lord
c. Esso-Babcock & Wilcox adsorbent
d. Formate scrubbing
e. Ammonia scrubbing
f. Westvaco char
g. Molten carbonate
h. Sodium bicarbonate adsorption
i. Modified CI aus
k. Catalytic chamber.
I. Ionics/Stone & Webster
m. Alkalized alumina
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• Identify the leachate water pollution constituents and quantities resulting from
land and ocean disposal of residues.
• Evaluate the potential effects of disposing the residues into different soil-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.
Literature reviews, and the results from residue characterization and pilot test columns
evaluation were used to determine the potential environmental impacts of disposing solid
residues from fluidized-bed operations. Residues from both the fluidized-bed combustion
of high sulfur coal and fluidized bed gasification of high sulfur residual oils were tested.
Residues,obtained from three pilot plants, are identified in Table 6; the symbol abbrevia-
tions shown will be used throughout the report in reference to the three pilot plants. The
glossary describes unique report terminology and abbreviations.
In general, the literature search provided information on the disposal and environmental
impacts of similar residues such as coal ash or limestone SO 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 FBC and CAFB 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 developing a detailed monitoring pro-
gram for the laboratory and column tests.
The laboratory studies, including residue characterization, were used to constuct
pilot-scale test columns which simulated land and ocean disposal environments on a small
scale. The land disposal simulated environments which were evaluated were limestone
and dolomite quarries, sanitary landfill, abandoned coal mine, ocean, and sandy, clayey
and silty soils. All leachate was collected and analyzed, and profiles of the leachate
results for the various disposal methods were determined.
Studies were also undertaken to determine the possibility of recovering and marketing
the residues instead of disposing of them. Laboratory tests were conducted to determine
the feasibility of using these residues for commercial products. These tests compared the
properties of materials produced using residues with those made with conventional 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 treating residues was initiated to establish whether
treatment can enhance product use or is required for disposal.
-------
Symbol
CFA"
FSFA°
VFA
VSBM
NJFA
NJSBM
EFAb
ESBMb
lAHLtO.
Residue
Source
Oil
Oil
Coal
Coal
Coal
Coal
Oil
Oil
IUI-lNllt-|f ft||t ?\v ur KCJ
Name or Residue
Cyclone fly ash
Fines, stack, regenerator
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
1 ULJt .1 , , "' -
Pilof Plant
tocaHdn
Esso; Abingdon, England
, Esso; Abingdon, England
Pope, Evans, and Robbins;
Alexandria, Virginia
Pope, Evans, and Robbins;
Alexandria,V?rginia
Exxon; Linden, New Jersey
Exxon; Linden, New Jersey
Esso; Abingdon, England
Esso; Abingdon, England
CFA and FSFA residue were not used in the latter part of this study because of insuf-
, ficient quantities.
EFA and ESBM were obtained to replace the CFA and FSFA residues.
-------
CHAPTER 2
SUMMARY
Introduction
The overall purpose of the proposed work was 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 were to determine:
1. The physical and chemical 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 purposes.
5. Pretreatment requirements for the residues, prior to their disposal.
Technical Approach
Literature reviews and laboratory tests, including residue characterization and pilot test
columns evaluation, were done to determine the environmental impacts of disposal of solid
residues from fluidized-bed operations. Residues from fluidized-bed combustion of high-
sulfur coal and fluidized-bed gasification of high-sulfur residual oils were obtained from
three pilot plants; two were supported by the Environmental Protection Agency, and one
was supported by Energy Research and Development Administration. The three plants were:
Pope, Evans, & Robbins-FBM Combustion Laboratory, Alexandria Virginia, burning Pennsyl-
vania coal; Exxon Research £ Engineering Company, Linden, New Jersey, burning Illinois
fuel; and Esso Petroleum Company, Limited, Abingdon, Qxon, England, gasifying No. 6
Venezuelan oil.
The literature search provided information on the disposal, reuse, and environmental impacts
of similar residues, such as coal ash or SCL limestone scrubber wastes. Information on the
types of waste residues from these processes summarized in laboratory and pilot test reports
were also obtained. From these sources, estimates were made of the conditions for and the
levels of pollutants anticipated from the wastes in various environments. Process descrip-
tions of material flows for the three plants were obtained from the Environmental Protection
Agency and The Energy Research and Development Administration authorities. Models of
the subject disposal environments were developed from the literature and were used to
predict the various natural site conditions, limits, and goals.
-------
A comprehensive program of residue characterization was initiated to determine the
chemical and physical properties of the six fluidized-bed residues. The resultant physical
property data was used to hydraulically design 36 pilot test columns for leachate sfudies.
The resultant chemical property data was used to determine the constituents to be monitored
during the test columns study.
Pilot plant type studies were used to simulate, on a smaller scale, eight disposal environ-
ments: limestone and dolomite quarries, sanitary landfill, abandoned coal mine, ocean
and sandy, clayey and silry soils. By evaluating pilot scale test columns, the environ-
mental variables that would affect the behavior of the residues in natural environments
were controlled. All leachate was collected and analyzed, and precise analytical profiles
of the residues and their disposal conditions were established. Large-scale field test prog-
rams were postponed when it proved impossible to obtain sufficient quantities of residues.
To compensate, the pilot scale test columns study and product testing were expanded.
Studies were undertaken to determine the possibility of recovering and marketing the
residues instead of disposing of them. The results of bench tests were used to evaluate the
residues' uses in the manufactuing of certain commercial products. These tests compared
the properties of the recovered product with that produced using conventional raw materials.
The use of residues in concrete, asphalt, soil cement, lime-fly ash-aggregate and lime-fly
ash-cement, aggregate mixtures, and as load bearing fill were evaluated. 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 also
investigated. A variety of crops (tomato, spinach, and lettuce) were grown in mixtures of
fluidized-bed residue and soil. The use of the residues as a soil conditioner and neutralizer
of acidic soil was evaluated. Acidic soils may contain high levels of boron 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 has been used to help increase the pH but the residues could presumably replace the
lime, and thus decrease these toxic metals. Conversely, residues provide an excellent
source of trace metals and nutrients needed by plants.
8
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CHAPTER 3
CONCLUSIONS
Fly ash and spent-bed residues from coal combustion and oil gasification in fluidized beds
were characterized for their physical and chemical properties, evaluated for their impact
on simulated land and ocean environments, and assessed for reuse potential. The residues
were obtained from cooperating pilot plants operated by representatives of Exxon/L?nden/
New Jersey; Pope,Evans, and Robbins, Alexandria,Virginia; and Esso,Great Britain.
The specific residues studied are listed in Table 6. The following conclusions are based
upon the investigations described in the body of the report.
Literature Review
1. A comprehensive review of literature indicated that no historical environmental
data existed on coal fluidized-bed combustion and oil gasification, other than progress
reports on the various pilot plants and technologies currently under development.
2. There was no reported experience with operating a full-scale commercial fluidized-
bed power plant prior to or during this investigation.
3. The literature review and data developed from over 200 different sources during the
duration of this project report indicated the fol lowing 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 limestone and
fly ash, while conventional coal combustion residues come from dolomite or lime
scrubber sludges and fly/bottom ashes.
• Fluidized-bed combustion normally produces solid residues, whereas conventional
combustors with scrubbers produce liquid sludges as well as some bottom ash solids.
• Test fluidized-bed fly and bottom ash samples were dry, whereas conventional
combustion plant ashes were wetted to quench burning coals and to cool the residues.
• The FBC residue samples had higher specific gravities (generally 2.6 to 2.8) than
conventional fly ash, and thus would not be as suitable for use in lightweight con-
crete and structural fills.
• The FBC fly/bed test residues were recirculated and hence contained less or-
ganic material compared to conventional unrecirculated residues.
Residue Characterization
H. The measurement of the moisture content indicated that the fluidized-bed residues,
when received, contained no significant moisture.
-------
2. All residues except NJFAreactedexothermically, reaching temperatures upto220 C
within 16 minutes after addition of water. These reactions were attributed to lime slaking.
3. The fluidized-bed material particle sizes as received were in the range of fine,
sandy soil, (0.1 to 1 .Omm diameter) and the specific gravities (2.6 to 2.8 for all the resi-
dues except EFA which was 2.02) were similar to normal soils.
4. BOD (biochemical oxygen demand) test results indicated that residue leachates
contained constituents which acted as temporary inhibitors of microorganism growth.
5. The leachates from the fluidized-bed residues were highly basic(generally greater than
a pHof 11); thus, the residues maybe used to neutralize acidic soils and other acidic material.
6. The solubility characteristics of the fluidized-bed residues were influenced by
changes in the pH of the solution added to the residues. Using, soluble salt extraction
tests (shake tests), it was determined that an acidic pH generally increased the leaching
of heavy metals and increased the concentration of calcium by 2,000 to 4,000 percent.
The solubility of sulfate was much greater in the base soluble extracts than in the acid
and water soluble fractions.
7. Bench scale leaching tests indicated that chlorides from VFA, VSBM, and ESBM,
and zinc from NJFA were readily leached; whereas chlorides from NJFA, NJSBM, and
EFA were leached at a slower and a relatively constant rate. Sulfates, Iron, nickel,
lead, and zinc (other than NJFA) were also leached at a slower, yet constant rate.
Pilot Column Studies of Residual Disposal
Eight simulated residue disposal environments were evaluated in 20.3 cm diameter by 3 m
high test columns. The environments included limestone and dolomite quarries, sanitary
landfill, coal mine, ocean environment, and sandy, clayey, and siIty soils.
1 . The sanitary landfill and the sandy, clayey, and silty soils were shown to be the
most effective simulated environments for disposing of fluidized-bed residues. The other
four simulated environments reduced the concentrations of trace metals and other consti-
tuents in the residue leachate, but not to the extent of the former environments.
2. Some of the residues, particularly NJFA and VSBM, solidified and became imper-
vious to water several months after placement in the columns. The solidification of the
residues was caused by consolidation and hydrolization.
3. Of the four most effective simulated environments, the sanitary landfill may be
considered the best environment for disposing of fluidized-bed residues. The sanitary
landfill test columns were, by far, the most effective in removing sulfate (some 90 per-
cent compared to 25 to 75 percent removal from the other environments). Disposal of the
highly alkaline fluidized-bed residues would be most beneficial in neutralizing the acidic
content of the sanitary landfill.
10
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4. The residues from Esso, Great Britain,contained higher quantities of constituents/
and their disposal in general showed higher contamination of the water passing through
the test columns.
5. The simulated disposal of VFA onto any of the test environments resulted in less
water pollution impact than the other residues,i.e.,the leachate constituents exceeded
the interim primary drinking water quality criteria only 20 percent of the time (16 percent
when leached through the sanitary landfill simulated environment), while the other re-
sidues exceeded the permissible drinking water criteria mope than 28 percent of the time.
6. The EPA primary drinking water contamination level for zinc (5:0 mg/l) in the
test column leachates was not exceeded, and the recommended chloride level (250 mg/l) was
exceeded only by the leachate coming from the EFA and ESBM residues for all environments.
7. During the last eight months of the pilot test columns' study, the water quality
criteria for copper (1.0 mg/l),inercury (0.005 mg/l),and nitrate (10 mg/l),were not ex-
ceeded for any simulated environment, and the recommended irrigation water contaminant
level for aluminum (5.0mg/l) was not exceeded. Only NJFA and NJSBM leachates from
the dolomite test column and the NJSBM leachate from the coal mine test column exceeded
the cadmium (0.01 mg/l) water quality criteria.
Comparison of Difference Leaching Methods.
This study provided four basically different methods for evaluating the leaching charac-
teristics of residue materials. The four accelerated test methods, as described in Chapter
8, were total residue digestion, soluble salt extraction test, residue leaching test, and
pilot column leaching test. The results show that there were no consistent relationships
in the data among the four methods; however, the following conclusions can be made.
(1) The "total residue acid digestion" did not replicate the leaching characteristics
of residues in the natural water environment. The digestion broke down the residue into
a totally soluble form which generated some higher constituent concentrations which were
not obtained in the water leaching. (2) The results of the "soluble salt extraction"
analyses (i.e.,the shake test) showed that incomplete leaching occurred. These extracts
showed that highly soluble chlorides as well as other constituents were lower in concen-
tration than those which were obtained by the "pilot column" leaching tests. Thus, the
"soluble salt extraction" (shake test) was not accurate in interpreting the potential leach-
ing of residues in the environment tested. (3) The bench scale "residue leaching test"
generally gave values higher than those found in the larger pilot-scale column leaching
tests. This is understandable because in the larger columns, the stratum simulation of the
environment attenuated some of the dissolved constituents. No two methods gave similar
results; however, since the residues percolated through known subsurface materials, the
analytical results from the pilot test columns tests appeared to most effectively simulate
the potential leaching impacts of residues on the natural environment.
Reuse Potential for Fluidized-Bed Residues.
The FBC fly ash and bed materails have potential for many beneficial reuses, such as
11
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additives for concrete, road bed stabilization, fill material, soil stabilization, soil cement,
and brick manufacture. They also have potential use in neutralization of acid mine drainage,
rectification of acidic or other deficient soils in agricultural pursuits, water treatment,
roadway de-icing, and so forth. Fluidized-bed residues have a potential for many uses
presently provided by clay,lime, or dolomite.
1. The potential market for fluidized-bed residues requires development. Only
a small amount (only about 17 percent of the conventional coal ash) has been reused since
1968. However, the potential market for fluidized-bed residues may be greater because
of the valuable high calcium and magnesium content present. Although use of high-ash
fuels has increased as low-ash fuels have been depleting, the changeover to reusing
fluidized-bed residues may be slow because potential users will stay with the available
large quantities of conventional coal or oil ashes, and will resist adopting a new residue
until its value has been proven. Thephysical andchemical characteristics of the fluidized-
bed residues were found to be substantially different from that of conventional coal or
oil ash residues.
2. Thecompressivestrengthofconcretegenerallyincreasedwiththeaddition of five
percent VSBM,NJFA,and VFA. The other fluidized-bed materials did not improve the
compressive strength of the concrete.
3. Fluidized-bed residues may be added to portland cement as a partial replacement
for some aggregate and to reduce the amount of costly cement. The substitution would
save about $0.50 per kkg of equivalent strength concrete.
4. The use of FBC residues in concrete would be economically feasible if their cost
to the concrete mix purchaser was about $0.01 (1978 prices) per kg of residue. Based on
the above cost plus transportation costs of $0.02 per kkg-km for rail freight and $0.04 per
kkg-km for truck haul, FBC residues could be competitive with alternative cement and
aggregate materials at distances up to 472 km by rail and 235 km by truck.
5. Substitution of the fluidized-bed residues for part of the aggregate in asphalt did
not significantly benefit nor adversely affect the asphalt compression strength. Testsshowed
that up to 92 percent of the aggregate could be replaced. Based on this percentage, a 5
percent decrease in the cost of asphalt pavements or curb applications could be expected.
6. The use of FBC residues in asphalt would be economically feasible within 250 km
by rail (at $0.02/kkg-km) and 125 km by truck (at $0.04/kkg-km) of an FBC power plant
(this assumes a Los Angeles,California, 1978 price of $4.96/kkg for asphalt aggregate).
7. Preliminary potting tests to investigate potential agricultural crop application
yields, showed that fluidized-bed residues,applied at rates from 2.2 to 11.2 kkg per
hectare, can be used beneficially as a soil conditioner when soils are acidic, high in
heavy metals, or deficient in trace metals. The height of the tomato plants increased
from 15 to 70 percent with the application of the residues.
12
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8. The economic feasibility of using FBC residues to replace slaked lime for elevating
soil pH will depend on the alkalinity of the residues. The values of NJFA and NJSBM
residues would be $4.80 and $11.80 per kkg, respectively, at a Los Angeles 1978 price
of $65 per kkg for slaked lime. At these prices the NJFA and NJSBM residues could be
economically competitive at distances up to 240 and 590 km if hauled by rail,and half
these distances if hauled by truck.
9. Substitution of FBC residues for calcium carbonate as a source of calcium can be
economically feasible for selected crops grown in alkaline soils containing a very high
sodium ratio. Tests indicated that the added value of FBC residues relative to calcium
carbonate to be $268 per kkg (of which $255 was from increased yield).
10. The fly ash and spent bed materials' high pH (9 to 12) indicated they are usable
for neutralizing acid mine drainage. The economic feasibility of reclaiming residues de-
pends on the distance (transportation cost) between the FBC plant and the acid mine drain-
age, as well as on the cost of alternative landfill disposal (cost of operation and environ-
mental controls near the FBC plant.
11. Since the FBC residues were found useful as an agricultural soil conditioner, they
have excellent potential for reclaiming surface-mine spoil areas or other barren land.
12. The fluidized-bed residue can also be reclaimed as a road construction material
because of its characteristics. It is also usable for de-icing roads.
13. Fluidized-bed residues are a bulky material,and can be most economically used
locally in order to avoid high transportation costs.
14. Fluidized-bed residues have potential as a substitute for commercial lime,dolomite,
clay, ashes or inert fill wherever these materials are employed.
13
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CHAPTER 4
RECOMMENDATIONS
1. The pilot-scale test columns study has given valuable information for evaluating
the environmental impact of disposing fluidized-bed residues onto land and ocean disposal
sites. This work should be expanded to include the investigation and evaluation of the
six residues in large-scale field cells, which was originally included in the contract scope
of work. The unavailability of sufficient quantities of residues necessitated a postpone-
ment of this expanded study; therefore, it is recommended that the field tests be initiated
when the fluidized-bed combustion pilot plants operations can provide sufficient resi-
dues.
2. Further pilot-scale columns testing, in which the depths of the simulated environ-
ments more nearly equal those found under natural conditions, should be conducted.
Increasing the heights of the test columns through which the leachate may pass will more
nearly duplicate the natural environment leaching characteristics.
3. This report presented preliminary evidence that no two tests, for measuring the
leaching characteristics of residues, gave similar results. A detailed study comparing
various methods for determining the leaching characteristics of fluidized-bed residues or
other potential pollutant materials is needed. In particular, the following should be in-
cluded in the study; leachate tests for large-scale field cells, small 3-ft square or 5-ft
square test plots, and pilot-scale test columns; leaching tests of residues under various
quantities of applied water; soluble salt extractions with variable ratios of water to sample;
and analyses from the total digestion of the residues.
4. Disposal of fluidized-bed residues onto actual disposal sites should be initiated.
Close monitoring of several constituents would be needed to evaluate the impact on the
terrestrial environment.
5. Market and field studies to determine the potential marketability of the fluidized-
bed residues for different feasible uses should be continued. Uses would include concrete,
asphalt, soil cement, acid mine drainage control, and acid mine soil reclamation.
6. The preliminary study in the potential agricultural application of the fluidized-bed
residues should be expanded.
7. The toxicity of leachate from fluidized-bed residues disposed in different environ-
ments should be further investigated. This can be accomplished by standardized bio assay
methods, such as bacteriological counts, biochemical oxygen demand, fish exposure or
other procedures.
14
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CHAPTER 5
FLUIDIZED-BED COAL COMBUSTION
Introduction
In fluidized-bed combustion, a granulated bed material (limestone or dolomite) encom-
passes the pulverized burning coal . In most fluidized bed combustors the bed and fuel
are fluidized by fuel injection oir and combustion air. The calcareous bed materials
absorb sulfur oxides, reducing their emission into the environment. This process gener-
ates large quantities of spent dolomite or limestone materials, magnesium, or calcium
sulfate, ash and some unburned coal. This sorbent material may be either generated and
recycled, or removed from the plants for disposal .
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 provide additional heat. In boilers without heat exchange tubes
in direct contact with the fluidized-bed, hot off-gases generated all the steam by con-
ventional fashion.
The start-up of an atmospheric fluidized-bed boiler requires heafing a portion of the bed
to 315° C to ignite the injected coal . After ignition, the temperature of the bed rises
until 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 normal equilibrium. Ex-
cellent 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 generation
surfaces reduces the steam tubing requirements and also permits operation at lower and
more uniform bed temperatures. The lower temperatures reduces NOX emissions and slag
and decreases equipment corrosion.
Process Descriptions
There are two fluidized-bed combustion modes, with either complete or partial combus-
tion 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):
+ S +3/2O2 - *
In the second mode (called two-step or oxygen deficient combustion), less than the
stoichiometric amount of oxygen is added to the fluidized bed. This results in the formation
15
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Flue
Fuef Injection Pipes
Fluidized Bed
Air Distribution Grid
Boiler Tubes
Figure 1. Direct contact Fluidized-bed steam generator.
Source: 104.
16
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of calcium sulfide (CaS) which can be converted to $©2 and CaO by roasting it in air or
in oxygen, or to CaCOg and HLS by reaction with water and CO^. SO- or H_S can be
converted to sulfur (in a Claus plant) or to H SO . (in an acid plant).
The three basic types of plant operation for the fluidized-bed combustion of coal are:
(1) once-through (high or low pressure), (2) one-step regeneration (high or low pressure),
and (3) two-step regeneration (high-pressure only).
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 re-
quires 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 generates 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 sorbent plus the solid
ashes from the burned coal and the chemical combination of sulfur and other reactive
materials. The total weight of residues from the fluidized bed combustion process noted
in Table 7 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. Detailed description of the fluidized bed com-
bustor units is presented in Appendix D. In addition, the fluidized-bed oil gasification
process, including the Chemically Active Fluid-Bed (CAFB),developed by Esso, is des-
cribed in Appendix E.
17
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00
Electrical
Generator
Compressor
Coal Limestone
Heat Recovery
(Boiler Feed Water)
Participate
Removal
Waste
Residue
Steam
Turbine
Waste
resi-
due
Condensor
Fluidized Bed
Boiler
Boiler Feed
Water
Stack
Source: 104.
Electrical
Generator
3 Circula-
tion
Water
Heat Recovery
(Flue Gas)
Circulation Water
Discharge
Figure 2« Once-through pressurized fluidized bed boiler power plant,
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TABLE 7. COMPARISON .OF.'FBC SORBENT PROCESSES
One Step-10 atm 1atmP~ T c ^ TL L
|mpact 1% S02 2%S02 10% SOj Two SteP Once Through
Ab Bb Ab Bb Ab Bb Ab Bb (^'^•'^)
^••^•i mill I »»^——..!-..• • •! _^«»»^«^»••••-^•.^.^•.^•fc-n.^^i^—••.•••i^^J^—•—«».^a»Ji^^fcj.^^-..a n».i -i^.i»*i •• '.»- —ij. I ..••——•—••••—^—••-.•••^•^^•••^•••-^••^•.•a
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 (milIsAwhr) 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/Tir) 221 229 211 216 202 205 212 218 195 195
Dolomite input (kkg/hr) 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
- 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 ]Q ]Q ]Q ]Q ]Q 3Q ^5
(continued)
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CHAPTER 6
RESIDUE CHARACTERIZATION
Purpose
The purpose of this subtask was to determine the chemical and physical properties of FBC
residue samples and the stratum materials used in pilot scale column studies. This provided
a preliminary screening of potential environmental effects arid direction of subsequent^
efforts. The results were used in planning and conducting the pilot-scale column studies
of residue disposal and in testing commercial and agricultural applications.
Residue Characteristics
The chemical composition of ash and spent bed material was dictated, to a large extent,
by the composition of the bed material and the fuel. Natural materials were largely im-
pure, and both coal and oil as well as limestone and dolomite contained variable traces
of most metals. Combustion and other high temperature reactions produced ashes and spent
bed material containing many of these trace metals. The specific chemical composition
of a given ash or spent bed material was dependent on the combustion parameters (inclu-
ding the pressure),the fuel,and the bed material; and,as a result,the composition of ash
and bed material varied 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 determined the actual
pilot plant test operating conditions; and obtained analyses of the raw fuel and sorbent feeds.
(See Table 8.) Given this latter information, it was possible to relate our test results
to future production conditions.
Tables 9 through 11 give available analyses of coal and limestone feeds provided by some
of the experimental plants. The composition of fossil fuels used in these experiments
varied widely. The percentages of sulfur in the coal ranged from 0.75 to 4.46, and about
1.28 in the coke (on a dry basis). Venezuelan' No. 6 oil, used in the Esso gasifier,had
a sulfur content of about 2.5 percent.
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. Magne-
sium, 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 0.89 percent titanium in the coal used for the PER plant. Unfortunately,
not all the experimental plants that supplied residues were able to provide complete
chemical analysis or other descriptive information about the raw materials that were used.
20
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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
TABLE 8,.
Run Temp.
No. C
N.A*. 815 to
870
30.4 835
(avg.)
10 860 to
950
PILOT PLANT OPERATION
Excess Air .. , _
... „, Fuel Type
Vol. % /r
High sulfur
bituminous
18 coal
Sewickley,
Pa.
16.1 Illinois
N6
No. 6
N.A.a heating oil
Venezuela
FOH CHARACTERIZED RES10UFS
Sulfur D , c u L Ca/S molar
Bed Sorbent ' , ,.
% feed ratio
Calcined
limestone
4to-4.5 Germany Valley Variable
& Greer,
W. Va.
42 to 4£ Grove 3.7
limestone
2.5 Lime' BCR 1359 1 (avg.)
U.S.A.
Flue SO2
ppm
Variable
894
200
a N, A. = Not Available.
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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
4.46
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
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
aCalculated values.
"Personal Communication, Robert R. Reed,Pope,Evans and Robbins,lnc. to Ralph Stone,
Ralph Stone and Company,Inc.,March 23, 1976."
22
-------
TABLE 10. CHARACTERIZATION OF POPE, EVANS, AND ROBBINS
LIMESTONE SAMPLES (percent-one by
Constituent
Calcium carbonate
(CaC03)
Magnesium carbonate
(MgC03)
Ferric oxide (Fe~O«)
Alumina (ALOJ
Silica (SiO2)
Sulfur (S)
Greer Limestone
75.0
4.0
0.75
3.3
9.5
0.3
Germany Valley Limestone
98.3
0.5
0.2
0.5
0.6
0.15
"Personal Communication, Robert R. Reed,Pope,Evans and Robbins,lnc. to Ralph Stone,
Ralph Stone and Company,Inc. March23, 1976" •
TABLE 11. CHARACTERIZATION OF EXXON MIN1PLANT COAL SAMPLES
Constituent
Moisture
Ash
Volatiles
Carbon
Hydrogen
Nitrogen
Oxygen
Chlorine
Sulfur
As Analyzed
3.3
9.95
10.00
67.71
4.77
1.17
9.19
0.05
4.20
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
"Personal Communication. R.C. Hoke,Exxon Research and Engineering Co., to Ralph Stone,
Ralph Stone and Company,Inc. March 19, 1976.
23
-------
Experimental Procedures
Chemical Composition
The preliminary chemical tests of the residue samples consisted of: 1) characterization
after perchloric acid digestion; 2) determination of their water,basic,and acid soluble
fractions, and 3) determination of their sequential water leaching characteristics. All
the analyses 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.
Total Residue Digestion. The total chemical compositions of the residue samples were
determined after perchloric acid digestion. One gram residue samples were digested accor-
ding to the procedure referenced in Appendix A. The only significant departure from this ^
procedure was the use of nickel instead of platinum utensils; therefore, total nickel analysis
was not performed.
Soluble Salt Extraction. The solutions to be analyzed were prepared by placing TOO g
samples of each type of residue, as received, in a flask and adding either 250 ml of dis-
tilled water, 1.0 N NaOH, or 1.0 N HNOg in accordance with EPA-recommended pro-
cedures as further described in Appendix A. After mixing for twenty-four hours,the solu-
tions were filtered and the filtrate analyzed to determine the constituents in the acid,
base, and water soluble residue extraction, including pH, COD, BOD, and TDS.
The BOD,, 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 dhloride, sodium phos-
phate, potassium phosphate, and ferric chloride.
Residue Leaching Tests. Preliminary bench-scale leaching tests were conducted in
the laboratory on residue samples prior to the construction of the pilot-scale test columns.
The purpose of these accelerated tests was to estimate the long-term leaching character-
istics of the residues. Two hundred and fifty gram samples of each residue were placed in
30.48-cm high and 5.08-cm ID plastic columns. Figure 3 illustrates the column opera-
tions. The six volumes of water was added at the rate of 250 ml per leaching cycle. For
the NJFA, NJSBM,VFA,and VSBM, leachate was collected by gravity percolation once
a week for six weeks. For the residues from Esso,Great Britain, accelerated small-scale
column leaching was also developed to simulate 52 separate 250 ml leaching cycles in a
period of several weeks.
Bench-scale leaching studies were also conducted on the various strata! 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.
24
-------
FigureS. Laboratory-scale column leaching,
25
-------
TABLE 12. STRATIGRAPH1C MATERIALS SIMULATED IN LEACHINGTESTS.
Stratigraphic
Unit
Sandstone
Sandstone
Claystone
Dolomite
Limestone
Granite bedrock
Simulant
Material
H6 Silica sand
#60 Silica sand
^60 Silica sand
clay (kaolin)
Coarse meal grade dolomite
Coarse meal grade limestone
Granitic pea - gravel
Decomposed granite
Quantify (g)
300
300
240
60
300
300
225
75
Bituminous coal
Coarse ground lump
bituminous coal
TOO
26
-------
Chemical Properties
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.
Cation Exchange Capacity. The cation exchange capacities of the residues and strata I
materials were measured to indicate the amount of interchange that could occur as a result
of leachate water moving through the various strata 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 referenced in Appendix A.
Slaking Test One feature of some of the pilot plant residues, as received was their
extreme exotliermaI activity upon addition of water. The primary cause was lime slaking:
CaO + H20 *- Ca(OH)2 + heat.
The slaking test involved measuring the amount of heat released from each residue ma-
terial . After a 3.8 liter volume of water was added to 13.6 kg of residue, the mixture
was continually stitred, and the rise in temperature was recorded.
Physical Properties
Residue samples to be slaked were covered with water and allowed to react. When all
activi ty 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.
Particle S?.ze Analysis.. The procedure used complied with ASTM D422 as referenced
in Appendix A. A 500 g sample of each slaked and unslaked residue was sieved, using a
number 4, 10, 20, 40, 80, 100, and 200 sieves. Hydrometer analyses were not per-
formed on spent bed materials because the residues were partially soluble. Hydrometer
analyses were conducted on slaked samples for the fly ashes.
Specific Gravity. Specific gravity measurements were made for test residues to es-
tablish their physical characteristics for aggregate or other possible uses. The method used
was that shown in ASTM D854 (see Appendix A), 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 D854 type analysis.
27
-------
Moisture Content. The moisture content of the residues, as received, were determined
by following the procedures in ASTM D2216, as referenced in Appendix A.
Degree of Saturation
Degree of saturation was obtained by substituting into the formula:
WG
S = -- , where
W = moisture content 1/w = unit weight of water
G = specific gravity 1/d = unit weight of residue
Loose Dry Density. The dry density of each residue, both slaked and unslaked, was de-
termined by pouring 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.
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 papef
covered with water, and allowed to drain under the force of gravity. The sample, cov-
ered to prevent evaporation, was allowed to stand until there was no further 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 residues.
Permeability. Data was obtained following the procedure described in the Standard Meth-
od of Test for Permeability of Granular Soils (Constant Head); see Appendix A.
Results
Chemical Composition
Total Residue Digestion. The results of the total perchloric acid digestion of the flui-
dized-bed are shown in Table 13. The residues obtained from Exxon, Linden, New
Jersey, and from Pope, Evans, and Robbins, Alexandria, Virginia, contained high levels
of aluminum and iron. In fact, the iron content ranged from 1 to 7 percent of the total .
28
-------
TABLE 13. TOTAL DIGESTION CHARACTERISTICS
OF FLUIDIZED-BED RESIDUES
Constituent0
Aluminum
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Potassium
Sodium
Zinc
Fluidized-Bed Residue Type
NJFA
5,800
0.2
40
2.8
292
152
11,030
40
6,290
650
N.D.
7,200
80
92
NJSBM
960
< 0.1
120
4.0
192
168
1,830
32
2,530
475
N.D.
5,600
72
92
VFA
3,600
< 0.1
200
0.8
228
164
7,390
20
300
165
N.D.
8,400
112
80
VSBM
3,840
0.3
120
2.4
205
225
4,070
28
585
315
N.D.
19,400
192
208
EFA
240
N.D.b
160
1.6
176
180
48
24
375
120
N.D.
6,000
64
32
ESBM
N.D.
0.4
520
2.4
152
148
N.D.
16
1,895
215
N.D.
1 1 ,400
144
28
L All values are reported as mg constituent/kg residue.
N.D. - not detected.
29
-------
The residues from Esso,Great Britain, however, contained relatively little aluminum and
iron. The NJFA,NJSBM, and ESBM contained from 2,000 to 6,000 mg/kg of magnesium
while the magnesium content ranged from 120 to 315 mgAg In the VFA,VSBM,and EFA.
The residues contained similar quantities of the other metals which were analyzed.
Soluble Salt Extraction. The laboratory extraction tests wherein residue was added to
water/an acidic solution, and a basic solution, to characterize their soluble fractions are
presented in Tables 14 through 17. The BOD results are. shown graphically in Figure 14.
Results of the tests for residue characterization showed water soluble fractions in NJFA
were higher than acid soluble fractions for boron and magnesium, and higher than base
soluble fractions for nitrate. Water soluble fractions in NJSBM 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 VFA 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 VSBM, 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 EFA, except chloride, nitrate, and phosphate, were less in the
water soluble fraction than in the acid soluble fractions. The water soluble fraction ex-
ceeded the base soluble fraction for chloride, nitrate, phosphate, aluminum, calcium,
chromium, iron, lead, manganese, molybdenum, silver, and zinc ions. For the
ESBM, the acid soluble fractions exceeded the water soluble fractions for all the con-
stituents except sulfate, boron, and molybdenum, and the water soluble fractions
exceeded the base soluble fractions for all the constituents except sulfate, aluminum,
arsenic, beryllium, magnesium, and zinc.
CFA water soluble fractions were less than acid soluble fractions for all constituents and
exceeded base soluble fractions for nitrate, aluminum, calcium, iron, magnesium, man-
ganese, molybdenum, silver,and zinc. FSFA water soluble fractions exceeded acid solu-
ble fractions for nitrate, arsenic,boron,cadmium, calcium, iron,lead,magnesium,moly-
bdenum, and silver. Due to a shortage of residues for analysis, some acid and base soluble
fractions were not determined.
Comparisons of the results from the soluble salt extraction test shows that the sol ubi I ity of cer-
tain constituents are greatly affected by pH. That is, low pH generally increased the solubi-
lityof heavy metals and greatly increased the calcium content by2,000 to 4,000 percent.
The increased solubility of the calcium in the acid extraction may have been caused by
the reaction of insoluble calcium salts with the 1.0 N HN
-------
TABLE 14. SOLUBLE SALT EXTRACTION CHARACTERIZATION OF RESIDUES0
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
f\
NDd
27
4
1,190
—
ND
—
0.61
ND
1,805
—
—
ND
2.5
10
—
ND
—
24
ND
22
ND
Fly Ash
Acidb
Soluble
0.0
__
__
ND
—
182
5,300
—
.._
—
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
—
__
—
0.88
0.2
ND
—
—
1.6
6.0
2,360
—
ND
—
—
0.4
—
0.5
Spent Bed Material
Water Acidb BaseC
Soluble Soluble Soluble
12.2
4,188
51.4
_J
ND
26
ND
1,900
0.06
--
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
--
ND
ND
0.5
96,754
—
1.07
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
—
ND
0.97
0.2
ND
—
0.12
1.8
5.9
3,200
ND
ND
0.75
—
0.3
—
0.2
a
Al I concentrations in mg constituent residue, dry weight after extraction (24 hr* shake test).
1 f\ M LJK.1^
l.ON HNO3
j 1.0 N NgOH.
None detected = ND.
g
, — Analysis not performed
See Figure 11 .
31
-------
TABLE 15. SOLUBLE SALT EXTRACTION CHARACTERIZATION OF RESIDUES
II. 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
_»
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
__
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
c
Base
Soluble
12.9
—
—
—
6.21
ND
ND
17,400
ND
•V— •
ND
0.83
0.2
ND
—
ND
1.7
7.1
10
ND
ND
ND
—
0.3
—
1.0
Spent Bed Material
Water Acidb Base°
Soluble Soluble Soluble
12.2
4,064
57f8
—
ND
28
ND
1,640
0.06
._
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
WM
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
__
ND
0.72
0.3
ND
—
0.12
2.2
7.6
ND
ND
7
0.75
_-
0.4
__
0.4
, Al I concentrations in mg constituent/kg residue, dry weight after extraction (24 hr shake test).
b!.ONHNO3.
j 1.0 N NaOH.
None detected'= ND.
r — Analysis not performed.
See Figure 11.
32
-------
TABLE 16. SOLUBLE SALT EXTRACTION CHARACTERIZATION OF RESIDUES*
III. ESSO, GREAT BRITAIN
Constituent
PH
Totai dissolved solids
COD
BOD
Chloride
Nitrate
Phosphate
Sulfate
Aluminum
Arsenic
Berrylliuni
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Silver
Sodium
Zinc
, Al 1 concentrations in
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
Spent Bed Material
Base
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
ND
1.5
—
0.15
— •
0.025
Water
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
Acidb
Soluble
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
Base0
Soluble
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
mg constituent/kg residue, dry weight after extraction (24 hr shake test) .
j 1.0 N NaOH.
None detected = ND.
? — Analysis not performed.
See Figure 11.
33
-------
TABLE 17. SOLUBLE SALT EXTRACTION CHARACTERIZATION OF RESIDUES
IV. ESSO, GREAT BRITAIN
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
° All concentrations in
Water
Soluble
12.1
3,808
19^.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 Ashd"
Acid
Soluble
6.2
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
Base
Soluble
"TO** ""
—
—
—
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
252.3
n
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
Fly Ashe
Acidb
Soluble
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
mg constituentsAg residue, dry weight after extract ion (24 hr shake test)"
d
1.0 N NaOH.
Cyclone fly ash.
Fines, stack fly ash.
f None detected = ND.
P — Analysis not performed.
See Figure 11.
34
-------
Oi
o
CO
300
285
270
255
240
225
210
195
180
165
150
135
120
105
90
75
60
45-
30-
15-.
0
f
Legend
• Standard (Control)
* NJSBM
* VSBM
o CFA
NJFA
FSFA
f:
See Table 6
letter code.
1 2
for explanation of
3
Day
Figure 4. BOD from residue water extracts.
-------
quite soluble calcium salt. High pH was found to have greatly increased the solubility
of sulfate and magnesium. Comparison of the results also showed that EFA and ESBM were
much higher in chlorides.
The BOD- test was used to measure the biochemical rate of decomposition of the residues'
water extracted samples. The solutions with added residues showed a lag time of two days
during which the BOD was inhibited. After the second day, the BOD of each residue
sample increased so that the 5-day biochemical oxygen demand was nearly as high as the
control sample. The results indicated that the leachates contained constituents which
acted as temporary inhibitors to microorganism growth.
Residue Leaching Test. The results of the accelerated residue leaching tests are shown
in Figures 5 to 7. Chlorides from NJFA and NJSBM,sulfates, calcium,iron, nickel,lead,
and zinc (except from NJFA), were leached at a relatively constant rate. The constituents
extracted from the EFA and ESBM maintained a fairly constant rate of leaching even after
100 liters of water per kilogram of residue passed through the bench scale columns. The
chlorides from VFA,and VSBM, and the zinc from NJFA were nearly completely leached
from the residues after six times the residues' weight of water had passed through the
columns. All the constituents leached from the residues were extracted readily.
The results of the bench-scale leaching test for the stratal materials are listed in Tables
18 to 24. All the stratal materials were leached. The stratal materials contained sub-
stantial quantities of sulfate (except the limestone and dolomite) and sodium. Nearly
all the sulfate was leached after 750 ml was passed through the columns; whereas,only
a fraction of the sodium appeared to have been extracted. The limestone leachate
contained traces of cadmium and potassium, while traces of arsenic,calcium,lead, and
potassium were leached from the dolomite sample. Traces of arsenic,calcium,and lead
were found in the bituminous coal; and the granite bedrock stratal material contained
traces of arsenic and calcium. The ^16 and *60 silica sand leached chlorides and po-
tassium, while chlorides and traces of arsenic,calcium,iron,and magnesium were found
in the claystone leachate.
Chemical Properties Tests
The acid neutralization capacities are found in Table 25. The values ranged from 2.6
equivalents of 1.0 N hydrochloric acid per kg for VSBM to 78.1 for the EFA. These
results were useful in indicating the potential for using fluidized-bed residues to con-
dition acidic soils.
The cation exchange capacities of the residues and the stratal materials are shown in
Table 26. EFA had the greatest exchange capacity at 13.6 ml per 100 g of residue.
NJSBM and ESBM had exchange capacities of 1.9 mg per 100 ml, while VFA and VSBM
were found to have 2.4 mg per 100 ml. NJFA was rated at 0.5 mg per 100 ml. The
cation exchange capacity for the stratal materials tested ranged from 0.6 for limestone
to 26.6 mg per 100 ml for decomposed granite.
36
-------
£•
•+-
|| 300
n\
5l
i| 200
|1 100
J m
O —
-
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0246
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0.15
0.10
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i
Fe
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«Aff> — T ' T " "T" r i r
0246
Leachate ratio (I/kg) Leachate ratio (I/kg)
£.
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o — \
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) 100 200 300
Leachate ratio (I/kg) Leachate ratio (I/kg)
£
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D v
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u -
i .
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- /
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.» — - • —
£--)*~ ' » ' ' '
Zn Legend
NJFA
NJSBM
Notes
Leachate ratio = Water : Residue
0246
Leachate ratio (I/kg)
Figure 5 . Leaching characteristics of NJFA and NJSBM.
37
-------
£
§5> 1,000
Q) £
| U 500
ll
Cl
1.0
s,"*~
- /' ^. — •— 0.5
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0246 0246
Leachate ratio (I/kg) Leachate ratio (I/kg)
x
|^ 2000
D)
2JP 1500
1 "S 1000 '
| o 500-
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Ca
x>^ 100
/ <^
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- x"-^
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.
,'
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0246 0 50 100 200 300
Leachate ratio (I/kg) Leachate ratio (i/kg)
>.
o "TO ?0
3 -* Z'U
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jj. K5
Jz •§ i.o
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0246 0246
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B^ 0.2
°"^J
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11
Leachate ratio (I/kg) Leachate ratio (I/kg)
Zn
Legend
xx ' — , VSBM
Xx"
^•^ Notes
" x^ Leachate ratio = Water : Residue
2 A A siyimics t-uicujarea value
Leachate ratio (I/kg)
Figure 6. Leaching characteristics of VFA and VSBM.
38
-------
J—
O O)
olf 10
— Q>
D -C
£ ° 5
3 i«
u .2
a
/
'. /
f ^^* m
^^ *
"" / -*
f m
^^ t ! t I 1 « 1
0 50 100 150 .
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_ <^
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O TO 4 n
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II 3.0
~S .a
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Leachate ratio (I/kg)
Zn
— S *
/x'*
^*"
y^
^ i i t i i i i , , ,
0 50 100 150
Leachate ratio (I/kg)
0 50 100 150
Leachare ratio (I/kg)
200
150
100
50
Ni
0 50 150 250
Leachate ratio (I/kg)
S0
200
150
100
50
0 50 100 150
Leachate ratio (I/kg)
Legend
EFA
ESBM
Note
Leachate ratio = Water : Residue
Figure 7. Leaching characteristics of EFA and ESBM.
39
-------
TABLETS. LABORATORY LEACHING0 TESTS; LIMESTONE
Constituent"
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.5
<5
<0.1
10.0
<0.001
—
0.01
<0.05
<0.05
0.6
<0.01
<0.0002
3.0
74rO
<0.01
Total Volume of Leachate
500
8.8
<5
<0.1
19.0
1.6
—
—
<0.05
<0.05
<0.01
<0.01
<0.0002
<0.1
68.0
<0.01
(m!)
750
8.9
<5
—
6.0
1.6
0.7
0.01
<0.05
<0.05
<0.01
<0.01
<0.0002
1.0
63.0
<0.01
a Water percolated through the bench scale residue sample.
bMg/l except for pH.
40
-------
Constituent
pH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium -
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.6
< 5
< 0.1
9.0
0.8
—
<0.01
2.2
< 0.05
0.1
< 0.01
< 0.0002
8.0
103.0
< 0.01
Total Volume of Leachate
500
8.8
<5
"0.1
3.0
0.8
—
—
0.1
<0.05
<0.01
< 0.01
< 0.0002
< 0.1
61.0
< 0.01
(ml)
750
9.2
<5
<0.1
< 1.0
0.8
0.6
ND
< 0.05
< 0.05
< 0.01
< 0.01
< 0.0002
< 0.1
60.0
< 0.01
aWater percolated through the bench scale residue sample.
Mg/l except for pH.
41
-------
TABLE 20. LABORATORY LEACHING TESTS'" BITUMINOUS COAL
Constituent"
PH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.0
< 5
<0.1
232.0
2.5
—
< 0.01
3.6
< 0.05
< 0.01
< 0.01
< 0.0002
4.0
80.0
< 0.01
Total Volume of Leachate
500
8.8
< 5
< 0.1
42.0
5.0
—
—
0.3
< 0.05
<0.01
<0.01
< 0.0002
<0.1
56.0
<0.01
(ml)
750
8.8
< 5
—
10.0
2,5
< 0.1
<0.01
0.9
< 0.05
< 0.01
< 0.01
< 0.0002
1.0
64.0
<0.01
a Water percolated through the bench scale residue sample.
b Mg/l except for pH.
42
-------
TABLE 2V. LABORATORY LEACHING0 TESTS: CLAYSTONE
Constituent
PH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.2
65
< 0.1
141.0
0.8
—
< 0.01
0.4
0.1
< 0.01
0.1
< 0.0002
< 0.1
161.0
< 0.01
Total Volume of Leachate
500
8.8
<5
< 0.1
9.0
1.6
< 0.1
—
< 0.05
< 0*05
< 0.01
< 0.01
< 0.0002
< 0.10
97.0
< 0.01
(ml)
750
9.0
<5
-_
2.5
1.6
< 0.1
< 0.01
< 0.05
< 0.05
< 0.01
< 0.01
< 0.0002
< 0.1
71.0
< 0.01
a Water percolated through the bench scale residue sample.
k Mg/l except for pH.
43
-------
TABLE-22.. LABORATORY LEACHING 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
< 0.1
123.0
< 0.001
—
0.01
< 0.05
< 0.05
< 0.01
< 0.01
< 0.0002
3.0
168.0
< 0.01
Total Volume of Leachafe
500
8.8
<5
<0.1
30.0
< 0.001
—
—
< 0.05
< 0.05
< 0.01
< 0.01
< 0.0002
< 0.1
77.0
< 0.01
(ml)
750
9.1
< 5
—
5.0
1,6
< 0.1
< 0.01
< 0.05
< 0.05
< 0.01
0.7
< 0.0002
2.0
70.0
< 0.01
Water percolated through the bench scale residue sample.
Mg/l except for pH.
44
-------
Constituent
pH
Chloride
Nitrare
Sulfate
Arsenic
Boron
Cadmium
Calcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
10.0
9.0
<0.1
103.0
0.8
—
<0.01
3.7
<0.05
0.2
<0.01
< 0.0002
50.0
245.0
< 0.01
Total Volume of Leachate (ml)
500
8.8
< 5
< 0.1
12.0
< 0.001
—
—
< 0.05
< 0.05
< 0.01
0.03
< 0.0002
< 0.1
68.0
< 0.01
750
8.8
<5
—
7,0
< 0.001
< 0.10
< 0.01
< 0.05
< 0.05
< 0.01
< 0.01
< 0.0002
< 0.1
62.0
< 0.01
a Water percolated through the bench scale residue sample.
Mg/l except for pH.
45
-------
TABLE 24. LABORATORY LEACHING TESTS: GRANITE BEDROCK
^ . b
Constituent
PH
Chloride
Nitrate
Sulfate
Arsenic
Boron
Cadmium
Cblcium
Iron
Lead
Magnesium
Mercury
Potassium
Sodium
Zinc
250
9.2
< 5
- < o.i
34.0
2.5
—
< 0.01
1.0
< 0.05
< 0.01
< 0.01
—
< 0.1
72.0
< 0.01
Total Volume of Leachate
500
8.8
< 5
< 0.1
10.0
< 0.001
—
__
< 0.05
< 0.05
< 0.01
< 0.01
< 0.0002
-------
TABLE 25 . RESIDUE ACID NEUTRALIZATION CAPACITY
Residue Neutralization Capacity
Type (equivalent of 1 N HCI/kg residue)
NJFA 17.5
NJSBM 26.0
VFA 8.8
VSBM 2.6
EFA 78.1
ESBM 35.5
TABLE 26 . RESIDUE AND COLUMN MATERIAL CATION EXCHANGE CAPACITY
Material CEC meq/lOOg residue
EFA 13.6
ESBM 1-9
VFA 2.4
VSBM 2.4
NJFA 0.5
NJSBM I-9
Limestone °'6
Dolomite 1 -9
Bituminous coal 2.7
Clay stone/sand, 4:1 7-2
Decomposed granite 26.6
#16 Silica sand ] '4
#60 Silica sand 2'8
Residues were slaked before determining CEC.
47
-------
Slaking results for the residues are shown in Figures 8 and 9. The slaking temperature
for NJSBM reached a maximum of 220° C after 1,000 sec. The temperature of the VFA,
VSBM, and EFA also increased with the addition of 3.8 I of water to 13.6 kg dry residue.
NJFA did not show any signs of exothermic reaction with water, probably due to a lower
content of lime. In fact, VFA probably contained less calcium oxide than VSBM since the
fly ash rose to a maximum of 35° C compared to the spent bed residue which reached a
temperature of 100° C.
Physical Properties
The results from the hydrometer and the sieve analyses were plotted together, and are
presented in Figures 10 and 11. Additional sieve analyses for the strata material are also
shown in Figures 12 to 14.
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 sizes, as received,
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 ex-
ception was unslaked Esso spent bed materials whose paricle size distribution corresponded
to a typical sand.
The specific gravity, moisture content, degree of saturation, loose dry density,and the
water-holding capacity determined for the fluidized bed residues are listed in Table 27.
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 of 2.02 was less than that for normal soils.
The spent bed residues were partially dissolved,thus, their specific gravity was not deter-
mined. The residues "as received" had no moisture content, and as a result, the degree
of saturation was zero for all the residues. The addition of water to the dry residues
changed the dry densities of all the residues tested except VFA. The dry density of the
EFA and ESBM decreased by 37 and 49 percent dry weight after slaking. NJSBM, on the
other hand, increased from 0.73 g/cc before slaking to 1.08 g/cc after slaking, a 48
percent increase. The ability of dry slaked residues to hold moisture, termed their water-
holding capacity, ranged between 0.44 and 0.98 grams of water per gram of dry sample.
The results of the permeability tests for the residues and stratal materials are shown in
Table 28. The hydraulic conductivities ranged from 6.8 x 10*4 to 3.7 x 10~^ cm/sec for
the residues; and, for the stratal materials, the permeability values ranged between
1.6 x 10~4 for sandy loam to 8.2 x 10~2 cm/sec for gravel.
The results of the physical and chemical characterization of the fluidized-bed residues
and the stratum materials were the basis for planning the construction of the larger pilot
test columns (see Chapter 6) which more closely simulated specific disposal environments.
48
-------
220 C after 1000 sec
Time (rain)
Figure 8. Temperafure change from water addition to dry residues.
-------
EFA
10
4812 1620
40
Figure 9.
80
Time (mln.)
100
120
Temperature change from wafer addition to dry residues.
-------
Legend
° NJFA, unslaked
O NJFA, slaked
A NJSBM, unslaked
A NJSBM, slaked
O VFA, unslaked
D VFA, slaked
O VSBM, unslaked
O VSBM7 slaked
1.0
0.1
Diameter (mm)
Figure 10. Particle size analyses: coal combusHon residues.
OTOOT
-------
100
90
80
70
-v
£ 60
"« 50
en >- 3U
-4-
O)
fc 40
c
30
20
10
0
Legend
O CFA, unslaked
O CFA, slaked
A EFA, unslaked
A EFA, slaked
D ESBM, unslaked
D ESBM, slaked
O FSFA, unslaked
o FSFA, slaked
1.0 0.1 0.01
Diameter (mm)
Figure 11. Particle size analyses « oil gasification residues.
.001
-------
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
Diameter (mm)
Figure 12. Particle size analysis: pea gravel, granite bedrock, and large gravel.
-------
Legend
o Si 11 ca sand1 (#60)
A Silica sand (#16)
O Decomposed granite
1.0 0.1
Diameter (mm)
Figure ]3, Particle size analysis.-silica sand and decomposed granite.
0.01
-------
Legend
o Bituminous Coal •*-Composite Sample
D VMiite Marble (Dolomite)—Composite Sample
A Limestone—Composite Sample
Diameter (mm)
Figure 14. Particle size analysis: coal, dolomite, and limestone.
-------
TABLE 27 RESIDUE PHYSICAL PROPERTIES
_ . „ • — — . " — -i r - •- c:- _. • - ^TV^ '_ii . — -i— i— _____ _ _ _ . ... _ _ r
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
Content b
(%dry wt.)
0
0
0
0
0
0
0
0
Degree of
Saturation*3
(%dry wt.]
0
0
0
0
0
0
0
0
Dry Density
Before After
| 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
0.88
0.67
0.78
0.76
Water- hoi ding
Capacity
(« H2° ]
\ g Residue /
0.66
0.50
0.74
0.44
0.70
0.98
0.76
0.78
, After slaking.
As received.
0 Not obtainable, as some portion of the material in question enters into solution.
-------
TABLE 28. PERMEABILITY OF RESIDUES AND COLUMN MATERIALS
' Hydraulic Conductivity R
Description (cm/se c)
Residue
PER Virginia fly ash • 1.9 x
J A
Exxon. New Jersey fly ash 6.4 x 10~
•+0 f -_- — - -_r A
PER Virginia spent bed material (slaked) 1.9 x 10"~
. - <*• i . ""<
Esso, England spent bed material (slaked) 6.8 x 10~
Exxon New Jersey spent bed material (slaked) 3.7 x 10~o
Esso, England fly ash (slaked) 1.6 x 10"
Column Material
Limestone (granular) 1.0 x 10 „
Dolomite (granular) 5.9 x 10 o
Bituminous Coal (granular) 6.1 x 10 _
Sanitary landfill 7.0 x 10_3
Claystone (4:1, #60 sand to clay)* 1.64x 10l
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~^
Sandy loam 1.6 x10 ~
Granite bedrock (3:1 p-gravel to decomposed granite)* 5.2 x 10«
Gravel 8.2 x 10"
By weight
57
-------
CHAPTER 7
PILOT COLUMN STUDIES OF RESIDUE DISPOSAL
Purpose
The primary purpose of this study was to evaluate the possible impacts of residue disposal
on different environments. The first step in this evaluation was to simulate likely disposal
locations on a pilot scale. This was done to allow testing under defined conditions/and
to control the physical and climatic variables which would otherwise affect the behavior
of the residues in natural environments. In the following section,the construction and
evaluation of the simulated disposal environments are presented.
Simulated Sedimentary Environmental Columns
Pilot test columns with simulated natural environments were constructed in 20.3 cm ID
PVC pipe. The various environments, chosen to simulate potential natural disposal sites,
were limestone and dolomite quarries,sanitary landfill, coal mine,ocean, and sandy,
clayey, and silty loam soils. A description of the columns constructed are presented in
Table 29, by number code, environment, and residue type tested. For each simulated
disposal environment, stratigraphic configurations were developed using the literature
search data and scaled to fit within the column's dimensions. Typical actual environ-
ments and the stratigraphic configurations of the test columns are described in the follow-
ing paragraphs (see Figure 15, legend for test column disposal environments).
Limestone and Dolomite Quarries
Actual Location. An abandoned limestone quarry might contain 20 to 40 percent limestone;
this remaining unquarried limestone would normally be left in place because it was of
poor quality, or not economically feasible to mine. The sedimentary sequence
of the quarry would orobaMy consist of a series of limestone, shale, .and sandstone
beds. This type of strata occurs with varying percentages relative to each
other. No "typical" strata below a limestone or dolomite quarry exists. It might be all
sandstone,shale, or a combination of any of the latter three types of strata. For this
reason, an arbitrary "known" sequence was selected from a real world quarry (see Table
30).
Test Column. The test columns represented a configuration in which residues would be
deposited in an abandoned quarry pit and underlain by the thickness of strata shown in
Table 30 (assuming a depth to the groundwater table of about 30 m). In this 30 m section,
below the residues, there would be 14.2 m of limestone,!. 04 m of c!aystone,and 14.2 m
of sandstone. Figuresl6 and 17 show the actual composition of the simulated limestone
and dolomite quarries. Relatively impermeable materials,such as claystone, were mixed
with standard Ottawa sand to provide greater permeability, thus resulting in reduced
scale coefficients. Obviously, standard claystone is so impervious that without the
increase in permeability provided by the sand mixture, there would have been no signifi-
cant column leachate. In nature, however, there is slow water movement over large areas
58
-------
TABLE29 . COLUMN AND RESIDUE IDENTIFICATION
Operating Conditions of Test Runa
Column
No.
1
2
3
4
5
6
, 7
> 8
9
10
11
12
13
14
15
16
17
18
19
20
Environment
Ocean
Limestone
Limestone >
Limestone
Limestone
Dolomite
Dolomite
Dolomite
Dolomite
Landfill
Landfill
Landfill
Landfill
Coal mine
Coal mine
Coal mine
Coal mine
Ocean
Ocean
Ocean
Residue
VSBM
NJSBM
VSBM
NJFA
VFA
VSBM
NJSBM
NJFA
VFA
VFA
VSBM
NJFA
NJSBM
VSBM
NJSBM
NJFA
VFA
NJFA
NJSBM
VFA
No.
NAb
19.7
NA
19.7
19.7
19.7
NA
19.7
19.7
19.7
19.7
19.7
19.7
Date
NA ~
8-28-75
8-28-75
8-28-75
8-28-75
NA
8-28-75
8-28-75
8-28-75
8-28-75
8-28-75
8-28-75
Average
Temperature Fuel Type
(°C)
843 Sewickley
coal
905-910 Champion
coal
(eastern)
843 Sewickley
coal
Excess Bed Ca/S Average
Air Sorbent rnfr Flue SO^
(%) (ppm)
18 Germany Variable Variable
Valley
limestone
9.4 Grove 2.5 360
limestone
18 Germany Variable Variable
Valley
limestone
(continued)
-------
TABLE 29 (Cont.)
Operating Conditions of Test Runa
Column
No. Environment Residue No
Average Excess Bed
Date Temperature Fuel Type Air Sorbent
Ca/o Average
mfr Flue SO
(ppm)
21 Ocean EFA N
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
A 11-1
1 i
0-75 89(
*
\
3 #6
i i
oil 5-
i
10 BCR 1
359 lime 1
i i
2(
i
DO
• Operating conditions at the pilot plant test site.
NA - Not available.
-------
BITUMINOUS COAL
(coarse ground lump bituminous coal)
CLAYSTONE
(clay and *60 silica sand)
DOLOMITE
(coarse meal grade dolomite)
GRANITE BEDROCK
(granific P-gravel and decomposed granite)
GRAVEL
(P~grave!)
SOIL HORIZON A
(sand, silt and clay loams)
SOIL HORIZON B
(sand, silt and clay loams)
LIMESTONE
(coarse meal grade limestone)
RESIDUES
SANDSTONE
mesh silica sand)
SANDSTONE
mesh silica sand)
SANITARY LANDFILL
(solid waste)
Figure 15 . Legend for test column disposal environments.
61
-------
TABLE 30. REPRESENTATIVE THICKNESSES OF LIMESTONE. &
Limestone Quarry .
Material
Limestone
Clays tone
Sandstone
Representa-
tive Stratum ^
Thicknesses (m)
14.2
1.4
14.2
Scale (a) .
Coefficient
15.7
3.9C
15.7
Material
Dolomite
Claystone
Sandstone
Dolomite Quarry
Representa-
tive Stratum
Thicknesses (m)
14.2
1.4
14.2
Scale (o)
Coefficient
15.7
3.9<=
15.7
a Thickness of layer in field to thickness of simulated layer fn column.
Excludes odd-mixed ^60 sand.
£
, As mixed, includes sand with clay in column, for increased permeability,
Includes odd-mixed *60 sand from claystone layer.
Source: 30, 49, 106.
62
-------
20
cm
£
o
o
CO
E
o
E
u
E
L>
£
u
IO
"
]p*--J*.l •''<•". V * •
"**•**-*» '-' 1 v"^ •'
t . r . r. r
:rir i£.r
I_Ltirr'
: * i i ' r1
I 1 T 1
£#£
*•( ^ t' L >
1 . *,;•.'
T^TpS-^T
?
.^ *! f\ "•* v
'",..v...:...v.;.:
,*,•.*.•.•-*.'.•.• •
•\''J'''/:
Freeboard
Residues
Sandstone (#60 sand)
Lirnesfone
CollecHon
Lysime^ers
Claystone
Sandstone (*60 sand)
Sandstone (*16 sand)
Gravel
1
Figure 16 . Abandoned limestone quarry test column.
63
-------
20 cm
E
u
o
CO
E
o
E
u
E
u
:X^v5<
Freeboard
Residue
Sandstone (#60 sand)
Dolomite
Collection
Lysimeters
Claystone
Sandstone (*60 sand)
Sandstone
sand)
Gravel
Figure 17. Simulated sedimentary environment: dolomite quarry test column,
64
-------
and, hence, considerable leaching through the claystone with time. Therefore, the test
columns provided an accelerated type leachate test of what could occur in nature.
Sanitary Landfills
Actual Location. Sanitary landfills are made of diverse materials (a 1 to 10 meter mix of
inert residues and organic solid waste, covered with about 15 cm layers of soil), placed in
natural ground. A summary of the estimated residential and commercial solid waste
generation which may be found in an actual landfill is shown in Table 31. Sanitary land-
fill was assumed to be 3 m of mixed refuse to 0.15 m of soil fill/lift,i.e.,95 percent
solid waste, and 5 percent cover soil. Both residues and refuse landfill can generate
pollutants when saturated with water.
Test Column. The sanitary landfill materials used in the test columns were prepared
according to the solid waste percentages shown in Table 31. The "as mixed" percentages
varied slightly,and are shown in Table 32. Organic solid waste and inert residues were
separated for physical testing after preliminary leaching tests. The arbitrarily selected
real worfd landfill environment with a known municipal-type solid waste mixture was
next placed in the test columns as shown in Figure 18. Assuming a depth of 30 m 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 33. The
scale coefficients of approximately 1:12 were chosen to conveniently replicate the strata
in the test column. Again, claystone was admixed with standard Ottawa sand to increase
leachate permeability, thus resulting in lower column scale coefficients.
Coal Mine
Actual Location. A typical abandoned coal mine would be underlain by a sequence of
shale,sandstone,Iimestone,and minor coal seams - the dominant sequence being shale
(see Figure 19). Residues could be disposed in an abandoned mine underlain by similar
strata.
Test Column. The test columns represented the abandoned coal mine environment which
was assumed to be underlain by the thicknesses of strata, listed in Table 34, with a 30 m
depth to groundwater. The strata configuration in the column was as illustrated in
Figure 20.
Ocean Environment
Actual Location. Residue wastes have been disposed into the ocean in many ways in-
cluding barging and open ocean dumping, piping the wastes in the form of a slurry onto
the ocean floor (or into a submarine canyon), or using the residues to fill and create land.
Test Column. The ocean environment test columns replicated a filled-land type of dis-
posal where only the tidal portion of the residue fill would be flushed by sea water for an
extended period of time (also waves and land drainage will cause some flushing). The
65
-------
TABLE 31» ESTIMATED 'RESIDENTIAL AND COMMERCIAL SOLID WASTE GENERATION
Product Source Categories ,
"As Generated" Basis (kkg x 10 )
Materials £ -73 8 £ g> 2 g „ | 1 fe
g- g J g '5>oJc§Jo>| fc t
8- ° g 'S-o - _g '§• "5 .2 £-5 ^ .§ £ •£ .g
wj v D •£- C "^ ^- v* "•*- r* C "^ -C rt x-\ ^
|l| 5°i si| Pld-8 £0
Paper 9.3 18.5
Glass — 10.1
Metals — 5.5
Ferrous — 4.9
Aluminum -- 0.5
Other non-ferrous — 0.1
Plastics tr 2.3
Rubber and leather — tr
Textiles tr tr
Wood _--_ _K6
Non-food product 9.3 38.0
tra tr 7.6
tr tr — 0.9
1.7 0.1 tr 3.4
1.5 tr — 3.2
0.1 tr — 0.1
0.1 tr ~ 0.2
0.1 0.2 1.2
'tr 0.5 2.4
0.5 0.5 0.6
_r- _ _?_«1_ _?_ °'5_
1.9 2.9 1.1 16.6
Material Totals
As Generated As Disposed
Basis Basis
kkgxlO6 Percent kkg x 106 Percent
35.5
11.0
10.8
9.6
0.7
0.4
3.8
3.0
1.6
4.2
69.9
31.3 42.9
9.7 11.3
9.5 11.4
8.5
0.6
0.3
3.4 4.3
2.6 3.1
1.4 1.8
3.7 4.2
61.7 79.1
37.8
10.0
10.1
—
«._
--
3.8
2.7
1.6
3.7
69.7
tofals
(Continued)
-------
Materials
Food waste
Product totals
c^j Yard waste
Miscellaneous
inorganics
Total waste
"As
111 I
o. w N o~a
i/j _\s U >l -i C
> o o> co
Product Source Categories ,
Generated" Basis (kkg x 10 )
Packaging
Major
Household
Appliances
Furniture
and
Furnishings
Clothing and
Footv/ear
As
u 42
-------
TABLE 32. SANITARY LANDFILL TEST COLUMN-AS MIXED,
Materials
Kg
Percent
Description
Paper
Glass
Metals
Plastics
Rubber and Leather
Textiles
8.39
2.27
2.15
0.86
0.59
0.23
Wood 0.77
Non-Food Product Total 15,26
Food Waste 3.18
Product Total
Yard Waste
18.44
3.40
Miscellaneous Inorganics 0.39
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
Total
22.23
15.3 Miscellaneous yard waste.
1.7 River gravel and silica sand.
100.0
68
-------
20cm
E
o
o
E
o
O
CO
E
y
••s^ _
^
E
o
E
o
o
CO
o
CO
K-
E X
o
Os
E
o
•\
^•»;
E
o
CO
1
n
_1^'.^ . -r-^- /**•*.
' * >^ V
•;-£«
* ^ A~*<
r AH- p :
; f *
VS^
n.
! !jy
'.'•4A"!?^(&
l.v^^Ss
^
B
.•.•,--• .-.-.-.•.-.•^
•.•-•.".•.'.•»•.•*•.•
&•:••/$
\
Freeboard
Residues
j
Sandstone (^ 1 6 sand)
~\
Sanitary landfill
®
\ Claystone
g^^-Col lection
lysimeter
/ Sandstone (^60 sand)
/ — -/*
/ Sandstone (* 16 sand)
®
Granite bedrock
y Sandstone C^' 6 sand)
. ^^
Gravel
Figure 18- Sanitary iandfill test column.
69
-------
TABLE 33 . 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.T
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.
70
-------
Coal
V_l" L Limestone
M_
— X
— J*—
— X. —
j=£i-£i
Jl=?>r5=-
> M I
71- I
(| |
1 1 i -
\ ' '
C~ f. T .1.
jfe
-fc
I 1 j
1
I I
- L r
Meters
1.83
0.3
0.6
"0.46
0.15
0.-6
Shale
1 .52 Limestone
0.76
0.3
o.is
1.40
0.02
0.15
0.015
0.92
0.30
0.79
1 .83
Shale
Legend
flc ShoU
/:;•' Sittitontor
t->-'. »ondj»ooe
-*-33B cool
f^~ Rtdondgretn
C.xi shale
Vs^ Slack thai*
( •• ConglQnwrolts
Figure 19. Stratigraphic section of a typical coal mine.
Source: 106.
71
-------
TABLE34. REPRESENTATIVE THICKNESS OF COAL
MINE SIMULATION TEST COLUMNS
KA , . , Representative Stratum Column Layer _ . _ ,r. . a
Material TL- i / \ TL- i / \ Scale Coefficient
Thickness (m) Thickness (m)
Bituminous Coal
Limestonei
Clay stone
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
• 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.
72
-------
20cm
£
CJ
CN
U-
E
o
>0
E
u
o
CO
£
u
<>
-*
^
E
u
5
E
u
a
P
o ,
OS/
V
0
3
E
o
rx
CM
^f
^g
O
CO ,
&&£tf
>S>v-:'!
tt'?v*
;^,f
ft--:'-:^
r^-i: ••••.<
^'^m
M^
'•i .*:-•-:,*-•
^•^<;;
A'_'J ^iiVl^'l
iiia^l^l
iiiailia
3i^=ra
;K?«(%SI
^^
^sa^%
sis^sssass
flM
^^®P»s
gft^g!!!3®
!!!!i^;;!"!
LJHfpi^
i!-iltfc
• i ' iOV' i
1 l 1TJS
i • F.,1 rl
T r L 11 *
1 ,. T r.-J-u-
, '. I..^1-.-f-
'r'.'.''i
I I 1 L
'_ T rr i -*- .
In T ' ' ,.1
wfe
"*• J r1 'j~**.
^
'•:*&*
V?;.r.?
^&r
1
Freeboard
Residue
Sandstone (ff 16 sand)
~v_
Bituminous coal
[
\ Claystone
\ Sandstone (^60 sand)
gL l_ .,
^^ Collection
/Lysimeters
/
/ Limestone
3»
Sandstone (*60 sand)
— ' Sandstone (^16 sand)
Gravel
I
Figure 20. Abandoned coal mine test column,
73
-------
number 60 sand used in the test column represented the deposited sandy base over which
the residues might be placed when filling was initiated. The structure of the ocean test
columns is shown in Figure 21.
Sandy/Clayey/ and Silty loam Environments
Actual Location. The sandy, clayey, and silty loam soils represent common land disposal
environments. Actual samples were found in the field according to the desired classifica-
tion, and the local in-situ locations established from the USDA-Soil Conservation Service
study described in the report, Soils of the Malibu Area.
Test Columns. Silty loam from the Castaic series was selected for the silty loam test soil.
Clay from the Cropley series was used for the clayey loam test soil, and very fine sandy
loam from the Huerhuero series for the sandy loam test soil. Table 35 shows the soil
characteristics, and Figure 22 indicates the locations from which these representative
soil samples werei obtained.
The silty and clayey loam test columns were admixed with number 60 mesh silica sand at a
rate of 4:1 sand to soil mixture by weight, to achieve satisfactory leachate drainage. The
strata configuration for the test columns is shown in Figure 23.
The 4:1 sand-to-soil mixture was also used in the other columns as a permeable,relatively
inert "filler." This allowed leachate movement through the simulated subsurface environ-
ments .
Pilot Test Column Construction
Column Preparation
A PVC pipe (20.3 cm ID) which was cut to a 3.05 m length served as a test column. The
simulated environment was marked on the column, as were locations for layer interfaces,
observation ports and soil moisture (lysimeter) ports. The lysimeterand 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, with a plastic drain spout glued into place.
After the columns were washed, cleaned and dried, the bottom cap was glued to the pipe
walls. Finally, the columns were bracketed in a vertical position to a supporting wall
and backfilled.
Column Material Preparation
Most of the column fill materials were usable when delivered. However, due to the im-
pervious characteristics of the extremely fine-grained claystone, it was apparent that
the 100 percent claystone and other impervious layers would not permit practical leachate
drainage. Permeability tests were performed on several different ratios of sand and clay
mixtures. The mix that provided a reasonable permeability coefficient, employed a ratio
of about a 3:1 by weight ratio of number 60 mesh silica sand to clay. Homogeneous
74
-------
20
cm
E
u
-o
-sf
E
o
8
E
u
E
o
CO
Collection
1® Lysi meter
Freeboard
Residues
Sandstone ^60 sand)
Sandstone (* 16 sand)
Gravel
§
Figure 21, Simulated sedimentary environment: sea water test column.
75
-------
TABLE 35 . 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. Nohcalcareous 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 Wbcky 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
-------
1 _~~ _ ~ .. \ ^
L 1 — 4- \"
~
PACIFIC
OCEAN
Clay loam
Sandy loam
Silty loam
0.5 1.0km
Scales 7.7 cm = 1.0 km
1 cm =0.13 km
Figure 22. Original location of representative soil samples.
77
-------
20 cm
E
u
8
E
u
•o
E
u
10
u
in
o
CN
GO
?:»/,
Freeboard
Residue
Sandstone (#16 sand)
Sandy Loam
or
Clay Loam
or
Silty Loam
Sandstone
Gravel
sand)
Figure 23: Simulated sedimentary environments: sandy,clay, and silty loam test column,
78
-------
batches were prepared in 5 to 10 kg quantities which were more easily handled. The
granitic limestone and other rock materials also required crushing to achieve the desired
permeability.
Standard particle size analyses were performed on all materials added to the test columns
(see Figures 10 through 14). Detailed grading analyses and other tests were performed in
order to establish practical design parameters which would accomplish the following:
1) prevent movement and clogging (piping of finer material into the coarser materials);
2) provide sufficient permeability to allow accelerated leaching; and 3) assure classified
reproducible grain sizes of standard materials. Table 36 presents the criteria used, and
Table 37 summarizes the results of the grading analysis.
The bulk densities were determined for the column materials, and these values were com-
pared with known densities of materials that exist in the field (see Table 38). Field
densities of typical construction materials were obtained from various dependable sources.
The densities of materials in the test columns were calculated using the actual weights of
materials added, divided by the volume of the filled columns. The ratios of these latter
densities indicated (as expected) that the actual densities of the materials placed in the
relatively small columns were less than that which normally prevail under field conditions.
As indicated, large-sized raw materials were first prepared by granulation and, hence,
provided a greater surface area exposed for accelerated reactions and greater percolation
flow than the coarser natural rocks. In the field, the natural rocky materials would have
less direct surface area exposed to percolating water moving through the strata. At specific
disposal sites, the amount of surface area exposed per meter of strata is a variable that
must be determined for: porosity, capillarity,and the extent of fractures and/or permea-
bility for each component subsurface material. Obviously, simplistic comparisons could
not be made of surface area exposed per meter of column test material versus the surface
area exposed per meter of stratum in the field.
Residue Preparation
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.
Column Filling
A filter paper (20.3 cm diameter,number 1 qualitative) with a plastic screen on top
(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.
Each column was filled with materials to simulate various strata in the quantities shown
in Table 39, and according to the depths established during the literature search. Care
79
-------
_ TABLE 36'. CRITERIA DEFINITION FOR GRADING ANALYSIS.
Objective Criteria '
1) Prevention of erosion and clogging P (filter)
(piping of finer material through — - , — ^ — < 4 to 5
. . l\ '-'rMT (SOil)
coarser material) 85
2) Permeability sufficient to prevent the D (filter)
buildup of large seepage forces - - -, — m — >4 to 5
r D15 (soil)
3) Approximately parallel grain size 50 filter) «^
curves 'U ~
D = diameter such that x percent of material is finer.
b X
filter = layer above, soil = layer below.
Source: 25,154.
80
-------
TABLE 37 . COLUMN MATERIALS GRADING ANALYSIS
^\F]|ter
Soil ^X.
Limestone
Dolomite
#16 Silica
Sand
#60 Silica
oo Sand
' P-Gravel
Coal
Claystone 4:1
Granite
Bedrock 1:1
Granite
Bedrock 3:1
r
#16
Limestone Dolomite Silica
Sand
2Marg.a'b
2 Marg.
2 2
2 2Marg. 2Marg.
222
2 2Marg.
2 Marg.
2
.... n ~ , .„ , r-i L Granite Granite
S,l,ca- P-Gravel Coal Claystone ^^ ^^
Sand hi 3:1
2 2Marg. 2
2 1 2
2 o.k. 2 22
1,3 2 Marg. 2Marg. 3
2 2
2 o.k. 2
o.k.
2 o.k.
2 o.k.
P Numbers indicate grading analysis criteria definition shown in Table 34 ,
Marg. = Marginal,
-------
TABLE 38 . MATERIAL DENSITIES OF NATURAL STRATA AND TEST COLUMNS
Material
P-Gravel
^16 Silica Sand
#60 Silica Sand
Clay: Sand
|5§ Limestone
Dolomite
Granite Bedrock
Sol id Waste
Bituminous Coal
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
Height
(cm)
18
6
9
55
200
49
52
91
46
91
61
61
61
Test Column
Area
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
Volume
(cu cm)
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
Density
(g/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
Density of
Field Rocks
(g/cc)
2.72d
2.32°
2.32
2.32
2.32
2.42C
2.42
2.71
2.71
2.85
2.72d
0.594
1.25
Ratio of Densities
Column:Field
(g/cc)
0.79:1
1.23:1
0.97:1
0.68:1
0.67:1
0.60:1
0.60:1
0.65:1
0.71:1
0.53:1
0.67:1
1 .06:1
0.71:1
.Sandstone
1:3 by weight
.Shale
Granodiorite
Source: 51,98.
-------
TABLE 39, MATERIALS IN TEST COLUMN LAYERS BY WEIGHT
Column Layers in . .
Order of Addition Limestone
Quarry
Pea gravel (.95 cm)
Pea grave! (.64cm) 12.2°
Silica sand ^16 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: Siity 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.
-------
was taken to add the bottom pea gravel layer slowly to avoid damage to the column's
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 circumfer-
ence.
During column filling, the leachate collection lysimeters were placed in the test columns
as shown in Figures 16 to 18, 20,21 ^and 23, with the lysimeter generally located in the
layer above the collection tube opening. Each lysimeter was made from a (1-bar) porous
ceramic cup which 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
number 200-mesh silica sand, applied in a thick slurry. The ceramic lysimeters were
placed in a surrounding Ottawa-type fine sand bed held in place by a cotton bag. Filling
of material was stopped just below each column opening, and the lysimeter assembly was
then lowered in place with a nylon string. The outlet tube was threaded through the col-
umn wall hole, and a rubber stopper was placed on the outlet tube and then secured in the
hole (see Figure 24 for the lysimeter schematic assembly and its placement in the columns).
The lysimeter elevation was adjusted above the outlet port. Column filling was then re-
sumed. When the lysimeters were covered with compacted materials to a depth of 15 cm
or more, the string was removed. For the soil environment test columns, the leachate
lysimeters were left attached to the string for several days while the columns were flushed
with tap water, and the simulated strata thus compacted. After washing the test columns
(see the following section) filter paper (20.3 cm diameter,*! qualitative) was placed in
the columns above the stratum materials and the residue was added. The quantities of the
fluidized-bed residues added to each column are shown in Table 40. The external leachate
drainage collection tubing and storage flasks,connectors, and manifold were installed as
shown in Figure 25.
Sample Bottle Labeling
Each lysimeter was provided with its own sample collection flask,labeled with the appro-
priate identifying column outlet number. All lysimeters, drains, and columns were uni-
formly identified sequentially from the bottom of the column up, starting with the bottom
drain. Leachate sample collection bottles were placed and labeled according to the
following code sequence: column number, column abbreviation, lysimeter letter, and
lysimeter location; a typical leachate column sample label was as follows: 2 LQ-C-
top lysimeter.
Column Washing
Before adding the test residues and monitoring the leachate reactions, the strata materials
in each column were flushed with tap water to establish the column's base-line leachate
quality and flow quantity. Tap water was added daily for at least two weeks until the
laboratory chemical analysis revealed a nearly constant level of leached constituents.
84
-------
Porous Ceramic Cup
#200 Mesh Silica Sand
Cot fon Cover
Column Material
Test
Column Wai!
Rubber Stopper
Polyefhelene Tubing
Figure 24. Lysimeter construction and test column placement.
85
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TABLE 40. RESIDUES ADDED TO COLUMNS
Residue Type
Quantity 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.
86
-------
T .
Figure 25. Outdoor columns leachate sampling apparatus.
87
-------
To determine the flow rate characteristics of each column,the outlet drains were kept open
for two days following each water addition until there was no further leachate flow into
the drain. A volume of 7.6 liters of tap water was added each time to the column inlet,
and the rate of water leached for each time period was intermittently measured over a
period of 27 to 30 hours. In Column 14, the residue quickly solidified, in situ, in spite
of the bench scale tests, and the water was perched over the top layers. This column was
immediately repacked with a larger sand mixture to eliminate the percolation obstruction.
All the columns were thus successfully proven to initially drain percolated water.Typical
column percolation data are shown in Figures 26 to 30. Each residue sample was then
mixed with the standard Ottawa sand to achieve a known permeable condition, and then
placed in the test columns on top.
Leachate Sampling and Analyses
Water Addition
Tri-weekly (every Monday,Wednesday,and Friday afternoons) a chemically known potable
water (see Table 41) was routinely added to all columns, except for the ocean disposal
columns which received sea water (see Tables 42 and 43). The low TDS potable water
was employed to simulate natural conditions since most drainage runoff contains similar
dissolved solids. The potable water supply source was natural runoff. 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. Procedures 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 environment rather than
in the former tidal prism environment.
Leachate Sampling Procedure
Leachate samples from the column drains and lysimeters were collected to analyze the
results of the previous day's water addition.
1. During weeks one through 52, the lysimeters and the drains were sampled Monday,
Wednesday, and Friday. After week 52, only the drains were sampled once a week on
Friday.
2. In the morning, the column lysimeters were sampled simultaneously using a system of
interconnecting tubing and flasks linked to a vacuum pump. Figure 31 illustrates a sche-
matic of a typical test column leachate collection system. A vacuum of about 635 mm
of mercury applied for five to six hours normally provided sufficient sample for analyses.
If there was insufficient sample at the end of the day, pumping was maintained until the
amount needed for the analyses was obtained. Conversely, the leachate valves were
-------
500
residue added
/'
1 j j r 1 j j r j J
200 400 600 800 1000 1200 1400 1600 1800 2000
Time (minutes)
Figure 26 . Drainage through limestone quarry columns.
89
-------
c
o
d
7500 -i
7000 -
6500 -
6000 -
5500 -
5000 ~
4500 -
4000 -
3500 ~
3000 ~
2500 -
2000 -
1500 -
1000 -
500
Legend
Column Number
6
7
8
9
6 after residue
added
. —i 1 1 1 i i r n—i
200 400 600 800 1000 1200 1400 1600 1800 2000
Time (minutes)
Figure 27 . Drainage through dolomite quarry columns.
90
-------
Legend
£ 4000 -4
£ 3500 -1
D
Column Number
10
11
12
T , 1 1 1 T
200 400 600 800 1000 1200 1400 1600 1800 2000
Time (minutes)
Figure 28. Drainage through sanitary landfill columns.
91
-------
Legend
J.
fc_
"o
<•!_
O
£•
•—
"c
o
a
7500 -
7000 -
6500 -
6000 -
5500 -
5000 ~
4500 -
4000 -
3500 -
3000 -
2500 -
2000 -
1500 -
1000 -
500 ~
Column Number
1.1
15
16 ^
14 after residue add^d /
•''""/""
/ /
/ /
/ /
/ /
/ /
/ /
/ /
/ /
/ / /
/ / /
/ / /
/ / ./
// X
' /
//' / s
// X ^
!/ / ^'
A / .^^^ ^*
/' ^^^-^
/ .it -X^^ ^^-*~^
//J s^ _— ••""^
y ? s* —
/x .-ir^-~~~
&•-• '^^ - - .
200 400 600 800 1000 1200 1400 1600 1800 20QO
Time (minutes)
Figure 29 • Drainage through coal mine columns.
92
-------
7500 -*
7000 -
500
after residue
added
j j 1 1 1 1 1 1
200 400 600 800 1000 1200 1400 1600 1800 2000
Time (minutes)
Figure 30 . Drainage through ocean disposal columns.
:93
-------
TABLE 41 . COMPLETE ANALYSIS OF LOS ANGELES OWENS RIVER AQUEDUCT
JJPOTABfrE WATER) COLUMNS TEST
Analysis 1975-1976 Averages Analysis
Spec .Elec. Cond.
(K x 106)
TDR (Calc.)b
Total Hardness (CaCO3)
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 (amnonia)
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
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 in mg/l, except as noted.
^Total dissolved residue = Anions + Cations + CO3 + HCO.T/2 + SiO
Source: 185.
94
-------
TABLE 42 .. CONSTITUENTS PRESENT IN SEA WATER
Constituent
Chloride
Sodium
Sulfate
Magnesium
Calcium
Potassium
Bromide
Carbon
Strontium
Boron
Silicon
Fluoride
Nitrogen (comp.)
Aluminum
Rubidium
Lithium
Phosphorous
Barium
Iodide
Arsenic
Cl = 19.00%oa
mg/kg
18,980
10,560
2,650
1,270
400
380
65
28
13
4.6
0.02-4.0
1.4
0.01-0.7
0.5
0.2
0.1
0.001-0.10
0.05
0.05
0.01-0.02
Constituent
Iron
Manganese
Copper
Zinc
Lead
Selenium
Cesium
Uranium
Molybdenum
Thorium
Cerium
Silver
Vanadium
Lanthanum
Yttrium
Nickel
Scandium
Mercury
Gold
Radium
Cl = 19.00°/oo
mgAg
0.002-0.02
0.001-0.01
0.001-0.01
0.005
0.004
0.004
0.002
0.0015
5x1 0"4
5x1 0"4
4x10-4
3x1 O"4
3x1 0'4
3x1 O-4
3x1 O-4
IxlO'4
4x10-5
3x1 0~5
6x1 0~6
0.2-3.0xlO"10
Cl=19.00 °/oo denotes a chlorinity of 19.00 parts per thousand.
Source: 190
TABLE 43. SEA WATER APPLIED TO THE TEST COLUMNS
1976-1977 Averages
Constituent
mg/l
Sulfate
Iron
Nickel
Lead
Zinc
2368
2.1
0.7
3.0
0.2
95
-------
Lysimeter
Tube
V
Typical
^.Clamp
Valve
Leachate
Bottom
Dram Collection
Bucket
.Collection Flask
1/4" Polyethelene Tubing
Y Connector
ToVacuum Pump
Moisture Trap
Figure 31 . Typical test column leachate collection system schematic.
96
-------
shut off sooner than the five to six hours if sufficient amounts of sample were obtained
in order to maintain a simulated groundwater profile.
3. After the vacuum pump was started, a graduated collection container was placed
beneath each drainage tube, and the drainage valve was opened.
4. At the end of the day, the amount of leachate collected in each container was noted
and the leachate sample was taken.
5. Equal amounts of daily samples were composited to make up each, weekly sample of
250 ml. These composite samples were used for the laboratory analysis.
6. After sampling, all outlet vales for the lysimeters and the drains were closed and
tap or ocean water was applied to the columns as described above.
Leachate Analyses
During the first 25 weeks of each column's operation, weekly composites were sampled;
thereafter, the frequency of laboratory sampling was reduced to one per each two-week
period, and after 32 weeks, to one per each four week period. During the first 40 weeks,
pH, specific conductance, total dissolved solids, chloride, sulfate, iron, nickel, lead and
zinc were analyzed at the request of the EPA project officer. Beginning on week 40,
additional constituents were analyzed. These were aluminum, boron, calcium, cadmium,
copper, mercury, nitrate, total organic carbon, and chemical oxygen demand. The
monthly composite samples were collected and analyzed during the first 65 weeks of
column operation; however, only drain samples were collected thereafter because of in-
creased costs. AM the drain samples following the 53rd week were composited over a
four-month period before chemical analysis in order to reduce costs. Each composite
sample was analyzed according to the EPA recommended procedures, referenced in
Appendix A. The analytical results of the test column leachate analyses were then sta-
tistically evaluated using a HP 9830A computer. The statistics included average values,
percent removal from each stratum layer, computerized plotting of constituent concen-
tration versus water applied, and comparison of the constituents with the water quality
criteria.
Column Operation During Testing
After the pilot test columns had been in operation for approximately one year, the fluid-
ized-bed mixtures and the clay stratum consolidated and reduced the percolation signifi-
cantly. Furthermore, the leachate precipitated minerals on the ceramic lysimeters and
caused fouling. Because the quantity of leachate sampled from many of the columns was
insufficient for analyses, those columns were dismantled and repacked after correcting
the problems. Columns 1,2,3,6,8,10,14,17,26,28, and 33 through 36 were thus dis-
mantled. Two factors induced restriction of the water percolation in the columns: first,
hardening of the residue at the top of the column and, second, consolidation of the si-
mulated clay type sedimentary materials. Thus, the percolation was eventually
97
-------
reduced to the point that it prevented movement of the leachate.
In summary, the dismantled columns 1,8,33,and 34 appeared to contain hardened residues;
columns 2,3 and 14 showed hardened column stratum material; and columns 33,34, and
36 showed some signs of fouled lysimeters. The columns were rebuilt with new lysimeters
and sand, and put into operation.
After the first few weeks of operation, many of the columns began leaking in the proximity
of the lysimeter ports but they were promptly repaired. Leaks also developed occasionally
throughout the column test period, and were immediately fixed. After the conclusion of
the pilot columns' tests, ali the columns were dismantled and inspected. These observa-
tions are summarized in Table 44. The NJFA in all but the dolomite and the soil environ-
ments had hardened into a rock-like state. The NJFA in the dolomite test column was
firm, but sandy. The VSBM and the ESBM residues in the limestone,dolomite, and sanitary
landfill columns (except ESBM in the sanitary landfill column), and the EFA in the lime-
stone environment were found to be soft and clayey in texture. In each of the other test
columns, the residue was found to be sandy in appearance. The claystone sand mixture
layers in the test-columns were generally moderately consolidated in texture. Exceptions
included limestone and dolomite test columns containing the NJFA residue which was not
consolidated. The sanitary landfill environments emitted a septic-type of odor and had
blackened the claystone layer lying directly below the sanitary Icn drill. The sandy soil
test column containing EFA had blackened and emitted a septic type odor.
Results and Statistical Evaluation
The average and maximum values, shown in Table 45 to 50 summarizes the results obtain-
ed from over 80 weeks of the test columns operations. In general, the results show that
the fluidized-bed residues from the pilot plants operated at Exxon,Linden,New Jersey and
Pope,Evans, and Robbins,Alexandria,Virginia leached lower chloride and greater sulfate
concentrations than the residues obtained from Esso, Great Britain. The sandy,clayey,and
silty soils test columns leached higher concentrations of chlorides and iron than did the
other types of simulated environments. Lastly, the simulated sanitary landfill leached
much less suifates, particularly from the VFA, than the other test columns. Further evalu-
ations of the analytical results are presented in the following paragraphs.
Rainfall Analogy
The analytical results of the pilot test columns were equated to potential natural disposal
sites. This was done by establishing a direct relationship between the actual volume of
water applied to the test columns and the rainfall one might expect in a specific natural
environment. The total volume applied to each test column during the duration of this
study varied from 170 to 1200 liters because of consolidation and hydrolization of some
residues and strata materials. Also, test columns were set up at a later date; consequently,
the water applied to these columns was considerably less than the 900 to 1200 liters
applied to the earlier columns. Therefore, a constant volume of applied water was es-
tablished. Over 250 I were added to all but one of the test columns; thus, a 250 I applied
98
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TABLE 44 . SUMMARY OF FLUIDIZED BED COMBUSTION COLUMN CONTENTS
Environment
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Dolomite
Dolomite
Dolomite
Dolomite
Dolomite
Dolomite
Residue
NJFA
NJSBM
VFA
VSBM
EFA
ESBM
NJFA
NJSBM
VFA
VSBM
EFA
ESBM
Physical State of Residue
Moisture Consistency
Medium
Medium
Medium
Medium
Medium to
high
Medium to
high
Medium to
high
Medium
Medium
Medium
Medium to
high
Medium to
Hard
Loose
Loose
Soft
Soft
Soft
Firm
Soft
Loose
Soft
Soft
Soft
Appearance
Rocky
Sandy
Sandy
Clayey
Clayey
Clayey
Sandy
Clayey
Sandy
Clayey
Sandy
Clayey
Comments
No hard material in the other
layers
Claystone layer was moderately
hard
Claystone layer was moderately
hard
Claystone layer was moderately
hard
Claystone layer was moderately
hard
Claystone layer was moderately
hard
No hard material in other layers
Claystone layer was moderately
hard
Claystone layer was moderately
hard
Claystone layer was moderately
hard
Claystone layer was moderately
hard
Claystone layer was moderately
high
hard
-------
TABLE 44 (continued)
Environment
Residue Physical State of Residue
Moisture Consistency Appearance
Comments
Sanitary Landfill
Sanitary Landfill
Sanitary Landfill
o Sanitary Landfill
Sanitary Landfill
Sanitary Landfill
NJFA
Medium
NJSBM Medium
VFA Medium
Hard
Soft
Soft
VSBM Medium to Soft
high
EFA
ESBM
Medium
Medium
Loose
Loose
Rocky
Sandy
Sandy
Clayey
Sandy
Sandy
Coal Mine
Coal Mine
Coal Mine
NJFA
NJSBM
VFA
Medium
Medium
Medium
Hard
Soft
Loose
Rocky
Sandy
Sandy
Landfill layer was black with
septic type odor. Claystone
layer was moderately hard
Landfill layer was black with
septic type odor. Claystone
layer was moderately hard
Landfill layer was black with
septic type odor. Claystone
layer was moderately hard
Landfill layer was black with
septic type odor. Claystone
layer was moderately hard
Landfill layer was black with
septic type odor. Claystone
layer was moderately hard
Landfill layer was black with
septic type odor. Claystone
layer was moderately hard
Claystone layer was moderately
hard
Claystone layer was moderately
hard
Claystone layer was moderately
hard
-------
TABLE44 (continued)
Environment
Coal Mine
Coal Mine
Coal Mine
Ocean
Ocean
Ocean
Ocean
Ocean
Ocean
Sandy Loam
Sandy Loam
Clay Loam
Clay Loam
Silty Loam
Silty Loam
Residue
VSBM
EFA
ESBM
NJFA
NJSBM
VFA
VSBM
EFA
ESBM
EFA
ESBM
EFA
ESBM
EFA
ESBM
Phys
Moisture
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
Medium
ical State of Residue
Consistency
Soft
Loose
Loose
Hard
Soft
Loose
Soft
Soft
Soft
Loose
Loose
Soft
Loose
Loose
Loose
Appearance
Sandy
Sandy
Sandy
Rocky
• Sandy
Sandy
Sandy
Sandy
Sandy
Sandy
Sandy
Sandy
Sandy
Sandy
Sandy
Comments
Claystone layer was moderately
hard
Claystone layer was moderately
hard
Claystone layer was moderately
hard
No hard material in other layers
No hard material in other layers
No hard material in other layers
No hard material in other layers
No hard material in other layers
No hard material in other layers
Sandy loam layer was black with
septic odor
No hard material in other layers
Clay loam layer was quite moist
No hard material in other layers
No hard material in other layers
No hard material in other layers
-------
TABLE 45 . VARIATION IN LIMESTONE QUARRY COLUMN LEACHATE CONSTITUENTS
Number
Residue0 of Cl
Type Analyses ovg max
NJFA 33
Top lysimeter
Bottom lysimeter
Drain
NJSBM 33
Top lysimeter
Bottom lysimeter
Drain
VFA 33
Top lysimeter
Bottom lysimeter
Drain
VSBM 36
Top lysimeter
Bottom lysimeter
Drain
EFA 24
Top lysimeter
Bottom lysimeter
Drain .
ESBM 24
Top lysimeter
Bottom lysimeter
Drain
29
26
24
32
32
32
34
26
23
34
30
30
113
110
67
132
118
125
91
72
70
49
96
82
100
75
62
105
115
133
400
645
246
357
410
700
Range of Concentration (mg/l)
SO4= Fe Ni Pb Zn
avg max avg max avg max avg max avg max
1102
1132
1231
795
528
517
687
844
661
920
606
495
903
599
618
506
357
298
1700
1600
2000
1220
970
780
1300
1500
1180
1800
1790
1780
1340
1180
1800
2250
900
2750
0.10
0.11
0.08
0.10
0.10
0.07
0.09
0.09
0.08
0.14
0.13
0.08
0.06
0.09
0.13
0.12
0.11
0.12
0.42
1.20
0.30
0.30
0.78
0.30
0.40
0.60
0.80
0.60
1.20
0.50
0.14
0.35
1.10
0.55
0.50
0.35
0.19
0.17
0.18
0.33
0.22
0.18
0.17
0.18
0.13
0.23
0.14
0.14
0.24
0.30
0.24
0.37
0.38
0.38
0.48
0.38
0.46
0.90
1.32
0.78
0.48
1.10
0.60
0.92
0.50
1.34
0.60
1.10
1.00
1.60
1.40
1.50
0.11
0.10
0.11
0.17
0.12
0.12
0.13
0.10
0.09
0.29
0.15
0.12
0.10
0.15
0.11
0.22
0.23
0.23
0.30 0.05
0.20 0.07
0.40 0.03
0.70 0.07
0.60 0.08
0.30 0.03
0.30 0.03
0.30 0.03
0.30 0.02
1.80 0.03
1.50 0.08
1.10 0.02
0.30 0.07
0.60 0.06
0.30 0.06
0.60 0.05
0.60 0.07
0.60 0.06
0.21
0.45
0.16
0.45
0.84
0.08
0.10
0.09
0.05
0.13
0.85
0.08
0.30
0.30
0.30
0.14
0.45
0.15
See Table 6 for residue identification.
-------
TABLE 46 . VARIATION IN DOLOMITE QUARRY COLUMN LEACHATE CONSTITUENTS
o
CO
, a Number
Residue r
TXPe Analyses
NJFA 33
Top lysi meter
Bottom lysimeter
Drain
NJSBM 33
Top lysimeter
Bottom lysimeter
Drain
VFA 33
Top lysimeter
Bottom lysimeter
Drain
VSBM 34
Top lysimeter
Bottom lysimeter
Drain
EFA 24
Top lysimeter
Bottom lysimeter
Drain
ESBM 24
Top lysimeter
Bottom lysimeter
Drain
Cl"
avg max
28
28
32
28
25
27
35
33
31
30
25
25
299
235
193
227
181
138
47
55
76
87
87
87
172
160
140
60
50
54
2418
2280
1459
1596
1459
555
Range of Concentration (mg/l)
SO4= Fe Ni
' avg max avg max avg max
1035
1094
1090
735
560
337
395
381
350
823
734
581
903
591
433
315
352
257
1570
1670
1700
1210
920
700
1340
1450
1330
1320
1300
1150
1554
920
1260
2300
3150
2450
0.12
0.12
0.05
0.13
0.12
0.09
0.11
0.12
0.08
0.16
0.07
0.07
0.09
0.08
0.08
0.11
0.12
0.12
1.20
0.90
0.60
0.40
0.90
0.60
1.37
1.02
0.70
0.80
0.30
0.30
0.50
0.35
0.30
0.75
0.65
0.70
0.19
0.20
0.16
0.19
0.20
0.16
0.16
0.13
0.10
0.30
0.17
0.16
0.26
0.22
0.16
0.33
0.42
0.51
0.51
0.48
0.35
0.51
0.48
0.35
0.46
0.34
0.37
0.85
0.34
0.65
0.60
0.60
0.60
1.90
1.60
1.90
Pb Zn
avg max avg max
0.13
0.08
0.07
0.13
0.08
0.07
0.07
0.07
0.04
0.26
0.11
0.10
0.15
0.09
0.11
0.17
0.18
0.18
0.60 0.03
0.20 0.04
0.30 0.02
0.60 0.03
0.20 0.04
0.30 0.02
0.30 0.04
0.30 0.04
0.20 0.02
1.20 0.07
0.40 0.05
0.50 0.03
0.44 0.06
0.30 0.04
0.30 0.08
0.70 0.06
0.70 0.09
0.80 0.07
0.07
0.12
0.07
0.07
0.12
0.07
0.09
0.12
0.08
0.40
0.16
0.11
0.14
0.12
0.17
0.21
0.62
0.28
See Table 6 for residue identification.
-------
TABLE 47 . VARIATION IN SANITARY LANDFILL COLUMN LEACHATE CONSTITUENTS
Number
Residue0 of Cl~
Type Analyses avg max
NJFA 31
Top lysi meter
Middle lysimeter
Bottom lysi meter
Drain
NJSBM 31
Top lysi meter
Middle lysimeter
Bottom lysimeter
Drain
VFA 33
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
VSBM 36
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
EFA 24
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
ESBM 24
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
68
45
29
33
54
48
37
32
38
32
31
28
55
48
33
33
105
135
110
98
150
111
146
164
180
163
54
79
127
122
120
76
150
154
147
84
110
122
107
105
312
766
304
633
565
530
433
475
Range of Concentration (mg/1)
SO4= Fe Ni
avg max avg max avg max
390
356
602
256
170
184
124
107
101
86
73
46
280
367
414
381
653
935
950
938
109
284
319
685
1150
920
1140
1030
994
1350
878
747
1110
880
735
410
1285
1410
1370
1200
1150
1540
1500
2400
680
2550
2750
4000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
- • o
.22
.19
.15
.11
.20
.18
.14
.14
.13
.13
.12
.11
.15
.18
,15
.19
.34
.34
.31
.38
.37
.38
.40
.52
1.00
0.70
0.50
0.40
0.80
0.60
0.32
0.60
0.40
0.40
0.68
0.40
0.70
1.00
0.60
1.20
0.90
0.70
0.70
1.00
0.60
0.90
1.00
1.70
Pb
avg max
0.51
0.39
0.09
0.07
0.11
0.10
0.08
0.05
0.09
0.06
0.07
0.07
0.22
0.16
0.21
0.15
0.11
0.09
0.07
0.07
0.16
0.19
0.19
0.19
4.70
5.50
0.40
0.30
0.60
0.30
0.30
0.30
0.40
0.30
0.39
0.22
1.50
0.70
1.30
0.90
0.31
0.30
0.30
0.40
0.30
0.50
0.60
0.40
Zn
avg max
0.04
0.03
0.03
0.03
0.04
0.03
0.05
0.02
0.03
0.03
0.04
0.03
0.04
0.06
0.03
0.02
0.05
0.06
0.08
0.05
0.09
0.10
0.10
0.09
0.30
0.20
0.10
0.20
0.30
0.20
0.42
0.19
0.30
0.20
0.30
0.20
0.20
1.24
0.32
0.09
0.10
0.40
0.98
0.21
0.33
0.25
0.30
0.40
See Table 6 for residue Identification.
-------
TABLE 48 . VARIATION IN COAL COLUMN LEACHATE CONSTITUENTS
o
Oi
Residue
Type
Number
of
Analyses
Range of Concentration (rng/1)
Cl SO4~ Fe
avg max avg max avg max
Ni
avg max
Pb
avg max
Zn
avg max
NJFA 34
Top lysimeter 33 87 982
Middle lysimeter 31 59 890
Bottom lysimeter 29 65 1058
Drain 32 65 944
NJSBM 34
Top lysimeter 38 93 799
Middle lysimeter 36 156 727
Bottom lysimeter 37 88 564
Drain 34 97 444
VFA 34
Top lysimeter 31 90 332
Middle lysimeter 31 88 613
Bottom lysimeter 25 86 339
Drain 30 85 328
VSBM 31
Top lysimeter 48 85 589
Middle lysimeter 33 100 439
Bottom lysimeter 45 305 360
Drain 34 138 283
EFA 24
Top lysimeter 116 540 706
Middle, lysimeter 123 775 588
Bottom lysimeter 109 417 623
Drain 79 246 686
ESBM 24
1700
1400
1600
1500
1160
1150
840
880
1330
1660
1420
1370
1484
1380
1400
1480
1300
1500
1500
2150
0.17
0.14
0.08
0.09
0.08
0.11
0.08
0.08
0.07
0.11
0.07
0.05
0.07
0.14
0.09
0.06
0.05
0.08
0.09
0.07
1.84
1.32
0.33
0.60
0.50
0.50
0.40
0.33
0.30
0.45
0.20
0.48
0.30
1.80
0.67
0,47
0.22
0.30
0.35
0»20
0.19
0.19
0.16
0.17
0.19
0.22
0.16
0.22
0.22
0.25
0.17
0.20
0.16
0.17
0.12
0.10
0.21
0.27
0.24
0.27
0.55
0.80
0.56
0.75
0.78
0.90
0.80
0.90
1.84
2.08
2.12
1.88
0.80
0.70
0.39
0.60
0.70
1.10
0.80
2.00
0.11
0.10
0.08
0.08
0.11
0.12
0.06
0.11
0.07
0.15
0.06
0.08
0.17
0.11
0.10
0.10
0.11
0.16
0.13
0.16
0.30
0.30
0.50
0.30
0.40
0.60
0.40
0.50
0.30
0.80
0.20
0.30
0.90
0.60
0.60
O.o0
0.30
0.50
0.50
0.70
0.09
0.08
0.02
0.03
0.04
0.05
0.02
0.04
0.05
0.12
0.02
0.03
0.06
0.09
0.03
0.04
0.06
0.04
0.04
0.05
0.30
0.55
0.07
0.12
0.17
0.48
0.12
0.50
0.47
0.62
0.11.
0.09
0.80
0.60
0.19
0.23
0.30
0.30
0.20
0.15
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
179
104
95
107
760
350
390
432
340
560
324
240
1100
5600
3600
1700
0.13
0.13
0.11
0.15
0C55
0.45
0.40
0.85
0.47
0.38
0.37
0.30
3.00
2.10
2.60
1.40
0.21
0.20
0.15
0.18
0.70 0.06
0.80 0.06
0.70 0.05
0.80 0.06
0.17
0.32
0.28
0.20
aSee Table 6 for residue identification.
-------
TABLE 49. VARIATION IN OCEAN COLUMN LEACHATE CONSTITUENTS
Number - Range of Concentration (mg/1)
Residue0 of Ci~ SO4= Fe Ni
Type Analyses QV9 max av9 max Qvg ma* avg max
NJFA 32
Top lysimeter
Drain
NJSBM 42
Top lysimeter
Drain
VFA 32
Top lysimeter
Drain
VSBM 37
Top lysimeter
Bottom lysimeter
Drain
EFA 22
Top lysimeter
Drain
ESBM 24
Top lysimeter
Drain
3690
3288
1708
2065
3013
3290
1496
1296
1328
1367
1393
-
1621
1657
7520
8610
3200
4200
5400
5500
3500
2380
2400
2100
2050
3150
2500
1.22
0.67
0.70
0.76
0.71
0.68
0.86
0.89
0.89
0.64
0.68
0.63
0.66
7.16
2.90
2.79
3.11
0.10
2.69
6.50
3.50
4.80
1.65
1.65
2.05
2.05
2.56
2.00
1.69
1.86
1.98
1.89
1.38
1.32
1.45
1.96
2.01
2.05
2.11
6.80
6.00
3.65
3.88
8.00
6.00
3.40
1.32
4.04
2.60
2.50
3.00
3.20
Pb
avg max
0.69
0.61
0.52
0.56
0.50
0.56
0.82
0.76
0.77
0.44
0.53
0.55
0.59
1
1
1
1
1
1
.70
.60
.90
.90
.50
.60
2.80
2.50
2.40
1,
1
1
1
.20
.00
.50
.20.
Zn
avg max
0.35
0.17
0.28
0.11
0.29
0.15
0.42
0.22
0.15
0.12
0.12
0.11
0.11
1.95
0.82
1.16
0.30
2.31
0.39
1.85
0.70
0.33
0.30
0.25
0.33
0.27
See Table 6 for residue identification.
-------
TABLE50 . VARIATION IN SANDY, CLAYEY, AND SILTY SOILS COLUMN LEACHATE CONSTITUENTS
Number
Residue of
Type Analyses
Sandy Loam
EFA 24
Top lysi meter
Middle lysimeter
Bottom lysi meter
Drain
ESBM 24
Top lysi meter
Middle lysimeter
Bottom lysimeter
Drain
Clay Loam
EFA 24
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
ESBM 24
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Silty Loam
EFA 24
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
ESBM 24
Top lysimeter
Middle lysimeter
Bottom lysimeter
D_ra.in
a See Table 6 for residue
Range of Concentration
C!"
avg
in
96
121
128
197
191
152
140
114
123
129
112
223
274
178
208
77
64
121
97
152
176
193
_L§5 .
max
290
251
690
446
1120
625
370
591
500
528
840
312
929
776
500
1277
218
208
730
470
520
825
640
579
so4-
avg
369
192
144
293
495
479
353
177
953
1287
920
993
976
1040
1136
990
317
469
379
663
114
100
57
62
max
1180
1000
1050
1400
1100
2100
1600
1980
3640
2300
2550
4050
4770
4500
2720
3675
640
900
920
1600
975
681
210
300
Fe
avg
4.14
4.50
12.93
7.56
0.42
1.70
1.85
4.13
1.14
1.64
0.51
1.25
0.55
0.24
0.52
0.48
0.17
0.14
0.18
0.35
0.15
0.12
0.11
0.09
max
31.5
31.5
37.0
30.0
5.5
19.0
22.0
28.0
8.00
5.70
2.10
2.55
6.00
0.50
1.85
1.65
0.80
0.30
0.85
1.80
0.30
0.25
0.20
0.20
identification.
(mg/l)
Ni
avg
0.50
0.25
0.24
0.23
0.50
0.49
0.43
0.19
0.73
0.67
0.54
0.59
0.67
0.59
0.40
0.29
0.26
0.27
0.26
0.24
0.38
0.31
0.31
0.19
max
0.80
0.50
0.60
0.40
0.90
0.90
1.10
0.40
7.80
7.60
7.80
8.80
1.90
1.90
0.80
0.50
0.50
0.40
0.50
0.40
0.60
0.50
0.60
0.60
Pb
avg
0.11
0.11
0.07
0.06
0.23
0.20
0.15
0.07
0.15
0.12
0.06
0.10
0.25
0.25
0.17
0.12
0.20
0.14
0.13
0.18
0.12
0.13
0.18
0.08
Zn
max avg
0.40 0.06
0.80 0.04
0.30 0.03
0.20 0.04
0.46 0.07
0.60 0.06
0.70 0.07
0.50 0.04
0.30 0.06
0.30 0.05
0.20 0.04
0.39 0.06
0.70 0.06
0.70 0.06
0.60 0.04
0.60 0.05
1.00 0.03
0.50 0.02
0.30 0.03
0.50 0.23
0.30 0.04
0.40 0.03
0.90 0.03
0.30 0.02
max
0.09
0.07
0.06
0.08
0.12
0.10
0.24
0.12
0.44
0.15
0.13
0.46
0.35
0.26
0.08
0.12
0.10
0.04
0.05
4.00
0.22
0.09
0.06
QJ24.
-------
volume was chosen to estimate real world rainfall data. Knowing the inside diameter of
the columns,the 250 I volume of applied water was determined to be equivalent to 38.64
meter of precipitation. Assuming a specific real world annual precipitation of 76 cm and
an 80 percent runoff coefficient ,the 250 I applied rate was considered equivalent to a
50-year in-situ normal percolation condition for an average land surface.
Constituent Removal Through the Cofumn Strata
The removal efficiency of the various simulated environments was calculated for each type
of residue. The results are shown in Tables 51 to 56. The upper portion of each table
lists the total weight of constituents contributed by the application of 250 I of potable
water (or sea water for the ocean environment test columns). The total weight of the con-
stituents in the residues are also listed.
Having established the total amount of constituents added to each test column, the per-
cent removed from each stratum was next calculated. The weights of constituents con-
tributed by the applied water and the quantity loss through the lysimeter ports were taken
into consideration. The results are,therefore, representative of the quantity leached only
from the residues.
The sanitary landfill column strata was the most effective environment for removing sulfate.
The other environments generally were moderately,but less efficient, in attenuating sul-
fate. Most of the simulated environments were efficient in attenuating the heavy metals.
The only exception was zinc,which readily leached through the limestone,dolomite/sani-
tary landfill,and the ocean (except the columns containing NJFA,VSBM,EFA,and ESBM
columns. Zinc also readily leached through the soils columns containing ESBM. Fairly
low percentages of lead removal were found in the ocean environment containing NJFA,
the sanitary landfill test column containing EFA,and all but the soils simulated environ-
ments containing ESBM. The leachate collected from the sandy and clayey soil test
columns contained high quantities of iron. The total quantities of iron in these latter
bottom leachates were 10 to 30 times higher than the quantity found in the residues,due
to high iron content in the natural soils. The silty soil test columns' drain leachates did
not have excessive amounts of iron. In general,chlorides readily leached through the
strata layers of the test columns. The only exceptions were the columns containing NJFA
which retained moderate amounts of chloride. Overall,the sanitary landfill simulated
environment showed the highest removal rate for NJFA,NJSBM,VSBM,and ESBM leachate
constituents. The coal mine test column was the next best environment for removing the
leached constituents from the fluidized-bed residues. For the disposal of the EFA,all the
simulated environments,except the ocean test column showed overall high removal effi-
ciencies.
Constituent Concentrations in the Test Columns' Drain Leachate
Figures 32 to 67 show the change in the concentration of the constituents found in the
test column drain leachates with the quantity of water applied. These data include the
results for the limestone and dolomite quarries,the sanitary landfill,and the coal mine
108
-------
TABLE 51. CONSTITUENTS REMOVED BY THE TEST COLUMNS; NJFA
Total Weiaht of Constituent Aonlu
Source0
Water ^potable)
Sea Water (ocean columns)
Residue -NJFA
Environment and Layer
Limestone
Environment
Claystone
Sandstone
Total removed
Dolomite
Environment
Claystone
Sandstone
Total removed
Sanitary landfill
Environment
Claystone
Sandstone
Granite
Total removed
Coal (bituminous)
Environment
Claystone
Limestone
Sandstone
Total removed
Ocean
Sandstone (upper)
Sandstone (lower)
Total removed
ci-
3,000
—
U5,500
Percent
cr
43
15
5
63
61
0
0
61
1
26
15
0
42
37
0
23
0
60
—
—
—
S04
5,000
675,000
420,000
Fe
20
525
45
Ni
<0.2
175
25
^ Column (n}
Pb Zn
2
750
55
ofConstituent Removed from Each Strntn
S04
41
0
0
41
31
0
5
36
74
2
0
10
86
42
6
0
3
51
10
21
31
Fe
31
16
15
62
4
3
37
42
—
—
—
__
—
18
0
56
0
74
4
54
58
Ni
4
0
68
72
60
0
19
79
72
4
4
0
80
4
0
87
0
93
28
38
66
Pb
35
14
11
60
29
9
2
40
9
0
31
17
57
16
2
22
0
40
31
2
33
2
55
200
,ayer_
Zn
85
1
2
88
83
6
0
89
4
33
42
2
81
85
4
1
1
91
24
11
35
All quantities of water and percentage values were based on the addition of 250 I
of water to the test columns.
109
-------
TABLE 52 . CONSTITUENTS REMOVED BY THE TEST COLUMNS; NJSBM
Total Weiaht of Constitui
Source0
Water ^potable)
Sea Water (ocean
Residue -NJSBM
ci-
3,000
columns) —
11,000
J?ercani
SC>4
5,000
675,000
350,000
Fe
20
525
30
snt ADD! I
Ni
< 0.2
175
20
of ConstijxrejiiLRejmiveiLfcQin_
ed to CoJumn 'a^
Pb
2
750
55
JzacbJSjrata-
Zn
2
55
710
|_pyer
Environment and Layer Cl~ $04 Fe Ni Pb Zn
Limestone
Environment 30 58 50 10 4 95
Claystone 2 5 5 6 40 1
Sandstone 0 0 25 57 5 1
Total removed 32 63 80 73 49 97
Dolomite
Environment 36 35 7 30 25 89
Claystone 0 21 50 29 18 5
Sandstone 0 8 6 6 11 0
Total removed 36 64 63 65 54 94
Sanitary landfill
Environment 4 94—60 33 92
Claystone 12 3 — 15 2 0
Sandstone 15 0 — 0 95
Granite 4 0 — 10 6 1
Total removed 35 97 — 85 50 98
Coal (bituminous)
Environment 43 47 53 5 22 0
Claystone 5 50080
Limestone 0 8 14 88 0 99
Sandstone 0 5 00.30
Total removed 48 65 67 93 33 99
Ocean
Sandstone (upper) — 68 53 40 67-80
Sandstone (lower) — 3 0 53 00
Total removed ~ 71 53 93 67 80
a All quantities of water and percentage values were based on the addition of 250 I of
water to the test columns.
110
-------
TABLE 53. CONSTITUENTS REMOVED BY THE TEST COLUMNS: VFA
Source0
Water ^potable)
Sea Water (ocean columns)
Residue - VFA
Environment and Layer
Limestone
Environment
Claystone
Sandstone
Total removed
Dolomite
Environment
Claystone
Sandstone
Total removed
Sanitary landfill
Environment
Claystone
Sandstone
Granite
Total removed
Coal (bituminous)
Environment
Claystone
Limestone
Sandstone
Total removed
Ocean
Sandstone (upper)
Sandstone (lower)
Total removed
a-
3,000
—
9,500
-EencenL
cr
i
34
18
53
2
10
22
34
11
21
7
16
55
42
0
24
0
66
—
SO4
5,000
675,000
275,000
of Consh'h
SO4
24
10
2
36
36
1
3
40
89
1
4
0
94
27
0
9
7
43
28
0
28
Fe
20
525
50
Ni
<0.2
175
65
Pb
2
750
115
jenfr Removed from Each Sfrnl
Fe
52
4
0
56
8
13
23
44
M_
__
—
42
0
18
4
64
64
0
64
Ni
86
3
2
91
80
0
2
82
92
0
0
2
94
5
0
85
0
90
46
36
82
Pb
58
5
17
80
58
5
7
70
70
5
0
9
84
3
16
20
35
70
0
70
Zn
2
55
150
•a Laver
•»—*->*/ •"••• •
Zn
79
5
84
87
1
0
88
86
0
89
74
12
86
73
0
72
All quantities of water and percentage values were base on the addition of 250 I of
water to test columns.
Ill
-------
TABLE 54 . CONSTITUENTS
REMOVED
Total Weiahf of
Source0
Water ^potable)
Sea Water (ocean columns)
Residue - VSBM
Environment and Layer
Limestone
Environment
Claystone
Sandstone
Total removed
Dolomite
Environment
Claystone
Sandstone
Total removed
Sanitary landfill
Environment
Claystone
Sandstone
Granite
Total removed
Coal (bituminous)
Environment
Claystone
Limestone
Sandstone
Total removed
Ocean
Sandstone (upper)
Sandstone (middle)
Sandstone (lower)
Total removed
ci-
3,000
— -
9,500
Percent
cr
24
15
8
47
26
16
0
42
8
18
10
0
34
1
13
0
0
14
—
—
—
—
SO4
5,000
675,000
400
BY THE TEST COLUMNS: VSBM
Constituent ADD! let
Fe
20
525
50
Ni
<0.2
175
30
J to folijr
Pb
2
750
70
nnlfl)
Zn
2 '"•
55
150
of Consfy-gent Removed^ from fach Sh-ata 1 aver
S04
41
7
3
51
46
3
4
53
62
0
7
9
78
41
11
0
2
54
63
5
0
68
Fe
16
35
11
62
6
45
19
70
—
—
—
—
—
78
0
6
14
98
40
14
0
54
Ni
87
7
3
97
70
11
0
81
3
0
92
3
98
57
3
37
0
97
67
25
0
92
Pb
10
22
f\f\
23
55
44
0
21
65
28
0
18
20
66
34
0
21
0
55
59
5
0
64
Zn
11
42
67
47
9
0
56
A n
42
27
0
12
81
50
16
7
2
75
0
14
36
50
a All quantities of water and percentage values were base on the addition of 250 I of
water to the test columns.
112
-------
TABLE 55. CONSTITUENTS REMOVED BY THE TEST COLUMNS: EFA
Total Weiaht of Consiituent Anal!
Source0
Water (potable)
Sea Water (ocean columns)
ci-
3,000
Residue -EFA 150,000
Environment and Layer
Limestone
Environment
Claystone
Sandstone
Total removed
Dolomite
Environment
Claystone
Sandstone
Total removed
Sanitary landfill
Environment
Claystone
Sandstone
Granite
Total removed
Coal (bituminous)
Environment
Claystone
Limestone
Sandstone
Total removed
Ocean
Sandstone (upper)
Sandstone (lower)
Total removed
.Eetcent
cr
74
0
8
81
5
23
11
39
75
0
10
0
85
72
0
6
2
80
—
—
—
SO4
5,000
675,000
320,000
Fe
20
525
70
Ni
<0.2
175
200
of Constituent Removed from
SOj
26
39
0
65
38
22
0
60
58
0
0
0
58
35
18
0
0
53
65
0
65
Fe
91
0
0
91
79
0
0
79
—
—
—
—
—
87
0
0
3
90
70
0
70
Ni
94
0
0
94
96
0
0
96
94
0
0
2
96
96
0
1
0
97
92
0
92
ed to CfiJjLIJDP ^a^
Pb
2
750
TOO
Each Strata J
Pb
36
0
15
51
53
0
14
67
7
0
0
21
45
0
0
46
32
34
Zn
2
55
80
LoYfiC.
Zn
61
0
4
65
90
0
0
90
76
4
0
89
f f
65
0
1 1
12
0
77
4
(Continued)
113
-------
TABLE 55
Total Weiaht of
Source0 Cl~ SO4.
Wcter : (potable) 3,000 5,000
Sea Water (ocean columns) -- 675,000
Residue - EFA 75,000 375,000 ,
(Cont.)
Qsosti^nLABQligdJoJ^okmn.
Fe
20
525
70
.Ni Pb
<0.2 2
175 750
200 100
(g)
Zn
2
55
80
Percent of Constituent Remove cTFromEaefi Strofg Layer
Environment and Layer Cl~ 504 Fe Ni Pb Zn
Sandy loam
Top
Middle, upper
Middle, lower
Bottom
Total removed
Clayey loam
Top
Middle upper
Middle lower
Bottom
Total removed
Silty loam
Top
Middle, upper
Middle, lower
Bottom
Total removed
85
1
0
0
86
91
0
< 1
< 1
91
85
4
0
< 1
89
69
8
4
0
81
51
0
11
0
62
69
0
2
0
71
—
—
—
—
c
—
—
—
—
44
11
0
0
55
96
1
1
0
98
98
0
0
0
98
98
0
0
0
98
13
46
1
0
60
37
11
13
0
61
1 •
26
0
6
7
39
75
4
5
0
84
71
4
7
0
82
38
27
0
0
65
All quantities of water and percentage values were based on the addition of 250 I of
, water to the test columns.
Total volume applied to column was 170 I,resulting from reduced permeability.
Very high concentrations of iron were found, not representative of actual removal efficiency.
114
-------
TABLE 56. CONSTITUENTS REMOVED
BY THE TEST COLUMNS: ESBM
Total JWeiflht of Constituent Aoolied to Column (a\
Source0
Water (potable)
Sea Water (ocean columns)
Residue - ESBM
Environment and Layer
Limestone
Environment
Claystone
Sandstone
Total removed
Dolomite
Environment
Claystone
Sandstone
Total removed
Sanitary landfill
Environment
Claystone
Sandstone
Granite
Total removed
Coal (bituminous)
Environment
Claystone
Limestone
Sandstone
Total removed
Ocean
Sandstone (upper)
Sandstone (lower)
TnK-il romni/etrl
ci-
3,000
—
75,000
Percent
cr
49 .
0
0
45
0
12
36
48
36
15
0
0
51
4
52
4
0
60
—
MM
SQ4.
5,000
675,000
375,000
Fe
20
525
50
.Ni
0.2
175
345
Pb
2
750
200
oFConstituent RemovedTrom Each Strati
SOj
50
7
0
57
65
0
3
68
89
0
0
0
89.
28
0
24
2
54
61
0
61
Fe
64
0
0
64
64
0
1
65
«*M
— —
•*•*
~
— —
56
0
6
0
62
66
66
Ni
96
0
1
97
93
0
93
92
0
1
94
95
0
0
0
95
94
94
Pb
39
0
39
36
0
36
45
0
0
j _
45
8
16
2
9
A •_
35
34
34
Zn
2
55
125
S-Layen.
Zn
44
0
44
55
0
55
59
0
t f\
62
45
7
cc
55
11
o
V
11
(Continued)
115
-------
TABLE 56 (Cont.)
Source0
Total Weightrof ConstituentAppliedtp Cojumn (g)
Cl- SO4. Fe Ni Pb Zn
Water" ^potable)
3,000 5,000 20 0.2 22
Sea Water (ocean columns)
Residue - -ESBM
75,000 375,000 50 345 200 125
Environment and Layer
.Bercent of Const?tuent Removed from. tqcJl_Sicgia,layej_
Cl- S04 Fe Ni Pb Zn
Sandy loam
Top
Middle, upper
Middle, lower
Bottom
Total removed
Clayey loam
Top
Middle, upper
Middle, lower
Bottom
Total removed
Silty loam
Top
Middle, upper
Middle, lower
Bottom
Total removed
36
0
12
7
55
44
0
35
0
79
54
0
0
0
54
67
1
7
8
83
53
0
0
7
60
93
4
<1
0
97
'b
k^
—
—
—
— b
—
—
—
—
53
0
0
0
53
94
1
0
1
96
96
0
1
0
97
98
0
0
0
98
24
7
8
26
65
27
8
15
5
55
50
4
0
3
57
•
52
4
14
9
79
59
1
7
3
70
83
0
0
1
84
a All quantities of water and percentage values were based on the addition of 250 I of
water to the test columns.
Very high concentrations of iron were found, not representative of actual removal efficiency.
116
-------
120
0)
.£ 60
E
Q
U
Figure 32
NJFA
Chloride
400 800
Total Water Applied (I)
1200
2,000 -
Figure 33
NJFA
Sulfate
400 800 1200
Total Water Applied (I)
Figure 34
NJFA
Iron
0.4r-
400 800
Total Water Applied (I)
Legend: Limestone quarry;
1200
I
•o
JO.2
Q
•^
Z
Figure 35
NJFA
Nickel
0 400 800 1200
Total Water Applied (I)
• Dolomite quarry; •— Sanitary landfill; Coalmine
Figures 32 to 35 . Chlorlde/sulfate/ iron, and nickel leached from test columns: NJFA.
-------
00
_ u.o
D)
0)
C
1 0.4
_Q
Q-
0
120
v^
^
-a
| 60
Q
"
0
Figure 36
NJFA
Lead
/,
1r~ 7"^ — * — i "^-- .
400 800
Total Water Applied(l)
Figure 38
NJSBM
Chloride
fi\
11
r\ ^\
[ V^xSCSS^
1 " •
400 800
Total Water Applied (1)
1 a/tansJ* 1 imaeh*>na nnnrr\/>
• i
1200
i
1200
0.4
D>
-a
-------
0.2
I
-a
a>
I 0.1
(U
Figure 40
NJSBM
Iron
400 800
Total Water Applied (I)
1200
|
-o
V
's
o
Figure 41
NJSBM
Nickel
0
400 800
Total Water Applied (I)
1200
T3
-------
TJ
o
s
Q
U
Figure 44
VFA
Chloride
400 800
Total Wafer Applied (I)
1200
2,000 t-
Figure 45
VFA
Sulfate
0
400 800
Total Wares-Applied (I)
1200
to
o
Figure 46
VFA
Iron
0
1200
Figure 47
VFA
Nickel
400
400 800
Total Water Applied (I)
Legend: Limestone quarry; —•— d olomite quarry; —
Figures 44 to 47 . Chloride^sulfate, iron, and nickel leached from test columns: VFA.
800 1200
Total Water Applied (I)
sanitary landfill; coal mine
-------
0.8
|
1 0.4
_Q
Q-
Figure 48
VFA
Lead
400 800
Total Water Applied (I)
1200
0.4
|
0.2
c
N
0
Figure 49
VFA
Zinc
400 800
Total Water Applied (I)
1200
120r-
u
Figure 50
VSBM
Chloride
Legend:
400 .800
Total Water Applied (I)
Limestone quarry;
2,000
a>
a 1,000
o
CO
Figure 51
Chloride
VSBM
Sulfate
1200
dolomite quarry;
400 800 1200
Total Water Applied (I)
sanitary landfill; coalmine
Figures 48 to 51 . Lead, zinc, chloride, and sulfate leached from test columns: VFA and VSBM.
-------
0.2L_
Figure 52
VSBM
Iron
0 400 800
Total Water Applied (I)
1200
0.4 -
0
Figure 53
VSBM
Nickel
400 800 1200
Total Water Applied (I)
0.8 _
Figure 54
VSBM
Lead
0 400 800
Total Water Applied (I)
Legend: Limestone quarry;
1200
0.4r
g. 0.2
'§
Q
c
N
dolomite quarry;
Figure 55
VSBM
Zinc
400 800 1200
Total Water Applied (I)
sanitary landfill; coal mine
Figures 52 to 55 . lron,nickel,lead, and zinc leached from test columns: VSBM.
-------
500*-
Figure 56
EFA
Chloride
400 800
Total Water Applied (I)
1200
O)
-------
0
Figure 60
EFA
Lead
400 800
Total Water Applied (I)
1200
0.4
D)
(I)
.E 0.2
S
Q
c
N
0
Figure 61
EFA
Zinc
400 800
Total Water Applied (I)
1200
500 -
U
Figure 62
ESBM
Chloride
0 400 800
Total Water Applied (I)
Legend: Limestone quarry; •
1200
27000|-
Figure 63
ESBM
Sulfate
1200
dolomite quarry; — •- —
400 800
Total Water Applied (I)
sanitary landfill; coal mine
Figures 60 to 63 . Lead/zinc/chloride/and sulfate leached from test columns: EFA and ESBM.
-------
2.0
Q
•£
i.o
Figure 64
ESBM
Iron
400 800
Total Water Applied (I)
1200
0.8,
Figure 65
ESBM
Nickel
400 800
Total Water Applied (I)
1200
Ol
Figure 66
ESBM
Lead
0.
) 400 800
Total Water Applied (I)
Legend: Limestone quarry;
1200
Figure 67
ESBM
Zinc
dolomite quarry;
400 800 1200
Total Water Applied (I)
-sanitary landfill; coal mine
Figures 64 to 67 . Iron,nickel,lead,and zinc leached from test columns: ESBM.
-------
environments. The ocean test column results were not plotted because the leachate
contained a high percentage of constituents attributed to the natural sea water applied;
therefore,the impact of the residue,alone,could not be determined. The results for the
soil loam simulated environments were also not plotted because similar behavior was found
for all the constituents.
For nearly all the test columns' environments, chlorides,sulfates,iron,and nickel were
readily leached during the first 50 to 100 I (equivalent to 7 to 14 meters of assumed rain-
fall) of applied water infiltrations. This can be readily seen by the peak concentrations
as shown in the plots. Broad peaks, indicative of major leaching, were seen for the sul-
fate and iron constituents leached from the NJFA,NJSBM,VFA and VSBM. Broad peak
concentrations also occurred for chloride and nickel constituents leached from the Esso
residues. Fairly constant leaching of lead and zinc occurred throughout the test period
as shown by the small peaks and valleys plotted in the figures. For the NJFA,NJSBM,
VFA, and VSBM leachates, the sanitary landfill and the coal mine simulated environ-
ments generally had lower concentrations of constituents than the other test column
leachates. The dolomite quarry test column leachates generally contained less constitu-
ents in the EFA and ESBM leachates.
Comparison of Constituents Leached with Surface Water Criteria
Table 57 lists the 1975 Environmental Protection Agency interim drinking water regula-
tions and the surface water criteria for public water supplies as mandated in the California
Administrative Codes. Table 58 lists the recommended maximum concentrations of trace
elements in irrigation water. The leachate analyses were compared with these surface
and drinking water criteria to determine the possible impact of the residues on ground-
water quality. The results are shown in Tables 59 to 63 . The quality of water applied
to the columns and leached past the lysimeters were used to calculate the percentages
for which each constituent exceeded the noted water quality criteria. The summation of
the quantity of water associated with each composite sample, for which the water quality
criteria was exceeded, was divided by the total quantity of water applied to the column
or passing by the lysimeter (as listed in Tables 59 to 63). Each fraction was multiplied
by 100 to convert it to a percent. As noted earlier in this chapter 50 I of applied water
to each column was considered to be equivalent to 7 meters of in-situ percolation condi-
tion for an assigned average rainfall land surface. Therefore, the percentage values as
shown in Tables 59 to63 relate to the percent of leachate volume expected to be
generated at such a site which would exceed the noted water quality criteria.
Chloride concentrations did not exceed the water quality criteria in any environment on
which the Exxon, New Jersey and the Pope, Evans, and Robbins, Virginia residues were
added. From 3 to 30 percent of the leachate from the EFA and ESBM exceeded the
chloride water criteria; the residues from the Esso pilot plant, Great Britain, contained
nearly ten times the quantity of chlorides as did the United States-processed residues
(see Table 16, Chapter 5). For most of the simulated environments, 50 to 90 percent of
the leachate volume exceeded the sulfate water quality criteria. The notable exceptions
126
-------
TABLE 57 . EPA INTERIM PRIMARY DRINKING WATER REGULATIONS J9751 AND
WATER QUALITY CRITERIA FOR BENEFICIAL USES2
EPA Interim Primary Water Quality Critgria for Beneficial Supplies
Drinking Water Regulations Municipal Agricultural Industrial Recreational Recreational Aquatic,
b Maximum (1) (2) Habitat
Constituent Contaminant Level
Physical
Color
Odor (number)
Temperature
Turbidity (JTU) le
Suspended Solids
Transparency (feet)
vj Inorganic Chemicals
'otal Alkalinity
Aluminum
Arsenic 0.05
Ammonia (as N)
Barium 1 .0
Berylium
Boron
Chloride
Chlorine'
Cadmium
Chromium 0.05
Cobalt
Carbon Dioxide
Copper
Cyanide
15/-
3/-
"""" r
5/-f
—
—
—
—
OJ
—
1.0
.1/.5
1.0
250/1 ,000
—
0.01
0.05
— -
—
l.O/-
.01/0.2
_-
__
__ --
__ __
5,000
—
—
5/20 . -
.1/2.0' —
—
— .
_..
0.5/2-10
70/300-1,000 600
—
.01/.05 —
.10/1.0 —
.05/5.0 --
—
.2/5.0
—
15/100
32/256
30°C
—
20/100
4
—
—
«
—
—
~
—
—
—
—
—
—
—
—
—
15/100
32/256
30°C
~
20/100
4
—
—
--
--
__
--
—
__
—
—
--
--
—
—
—
—
—
5°F above not.
10 or 10%
above natural
—
—
L
20h
0.1
0.01
0.01
0.5
—
—
—
0.003
0.003
0.05
—
15*
0.01
0.005
Continued
-------
TABLE 57 . (Continued)
EPA Interim Primary Water Quality Critgria for Beneficial Supplies
Drinking Water Regulations Municipal Agricultural Industrial Recreational Recreational Aquatic .
b Maximum (1) (2) Habitat
Constituent Contaminant Level
Inorganic Chemicals (Cont.) . ,
Fluoride
CaC03
Iron
Lead
Lithium
Manganese
Mercury
Molybdenum
- Nickel
00 NO + N02 (as N)
pH (units)
Selenium
Silver
Sodium Absorption
Ratio (SAR)
Sulfate
Sulfite
IDS
EC (umhos/cm)
Uranyl ion
Vanadium
Zinc
1.4-2.4"
__
0.05
__
__
0.005
-.-
—
10
0.01
0.05
—
__
__
__
__
__
—
—
—
0.8-1.7
500/-
0.3
0.05
__
0.05/-
0.005
—
—
10
6.0-8.5
0.01
0.05
—
250-500
«
500/1,500
—
5
—
5/-
1.0/15.0"
850
5.0/20.0
5,0/10.0
2.5
0.2/10.0
—
0.01/0.05
0.2/2.0
5.5-8.S/ — 6.5-8. 3/ 6.5-8.3
4.5-9.0 6.0-9.0 6.0-9.0
0.02
—
4.0/10-20
680
-- __ _- __
1,000
—
—
0.10/1.0
2.0/10.0
1.5
0.5
0.01
--
0.02
0.001
—
0.002
6.5-8.51
0.005
0.001
--
__
0.002
if50oq
3,000h
—
—
0.02
Continued
-------
TABLE 57 (Continued)
S3
•O
EPA Interim Primary
Drinking Water Regulations
Maximum
Contaminant Level
Water Quality Criteria for Beneficial Supplies
Municipal Agricultural Industrial Recreational Recreational Aquatic
(1) (2) Habitat
Organic Chemical
MBAS
Oil and grease
Phenols
PCB's
Phthalate esters
0.05/0.5
o.ooi/-
1.0-2.0
0/5.0
1.0-2.0
0/5.0
0
0.01
0.0001
0.3
Chlorinated hydro-
carbons
Endrin
Lindane
Methoxychlor
Toxaphene
Chlorophenoxys
2,4-D
2,4,5-TD silvex
ABS
Carbon alcohol extract
Carbon chloroform
extract
COD
LAS
Biological Properties
Total coliform (per
100ml)
Fecal coliform
(per 100 ml)
Dissolved oxygen
Toxicity a-
.0002
.004
.1
.005
.1
.01
0.15
75
100/10,000 5,000/-
20/2,000 1,000/-
Continued
200
2,000
1.0
0.2
1,000"
90% of natural
1.0
-------
TABLE 57 (Continued)
EPA Interim Primary
Drinking Water
• Maximum
Constituent Contaminant
Radioactivity
Gross beta (pc/1 )
Radium 226 (pc/1)
Strontium 90 (pc/1)
Regulations Municipal
Level
1,000
3
10
Water Quality Criteria for Beneficial Supplies
Agricultural
1,000
3
10
Industrial Recreational Recreational Aquatic
,, N /0\ Habitat
(1 ) (2)
100-1,000
1-3
2-10
Where two values appear (e.g.,a/b), the first number represents a threshold concentration,and the second represents
a limiting concentration. All single numbers represent limiting concentrations. Limiting concentrations are suggested
• as 90 percent!le limits, not to be violated by controlling factors more than 10 percent of the time.
_, Values are in terms of mg/l unless otherwise noted,
o j Cooling water requirements for fresh water once through.
Includes COMM,WARM,COLD,BIOL,SAL,WILD,RARE,MAR,MIGR,SFWN,except where otherwise noted.
, Monthly average, 5TU for an average of the consecutive days.
As measured by Secchi disc or expressed as percent light transmittance at prescribed depth.
? Applicable only as 10 percent above background for COMM,BIOL,SAL,and MAR.
. Applicable only to fresh waters; e.g.,WARM,COLD, WILD,RARE,MlGR,SPWN.
. Residual chlorine.
! Dependent on temperature from below 12°C to 32.5 C; higher limits for lower temperatures.
. Concentrations for water used by livestock are more stringent. They are: arsenic 0.05/1.0 and fluoride 1.0/5.0.
Applicable only to WARM,COLD,RARE,MlGR,and SPWN; COMM,BIOL,SAL, and MAR are 7.0-8.5 units pH; WILD
Is7.0-.2pH.
Applicable only to WARM,COLD, RARE,and SPWN; WILD is 1%- natural per 24 hrs.
Applicable only to COMM,BIOL,SAL,and MAR.
" Monthly average for the membrane filter technique.
^ Based upon summation of ratios of concentrations of potential toxicants and permissible concentrations; values for COMM,
BIOL,SAL,and MAR should not exceed 0.4.
Source: 162, 186.
m
n
-------
TABLE 58 . RECOMMENDED MAXIMUM CONCENTRATIONS OF
TRACE ELEMENTS IN IRRIGATION WATERS
Element
For Waters Used Continuously
on All Soil
mg/l
For Use up to 20 Years
on Fine-Textured Soils
of pH 6.0 to 8.5
mg/l
Aluminum
Arsenic
Beryllium
Boron
Cadmium
Chromium
Cobalt
Copper
Fluoride
Iron
Lead
Lithium
Manganese
Molybdenum
Nickel
Selenium
Zinc
5.0
0.10
0.10
0.75
0.010
0.10
0.050
0.20
i.o
5.0
5.0
u
2.5b
0.20
0.010
0.20
0.020
2.0
20.0
2.0
0.50
2.0-10.0
0.050
1.0
5.0
5.0
15.0
20.0
10.0
« ,-b
2.5
10.0
0.050C
2.0
0.020
10.0
These levels will normally not adversely affect plants or soils. No data are available
.for mercury,silver,tin,titanium,tungsten.
Recommended maximum concentration for irrigating citrus is 0.075 mg/l.
C For only acid fine-textured soils or acid soils with relatively high iron oxide contents.
Source: 187.
131
-------
TABLE 59. COMPARISON OF LIMESTONE COLUMN LEACHATE CONSTITUENTS
WITH WATER QUALITY CRITERIA FOR MUNICIPAL WATER SUPPLIES'*
== == Total Percent" Constituent Exceeded Wafer UualTfy CriterToe
Residue Type Wafer Cl SO^ " fe Pb Zn
and Sample Point (|;ters) (250 mg/lr (250 mg/IP (0.3 mg/l)P(0.05 mg/l)c(5.0 mg/l)b
NJFA
Top lysimeter
Bottom lysimeter
Drain
Average
NJSBM
Top lysimeter
Bottom lysimeter
Drain
Average
VFA
Top lysimeter
Bottom lysimeter
Drain
Average
VSBM
Top lysimeter
Bottom lysimeter
Drain
Average
EFA
Top lysimeter
Bottom lysimeter
Drain
Average
ESBM
Top lysimeter
Bottom lysimeter
Drain
Average
883
735
530
936
656
412
906
697
488
659
482
319
593
478
382
560
475
388
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
8
4
0
4
15
20
20
18
88
90
92
90
78
80
87
82
67
90
79
78
81
69
64
71
96
81
86
88
72
58
15
48
14
7
7
10
2
10
3
5
5
10
4
6
22
14
7
17
0
3
8
4
4
3
15
8
78
86
81
81
91
83
84
86
76
77
73
75
79
58
63
67
70
81
88
80
96
78
87
88
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.Permissible criteria for each constituent is given in parenthesis.
Water quality criteria for municipal water supply.
Maximum contaminant level for the EPA interim primary drinking water regulation, 1977.
The leachate analyses and the volume of water applied during the last four months of the
monitoring program were not included in the calculations because only the drain leachates
were sampled and analyzed.
CThe values include only the constituents leached from the residue. The quantities of metals
and ions resulting from the applied water were not included in the calculations.
132
-------
TABLE60
COMPARISON OF DOLOMITE COLUMN LFACHATE CONSTITUENTS
^H_WATER_QUAUTY CRITERIA FOR MUNICIPAL WATER
Residue Type
and Sample Point
NJFA
Top lysimeter
Bottom lysimeter
Drain
Average
NJSBM
Top lysimeter
Bottom lysimeter
Drain
Average
VFA
Top lysimeter
Bottom lysimeter
Drain
Average
VSBM
Top lysimeter
Bottom lysimeter
Drain
Average
EFA
Top lysimeter
Bottom lysimeter
Drain
Average
ESBM
Top lysimeter
Bottom lysimeter
Drain
Average
fo1a[~
Water
(liters)
874
600
355
898
665
431
907
633
363
1024
695
377
583
460
338
545
415
285
Percent
cl "
(250 mg/lf
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
19
22
23
21
17
18
29
21
Const; tuenflrx
• SO4 ,
'1250 mg/lf
91
91
90
91
86
86
61
78
37
43
34
38
95
95
88
93
96
87
68
84
26
18
16
20
Fe .
(0.3 rng/1)'
8
12
8
9
16
4
3
8
8
8
5
7
21
11
5
12
6
7
3
6
4
4
12
7
fer QuaTrty~Cr7i
Pb
3(0.05mg/l)c{5
77
75
58
70
91
64
65
73
53
65
37
52
85
68
87
80
62
47
61
57
62
69
80
71
=r=j==5=:
.0 mg/l)b
n
V
o
o
0
V
0
o
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
^Permissible criteria for each constituent is given in parentheses.
Water quality criteria for municipal water supply.
^Maximum contaminant level for the EPA interim primary drinking water regulations, 1977.
The leachate analyses and the volume of water applied during the last four months of the
monitoring program were not included in the calculations because only the drain leachates
were sampled and analyzed.
CThe values include only the constituents leached from the residue. The quantities of metals
and ions resulting from the applied water were not included in the calculations.
133
-------
TABLE ' 6'1 . COMPARISON OF SANITARY LANDFILL COLUMN LEACHATE
CONSTITUENTS WITH SURFACE WATER CRITERIA
FOR MUNICIPAL WATER SUPPLiESd
Residue Type
and Sample Point
NJFA
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
NJSBM
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
VFA
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
VSBM
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average —
EFA
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
ESBM
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
"Total
Water
(liters)
447
355
262
169
577
537
496
447
461
424
387
353
595
517
443
368
666
554
443
330
564
466
373
285
PerceriV Const! ruentTxceel3ecrWciiTerT3uarTfy Criteria6"
Cl , S04 , Fe , Pb Zn ,
(250 mg/l f' 1250 mg/i) (0.3 m3//lf (0.05 mg/l) (5.0 mg/1)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
7
21
9
10
8
4
17
16
11
52
56
69
33
53
34
30
22
27
28
9
10
9
6
9
44
44
53
47
47
90
94
95
98
94
13
38
35
15
26
95
72
59
47
68
75
68
63
50
64
55
54
59
58
57
74
85
70
64
74
84
— 65
59
47
64
68
66
64
67
66
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
' — ~~~~~—
0
0
0
0
0
0
0
0
0
0
Water quality criteria for municipal water supply.
"•Maximum contaminant level for the EPA interim primary drinking water regulation, 1977.
The leachate analyses and the volume of water applied during,the last four months'of the*
monitoring program were not included in the calculations because only the drain leachates
were sampled and analyzed.
eThe values include only the constituents leached from the residue. The quantities of metals
and ions resulting from the applied water were not included in the calculations.
134
-------
TABLE 62. COMPARISON OF COAL COLUMN LEACHATE CONSTITUENTS WITH
WATER QUALITY CRITERIA FOR MUNICIPAL WATER SUPPLIES^
Residue Type
ancTSample Point
NJFA
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Average
NJSBM
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Average
VFA
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Average
VSBM
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Average
EFA
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Average
ESBM
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Average
Total
Water
(liters)
561
508
454
401
826
722
620
517
844
781
719
657
422
367
297
231
590
468
346
224
602
487
371
256
PercenFCbnsti tueriFTExceeleirWcri
Cl .
(250 ma/lf '
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
10
10
10
0
8
15
11
4
13
11
. so4
°(250 mg/|)b
89
90
89
92
90
87
90
86
79
86
,
27
66
29
30
38
68
59
58
60
61
87
84
81
70
81
33
45
46
34
39
Fe
(0.3 mg/l)
7
8
4
5
6
7
6
5
4
6
4
4
0
4
3
6
8
9
0
6
0
2
3
0
1
6
10
7
9
8
ter~Quaf i ty-UrrFertae
Pb
3(0.05mg/l)C(5
76
72
53
53
63
73
53
35
65
56
51
75
47
58
58
58
59
59
37
53
74
91
66
89
80
96
93
86
74
87
Zn b
.0 mg/l)
n
w
n
V
n
V
o
V
o
o
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
, Permissible criteria for each constituent is given in parenthesis.
Water quality criteria! for municipal water supply.
C Maximum contaminant level for the EPA interim primary drinking water regulation, 1977.
d The leachate analyses and the volume of water applied during the last four months of the
monitoring program were not included in the calculations because only the drain leachates
were sampled and analyzed.
6 The values include only the constituents leached from the residue. The quantities of metals
and ions resulting from the applied water were not included in the calculations.
135
-------
TABLE 63 . COMPARISON OF SANDY, CLAYEY, AND SILTYSOILS
COLUMN LEACHATE CONSTITUENTS WITH ,
WATER QUALITY CRITERIA FOR MUNICIPAL WATER SUPPLIES
Residue Type
and Sample Point
Sandy Loam
EFA
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
ff n i i
ESBM
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
Clay Loam
EFA
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
VSBM
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
Sifty Loam
EFA
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
ESBM
Top Lysimeter
Middle Lysimeter
Bottom Lysimeter
Drain
Average
Tatar
Water
(liters)
224
202
177
156
394
291
201
112
171
123
89
61
254
202
141
79
575
430
294
163
585
479
366
265
Tercent Constituent txceeded Water
Cl
(250 mg/lf'i;
3
3
11
11
7 "~"~
'•"^ - ---^.---v^^^.-wr
13
18
27
18
19 "
0
19
11
4
19""J~
37
44
13
30
!31
*
0
0
13
1
^3 " "~
18
20
20
20
19
S04 u
>50 mg/l)D
71
45
25
34
44"" """""""
- -—^
58
41
22
5
31
95
93
66
64
80
46
46
71
57
55
53
63
51
41
52
-""
3
19
0
19
10
Fe h
(0.3 mg/IHO
80
86
66
80
78
- "• • ***- «*.)«-..
12
14
63
. 57 _
36
60
59
40
51
53 '*
„
43
37
56
54
47
*"" '~"~~ " "
4
3
8
2
4""
n - -"
4
0
0
0
1
"Quality Criferiae
Pb
.05mg/lf(5.
53
49
31
43
44
56
57
66
24 ., .
50
60
59
42
76
59 *"*"""""
'
70
72
90
. 78
77
""•"w
63
76
80
94
80 "
78
78
68
98
80 ~~
0 mg/l)b
0
0
0
0
^urt-V- '
0
0
0
0
0"}
0
0
0
0
0)
0
0
0
n
•7
0
0
0
0
0
0
0
0
0
0
L Permissible criteria for each constituent is given in parenthesis.
Water quality criteria for municipal wafer supply.
, Maximum contaminant level for the EPA interim primary drinking water regulation, 1977.
The leachate analyses and the volume of water applied during the last four months of the
monitoring program were not included in the calculations because only the drain leachates
were sampled and analyzed.
6 The values include only fhe const!hjents leached from the residue. The quantities of
metals and ions resulting from the applied water were not included in the calculations.
136
-------
were the NJSBM and VFA leachates from the sanitary landfill test columns Only 9 and
\8 P™?f !?h,S 'ef haf!' resPectiveIv' exceeded the water quality criteria. Likewise,
the ESBM added to the dolomite, sanitary landfill, and the sandy and silry soil simulated
environments resulted in relatively low sulfate concentrations. For nearly all the test
columns more than 90 percent of the leachate exceeded the Environmental Protection
Agency maximum contaminant level for lead; whereas, only 7 percent of the leachate
volume exceeded the recomnrended iron concentration. Some 35 to 80 percent of the EFA
and ESBM leachates from the sandy and clayey soil test columns exceeded the recommended
surface water limits for iron; however, as mentioned earlier in this chapter, the excessively
high iron concentrations were probably due to iron leached from the soils. The recom-
mended water quality criteria for zinc was not exceeded.
In general, the VFA showed the lowest percentage of leached contaminants which exceed
the water quality criteria and, hence, appeared to contribute the shortest pollution
creation period. Similarly, the sanitary landfill and the coal column test environments
showed the lowest percentages of leachate volume for which the constituents appear to
present the best environments for disposing fluidized-bed residues, particularly for the
VFA type. The ocean simulated environment wasi not evaluated for constituent contamina-
tion because of the high concentrations of some constituents attributed to the sea water.
Summary of Addition Analytical Results
After the 40th week of the test columns operation, the leachates were analyzed for
additional constituents. These constituents included aluminum, calcium, cadmium, cop;-
pe^mercury,boron,chemical oxygen demand(COD),nitrate-"nitrogen/and total organic
carbon. Since these tests were not started until after the 40th week of the test columns
operation, and a maximum of five analyses were determined for each constituent, only
preliminary evaluation of the results could be done. The minimum, maximum, end
average values for these constituents are tabulated in Tables 64 to 70 . Included in
these tables are the continued test results for pH, specific conductance, and total
dissolved solids.
The recommended irrigation water contaminant level for aluminum was not exceeded in
the leachate samples from any of the test columns. The highest levels of aluminum (above
1.0 m/l)were found in the ESBM leachate from the limestone, dolomite, sanitary landfill,
coal mine and clayey soil test columns, while most of the other test columns leached less
than 0.5 mg/l of aluminum. The cadmium concentration in the drain leachates generally
did not exceed the municopal water qualify criteria of 0.01 mg/l. The only exceptions
were the NJFA and NJSBM leachates from the dolomite simulated environments and the
NJSBM leachate from the coal mine test column; the concenfrations averaged only 0.02
mg/l.
In general, the leachates from sanitary landfill test columns were higher than from the
other simulated environments, and the VFA leached less calcium than the other flu,d,zed-
bed materials. The ocean simulated disposal sites showed high concentrates of calcium,
but much of this was due to the calcium content in the applied sea water.
137
-------
TABLE 64. LEACHATE ANALYSES OF THE TEST COLUMNS FROM THE NJFA°
CO
oo
Environment
Test
Column
Limestone
Top lysimeter
Bottom lysimeter
Drain
Dolomite
Top lysimeter
Bottom lysimeter
Drain
Sanitary landfill
Top lysimeter
Middle, lysimeter
Bottorm lysimeter
Drain
Coal mine
Top lysimeter
Middlei lysimeter
Bottom lysimeter
Drain
Ocean
Top lysimeter
Drain
Aluminum Cadmium
(5.0 rng/l)a'b'c (0.01 mg/l)d
Avgf
0.33
0.55
0.43
0.17
0.27
0.38
0.05
0.23
0.13
0.14
0.1
0.37
0.27
0.17
0.07
0.22
Min,
0.30
0.50
0.29
0.1
0.1
0.20
<0.02
<0.02
0.10
0.11
<0.02
0.10
0.20
0.13
<0.02
0.20
Max. Avg. Min.
0.40<0.0.1<0.01
0.6 O.OK0.01
0.80<0.01<0.01
0.2 O.OK0.01
0.5 0.02 0.01
0.70 0.02<0.01
0.10<0.01<0.01
0.50<0.01<0.01
0.20 0.01<0.01
0.20 O.OK0.01
0.20<0.01<0.01
0.30<0.01<0.01
0.30<0.01<0.01
0.30<0.01<0.01
0.10 0.08 0.06
0.30 0.09 0.05
Max.
0.02
0.04
0.06
0.02
0.04
0.03
0.02
0.01
0.03
0.06
0.01
0.01
0.01
0.01
0.09
0.11
Calcium
(no criteria)
Avg.
272
237
228
386
408
260
401
362
306
333
232
261
248
161
955
540
Min
171
160
109
282
264
202
160
262
127
107
164
144
138
101
420
202
. Max
425
275
500
450
460
480
675
515
515
480
270
370
365
325
2,400
2,400
Copper
(1.0mg/!)d
. Avg. Min.
O.OK0.01
O.OK0.01
<0.01<0.01
0.01 0.01
0.02 0.01
0.02 0.01
<0.01<0.01
<0.01<0.01
O.OK0.01
0.01<0.01
<0.01<0.01
<0.01<0.01
<0. 010.01
O.OKO.OI
0.08 0.06
0.09 0.05
Max,
0.02
0.04
0.06
0.02
0.04
0.03
.0.01
0.02
0.03
0.06
0.01
0.01
0.01
0.01
0.09
0.11
Mercury
(0.005mg/lf
, Avg. Min. Max.
0.0004 0.0003
0.0011 0.0011
0.0006 0.0005
0. 0003 <0. 0002
0. 0002 <0. 0002
0. 0004 <0. 0002
<0. 0002 <0. 0002
0.0004 0.0003
0.0007 0.0003
0.0006 0.0003
— .
0.0006 0.0006
0.0004 0.0004
0.0006 0.0005
0.0003 0.0003
0.0005 0.0003
0.0006
o.oon
0.0012
0.0006
0.0003
0.0005
<0.0002
0.0006
0.0010
0.0010
—
0.0006
0.0004
0.0012
0.0003
0.0006
Continued
-------
TABLE 64 (Continued)
Environment Boron .
Test (1 .0 mg/!)d
Column Avg.* Min. Max.
Limestone
Top lysi meter 1 .00
Bottom lysi meter 0.03
Drain 1 .20
Dolomite
Top lysi meter 0.50
Bottom lysimeter 0.50
Drain 0.80
Sanitary landfill
Top lysimeter 0,40
Middle lysimeter 0.45
Bottom lysimeter 0.50
Drain 2.60
Coal Mine
Top lysimeter 0.70
Middle lysimeter 0.60
Bottom lysimeter 0.70
Drain 1 .00
Ocean
Top lysimeter 1 .55
Drain 3.60
0.55
0.10
0.60
0.15
0.15
0.30
0.40
0.45
0.40
0.40
0.50
0.50
0.70
0.50
0.10
1.70
1.30
0.45
1.55
0.65
0.80
1.00
0.40
0.50
0.60
4.20
0.80
0.70
0.70
1.30
2.95
4.10
Nitrate as Nitrogen
(10mg/l asN)e
Avg. Min. Max.
0.43
0.31
1.53
0.25
0.27
0.71
0.49
1.28
0.45
1.09
0.92
0.88
0.83
0.70
0.99
0.26
0.16
0.09
0.23
0.14
0.19
0.14
0.07
<0.01
0.19
0.92
0.43
0.34
0.25
0.23
0.99
0.18
0.70
0.53
2.10
0.35
0.35
3.50
0.90
2.56
0.70
1.61
1.40
1.41
1.41
2.92
0.99
0.6
PH d
(6.0 to 8. 5)
Avg. Min. Max.
8.8
9.0
8.1
8,8
8.9
9.2
6.9
7.4
7.6
7.25
7.8
8.5
9.3
8.45
7.3
7.05
8.15
7.55
7.8
8.05
8.5
8.75
.6.75
7.0
7.25
7.1
7.6
7.5
8.8
7.5
7.1
6.8
9.5
11.5
8.55
9.55
9.3
9.5
7.2
7.8
8.05
7.5
8.2
9.7
10.1
11.1
7.7
7.35
Specific Conductance
( umhos)
Avg . Mm . Max .
1,540
2,090
1,570
2,360
2,240
2,200
1,490
1,460
1,320
1,590
1,850
1,450
2,315 2,160
1,680
1,545
1,460
1,460
1,620
1,560
1,350
,350
,440
,370
,340
,530
,430
,250
48,800 45,000
38,900 36,000
1,570
3,250
1,970
2,960
2,510
2,650
2,470
2,010
1,650
1,670
1,580
1,700
1,690
1,570
52,600
45,400
? All constituents are reported in mg/l unless otherwise noted.
The value in parentheses is the permissible contamination level as presented in Tables 56 and 57.
*j Recommended maximum concentration in irrigation waters (see Table 57 ).
Municipal water quality criteria (see Table 56 ).
f EPA interim primary drinking water regulation (see Table 56 ).
Avq = Includes.the average of 2 to 4 analyses of monthly composit
analyses of monthly composites and one analysts of a four-month composite.
-------
TABLE 65. LEACHATE ANALYSES OF THE TEST COLUMNS FROM THE NJSBM
Environment
Test
Column
Limestone
Top lysimeter
Bottom lysimeter
Drain
Dolomite
Top lysimeter
Bottom lysimeter
Drain
Sanitary landfill
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Coal mine
Top lysimeter
Middle lysimeter
Bottom lysimerer
' Drain
Ocean
Top lysimeter
Drain
Aluminum Cadmium Calcium
(5.0mg/l)a'b'c (0.01 mg/l)d (no criteria)
Avg.f
0.20
0.33
o.n
0.20
0.33
0.16
0.33
0.17
0.20
0.41
—
0.15
0.23
0.13
0.07
0.42
Min.
0.10
0.20
0.09
0.10
0.20
0.14
0.20
0.10
0.10
0.10
—
0.10
0.10
0.10
<0.02
0.20
Max. Avg.
0.30<0.01
0.50 0.02
0.20<0.01
0.30 0.01
0.50 0.02
0.20 0.02
0.5CX0.01
0.2CX0.01
0.30<0.01
O.cXKO.Ol
-- 0.02
0.20 0.02
0.50 0.01
0.30 0.02
0.10 0.06
0.51 0.09
Min.
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.02
<0.01
<0.01
<0.01
0.06
0.06
Max . Avg .
0.02 552
0.05 245
0.02 290
0.03 712
0.06 547
0.02 380
0.01 800
0.01 334
0.01 227
0.01 236
0.03 —
0.03 232
0.05 237
0.10 295 •
0.061,027
0.11 950
Min.
128
315
115
375
370
205
500
125
68
156
—
126
136
202
255
255
Copper
(1 -0 mg/l)d
Max. Avg. Min .
900 <0
106 <0
900 <0
1,180 0
900 0
652 0
1,100<0
670<0
280<0
480<0
~ 0
300 0
350 0
615 0
3,400 0
3,500 0
.OK0.01
.01 0.02
.OK0.01
,04<0.01
.02<0.01
.03<0.01
.OK0.01
.OK0.01
.OK0.01
.OKO.Ot
.02 0.02
.02 0.01
,02<0.01
.03<0,01
.06 0.06
.09 0.06
Mercury
(0.005mg/lf
Max. Avg. Min. Max.
0.02
0.05
0.03
0.10
0.06
0.10
0.01
0.01
0.01
0.02
0.03
0.03
0.05
0.10
0.06
0.11
__ __ __
__ __ —
0.0018<0.0002
0.0006 0.0005
—
0.0027<0.0002
0.0020<0.0002
0.0003 0.0003
0.0040 0.0040
0.0004 0.0002
-_ __
—
0.00090.0009
0.00070.0003
0.00050.0005
0.00260.0002
0.0021
0.0007
—
0.0042
0.0050
0.0003
0.0040
0.0005
__
—
0.0009
0.0019
0.0005
0.0038
Continued
-------
TABLE 65 (Continued)
Environment Boron .
Test (1 .0 mg/l)
Column AvgJ Min, Max.
Limestone
Top lysimeter 0.20 <0. 10 0.25
Bottom lysimeter 0.15 <0.01 0.25
Drain 0.45 <0.10 0.60
Dolomite
Top lysimeter 0.25 <0.10 0.45
Bottom lysimeter 0.10 <0.10 0.20
Drain 0.40 <0.10 0.50
Sanitary landfill
Top lysimeter 0.30 0.20 0.35
Middle lysimeter 0.1 5 0.100.20
Bottom lysimeter 0.20 0.10-0.35
Drain 0.30 0.10 0.45
Coal mine
Top lysimeter 0.30 0.30 0.30
Middle lysimeter 0.75 0.700.80
Bottom lysimeter 0.60 0.40 0.75
Drain 2.50 0.10 4.20
Ocean
Top lysimeter 2.60 2.60 2.65
Drain 4.20 4.00 4.30
Nitrate as Nitrogen6
(10 mg/l as N)
Avg. Mm. Max.
0.34
0.35
0.36
0.34
1.32
0.26
~
0.30
2.17
0.35
~
1.86
0.80
0.55
0.32
0.22
0.34
0.35
0.20
0.34
1.32
0.13
—
<0.01
0.53
0.10
—
1.86
0.25
0.36
0.32
0.16
0.34
0.35
0.44
0.34
1.32
0.70
—
0.60
3.80
1.32
—
1.86
1.34
1.32
0.32
0.46
F
(6.0
Avg.
10
10
12
12
10
12
12
9
9
9
—
8
8
12
7
7
.8
.2
.0
.5
.2
.1
.2
.2
.0
.7
.2
.0
.0
.45
.9
.ud
to 8. 5)
Min.
8
8
11
12
8
11
12
7
7
6
-
7
7
11
7
7
.1
.3
.8
.4
.6
.9
.0
.55
.45
.8
-
.8
.6
.9
.2
.75
Max.
12.2
12.2
12.4
12.6
11.9
12.4
12.4
11.9
11.9
11.7
—
8.55
8.8
12.2
7.75
8.3
Specific Conductance
( n mhos)
Avg. Min. Max.
4,870
2,220
3,080
8,770
2,660
4,490
7,720
2,660
2,380
2,375
1,380
1,450
1,560
3,620
35, 100
39,300
3,990
1,450
1,860
8,500
1,150
3,615
7,420
1,660
1,600
1,780
1,380
1,320
1,460
3,120
33,200
36,000
5,750
2,990
5,440
8,970
4,180
4,770
8,110
3,660
3,770
2,760
1,380
1,550
1,610
4,800
38,400
48,400
.All constituents are reported in mg/l unless otherwise noted.
The value in.parentheses is the permissible contamination level as presented in Tables 56 and 57.
. Recommended maximum concentration In irrigation waters (see Table 57 ).
Municipal water quality criteria (see Table 56 ,).
, EPA interim primary drinking wafer regulation Uee I able 5t>).
f Avg = Includes the average of 2 to 4 analyses of monthly composites and one analysis or a tour-month composite.
-------
TABLE 66, LEACHATE ANALYSES OF THE TEST COLUMNS FROM THE VFA
Environment
Test
Column
Limestone
Top lysimeter
Bottom lysimeter
Drain
Dolomite
Top lysimeter
Bottom lysimeter
Drain
Sanitary landfill
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Coal mine
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Ocean
Top lysimeter
Drain
Aluminum Cadmium
(5.0rng/l)a'b'c (0.01 mg/l )d
Avg.f
0.23
0.20
0.39
0.40
0.43
0.42
0.13
0.20
0.10
1.32
0.03
0.25
0.23
0.36
0.13
0.29
Min .
0.10
0.20
0.34
0.20
0.30
0.30
<0.02
0.10
0.10
0.20
<0.02
0.20
0.10
0.09
0.10
0.20
Max. Avg.
0.40<0.01
0.20<0.01
0.6CK0.01
0.7CK0.01
0.70 0.03
0.7CK0.0.1
0.20<0.01
0.30<0.01
0.10 0.01
1.9CK0.01
0.10<0.01
0.30<0.01
0.40<0.01
1,10<0.01
0.20 0.06
0.6 0.09
Min .
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.05
0.05
Calcium Copper
(no criteria) (1 .0 mg/l)
Max. Avg.
0.01
0.01
0.02
0.01
0.07
0.04
0.01
0.01
0.03
0.03'
0.01
0.01
0.01
0.01
0.09
0.11
84
126
84
111
116
62
195
195
188
159
185
188
184
143
795
403
Min.
57
70
58
93
106
51
88
91
102
60
110
122
125
108
106
173
Max . Avg . Min .
120 <0.01<0.01
215
-------
TABLE 66 (Continued)
Environment
Test (1
Column Avg.
Limestone
Top lysimeter 0.40
Bottom. lysimeter 0.25
Drain 0.85
Dolomite
Top lysimeter 1 .10
Bottom lysimeter 0.75
Drain 1 .80
Sanitary landfill
Top lysimeter 0.95
Middle lysimeter 0.95
Bottom lysimeter 0.95
Drain 1 .30
Coal mine
Top lysimeter 1 .00
Middle lysimeter 0.90
Bottom lysimeter 0.95
Drain 0.40
Ocean
Top lysimeter 3.50
Drain 5.10
-•- • - . . .. . — i —
Boron ,
.0 mg/l)d
Min. Max.
0.15
<0.10
<0.10
0.85
0.50
1.20
0.75
0.90
0.75
0.85
0.85
0.80
0.75
<0.10
1.70
1.70
0.55
0.60
1.32
1.20
1.00
2.05
1.00
1.00
1.15
1.50
1.10
1.10
1.10
0.95
5.30
5.85
Nitrate as Nitrogen6
(10 mg/! as N)
Avg. Min. Max.
0.30
0.24
0.45
0.70
0.26
0.01
0.97
0.13
3.10
0.13
2.38
1.94
1.75
1.06
—
3.60
0.26
0.04
0.05
<0.01
0.26
<0.01
0.97
<0.01
3.10
<0.01
1.10
0.34
0.39
0.26
—
3.60
0.35
0.44
0.58
1.40
0.26
0.02
0.97
0.26
3.10
0.26
3.66
3.54
3.10
4.43 '
--
3.60
PHrf
(6.0 to 8. 5)
Avg. Min. Max.
8.7
9.0
11.3
8.45
8.0
8.0
7.3
7.25
7.1
7.3
8.8
8.6
8.9
7.7
7.8
7.8
8.2
8.5
10.5
7.85
7.75
7.5
7.05
6.6
7.0
7.0
8.7
8.0
8.5
7.5
7.7
7.55
9.5
9.7
11.8
9.2
8.3
9.3
7.5
7.75
7.2
7.35
8.9
9.1
9.4
8.5
7.9
8.1
Specific Conductance
( // mhos)
Avg. Min. Max.
620
850
1,470
735
1,470
715
1,320
1,350
1,410
1,185
1,240
1,190
1,300
1,710
39,500
38,800
609
800
775
680
1,470
635
660
500
520
960
700
740
700
615
630
900
1,800
790
1,470
820
1,810
2,060
2,020
1,780
1,670
1,570
1,690
2,890
38,600 40,500
36,000 44,800
.All constituents are reported in mg/l unless otherwise noted.
The value in parentheses is the permissible contamination level as presented in Tobies 56 and 57 .
. Recommended maximum concentration in irrigation waters (see Table 57).
Municipal water quality criteria (see Table 56).
EPA interim primary drinking"water regulation (see Table 56 ).
f AVg == Includes the average of 2 to 4 analyses of monthly composites and one analysis of a four-month composite.
-------
TABLE 67 . LEACHATE ANALYSES OF THE TEST COLUMNS FROM THE VSBM
Environment
Test
Column
Limestone
Top lysimeter
Bottom lysi meter
Drain
Dolomite
Top lysimeter
Bottom lysimeter
Drain
Sanitary landfill
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Coal mine
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Ocean
Top lysimeter
Bottom lysimeter
Drain
Aluminum
(5.0 mg/f)a'b'c
AvgJ
0.23
0.30
0.50
0.25
0.24
0.21
0.05
0.33
0.30
0.14
0.33
0.13
0.30
0.24
0.30
0.35
0.23
F Min.
0.20
0.30
0.33
0.20
<0.02
0.19
<0.02
0.20
0.20
0.09
<0.02
<0,02
0.10
0.12
0.10
0.20
0.30
Cadmium Calcium
(0.01 mg/l)d (no criteria)
Max. Avg. Min.
0.30 0.
0.300.
1.2CKO.
0.30 0.
0.50 0.
0.30<0.
0.01<0.
0.50<0.
0.40<0.
0.2CKO.
0.60<0.
0.20<0.
0.9CKO.
0.70X0.
0.50 0.
0.64 0.
0.54 0.
OK0.01
OK0.01
OKO. 01
02<0.01
OK0.01
OK0.01
OK0.01
OK0.01
OK0.01
OK0.01
OK0.01
01O.01
OKO. 01
OK0.01
04 0.03
04 0.03
10 0.07
Max. Avg.
0.04 309
0.01 153
0.01 86
0.05 235
0.03 246
0.01 234
<0.01 58
<0.01 147
0.01 165
0.02 318
0.01 424
0.01 327
0.01 296
0.01 334
0.07 1,403
0.05 1,552
0.202,370
Min,
184
80
80
160
20
26
34
38
14
168
202
181
•170
127
522
782
1,100
Copper
0.0mg/l)d
, Max. Avg . Min .
450 0
190 <0
110<0
390 0
415 0
900 <0
70 <0
250 <0
225 <0
480 <0
675 <0
525 <0
482 <0
515 <0
3,400
2,300 0
5,020 0
,02<0.01
.OKO. 01
.OKO. 01
.02<0.01
.OKO. 01
.OK0.01
Max.
0.04
0.01
0.01
0.05
0.03
0.01
.OKO. OKO. 01
.OKO.OKO.Ol
.OK0.01
.OKO. 01
.OK0.01
.01<0.01
.OK0.01
.OKO. 01
-
.05 0.03
.10 0.06
0.01
0.02
0.01
0.01
0.01
0.01
—
0.06
0.20
Mercury
(O.OOSmg/lf
, Avg. Min. Max,
0.00060.0006
0.00080.0007
0.0009O.0002
—
—
0.00050.0002
0.0004 0.0004
0.0002 0.0002
—
0.00040.0002
—
0.0009 0.0009
—
0.00060.0005
—
0.00100.0010
0.00320.0006
0.0006
0.0008
0.0012
—
—
0.0006
0.0004
0.0003
—
0.0005
.—
0.0009
0.0005
—
0.0010
0.0040
Continued
-------
TABLE 67 (Continued)
Environment
Test (1
Column Avg.
Limestone
Top lysimeter 0.10
Bottom lysimeter 0.10
Drain 0.60
Dolomite
Top lysimeter 0.10
Bottom lysimeteKO.10
Drain 0.40
Sanitary landfill
Top lysimeter 0.15
Middle lysimeter 0.15
Bottom lysimeter 0.55
Drain 1 .05
Coal mine
Top lysimeter 0.25
Middle.lysimeterO.10
Bottom lysimeter 0.15
Drain 0.50
Ocean
Top lysimeter 0.25
Drain 0.20
Boron .
.0 mg/l)d
Min. Max.
<0.10
<0.10
<0.10
<0.10
0.15
0.10
0.90
0.20
<0.10O.10
<0.10
0.10
<0.10
0.10
0.15
0.15
0.10
0.10
0.10
<0.01
0.10
0.55
0.15
0.25
0.90
1.75
0.45
0.15
0.20
0.75
0.45
0.50
Nitrate as Nitrogen6
(10 mg/l as N)
Avg. M.in. Max.
0.33
0.30
0.14
0.35
0.26
0.23
0.13
<0.01
1.17
0.48
0.97
2.04
0.88
0.85
0.34
0.50
0.21
0.15
0.08
0.35
0.26
0.16
0.07
<0.01
0.84
0.16
0.97
0.53
0.88
0.22
0.34
0.26
0.44
0.44
0.35
0.35
0.26
0.40
0.19
<0.01
1.50
1.50
0.97
3.54
0.88
3.54
0.34
0.56
(6.0 to 8.5)
Avg. Min.
10.3
10.7
9.5
9.8
-10.2
11.9
7.8
7.6
9.0
7.3
11.4
10.6
11.2
11.0
10.8
11,8
9.0
10.4.
11.7
7.9
,8.3
.11.8
7.3
7.3
7.45
7.2
11.2
8.4
10.8
8.2
9.1
11.5
Max.
11.8
11.2
8.2
11.8
12.0
12.4
8.3
8.3
11.65
7.6
11.5
11.8
11.6
12.0
11.8
12.2
Specific
( f-
Avg.
2,060
1,310
1,130
2,560
2,500
2,970
895
1,180
1,480
1,700
2,330
1,890
1,970
2,740
27,600
44,400
Conductance
i mhos)
Min. Max.
1,815
1,190
1,080
1,645
1,260
1,680
790
1,140
1,440
1,440
1,750
1,540
1,670
1,390
15,600
37,100
2,530
1,430
1,240
3,470
3,120
5,750
1,000
1,220
1,530
2,080
2,990
2,310
2,270
3,480
40,600
47,100
, All constituents are reported in mg/l unless otherwise noted.
The value in parentheses is the permissible contamination level as presented in Tables 56 and 57.
. Recommended maximum concentration in irrigation waters (see Table 57 ).
^ Municipal water quality critieria (see Table 56 ).
EPA interim primary drinking water regulation (see Table 56).
f
Avg = Includes the average of 2 to 4 analyses of monthly composites and one analysis of a four-month composite.
-------
TABLE 68. LEACHATE ANALYSES OF THE TEST COLUMNS FROM THE EFA
Environment
Test
Column
Limestone
Top lysimeter
Bottom lysimeter
Drain
Dolomite
Top lysimeter
Bottom lysimeter
Drain
Sanitary landfill
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Coal mine
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Ocean
Top lysimeter
Drain
Aluminum
(5.0mg/l)a'b'c
AvgJ
0.10
0.25
0.21
0.13
0.65
1.56
0.25
0.03
0.23
0.17
0.37
0.20
0.27
0.46
0.20
0.28
f Min.
0.10
0.10
0.02
0.10
0.10
0.10
0.10
<0.02
0.10
0.05
0.10
<0.02
0.10
0.30
0.10
0.10
Cadmium Calcium
(0.01 mg/l)d (no criteria)
Max. Avg. Min,
0.10 0
0.40 0
0.30 0
0.20 0
1.40 0
2.19<0
0.40 0
0.10<0
0.50<0
0.20O
0.70 0
0.30O
0.60
-------
TABLE 68'(Continued)
Environment
Test
Column
Sandy soil
Top lysi meter
Middle lysimeter
Bottom lysimeter
Drain
Clayey soil
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Silty soil
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Aluminum
Avgf Min.
0.23
0.40
0.07
0.23
0.27
0.08
0.23
5.78
0.28
0.38
0.55
0.98
<0.02
<0.02
<0.02
0.08
0.20
<0.02
<0.02
0.20
<0.02
<0.02
0.20
0.10
Cadmium
Max . Avg . MI n . Max .
0.70 0.02<0.01
0.70 0.02 0.01
0.10 0.02 0.01
0.70 O.OK0.01
0.4CK0.01<0.01
0.10<0.01 0.01
0.30<0.01<0.01
9.86 O.OK0.01
0.70<0.01<0.01
1.0CK0.01<0.01
0.9CKO.OK0.01
1.55<0.01<0.01
•
0.05
0.03
0.03
0.03
0.01
0.01
0.01
0.03
0.01
0.01
0.01
<0.01
Calcium
Avg. Min.
277
291
130
144
554
370
423
103
322
257
174
426
210
237
75
no
193
200
230
40
65
46
50
287
Copper
Max. Avg. Min. Max.
360 0.03 <0.01
365 0.02 0.01
178 0.02 0.01
255 0.01 <0.01
915<0.01 <0.01
540 0.01 0.01
615<0.01 <0.01
353 0.01 <0.01
730<0.01 <0.01
660<0.01 <0.01
270<0.01 <0.01
0.05
0.03
0.03
0.03
0.01
0.01
0.01
0.03
0.01
0.01
0.01
480<0.01 <0.01<0.01
Mercury
Avg. . Min,
0.0018
0.0012
0.0004
0.0009
0.0009
0.0007
0.0004
0.0005
0.0007
0.0010
0.0004
0.0013
0.0014
0.0008
0.0002
0.0004
0.0001
0.0004
0.0003
0.0003
0.0001
0.0007
0.0001
0.0003
Max
0.0024
0.0018
0.0006
0.0034
0.0017
0.0009
0.0005
0.0009
0.0013
0.0012
0.0007
0,0057
Continued
-------
TABLE 68 (Continued)
Environment Boron .
Test 0 -0 mg/l)d
Column Avg. Min. Max.
Limestone
Top lysi meter 0.25
Bottom lysimeter 0.20
Drain 0.25<
Dolomite
Top lysimeter 0.25
1 *
Bottom lysimeterO.10<
Drain 0.25<
Sanitary landfill
Top lysimeter
-------
TABLE 68 (Continued)
Environment _
T . Boron
Test
Column Avg. Min.
Sandy soil
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Clayey soil
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Silty soil
Top lysimeter
Middle lysimeter
Bottom
Drain
0.15 0.15
0.10 <0.10
0.10 <0.10
0.30 0.20
0.45 0.10
0.20 0.20
0.35 0.30
0.65 0.55
0.25 0.25
0.15 0.15
0.10 <0.10
0.45 0.15
Max.
0.20
0.20
0.15
0.35
0.90
0.25
0.45
0.70
0.25
0.20
0.25
0.65
Nitrates
Avg. Min.
<0.01
1.64
1.97
1.48
0.97
0.64
0.27
0.58
1.99
0.85
0.88
0.09
0.01
0.86
1.43
1.09
0.97
<0.01
<0.01
0.55
1.99
0.48
0.75
<0.01
Max,
0.01
2.41
2.50
3.21
0.97
1.25
0.53
0.70
1.99
1.21
1.01
0.53
Avg.
7.2
7.6
8.2
7.6
11.4
8.3
7.55
7.8
9.5
10.1
11.8
12.1
— "T
PH
Min.
6.9
7.4
7.9
7.2
11.1
8.1
7.3
7.0
7.9
8.5
11.5
12.1
Max.
7.5
7.9
8.5
7.8
11.6
8.5
7.8
8.1
12.3
12.2
12.1
12.2
Specific Conductance
Avg. Min Max.
1,390
1,235
810
1,150
1,720
1,410
1,910
2,320
2,970
2,450
1,970
4,620
1,300
1,100
760
1,040
1,670
1,250
1,850
1,560
675
405
800
2,700
1,440
1,370
840
1,200
1,780
1,570
1,970
3,900
7,520
6,460
3,540
5,280
, All constituents are reported in mg/l unless otherwise noted.
The value in parentheses is the permissible contamination level as presented in Tables 56 and 57.
. Recommended maximum concentration in irrigation waters (see Table 57 ).
Municipal water quality criteria (see Table 56 ).
, EPA interim primary drinking water regulation (see Table 56 ).
Avg = Includes the average of 2 to 4 analyses of monthly composites and one analysis of a four-month composite.
-------
TABLE 69. LEACHATE ANALYSES OF THE TEST COLUMNS FROM THE ESBM
en
o
Environment
Test
Column
Limestone
Top lysi meter
Bottom lysimeter
Drain
Dolomite
Top lysimeter
Bottom lysimeter
Drain
Sanitary landfill
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Coal mine
Top lysimflter
Middle lysimeter
Bottom lysimeter
Drain
Ocean
Top lysimeter
Drain
Aluminum
(5.0mg/l)a'b'c
Avg.f Min.
0.25
0.24
3.25
0.20
0.23
1.27
0.65
0.35
0.38
1.70
0.17
0.50
0.24
2.68
0.23
0.28
0.10
<0.02
0.10
0.20
0.20
1.10
0.20
0.10
0.30
1.10
<0.02
0.10
0.10
0.40
0.10
0.18
Cadmium Calcium
(0.01 mg/l)d (no criteria)
Max. Avg , Min,
0.40 0
0.70<3D
5.80O
0.20O
0.300
1.6000
1.20O
0.60O
0.60O
3. 10
-------
TABLE 69 .Continued)
Environment-
Test
Column
Sandy soil
Top lysimeter
Middle lysi meter
Bottom lysi meter
Drain
Clayey soil
Top lysi meter
Middle lysimeter
Bottom lysimeter
Drain
Silty soil
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
Aluminum
Avg.* Min.
0.60
0.63
0.25
0.46
0.18
0.48
0.10
2.49
0.20
0.25
0.30
1.08
0.10
0.20
<0.02
<0.02
<0.02
<0.02
<0.02
0.20
0.20
0.20
0.30
0.30
Cadmium
Max. Avg. Min.
1.6(X0.01<0.01
0.9CXO.OK0.01
0.50 O.OK0.01
0.72<0.01<0.01
0.40<0.01<0.01
1.8CKO.OK0.01
0.20 O.OK0.01
4.KXO.OK0.01
0.2(X0.01<0.01
0.3CKO.OK0.01
0.30
-------
TABLE 69 (Continued)
en
ro
Environment
Test (1
Column Avg.*
Limestone
Top lysimeter 0.20
Bottom lysimeter<0.10
Drain 3.20
Dolomite
Top lysimeter 0.15
Bottom lysimeter 0.35
Drain 0.20
Sanitary landfill
Top lysimeter 0.15
Middle lysimeter 0.10
Bottom lysimeter 0.10
Drain 1 .35
Coal mine
Top lysimeter 0.15
Middle lysimeterO.10
Bottom lysimeter 0.10
Drain 0.20
Ocean
Top lysimeter 0.75
Drain 0.25
Boron .
.0 mg/l)
Min. Max.
0.10
<0.10
<0.10
0.10
0.20
<0.10
<0.10
<0.10
<0.10
0.10
0.10
0.25
0.10
5.50
0.20
0.50
0.25
0.35
0.15
0.15
2.05
0.20
<0.1CK0.10
<0.10
<0.10
0.35
0.15
0.15
0.25
1.15
0.53
Nitrate as Nitrogen6
(10 mg/l as N)
Avg. -Min. Max.
0.28
0.22
0.39
1.98
0.66
1.32
0.27
2.44
1.00
0.29
0.22
. 1.39
1.65
1.05
_-
0.14
<0.01
<0.01
<0.01
0.19
0.44
0.04
<0.01
0.50
<0.01
<0.01
<0.01
0.57
0.98
0.33
„
0.14
0.57
0.44
1.99
3.76
0.88
7.54
0.53
4.38
1.99
0.36
0.44
2.21
2.32
1.77
—
0.14
PHd
(6.0 to 8.5)
Avg. Min. Max.
8.4
12.1
12.2
10.3
9.9
12.3
12.0
9.4
9.5
12.3
12.0
12.6
12.0
12.1
11.7
11.6
8.0
12.0
12.1
8.3
8.7
12.1
11.8
7.5
7.9
11.9
11.2
12.4
12.0
12.0
10.9
11.3
8.7
12.2
12.4
12.3
12.2
12.4
12.4
12.4
12.0
12.4
12.5
12.9
12.1
12.4
12.2
12.0
Specific Conductance
( fj mhos)
Avg, Min. Max.
750
2,795
2,880
5,180
404
4,750
3,540
2,600
1,850
5,060
2,760
4,890
2,840
2,760
33,100
37,400
515
1,750
1,800
5,180
370
2,740
1,630
560
765
3,280
670
4,340
1,930
1,690
28,500
36,000
960
3,540
4,830
5,180
439
5,640
6,930
6,580
4,000
6,000
5,160
5,450
3,780
4,490
35,200
40,700
Continued
-------
TABLE 69 (Continued)
en
CO
Environment1 „
T . Boron
Test
Column Avg. Min.
Sandy soil
Top lysimefer
Middle lysimeter
Bottom lysimeter
0.25
0.30
0.20
Drain <0.10
Clayey soil
Top lysimeter
Middle ly si meter
Bottom lysimeter
Drain
Silty soil
Top lysimeter
Middle lysimeter
Bottom lysimeter
Drain
0.20
0.45
0.20
0.80
0.12
0.14
0.10
0.60
0.10
0.15
0.15
<0.10
0.10
0.15
0.20
0.15
0.10
0.14
<0.10
<0.10
Max.
0.55
0.40
0.20
0.20
0.35
1.00
0.25
1.20
0.15
0.14
0.15
1.00
Nitrates
Avg. Min.
<0.01 <
2.39
0.35
1.08
2.11
1.34
1.10
0.94
<0.01<
<0.01<
0.64
0.85<
O.OK
0.81
0.01
1.06
1.72
1.34
1.10
0.89
O.OK
O.OK
0.19
0.01
Max.
0.01
3.96
0.70
1.10
2.50
1.34
1.10
1.12
0,01
0.01
1.08
4.43
pH
Avg. Min.
11.3 10.9
11.5 11.3
9.2 7.0
7.4 6.9
9.15 7.3
9.0 7.8
8.3 7.3
9.1 8.7
9.4 7.8
9.35 7.7
9.65 8.3
12.3 12.3
Max.
11.6
11.8
11.4
7.6
12.0
10.8
9.1
9.3
12.2
12.4
12.3
12.4
Specific Conductance
Avg. Min Max.
950
1,410
1,080
950
1,960
1,820
2,020
2,120
2,920
4,000
2,860
6,510
680
1,170
840
750
860
1,450
1,415
1,490
1,080
1,170
485
5,300
1,210
1,800
1,440
1,080
4,140
2,560
2,670
3,380
4,760
6,830
7,440
7,080
a All constituents are reported in mg/l unless otherwise noted.
The value in parentheses is the permissible contamination level as presented in Tables 56 and 57.
. Recommended maximum concentration in irrigation waters (see Table 57).
Municipal water quality criteria (see Table 56 ).
f
EPA interim primary drinking water regulation (see Table 56 ).
Avg =lncludes the average of 2 to 4 analyses of monthly composites and one analysis of a four-month composite.
-------
TABLE 70 . LEACHATE ANALYSES OF THE TEST COLUMNS0
Drain Leachate Chemical Oxygen Total Organic Carbon
from Test Column Demand (no criteria) (no criteria)
Avg..dMin. Max. Avg. Min. Max.
NJFA
Limestone
Dolomite
16
< 10
Sanitary landfill 28
Coal mine
Ocean
NJSBM
Limestone
Dolomite
< 10
<250
30
22
Sanitary landfill 212
Coal mine
Ocean
VFA
Limestone
Dolomite
20
250
14
< 10
Sanitary landfill 30
Coal mine
Ocean
VSBM
Limestone
Dolomite
15
296
20
22
Sanitary landfill 28
Coal mine
Ocean
EFA
Limestone
Dolomite
28
<250
24
18
Sanitary landfill 234
Coal mine
Ocean
Sandy soil
Clayey soil
Silty soil
11
<250
83
< 10
46
< 10
< 10
< 10
< 10
<250
< 10
< 10
< 10
< 10
<250
< 10
< 10
< 10
< 10
<250
< 10
< 10
< 10
< 10
<250
< 10
< 10
147
< 10
< 25
< 10
46
40
47
12
510
113
68
345
49
490
61
< 10
115
84
504
55
61
47
40
<250
39
27
418
16
345
no
< 10 < 10
29
76
6
8
392
4
8
24
14
159
7
7
7
5
126
8
22
14
12
216
19
29
22
15
138
47
8
279
58
42
4
5
45
2
6
24
13
70
4
4
4
2
58
3
2
8
9
59
17
19
16
12
127
14
8
210
22
24
8
11
238
7
10
24
14
248
10
10
10
8
195
14
43
20
14
374
21
39
27
18
150
80
9
318
93
59
Total Dissolved Solids
(500 mg/l)c
Avg . Min . Max .
1
2
36
1
1
1
1
37
,375
,081
777
932
,884
,040
,671
,528
,033
,234
557
390
535
633
34,397
667
915
1,198
1,345
1,144
1,318
758
490
33,585
664
1,120
700
310
32,440
270
340
482
365
31,538
450
642
946
330
40,16731,500
690
563
2,122
845
35,778
352
1,309
929
352
380
1,090
720
34,304
444
574
795
1,740
2,348
786
1,250
38,092
2,170
2,920
1,722
1,310
38,552
667
551
820
1,160
36,256
754
2,065
1,578
1,674
43,948
1,440
1,150
2,810
1,345
36,348
630
4,250
962
(Continued)
154
-------
TABLE 70 (Continued)
Drain Leachafe Chemical Oxygen Total Organic Carbon
from Test Column Demand (no criteria) (no criteria)
Avg:? Min. Max. Avg. Min. Max.
Total Dissolved Solids
(500 mg/l)c
Avg. Min. Max.
ESBM
Limestone
Dolomite
Sanitary landfill
Coal mine
Ocean
Sandy soil
Clayey soil
Silrysoll
28
26
221
35
<250
90
354
68
< 10
< 10
169
< 10
<250
64
120
44
42
67
357
55
347
182
929
122
8
8
110
12
9
76
86
48
6
4
81
10
8
3
85
32
10
12
138
15
10
149
87
63
1
1
37
1
1
769
,183
,393
394
,574
500
,587
,382
1
33
1
1
574
980
,100
172
,760
422
,298
,380
1,270
1,232
1,568
945
39,790
660
2,440
1,382
.All constituents are reported in mg/l.
The value in parentheses is the permissible contamination level as presented in Table 56
. Municipal water quality criteria.
Avg = Includes the average of 2 to 4 analyses of monthly composites and one analysis of a
four-month composite.
155
-------
The municipal water quality criteria for copper was not exceeded. Most levels of copper
found in the leachates were less than 0.02 mg/I. The Environmental Protection Agency
primary drinking water maximum contaminant levels for mercury and nitrate were not
exceeded. The boron water quality criteria level was generally not exceeded. Only the
NJFA, NJSBM, and the ESBM leachates from the sanitary landfill, coal mine,, and
limestone, respectively, average concentrations higher than 2.0 mg/I.
The leachates generally were more basic than the recommended optimum pH range of
6.0 to 8.5. Only the NJFA, and VFA, residues resulted in leachates which come within
the recommended pH ranges. The recommended limits for total dissolved solids of 500 mg/I
was generally exceeded; however, the total dissolved solids usually did not exceed the
concentration of 1,000 mg/I.
The following paragraphs further evaluate the data presented in Tables 64 through 70.
In the discussion, those constituents which generally decreased in concentration after
percolating from the top lysimeter leachate to the drain leachate were considered to have
been attenuated, or retained, in the columns' environment. Conversely, the constituents,
which generally increased in concentration with passage through the test columns were
considered to have been readily leached from the in-situ media.
For the NJFA test columns, as shown in Table 64, aluminum readily leached through the
dolomite, sanitary landfill and the ocean column simulated environments; an average of
0.08 mg/I cadmium and copper were found in the ocean column' environment, whereas
all the other columns' environments showed more than 0802 mg/I; boron was readily leached
from the sanitary landfill, coal mine, and ocean columns' environments; nitrates, in the
limestone quarry column environments was readily leached, while the ocean column
environment showed a retention of nitrates; there appeared to be no other significant
differences.
The Table 65 results from the NJSBM column leachates showed that aluminum was readily
leached from the ocean column environment; cadmium and copper averaged about 0.8
mg/I in the ocean column environment, while the other columns simulated environments
contained no more than 0.02 mg/I; calcium was retained in the limestone, dolomite, and
the sanitary landfill columns simulated environments; boron was readily leached from the
coal mine and ocean columns' environments; the pH of the leachate increased in the lime-
stone and coal mine columns' environments and decreased in the sanitary landfill column
environment leachates. The specific conductance decreased in the limestone/ dolomite/
and sanitary landfill columns' environments, and increased in the coal mine column:
environment leachate. No other significant trends were apparent.
The VFA leachate results shown in Table 66, showed that aluminum was readily leached
from the sanitary landfill column1 environment; the ocean column environment averaged
about 0.8 mg/I cadmium and copper; cadmium was held in the dolomite and ocean
columns' environments; boron was attenuated in the sanitary landfill columns and readily
leached from the ocean environment columns; the nitrate concentration decreased rapidly
on the applied wastes which passed through the dolomite sanitary landfill columns, and
156
-------
coal mine column environments; only the limestone column environment showed any
change in the leachate pH, that is, the pH increased from 8«7 to 11.3 as the water perco-
lated through the test column; no other significant differences were observed.
For the VSBM test columns, as shown in Table 67, the cadmium and copper concentration
in the ocean leachate columns averaged about 0.7 mg/l; calcium in the sanitary landfill
and the ocean column simulated environments was readily leached while the limestone
column environment attenuated the calcium; boron leached through all but the ocean
column environment; the nitrate was attenuated in the limestone column environment;
the leachate Ph decreased in the limestone column environment and increased in the dolo-
mite column environment, and the specific conductance decreased in the limestone column
environment and increased in the sanitary landfill column environment.
The EFA residue as shown in Table 68, indicated the following leachate effluent chemical
characteristics: aluminum was leached from the dolomite, clayey soil, and the sllty soil
columns' simulated environments; the dolomite, sandy soil, and clayey soil columns'
environments attenuated the calcium and the ocean columns' environments' leachate con-
tained about 0.06 mg/l cadmium and copper; the coal mine test column attenuated the
boron; nitrate was readily leached from the limestone, clayey soil, and silly soil test
columns, while nitrate was retained by the dolomite test column simulated environment;
the leachate pH increased with passage through the limestone and silty soil test columns'
simulated environments and decreased while passing through the coal mine and the clayey
soil test columns; the specific conductance decreased from 8,020 to 2,110 mhas after
passing through the dolomite test column environment; no other significant trends were
noted.
The ESBM leachate, as shown in Table 69, showed the following trends: aluminum was
readily leached from the sanitary landfill, the coal mine, and the clayey and silty soil
test columns' simulated environments; cadmium and copper averaged about 0.12 mg/l in
the ocean leachate; boron was readily leached from all the test columns' simulated
environments, except the dolomite quarry and sandy soil; niirates were retained in the
clayey soil test columns, while nitrates were leached by the coal mine and the silty soil
test columns' simulated environments; the pH decreased in the sandy soil column environ-
ments and increased in the limestone, dolomite, and the silty soil columns' simulated
environments as the water leached through the test columns; and an increase in the specific
conductance occurred as the applied water passed through the limestone and silty soil
test columns. There were no other apparent significant differences or trends.
The results fou.id in Table 70 show the following differences. The COD was significantly
higher, above 200 mg/l, in the sanitary landfill column leachates coming from the
NJSBM, EFA, and ESBM residues, and in the clayey soil column leachate percolating
from the ESBM residue. The ocean simulated environment, of course, was high in COD
because of the highly saline sea water. Generally, all the other column leachates
averaged less than 50 mg/l chemical oxygen demand (COD). Likewise, the sanitary land-
fill column leachate showed significantly higher total organic carbon (TOC), from 110 to
392 mg/l, for all the residues. The ESBM leachate passing through the sandy, clayey,
157
-------
and silty soil columns' environments ranged from 48 to 86 mg/l. All other TOC results
were generally lower than 20 mg/l. The VFA leachate had the lowest total dissolved
solids than any of the other residues, ranging from 390 to 633 mg/l.
158
-------
CHAPTER 8
COMPARISON OF THE RESIDUE CHARACTERIZATION
AND LEACHING METHODS
An outcome of the fluid!zed-bed residue characterization (Chapter 5: Tables 13 to 17) and
the pilot test column study (Chapter 6: Tables 44 to 49) was that the studies provided four
basically different methods for determining the leaching characteristics of the residue
material. The four procedures are described below:
1. Total Residue Digestion: a sample of the residue was digested in perchloric acid and
the subsequent digestate was analyzed.
2. Soluble Salt Extraction: after the addition of distilled water, 1.0 N hydrochloric
acid, or 1.0 N sodium hydroxide, the residue sample was shaken for 24 hours and filtered;
the resultant filtrate was analyzed for soluble content.
3. Residue Leaching Test: water was passed through a sample of the residue packed in a
5cm 10 by 30 cm high column, and the result ing leachate was analyzed. (See Figures 5 to 7).
4. Pilot Column Leaching Test: a sample of the residue was placed onto layers of siratum
material contained in a larger (20.3 cm diameter x 3 m depth) column; and the leachate,
after passing through the simulated environment, was analyzed.
The results obtained from the four different procedures ore shown in Tables 71 to 76. The
values for the Pilot Column Leaching Test were calculated by multiplying the average con-
centrations, in mg/I (see Tables 44 to 49) by the total volumes of water applied to the
test columns, in liters, and by dividing these results by the total kg residue added to the
columns. A comparison of the methods indicate that no two procedures gave similar results.
The total residue digestion generally resulted in much higher concentration levels. In
particular, the concentrations of aluminum, copper, iron, manganese, and potassium found
in the digestate were almost always 100 to 1,000 times greater than the constituent content
found in any of the leaching processes. Magnesium showed similar characteristics for
VSBM, EFA, and ESBM; however, the base soluble extract of NSFA and NJSBM and the
acid soluble extract of VFA gave results which were no lower than one-half the concen-
tration found in the digested sample. Calcium was not determined by total digestion; how-
ever, apparently the total content of calcium (3 to 7 percent) was extracted from acid
soluble fraction. The total residue digestion procedure generally resulted in concentrations
much higher than those found in any leaching method because the digestion broke down the
solid residue into an entirely soluble form; therefore, this method was not suitable for
evaluating the potential leaching characteristics of residues on the natural environment. __
The results from the soluble salt extraction procedure (i.e., the shake test) have been used
to equate the potential impact of residues and other materials on disposal sites. For some
constituent, particularly those which are highly ionic (for example, potassium, sodium and
chloride), the extraction process may approximate the concentration levels found in the
leachate from an actual disposal site; however, this study showed that there was no
159
-------
TABLE 71 . COMPARISON OF FOUR METHODS FOR DETERMINING THE LEACHING
CHARACTERISTICS OFNJFA
mg Constituent/kg Residue
Constituent
Chloride
Sulfafe
Aluminum
Arsenic
Cadmium
Calcium
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Sodium
Zinc
Total
Residue
Digestion
—
53,600
5,800
0.2
2.8
—
—
1 1 ,030
40
6,290
650
—
7,200
80
92
Soluble Salt Extraction
Water Acid Base .
Soluble Soluble Soluble
< . 5 < 5 6
1,190 5,300 26,000
— •
< 0.1
<0.1 0.2 0.2
1,805 34,600 < 10
__
_
1.3
1.3
— •
—
0.9
~
~
1.8
Dolomite
Quarry
290
10,600
__
~
--
—
—
1.9
1.4
~
—
0.3
—
—
1.3
Sanitary
Landfill
200
2,350
~
--
~
~
~
._
0.8
--
«
0.2
__
—
0.7
Coal
Mine
340
14,900
—
~
—
«
—
1.9
2.6
—
—
0.8
>_
~
1.6
b ^
Ocean
Disposal
__
11,350
—
—
—
—
—
0.6
1.4
—
—
0.3
—
—
6.1
a in • t 10 A Hi. t f \ IM C
I I IOC VU1 UC» YT Cl ff 11 1C IC9UII3 VJ 1 I »rf I \A IMIIW vi i v,* » —i - t i i v I j v * TT v^i ^ i ^wi j"~*** *r^>t*'i/ MV» i rxi iv^y i ^^i n wi iN*di^«
, the columns. The concentrations of the constituents would increase with increasing water addition.
The results were for the drain leachate.
-------
TABLE 72. COMPARISON OF FOUR METHODS FOR DETERMINING THE LEACHING
CHARACTERISTICS OF NJSBM
mg Constifuent/kg Residue
Constituent
Chloride
Su! fate
Aluminum
Arsenic
Cadmium
Calcium
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Sodium
Zinc
Total
Residue
Digestion
--
~
960
—
4.0
—
168
1,830
32
2,530
475
—
5,600
72
92
Soluble Salt Extraction
Water
Soluble
< 5
1,900
0.06
—
< 1.0
6,010
0.5
< 1.0
2.4
95
0.02
0.5
32
89
<0.2
Acid
Soluble
< 5
1,000
0.26
—
o;s
96,750
1.1
7.6
1.4
< 10
0.95
7.7
32
<1.0
1.0
Base
Soluble
8
17,400
<1.0
—
0.2
< 10
0.12
1.8
5.9
3,200
<0.02
0.75
248
--
0.2
Residue
Leaching
Test0
700
35,070
—
—
—
8,700
—
—
5.0
—
—
—
—
—
0.8
Limestone
Quarry
875
7,460
—
—
—
.-
—
0.6
1.4
—
—
0.3
—
—
1.0
Pilot Column Leachinq Test
Dolomite
Quarry
700
8,140
__
—
—
—
—
1.0
1.7
—
— -
0.4
—
—
2.0
Sanitary
Landfill
575
2,125
--
—
—
—
—
—
2.7
—
—
0.4
—
—
0.8
Coal
Mine
350
6,335
—
—
—
-.
—
0.90
2.4
—
—
1.2
—
—
1.0
b
Ocean
Disposal
—
9,920
—
-.
—
—
—
1.2
1.8
—
—
0.2
—
-.
1.8
These values were the results after a ratio of 25.0 liters of water {or sea water) per kilogram of residue were passed through the
.columns. The concentration of the constituents would increase with increasing water addition.
The results were for the drain leachate.
-------
NJ
TABLE 73 . COMPARISON Of FOUR METHODS FOR DETERMINING THE LEACHING
CHARACTERISTICS OF VFA
mg Constituent/kg Residue
Constituent
Chloride
Sulfate
Aluminum
Arsenic
Cadmium
Calcium
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Sodium
Zinc
Total
Residue
Digestion
—
—
3,600
<0.1
0.8
—
164
7,390
20
3,000
165
—
8,400
112
80
Soluble Salt Extraction
Water
Soluble
NDC
1,600
ND
—
ND
540
0.02
0.5
1.6
96
0.02
0.25
33
145
0.08
Acid
Soluble
ND
1,050
1.2
—
0.5
32,000
0.92
11.0
1.3
1,940
0.87
7.7
276
ND
1.1
Base
Soluble
6
17,400
ND
—
0.2
ND
ND
1.7
7.1
10
ND
ND
—
—
1.0
Residue
Leaching
Test0
850
33,000
—
—
—
10,300
—
1.9
5.6
— •
—
—
—
—
0.83
Limestone
Quarry
385
15,620
--
~
—
—
—
1.6
2.0
—
—
0.4
—
—
1.7
Pilot Column Leachinq Test
Dolomite
Quarry
330
7,925
—
—
—
—
--
1.0
1.1
—
—
0.4
—
—
0.7
Sanitary
Landfill
455
1,475
—
—
—
—
—
—
1.6
—
—
0.6
—
—
1.2
Coal
Mine
680
19,100
—
—
—
—
—
1.2
6.9
—
—
0.9
—
—
2.6
b
Ocean
Disposal
__
24,000
—
—
—
—
—
0.8
1.7
—
—
1.0
—
__
2.3
These values were the results after a ratio of 27.6 liters of water (or sea water) per kilogram of residue were passed through the
columns. The concentration of the constituents would increase with increasing water addition.
The results were for the drain leachate.
c ND -not detected.
-------
TABLE 74. COMPARISON OF FOUR METHODS FOR DETERMINING THE LEACHING
CHARACTERISTICS OF VSBM
mg Constituent/kg Residue
Constituent
Chloride
Sulfate
Aluminum
Arsenic
Cadmium
Calcium
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potass! urn
Sodium
Zinc
Total
Residue
Digestion
—
12,200
3>840
0.3
2.4
—
225
4,070
28
585
315
—
19,400
192
208
Soluble Salt Extraction
Water
Soluble
NDC
1,640
0.06
— •
ND
750
0.5
0.1
1.1
22
0.02
0.5
6.3
178
ND
Acid
Soluble
ND
1,050
0.26
«
0.5
32,000
1.07
6.6
1.5
22
0.95
7.7
276
100
0.3
Base
Soluble
23
32,500
ND
—
0.3
ND
0.12
2.2
7.6
ND
ND
0.75
~
— •
0.4
Residue
Leaching
Test0
500
27,850
—
—
--
6,900
~
1.4
4.9
--
—
— -
—
-_
0.55
Limestone
Quarry
215
7,250
~
—
—
~
--
0.7
1.2
—
—
0.07
— •
—
—
Pilot Column Leachinq Test
Dolomite Sanitary
Quarry Landfill
145 350
3,950 4,580
_.
—
—
—
—
0.4
0.4 1.9
__
—
0.07 0.15
—
—
—
Coal
Mine
450
5,800
—
—
—
— -
—
0.2
1.6
—
—
0.4
—
__
—
b
Ocean
Disposal
—
6,780
—
—
—
—
—
0.6
1.3
—
—
0.3
--
__
—
These values were the results after a ratio of 18.4 liters of water (or sea water) per kilogram of residue were passed through the
.columns. The concentration of the constituents would increase with increasing water addition.
The results were for the drain leachate.
CND - not detected.
-------
TABLE 75. COMPARISON OF FOUR METHODS FOR DETERMINING THE LEACHING
CHARACTERISTICS OF ERA
o
Constituent
Chloride
Sulfate
Aluminum
Arsenic
Cadmium
Calcium
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Sodium
Zinc
Total
Residue
Digestion
—
—
240
NDC
1.6
—
180
48
24
375
120
—
6,000
—
32
nig
Constituent/kg Residue
Soluble Salt Extraction
Water
Soluble
1 1 ,200
4,380
0.25
ND
ND
4,500
ND
1.0
0.08
1.0
0.08
1.2
50
245
0.15
Acid
Soluble
5,000
2,625
1.75
0.05
0.08
70,000
2.2
7.0
ND
1.3
0.75
8.0
232
270
0.3
Base
Soluble
10,000
24,310
ND
ND
0.05
315
ND
0.2
ND
1.0
0.03
1.5
—
—
0.02
Residue Limestone
Leaching Quarry
Testa
6,850 1,000
30,000 10,850
__
__
— -
~
__
6.3 1.1
4.4 4.0
— .'
—
18 1.0
—
—
0.75 1.4
Pilot Column Leachinq Test
Dolomite Sanitary
Quarry Landfill
3,800 1,525
7,300 17,360
—
__
—
__
~
1.0
2.5 6.0
—
__
1.6 0.8
~
—
1.0 0.3
Coal
Mine
780
8,500
—
--
—
—
—
0.4
3.0
—
—
0.6
—
—
1.5
b
Ocean
Disposal
—
7,200
—
._
—
~
—
1.4
2.0
—
—
1.1
—
—
1.2
° These values were the results after a ratio of 22.0 liters of water {or sea water) per kilogram of residue were passed through the
columns. The concentration of the constituents would increase with increasing wafer addition.
The results were for the drain leachate.
c ND - not detected.
-------
TABLE 76, COMPARISON OF FOUR METHODS FOR DETERMINING THE LEACHING
CHARACTERISTICS OF ESBM
tng Constituent/kg Residue
Constituent
Chloride
Sulfate
Aluminum
Arsenic
Cadmium
Calcium
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Sodium
Zinc
Total
Residue
Digestion
—
.
—
0.4
2.4
—
148
ND
16
1,895
215
—
11,400
144
28
Soluble Salt Extraction
Water
Soluble
8,200
3,380
0.25
NDC
0.05
4,750
0.5
1.7
0.17
1.0
0,1
0.25
ND
40|
0.15
Acid
Soluble
12,500
250
1.25
0.1
0.28
75,000
2.0
6.0
ND
1.3
0.6
7.5
ND
45
0.30
Base
Soluble
10,280
4,625
1.0
ND
ND
60
ND
ND
ND
1.0
ND
ND
—
—
ND
Pilot Column Leachinq Test
Residue Limestone Dolomite Sanitary
Leaching Quarry Quarry Landfill
Test0
6,100 5,350 4,700 2,600
54,000 15,300 9,700 22,300
—
__
—
—
._
8.2 3.2 2.2
7.9 15.6 16.8 11.4
—
—
54 1.7 2.5 1.3
—
0.78 9.6 5.5 4.1
Coal Ocean
Mine Disposal
2,750 —
7,300 18,000
—
—
,_
..
__
3.2 1,8
6.9 14.8
—
—
1.1 2.4
—
—
3.8 10.6
These values were the results after a ratio of 39.4 liters of water (or sea water) per kilogram of residue were passed through
.columns. The concentration of the constituents would increase with increasing water addition.
The results were for the drain leachate.
c ND -not detected.
the
-------
consistent relationship between the constituent levels found in the soluble salt extracts
and those found in the leachate from the residue or the pilot column leaching tests. The
chloride concentrations found in the soluble salt extracts of the NJFA, NJSBM, VFA, and
VSBM were almost neglible compared to the concentration levels (greater than 100 mg/kg
residue) found in the leachate from the residue and the pilot column tests. On the other
hand, the soluble salt extracts from Esso, Great Britain residues generally contained higher
chloride concentrations than the pilot column leachate samples. Furthermore, the sulfate,
iron, and zinc concentrations were almost always less in the water soluble portion of the
extracts. The water soluble extracts of lead and nickel more nearly approximated the
constituents' concentration found in the pilot column leaching test.
The residue leaching test almost always resulted in higher constituent concentration (the
only exception was zinc) when compared with the values found in the pilot column leach-
ing test. This was not unexpected because, although both methods leached constituents
with passage of water through a column, the leachate in the larger pilot-scale test column
passed through additional layers of stratum material. Thus, less bypassing occurred which
resulted in lower leachate concentrations.
In summary, the total residue digestion method did not relate directly to the leaching
characteristics of the fluidized-bed residues. The analytical data obtained from the
soluble salt extractions generally did not approximate the results found by the pilot test
column leaching test; most of the results from the extractions showed lower concentrations,
sometimes the chloride concentrations were greater, and rarely did the analytical results
compare favorably with the pilot test column leachate results. The residue leaching test
proved to give results that were greater in concentrations than those found in the pilot
column leaching tests. No two procedures gave similar results; and consequently, since
the pilot test columns skidy provided percolation of the residues' leachate through sub-
surface materials, the analytical data from the pilot column leaching test appears to most
effectively predict the potential leaching impacts of residues on the natural environment.
166
-------
CHAPTER 9
RECOVERY POTENTIAL FOR FLUIDIZED-BED RESIDUES
Introduction
Coal combustion has generated large quantities of residues. In 1972, for example, approxi-
mately 30 million kkg of coal residues were produced. Residue quantities were projected
to increase substantially during the period 1970-90, primarily as a result of increased power
demand. During that period, the electric utility industry was predicted to increase its
consumption of coal by TOO 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 necessitate less discharge to the environment; consequently,
the more efficient fluidized-bed plants may be favored over conventional coal combustion
and oil gasification processes. Third, f luidized-bed coal combustion and oil gasification
methods may be adopted by a significant portion of the industry. Both the once-through and
the regenerative limestone/dolomite fluidized-bed systems have generated substantially more
residues than conventional systems, although the increase has been greatest with once-through
systems. Preliminary work suggests that once-through systems are favored by current eco-
nomics: the projected expense of regeneration (less the value of recovered sulfur products)
appeared to be greater than the saving from reduced limestone consumption. 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 discusses possible residue application areas and the market prospects for flui-
dized-bed residues. The following topics were considered:
• Overall recovery prospects for fluidized-bed residues.
• Review of the 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 (lime-fly ash-aggregate and lime-cement-fly ash
aggregate), acid mine drainage treatment, and road ice control.
• Preliminary assessment of market potential for residue applications.
Overall Reuse frospects
The history of reclaiming conventional coal ash provided an insight into what the utilization
prospects for fluidized-ted residues might be. Relatively little of the conventional ash
generated has found its way into productive use. Until about 1968, the ash utllfatiq^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, although in total quant.ties
reuse has continued to increase. The utilization rate has remained low even though many
167
-------
technically sound applications have been developed which could potentially absorb more
than the annual quantities generated. Table 77 presents the estimated maximum, tech-
nically feasible, utilization potentials. Although many reuse applications exist, it is not
likely that the utilization rate will consume the available supply in the near future because
of the following reasons:
« Technical complexity of the application. Rjtential 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.
Many of these barriers may be overcome in time, but unless further recovery incentives
are provided, most of the increased residues will not be reclaimed and, instead, will
require disposal. This conclusion must be modified for fluidized-bed residues, however,
since their composition and characteristics are substantially different from those of con-
ventional combustion ash residues. This is illustrated in Tables 78 and79 , which
compare the composition of conventional coal ash, modified ash (MFA), and fluidized-bed
ash. The lime or dolomite modified fly ash was generated by flue gas desulfurization
(FGD) systems (e.g., wet limestone scrubbers) and fluidized-bed combustors. Since
diffences affect the suitability of a residue for a given application, it is difficult to
predict the potential successes or failures of FBC residue applications. The FGD residues
(particularly those from dry systems) were quite similar to fluidized-bed residues; hence,
the recovery potential of FGD and fluidized-bed residues may be compared with some
reliability.
Provided that suitable reclaimable materials are available, a potential user's decision
will be based on the relative prices of conventional and residue materials, transportation,
and necessary preprocessing of the residues over that required for the competing conven-
tional material. A potential user will use materials which reduce his production costs and
maintain desired product quality.
There has been considerable literature published on applications and potential uses for
residues from conventional coal combustion, municipal waste incineration, and lime-
limestone scrubbing used for air pollution control on high sulfur fossil fuel units. These
are summarized in the following sections.
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
168
-------
TABLE 77 . ESTIMATED ASH UTILIZATION POTENTIAL (1Q6 kkq/vr)
Maximum
Utilization
Use Technically
Feasible
iQ7n
Utilization
Estimated
Utilization
1971
Conditions
Potential
Improved
Utilization
Fly ash concrete (structural,
mass and concrete products)
Lightweight aggregate
Raw material for cement clinker
Bricks
Filler in bituminous products
Base stabilizer for roads ^Pa)
Agriculture and land recovery
(AP)
Control of mine subsidence and
fires
Structural fill for roads
construction sites, land,
9-14
12
12
9
1-2
0.49
0.19
0.15
0.12
OJO
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
—
—
___
169
-------
TABLE 78. COMPARISON OF ASH COMPOSITION (%)
Constituent
s;o2
ALO0
2 3
Fe2°3
Ti02
CaO
MgC
Na20
K20
S°3
C
H2O soluble
Coal
Ash
49.10
16.25
22.31
1.09
4.48
1.00
0.05
1.42
0.73
2.21
2.51
TABLE 79 .
Constituent
Fe2°3
CaO
MgO
S03
Lime Modified Dolomite Modified Lignite Ash
Ash
30.85
13.70
11.59 ,
0.68
33.58
1.49
1.12
0.71
2.20
1.12
22.11
COMPARISON QF
Ash
30.81
12.54
10.72
0.42
17.90
14.77
0.72
0.99
8.09
1.76
—
FBC RESIDUE COMPOSITIONS
32.60
10,70
10.0
0.56
18.00
7.31
0.87
0.68
2.60
0.11
8.55
Ash Composition (%)
Exxon
9
13
0
5
H20 soluble 0
Miniplant Pope
.99
.44
.61
.81
.21
, Evans and Robbins Plant
15.71
4.9
0.32
4.56
0.42
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.
170
-------
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 may consist of finely divided spheroids of siliceous glass ranging from
1 to 50 microns in diameter. Some of these spheroids can be considerably finer than
portland cement, and a minor fraction may consist of larger, irregularly shaped particles,
some opaque and some transparent or translucent. Carbon may be 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 ash in the United States has ranged 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; variations in steam load, draft, and combustion controls; and operator skill.
About 70 percent of the coal ash residue may be collected as fly ash.
The bottom ash may be collected either as an ash or slag depending on the particular
boiler design. The ash ranged from grey to black in color,wasi quite angular and had a
porous surface. The slag particles normally were black/angular particles having a glass-
like appearance. The bottom ash particles may be an average particle diameter size of
2 .5 millimeters, and an average specific gravity of about 2.5. When there have been
recovery markets for the fly ash, the fly ash has been handled dry by using a pneumatic
system, storing in silos or bins on the plant site, and then transporting in closed tank
trucks or rail cars. Slags to be sold were generally collected from quench tanks below
the boilers to draining bins and then stored in piles until marketed. Bottom ash and slag,
as granular materials, lent themselves to mechanical handling schemes.
Pulverized coal-fired units may be characterized as "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 amounted to only 20-25 percent of the total ash.
Coal Ash Utilization
United States
Table 80 compares ash production and utilization for the period from 1966 to 1972. By
1972, only about 16 percent of the ash and slag produced by coal combustion plants was
reclaimed (11 A 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
Table81 ; estimated 1976 ash generation Is included for comparison. The mam appl.ca-
tions were as an additive to cement, a fill material for road and other construction and
a filler in asphalt mix. The 'Vniscellaneous" use category was also quite Jorge; Table 82
lists some of the applications aggregated under that heading. It can be inferred that a
171
-------
TABLE 80 . COMPARATIVE ASH PRODUCTION AND UTILIZATION, 1966-1972
Production
(Meg)
Fly ash
Bottom ash
Boiler slag
Total
S
Utilization
Total (kkg)
Fly ash (%)
Bottom ash (%)
Boiler slag (%)
Total (%)
1966
15,533,855
7,317,065
22,850,920
1966
2,767,520
7.9
21.0
—
12.11
1967
16,701,139
8,283,915
—
24,985,053
1967
3,442,507
8.2
25.0
—
13.78
1968
17,974,729
6,585,446
2,317,466
26,877,641
1968
4,711,932
9.6
25.0
57.8
17,53
1969
20,234,314
7,295,595
2,739,954
30,269,863
1969
4,814,215
8.13
25,0
57.8
15.90
1970
24,074,886
8,972,920
2,541,455
35,589,261
1970
4,622,704
8.13
18.63
39.06
13
1971
25,175,333
9,125,341
4,509,421
38,810,095
1971
7,805,163
11.7
16.03
75.21
20
1972
28,855,791
9,682,256
3,430,664
41,968,711
1972
6,872,381
11.4
24.3
35.3
16.3
Source:
-------
TABLE 81 . ASH COLLECTION AND UTII IZATIHN T07T
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 ptoducts
Structural concrete
Dams and other massive concrete
Lightweight aggregate
Fly Ash (kkg)
94,550
15,001
1 60,725
1 68,256
64,784
162,294
• ' ' • *
Bottom
Ash (kkg)
NAa
NA
32,094
NA
NA
12,648
Boiler
Slag (kkg)
83,440
NA
68,551
NA
NA
NA
Fill material for roads, construction 329,663 484,156 2,384,924
sites, etc.
Stabilizer for road bases, parking areas, 33,511 7,149 44,964
etc.
Filler in asphalt mix 133,953 2,570 74,118
Miscellaneous 89,633 431,299 388,305
Total 1,252,370 969,916 3,044,302
Ash removed at plant site at no cost to utility
but not covered in categories
listed under "ash utilized" 1,698,938 492*514 346,346
Total ash utilized 2,951,308 1,462,430 3,390,648
Ash removed to disposal areas at company 22,224,448 7,663,065 1,117,941
e'xpense
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.
173
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TABLE 82 . 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 Sandblasting grit
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.
174
-------
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 83 .
Yearly fluctuations in coal ash used suggest that the trends were influenced by market
factors; thus, valid projections for future consumption were complex to make. Boiler slag
has been found useful in increasing the skid resistance of road pavements. Also, a modi-
fied CMS-2 emulsified asphalt was made with bottom ash. This use increased because of
the need to conserve fuel. In addition, the cost of this road paving material in areas near
coal burning power plants was reduced by about one-half through use of this special type
of emulsified asphalt. 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 indicated that large quantities of coal ash could also be effectively used
for agriculture and land reclamation products. The use of coal ash for lightweight aggre-
gate initially looked promising, but in the last few years this 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, near the power plant.
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 was transported from a source at an average 1976
cost of $0.04 per kkg-km (1 8 to 27 kkg per truck). The cost of loading and unloading was
about $2.00 per truck load. Furthermore, trucks can be expected to operate with maximum
economy only in a range of about 150 to 175 miles, depending on road conditions. This
would enable 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 competed with natural raw materials and
cement industry products. Its use was hampered by the fact that 1976 freight rates for
shipping fly ash were about 20 percent higher than for the natural products because of
tariffs that gave an advantage to natural or virgin materials over secondary materials.
In 1971, the Federal Republic of Germany used 79 percent of its total ash production of
6,500,000 kkg, France used 65 percent of its production of 4,185,000 kkg, and the
United Kingdom used 54 percent of its production of 10,370,000 kkg.IJ/ 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 concrete. Construction
fills accounted for about 28 percent of the total used. Miscellaneous uses included coal
mine fire control, addition of fly ash to foundry sand, component of blasting compounds
for cleaning metal surfaces, and manufacture of acoustical block, pesticides, soaps, etc.
The wet weight of fly ash produced in Great Britain per compacted cubic meter was between
1.17and 1.44 kkg/m3 depending on the source and moisture content of the material. This
compares favorably with the weight of traditional (British ) fill material, as shown ,n Table 84,
175
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TABLE83. KNOWN USES FOR ASH REMOVED FROM PLANT
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
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
(kka)
NAp
NAp
150,714
NAp
NAp
208,105
NAp
NAp
NAp
NAp
NAp
NAp
1,932
360,751
r^Jot applicable.
DNot available.
Source: 31.
176
-------
TABLE 84 . DENSITY OF FLY ASH COMPARED WITH TRADITIONAL FILLS
Material Compacted Density
(kkg/cu m)
.- - - . _j - -.._.-.. . . . _ __ _ __ T- _ - TI
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.
177
-------
The low density ash was found to be useful for road fill, especially when embankments had
to be constructed over poor soil support such as compressible alluvial clay or silt. In such
situations, excessive road foundation weight could produce settlement beyond allowable
limits, and may even cause complete failure of the subsoil foundations.
The stability of the fly ash is such that it has been used in Great Britain behind bridge
abutments, etc. Fly ash's pozzolonic characteristics cause 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 has also been used as an excellent draining
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 equip-
ment, even in confined areas.
Fly ash has been used throughout the United Kingdom and other European countries for
load-bearing structural fills at industrial sites, schools, and other locations since it
exhibited excellent load-bearing and foundation strength. Furthermore, because of its
low density and self-hardening capacity, fly ash made an ideal stabilized sub-foundation
support forbuildingsbuilton unstable ground. In addition, fly ash has been ideal fortrenching
as deep trenches can be excavated using minimal trench supports. An ash fill, after
hardening provided an excellent material for excavation and so it has been ideal for loca-
ting pad foundations, manholes, utilities, etc. Ash has been found to be a stable alkaline
type material. Corrosion tests have demonstrated few adverse effects on cast iron, lead,
copper, PVC, or ceramic pipes embedded in ash fills.. It has been important7however, to
remove all the soluble salts that are present by leaching new ash in order to prevent electro-
lytic metal corrosion or water pollution. Table 85 summarizes the hard coal and lignite
ash production and utilization in Europe and the United States in 1967, 1969, and 1971. The
European countries have utilized the ash residue extensively.
Specific Applications for Coal Ash
This section considers the following reported specific experience with the recovery of
coal ash and limestone wet scrubber residues:
• Concrete
• Stabilized road bed construction
• Fill material
• Soil stabilization
• Neutralization of acid mine drainage
• Soil cement
178
-------
TABLE85 .DEVELOPMENT OF ASH PRODUCTION AND USE IN THE
ECONOMIC COMMISSION FOR EUROPE REGION0
Ash Source
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
003kkg)
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
(TO3 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
(!03kkg)
59,922
42,781
102,703
36,353
449
36,802
T971
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
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.
NA - Not available.
Source: 132.
-------
• Acid soils, rectification in agriculture
• Brick manufacture
• Wastewater treatment
For this report, several experimental applications were evaluated as follows:
Concrete
The concrete can be improved by the addition of coal fly ash. Fly ash strength, resistance
to sulfate attack, workability, and permeability may also help control shrinkage and evo-
lution of heat during setting. Fly ash concrete reportedly clings less tenaciously to form
and retains sharper corners and details, thus, enhancing the concrete's architectural value.
Fly ash has been valuable in cement and concrete primarily because it is a pozzolan. Poz-
zolons are siliceous-aluminous materials that have little or no cementitious value themselves,
but, 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 can also act as a mechanical filler supplementing or replacing fine
(sand) aggregate. Its spherical shape improved the workability of the plastic concrete and
the ease with which it is finished. In domestic sewers, concrete has been 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 sulfuric acid attack.
Most fly ash concretes may need the addition of an air-entraining agent to achieve a
similar air content to that obtained for regular concrete. Entraining agent requirements
for a constant air content increased with the percentage of fly ash and its carbon content.
Specifications for 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 have been 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 has depended almost entirely on its quality, generation, loca-
tion, 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.
There have been some materials handling problems associated with the use of fly ash in
concrete. Low viscosity, for instance, have caused difficulties in feeding and weighing.
The extreme fineness of fly ash can lead to air pollution and other characteristics such as
poor insulating properties of concrete used in electrical boxes and switches. R-oper design
of feeders and scales as well as the installation of dust-collecting systems can help reduce
these difficulties.
180
-------
Stabilized Road Bed Construction
The use of granular materials in base and sub-base construction for road and airfield pave-
ments has run into billions of kkg per year. Because of the vast quantities of materials
needed for this type of construction, a promising market for utilizing fly ash exists. There
has also been a substantial increase in the use of lime-fly ash aggregate (LFA) and lime-
fly ash-cement aggregate (LCFA) mixtures in pavement construction during recent years.
Many state and federal agencies have expanded their specifications to include LFA and
LCFA as acceptable paving materials. Based on their properties, great potential markets
can be developed for the use of LFA and LCFA materials in road construction.
LFA mixtures include blends of aggregate, lime, fly ash, and water which, when compacted
to a relatively high density, produce hard surface paving materials; LCFA contains cement
in addition to the other 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 ranged from 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 was used in the LCFA mixtures, the ratio of lime to cement was usually 3:1 to 4:1.
The optimum fly ash content for a particular mix was the quantity needed to achieve maxi-
mum density in the compacted mixture, that is, it filled the voids in the aggregate lime
content. The optimum mix content should 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 has been the
cyclic freeze-thaw ASTM C593. Figure 68 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 existed, durability of the material was improved. All paving
materials in which the aggregate particles were bound together with binders such as
cement, asphalt, or lime fly-ash changed dimensions with temperature and moisture condi-
tions. Good pavement performance required that the coefficients of linear thermal expan-
sion 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 69 . As a general rule, the coefficients of linear thermal expansion for
hardened LFA and LCFA materials can be taken as 5 x 10"6, or about the same as port-
land csment concrete.
The higher the compressive strength, the better the quality of the LFA mixture.The strength
of LFA and LCFA was time and temperature dependent. Time and temperature versus
strength relationships for typical LFA and LCFA are shown in Figures 70 and 71 , respec-
tively. The data in Table 86 shows how the strength and durability of the well-graded
aggregate varied with the fly ash content.
181
-------
26 28
Legend
Period of constant 49X temperature
Period of ten freeze-thaw cycles
Source:23
Figure 68
Effect of freeze-thaw cycles on LCFA compress!ve strength.
182
-------
60
40
0)
D)
Q)
4)
D)
O
u-20
-40
Legend
49 -7 49 -7 49
Temperature (°0
.-6
-7
49
Saturated specimens; 6 = 8.0 x 10
Unsaturated specimens; € = 5.8 x 10
Source: 23.
Figure 69. Change of length with temperature for cured LFA specimen.
183
-------
120
E
o
cr
s
D>
O>
3
CL
I
u
90 -
60
30
20
40 60
Curing Time (days)
80
100
LFA Components (%)
Lime—2.5
Fly Ash—10
Aggregate—87.5
Source: 23.
Figure 70 . Effect of curing time and temperature on LFA compresstve strength.
184
-------
120
E
u
O)
O)
c
O
o.
O
U
90
60 L
30
50
60
Curing Time (days)
Source: 23.
Figure 71. Effect of curing time and temperature on LCFA compresslve strength.
185
-------
TABLE80: 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
toss (%) Strength
(kgf/sq cm)
100
23
45
100
58
10
0
49
69
0
3
58
All samples contain 3 percent lime.
Source: 23.
186
-------
Figure 72 shows the effect of lime content on compressive strength of LFA mixtures; Figure
73 shows 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 Newark, New Jersey Port Authority airport.
A recent survey of the Newark airport facilities found that the primary runway and taxiway
system was in excellent condition. LFA and LCFA materials have also been used extensively
by the Port Authority 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 have not been fully exploited. The paving material market is
large, and with additional effort on a national level, it appears that this market could
absorb a substantial portion of the fly ash produced.
Fill Material
Most fly ash applications have required large 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
of fly ash as a fill material are its grain size, density, compaction characteristics, shear
strength,and permeability.
The compacted dry density of fly ash ranges from 1 to 1 .5 g/cu cm, which provided a
dense weight when compared with most conventional fill materials; the optimum moisture
content ranged from 18 to 30 percent by weight. The permeability of compacted fly ash
is low, typically in the range of ]Q to 10"** cm per minute; however, it is satisfactory
for more homogenous, compacted fill applications. Apart from slight solubility in water,
the fly ash has proven to be chemically stable, with little deterioration occurring on expo-
sure to the atmosphere. Also, since the soluble content becomes partially fixed after parti-
cipation in the pozzolanic action, leachate water passing over or through the fly ash fill
will pick up somewhat reduced quantities of soluble chemicals. With portland cement, the
strength characteristics were enhanced by the pozzolanic action, and the fly ash/concrete
mixtures showed a gradual increase of strength with time.
Flyash's low unit weight and low compressibility helped 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 Grossblidgertroff Station of Houilleres du Bassin Lorraine
(HBL) in eastern France. Fly ash fill dams were constructed in the valley, and the area
behind them was then filled with water from a small tributary stream of the Soar River.
Waste ash from the generating station was later backfilled to reclaim the land.
The major risks encountered with compacted fly-ash fills have been ash erosion (both
internally and externally) and liquefaction. Internal erosion can be controlled by a pro-
perly 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 fill shear
resistance to almost zero. This is caused by collapse of the structure of the material asso-
187
-------
E
u
o>
o
0)
70
£ 35
o
O
36 Days at 21°C
7 Days at 2T°C
8
Lime Content (%)
12
16
Source; 23.
Figure 72 . Effect of lime content and curing conditions on LFA strength.
188
-------
100
95
g,
o
•—•
£
£ 90
«n
C
-------
ciated 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.^ A variety of stabilization methods have been available;
however, no one method has been best for all soil types because each soil differs markedly
in its properties and its reactions to different stabilization methods. LFA and LCFA mixtures
are two materials which have been successfully used for soil stabilization in many applica-
tions, and a strong techno logy concerning their use has developed.
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 reacted
to form complex silicates and aluminate which in turn reacted with the calcium hydroxide
and magnesium oxide present in lime to form a cementitious matrix. The difference between
LCFA and LFA mixtures was 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 depended
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 to 9 percent lime, and 10 to 25 percent fly ash have been used in clay type soils.
Silty soils composed of less than 10 percent clay were stabilized with lime alone,or
with a lime/fly ash ratio of about 1:2. Silty soils containing greater amounts of clay
required larger percentages of fly ash.
Sandy soils almost always needed 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 pozzolanic. However, the addition of fly ash has
produced better results. A lime-fly ash ratio of 1:5 has been common for sandy soils alone,
but specific mixes can improve their strength and durability.
Coarse soils generally needed little (2-4 percent) or no lime to meet stability requirements
190
-------
u f uA,u COntaT9 cla/ °r cal^he can be further enhanced
by the add.tion of fly ash (lime/fly ash rat.os of 1:5 were 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 not only con-
tributed to the natural pozzolanic qualities of the above mixtures, but also improved the
gradation which resulted in greater strength.
l'me- Dolomite limes (quicklime and monohydrate) resulted in 30 percent stronger products
than the calcitic limes, excepth in kaolinitic material where the strengths were about the
same. Currently, it is believed that the MgO in dolomitic limes acts as a catalyst in the
soil-lime reaction. Calcium to magnesium ratios of 1:1 and 2:1 were optimal, and most
commercial dolomitic monohydrate limes were within these limits. No optimum ratio of
lime to fly ash has been found which satisfactorily stabilizes all soils. Since 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 maximize the strength in the hardened product, the moisture content of the
LFA/LCFA mixture was at or near optimum. Optimum moisture content varied, depending
on the lime/fly ash ratio. In general, the moisture content, which has resulted in the
maximum bulk density of the lime-fly ash mixture, was slightly higher than that needed for
the maximum hardened strength. The carbon content and fineness of the fly ash, as well
as the flocculating effects of the lime, all affected the moisture content. Determining
the optimum moisture content for a particular mix of lime, fly ash, and aggregate can
be facilitated by preparing a diagram similar to Figure 74 . In this case, limits of 50:50
soil-lime, 50:50 soil-fly ash, and 100 percent aggregate were selected. Laboratory
analysis determined that the optimum moisture concentrations for these limes were 29.2,
17.9, and 16.7, respectively. Intermediate moisture concentrations were scaled off as
shown from 18 to 28 percent. The approximate optimum moisture content can then be
read for any soil mix within the original limits.
Neutralization of Acid Mine Drainage
Acid mine drainage (AMD) has annually caused millions of dollars of environmental damage.
Polluted water taken by downstream users for industrial, agricultural,or potable applica-
tions may have required additional pretreatment; fish and vegetation have been killed,
agricultural land damaged, and an area's recreational value reduced. The problem arose
when mining activities exposed pyrites and marcasites to the oxygen in the air. In the
presence of moist air, sulfuric acid was formed. Every kg of iron sulfide exposed had
the potential to produce as much as 1 .6 kg of sulfuric acid. The extent of the pollution
damage depended on how much sulfide oxidation had occurred and how much acid had
been released into the environment.
There are two basic approaches to dealing with AMD: prevent its formation or prevent it
from contaminating ground or suface waters. One approach which has been tried experi-
mentally was to collect the acidic drainage as it formed and pump it to storage and treat-
ment facilities where it was neutralized with lime or other chemicals before discharge.
191
-------
29.2
Soil
16.7
Figure 74 . LFA moisture correlation chart.
192
-------
Th.s has proven to be an expensive alternative, especially if a treatment plant is needed
for every coal mine, operating or abandoned. Since the formation of acid is initiated by
oxygen, attempts have also been made to prevent contact between the sulfides and
air or
... - i— — -»»•.•»«». i w^ i TV ecu i nc sui i iues ana air <
water. Mines have been sealed to prevent water infiltration or exclude air, but results
have not been successful.
Work has been done with using conventional coal fly ash residues for reclamation of sur-
face-mine spoils.^ The residues provided nutrients needed by the soil, served as a condi-
tioner, and their al kaUnity has also reduced the AMD.
Our preliminary analysis suggested that fluidized-bed residues could be used to neutralize
AMD, both from strip and subsurface mines. Neutralization capacity varied widely with
the type of residue (see Figure 75 ),-thus potential use for AMD control will depend
partially on the characteristics of the specific residues available.
The marketing potential of fluidized-bed residues for AMD is limited since coal combustion
may be removed from the mining production process. Moreover, the demand for residues
would depend primarily on environmental regulations, i.e. the more restrictions placed on
AMD and the more stringent the requirements on strip-mine reclamation, the higher will
be the future demand. Power producers must, as part of their normal production process,
dispose of the residues generated. They will dispose of them by the least expensive means.
The assumption of a zero f.o.b. price at the power plant for the residue 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 pay for some, if not
all,of the freight charges.
In general, residues would most likely be used for AMD control when the mine site is as
close as 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. Additionally, special
environmental protection measures and other costs would likely be incurred by a landfill
operator, rather than by the mine operator. It is likely, therefore, that fluidized-bed
residues could be economically shipped somewhat farther for AMD neutralization than for
normal landfill disposal.
Assuming the application is technically feasible and there are significant regulations
concerning AMD, the market potential for fluidized-bed residues will be primarily deter-
mined by the location of mine sites relative to power plants. Residues from coal-burning
plants are at this time (1978) 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 have been in particularly close proximity. If fluidized-bed
oil gasification becomes widely adopted, many other areas will have a nearby source of
residues. Coal fired combustion plants are being encouraged throughout the United States,
and can be expected to become more common in most states.
193
-------
X
Q.
14
13
12
11
10
9
8
7
6
5
4
3
2
1
I I I 1 I i 1 I I 1
i l i I I I
Legend
• Control
0 VFA
0 VSBM
D NJFA
n NJSBM
A CFA
A FSFA
I i 1 I I _) i
5-380
L J I I
0 1020304050
100
150
200
250
300
350
ml H20
Figure 75. pH of leachare for acid mine drainage control.
-------
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 cements typically provide
modu^s of elasticities which range from 100,000 (for clayey soils with little cement) up
to 10 (for stronger mixtures), and have proven to be far more elastic than concrete. Soil
cement mixtures have been used for base courses under pavement, roadway shoulders,
patching, ditch and channel linings, and dam facings.
In general, there are three types of soil cement: compacted soil cement, cement modified
soil, and plastic soil cement. Compacted soil cement contained the stoichiometric amount
of cement to harden the soil,and the stoichiometric amount of water to hydrate the cement.
Just enough cement and water are added to the soil to change its chemical and physical
properties. Addition of cement to soil reduced the soil's plasticity and waterholding capa-
city, and increased its bearing value. Plastic soil cement should contain 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 has been 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 word "soil" as used in "soil cement" means any combination of gravel, sand, silt, clay,
or filler (such as cinders, shale, and chat). 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 have been the most desirable soil cement
aggregates and generally have required the least amount of cement for satisfactory curing.
Coase soils containg 55 percent or more material passing through 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 increased as the percentage of fines de-
creased. 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. Silty and clayey soils have been 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 has
depended on soil type and design load. Any type of portland cement which complies with
ASTM or AASHTO specifications has been satisfactory. Types 1 and 1 A, normal and air-
entraining portland cements are the most commonly used. Tables 87 and 88 show repre-
sentative cement concentrations for various soil types.
195
-------
TABLE 87. AVERAGE CEMENT_REQUIREM_ENTS OF_MIS CELL A NEOUS^ MATERIALS^
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 88. 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.
196
-------
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 ofTest 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 has generally been mixed in-situ or less commonly away from the
construction site and then trucked in. In-place mixing has been more economical, while
off-site mixing has been used only when the quantity or quality of the aggregate at the
site was 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 provided a better control over the amount and blending of the compo-
nents. Groundmixing has been less costly and usually faster; it can be done using a dump
truck or even by hand. Compaction was usually done by rollers; however, in sandy soils
or coarse soils lacking in fines, compaction had to be done by vibration. Curing soil
cement mixtures have had to be protected from the weather in order to prevent moisture
imbalance. Bituminous coatings were generally used, but dirt, straw, and paper have all
been successfully applied.
Acid soils, Rectification in Agriculture
Coal ash residues can be used to eliminate acid type agricultural soils. Soil pH is an
important factor in determining the solubility of many compounds such as the concentration
of heavy metals present in crops. It has been observed that in a strongly acidic soil,
large amounts of metals such as iron, aluminum, and manganese may dissolve and be
adsorbed on the surface of the soil particle. Plants can easily take up metals in
this form.1*1 Soil with a safe toxic metal content at pH 7 can easily be lethal to most
crops at pH 5.5. However, it has also been found that an increase in pH has decreased the
plant uptake of heavy metals. Application of sewage sludge or effluent irrigation have
generally tended to lower the soil pH, and the addition of calcerousor magnesium com-
pounds to soil have been used to correct or eliminate acidic soil conditions.
Related information of the effects of zinc level and soil pH on chard plants are shown rn
Table 89 . 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 was significantly reduced when
the soil pH was increased by the addition of lime.
Addition of sulfur has been shown to reduce the soil pH. The reduction of soil pH was
directly proportional to the quantity of sulfur added, lowering the soil pH increased the
concentration of metals as well as certain other elements such as silicon, phosphorus and
potassium, as shown in Table 90 .
The Virginia Polytechnical Institute, in another field test using fly ash as a fertilizer, was
197
-------
TABLE 89. 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 90... EFFECTS OF SOIL PH ON SOYBEAN PLANT'S MINERAL UPTAKE
Elements
in ppm
Fe
Mn
Zn
Co
Mo
Al
B
N?
Si
P
K
Soil
7.4°
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
Increase _ ,a
261.2 5.6
444.6 8.5
170.0 1.72
186.3
132.6
170.8
170.8
175.0
190.0
151.1
149.7
g 1 .plant
6.*
18.5
47.7
2.87
*
° No sulfur added.
b 10% sulfur added.
P154619-5-1 soybean variety.
Source: 192.
198
-------
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
sires has proven that fly ash could act as a neutralizing agent, diluent, and soil condi-
tioner to provide needed nutrients which enhance vegetation growth.^
The United States Park Service, Washington, D.C., has been testing sintered fly ash for
use as an additive to soils subjected to continuous use (bicycle paths, camping areas,
hiking trails, picnic areas). In this application, sintered fly ash would be added because
of 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 parti-
cular 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 information on the tolerance levels for many fly ash constituents which
when exceeded, contributed to a poor quality brick. These constituents included: water
soluble minerals, water soluble sulfur, carbon, iron, and the alkaline earths. The first
commercial fly ash brick plant using the process developed at the Coal Research Bureau
has been operating in Edmonton, Alberta. The plant has a design capacity of 35 million
bricks per year. Economic studies currently under way indicated that the cost of the Coal
Research Bureau process was less than that of the conventional clay-brick manufacturing
process. At the time of this report, several firms were currently examining the process for
commercial exploitation. Research was under way on coloring and texturing the brick,
and on producing large size bricks.
Water Treatment
Fly ash as a treatment material for reclaiming small eutrophic or algae-overgrown lakes
was being investigated at Notre Dame University. It has been shown that fly ash can
remove phosphates in the water and seal the bottom mud so that the release of pollutants
can be controlled. A process for the removing of phosphates from water by using fly ash
has been developed at the Polytechnic Institute, Brooklyn, New York. When used for water
treatment, fly ash can (1) increase the growth of floes and thus enhance settling, (2) con-
dition 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 were being developed at Washington State University. One appli-
cation, known as "syntactic foam," was used to achieve buoyancy in deep ocean environ-
ments. Syntactic foam was formed by vacuum impregnating cenospheres with an appropri-
ate resin. Research on aerospace applications of cenospheres has been under way 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 us.ng cenospheres
199
-------
in the production of tape for fire-proofing and insulating high-voltage electrical cable
has been developed by the Quelcor Corporation.
Specific Applications of Li me/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 had 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
which have been considered are:
• 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 compo-
nent and to neutralize acidic soil. Modified fly ash may also increase the concentrations
of boron and other trace elements, and also increase the texture and drainage character-
istics of soils. Further research is needed to determine if pollution would be created by
water leaching.
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
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 buildings
is Sweden and West Germany have been constructed, in part, using this material. Aera-
ted concrete is a light-weight structural material consisting of small non-communicating gas
200
-------
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 76 . It was
necessary to add cement and a gas-producing agent to the modified fly ash in*making this
product. After the concrete was poured into the mold, the form was autoclaved for 16
hours. Commercial aerated material can be sawed, nailed, drilled, screwed, or glued
like 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 insula-
ting 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 77 is a process flow sheet for the manufacture of poured concrete materials. The
material was poured into molds for curing and autoclaved for 16 hours. The resulting
poured concrete block had a density of 1 .5 g/cu cm. The residue did 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 SCXcapture or marketing problems would result since processing would occur
below fne temperature for sulfur dioxide regeneration.
• Little or no storage or curing time would be required before use since structural
materials produced have been shown to be durable, pre-shrunk, and pre-strengthened.
• No exotic equipment would be required for production.
• Minimum pollution would occur at the plant since all rejects and process waters
may be recycled.
• A potentially large market may exist in low-cost housing or other construction.
Because absorbed sulfur dioxide is liberated when modified fly ash is heated, it was neces-
sary to find a technique for totally using the ash which would either lock the sulfur into
the final product or not require heating. Autoc laving has had 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 foamed concrete, and concrete materials.
Calciums! licate (CS) brick production has been examined as a potentially large tonnage appli-
cation of limestone modified fly ash. Bricks produced by this method have the advantage of
binding the sulfur components within a calcium-si licate matrix, and have surpassed the stan-
dards for conventional sand-lime brick. Figure 78 is a process flowsheet forthe production
of CS brick. Mixing and humidity curing have been two important process parameters in produ-
cing CS brick. Promising areas for using calcium si licate brick include low-cost construction
materials, interior walls, decorative walls, patios, and thermal or acoustic insulation.
201
-------
Mech Preclp - 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
2> 16kgf/sq cm, 185C
Air Drying
(72 hours)
51% H20
@60C
J
Source: 46.
Figure 76 . Aerated or foamed cellular concrete production flow diagram.
202
-------
Silica Sand
Wet Collected Limestone
Modified Fly Ash
(10% Slurry)
Dewater Ash to 58%
50% Ash + 11% CaO
+ 39% Sand
Paddle Mixer
(10 Minutes)
Pouring into Molds
24 hours Them a I Set (HOC)
Lime (CaO) 96% Pure
Autoclave, 16 hours
@ 16kgf/sq cm, 185 C
Air Drying
(72 hours)
Source: 46.
Figure 77 • Formed concrete production flow sheet.
203
-------
Silica Sand
30 x 100 Mesh
Wet Collected Limestone
Modified Fly Ash (1% Slurry)
Dewater Ash to
34% H2O
50%FlyAsh + ll%CaO
+ 39% Silica Sand
Paddle Mixer (10 min)
@20.4%H2O
Slaking Reactor
(1 hour)
Forming Pressure
200 kgf/sq cm,
17.7% H2O
Lime (CaO)
96% Pure
24-Hour Humidity
Storage: 95% Humidity
atSTP
Autoclave
8hr, 16kgf/sqcm,185C
Air Drying
(72 hours)
Figure 78 . CS brick production flow diagram-.
204
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Potential Structural Materials Applications of FIuidized-Bed Residues
Several beneficial materials applications for conventional coal-combustion residues were
discussed earlier in this chapter. Because of limited material, it was not possible to under-
take 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 91
Concrete and asphalt are discussed separately below.
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 Cl 92-69 ("Standard Method of Making and Curing Concrete Test Specimens in
the Laboratory"); the cylinders were approximately 5 cm in diameter by 10 cm in length.
Table 92 gives the composition of each batch. The mixtures are considered "rich mixes"
because of the high cement content (approximately 15 percent).
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 diameters of the
cylinders were measured to obtain average cross-sectional area; the results are shown in
Tables 93 and 94 . Each cylinder was then capped to prepare them for the actual compres-
sive strength tests. The results of the tests are presented in Table 95 for the seven day
curing and in Table 96 for the twenty-eight day curing.
Results. The results are shown graphically in Figures 79 to 82 , 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 ash (7-day cure) and spent bed materials from the Exxon, New Jersey,
pressurized miniplant. On the contrary, with the exception of VFA (28-day cure) and the
EFA (7-day cure), 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 compressive strengths greater than the control specimens:
5 percent VSBM/7-day cure; 5,15, and 25 percent VSBM/28-day cure; 5,15, and 25
percent NJFA/28-day cure; and 5 percent VFA/28-day cure. The 25-percent NJFA/
7 day cure material was nearly equal to the control.
205
-------
TABLE 91 . POTENTIAL STRUCTURAL MATERIALS APPLICATIONS:
TESTS PERFORMED
Application Test Description Method
Concrete Compress!ve 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.
206
-------
TABLE %t COMPOSITION OFCONCRETE TEST C.Y\
Batch Type of.
No. 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
I Two samples for each batch.
Residue source code presented in Table 6.
207
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TABLE 93 . DIAMETER AND AREA OF CONCRETE TEST CYLINDERS:
SEVEN-DAY CURE
Batch
No.0
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.??
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
HM^^B^^^^^H^^^^^B^^^^^^^^MBMMMMlva
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.
208
-------
TABLE 94. 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
Diameter (cm)
.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
b
5.29-
S.-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
5140
5.40
5.40
5.40
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. m , .
b First sample of the batch; two diameter measurements taken to minimize effect of
random irregularities. ... rf . t
C Second sample of the batch; two diameter measurements taken to mmimize effect of
random irregularities.
209
-------
TABLE 95. RESULTS OF COMPRESSIVE CONCRETE STRENGTH TEST
AFTER SEVEN 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
25.7
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.
-------
JABLJJ6, JiESULTS OF COMPRESS (VE CONCRETE STRENGTH TEST AFTER TWE NTY-EIGHTDAVS
Batch No.
1
2
3
4
5
6
7
8
9
10
ro "
- 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 ~J
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.
-------
300r-
250
E
u
JC
15>
20C
to 150
0)
£
§• 100
o
U
50-
Legend
• Control
A NJFA
O VFA
D VSBM
I
10 15 20
Residue Content (% by weight)
25
30
Figure 79. Concrete, compress! ve strength tests: NJFA, VFA, VSBM after seven day cure.
-------
300
250
6
u
200
1...1
150
K,
_- 0)
w >
01
100
50
Legend
• Control
A NJFA
O VFA
D VSBM
I
Figure 80
_L
10
25
15 20
Residue Content (% by weight)
Concrete oppressive strength tests: 'NJFA, VFA, VSBM after 28-day cure.
30
-------
300
250
" 200
.sr
&
_c
.•f-
CD
g 150
o>
0)
1100
d
50
Legend
* Control
NJSBM
® ESBM
® EFA
1
i
I
10
25
30
15 20
Residue Confent (% by weight)
Figure 81. Concrete compressive strength tests; NJSBM,ESBM,.E FA after seven day cure.
-------
NO
Ol
Legend
• Control
A NJSBM
O EFA
D ESBM
t
I
1
10 15 20
Residue Content (% by weight)
25
30
Figure 82. Concrete compressive strength tests: NJSBM, EFA, ESBM after
28 day cure,
-------
Asphalt
Procedure. Residues were rested as replacements for aggregate filler in asphalt. Samples
were made and tested for compressive strength following the procedures outlined in ASTM-
D-l 074; 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 97 summarizes the sample compositions.
All residues were slaked before being added to the asphalt mixtures. Unslaked residues
produced poor results, particularly the NJSBM. 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 83 ).
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 1 0.1 6 + 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.
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 84 through 87 ). In some cases, test specimens containing NJSBM showed signi-
ficantly increased strength (specimens 7-day cure/90 percent residue, and 29-hour cure/
45 percent residue). Major reduction in strength also occurred (7-day cure/82 percent
NJFA).
Potential Agricultural Application of FBC Residues
Plants, to complete their life cycle development, require some traces of zinc, copper,
iron, manganese, 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 micronutrients, and the latter, macronutrients. Any material which
contains these nutrients in plant-available form has potential value as a soil conditioner.
Fluidized-bed fly ash and spent bed residue materials contained most of the micronutrients
and some of the macronutrients necessary for plant growth, as shown in Tables 13 to 17
which present the results of the residue chemical characterizations. These residues, because
of their compostion and particle size, have excellent potential as a good soil conditioner
with considerable nutritive value.
Acidic soils which occur in humid regions (such as the eastern United States), may cause
the calcium and magnesium ions to be gradually leached, and farming may accelerate this
leaching process. Soil pH is also a major influence in plant growth. Most plants grow
216
-------
__ _ — ____.
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,
Aggregate
92
72
47
ta»M
82
—
82
—
92
—
Percent by Weight
Fly Ash or
Bed Material
—
20
45
92
—
82
—
82
—
91 .76-85
Other
Components
—
—
—
—
10 cement
10 cement
10 lime
10 lime
0.24 - 7*HCL
0.24-7* HCL
\f
Depending on type of residue
217
-------
Figure 83 . Result of reaction between residues and emulsified asphalt.
218
-------
lOOr-
80
u
60
ro
2
> 40
r
u
20
Legend
• Control
A VSBM
O NJSBM
D ESBM
I
I
10
20
30
40 50 60 70
Residue Content (% by weight)
80
90
TOO
Figure 84. Asphalt compressive strength tests: VSBM, NJSBM, ESBM after 29 hour cure.
-------
lOOr-
E
u
80
B> 60
I 40
fi
o.
o
U
20
Legend
• Control
A VSBM
O NJSBM
O ESBM
I
j
20
30
40 50 60 70
Residue Content (% by weight)
80
90
100
Figure 85C Asphalt compresslve strength tests: VSBM, NJSBM, ESBM after seven day cure.
-------
100r~
80
£
u
I
O)
40
a.
6
o
U
20
Legend
• Control
O NJFA
O EFA
J_
I
J
10
20
30
40 50 60 70
Residue Content (% by weight)
80
90
100
Figure 86. Asphalt compress!ve strength tests: NJFA, EFA after 29 hour cure.
-------
100,-
Legend
80
• Control
O NJFA
O EFA
u
60
NJ
o>
.> 40
0)
a.
o
U
20
1
_L
10
20
30
40 50 60 70
Residue Content (% by weight)
80
90
TOO
Figure 87. Asphalt compress!ve strength tests: NJFA, EFA after seven day cure.
-------
best between the range of 7.0 to 7.5, hence, both higher and lower pH's may be detri-
mental .
In acidic soils, large amounts of iron, aluminum, manganese, copper, lead, cadmium,
and zinc may also enter into solution and be adsorbed on the surface of the soil particfes
in a form that plants can readily assimilate. High levels of soluble manganese, iron, and
other metals may interfere with crop growth, but liming can correct this condition. In
contrast, molybdenum is more soluble in alkaline soils than in acidic soils, and thus uptake
of this micronutrient may be increased with liming. Nevertheless, if soil has a pH greater
than 8.0, most of the trace elements are fixed (less soluble) in the soil matrix and are
unavailable to plants. Fluidized-bed residues can act as a liming agent and may be used
as an excellent soil conditioner to increase the soil pH, reduce soil acidity, and thus
lessen the leaching of magnesium and calcium, and prevent excessive uptake of toxic
heavy metals to plants.
The potential for residue agricultural applications was evaluated in a series of small-
scale preliminary type plant growth tests. Table 98 presents the test program schedule.
Maize was also planted and harvested; however, this program was discontinued at the
request of the Environmental Protection Agency authorities before analyses of the maize
crops were started. Likewise, the analytical evaluation of Experiments 2, 3, and 4 were
not completed prior to the Environmental Protection Agency request.
Experiment 1 . Cherry Tomatoes
Procedure. Small cubicle plastic pots with about 1 .06 cu cm volume were filled with a
commercial potting mixture (Supersoil). The average weight of potting mixture used was
about 400 grams. The pots were too small to permit the test plants to complete their en-
tire life cycle. Residues were mixed into potting mixture at application rates of 75, 150,
225, and 300 grams per pot, which corresponded to field application rates of 67.2, 134.4,
201.7, and 268.9 kkg per hectare. Six residues were tested: CFA, FSA, VFA, VSBM,
NJFA, and NJSBM (these are identified in Chapter 1, Table 6) There were eight pots^
per residue and two control pots. Fertilizer was surface-applied to each of the soil/resi-
due (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), and several plants germi-
nated; each pot was subsequently thinned to one plant per pot. There were two replica-
tions for each residue application rate; this was done 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
Photographs of the harvested tomato plants were presented in the first annual report (T1
223
-------
TABLE 98 . PLANTING SCHEDULE FOR AGRICULTURAL TESTS
N>
No.0'
1
2-A
2-B
Date of
Planting
27 March 1976
12 June
1 8 August
Harvesting
7 May
29 July
15 February, 1977
Crop
Tomato
Tomato
Tomato
Residue/Soil Weight
(g/400 g of soil, dry wt)
75,150,225,300
2.5,12.5,25.0,37.5
None added
Remarks
Completed
Completed
Evaluate effects
3 15 January 1977
4 1 February
7 March
30 March 1977
Spinach
Lettuce f,g
2.5,7.5,10.0,12.5
2.5,7.5,10.0,12.5
of single addition
on second rotation
Crop had high salt
tolerance and
edible leaves
Numerals refer to a given set of pots in which crops were planted sequentially; letters refer to specific rotation in any
, given set of pots.
Six residues were tested (CFA,FSFA,NJFA,NJSBM,VFA,VSBM)/with one set of pots for each residue type, and one
set as a control. 1,000 cu cm pots were used.
Cherry tomatoes.
Green leaf spinach.
EFA and ESBM residues were tested,rather than CFA,FSFA residues.
f
Green leaf lettuce.
-------
represented the lowest appl.cohon rate and T the highest). No pictures were shown of
CFA or FSFA because the tomato plants d.d not grow at all In those fluldlzed-bed oil gasi-
fication res.dues. The very high soil pH produced by the residues significantly suppressed
root development for all res.dues at all application rates. Also, plant growth was signi-
ficantly 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 were
differences among the six residues in their effects on plant growth, and (2) at these high
application rates, there were significant negative impacts on plant growth and root deve-
lopment. Based on these conclusions, a second experiment was devised to test the impact
of lower application rates.
Experiment 2-a. Cherry Tomatoes
Procedure. This experiment was Identical to the previous one, except as noted. Appli-
cation rates were 2.5, 12.5, 25.0, and 37.5 grams per pot, corresponding to field appli-
cation 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 during the first three weeks 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 following the procedures
referenced in Appendix A.
Results, Photographs taken of the test plants just before harvesting are shown in Figure
88. The impact of residue application on plant growth is given quantitatively in Table
99, and graphically in Figures89 and 90 . Table 99 also presents the wet and dry
weight and the ratio of wet to dry weight.
The results indicated that there was significant improved growth response at equivalent
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 excessive application rates equiva-
lent growth response at all the application rates tested for the VSBM, and NJSBM residues.
Plant tissue percent dry weight increased from 5 to 80 percent with all residue types for
equivalent application rates of 2.2 and 11 .2 kkg per hectare. For CFA, the percent dry
weight of plant tissue decreased significantly at a 22.4 kkg per hectare application rate in
relation to the control plantings.
The standard commercial potting mixture used in the experiments had a high level of humic
acid with, consequently, a low pH (about 5.5). Since the fly ash and spent bed residues
were quite alkaline, adding them to the potting mixture raised the soil pH (as shown in
Tables lOQand 101). The effect on plant growth plotted against soil pH is presented in
Figure 91 . This latter figure shows the growth improvements (in comparison to the control
plantings when the pH was In the normal range from 6.2 - 7.8. This growth improvement
is almost certainly partially the result of the residues having increased the pH to more
optimal values and providing adsorption of desirable trace elements.
225
-------
Control T
PER, Virginia fly ash
PER, Virginia spent bed material
Control T
Exxon, New Jersey fly ash
Exxon, New Jersey spent bed material
Control T
Esso, England cyclone fly ash
Figure 88 .
Esso, England fines, stack fly ash
Experiment 2-A, tomato plant growth.
226
-------
TABLE 99 . EXPERIMENT 2-A: TOMATO PLANT
GROWTH RESULTS
Treatment
Code
Control
CFA
FSFA
VFA
VSBM
Application
Rate
(kkg/ha)
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
Rlb
31
30
34
15
5
33
27
19
14
36
37
36
43
43
39
35
35
Plant Height
R2b
28
30
33
20
. 16
35
35
22
9
43
43
43
37
45
40
35
43
(cm)
R3b
17
29
35
11
13
41
36
19
8
45
45
47
43
40
41
36
37
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
(g)
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
(continued)
-------
TABLE98 (Cont.)
Application
Treatment Rate
Code0 (kkg/ha)
NJFA 2.2
11.2
22.4
33.6
NJ
10
03 NJSBM 2.2
11.2
22.4
33.6
Rb
Rl
43
33
10
5
37
45
43
37
Plant Height (cm)
Rb
R2
36
40
8
8
39
43
45
32
*3b
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
• Residue source code presented in Table 6,
Replicate
-------
to
>o
D 20
Q)
15
10
5
-
D VFA
A FSFA
O CFA
_L
_L
I
10 20 30
Residue Concentration (kkg/ha)
a See Table 6 for explanation of letter code.
Figure- 89 . Mean tomato plant height, Experiment 2: VFA, FSFA, CFA
40
-------
45 r-
u
§ 20
15
10
5
O NJSBM
a VSBM
O NJFA
10
I
20 30
Residue Concentration (kkg/ha)
40
a See Table 6 for explanation of letter code.
Figure 90 , Mean tomato plant height * Experiment 2 j NJSBM, VSBM, NJFA.
-------
TABLE 100. pH OF SOil-RESIDUE MIXTURE
Application
Treatment Code Rate
(kkg/hcO
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
R2C
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
R3C
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
231
-------
TABLE 101 .PH OF SOIL RESIDUE MIXTURE AFTER CROP 2 HARVEST
Treatment Code
Control
CFA
FSFA
VFA
VSBM
NJFA
NJSBM
Application
Rate
(kkg/ha)
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
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
R2C
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
232
-------
_c
D)
45
40
35
30
25
KJ <"
CJ X
CO
§ 20
15
10
Legend
• VFA
A VSBM
O NJFA
O FSFA
D NJSBM
• CFA
1
JL
Figure 91..
789
Sol! pH
Tomato plant growth vs. soflpH, Experiment 2-A.
10
-------
The biodegradation of the residue materials by soil microorganisms may also have released
micronutrients 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 91 shows, there is considerable variability in plant tissue analytical
results for a given pH. Since the various residues differ substantially in chemical compo-
sition, it may be tentatively assumed that this dispersion reflects differences in the availa-
bility and quantity of nutrients that were provided to the test plants in the residues.
Results for chemical analyses of plant tissues are given in Table 102. Those results which
show significant variability are graphically represented in Figures 92 to 95 . Tomato
plants test-grown on residue-treated soil showed significantly lower concentrations of ana-
lyzed levels for heavy metals than the control plants. This effect is undoubtedly pH-related
In contrast, for the most part, sulfate concentrations were not significantly different with
residue-treated or control test soil plantings. Exceptions were FSFA/T~ VFA/T,, NJFA/L,
and NJSBM/T., T», and T,. There was no significant difference in the concentration or
magnesium between the control and residue-treated soil growth except for NJFA/OL. All
residue-treated vegetation (except VFA/T.J showed significantly higher concentrafions of
calcium,which was associated with cell turgidity. Although the calcium concentration was
higher in the treated plants, they did not show signs of toxic calcium levels.
Experiment 2-B. Cherry Tomatoes
Procedure. Germinated cherry tomato seeds were replanted in the same pots of soil used
in Experiment 2-A. No further application of residues was provided so that the effects of
a single addition of residue on a second crop planting could be evaluated. Because Experi-
ment 2-A showed significant improved growth response at equivalent application rates of
2.2 and 11 .2 kkg per hectare, the experiment was limited to these two latter equivalent
application rates. Tomato planting was perfomed on August 18, 1976, and harvesting
occurred on February 15, 1 977. All other aspects of Experiment 2-B were similar to
Experiment 2-A.
Results. Results of the plant tissues' chemical analyses are tabulated in Table 103 . Some
of the results, showing wide variability for different added residues are graphically illustra-
ted in Figures 96 to 103. The calcium contents for all the residue-treated crops were
generally equal to or lower in concentration than the control crops. With only one ex-
ception, the calcium concentrations were lowest in the plants grown in the soil containing
the equivalent of 2.2 kkg of residues per hectare. The calcium content in the VSBM
residue continued to decrease in the soil containing the equivalent of 11 .2 kkg of residue
per hectare. Magnesium showed no significant difference in concentration between the
control and the residue-treated test vegetation, except for NJSBM/T,.,, which showed
a significant reduction in magnesium concentration.
Likewise, the concentration of cadmium and copper generally was not significantly different
between the control and the residue-treated test tomato plants. The only exceptions were
plants grown for CFA/L, and VFA/^ and T2 soil mixtures; these plants contained a much
higher concentration oFcadmium than the control plants did. With the exception of CFA/L,
234
-------
TABLE 102. EXPERIMENT 2-A : TOMATO PLANT TISSUE, CHEMICAL ANALYSIS
Oi
Treatment
(residual
code)
Control
CFA/T!
T2
FSFA/TJ
T2
NJFA/TJ
T2
NJSBM/H
T2
TS
T4
VFA/TJ
T3
T
VSBM/Tj
T2
T4
AppUcatior
Rate
(kkg/ha)
0
2.2
11.2
2.2
11.2
2.2
11.2
2.2
11.2
22.4
33.6
2.2
22.4
33.6
2.2
11.2
33.6
Ca
0.08
0.19
0.19
0.22
1.22
0.12
0.15
0.38
0,30
0.86
0.66
0.12
0.05
0.37
0.17
0.16
0.56
Constituents
Mg
(%)
0.158
0.197
0.145
0.155
0.202
0.135
0.523
0.182
0,130
0.178
0.170
0.153
0.151
0.148
0.211
0.102
0.140
SO, Cd
1.65
1.50
1 .00
0.60
4.30
0.90
3.75
2.60
1.60
3.70
3.40
1.40
0.80
2.30
1.60
0.50
1.90
Cu Fe
130
90
N.D.
N.D.
N.D.
70
N.D.
20
20
N.D.
20
90
30
30
— -N.D.
40
60
Mn Pb
ppm
68
93
14
3
14
22
N.D.
16
10 —
12 —
N.D.
18
17
6
N.D. —
N.D. —
N.D.
Zn
51
20
2
20
2
6
0.1
1
1
N.D.
4
10
5
4
2
7
3
Ag
—
—
—
—
—
—
_-
—
—
—
—
—
—
—
—
—
- —
-------
S3
CO
O-
1.0
0.8
0.6
o
u
520.4
Legend 0.2
o NJFA
a NJSBM 0
A VFA
* VSBM
o CFA
• FSFA
Figure 92
O.of'
10 20 30
Residue Concentration (kkg/ha)
Figure 94
10 20 30
Residue Concentration (kkg/ha)
20 -
10 20 . 30
Residue Concentration (kkg/ha)
Figure 95
10 20 30
Residue Concentration (kkg/ha)
Figures 92 to 95. Experiment- 2-A: Analytical results of calcium, magnesium, sulfate, and managanese.
-------
TABLE 103. EXPERIMENT 2-B:
K>
Treatment
(residual
code)
Control
CFA/TI
T2
FSFA/TJ
NJFA/T!
NJSBMAi
"\2
VFA/T!
T
VSBM/TI
To
Application
Rate
(kkg/ha)
0
2.2
11.2
2.2
2.2
11.2
2.2
11.2
2.2
11.2
2.2
11.2
•-! • —".•_' 1 .-.tf • - ..._...., . ... , ._.„.,.....,.. F „ .. , . .... . •' •
Constituents
Co
0.27
0.23
0.28
0.07
0.13
0.16
0.12
0.17
0.15
0.22
0.21
0.05
0
0
0
0
0
0
0
0
0
0
0
0
Mg SQi
' '°)
.166 —
.140 —
.146 —
.134 —
.186 —
.136 —
.122 —
.010 —
.129 —
.134 --
.132 —
.160 —
Cd
0.07
0.10
0.42
N.D.
N.D.
0.10
0.05
0.10
0.37
0.57
0.10
N.D.
Cu
4.8
2.0
6.0
5.8
2.3
3.5
2.0
3.8
2.8
3.0
3.5
3.5
Fe
11.3
12.8
53.3
57.8
15.1
15.4
194
8.1
3.1
5.3
1.2
193
Mn
ppm
32.6
19.4
19.5
36.7
32.5
31.6
16.7
25.5
33.4
50.5
34.3
19.4
Pb
N.D.
N.D.
7.0
N.D.
N.D.
N.D.
N.D.
N.D.
2.2
N.D.
N.D.
N.D.
Zn
49.7
30.2
52.5
30.9
23.2
32.7
73.2
21.5
28.3
27.6
30.9
26.6
Ag
1.3
3.1
1.0
3.5
2.0
2.2
3.4
2.3
5.8
6.0
3.6
3.3
-------
CO
GO
CO
Legend
o NJFA
H NJSBM
* VFA
A VS3M
o CFA
• FSFA
0.5
0.4
o 0.3
U
0.2
0.1
F-gure 96
0.25 r
2 4 6 8 10 12
: Residue Concentration (kkg/ha)
ppm
2 4 6 8 10 12
Residue Concentration (kkg/ha)
Figure 97
10
8
=> 6
u
246 8 10 12
Residue Concentration (kkg/ha)
Figure 99
2 46 8 10 12
Residue Concentration (kkg/ha)
Figures 96 to 99. Experiment 2-B; Analytical results of calcium, magnesium, sulfate, and
manganese
-------
Legend
o NJFA
» NJSBM
* VFA
* VS3M
o CFA
• FSFA
CO
•o
194 ppm
193 pprn1
Figure 100
T
24 6 8 10 12
Residue concentration (kkg/ha)
024 6 8 10
Residue concentration (kkg/ha)
•f
I
60
50
40
30
20
10
2 4 6 8 10
Residue concentration (kkg/ha)
24 6 8 10 12
Residue concentration (kkg/ha)
Figures 100 to 103. Experiment 2-B: Analytical results of iron, manganese, zinc, and silver.
-------
FSFA/T,, NJSBM/T,, and VSBM/T9, the vegetation containing the residue was nearly
equal to or lower in iron concentration than the control test vegetation. The exceptions
were NJSBM/'L and VSBM/T2 which contained relatively high concentrations of iron at
194 mg/l and 193 mg/i, respectively. This is approximately a 17-fold greater iron con-
centration than in the first cropping (see Experiment 2-A). The sharp rise in iron concen-
tration may have been due to a possible decrease in pH. Lead was not detected in any
of the plant samples except CFA/T2 and VFA/T-j . Except for NJSBM/T^, the zinc con-
centrations in the plant samples grown In the residue enriched sol!, were nearly equal to
or less than the tomatoes grown in the control soil. Silver concentration in the enriched
soil test plants was greater than the control in all but the CFA/X residue mixture.
In general, the second crop growth (Experiment 2-8) showed test results similar to the
original crops (Experiment 2-A), A significant difference was noted in the concentration
of calcium. In the original test growth, the tomato plants took up more calcium in the
residue-treated soil than in the control soil. In the second test planting, the calcium
uptake was less in the residue-treated tomato plants than in the control vegetation. Other
differences include a general decrease in the magnesium concentration, and a general
increase in the iron, manganese, and zinc concentrations during the second test planting
of tomatoes. The increases may have been due to a gradual decrease in the pH of the
soil. It should be pointed out, however, that the concentrations of these minerals in the
residue-treated plants were generally still less than the plants grown in the control test
potting soi I.
Experiments. Spinach
Procedure. The procedure for this experiment was identical to Experiment 2-A, except
for the following modifications. The residue application rates in the test soils were fur-
ther reduced. Thus, the application rates were 2.5, 7.5, 10.0, and 12.5 grams per pot,
which corresponded to equivalent field application rates of 2.2, 6.7, 9.0, and 11 .2 kkg
per hectare. These rates are identified as T,,JL, T3 , and T,, respectively. Germinated
spinach seeds were planted on January 15, 19777 and harvested on March 7, 1977. The
harvested leaves were digested and analyzed according to the procedures referenced in
Appendix A.
Results. The analytical results are tabulated in Table 104, and the results illustrating
significant variations between residues are graphically represented in Figures 104 to 109 •
The analyses of the spinach leaves showed trends similar to that found with tomato plants.
That is, concentrations of the minerals were generally lower in the residue-treated test
crops than in the control crop. The concentrations of manganese, zinc, molybdenum, and
silver were all lower in the residue-treated spinach than in the spinach grown In the con-
trol soil. Similarly, the spinach grown in the residue-enriched soil showed concentrations
of sodium and aluminum generally equal to or less than the spinach grown in the control
soil. Significantly, the concentrations of potassium, barium, and chromium were generally
higher in the residue-treated test spinach. In fact, CFA/X contained about seven times
the potassium levels found in the control plant. Further, calcium was equal to or less
in the test spinach grown in the residue applied at the equivalent rate of 2.2 kkg per
240
-------
TABLE 104. EXPERIMENT 3: SPINACH TISSUE,CHEMICAL ANALYSIS
Treatment
(residual
code)
Control
CFAAl
T2
T3
T
FSFA/Fi
T2
^,
T4
NJFA/TI
jo
T3
T4
NJSBM/T1
To
Tg
T.
VFA/TI
T2
T«
VSBM/4,
T2
T3
T4
Application
Rate
(kkg/ha)
0
2.2
6.9
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
Constituents
Ca
1.34
1.34
. 2.34
—
1.49
1.14
1.54
1.19
2.04
0.69
1.09
1.29
1.19
1.29
1.84
2.14
2.54
1.14
1.09
1.09
1.09
1.19
1.79
1.84
2.19
Mg SO4
(%)
4.00
2.14 -
3.20
—
2.80
3.22
3.22
4.06
3.92
2.36
3.84
1 .92
5.06
2.23
3.10
2.86
3.30
2.50
2.54
2.40
2.26
2.64
5.70
2.34
5.10
Cd
5.0
3.0
4.0
2.0
5.0
8.0
6.0
7.0
6.0
* 3.0
2.0
3.0
3.0
6.0
7.0
3.0
6.0
5.0
5.0
5.0
3.0
6.0
6.0
3.0
6.0
Cu
30
6
38
35
14
47
42
41
19
9
7
43
79
44
49
39
40
40
18
17
5
72
61
30
58
Fe
ppm
311
164
210
126
236
446
402
385
394
243
192
206
427
299
226
291
417
310
273
281
162
335
390
326
470
Mn
535
297
422
—
303
422
339
465
296
324
267
287
220
234
253
190
204
391
380
370
280
455
422
275
349
Pb
38
26
37
—
34
64
57
56
77
51
33
37
48
45
39
43
45
48
39
38
19
65
51
34
80
Z.n
270
180
229
__
157
191
234
194
214
81
74
72
56
66
54
46
50
119
93
85
98
90
145
174
68
(continued)
-------
TABLE 104 . (Continued)
Treatment
(residual
code)
Control
CFAAi
T2
T4
FSFA/TI
^2
T3
NJFA/T,
^2
T3
T
NJBM/Fi
T2
T3
1.
VFA.AI
T2
T
T4
VSBM/TI
T2
T3
T4
Application
Rate
(kkg/ha)
0
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
Constituents
K
%
1.23
1.29
8.40
—
1.58
1.42
1.36
1.31
3.13
2.15
1.95
1.55
1.87
1.90
1.73
1.43
1.45
1.65
1.65
1.58
1.97
1.36
1.56
1.27
1.75
Na
0.75
0.57
0.66
..
0.39
0.66
0.74
0.66
0.77
0.56
0.55
0.66
0.57
0.54
0.47
0.73
0.65
0.60
0.62
0.71
0.53
0.64
1.05
0.56
0.73
Ba
40
60
100
20
50
60
60
50
60
30
30
20
30
40
30
60
70
70
50
30
60
50
70
90
70
Al
2,020
40
510
200
950
2,200
1,910
2,460
1,350
1,030
1,160
1,120
650
1,890
320
1,270
1,170
1,020
3,090
2,470
1,680
720
1,930
390
1,110
Cr
ppm
5.0
6.0
6.0
2.0
6.0
13.0
11.0
8.0
10.0
7.0
11.0
14.0
14.0
8.0
5.0
6.0
8.0
8.0
7.0
9.0
7.0
7.0
9.0
9.0
12.0
Mo
17
ND
ND
ND
ND
8
ND
ND
ND
ND
ND
ND
ND
8
ND
ND
ND
8
ND
ND
ND
ND
ND
ND
ND
Ag
5.0
1.0
1.0
3.0
ND
1.0
2.0
2.0
2.0
2.0
ND
2.0
2.0
1.0
1.0
2.0
1.0
3.0
1.0
1.0
1.0
2.0
2.0
3.0
3.0
-------
j-egend
a NJFA
a NJS3M
* VFA
* VSBM
o CFA
• FSFA
c
U
5.
a.
02 4 6 8 10
Residue concentration (kkg/ha)
Figure 106
24 6 8 10 12
Residue concentration (kkg/ha)
o>
6.0
5.0
4.0
3.0
2.0
1.0
100
80
60
40
20
0
Figure 105
02 4 6 8 10
Residue concentration (kkg/ha)
Figure 107
2468 10
Residue concentration (kkg/ha)
12
12
Figures 104 to 107. Experiment 3: Analytical results of calcium, magnesium, cadmium, and copper.
-------
ro
fc
Legend
o NJFA
a NJSBM
* VFA
* VSBM
o CFA (EFA)
• FSFA (ESBM)
TOO
24 6 3 10
Residue concentration (kkg/ha)
12
Figure 110
Exp. 4
2 4 6 8 10
Residue concentration (kkg/ha)
j Figure 109 Exp. 3
80 -
60
I
20
1.0
0.9
0.8
0-7
0.6
0.5
2 4 6 8 10
Residue concentration (kkg/ha)
Figure HI
02 4 68 10
Residue concentration (kkg/ha)
12
Figures 108 to 111. Experiment 3 and 4: Analytical results of iron, lead, calcium, and magnesium.
-------
Educed Dran^tissue! wi h I ' *** """ ^ ^2' NJFA «* VFA residues which
produced plant tissues with lower concentrations than the^control soil for the entire range
of application rates Magnesium content was also less in all the vegetation tissue grown
,n the est so, I rmxtures containing the equivalent of 2.2 kkg per hectare of residue, and
generally was less m the crops grown with higher rates of residue applications. The only
plant samples that showed higher concentrations of magnesium than the plant tissues grown
,n the control soil, were the NJFVT4, VSBMAo and T, samples. For both cadmium and
copper, the chemical content results were variable. Generally, the spinach grown in
soil treated with CFA, NJFA, and VFA residues were lower in cadmium concentration than
the crop grown in the control soil, and the FSFA, NJSBM, and VSBM treated spinach were
higher in cadmium concentration. Likewise, the CFA, NJFA, except NJFAA,; and VFA
soil admixtures provided plant tissues with less copper concentration than the control crop.
Except for FSFA/T4/ VSBM/Tg, and NJSBM/T3 and T,, all the other residue-admixed
soils grew spinach resulting in highercopper concentration than the control crop.
Experiment 4. Lettuce
Procedure. This experiment was identical to Experiment 3, except that germinated lettuce
plants were set on February 1, 1977, and harvested on March 30, 1977, and the six residues
used in the experiment were EFA, ESBM, NJFA, NJSBM, VFA, and VSBM.
Results . The results of the analyses of the digested lettuce leaf tissues are shown in Table
105. In all cases, lettuce tissues from the residue-treated soil were significantly lower
in minerals such as cadmium, copper, iron, manganese, lead, zinc, potassium, aluminum,
chromium, and silver than the control soil residue. In addition, sodium was either equal
to or less in the residue-treated crop tissues than in the control crop tissues.
Molybdenum was not detected in any of the lettuce tissue samples. The only other consti-
tuents that varied in tissue chemical content were calcium and magnesium. These data
are graphically summarized in Figures 110 and 111. Nearly one-half of the crop tissues
grown in the residue-treated soil were higher in alkaline metals than the crops grown
in the control soil. Except for lettuce tissues grown in EFA/T3 and T., and NJSBM/T,,
the concentrations of calcium were lower in residue-treated lettuce than in the control
crop tissues.
Summary
These preliminary screening tests showed that the residues applied at reasonably low rates
may be beneficial to the growth of farm crops, particularly in soils with acid or trace
element deficiencies. Experiment 2-A indicated that low concentrations of residue in-
creased the pH of the soil, and therefore restricted the uptake of heavy metals by plant
tissues and, hence, even reduced their concentration in the p ant t.ssues. The soil pH
in Experiments 2,3, and 4 showed a general decrease of metal ,on concentrat.ons m the
residue-treated crop tissues which indicated that there may have been a trend of increased
PH and reduced metal ion plant uptake concentrations. With the various residues used m
pH and reduced metaMon p ^ P^ ^.^ |n equa,izing or reducing the metal ion
245 •
-------
TABLE 105. EXPERIMENT 4; LETTUCE TISSUES, CHEMICAL ANALYSIS
Treatment
(residual
code)
Control
EFAA,
T2
T3
TJ
ESBM/T.
T2
T3
NJFA/TT
T2
T3
T^
NJSBMAi
T2
T3
T4
VFAA]
T2
T3
T4
VSBMAT
T2
T3
T:
Application
Rate
(kkg/ha)
0
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
Constituents
Ca
0.90
0.70
0.90
0.95
1.00
0.85
0.65
0.75
0.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
70
85
60
80
90
10
60
55
85
85
75
80
70
70
60
75
85
Mg SO,
(%
)
0.78
0.60
0.93
0.68
1 .05
0.86
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
62
78
78
87
62
58
64
82
62
64
84
67
65
65
67
64
66
72
78
Cd
15.0
<1.0
1.0
1.0
1.0
3.0
1.0
2.0
2.0
3.0
2.0
200
2.0
<1.0
1.0
<1.0
1.0
1.0
1.0
T.O
1.0
3.0
3,0
2.0
3.0
Cu
27.0
8.0
8.0
9.0
10.0
17.0
4.0
9.0
11.0
10.0
8.0
8.0
8.0
9.0
8.0
7.0
10.0
10.0
10.0
8.0
9.0
9,0
12.0
17.0
9.0
Fe
ppm
376
161
197
210
246
283
148
187
213
214
150
133
282
215
126
128
194
147
177
134
180
162
241
156
173
Mn
300
116
135
111
115
87
72
115
78
38
29
31
30
53
40
38
47
92
86
43
78
48
69
77
77
Pb
54.0
10.0
16.0
18.0
22.0
34.0
13.0
19.0
16.0
19.0
9.0
15.0
15.0
22.0
6.0
4.0
29.0
8.0
9.0
15.0
10.0
15.0
22.0
14.0
16.0
Zn
199
85
82
71
61
91
55
64
60
92
61
46
46
57
61
48
81
72
74
57
69
60
70
62
116
(continued)
-------
TABLE 105 (continued)
Treatment
(residual
code)
Control
EFAAl
T2
T4
ESBMAi
T2
T4
NJFA/T,
T2
T3
•n
NJSBM/TI
T2
TA
VFA/Tj
TO
TS
T
VSBMAi
T2
T3
V
Application
Rate
(kkg/Tia)
0
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
2.2
6.7
9.0
11.2
K
c
i
4.98
1.80
1.66
2.20
1.96
1.36
1.82
1.45
1.62
1.23
1.31
1.50
1.27
1.27
0.97
1.57
1.11
1.70
1.41
1.39
1.43
1.42
1.13
1.11
1.28
Constituents
Na Ba
1.00
53.0©
0.72
0.65
1.03
0.70
0.71
0.85
0.93
0.74
0.64
0.61
0.70
0.75
0.57
0.68
0.68
0.53
0.50
0.65
0.63
0.70
0.70
0.57
0.53
50
30
40
30
40
60
80
30
30
30
30
40
30
30
30
30
100
30
20
20
30
30
30
30
40
Al
1,120
570
330
800
610
650
310
230
540
550
450
550
190
540
240
350
270
560
460
330
700
200
810
80 '
330
Cr
ppm
18
2
7
4
7
14
7
4
7
9
4
8
4
6
<1
2
3
5
9
6
8
3
8
3
6
Mo
ND
ND
ND
ND
.ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Ag
19.6
3.2
3.9
3.1
3.9
1.6
8.7
2.4
3.7
4.7
4.2
12.7
1.7
2.7
2.7
3.5
2.9
3.5
2.4
3.4
2.7
1.2
7.2
0.4
0.3
-------
concentration in the crops, except for the presence of higher cadmium and silver ion con-
centrations in the tomato tissues. Experiment 2-B plants grown in soil enriched with the
equivalent of 2.2 and 11 .2 kkg of residue per hectare indicated that the lower rate of all
residue application gave the most consistent results, and that the concentrations of metal
ions in the residue-treated crop tissues were generally equal to or lower than those in the
control crops.
Excessive concentrations of heavy metals, particularly cadmium, in plants utilized for
direct or indirect human consumption are undesirable, and may, in fact, be considered
dangerous for human consumption. Soils containing low pH, high metal concentrations,
or trace metal deficiencies appear to benefit most from residue applications. A more
detailed field scale test program is necessary to determine additional parameters for re-
claiming/applying the residues.
All residue types, soils and climatic crop growth were unique and may require specific
evaluation.
Marketing Analysis Methodology
The method of estimating the potential market for fluidized-bed residues in specific appli-
cations involved converting data on prices of transport, residues, and conventional materi-
als 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
markey. Figure 112shows 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. The 480 km distance is shown only for comparative purposes in order to illustrate
that an 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
ration, changes as market penetration increases, and other factors could limit penetration.
The value attributed to residues for any given use should not be considered as the estimate
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 pro-
cess is to Impute its value from the cost of the inputs replaced by the new input, holding
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 fiuidized-bed power plant (the new input). Suppose
further that the delivered price for ordinary lime is $2 per kg and that there is no esta-
blished market (and thus no price) for the residues. In this situation, the imputed value of
248
-------
§
>o
Legend
• Power plant site
0-240 km from power plant
km from power plant
Source; 54.
Figure 112 . Distance to large U. S. coal-fired power plants.
-------
the residues would be $1 per kg (delivered) base don 200 kg ($200) residues equalling 100 kg
($200) of lime as a soil conditioner. This means that if a market for residues were esta-
blished, 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 application
from the cost of the displaced inputs. This would be the case if it cannot be readily de-
termined how much of which inputs can be replaced by a unit of the new input at the
given output level. In such a 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.
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 .25per 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 300kg 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? Per-
haps, but only if several restrictive conditions were shown (or assumed) to hold. The
imputed value would be wrong, for instance, if a lower lime application rate could achieve
the same yield. It would also be wrong if a third input (a source of sulfuf 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 situ-
ation. 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 would be 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 standarized
within reasonable limits. Variations in residue parameters may limit its usability. Obvi-
ously, 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
250
-------
except™ of the West) w, II have ready, close-by access to residues. In many cases, ac-
cess to res.dues may even be better than for alternative conventional raw materials Ap-
proximate truck transport costs in 1 977 were $0.04 per kkgAm (with 18 to 27 kkg »r
truck). For short hauls, an extra charge of $1 .00 for loading and the same charge for
unloadmg has been assumed As stated previously, the maximum efficient range for truck
transport ., est.mated 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.54 For rail transport, a car-lot is about
50-54 kkg and transport cost about $0.02 per kkgAm, plus an additional fee for shaking
the car to complete unloading. !t should be noted that rail freight rates discriminate
about 20 percent against secondary materials (such as fly ash) in comparison to primary
materials.
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 z,ero, 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) increasing strict environmental regulations on waste disposal. Disposal cost
will vary from place to place, but can genrally range from $3 to $6 per kkg. Costs may
be even higher if special treatment is necessary prior to disposal. For example, chemical
fixation followed by land fill ing is one method of treating the residues from limestone
flue-gas desulfurization systems. The experience of several firms with that process is
shown on Table 106 .
Thus, certain applications not judged economically feasible if the residue cost was zero
at the power plant may be acceptable if the power plant paid for removal of the residues.
Because of the difficulties in estimating (1) what the utility would be willing to pay for
residue removal, and (2) the cost of insuring adequate residue quality, in the remainder
of the analysis, it will be assumed that these two factors balance one another and that the
residues are available at a zero cost.
Economic Analysis of Specific Applications
Concrete
Substantial research (discussed above) exists showing that adding fly ash to concrete can
improve the characteristics of the concrete. The fly ash can be used to replace aggregate
and, because it is also a pozzolan, a portion of the portland cement. Based on prelimi-
nary research results, concrete mixtures with approximately 5 percent residue content dis-
play improved strength characteristics. Table 107 compares the composition of the opti-
mal concrete mix (as determined in the testing program) containing res.dues to that of a
standard concrete mix (used as a control for the tests). The table also estimates the cost
savings from using residues as a partial substitute for aggregate and portland cement wh.ch
would result if residues were available at a free delivered price. Th.s saving would be
251
-------
TABLE \W. SLUDGE FIXATION COSTING ESTIMATES
All values are condifion and site dependent
Source
Cost
($/kkg,50% solids)
Remarks
Commonwealth Edison
Company, Will County
Station
Duquesne Light Company,
Phillips Station
International Utilities
Conversion Systems, Inc.
Chemfix
Dravo Corporation
6.50
9.41
5.78 •
11.00
5.50
7.98
1 .65-2.75
5.50
1 .65-3.30
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-s?te disposal; excludes capital costs.
252
-------
$0.50 per kkg of concrete. Since 53 kg of residues would be used In one kkg of concrete,
the .mputed 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
characteristics Imparted by the residues to the concrete results in a higher market 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 $0.02 per
kkg-km, and a zero f.o.b. price for the residues at the power plant site, residues could
be rail-hauled a distance up to 472 km and remain competitive. By truck, they could be
economically transported about one-half that distance.
TABLE 107 . RESIDUE VALUE FOR USE IN CONCRETE
,tem Composition Value($/kkg)a Cost Reduction
Control Residue Added Control Residue Added
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
a Based on a delivered cost (in Los Angeles) for portland cement of $52.78Akg and for
aggregate of $4.96Akg.
Value of residue to be imputed from savings from its use ($11.57 - $11.07 = $0.50Akg)
Asphalt
Coal ash has been used successfully as a replacement for aggregate in asphalt for some
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 conti-
nuous pugmill, 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 stockp.led for
future use. The well-graded ash usually requires no additional b ending. Using emulsified
asphalt makes heating and drying unnecessary, thus eliminating the need for relat.vely
costly hot bins or dryers.
Other examples of successful use of coal-ash residues in asphalt could be cited; but, even
253
-------
though the technology appears simple and sound, use in this application has remained
quite limited (approximately 180,000 kkg of residues in 1972)131 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 $0.02Akg-km) or 125 km by truck (at $0.04/kkg-km) and
be competitive.
Little work has been done on limestone or dolomite modified residues. Wet-collected
residues from flue gas desulfurization systems appear to have some promise in asphalt applic-
ations. However, if substantial dewatering or drying is required prior to use, the . cost
may be prohibitive. Fluidized-bed residues are collected dry, and appear to have a
higher potential. Preliminary tests were conducted to determine the technical feasibility
of using fluidized-bed residues in a mixture with emulsified asphalt. The results indicated
that up to 92 percent of the aggregate could be replaced. Table shows the approximate
savings which could be realized assuming a free delivered price for the residues, and 92
percent replacement. For any given transport distance (or delivered price for residues) the
net savings or costs per unit of asphalt can be easily calculated.
TABLE 108. IMPUTED VALUE OF RESI DUES IN ASPHALT APPLICATIONS
Item
Asphalt Component
Emulsified asphalt
Aggregate
Fly ash
Total
Composition (%)
Residue
Control Added
8
92
0
TOO
8
0
92
100
Value ($kkg)Q
Residue
Control Added
94.53
4.96
_0
99.49
94.53
0
b
94.53
Cost
Reduction
($/kkg)
0
4.96
0
4.96
Based on a delivered cost (in Los Angeles) for asphalt of $93.53/kkg and for aggregate of
b$4.96.
Value of residue to be imputed from savings from its use.
Agriculture
Fluidized-bed residues can improve crop growth and yield by (1) altering pH (the residues
are quite alkaline), (2) improving soil structure, (3) providing essential micronutrients
(Zn, Cu, Fe, Mn, B, Cl, Al), (4) providing sulfur, and (5) serving as a source for macro-
nutrients (O, C, H, N, P, K, Mg, Ca). Tnus, the residues can serve many functions as
254
-------
on agricultural mput. 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 Uni-
versity 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 the lower yield obtained. For example, the delivered
price of calcium carbonate in Los Angeles, California, is about $13.60 per kkg. Apply-
ing 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 as 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 field
test results.
However, one factor, transporting costs, suggests that such application could be economi-
cally feasible. Although the calcium content of available calcium carbonate is about
40 percent, in comparison to the residues' approximate 10 percent, a higher residue appli-
cation 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 cal-
cium carbonate 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 deter-
mined.
Test Plot D in Table 109 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
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 carbo-
nate, for a total value of $263 per 980 kg. This represents an imputed value for the spent-
bed material of $268 per kkg. However, there would likely be other inputs capable of
filling he same need, and the proper comparison would be without that mput There ,s
some evidence that in' certain types' of soil, the fluidized-bed res d-s will ach,eve
yields than will ordinary limestone, even at equal appl.cation rates The VPI study
identified "Woodstock loamy fine sand" as possibly being such a so.l type.
255
ler
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TABLE 109. FLU1DIZED-BED RESIDUES AS A SUBSTITUTE
FOR CALCIUM CARBONATE IN PEANUT GROWING
Application Rate Test Plot Yield ($/ha)
Material Appl ied (kg/ha) A B C D E Avg
Control
Calcium carbonate
Spent-bed material
0
980
980
1190
1420
1317
1097
1337
1151
1097
2109
2040
1225
1489
1739
1862
1894
1830
1457
1699
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 lime (Ca(OH)_). 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 trans-
ported 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 in order 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 an optimal soil pH in areas where large quantities
of nitrogen fertilizers are used. For several reasons, one of which is the expense of lime-
stone, 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 generated rate of 2 to 12 million kkg
per year for 1995. As discussed previously, however, there are also substantial impedi-
ments to large-scale utilization for this purpose, such as transportation costs and the need
for farmer education and acceptance.
256
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Information Service, Aug. 1973, Vol. Ill, p. 37-82.
121 . Pope,Evans and Rabbins, Inc. Characterization and Control of Gaseous Emissions from
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July 1972.
124. Pope,Evans and Robbins,Inc. Study of Characterization and Control of Air Pollutants
from A Fluidized-Bed Combustion Unit - The Carbon Burnup Cell. CPA 70-10. Pre-
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125 . Quade, R.N. "Nuclear Energy for Coal Gasification." In White, Jack W. and
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126. Rehsi, S.S. "Studies on Indian Fly Ashes and Their Use in Structural Concrete."
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267
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' 130. Rossoff, J., et al. "Technical and Economic Factors Associated with Ffy Ash
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California, July 1971.
131. Rossoff, J., and R.C. Rossi. Disposal of By-Products from Non-Regenerable Flue
Gas Desulfurizction Systems: Initial Report. EPA-650/2-74-037-a. Prepared for
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133. Selmezi, J.G. and R.G. Knight, "Properties of Powerplant Waste Sludges," Pro-
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134. Shaver,R.G. "A Solvent-Refined Coal Process for Clean Utility Fuel." In Gould,
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135. Simpson, J.B. and J.E. Richey. "The Geology of the Sanquhar Coalfield and Ad-
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1936.
136. Slonaker,J.F. and J.W. Leonard. "Review of Current Research on Coal in the U.S."
Proceedings: Third international Ash Utilization Symposium, Pittsburg, Pa., March
13-14, 1973.
137. Smith,P.M., "Large Tonnage Use of PFA in England and Other European Countries."
In Proceedings; Third International 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.
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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
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268
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141 . Staff of Research and Education Association. Pollution Control Technology. New
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142. Personal Communication. R.M. StatnickAJ.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-1AG-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: Fluidized 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. "1
Processing Sludges from Lime/Limestone Wet Scrubbing Processes for Disposal or I
Recycle and Studying Disposal of Fluidized Bed Combustion Waste Products. Quarter- J
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 Office of 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-Q53 d. Prepared for U.S.
Environmental Protection Agency. Aug. 1973.
269
-------
154. U.S. Army Corps of Engineers, "Drainage and Erosion Control-Subsurface Drainage
Facilities for Airfields/1 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-207 516. National
Technical Information Service, Oct. 1971, p. I!I 1-IV 65.
156. U.S. Department of the Interior. List of Coal 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.
(Solid Waste Management Series SW-147.)
158. U.S. Environmental Protection Agency. Development Document for Proposed
Effluent Limitations Guidelines and New Source Performance Standards for the
Steam Electric Power Generating Point Source Category. EPA 440/1-73/029.
Washington: U.S. Government Printing Office, March 1974.
159. U.S. Environmental Protection Agency. Economic Analysis of Proposed Effluent
Guidelines, Steam Electric Power Plants. EPA 230/1 -73-006. Washington; U.S.
Government Printing Office, Sept. 1973.
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ference on Fluidized-Bed Combustion. EPAAP-109. Research Triangle Park,
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161. U.S. Environmental Protection Agency. Proceedings; Symposium on Flue Gas De-
sulfurization, New Orleans, March 1976, Vols. land II. EPA-600/2-76-136a.
Washington: GPO, May 1976.
162. U.S. Environmental Protection Agency. Interim Primary Drinking Water Regulations,
July 1975. EPA-40CFR/141. ! : "! ~~~~
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 R3/73/033.
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270
-------
166. Walker, George W. The Cqiera Limestone In San Mateo and Santa Clara Counties.
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Engineering, 6 (9): 50-51, Sept. 1974.
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Involving Coal Pyrolysis and Gasification." In L.G. Masse/, Coal Gasification.
Washington,D.C.: American Chemical Society, 1974, p. 9-S8T
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
Fluidized Bed Combustion Program. 76-9E3-FBCOM-R1. Monthly Progress Report,
December 1975. Prepared for the United States Environmental Protection Agency.
171. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized-Bed Combustion Program. 76-9E3-FBCOM-R3. Monthly Progress Report,
January 1976. Prepared for the United States Environmental Protection Agency.
172. Westinghouse Research Laboratories. Experimental and Engineering Support of the
Fluidized-Bed Combustion Program. 76-9E3-FBCQM-R4. Monthly Progress Repr.1*f
February 1976. Prepared for the United States Environmental Protection Agency.
173. Westinghouse Research Laboratories. Experimental and Engineering 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 Repart,
Aprii 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.
27J
-------
178. Wesringhouse 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
Fluid?zed-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
1 976. Prepared for the U .S^Envfronmental 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), Department of the Army, June 1976.
184. Yeager,K.E. "The Effect of Desulfurization Methods on Ambient Air Quality." In
Gould, R.F. Pollution Control and Energy Needs. Washington,D.C.: American
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"Complete Analyses of Major Los Angeles Water Sources, 1975-1976 Averages."
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Criteria, 1972. Washington, D.C.: United States Government Printing Office, 1974.
188. Portland Cement Association. Soil-Cement Laboratory Handbook. Skok?e,lll.; 1971.
189. Sverdrup, H.V.,Martin W. Johnson, and Richard Fleming. The Oceans - Their Physic^
Chemistry, and General Biology, (p.176 ) Prentice Hall, Inc., 1942.
190. 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.
272
-------
191. 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 HouseJ1 Plant and Soil, pp. 44,359-365 (1976).
192. American Society for Testing and Materials. Annual Book of ASTM Standards.
Part 19, 1974.
273
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APPENDIX A
LABORATORY ANALYTICAL METHODS
Chemical analyses were performed on leachate from the laboratory-scale columns, the
pilot scafe 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 through A-3.
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 scat-
tered 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.
274
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TABLEA-J. SQIL^PREPARALQRY METHODS
Purpose
Method
Reference0
(page number)
Total Residue Characterization
Soluble Fraction Analyses
Cation Exchange Capacity
Tomato Plant Analyses
Hydrofluoric and perchloric
acid digestion
Water extraction
Acid extraction (1.0 N
nitric acid)
Base extraction (1.0 N
sodium hydroxide)
Sodium saturation
Wet digestion
1019
935
935b
935°
899
nd
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 distilled water.
Same as water extraction, except sodium hydroxide solution was substituted for distilled
water.
Sub-committee of NC-118. Sampling and Analysis of Soils, Plants, Waste Waters, and
Sludge. Research Publication 170, Agricultural Experiment Station, Kansas State
University, Manhattan, Kansas.
TABLE A-2, SOIL TESTS
Test
Moisture Content
Particle Size Analysis
Permeability
Specific Gravity
Method
Gravimetric , oven-drying
Hydrometer
Constant Head
Pychometer
Serial
Designation
D2216
D422
D2434
D854
Page Number
276
70
294
157
Source: 192.
275
-------
TABLE A-3. ANALYTICAL METHODS
Performed on
Parameter
Metals
Aluminum
Arsenic
Beryllium
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potasium
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
LCLb
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
PCLC
X
X
X
X
X
X
X
X
X
X
X
X
Reference6
p pd Method (page number)
Colorimetric
(Eriochrome cyanide R)
Colorimetric (Silver
diethyldithiocarbamate
Atomic Absorption
Atomic Absorption
Flame Emission
Atomic Absorption
Atomic Absorptiori
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)
- Colorimetric (Brucine)
X Electrometric
Colorimetric (Ascorbic Acid)
X Turbidi metric
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
u
Mono me trie 1558"
X
X
Dichromate reflux
Low Levels
High Levels for Saline Samples
21
25
(continued)
276
-------
TABLE A-3 (continued)
e
0 RC - Residue characterization.
° LCL - Lab column leachate.
0 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, 19/4.
Analyzed on 1:1 plant/distilled water mixture.
9 American Public Health Association, Standard Methods, 14th ed., Washington, D. C.,
1976.
American Society of Agronomy. Methods of Soil Analysis,Part 2. Madison, Wisconsin,
1965.
277
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APPENDIX B
SAMPLE DATA SHEET
SURVEY OF PILOT 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 Chapmen: 1346 Willow Road, Mertlo Park, California 94025) on the residues From the
fiuidized bed combustion o? coal and the gasification of high-sulfur fuel olfs. 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.
1 0954 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-update:
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:
278
-------
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/min):
d. Average particle size of bed material (cm):
e. Mode of operation
(1) Number of stages:
(2) ( ) Batch; ( ) continuous (check one)
(3) ( ) Once through; ( ) regenerated (check one)
f. Coal or oil feed rate (kg/hr):
g. Air requirements (scfm):
h. Fuel hydrogen requirements (scfm):
?. Combustion efficiency:
j. Power output (kwhr):
k. Heat released (Btu/lir):
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:
279
-------
4. Operating Information (cent.)
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.
280
-------
APPENDIX C
CHARACTERIZATION OF SIMILAR RESIDUES
Coal Ash
Coal 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 United States coal. A breakdown of these minerals is given in Table C-l .
Table C-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 C-3.
During combustion, the inorganic minerals in the coal were subjected to furnace temper-
atures between 1400 C and 1700 C. At these temperatures, the minerals can react to
form mullite, quartz, hematite, and calcium sulfate. The distribution range for these
mineral phases is compiled in Table C-4.
Fly ash generally occurred as fine spherical particulates ranging in diameter from 0.5
to 100 , and had an average diameter of 7 . The color of fly ash can range from light
tan to gray to black, depending on the iron and carbon content. The pH of fly ash can
vary from 6.5 to 11 .5 and can average about 11. A summary of the typical physical prop-
erties of fly ash is presented in Table C-5. Figure C-l diagrams the concentration range
of the major constituents in United States 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 can have a glassy
appearance.
The fly ash modified by limestone or dolomite injection into boilers has significantly dif-
ferent 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 54.
Municipal Incinerator Residue
During incineration, furnace temperatures were between 980 and 1100 C, with flame
temperatures at approximately 1400° C. This process resulted 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 was a wet,complex mixture of metal,
glass, slag, charred and burned paper, and ash. It was the ash that was important here
because its chemical composition was very similar to that of fly ash from coal burning
boilers. In comparison, the fly ash was predominantly 200 microns in size, and consisted
of wood and paper ash, aluminum foil, carbon particles, metal pins and wire, glass, sand,
281
-------
TABLE C-1. COMMON MINERALS IN U.S. COALS
Pyrite, marcasite - FeSj Quartz -
Chalcopyrite - CuFeS^ Siderlte - FeCO~
(7)
Arsenopyrite - (FeSj • FeAs2) Kaolinite - ALSI2O_(OH),
SHbnite - Sb0S,, Dolomite - CaMg(CQ, L
A o o *.
Gypsum - CaSO4 • 2H2O Apatite - Ca5(F, Cl, OH) (PO
Calcite - CaC03 Mica - KAl^Si, Al)3 O]Q (OH)2
TABLE C-2. CHEMICAL CONSTITUENTS OF COAL ASH
Constituents
Silica (SiO2)
Alumina (ALO )
Ferric oxide (Fe^O_)
Calcium oxide (CaO)
Magnesium oxide (MgO)
Titanium dioxide (TIO«)
Potassium oxide (K«O)
ft
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)
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
Average
48
26
15
5
2
1
2
1
2
4
Trace
Trace
Trace
Trace
Trace
Trace
Trace
Trace
Alkalies Source:
282
-------
TABLE C-3. CHEMICAL CONSTITUENTS OF CCAL ASH
Soluble Ions Range (for 1 -1.7% dry solids)
,LJL
Ca 200 - 850 ppm
.. -H-
Mg 185 - 400 ppm
SO4~ 200 - 250 ppm
K Trace
Na Trace
POr 0-5 ppm
BO~ 0-10 ppm
Source: 128.
TABLE r-4. MINERAL PHASES FOUND IN COAL ASH
Phase Percent
Quartz 0-4
Mullite 0-16
Magnetite 0-30
Hematite 1-8
Glass 50-90
Source: 126.
283
-------
TABLE C-5 . PHYSICAL PROPERTIES OF FLY ASH FROM PULVERIZED
COAL FIRED PLANTS
Constituents
Unit
Range
Range of particle size
Average percent passing No. 325 sieve
Bulk density (compacted)
Specific gravity
Specific area/gram
microns
percent
kg/cu m
cu
cm/g
0,5-100
60-90
1,100-1,300
2.1-2.6
3,300-6,400
Source: 69.
284
-------
ou
50
40
CxT
^
c
'•§ 30
•»-
c
4)
oo £
01 u
U 20
10
. '
-
-
-
s
'
1
1
I
1
iO2 Al
i
1
I
li
1
1
1
203 Fe
! 1 1 i 1
" 1
K1 Average
1
L i
»
i
i
i
i 4
* ! i '
i ! & • A iig !
2O3 CaO MgO SOg Na2O Other I
Constituent
-
1
-
-
1
joss on
gnition
Source: 34.
Figure G-l. Concentration range and average of U, 5, fly ash consfituents.
-------
and iron scale. A general analysis of the inorganic components found in fly ash is pre-
sented in Table C-6. A comprehensive elemental analyses for four different municipal
incinerator fly ashes is presented in Table C-7. It has also been reported that small
amounts of cadmium, lead, and mercury have been found in fly ash samples.
Sludge From Li me-Limestone Scrubbing Processes
In Table C-87 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 C-9. The results of an X-ray ana-
lysis performed on these sludges are listed in Table C-10.
TABLE C-6. OXIDE ANALYSES OF INCINERATOR FLY ASH FROM TYPICAL REFUSE
Component
sio2
AI2°3
Fe2°3
CaO
MaO
Na00
2
K_0
2
Ti02
SO,
3
P2°5
ZnO
BaO
Total Oxide Content (%)
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.
286
-------
00
TABLEC-7 . ELEMENTAL HEAD SAMPLE ANALYSES OF MUNICIPAL
INCINERATOR FLY ASHES (% by weight)
Sample
F-l
F-2
F-3
F-4
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
Co
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 C-8. WET CHEMICAL ANALYSIS OF SLUDGE STANDARDS0
CO
STD 1
SiO2
AI203
Fe203
CaO
MgO
Na2O
K2O
Ti02
P205
C02
SO2
S03
CaCO3
46.
23.
13.
4.
0.
0.
2.
1.
0.
2.
-
0.
7
2
7
7
9
3
6
5
3
6
8
5.9
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 C~9,
Source: 144,
-------
TABLE C-9. IDENTIFICATION OF ARCS SLUDGE STANDARDS
Standard Description
I Fly ash from Connecticut Light and Power Company's Devon Station.
11 C-E sludge0—CaCOs. 150% of stoichrometric. 2,000 ppm SO2.
II! Kansas Power and Light sludge.
IV C-E sludge—Ca(OH)2. 38% to 50% of stoichiometric. 50 to 60%
SC>2 removal. Slurry feed 830 liters/min. Recycle 625 liters/min
with 210 liters/min blowdown.
V Union Elecfric sludge.
VI C-E sludge—CaCOg. 150% of stoichiometric. 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% SO^ removal.
135 kg/hr fly ash. 250 kg CaCO3.
Vi11 C-E sludge—I20 to 130% of stoichiometric Ca(OH)2. 90.8% re-
moval. 450 liters/min Ca(OH)2 slurry underbed. InFet SC^ 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.
° Sludge from the Combustion Engineering pilot plant.
Source: 144.
289
-------
TABLE C-TfO. X-RAY ANALYSIS OF APCS SLUDGES
Source: 144.
Standard Major Minor Trace
I Si09 Fe2O3 CaCO3
3AI«00-2Si00 FesO,
2 3 2 CaSO*
III Si09 Fe304 3AI203-SiO?
z CaCOs Ca(OH)2
2CaSO3-H2O CaSO4
MgO
IV 2CsSO3-H2O — SIO2
V SiO2 CaSO4-2H2O Ca(OH)2
CaCO3 2CaSO3-H2O
Fe304
~AbO
VI CaCO3 2CaSO3-H2O CaSO4
SIO2
VIA CaCO3 SiO2 2CoSO3-H2O
2A!2O3*2SiO2 CaSO4
VII 2CaSO3-H2O CaCO3 2CaSO3-H2O
CaSO4-2H2O
S'°2
VIII 2CaSO3-H2O CaCOs Ca(OH)2
SIO2
IX CaCO3 — 2CaSO3-H2O
CaSO4-2H2O
Ca(O?l)2
290
-------
APPENDIX D
DESCRIPTION OF FBC UNITS
PROVIDING RESIDUES
Pope> Evans, and Robbins 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 (sponsored 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 SO?
emissions. Major test variables and ranges were:
Coal type Medium and high sulfur
Bed temperature 815-1038 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 pre-mixed
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 SOo 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
rectangular 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
are shown in Figures D-l and D-2e
291
-------
Combusted Gases
Water Walled
Column
Fly Ash (fuel)
Feed Screw
Start-up Coal
Feed Screw
Injection
Air Line
Fuel Injection
Port
Source: 124.
Welded Seam Duct-
Sight Port
Water Cooled Hood
Light-off Burner Port
Thermocouple Ports
Water Wall
Auxiliary Feed
Ports (2)
Plenum Chamber
Figure D-l. FBC construction detail (side view),
292
-------
. Combusted Gases
Welded Seam Duct
1 Sight Port
Water-Cooled Hood
Water Jackets
Kaowool Gasket
Thermocouple Ports
Water Walled Column
Start-up
Coal Feed
Screw \
Fly Ash
Feed
Screw
ropane
Light-Off
Gas Burner
Fuel Injection
Air Line
2 Auxiliary Feed Ports
(one right, one left)
Combustion
Air Inlet
Source: 124.
FigureD-2: FBC construction detafl (Front view)
293
-------
Air passed into a plenum below the grid, through the grid buttons, and into the combustion
chamber to fluidize the bed material and to provide combustion oxygen. The bed material
generally consisted of sintered coal ash crushed and double-screened to a mesh sirs of < 8
to > 14 (or of limestone 1359 of mesh size < 8 to > 20). Bed temperature depended on
bed depth, which governed the total transfer surface at the water walls, and was monitored
using several thermocouples spaced vertically in the^combustor. The coal feed rate was
about 50 kg per hour for an energy input of 3.4 x 10 kcal per houi4. Before discharge,
combustion products passed through a heavy gauge welded seam duct, an inducted draff
fan, and a dust collector. The air flow rate was monitored by a Pitot tube in the entrance
duct, and a gate valve in the line provided air flow control to the unit. The coal feed
rate was controlled by a variable speed drive on the coal feed screw.
Full-Scale Boiler Module (FBM)
The rectangular bed of the sub-pilot scale atmospheric pressure unit had dimensions of 51
by 40.6 cm. It was contained in a rectangular enclosure in which each wall was a row
of vertical boiler tubes seal-welded gas-tight. Figure D-3 shows the internal construction
of the FBM. Its cross-section (46 by 183 cm) was roughly 7 times the FBC cross-section.
Air was directed upward from a plenum at the base of the unit through a grid and into the
bed area. Firing with a coal input of 363 kg per hour, the FBM produced 14 kg per sq cm
(gauge) steam at the rate of 2,268 kg per hour. Coal feed was controlled by the rotation of
a star feeder while sorbent material feed was controlled by a variable speed screw drive.
Ash circulation was by pneumatic transport from the dust collector through a star feeder con-
trol. Flue gas from the FBM was mixed with ambient air in the ducting above the unit to
reduce its temperature before entering the air preheater. Fly ash which dropped out of the
flue gas at that point was collected in the hopper. The bulk of the fly ash was retained in
a multiclone collector downstream. From the collector, the flue gas flowed through a long
duct to an induced-draft fan and then to the atmosphere. A balance damper was provided
this ducting to control pressure in the combustion chamber.
in
In the regenerator, sulfated limestone from the primary zone was circulated continuously
so that the carbon-bearina fly ash was burned at 1092 C with low excess air. SOO was
driven off in high concentrations and lime was recovered for reuse by the reaction;
CaSO4 + C + 1/2 O2 *- CaO + SO2 + CO.
Figure D-4 is the schematic flow diagram of the FBM and regenerator. Use of fuel gas for
CaSQ4 regeneration was avoided for economic reasons. Several long-duration tests were
conducted with rhe FBM to establish the effect of different parameters on the removal of
SC>2 and other pollutants.
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° <
294
-------
Ol
FBM Exhaust
A
FBM Gas
Breeching
Steam
Drum
Vertical Coal
Feeder Inlet
Down comers
Additive or
Ash Feed
Port (auxiliary)
Air Plenum
Grid Plate
Fluidized Bed
Header
Source: 124.
Figure l>-3-. Fluidized bed module: internal construction.
-------
CBC Flue, Gas to CBC
Dust Collector and Stack
To FBM
Dust
Collector
and Stack
Air
Heater
to
•o
Afr
Source: 121.
CBC (behind FBM)
Gas to Sample System
^ — -^
FBM
Connecting Slot
J
"*" *- -*=
S. l_ _!!.-__] C--
o o
Gravity Bed Feed
Drop Leg
Gas Outlet
Reg Gas Cooler
-s
=— •
X
\
UJ
V
<£
a. ij
E
D
CO
E
a
*
V 1
Bed Sampl
4-
c
'5
D,
t_
^f
0
•4—
E
(N
04
7
^^'
"o
*—
E
o
-I—
,g
5
1
7
e Line
Air Lift
Figure D-4« FBM and regenerator flow diagram.
-------
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 from 27 percent chromium
steel. The CBC was,an integral part of the FBM and was located at the back of the com-
bustor under the steam drum. Figure D-5 is the section view of the integrated FBM/CBC
unit. The CBC operated continuously and burned the carbon-containing fly ash from the
FBM.QCoaI 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 D-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(Cffice 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. TKe first phase of the
program involved the design and construction of a continuous fluidized-bed combustion/
lime regeneration pilot unit—the FBCR miniplant (shown in Figure D-7 ). Design para-
meters of the process (mainly combustor and regenerator) are shown in Table D.-1. 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, refractory-lined pipe with a final inside
diameter of 30 cm. It was designed with 5 flanged sections (each 90 cm 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 con-
structed 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 particulate 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 constant 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.
The second phase of the program involved a study of the factors influencing the formation
and the control of nitrogen oxides (NO ) in fluidized-bed combustion. For these studies,
a 7.6 cm 1D fluidized bed combustor and1 two smaller electrically heated fixed bed
297
-------
FBM Exhaust
_•.*.- - - - ' / '- ~J "-'"" y** *' •»' "•" •"- v "^ ^^ \_ ^ f
CBC
Exhaust
NO
O
00
Additive Ash
Port #1 (typical)
Gsal Feeder
(partial view)
2.5x5.1 cm
^^Intercommunication Slots
Access Door
Mushroom Feeder (fly ash)
Air Distribution Grid
Source: 124.
Figure 1>5. Section view of the Integrated FBM/CBC unit.
-------
Uncontrolled Flow
Paths
FBM
Controlled Flow Path
Key
Source: 124.
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 D-6. Bed material flow paths: FBM,CBC and regenerator.
299.
-------
City Water Cooling Water
g In Out
I
_i_
S
<» ** To Scrubber
Water Water
In Out !
1—SJu
Heat Exchanger
Reservoir
76 liters/min
@ 4.2 kg/sq cm
Water Out
Water In
}— Water Ou
c Water In
Limestone
&CoaI
Injection
Air
To
Scrubber
-a-
O
Air Compressor
5.6 cu m*/mm @ 12.3 kg/sq cm
•G
(gauge)
.. ro
Air Compressor
39.2cu m*/min
@ 8.8 kg/sq cm (gauge)
* Af STP
Source: 43.
Legend
CS - Cyclone Separator PF - Pulse Feeder
CV - Collector Vessel RV - Refill Vessel
Figure D-7* Pressurized FBC pilot plant, Linden, New Jersey.
-------
TABLL D-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
Gaoling load
Maximum material rates
Air
Coal
Limestone
Natural gas
^' output
cm
cm
°C
atm
m/sec
103kcal/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.
301
-------
reactors were used. An automatic instrument continuously measured NO,SO«, and O«
emissions. The operating factors that were studied included excess air level, tempera-
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 bteu 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 D-8.
302
-------
Vent
8
Feeder
Scale
N2 CO SO
02 NO
WTM
Instrument Calibration By-Pass
Coal
Hopper
and Feeder
Gas Rotameters
Cyclone and
Filter
Air
Condenser
Reactor
Water
Condenser
Refrigerator
T
Condensate
Figure D- 8 . Exxon FBC unit.
IR
Analyzer
IRCO
Analyzer
L
WTM
NO Analyzer
Polarographic
Analyzer
Intermittent
Gas Sampler
Source: 43
-------
APPENDIX E
FLUIDIZED-BED OIL GASIFICATION
Introduction
F!uidized-bed oil gasification provides the technology for utilizing high-sulfur residual oils
ond 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 tur-
bine power plant. Power-cycle schematics for low and high pressure alternatives are shown
in Figures E-l andE-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 use.
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^hrough oil gasification
system may be 50 to 70 percent less than a retrofit stack gas cleaning system.
Process Descriptions
Low-Pressure Gasification
The gasification/desulfurization operation was accomplished by either the regenerative or
the once-through mode. Figure E-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 E-l.
Regenerative Operation
The major components of the regenerative operation were the gasifier and regenerator vessels.
The gasifier was an air-fluidized bed of lime operated at 870° C withsubstoichiometric air
(a 20 percent of stoichiometric). Heavy residual oil was injected into the gasifier vessel
where it cracked and was partially combusted to form a hot,low-sulfur gas. Hydrogen
sulfide produced during gasification reacted with the lime to produce calcium sulfide and
water:
H2S + CaO *- CaS + H2O
The hot fuel gas was transported to the boiler burners where combustion was completed, and
the calcium sulfide was sent to the regenerator. The regenerator was an air-fluidized
vessel operated with a slight excess of air at about 1,000° C. Regeneration took place by
the reaction of oxygen with the calcium sulfide (spent lime) to give an SO9 rich stream
(of about 10 mole percent SOJ and a regenerated lime having a slightly decreased activity
compared to that of fresh lime:
304
-------
Cyclone
Stack Gas
Hot Fuel Gas
CO
8
Oil
Limestone
(CaCO3)
Regenerated
Limestone
or ^—
CaSO,
1800-3600 kcal/cum*
Particulates
Fluid!zed Bed
Gasifier/
Desulfurizer
1 Arm, 870 C
Spent
Limestone
Limestone
Processing
for Reuse or
Disposal
7
Booster
Fan
Conventional
Boiler
Turbines
Generator
Fan
*AtSTP.
Source: 104.
Figure E-l. Low pressure fluidizedbed oil gasification for power generation.
-------
CO
o
o
Cyclone
Hot Fuel Gas
1800-3600 kcal/cu ma
Parti culates
Oil »
Steam •
Lime- *
stone
(CaCOg)
Regenerated
Limestone
or _
Fluidized Bed
Gasifier/
Desulfurizer
10-15 arm, 870 C
CaSO
4
°AtSTP.
Source, 104.
Spent
Limestone
Limestone
Processing
for Reuse or
Disposal
High Temp.
Gas
Combustor
Stack Gas
teat
Recovery
Boiler
Turbine
f
Turbine
Generator
Air
Generator
Figure E-2. High pressure fluidized bed oil gasification for power generation.
-------
Once-through Mode
Combustion Air
Stack Gas
Combustion Air
Regenerative Mode
Stack Gas
i
CO
— l_ _
1
i Clean Fu<
1 Fuel Oil i
i
i
i '• i
; \~* —
i ^
Gasifier
k
i
Spent
^ Lime
(CaS)
i
1 , , „ t
;_ Sulfate
Generator
! '
CaS04
Disposal
»• *~i~ ~
»l Gas Boller
!»•
if
— — limosi-rtnp. Ft>t*A Limestone ^ .
Make-up
Temperature
Control Stream
Spent
Lime
(CaS) &
Air *- Reger
Legend
Gas
Liquid Ca
Solid Feed D's
Clean Fuel (
r
i
I
i
t
Regener
so2-
erator ~ -
Strec
i
S°4
Dosal
Boiler
j»as
r* j.u I /•>•!
ruel Uil
Temperature
Control Stream
ated Lime
Rich^ Sulfur
urn Recovery
Source; 104.
Solid Circulation
Figure E-3 . Modes of operation, fluidizedbed oil gasification plant,
-------
TABLE E-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 kca!/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 (su I fate 1,000
generator) temperature
Limestone make-up rate 1 mole CaO/mo!e sulfur
Air/fuel ratio 20% of stctchiometric
Limestone utilization 5% sulfur by wf. in bed
Fluidization velocity (m/sec) 2.4
Minimum fluidizafion 0.9
velocity (m/sec)
Particle sizes, avg, ( ju ) 2,000
Gosifier bed depth, staric(m) 0.8 - 1.1
870
820
3 moles CaO/mole sulfur
20% of stoichiometric
19% sulfur by wf. in bed
2.4
0,3
1,000
1.1-1.2
Source: 104.
308
-------
CaS + 3/2 O2 - »- CaO +
The SO2 stream was transported to a sulfur recovery system, and the regenerated lime was
returned to the gasifier along with an approximately stoichiometric amount of fresh make-up
limestone.
Once-Through Operation . The elements of the once-through operation were a gasifier
vessel and a sulfate generator, or a predisposal vessel . The operation of the gasifier was
the same as for the regenerative operation. The sulfate generator operated similarly to the
regenerator but a a lower temperature ( w 800° C), so that the calcium sulfide from the
gasifier Was converted to calcium sulfate rather than calcium oxide. The dry calcium
sulfate was disposed of, and the gas stream from the sulfate generator was sent to the gasi-
fier. A limestone addition rate of up to three times that used in the regenerative operation
was necessary to achieve sulfur removal of 90 to 95 percent.
High -Pressure Combined -Cycle Gasification
The high pressure combined-cycle gasification process was accomplished by either once-
through or regenerative operation. Table E-2 lists the factors specified for the conceptual
design of the high pressure fluid-bed oil gasification process. Figure E-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 E-5 con-
sists of a fluidized-bed gasifier/desulfurizer vessel, a limestfcne/dolomite regenerator, and
a sulfur recovery section. Residual oil was injected into the gasifier vessel and fluidized-
bed of lime operated at 870° C with substoichiometric air (14 to 25 percent of stoichio-
metric). This yielded (by cracking, partial combustion, and HLS absorption by the lime-
stone or dolomite) a hot fuel gas of low energy value and sulfided lime or dolomite. The
gas was transported to the combined cycle plant where combustion was completed, and the
sulfided lime or dolomite was sent to the regenerator. The regenerator may be designed
to produce gas rich in H«S or SO- and regenerated sorbent with a decreased activity.
The SO_ or H2S stream was transported to a sulfur recovery system, and the regenerated
sorbent was 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 CO2 and H2O to produce H2S:
2) Regeneration with air to produce
CaS + 3/2 02 - —CaO + SO
309
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TABLE E-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// 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)
With CO2/H2O regeneration; 1150 C with air regeneration *
Source: 104.
310
-------
Hot (870 C) Fuel Gas to
combined cycle plant
Limestone/Dolomite 30°C
Steam
Water
OJ
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
A
' Auxiliary Power (cooling water pumping, oil pumping,
[ solid circulation, compression for regeneration)
Booster Compressor
Air from GT Compressor (air/fuel ratio = 14-25% of
stoic hi ometric)
Source: 104.
Figure E~4 . Energy balances flow diagram,
-------
Clean Fuel Gas to Combined
Cycle Plant
Cyclone
Fines
Disposal
Fines
Disposal
or SO2 to
"Sulfur Recovery
Cyclone
CO
S3
.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
HLO and CO« or Mr
Figure E<-5 , Regenerative high-pressure oil gasification process.
-------
Table E-3 lists the gasification product compositions and fuel heat values for a high-
pressure fluidized-bed gasification system with limestone regeneration.
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 is 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 + 2O2 *- CaSO4.
Process Environmental Comparison
Table E-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
environmental effects of a conventional oil-fired power plant using limestone scrubbing.
The spent sorbent from the fluidized bed oil gasification/desulfurization process was t-
dry and granular ( « 6 mm). The composition was primarily calcium oxide and calcium
sulfide with small amounts of calcium suifate—the spent stone from regenerative operation
containing approximately 1 to 2 percent CaS and, from once-through operation, a pro-
jection of 30 to 80 percent CaS. Table E-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,Great Britain)
CAFB Pilot Plant
The Chemically Active Fluid-Bed (CAFB) developed by Esso reduces sulfur oxide pollution
while using high sulfur oil to produce power. The process used 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 had the additional benefit of removing vanadium before the final
combustion states and thus eliminating a source of internal boiler corrosion.
When oil was combusted under sub-stoichiometric conditions, the sulfur was trapped by
lime as calcium sulfide:
H2S + CaO »- CaS + H2O
CaS formed by the reaction of H2S and CaO in the gasifier fluid-bed was converted back
to CaO in a fluid-bed regenerator by contact with air:
CaS + 3/2 O2 »
313
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TABLE .E-3. GASIFICATION PRODUCT COMPOSITIONS
Gas
N2
H2
CO
co2
H20
CH4
C2H4
H2S
Low heating value (hot) (10^ kcal/cu m)
Composition
]4%A/f°
50.74
0.82
13.40
6.70
0.00
9.43
18.86
0.05
-y70
•BMMMHBIBMHmMMaMldlMmWlMmHIIMBI
(% by volume)
25% A/F
47.74
2.64
7.97
7.97
20.56
6.55
6.55
0.02
~ 40
Air/fuel ratio.
Source: 104.
314
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TABLE E-4. ENVIRONMENTAL IMPACT COMPARISON
Environmental Factors
Conventional Oil-
Fired Power Plant
with Limestone
•Wet Scrubbing
Conventional Oil-Fired
Plant with Arm-Pressure
Oil Gasification
Combined Cycle Power Plant
with
Pressurized Oil Gasification
Regenerative Once-through Regenerative Once-through
Plant capita! investment ($/kw)
Plant energy cost (mills/kwhr)
Limestone waste (kkg/day)
Water usage (kkg/day)
SO9 emission (kg/106 kcal)
*• e
NO emission (kg/10 kcal)
X f
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
jDJant
160
9.2
450-700
0.63
0.29
0.04
-50
5.0
2,300
power
ratio of 20% of stoichiometric; 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 rote 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.
-------
TABLE E-5. ADVANTAGES OF ATMOSPHERIC PRESSURE OIL GASIFICATION
OVER STACK GAS WET SCRUBBERS
1 . Corrosion and fouling problems minimized in SOo removal process and in boiler
(minimum SO and V)
A
2. No flue gas reheat required.
3. 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.
J\
10. Potential market for spent CaO
Source: 104.
316
-------
The amount of regenerated lime removed was made up by the addition of fresh limestone to
the combustor; sulfur was recovered during the regeneration process in several ways,such as
conversion to HLSO , or elemental sulfur.
The main unit of the CAFB process was the combustor and regenerator system which was
made of an insulated steel shell contained in a refractory concrete cast. The gasifier
and regenerator were cavities in a single refractory concrete block. One block contained
other cavities which made up the gasifier outlet cyclones, the gas transfer ducts, and
transfer lines through which soiids circulated. The gasifier product gas fired a 2,930 kw
pressurized water boiler. The hot water was heat-exchanged through a forced convection
cooling tower. The rest of the system consisted of the necessary biowers,pumps,and in-
struments 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 investigated
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
obtained from the Amuary Refinery of the Crude Petroleum Co. Pilot plant runs had em-
ployed 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 ex-
perimental results appears in Table E-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 E-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 had 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 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 CO2/ CO, O^ and for appropriate in-
formation 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 502,0^,CO, and
CO_. The desulfurizing efficiency of the gasifier was calculated from the analysis of
theTully 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.
317
-------
TABLE E-6. SUMMARY OF EXPERIMENTAL RESULTS
Batch Tests
1. 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.
318
-------
Air
Propane (for
start-up)
Oil
Air
Meter
Fuel
Metering
Pump
Fuel In'jector
Air
CAFB Batch Reactor
Sample Flame
Sample
-»»-Gas to
Analyzers
Flare
Source; 53,
Figure E-6. Esso,England batch reactor oil gasification system,
-------
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 inde-
pendently of fuel and air rates. The type of reactor used for these studies is shown in
Figure E-7.
320
-------
71 cm
84cm
Source; 53.
Outgoing Gas Will
Be Burned Here
External
Cyclone
"T
~"~18 cm"
13 cm
J_i— H_
\_ T
r
•n
^
— Refractory Lining
Fluid! zed Bed
Fuellnjection l4cm
1 '
Distributor
Cos Pieheater
Air Suoolv
Bed
Datum
Figure E-7 • Batch reactor.
321
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GLOSSARY AND ABBREVIATIONS
The reader is referred to technical literature for definitions of more specific technical
terms. The following glossary defines terms unique to and to clarify procedures used in
this study.
Bottom ash residue: The wasted spent bed material from the FBC combustion chamber.
Commonly a mixture of limestone or dolomite and coal or oil combustion products.
CFA: English fly ash
Constituent: Signifies any of the several chemical elements or ions analyzed,including
chloride,sulfate,iron,lead,nickel,and zinc.
EFA: English fly ash from the Esso Research Centre oil FBC pilot plant in Abingdon, England.
ESBM: English spent bed materials.
FBC: Fluidized-bed combustor.
Fluidized-bed residues: The residue left after the combustion of high sulfur coal or the gasi-
fication of high sulfur residual oils in the presence of granular limestone or dolomite.
The residues contain unreacted limestone and dolomite, calcium and magnesium sulfur
compounds,heavy metals,and coal and oil ash. The residues were fly ashes and spent
bed materials designated as EFA,ESBM,NFA,NSBM,VFA,and VSBM.
Fly ash residue: Particulate removed from the FBC gas stream.
FSFA: English fine stacks fly ash.
Lysimeter: A porous ceramic-tipped device used to extract,by means of a vacuum, a sample
of the column percolating liquid from the strata.
NFA: Refers to New Jersey fly ash from the Exxon coal FBC pilot plant in Linden, New
Jersey.
NSBM: New Jersey spent bed material.
Pilot column leeching test: Adding and percolating a known type and quantity of water
through residue and subsurface strata materials, in order to collect leachate samples at
various points in the column for analysis of constituents.
Pilot-scale test column (pilot test column or test column): A 20.3 cm ID by 3 meter long
PVC pipe which contained a simulated natural residue disposal environment.
Potting tests: Plants grown in various sized pots under controlled conditions to investigate
the effects of adding FBC residues to soils.
322
-------
Glossary and Abbreviations (con.)
Residue leaching test": Adding and percolating a known type and quantity of water in order
to collect leachate samples for analysis after they have passed through a small 5 cm ID
by 30.5 cm high laboratory bench scale column containing a known quantity of fluid-
ized-bed residues.
Simulated environments: Refers to the eight types of prepared layers of stratum materials
placed in pilot test columns that represent stratographic sections of different subsurface
ground conditions. Included are limestone and dolomite quarries, sanitary landfills,
abandoned coal mines, the ocean floor, and clay,sand and silt soils.
Soluble salt extraction test: Often called a "mixing test," it is a batch laboratory proce-
dure wherein the soil or dried plant test sample was mixed with distilled water and
agitated for 24 hours. The mixture was then filtered and the liquid passing through the f
filter was then analyzed for its constituents.
Total residue digestion test: The dissolving of a soil or plant test sample material by nitric
acid, percloric acid, and hydrofluoric acid, and then subsequently analyzing its con-
stituents.
VFA: Virginia fly ash from the Pope,Evans and Robbins coal FBC pilot plant in Alexandria,
Virginia
VSBM: Virginia spent bed material.
Water holding capacity: The quantity of water remaining in an initially dried fluidized-
bed material after adding water and allowing the water to drain through a filter.
323
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-78-107
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE Environmental Assessment of Solid
Residues from Fluidized-bed Fuel Processing:
Final Report
5 REPORT DATE
June 1978
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Ralph Stone and Richard L. Kahle
9. PERFORMING ORGANIZATION NAME AND ADDRESS
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 AN.D PERIOD COVERED
Final; 11/75-12/77
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES IERL-RTP project officer is Walter B. Steen, Mail Drop 61, 919/
541-2825. EPA-600/7-77-139 is an earlier related report.
16. ABSTRACT,
The report gives results of a 2-year study of the environmental assess-
ment of solid residues generated by fluidized-bed combustion (FBC) of coal and gasi-
fication of oil. Included are a literature search, chemical 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 an which residues might be used, and gave data on typical
soil and geologic conditions at the evaluated disposal sites. Laboratory tests inclu-
ded total chemical characterization, composition of acid-, base-, and water-soluble
fractions, cation exchange 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, solis, and the ocean. Water was added to columns on a prescribed sched-
ule 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 capa-
city of the disposal environment to attenuate degradation. Residue use was consider-
ed for concrete, asphalt, soil cement, and lime/flyash aggregate.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Assessments
Solids
Residues
Coal
Fluidized-bed
Processing
Combustion
Fuel Oil
Gasification
Water Quality
Leaching
Soils
Geology
Pollution Control
Stationary Sources
Environmental Assess-
ment
Fluidized-bed Combus-
tion
Acid Mine Drainage
13B
14B
07D
21B
21D
08G,08M
13H,07A
3. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
359
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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